Title of Invention

"A PROCESS FOR OXIDIZING N-(PHOSPHONOMETHYL)IMINODIACETIC ACID OR A SALT THEREOF"

Abstract A process for oxidizing N-(phosphonomethyl)iminodiacetic acid or a salt thereof, the process comprising contacting N-(phosphonomethyl)iminodiacetic acid or a salt thereof with an oxidizing agent in the presence of a transition metal containing oxidation catalyst comprising a carbon support having formed thereon a transition metal composition comprising a transition metal and nitrogen, wherein the process is characterized in that the oxidation catalyst is substantially devoid of a noble metal active phase, and the oxidation catalyst comprises carbon nanotubes at the surface of the carbon support.
Full Text FIELD OF INVENTION
[0001] This invention relates to the field of
heterogeneous catalysis, and more particularly to catalysts
including carbon supports having formed thereon
compositions which comprise a transition metal in
combination with nitrogen and/or carbon. The invention
further relates to the fields of catalytic oxidation and
dehydrogenation reactions, including the preparation of
secondary amines by the catalytic oxidation of tertiary
amines and the preparation of carboxylic acids by the
catalytic dehydrogenation of alcohols.
BACKGROUND OF INVENTION
[0002] Investigations to discover alternative
materials for use in catalysis concerning various types of
reactions have included evaluation of the suitability of
carbide and nitride materials. Generally, carbide and
nitride materials have been considered as possible
alternatives for use in various types of catalysis since
they exhibit "metal-like" properties (e.g., high melting
points, hardness and strength). Levy & Boudart report that
carbide and nitride materials exhibit catalytic properties
similar to those of noble metals. See Platinum-Like
Behavior of Tungsten Carbide in Surface Catalysis (Science,
181 (1973), 547-549).
[0 003] Supported carbide and nitride catalysts have
been described generally and reported as suitable for use
in various types of reactions. Slaugh et al. describe a
supported molybdenum carbide composition prepared by
impregnating hexamolybdenum dodecachloride onto a porous
aluminous (e.g., Al203) , siliceous or carbonaceous (e.g.,
active carbon) support which is then heated in a carbiding
atmosphere at a temperature of about 650°C to about 750°C.
See U.S. Patent No. 4,325,842.
[0004] Leclercq et al. report a catalytic reforming
process employing catalysts based on tungsten and
molybdenum carbides supported on alumina and active carbon.
See U.S. Patent No. 4,522,708. These catalysts are
prepared by successive impregnations of active carbon using ammonium molybdate and ammonium tungstate solutions which are evaporated to dryness in air, calcined in a nitrogen atmosphere which is followed by reduction of the tungsten and molybdenum oxides formed during calcination under a hydrogen atmosphere. These compounds are then heated under hydrogen to allow the active phase compounds to react with the carbon support to produce mixed carbides of tungsten and molybdenum.
[0005] Sherif et al. report carbon-supported Group
VIB metal (e.g., Cr, Mo, W) carbide-containing catalysts
formed by calcining a carbon support (e.g., activated
carbon and acid washed activated carbon) which has been
impregnated with a water-soluble precursor for the metal
carbide. See International Publication No. WO 95/32150.
[0006] Oyama reports interstitial alloys formed by
the incorporation of carbon, nitrogen, and oxygen into the lattices of early transition metals to produce a class of compounds with metallic character. See Preparation and Catalytic Properties of Transition Metal Carbides and Nitrides (Catalysis Today, 15, 179-200. 1992) [0007] Iwai et al. report carbonitrides consisting of a carbide and nitride of the metals of Groups IV, V, and VI prepared by calcining a precursor obtained by reacting polyphenol with the reaction product of ammonia and the halide of a Group IV, V, or VI metal. The precursor may also be obtained by reacting the reaction product of polyphenol and the halide of a Group IV, V, or VI metal with ammonia. See U.S. Patent No. 4,333,916.
[0008] Faubert et al. report on methods for preparing
iron-containing catalysts containing iron carbide particles prepared by activation of a precursor consisting of Fe hydroxide adsorbed on carbon black by hydrogen reduction and pyrolysis in the presence of acetonitrile. See Activation and characterization of Fe-based catalysts for the reduction of oxygen in polymer electrolyte fuel cells (Electrochimica Acta, Vol. 43, Nos. 14-15, pp. 1969-1984,1998)
[0009] Cote et al. report on methods for preparation
of non-noble metal based catalysts prepared by pyrolysis of
a transition metal hydroxide (e.g., vanadium, chromium,
iron, cobalt hydroxide) on carbon black including reduction
in the presence of hydrogen and heating in the presence of
acetonitrile. See Non-noble metal-based catalysts for the
reduction of oxygen in polymer electrolyte fuel cells
{Journal of New Materials for Electrochemical Systems, I,
7-16, 1998) .
[0010] Catalysts containing carbides or nitrides may
be advantageous in certain instances due to the absence of
a costly noble metal. One such reaction in which an active
catalyst which does not require the presence of a noble
metal may be advantageous is the oxidation of a tertiary
amine (e.g., N-(phosphonomethyl)iminodiacetic acid) to
produce a secondary amine (e.g., N-
(phosphonomethyl)glycine). N-(phosphonomethyl)glycine
(known in the agricultural chemical industry as
"glyphosate") is described in Franz, U.S. Patent No.
3,799,758. N-(phosphonomethyl)glycine and its salts are
conveniently applied as a post-emergent herbicide in an
aqueous formulation. It is a highly effective and
commercially important broad-spectrum herbicide useful in
killing or controlling the growth of a wide variety of
plants, including germinating seeds, emerging seedlings,
maturing and established woody and herbaceous vegetation,
and aquatic plants.
[0011] Various methods for making N-
(phosphonomethyl)glycine are known in the art. Franz (U.S.
Patent No. 3,950,402) teaches that N-
(phosphonomethyl)glycine may be prepared by the liquid
phase oxidative cleavage of
N-(phosphonomethyl)iminodiacetic acid (sometimes referred
to as "PMIDA") with oxygen in the presence of a catalyst
comprising a noble metal deposited on the surface of an
activated carbon support:
N o b l e M e t a l on
C a r b o n C a t a l y s t
( H O ) 2P ( O ) C H 2 N (CH2C02H ) 2 + 1 / 2 O2 ' *•
( H O ) 2P(O)CH2NHCH2C02 H + CO2 + HCHO
[0012] Other by-products also may form, such as
formic acid, which is formed by the oxidation of the
formaldehyde by-product; and aminomethylphosphonic acid
("AMPA"), which is formed by the oxidation of N-
(phosphonomethyl)glycine. Even though the Franz method
produces an acceptable yield and purity of N-
(phosphonomethyl)glycine, high losses of the costly noble
metal into the reaction solution (i.e., "leaching") result because under the oxidation conditions of the reaction, some of the noble metal is oxidized into a more soluble form and both PMIDA and N- (phosphonomethyl) glycine act as ligands which solubilize the noble metal.
[0013] In U.S. Patent No. 3,969,398, Hershman teaches
that activated carbon alone, without the presence of a
noble metal, may be used to effect the oxidative cleavage
of PMIDA to form N-(phosphonomethyl)glycine. In U.S.
Patent Nos. 4,624,937, Chou further teaches that the
activity of the carbon catalyst taught by Hershman may be
increased by removing the oxides from the surface of the
carbon catalyst before using it in the oxidation reaction.
See also, U.S. Patent Mo. 4,696,772, which provides a
separate discussion by Chou regarding increasing the
activity of the carbon catalyst by removing oxides from the surface of the carbon catalyst. Although these processes obviously do not suffer from noble metal leaching, they do tend to produce greater concentrations of formaldehyde byproduct when used to effect the oxidative cleavage of N-(phosphonomethyl)iminodiacetic acid. This formaldehyde by-product is undesirable because it reacts with N(phosphonomethyl)glycine to produce unwanted by-products (mainly N-methyl-N-(phosphonomethyl)glycine, sometimes referred to as "NMG") which reduce the N- (phosphonomethyl)glycine yield. In addition, the formaldehyde by-product itself is undesirable because of its potential toxicity. See Smith, U.S. Patent No. 5,606,107.
[0014] It has been suggested that the formaldehyde be
simultaneously oxidized to carbon dioxide and water as the
PMIDA is oxidized to N-(phosphonomethyl) glycine in a single
reactor, thus giving the following reaction:
(HO)2P(0)CH2N(CH2C02H)2
C a t a l y s t + O2
(HO)2P(0)CH2NHCH2C02H + 2C02 + H2O
[0015] As the above teachings suggest, such a process
requires the presence of both carbon (which primarily
effects the oxidation of PMIDA to form N-
(phosphonomethyl)glycine and formaldehyde) and a noble
metal (which primarily effects the oxidation of
formaldehyde to formic acid, carbon dioxide and water).
Previous attempts to develop a stable catalyst for such an
oxidation process, however, have not been entirely
satisfactory.
[0016] Like Franz, Ramon et al. (U.S. Patent No.
5,179,228) teach using a noble metal deposited on the
surface of a carbon support. To reduce the problem of
leaching (which Ramon et al. report to be as great as 30%
noble metal loss per cycle), however, Ramon et al. teach
flushing the reaction mixture with nitrogen under pressure
after the oxidation reaction is completed to cause redeposition
of the noble metal onto the surface of the
carbon support. According to Ramon et al., nitrogen
flushing reduces the noble metal loss to less than 1%.
Still, the amount of noble metal loss incurred with this
method is unacceptable. In addition, re-depositing the
noble metal can lead to loss of noble metal surface area
which, in turn, decreases the activity of the catalyst.
[0017] Using a different approach, Felthouse (U.S.
Patent No. 4,582,650) teaches using two catalysts: (i) an
activated carbon to effect the oxidation of PMIDA into N-
(phosphonomethyl)glycine, and (ii) a co-catalyst to
concurrently effect the oxidation of formaldehyde into
carbon dioxide and water. The co-catalyst consists of an
aluminosilicate support having a noble metal located within
its pores. The pores are sized to exclude N-
(phosphonomethyl)glycine and thereby prevent the noble
metal of the co-catalyst from being poisoned by N-
(phosphonomethyl)glycine. According to Felthouse, use of
these two catalysts together allows for the simultaneous
oxidation of PMIDA to N-(phosphonomethyl)glycine and of
formaldehyde to carbon dioxide and water. This approach,
however, suffers from several disadvantages: (1) it is
difficult to recover the costly noble metal from the
aluminosilicate support for re-use; (2) it is difficult to
design the two catalysts so that the rates between them are
matched; and (3) the carbon support, which has no noble
metal deposited on its surface, tends to deactivate at a
rate which can exceed 10% per cycle.
[0018] Ebner et al., in U.S. Patent No. 6,417,133,
describe a deeply reduced noble metal on carbon catalyst
which is characterized by a CO desorption of less than 1.2
mmole/g, preferably less than 0.5 mmole/g, when a dry
sample of the catalyst, after being heated at a temperature
of about 500°C for about 1 hour in a hydrogen atmosphere
and before being exposed to an oxidant following the
heating in the hydrogen atmosphere, is heated in a helium
atmosphere from about 20° to- about 900°C at a rate of about
10°C per minute, and then at about 900°C for about 30
minutes. The catalyst is additionally or alternatively
characterized as having a ratio of carbon atoms to oxygen
atoms of at least about 20:1, preferably at least about
30:1, at the surface as measured by x-ray photoelectron
spectroscopy after the catalyst is heated at a temperature
of about 500°C for about 1 hour in a hydrogen atmosphere
and before the catalyst is exposed to an oxidant following
the heating in the hydrogen atmosphere.
[0019] The catalysts of U.S. Patent No. 6,417,133
have proven to be highly advantageous and effective
catalysts for the oxidation of N-
(phosphonomethyl)iminodiacetic acid to N-
(phosphonomethyl)glycine, and for the further oxidation of
by-product formaldehyde and formic acid, and without
excessive leaching of noble metal from the carbon support.
It has further been discovered that these catalysts are
effective in the operation of a continuous process for the
production of N-(phosphonomethyl)glycine by oxidation of N-
(phosphonomethyl)iminodiacetic acid.
[0020] Carbon and noble metal sites on the catalysts
of U.S. Patent No. 6,417,133 are highly effective for
transfer of electrons in the oxidation of N-
(phosphonomethyl)iminodiacetic acid, and the noble metal
sites are especially effective for this purpose in the
oxidation of formaldehyde and formic acid. However, it
would be advantageous to have a multi-reaction catalyst and
reaction process which oxidizes PMIDA to N-
(phosphonomethyl)glycine while simultaneously exhibiting
desired oxidation of formaldehyde to carbon dioxide and
water (i.e., increased formaldehyde activity), and which
does not require the presence of a noble metal (e.g., a
carbide, nitride, or carbide-nitride containing catalyst).
Additionally or alternatively, it would likewise be
advantageous to have such a multi-reaction catalyst and
reaction process which does not require costly noble metal,
or which functions effectively with a reduced noble metal
content relative to catalysts currently available for
commercial manufacture of N-(phosphonomethyl)glycine or
other secondary amines.
[0021] Salts of iminodiacetic acid may be
phosphonomethylated to form PMIDA which, in turn, may be
oxidized to form N-(phosphonomethyl)glycine in accordance
with the above description.
[0022] See, e.g., Gentilcore, U.S. Patent No.
4,775,498 (disclosing a method to phosphonomethylate a salt
of iminodiacetic acid); Ebner, et al., U.S. Patent No.
6,417,133 (disclosing methods for oxidizing PMIDA).
[0023] Salts of nitrilotriacetic acid, for example,
are excellent chelating agents, and consequently may be
used as detergent builders, water-softening agents,
scouring aids, dyeing assistants, paper-coating agents,
scale inhibitors, and agents for preventing soap
degeneration. And many amino-carboxylic acid salts (e.g.,
salts of glycine, salts of iminodiacetic acid, etc.) may
also be neutralized to their corresponding acids and then
used, for example, as chelating agents; in food
preparations; and as raw materials for making
Pharmaceuticals, agricultural chemicals, and pesticides.
See, e.g., Franz, et al., Glyphosate: A Unique Global
Herbicide (ACS Monograph 189, 1997) at pp. 234-41
(disclosing the use of glycine and iminodiacetic acid
compounds as raw materials to form N-
(phosphonomethyl)glycine).
[0024] It has long been known that a carboxylic acid
salt may be prepared from a primary alcohol by
dehydrogenating the alcohol using a copper-containing or
silver-containing catalyst. In 1945, Chitwood first
reported forming a carboxylic acid salt (specifically, the
potassium salt of glycine) by oxidizing a primary alcohol
(specifically, monoethanolamine) in an alkaline environment
(specifically, in a mixture containing potassium hydroxide)
using a copper-containing catalyst (specifically, copper
metal or cupric oxide, which reportedly was reduced to
copper metal under the reaction conditions) or a silvercontaining
catalyst (specifically, silver metal or silver
oxide, which reportedly was reduced to silver metal under
the reaction conditions). See Chitwood, U.S. Patent No.
2,384,817. Chitwood, however, reported that coppercontaining
compounds are disadvantageous for this reaction
because the copper coagulates over time, thereby causing
the copper-containing compounds to have a short duration of
maximum catalytic activity. Chitwood also reported that
silver-containing compounds have relatively low activity
(the silver oxide also reportedly coagulates over time).
[0025] In 1988, Goto et al. reported forming a
carboxylic acid salt by oxidizing an ethanolamine compound
in an alkaline solution (specifically, an aqueous solution
containing the hydroxide of an alkali metal or an alkaline
earth metal) using Raney copper. See Goto et al., U.S.
Patent No. 4,782,183. Goto et al. reported selectivities
of at least 94.8% when dehydrogenating monoethanolamine,
diethanolamine, and triethanolamine to form salts of
glycine, iminodiacetic acid, and nitrilotriacetic acid,
respectively. Raney copper, however, is disadvantageous
because (like Chitwood's copper-containing compounds) Raney
copper deactivates over time. See, e.g., Franczyk, U.S.
Patent No. 5,292,936, Table 1 (showing the reaction time
for Raney copper to increase from 4 to 8 hours over 9
cycles).
[0026] Various developments have been reported which
address the instability of copper-containing catalysts when
used to dehydrogenate primary alcohols. Although these
developments have made the use of copper catalysts more
commercially viable, their results are still not entirely
satisfactory.
[0027] Ebner et al. report using a catalyst
comprising copper supported on an alkali-resistant support
(particularly a carbon support) to dehydrogenate primary
alcohols to make carboxylic acid salts. See Ebner et al.,
U.S. Patent No. 5,627,125. This catalyst also comprises
about 0.05 to about 10% by weight of a noble metal to
anchor and disperse the copper to the support. Although
the Ebner catalysts afford shorter reaction times relative
to previously disclosed copper-containing catalysts, their
catalyst may be relatively expensive due to the need for
the noble metal to anchor the copper to the support. Ebner
et al.'s catalyst often loses activity over time with use
(although the rate of deactivation is often less than the
rate of deactivation of the Franczyk catalysts). See,
e.g., Ebner et al., Table 1 (showing the reaction time
increasing from 103 to 150 minutes over 9 cycles) and Table
2 (showing the reaction time increasing from 61 to 155
minutes over 8 cycles). As with the Franczyk catalysts,
this problem tends to arise particularly where the primary
alcohol or the dehydrogenation salt product is a chelating
agent.
[0028] Morgenstern et al. report a process for
dehydrogenating a primary alcohol (e.g., amino alcohols
such as diethanolamine) to make a carboxylic acid salt
(e.g., disodium iminodiacetic acid) using a coppercontaining
or silver-containing catalyst including a metal
support (e.g., a metal sponge support) coated with the
copper or silver. See Morgenstern et al., U.S. Patent No.
6,376,708. The catalyst described by Morgenstern et al.
may further include a non-copper or non-silver metal
deposited on the support and having the copper-containing
or silver-containing catalyst active phase deposited
thereon. The catalyst of Morgenstern et al. is an
economical alternative to previously known coppercontaining
catalysts since it does not require an expensive
noble metal such as those which are required in the
catalyst described by Ebner et al. while exhibiting
acceptable and potentially improved durability and
activity. However, it has been discovered that the
catalyst described by Morgenstern et al. may lead to the
production of unwanted byproducts (e.g., sarcosine) which
may have an adverse impact on processes incorporating a
carboxylic acid salt produced using this catalyst.
[0029] Other reported copper-containing catalysts
contain a non-carbon support, such as, SiO2, A12O3/ TiO2,
Zr02, and the like. See, e.g., Akzo Nobel, WO 98/13140
(disclosing a catalyst consisting of copper on Zr02) .
These supports, however, tend to be vulnerable to attrition
under the reaction conditions normally present when
dehydrogenating a primary alcohol, and are therefore
usually less suitable than Ebner et al. ' s carbon supports.
Vulnerability to attrition tends to also cause these
supports to exhibit poor filtration characteristics.
[0030] Use of copper-containing and silver-containing
catalysts in other types of oxidation reactions has also
been reported. Applicants, however, are unaware of any
such disclosures which address the problems associated with
copper-containing or silver-containing catalysts in
processes involving the dehydrogenation of primary alcohols
to form carboxylic acid salts.
[0031] Thus, although positive advances have been
reported for converting a primary alcohol to a carboxylic
acid salt using a copper-containing catalyst, in particular
carbon-supported copper-containing catalysts, there
continues to be a need for a more economical catalyst that
has high surface area, has high activity, exhibits
stability (i.e., maintains its activity) over time with
usage, and minimizes the production of unwanted byproducts.
This need particularly exists where the primary alcohol
substrate and/or carboxylic acid salt product is a
chelating agent (e.g., a salt of iminodiacetic acid). A
need remains for alternative catalysts for the
dehydrogenation of alcohols, and in particular for the
dehydrogenation of diethanolamine to iminodiacetic acid, or
its salts. There is further need for such catalysts which
do not require the presence of a noble metal for anchoring
a copper active phase to a support. It is particularly
desirous to provide such alternative catalysts which are
effective for anaerobic dehydrogenation. The hydrogen
produced by the dehydrogenation of primary alcohols can
also be useful, particularly in the production of fuel
cells. For example, W.H. Cheng, in Ace. Chem. Rev., vol.
32, 685-91(1999), describes the conversion of primary
alcohols such as methanol to hydrogen as a safe and readily
transportable source of hydrogen fuel cells for a variety
of applications, most notably automotive applications.
SUMMARY OF INVENTION
[0032] This invention provides catalysts and methods
for preparing catalysts that are useful in various
heterogeneous oxidation and dehydrogenation reactions,
including the preparation of secondary amines by the
catalytic oxidation of tertiary amines and the preparation
of carboxylic acids by the catalytic dehydrogenation of
primary alcohols. The catalysts include supports,
particularly carbon supports, having formed thereon
compositions which comprise a transition metal in
combination with nitrogen and/or carbon and optionally a
further metal deposited on the modified support. The
oxidation catalysts disclosed herein are particularly
useful in the oxidative cleavage of PMIDA reagents such as
N- (phosphonomethyl)iminodiacetic acid to form an N-
(phosphonomethyl)glycine product. In such reactions, the
catalyst of the present invention have proven to be
effective in catalyzing the further oxidation of the
formaldehyde and formic acid by-products. The
dehydrogenation catalysts of the present invention are
particularly suited for the preparation of iminodiacetic
acid compounds by the catalytic dehydrogenation of
diethanolamine.
[0033] Briefly, therefore, the present invention is
directed to a catalyst comprising a carbon support having
formed thereon a transition metal composition comprising a
transition metal, nitrogen, and carbon. In a first
embodiment, the catalyst has a total Langmuir surface area
of at least about 600 m2/g. In a second embodiment, the
total Langmuir surface area of the catalyst is at least
about 60% of the total Langmuir surface area of the carbon
support prior to formation of the transition metal
composition thereon. In another embodiment, the micropore
Langmuir surface area of the catalyst is at least about
750 m2/g and at least about 55% of the micropore Langmuir
surface area of the carbon support prior to formation of
the transition metal composition thereon. In another
embodiment, the combined mesopore and macropore Langmuir
surface area of the catalyst is at least about 175 m2/g and
at least about 70% of the combined mesopore and macropore
Langmuir surface area of the carbon support prior to
formation of the transition metal composition thereon. In
a still further embodiment, the transition metal
composition is present on the carbon support in the form of
discrete particles and at least about 95% by weight of the
particles have a particle size, in their largest dimension,
of less than about 1000 nm.
[0034] In another embodiment, the catalyst comprising
a carbon support having formed thereon a transition metal
composition comprising a transition metal, carbon and
nitrogen further comprises carbon nanotubes at the surface
of the carbon support. The carbon nanotubes have a
diameter of at least about 0.01 p.m. In an alternative
embodiment, the carbon nanotubes have a diameter of less
than about 1 p.m.
[0035] In a further embodiment, the catalyst
comprises a carbon support having formed thereon a
transition metal composition comprising a transition metal
and nitrogen. At least about 5% by weight of the
transition metal is present in a non-zero oxidation state
and the catalyst has a total Langmuir surface area of at
least about 600 m2/g.
[0036] In another embodiment, the catalyst comprises
a carbon support having formed thereon a transition metal
composition comprising a plurality of transition metals and
nitrogen. The catalyst has a total Langmuir surface area
of at least about 600 m2/g.
[0037] In another embodiment, the catalyst comprises
a modified carbon support comprising a carbon support
having formed thereon a transition metal composition
comprising a transition metal, carbon, and nitrogen. A
metal selected from the group consisting of copper, nickel,
cadmium, cobalt, and combinations thereof is deposited on
the modified carbon support in a proportion of from about
2% to about 8% by weight of the catalyst.
[0038] In another embodiment, the catalyst comprises
a modified carbon support comprising a carbon support
having formed thereon a transition metal composition
comprising a transition metal, carbon, and nitrogen. An
active phase comprising copper is deposited on the modified
carbon support.
[0039] In another embodiment of the present
invention, the catalyst comprises a carbon support having
formed thereon a transition metal composition comprising a
transition metal, nitrogen, and carbon. The catalyst is
further characterized by its effectiveness for catalyzing
the oxidation of formaldehyde. More particularly, when a
representative aqueous solution containing about 0.8% by
weight formaldehyde and having a pH of about 1.5 is
contacted with an oxidizing agent in the presence of such
catalyst at a temperature of about 100°C, at least about 5%
of the formaldehyde is converted to formic acid, carbon
dioxide and/or water.
[0040] In yet another embodiment, the catalyst
comprising a carbon support having formed thereon a
transition metal composition comprising a transition metal,
nitrogen, and carbon is characterized by its effectiveness
for catalyzing the oxidation of formaldehyde in a
representative aqueous solution containing about 0.8% by
weight formaldehyde and about 6% by weight of N-
(phosphonomethyl)iminodiacetic acid and having a pH of
about 1.5. More particularly, at least about 50% of the
formaldehyde is converted to formic acid, carbon dioxide
and/or water when the representative aqueous solution is
contacted with an oxidizing agent in the presence of the
catalyst at a temperature of about 100°C.
[0041] In a further embodiment, the catalyst
comprises a supporting structure selected from the group
consisting of silica, alumina, and carbon supports. A
transition metal composition comprising a transition metal,
carbon, and nitrogen is formed on the support. At least
about 5% by weight of the transition metal is present in a
non-zero oxidation state and the catalyst has a total
Langmuir surface area of at least about 600 m2/g.
[0042] In a still further embodiment, the catalyst
comprises a carbon support having formed thereon a
composition comprising carbon, nitrogen, and an element
selected from the group consisting of Group IIA, tellurium,
selenium, and combinations thereof.
[0043] The present invention is further directed to
processes for the oxidation of an organic substrate using
the various embodiments of the oxidation catalysts
described above. In such processes, the organic substrate
is contacted with an oxidizing agent in the presence of the
oxidation catalyst.
[0044] In a further embodiment, the process for
oxidizing an organic substrate comprises contacting the
organic substrate with an oxidizing agent in the presence
of an oxidation catalyst comprising a carbon support having
formed thereon a transition metal composition comprising a
transition metal and nitrogen. The transition metal is
selected from the group consisting of copper, silver,
vanadium, chromium, molybdenum, tungsten, manganese,
nickel, ruthenium, cerium, and combinations thereof.
[0045] The present invention is further directed to
processes for the preparation of a catalyst comprising a
transition metal composition comprising a transition metal
and nitrogen on a porous carbon support. In one
embodiment, the porous carbon support is in particulate
form and a fixed or fluidized bed of the particulate porous
carbon support having thereon a precursor of the transition
metal composition is contacted with a vapor phase source of
a nitrogen-containing compound. The bed of the
particulate porous carbon support is heated while in
contact with the nitrogen-containing compound to form the
transition metal composition on the carbon support.
[0046] In accordance with another embodiment, the
process for preparing the catalyst comprises contacting the
porous carbon support having thereon a precursor of the
transition metal composition with a vapor phase source of a
nitrogen-containing compound. The porous carbon support is
heated to a temperature of from about 600 to about 975°C
while in contact with the nitrogen-containing compound to
form the transition metal composition on the carbon
support.
[0047] A further aspect of the present invention
provides dehydrogenation catalysts and processes for their
preparation and use in catalyzing the dehydrogenation of a
primary alcohol to produce a salt of a carboxylic acid.
[0048] In one embodiment, the catalyst comprises a
modified carbon support comprising a carbon support having
formed thereon a composition comprising carbon and a
transition metal selected from tungsten and molybdenum. A
metal selected from Group IB and Group VIII metals is
deposited on the modified carbon support.
[0049] In another embodiment a modified carbon
catalyst support is provided comprising a carbon support
and a composition comprising nitrogen and a transition
metal selected from the group consisting of molybdenum and
tungsten formed on the carbon support. A catalyst may be
formed by depositing a metal selected from Group IB and
Group VIII metals onto such a modified carbon support.
[0050] The invention is further directed to a process
for forming a catalyst comprising a transition metal
composition comprising carbon and a transition metal
selected from molybdenum and tungsten on a porous carbon
support. The process comprises contacting a hydrocarbon
and the porous carbon support having thereon a precursor of
the transition metal composition, thereby producing a
modified carbon support having the transition metal
composition formed thereon. A metal selected from Group IB
and Group VIII metals is deposited on the modified catalyst
support.
[0051] Another embodiment of the invention provides a
process for forming a catalyst comprising a transition
metal composition comprising nitrogen and a transition
metal selected from molybdenum and tungsten on a porous
carbon support. The process comprises contacting a
nitrogen-containing compound and the porous carbon support
having thereon a precursor of the transition metal
composition, thereby producing a modified carbon support
having the transition metal composition formed thereon.
[0052] The invention is further directed to a process
for preparing a salt of a carboxylic acid. The process
comprises contacting a primary alcohol with a catalyst in
an alkaline medium. The catalyst comprises a modified
carbon support having copper deposited thereon. The
modified carbon support comprises a carbon support having a
transition metal composition formed thereon. The
transition metal composition comprises a transition metal
and nitrogen or a transition metal and carbon.
[0053] Other objects and features of this invention
will be in part apparent and in part pointed out
hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] Fig. 1 is a Scanning Electron Microscopy (SEM)
image of a carbon supported molybdenum carbide having
copper deposited thereon.
[0055] Fig. 2 is a SEM image of a carbon supported
molybdenum carbide having copper deposited thereon.
[0056] Fig. 3 is a Transmission Electron Microscopy
(TEM) image of a carbon supported molybdenum carbide having
copper deposited thereon.
[0057] Fig. 4 is a SEM image of a carbon supported
molybdenum carbide having copper deposited thereon.
[0058] Fig. 5 is a High Resolution Transmission
Electron Microscopy (HRTEM) image of a carbon-supported
molybdenum carbide.
[0059] Fig. 6 is a SEM image of a carbon supported
molybdenum carbide.
[0060] Fig. 7 is a TEM image of a carbon supported
molybdenum carbide.
[0061] Fig. 8 shows the percentage of carbon dioxide
in the exit gas produced during N-
(phosphonomethyl)iminodiacetic acid (PMIDA) oxidation
carried out using various catalysts as described in Example
24.
[0062] Fig. 9 shows carbon dioxide profiles of PMIDA
oxidation carried out using various catalysts as described
in Example 25.
[0063] Fig. 10 shows carbon dioxide profiles of PMIDA
oxidation carried out using various catalysts as described
in Example 28.
[0064] Fig. 11 shows the carbon dioxide percentage in
the exit gas produced during PMIDA oxidation as described
in Example 29.
[0065] Fig. 12 shows the carbon dioxide percentage in
the exit gas produced during PMIDA oxidation as described
in Example 29.
[0066] Fig. 13 shows the carbon dioxide percentage in
the exit gas produced during PMIDA oxidation as described
in Example 29.
[0067] Fig. 14 shows the carbon dioxide percentage in
the exit gas produced during PMIDA oxidation as described
in Example 29.
[0068] Fig. 15 shows the results of the carbon
dioxide drop-point measurement comparison as described in
Example 32.
[0069] Fig. 16 shows carbon dioxide generation during
PMIDA oxidation carried out as described in Example 34.
[0070] Fig. 17 shows a comparison of the pore surface
area of various catalysts as described in Example 48.
[0071] Fig. 18 shows a comparison of the pore surface
area of various catalysts as described in Example 48.
[0072] Figs. 19-30 show X-ray diffraction (XRD)
results for catalyst samples analyzed as described in
Example 50.
[0073] Figs. 31-41 are SEM images of catalyst samples
analyzed as described in Example 51.
[0074] Fig. 42 is an Energy dispersive X-ray analysis
spectroscopy (EDS) spectrum of a catalyst sample analyzed
as described in Example 51.
[0075] Figs. 43 and 44 are TEM images of catalyst
samples analyzed as described in Example 51.
[0076] Figs. 45 and 46 are SEM Images of catalyst
samples analyzed as described in Example 51.
[0077] Figs. 47 and 48 are TEM images of catalyst
samples analyzed as described in Example 51.
[0078] Figs. 49-52 are SEM Images of catalyst samples
analyzed as described in Example 51.
[0079] Figs. 53 and 54 are TEM images of catalyst
samples analyzed as described in Example 51.
[0080] Figs. 55 and 56 are X-ray Photoelectron
Spectroscopy(XPS) results for samples analyzed as described
in Example 52.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0081] Described herein are catalysts containing a
transition metal composition formed on a carbon support.
The catalyst generally comprises a transition metal
composition comprising a transition metal and nitrogen, a
transition metal and carbon, or a transition metal,
nitrogen, and carbon. A transition metal composition
comprising a transition metal and nitrogen preferably
includes a transition metal nitride while a transition
metal composition comprising a transition metal and carbon
preferably includes a transition metal carbide. Transition
metal compositions including a transition metal, nitrogen,
and carbon may include both a transition metal nitride and
a transition metal carbide, and/or a transition metal
carbide-nitride.
[0082] In various embodiments, the catalyst comprises
a transition metal/carbon composition which includes a
transition metal carbide (e.g., molybdenum carbide). In
other embodiments, the catalyst comprises a transition
metal/nitrogen composition which includes a transition
metal nitride (e.g., molybdenum nitride). In still other
embodiments, the catalyst includes a transition metal
carbide (e.g., cobalt carbide) and a transition metal
nitride (e.g., cobalt nitride). In still further
embodiments, the catalyst includes a transition metal
carbide-nitride (e.g., cobalt carbide-nitride).
[0083] Catalysts of the present invention may be used
to catalyze liquid phase (i.e., in an aqueous solution or
an organic solvent) oxidation reactions and, in particular,
the oxidation of a tertiary amine (e.g., N-
(phosphonomethyl)iminodiacetic acid) to produce a secondary
amine (e.g., N-(phosphonomethyl)glycine). Advantageously,
the catalysts of the present invention including a
transition metal composition formed on a carbon support
also catalyze oxidation of the formaldehyde by-product that
is formed in the.oxidation of N-
(phosphonomethyl)iminodiacetic acid) to N-
(phosphonomethyl) glycine) .
[0084] In certain embodiments, the catalyst of the
present invention includes a noble metal deposited on a
modified carbon support including a transition metal
composition formed on a carbon support. Presence of the
noble metal generally enhances the effectiveness of the
catalyst in oxidation of the formaldehyde by-product of the
oxidation of N-(phosphonomethyl)iminodiacetic acid to N-
(phosphonomethyl)glycine) . Although the catalysts of the
present invention are advantageous in catalyzing the
oxidation of tertiary amines such as N-
(phosphonomethyl)iminodiacetic acid in the absence of a
noble metal, and may also be effective for the oxidation of
by-products such as formaldehyde, the presence of a noble
metal active phase may be preferable in some instances. By
evaluating experimental data for a particular substrate and
process, applying standard economic principles, those
skilled in the art can weigh the advantages of a noble
metal-free catalyst against a noble metal catalyst with
respect to yields, productivity, capital, depreciation,
labor and materials expense.
[0085] Also described herein are catalysts useful for
the conversion of a primary alcohol to a salt of a
carboxylic acid using a catalyst including a metalcontaining
(e.g., copper-containing) active phase deposited
over a modified carbon support including a transition metal
composition formed on a carbon support. Such catalysts are
suitable for converting a wide range of primary alcohols to
carboxylic acid salts. The term "primary alcohol" refers
to any alcohol comprising a hydroxy group attached to a.
carbon which is bound to two hydrogen atoms (e.g., RCH2OH).
Dehydrogenation of the primary alcohol yields a
carboxylic acid salt and hydrogen gas and is generally
carried out in a heated reaction zone containing the
primary alcohol, a base and a catalyst. In various
embodiments, a catalyst of the present invention is used
for the dehydrogenation of diethanolamine to disodium
iminodiacetic acid.
[0086] Further described herein are processes for
preparing transition metal compositions comprising a
transition metal and nitrogen, a transition metal and
carbon, or a transition metal, nitrogen, and carbon on a
carbon support. Also detailed herein are processes for
depositing a metal-containing active phase on a modified
carbon support including a transition metal composition
formed on a carbon support. Reference to deposition of a
metal-containing "active" phase onto catalysts including a
transition metal composition formed on a carbon support
(e.g., a modified carbon support) should not be taken as
exclusive of any catalytic activity of the transition metal
composition formed on the carbon support, or of the carbon
support itself. For example, the carbon support alone is
known to catalyze the oxidation of tertiary amines to
secondary amines, and the transition metal composition
possesses catalytic properties as well.
[0087] Generally, the supporting structure may
comprise any material suitable for formation of a
transition metal composition thereon and/or depositing a
metal-containing active phase onto a modified support
including a transition metal composition formed on a carbon
support. Preferably, the supporting structure is in the
form of a carbon support. In particular, carbon supports
are preferred for the conversion of primary alcohols to
carboxylic acid salts due to their resistance to the
alkaline environment of the reaction.
[0088] In general, the carbon supports used in the
present invention are well known in the art. Activated,
non-graphitized carbon supports are preferred. These
supports are characterized by high adsorptive capa'city for
gases, vapors, and colloidal solids and relatively high
specific surface areas. The support suitably may be a
carbon, char, or charcoal produced by means known in the
art, for example, by destructive distillation of wood,
peat, lignite, coal, nut shells, bones, vegetable, or other
natural or synthetic carbonaceous matter, but preferably is
"activated" to develop adsorptive power. Activation
usually is achieved by heating to high temperatures (800-
900°C) with steam or with carbon dioxide which brings about
a porous particle structure and increased specific surface
area. In some cases, hygroscopic substances, such as zinc
chloride and/or phosphoric acid or sodium sulfate, are
added before the destructive distillation or activation, to
increase adsorptive capacity. Preferably, the carbon
content of the carbon support ranges from about 10% for
bone charcoal to about 98% for some wood chars and nearly
100% for activated carbons derived from organic polymers.
The non-carbonaceous matter in commercially available
activated carbon materials normally will vary depending on
such factors as precursor origin, processing, and
activation method. Many commercially available carbon
supports contain small amounts of metals. In certain
embodiments, carbon supports having the fewest oxygencontaining
functional groups at their surfaces are most
preferred.
[0089] The form of the carbon support is not
critical. In certain embodiments, the support is a
monolithic support. Suitable monolithic supports may have
a wide variety of shapes. Such a support may be, for
example, in the form of a screen or honeycomb. Such a
support may also, for example, be in the form of a reactor
impeller.
[0090] In a particularly preferred embodiment, the
support is in the form of particulates. Because
particulate supports are especially preferred, most of the
following discussion focuses on embodiments which use a
particulate support. It should be recognized, however,
that this invention is not limited to the use of
particulate supports.
[0091] Suitable particulate supports may have a wide
variety of shapes. For example, such supports may be in
the form of granules. Even more preferably, the support is
in the form of a powder. These particulate supports may be
used in a reactor system as free particles, or,
alternatively, may be bound to a structure in the reactor
system, such as a screen or an impeller.
[0092] Typically, a support which is in particulate
form comprises a broad size distribution of particles. For
powders, preferably at least about 95% of the particles are
from about 2 to about 300 p,m in their largest dimension,
more preferably at least about 98% of the particles are
from about 2 to about 200 /zm in their largest dimension,
and most preferably about 99% of the particles are from
about 2 to about 150 jum in their largest dimension with
about 95% of the particles being from about 3 to about 100
/xm in their largest dimension. Particles being greater
than about 200 fim in their largest dimension tend to
fracture into super-fine particles (i.e., less than 2 jum in
their largest dimension), which are difficult to recover.
[0093] In the following discussion, specific surface
areas of carbon supports and the oxidation and
dehydrogenation catalysts of the present invention are
provided in terms of the well-known Langmuir method using
N2. However, such values generally correspond to those
measured by the also well-known Brunauer-Emmett-Teller
(B.E.T.) method using N2.
[0094] The specific surface area of the carbon
support, typically measured by the Langmuir method using
N2, is preferably from about 10 to about 3,000 m2/g (surface
area of carbon support per gram of carbon support), more
preferably from about 500 to about 2,100 m2/g, and still
more preferably from about 750 to about 2,100 m2/g. In
some embodiments, the most preferred specific area is from
about 750 to about 1,750 m2/g. In other embodiments,
typically the particulate carbon support has a Langmuir
surface area of at least about 1000 m2/g prior to formation
of a transition metal composition on the carbon support,
more typically at least about 1200 m2/g and, still more
typically, at least about 1400 m2/g. Preferably, the
Langmuir surface area of the carbon support prior to
formation of a transition metal composition on the carbon
support is from about 1000 to about 1600 m2/g and, more
preferably, from about 1000 to about 1500 mz/g prior to
formation of a transition metal composition on the carbon
support.
[00953 The Langmuir micropore surface area of the
support (i.e., surface area of the support attributed to
pores having a diameter less than 20 A) is typically at
least about 300 m2/g, more typically at least about 600
m2/g. Preferably, the Langmuir micropore surface area is
from about 300 to about 1500 m2/g and, more preferably,
from about 600 to about 1400 m2/g. The Langmuir combined
mesopore and macropore surface area of the support (i.e.,
surface area of the support attributed to pores having a
diameter greater than 20 A) is typically at least about 100
m2/g, more typically at least about 150 m2/g. Preferably,
the combined Langmuir mesopore and macropore surface area
is from about 100 to about 400 m2/g, more preferably from
about 100 to about 300 m2/g and, still more preferably,
from about 150 to about 250 m2/g.
[0096] For certain applications (e.g., hydrogenation,
petroleum hydrotreating, and isomerization), non-carbon
supports may be used with a catalyst containing a
transition metal composition formed on the support as
described herein. For example, silica and alumina supports
having Langmuir surface areas of at least about 50 m2/g.
Typically, these supports will have Langmuir surface areas
of from about 50 to about 300 m2/g.
[0097] Generally, supports having high surface areas
are preferred because they tend to produce a finished
catalyst having a high surface area.
[0098] Finished catalysts exhibiting sufficient pore
volume are desired so that reactants are able to penetrate
the pores of the finished catalyst. The pore volume of the
support may vary widely. Generally, the pore volume of the
support is at least about 0.1 cm3/g (pore volume per gram
of support) and, typically, at least about 0.5 cm3/g.
Typically, the pore volume is from about 0.1 to about 2.5
cm3/g and, more typically, from about 1.0 to about 2.0
cm3/g. Preferably, the pore volume of the support is from
about 0.2 to about 2.0 cm3/g, more preferably from about
0.4 to about 1.7 cm3/g and, still more preferably, from
about 0.5 to about 1.7 cm3/g. Catalysts comprising
supports with pore volumes greater than about 2.5 cm3/g
tend to fracture easily. On the other hand, catalysts
comprising supports having pore volumes less than 0.1 cm3/g
tend to have small surface areas and therefore low
activity.
[0099] Penetration of reactants into the pores of the
finished catalysts is also affected by the pore size
distribution of the support. Typically, at least about 60%
of the pore volume of the support is made up of pores
having a diameter of at least about 20 A. Preferably, from
about 60 to about 75% of the pore volume of the support is
made up of pores having a diameter of at least about 20 A.
[0100] Typically, at least about 20% of the pore
volume of the support is made up of pores having a diameter
of between about 20 and about 40 A. Preferably, from about
20 to about 35% of the pore volume of the support is made
of pores having a diameter of between about 20 and about 40
A.
[0101] Typically, at least about 25% of the pore
volume of the support is made up of pores having a diameter
of at least about 40 A. Preferably, from about 25 to about
60% of the pore volume of the support is made up of pores
having a diameter of at least about 40 A.
[0102] Typically, at least about 5% of the pore
volume of the support is made up of pores having a diameter
of between about 40 and about 60 A. Preferably, from about
5 to about 20% of the pore volume of the support is made up
of pores having a diameter of between about 40 and about 60
A.
[0103] Carbon supports for use in the present
invention are commercially available from a number of
sources. The following is a listing of some of the
activated carbons which may be used with this invention:
Darco G-60 Spec and Darco X (ICI-America, Wilmington,
Del.); Norit SG Extra, Norit EN4, Norit EXW, Norit A, Norit
Ultra-C, Norit ACX, and Norit 4x14 mesh (Amer. Norit Co.,
Inc., Jacksonville, Pla.); Gl-9615, VG-8408, VG-8590, NB-
9377, XZ, NW, and JV (Barnebey-Cheney, Columbus, Ohio); BL
Pulv., PWA Pulv., Calgon C 450, and PCS Fines (Pittsburgh
Activated Carbon, Div. of Calgon Corporation, Pittsburgh,
Pa.); P-100 (No. Amer. Carbon, Inc., Columbus, Ohio);
Nuchar CN, Nuchar C-1000 N, Nuchar C-190 A, Nuchar C-115 A,
and Nuchar SA-30 (Westvaco Corp., Carbon Department,
Covington, Va,); Code 1551 (Baker and Adamson, Division of
Allied Amer. Norit Co., Inc., Jacksonville, Fla.); Grade
235, Grade 337, Grade 517, and Grade 256 (Witco Chemical
Corp., Activated Carbon Div., New York, N.Y.); and Columbia
SXAC (Union Carbide New York, N.Y.).
[0104] The transition metal composition formed on the
carbon support generally comprises a transition metal and
nitrogen, a transition metal and carbon, or a transition
metal, nitrogen, and carbon. The transition metal is
selected from the group consisting of Group IB, Group VB,
Group VIB, Group VIIB, Group VIII, lanthanide series
metals, and combinations thereof. Groups of elements as
referred to herein are with reference to the Chemical
Abstracts Registry (CAS) system for numbering the elements
of the Periodic Table (e.g., Group VIII includes, among
others, iron, cobalt, and nickel). In particular, the
transition metal is selected from the group consisting of
copper, silver, vanadium, chromium, molybdenum, tungsten,
manganese, iron, cobalt, nickel, ruthenium, cerium, and
combinations thereof. In certain embodiments, the
transition metal composition includes a plurality of
transition metals (e.g., cobalt and cerium).
[0105] In certain other embodiments, a catalyst of
the present invention includes a composition comprising an
element selected from Group IIA (e.g., magnesium) and Group
VIA (e.g., tellurium, selenium), together with nitrogen,
carbon, and/or nitrogen and carbon formed on a carbon
support. For example, a catalyst of the present invention
may include a composition comprising magnesium, nitrogen,
and/or carbon and, in particular, magnesium nitride or
magnesium carbide-nitride. It should be understood that
the discussion herein regarding transition metal
compositions applies to these compositions as well.
[0106] Generally, the transition metal compositions
of the present invention include the transition metal in a
non-metallic form (i.e., in a non-zero oxidation state)
combined with nitrogen, carbon, or carbon and nitrogen in
form of a transition metal nitride, carbide, or carbidenitride,
respectively. The transition metal compositions
may further comprise free transition metal in its metallic
form (i.e., in an oxidation state of zero). The transition
metal compositions may also include carbide-nitride
compositions having an empirical formula of CNX wherein x
is from about 0.01 to about 0.7.
[0107] Typically, at least about 5% by weight of the
transition metal is present in a non-zero oxidation state
(e.g., as part of a transition metal nitride, transition
metal carbide, or transition metal carbide-nitride), more
typically at least about 20%, still more typically at least
about 30% and, even more typically, at least about 40%.
Preferably, from about 5 to about 50% by weight of the
transition metal is in a non-zero oxidation state, more
preferably from about 20 to about 40% by weight and still
more preferably, from about 30 to about 40% by weight of
the transition metal is in a non-zero oxidation state.
carbon support, general!
[0108] For catalysts including a transition metal
composition (e.g., transition metal nitride) formed on a
.y the transition metal composition
comprises from about 0.1
catalyst, more typicalli
comprises at least about 0.1% by weight of the catalyst
and, typically, at least about 0.5% by weight of the
catalyst. Typically, tjae transition metal composition
to about 20% by weight of the
from about 0.5 to about 15% by
weight of the catalyst, more typically from about 0.5 to
about 10% by weight of the catalyst and, still more
typically, from about 1 to about 12% by weight of the
aodiments, the transition metal
composition comprises fjrom about 1 to about 2% by weight of
the catalyst and, in others, from about 1 to about 1.5% by
weight of the catalyst.
[0109] Typically,
the transition metal composition is present in a proportion
of at least about 0.1%
the transition metal component of
by weight of the catalyst, more
typically at least about 0.5% by weight of the catalyst
and, still more typically, at least about 1% by weight of
the catalyst. Preferably, the transition metal component
is present in a proportion of from about 0.1 to about 20%
by weight of the catalyst, more preferably from about 0.5
to about 10% by weight of the catalyst, still more
preferably from about IL to about 2% by weight of the
catalyst and, even mors preferably, from about 1 to about
1.5% by weight of the catalyst.
[0110] The nitrogen component of transition metal
compositions comprising a transition metal and nitrogen is
typically present in a^ proportion of at least about 0.01%
by weight of the catalyst, more typically at least about
0.1% by weight of the
typically, in a propo:
catalyst, still more typically at
least about 0.5% by weight of the catalyst and, even more
tion of at least about 1% by weight
of the catalyst. Preferably, the nitrogen component is
present in a proportion of from about 0.1 to about 5% by
weight of the catalyst}., more preferably from about 0.1 to
about 3% by weight of the catalyst, even more preferably
from about 1 to about 2% by weight of the catalyst and,
still more preferably, from about 1 to about 1.5% by weight
of the catalyst.
[0111] In certain embodiments, the transition
metal/nitrogen .composition comprises cobalt and nitrogen
and, in various embodiments, cobalt nitride. Such cobalt
nitride typically has a:n. empirical formula of, for example,
CoNx wherein x is typically from about 0.25 to about 4,
more typically from about 0.25 to 2 and, still more
typically, from about 0
total proportion of at
.25 to about 1. Typically, the
least one cobalt nitride having such
an empirical formula (e.g., Co2N) is at least about 0.01%
by weight of the catalyst. Typically, the total proportion
of all cobalt nitride having such an empirical formula is
at least about 0.1% by weight of the catalyst.
[0112] In such embodiments, cobalt is typically
present in a proportion of at least about 0.1% by weight of
the catalyst, more typically at least about 0.5% by weight
of the catalyst and, more typically, at least about 1% by
weight of the catalyst Preferably, cobalt is present in a
proportion of from about 0.5 to about 10% by weight of the
catalyst, more preferably from about 1 to about 2% by
weight of the catalyst and, even more preferably, from
about 1 to about 1.5% by weight of the catalyst. In
certain embodiment, cobalt is present in a proportion of
from about 0.1 to about 3% by weight of the catalyst.
Further in accordance with such embodiments, nitrogen is
typically present in a proportion of at least about 0.01%
by weight of the catalyst and, more typically, in a
proportion of from about 0.5 to about 2% by weight of the
catalyst.
[0113] In certain embodiments, the transition
metal/nitrogen composition comprises iron and nitrogen and,
in particular, iron nitride. Such iron nitride typically
has an empirical formula of, for example, PeNx wherein x is
typically from about 0.25 to about 4, more typically from
about 0.25 to 2 and, still more typically, from about 0.25
to about 1. Typically, the total proportion of at least
one iron nitride having such an empirical formula (e.g.,
FeN) is present in a proportion of at least about 0.01% by
weight of the catalyst. Typically, the total proportion of
all iron nitrides having such an empirical formula is at
least about 0.1% by weight of the catalyst.
[0114] In such embodiments, iron is typically present
in a proportion of at least about 0.01% by weight of the
catalyst, more typically at least about 0.1% by weight of
the catalyst and, more topically, at least about 0.2% by
weight of the catalyst. Preferably, iron is present in a
proportion of from about 0.1 to about 5% by weight of the
catalyst, more preferably from about 0.1 to about 3% by
weight of the catalyst,
0.2 to about 1.5% by weight of the catalyst and, even more
preferably, from about 0
still more preferably from about
.5 to about 1% by weight of the
catalyst. In certain embodiments, iron is present in a
proportion of at from about 1 to about 2% by weight of the
catalyst and, in others, from about 1 to about 1.5% by
weight of the catalyst. Further in accordance with such
embodiments, nitrogen is
of at least about 0.01%
typically present in a proportion
by weight of the catalyst and, more
typically, in a proportion of from about 0.1 to about 2% by
weight of the catalyst.
[0115] In certain embodiments, transition metal/carbon
compositions comprise cobalt and carbon and, in certain
embodiments, cobalt carbide. Such cobalt carbide typically
has an empirical formula
typically from about 0.
about 0.25 to 2 and, st
to about 1. Typically,
of, for example, CoCx wherein x is
5 to about 4, more typically from
11 more typically, from about 0.25
the total proportion of at least
one cobalt carbide of such stoichiometric formula (e.g.,
Co2C) is at least about
such empirical formulae
0.01% by weight of the catalyst.
Typically, the total proportion of all cobalt carbide of
is at least about 0.1% by weight of
the catalyst.
[0116] In such embodiments, cobalt is typically
present in a proportion
the catalyst, more typi
of at least about 0.1% by weight of
:ally at least about 0.5% by weight
of the catalyst and, mor
weight of the catalyst,
proportion of from about
catalyst, more preferably from about 1 to about 2% by
weight of the catalyst and, still more preferably, from
about 1 to about 1.5% by
from about 0.1 to about
metal/carbon composition
particular, iron carbide
an empirical formula of,
i typically, at least about 1% by
Preferably, cobalt is present in a
0.5 to about 10% by weight of the
weight of the catalyst. In
certain embodiments, cobalt is present in a proportion of
3% by weight of the catalyst.
[0117] In certain embodiments, the transition
to about 1. Typically,
one iron carbide of suet
comprises iron and carbon and, in
Such iron carbide typically has
for example, PeCx wherein x is
typically from about 0.25 to about 4, more typically from
about 0.25 to 2 and, still more typically, from about 0.25
the total proportion of at least
stoichiometric formula (e.g.,
Fe3C) is at least about p.01% by weight of the catalyst.
Typically, the total proportion of all iron carbides of
such empirical formulae is at least about 0.1% by weight of
the catalyst.
[0118] In such embodiments, iron is typically present
in a proportion of at least about 0.01% by weight of the
catalyst and, more typically, at least about 0.1% by weight
of the catalyst. Preferably, iron is present in a
proportion of from about; 0 .1 to about 5% by weight of the
catalyst, more preferably from about 0.2 to about 1.5% by
weight of the catalyst and, still more preferably, from
about 0.5 to about 1% by weight of the catalyst.
[0119] It should be understood that the description
of transition metal compositions containing iron and cobalt
generally applies to transition metal compositions
containing other transition metals (e.g., cerium) listed
above.
[0120] In various embodiments, the transition metal
composition includes a transition metal, nitrogen, and
carbon. In certain embodiments, the transition metal
composition comprises cobalt, carbon, and nitrogen and, in
particular, cobalt carbp.de and cobalt nitride having
empirical formula of CoCx or CoNx, respectively, where x is
typically from about 0.25 to about 4, more typically from
about 0.25 to 2 and, still more typically, from about 0.25
to about 1.
[0121] Typically, a cobalt carbide and nitride having
such an empirical formula are each present in a proportion
of at least about 0.01% by weight of the catalyst and, more
typically, from about 0.1 to about 0.5% by weight of the
catalyst. Typically, the total proportion of all cobalt
carbides of such empirical formula is at least about 0.1%
by weight of the catalyst while the total proportion of all
cobalt nitrides of such empirical formula is typically at
least about 0.1% by weight of the catalyst.
[0122] In such embodiments, cobalt is typically
present in a proportion 'of at least about 0.1% by weight of
the catalyst, more typically at least about 0.5% by weight
of the catalyst and, more typically, at least about 1% by
weight of the catalyst. Preferably, cobalt is present in a
proportion of from about 0.5 to about 10% by weight of the
catalyst, more preferably from about 1 to about 2% by
weight of the catalyst and, still more preferably, from
about 1 to about 1.5% by weight of the catalyst. In
certain embodiments, cobalt is present in a proportion of
from about 0.1 to about 3% by weight of the catalyst.
Further in accordance with such embodiments, nitrogen is
typically present in a proportion of at least about 0.1% by
weight of the catalyst and, more typically, in a proportion
of from about 0.5 to about 2% by weight of the catalyst.
[0123] In certain embodiments, the transition metal
composition comprises iron, carbon, and nitrogen and, in
particular, iron carbide and iron nitride having empirical
formula of FeCx or FeNx, respectively, where x is typically
from about 0.25 to about 4, more typically from about 0.25
to 2 and, still more typically, from about 0.25 to about 1.
For example, Fe3C may be present and, additionally or
alternatively, FeN may also be present.
33
[0124] Typically, an iron carbide and nitride having
such an empirical formula are each present in a proportion
of at least about 0.01% by weight of the catalyst and, more
typically, from about 0.1 to about 0.5% by weight of the
catalyst. Typically, the total proportion of all iron
carbides of such empirical formula is at least about 0.1%
by weight of the catalyst while the total proportion of all
iron nitrides of such empirical formula is typically at
least about 0.1% by weight of the catalyst.
[0125] In such embodiments, iron is typically present
in a proportion of at least about 0.1% by weight of the
catalyst, more typically at least about 0.5% by weight of
the catalyst and, more typically, at least about 1% by
weight of the catalyst. Preferably, iron is present in a
proportion of from about 0.5 to about 10% by weight of the
catalyst, more preferably from about 1 to about 2% by
weight of the catalyst and, still more preferably, from
about 1 to about 1.5% by weight of the catalyst. In
certain embodiments, iron is present in a proportion of
from about 0.1 to about 3% by weight of the catalyst.
Further in accordance with such embodiments, nitrogen is
typically present in a proportion of at least about 0.1% by
weight of. the catalyst and, more typically, in a proportion
of from about 0.5 to about 2% by weight of the catalyst.
[0126] In various other embodiments the transition
metal composition comprising a transition metal, carbon,
and nitrogen may include a transition metal carbide-nitride
composition (e.g., cobalt carbide-nitride). For example,
the transition metal composition may include cobalt
carbide-nitride. In such embodiments, cobalt is typically
present in a proportion of at least about 0.1% by weight of
the catalyst, more typically at least about 0.5% by weight
of the catalyst and, still more typically, at least about
1% by weight of the catalyst. Preferably, cobalt is
present in a proportion of from about 0.5 to about 10% by
weight of the catalyst, more preferably from about, more
preferably from about 1 to about 2% by weight of the
catalyst and, still more preferably, from about 1 to about
1.5% by weight of the catalyst. In certain embodiments,
the cobalt carbide-nitride may be present in a proportion
of from about 0.1 to about 3% by weight of the catalyst.
Further in accordance with such embodiments, nitrogen is
typically present in a proportion of at least about 0.1% by
weight of the catalyst and, more typically, in a proportion
of from about 0.5 to about 2% by weight of the catalyst.
[0127] In various embodiments, the catalyst may
comprise cobalt carbide, cobalt nitride, and cobalt
carbide-nitride. In such embodiments, typically the total
proportion of such carbide(s), nitride(s), and carbidenitride
(s) is at least about 0.1% by weight of the catalyst
and, still more typically, from about 0.1 to about 20% by
weight of the catalyst.
[0128] In various other embodiments, the transition
metal composition may include iron carbide-nitride. In
such embodiments, iron is typically present in a proportion
of at least about 0.1% by weight of the catalyst, more
typically at least about 0.2% by weight of the catalyst,
still more typically at least about 0.5% by weight of the
catalyst and, even more typically, at least about 1% by
weight of the catalyst. Preferably, iron is present in a
proportion of from about 0.1 to about 5% by weight of the
catalyst, more preferably from about 0.1 to about 3% by
weight of the catalyst, more preferably from about 0.2 to
about 2% by weight of the catalyst and, still more
preferably, from about 0.5 to about 1.5% by weight of the
catalyst. Further in accordance with such embodiments,
nitrogen is typically present in a proportion of at least
about 0.1% by weight of the catalyst and, more typically,
in a proportion of from about 0.5 to about 2% by weight of
the catalyst.
[0129] In various embodiments, the catalyst may
comprise iron carbide, iron nitride, and iron carbidenitride.
In such embodiments, typically the total
proportion of such carbide(s), nitride(s), and carbidenitride
(s) is at least about 0.1% by weight of the catalyst
and, still more typically, from about O.I to about 20% by
weight of the catalyst.
[0130] In various other embodiments the transition
metal composition comprises nickel cobalt-nitride, vanadium
cobalt-nitride, chromium cobalt-nitride, manganese cobaltnitride,
copper cobalt-nitride, molybdenum carbide-nitride,
and tungsten carbide-nitride.
[0131] Further in accordance with the present
invention, the transition metal composition may include a
plurality of transition metals selected from the group
consisting of Group IB, Group VB, Group VIB, Group VIIB,
Group VIII, lanthanide series metals, and combinations
thereof. In particular, the transition metal composition
may include a plurality of transition metals selected from
the group consisting of copper, silver, vanadium, chromium,
molybdenum, tungsten, manganese, iron, cobalt, nickel,
ruthenium and cerium. For example, the transition metal
composition may comprise cobalt-cerium nitride, cobaltcerium
carbide, and/or cobalt-cerium carbide-nitride.
Other bi-metallic carbide-nitrides present in transition
metal compositions in accordance with the present invention
may be in the form of cobalt-iron carbide-nitride or
cobalt-copper carbide-nitride. One of such bi-transition
metal compositions (e.g., a bi-transition metal nitride)
may be present in a total proportion of at least about 0.1%
by weight and, more typically, in a proportion of from
about 0.1 to about 20% by weight of the catalyst. One or
more of such bi-transition metal compositions (e.g.,
nitride, carbide, and/or carbide-nitride) may be present in
a total proportion of at least about 0.1% by weight and,
more typically, in a proportion of from about 0.1 to about
20% by weight of the catalyst.
[0132] In certain embodiments, the transition metal
composition formed on the carbon support generally
comprises either or both of a composition comprising a
transition metal and carbon (i.e., a transition
metal/carbon composition) or a composition comprising a
transition metal and nitrogen (i.e., a transition
metal/nitrogen composition) in which the transition metal
is selected from molybdenum and tungsten. Transition metal
compositions formed on a carbon support containing
molybdenum or tungsten are useful as oxidation catalysts;
however, they are particularly useful as a modified carbon
support for a dehydrogenation catalyst.
[0133] Thus, in certain of these embodiments, the
transition metal/carbon composition comprises molybdenum
and carbon and, in a preferred embodiment, comprises
molybdenum carbide. Typically, molybdenum carbide formed
on the carbon support as part of the transition metal
composition comprises a compound having a stoichiometric
formula of Mo2C. In other embodiments, the transition
metal/carbon composition comprises tungsten and carbon and,
in a preferred embodiment, comprises tungsten carbide.
Typically, tungsten carbide formed on the carbon support as
part of the transition metal composition comprises a
compound having a stoichiometric formula of WC or W2C.
[0134] Similarly, transition metal/nitrogen
compositions may comprise molybdenum and nitrogen and, in a
preferred embodiment, comprises molybdenum nitride.
Typically, any molybdenum nitride formed on the carbon
support as part of the transition metal composition
comprises a compound having a stoichiometric formula of
Mo2N. Transition metal/nitrogen compositions formed on the
carbon support may comprise tungsten and nitrogen and, in a
preferred embodiment, comprises tungsten nitride.
Typically, any tungsten nitride formed on the carbon
support as part of the transition metal composition
comprises a compound having a stoichiometric formula of
W2N.
[0135] In various embodiments including transition
metal compositions comprising either or both of a
transition metal/carbon composition or a transition
metal/nitrogen composition in which the transition metal is
selected from molybdenum and tungsten, generally the
transition metal composition comprises at least about 5% by
weight of a catalyst including a transition metal
37
composition formed on a carbon support (i.e., a modified
carbon support). Such modified carbon supports are
particularly useful as modified carbon supports for
dehydrogenation catalysts formed by depositing a metalcontaining
active phase on the modified carbon support.
Typically, the transition metal composition comprises from
about 5% to about 20% by weight of the catalyst, more
typically from about 10% to about 15% by weight of the
catalyst, and, still more typically, from about 10% to
about 12% by weight of the catalyst. Generally, the
transition metal component of the transition metal
composition (i.e., molybdenum or tungsten and nitrogen
and/or carbon) comprises at least about 5% by weight of the
catalyst. Preferably, the transition metal component of
the transition metal composition comprises from about 8 to
about 15% by weight of the catalyst.
[0136] Transition metal compositions deposited on
carbon supports in accordance with the above discussion may
be incorporated into catalysts further containing a metal
containing active phase deposited over a modified carbon
support including such transition metal compositions formed
on a carbon support.
[0137] In processes for forming a transition metal
composition on the carbon support, a precursor of the
transition metal composition is first formed on the carbon
support by contacting the carbon support with a source
compound comprising the transition metal to be deposited.
[0138] Generally, the source compound is in the form
of a water-soluble transition metal salt selected from the
group consisting of halides, sulfates, acetates, nitrates,
ammonium salts, and combinations thereof. Typically, the
source compound is in the form of a transition metal salt
such as a transition metal halide. However, the selection
of the transition metal salt is not critical. For example,
to produce a transition metal composition comprising iron,
the source compound may comprise an iron halide (e.g.,
FeCl3) , iron sulfate (e.g., FeSOj , iron acetate, an
ammonium salt of iron (e.g., (NH4) 4Fe (CN) 6) , or combinations
thereof. Similarly, to produce a transition metal
composition comprising cobalt, the source compound may
comprise a cobalt halide (e.g., CoCl2) , cobalt sulfate
(e.g., CoS04) , cobalt acetate, or combinations thereof.
Similarly, to produce a transition metal composition
comprising molybdenum or tungsten, the molybdenum or
tungsten-containing salts are preferably water-soluble and
generally selected from the sodium, potassium and ammonium
salts. The salt may contain molybdenum as an anion, for
example, in the form of ammonium molybdate ( (NH4) 2MoO4~2) or
sodium molybdate (Na2MoO4) . In the case of a transition
metal composition comprising tungsten, the transition metal
salt may be selected from tungsten salts including, for
example, sodium tungstate and tungstophosphoric acid.
[0139] To form the precursor, a source compound is
contacted with the carbon support or a mixture may be
prepared comprising the source compound, for example an
aqueous solution of a salt comprising the transition metal,
and the carbon support is contacted with such mixture.
Advantageously, this may be accomplished by preparing an
aqueous slurry of a particulate carbon support in a liquid
medium (e.g., water), and adding to the slurry an aqueous
solution containing the salt which comprises the transition
metal. Alternatively, an aqueous slurry containing the
particulate carbon support can be added to an aqueous
solution containing the salt comprising the transition
metal. •
[0140] The amount of source compound contacted with
the carbon support or present in a slurry contacted with
the carbon support is not narrowly critical. Overall, a
suitable amount of source compound should be added to any
slurry containing the carbon support to provide sufficient
transition metal deposition. Typically, the source
compound is added to the carbon support slurry at a rate of
at least about 0.00005 moles/minute and, more typically, at
a rate of from about 0.00005 to about 0.0005 moles/minute.
Typically, the source compound is present in a suspension
or slurry containing the source compound and a liquid
medium in a proportion of at least about 0.01 g/liter and,
more typically, from about 0.1 to about 10 g/liter. The
carbon support is typically present in the suspension of
slurry in a proportion of at least about 1 g/liter and,
more typically, from about 1 to about 50 g/liter.
Preferably, the source compound and carbon support are
present in the suspension or slurry at a weight ratio of
transition metal/carbon in the range of from about 0.1 to
about 20. More preferably, the source compound and carbon
support are present in the suspension or slurry at a weight
ratio of transition metal/carbon in the range of from about
0.5 to about 10.
[0141] The rate of addition of the transition metalcontaining
salt to a slurry containing the carbon support
is not narrowly critical but, generally, is at least about
0.05 L/hour per L slurry (0.01 gal./hour per gal. of
slurry) of salt is added to the slurry. Preferably, from
about 0.05 L/hour per L slurry (0.01 gal./hour per gal. of
slurry) to about 0.4 L/hour per L slurry (0.1 gal./hour per
gal. of slurry) and, more preferably, from about 0.1 L/hour
per L of slurry (0.026 gal./hour per gal. of slurry) to
about 0.2 L/hour per L of slurry (0.052 gal./hour per gal.
of slurry) of salt is added to the slurry containing the
carbon support.
[0142] In certain embodiments in which the transition
metal composition formed on the carbon support includes
either or both of a composition comprising molybdenum or
tungsten and carbon or a composition comprising molybdenum
or tungsten and nitrogen, the method of precursor
deposition generally proceeds in accordance with the above
discussion. Typically, an aqueous solution of a salt
containing molybdenum or tungsten is added to an aqueous
slurry of a particulate carbon support. Typically, the
salt is added to the carbon support slurry at a rate of at
least about 0.00005 moles/minute and, more typically, at a
rate of from about 0.00005 to about 0.0005 moles/minute.
Typically, the salt is present in a suspension or slurry
containing the salt and a liquid medium in a proportion of
at least about 0.1 g/liter and, more typically, from about
0.1 to about 5 g/liter. The carbon support is typically
present in the suspension of slurry in a proportion of at
least about 1 g/liter and, more typically, from about 5 to
about 20 g/liter. Preferably, the molybdenum or tungstencontaining
salt and carbon support are present in the
suspension or slurry at a weight ratio of molybdenum/carbon
or tungsten/carbon in the range of from about 0.1 to about
20. More preferably, the molybdenum or tungsten-containing
salt and carbon support are present in the suspension or
slurry at a weight ratio of molybdenum/carbon or
tungsten/carbon in the range of from about 1 to about 10.
Generally, at least about 0.001 L of the molybdenum or
tungsten-containing salt solution per gram of carbon
support is added to the slurry. Preferably, from about
0.001 L to about 0.05 L transition metal salt per gram of
carbon support is added to the slurry. The salt is
typically present in the aqueous medium in such
concentrations at the outset of precursor deposition in
which a carbon support slurry is added to a solution or
suspension containing the source compound. Alternatively,
such concentrations of source compound generally represent
the cumulative total of source compound added to the carbon
support slurry in those embodiments in which the solution
or suspension of source compound is added to the carbon
support slurry.
[0143] The rate of addition of the molybdenum or
tungsten-containing salt to the slurry in such embodiments
is not narrowly critical but, generally, is at least about
0.05 L/hour per L slurry (0.01 gal./hour per gal. of
slurry) of salt is added to the slurry. Preferably, from
about 0.05 L/hour per L slurry (0.01 gal./hour per gal. of
slurry) to about 0.4 L/hour per L slurry (0.1 gal./hour per
gal. of slurry) and, more preferably, from about 0.1 L/hour
per L of slurry (0.026 gal./hour per gal. of slurry) to
about 0.2 L/hour per L of slurry (0.052 gal./hour per gal.
of slurry) of salt is added to the slurry.
[0144] It is believed that the pH of the transition
metal salt and carbon support mixture relative to the zero
charge point of carbon (i.e., in mixtures having pH of 3,
for example, carbon exhibits a charge of zero whereas in
mixtures having a pH greater than 3 or less than 3 carbon
exhibits a negative charge and positive charge,
respectively) may affect transition metal-containing
precursor formation. A transition metal salt having a
metal component (e.g., molybdenum) exhibiting a positive or
negative charge may be selected to provide bonding between
the carbon and the metal based on the pH of the support
slurry. For example, in the case of ammonium molybdate,
the majority of the molybdenum will exist as MoO4
2",
regardless of pH. However, the pH of the slurry may affect
adsorption of MoO4
2" on the carbon surface. For example,
when the carbon in the slurry has a zero charge point at pH
3, a greater proportion of Mo04
2~ will be adsorbed on the
carbon in a slurry having a pH 2 than would be adsorbed in
a slurry having a pH of 5. In the case of ammonium
tungstate or ammonium molybdate in a slurry having a pH of
from about 2 to about 3, substantially all of the
transition metal is adsorbed on the carbon support (i.e.,
less than about 0.001% of the transition metal remains in
the salt solution). The pH of the slurry may be controlled
by addition of an acid or base either concurrently with the
transition metal salt or after addition of the transition
metal salt to the slurry is complete.
[0145] Alternatively, the pH of the slurry of the
source compound and carbon support and, accordingly, the
charge of the carbon support may be controlled depending on
whether the transition metal component is present as the
cation or anion of the source compound. Thus, when the
transition metal is present as the cation of the source
compound the pH of the slurry is preferably maintained
above 3 to promote adsorption of transition metal on the
carbon support surface. In certain embodiments, the pH of
the liquid medium is maintained at 7.5 or above.
[0146] In various embodiments, transition metal is
present in the source compound as the cation (e.g., FeCl3
or CoCl2) . As the pH of the liquid medium increases, the
transition metal cation of the source compound becomes
partially hydrolyzed. For example, in the case of FeCl3,
iron hydroxide ions such as Fe(OH)2
+1 or Fe(OH)+2 may form
and such ions are adsorbed onto the negatively charged
carbon support surface. Preferably, the ions diffuse into
the pores and are adsorbed and dispersed throughout the
surface of the carbon support, including within the
surfaces of pores. However, if the pH of the liquid medium
is increased too rapidly, iron hydroxide (Fe(OH)3) will
precipitate in the liquid medium and conversion of the iron
ions to neutral iron hydroxide removes the electrostatic
attraction between iron and the carbon support surface and
reduces deposition of iron on the support surface.
Precipitation of iron hydroxide into the liquid medium may
also impede dispersion of iron ions throughout the pores of
the carbon support surface. Thus, preferably the pH of the
liquid medium is controlled to avoid rapid precipitation of
transition metal hydroxides before the occurrence of
sufficient deposition of transition metal onto the carbon
support surface by virtue of the electrostatic attraction
between transition metal ions and the carbon support
surface. After sufficient deposition of iron onto the
carbon support surface, the pH of the liquid medium may be
increased at a greater rate since a reduced proportion of
iron remains in the bulk liquid phase.
[0147] The temperature of the liquid medium also
affects the rate of precipitation pf transition metal, and
the attendant deposition of transition metal onto the
carbon support. Generally, the rate of precipitation
increases as the temperature of the medium increases.
Typically, the temperature of the liquid medium during
introduction of the source compound is maintained in a
range from about 10 to about 30°C and, more typically, from
about 20 to about 25°C.
[0148] Further in accordance with embodiments in
which the transition metal is present as the cation of the
source compound, after addition of the source compound to
the liquid medium is complete, both the pH and temperature
of the liquid medium may be increased. In certain
embodiments, the pH of the liquid medium is increased to at
least about 8.5, in others to at least about 9.0 and, in
still other embodiments, to at least about 9.0. Generally,
the temperature of the liquid medium is increased to at
least about 40°C, more generally to at least about 45°C
and, still more generally, to at least about 50°C.
Typically, the temperature is increased at a rate of from
about 0.5 to about 10°C/min and, more typically, from about
I to about 5°C/min.
[0149] After an increase of the temperature and/or pH
of the liquid medium, typically the medium is maintained
under these conditions for a suitable period to time to
allow for sufficient deposition of transition metal onto
the carbon support surface. Typically, the liquid medium
is maintained at such conditions for at least about 2
minutes, more typically at least about 5 minutes and, still
more typically, at least about 10 minutes.
[0150] In certain embodiments, the temperature of the
liquid medium is about 25°C and the pH of the liquid medium
is maintained at from about 7.5 to about 8.0 during
addition of the source compound. After addition of the
source compound is complete, the liquid medium is agitated
by stirring for from about 25 to about 35 minutes while its
pH is maintained at from about 7.5 to about 8.5. The
temperature of the liquid medium is then increased to a
temperature of from about 40 to about 50°C at a rate of
from about 1 to about 5°C/min while the pH of the liquid
medium is maintained at from about 7.5 to about 8.5. The
medium is then agitated by stirring for from about 15 to
about 25 minutes while the temperature of the liquid medium
is maintained at from about 40 to about 50°C and the pH at
from about 7.5 to about 8.0. The slurry is then heated to
a temperature of from about 50 to about 55°C and its pH
adjusted to from about 8.5 to about 9.0, with these
conditions being maintained for approximately 15 to 25
minutes. Finally, the slurry is heated to a temperature of
from about 55 to about 65°C and its pH adjusted to from
about 9.0 to about 9.5, with these conditions maintained
for approximately 10 minutes.
[0151] Regardless of the presence of the transition
metal in the source compound as an anion or cation, to
promote contact of the support with the transition metal
source compound, and mass transfer from the liquid phase,
the slurry may be agitated concurrently with additions of
source compound to the slurry or after addition of the
transition metal salt to the slurry is complete. The
liquid medium may likewise be agitated prior to, during, or
after operations directed to increasing its temperature
and/or pH. Suitable means for agitation include, for
example, by stirring or shaking the slurry.
[0152] For transition metal compositions comprising a
plurality of metals, typically a single source compound
comprising all of the metals, or a plurality of source
compounds each containing at least one of the metals is
contacted with the carbon support in accordance with the
preceding discussion. Deposition of precursors of the
component transition metals may be carried out concurrently
(i.e., contacting the carbon support with a plurality of
source compounds, each containing a transition metal for
deposition of a precursor) or sequentially (deposition of
one precursor followed by deposition of one or more
additional precursors) in accordance with the above
discussion.
[0153] After the transition metal salt has contacted
the support for a time sufficient to ensure sufficient
deposition of the source compound(s) and/or formation of
its(their) derivative(s), the slurry is filtered, the
support is washed with an aqueous solution and allowed to
dry. Typically, the salt contacts the support for at least
about 0.5 hours and, more typically, from about 0.5 to
about 5 hours. Generally, the impregnated support is
allowed to dry for at least about 2 hours. Preferably, the
impregnated support is allowed to dry for from about 5 to
about 12 hours. Drying may be accelerated by contacting
the impregnated carbon support with air at temperatures
generally from about 80 to about 150°C.
[0154] A source compound or derivative may also be
formed on the carbon support by vapor deposition methods in
which the carbon support is contacted with a mixture
comprising a vapor phase source of a transition metal. In
chemical vapor deposition the carbon support is contacted
with a volatile metal compound generally selected from the
group consisting of halides, carbonyls, and organometallic
compounds which decomposes to produce a transition metal
suitable for formation on the carbon support. Examples of
suitable metal carbonyl compounds include Mo(CO)6, W(CO)6,
Fe(CO)5, and Co(CO)4.
[0155] Decomposition of the compound generally occurs
by subjecting the compound to light or heat. In the case
of decomposition using heat, temperatures of at least about
100°C are typically required for the decomposition.
[0156] It may be noted that the precursor compound
may be the same as the source compound, or it may differ as
a result of chemical transformation occurring during the
process of deposition and/or otherwise prior to contact
with a nitrogen-containing compound, carbon-containing
compound (e.g., a hydrocarbon), or nitrogen and carboncontaining
compound. For example, where a porous carbon
support is impregnated with an aqueous solution of a source
compound comprising ammonium molybdate, the precursor is
ordinarily the same as the source compound. But where
vapor deposition techniques are used with a source compound
such as a molybdenum halide, the precursor formed may be
metallic molybdenum or molybdenum oxide.
[0157] Regardless of the method for formation of the
source compound or its derivative on the carbon support, in
certain embodiments the pretreated carbon support is then
subjected to further treatment (e.g., temperature
programmed treatment) to form a transition metal
composition comprising a transition metal and nitrogen, a
transition metal and carbon, or a transition metal,
nitrogen, and carbon on the carbon support. Generally, the
pretreated carbon support is contacted with a nitrogencontaining,
carbon-containing, or nitrogen and carboncontaining
compound under certain conditions (e.g, elevated
temperature) . Generally, a fixed or fluidized bed
comprising carbon support having the precursor deposited
thereon is contacted with a nitrogen and/or carboncontaining
compound. Preferably, the carbon support is
established in a fixed bed reactor and a vapor-phase
nitrogen-containing, carbon-containing, or nitrogen and
carbon-containing compound is contacted with the support by
passage over and/or through the bed of carbon support.
[0158] When a transition metal composition comprising
a transition metal and nitrogen is desired, typically the
pretreated carbon support is contacted with any of a
variety of nitrogen-containing compounds which may include
ammonia, an amine, a nitrile, a nitrogen-containing
heterocyclic compound, or combinations thereof. Such
nitrogen-containing compounds are typically selected from
the group consisting of ammonia, dimethylamine,
ethylenediamine, isopropylamine, butylamine, melamine,
acetonitrile, propionitrile, picolonitrile, pyridine,
pyrrole, and combinations thereof.
[0159] Typically, the carbon support having a
precursor of the transition metal composition deposited
thereon is contacted with a nitriding atmosphere which
comprises a vapor phase nitrogen-containing compound as set
forth above. In a preferred embodiment, the nitrogencontaining
compound comprises acetonitrile. Typically, the
nitriding atmosphere comprises at least about 5% by volume
of nitrogen-containing compound and, more typically, from
about 5 to about 20% by volume of the nitrogen-containing
compound. Generally, at least about 100 liters of
nitrogen-containing compound per kg of carbon per hour (at
least about 3.50 ft3 of carbon-containing compound per Ib
of carbon per hour) are contacted with the carbon support.
Preferably, from about 200 to about 500 liters of nitrogencontaining
compound per kg of carbon per hour (from about
7.0 to about 17.7 ft3 of carbon-containing compound per Ib
of carbon per hour) are contacted with the carbon support.
[0160] The nitriding atmosphere optionally includes
additional components selected from the group consisting of
hydrogen and inert gases such as argon. Hydrogen, where
present, generally may be present in a proportion of at
least about 1% by volume hydrogen or, more generally, from
about 1 to about 10% by volume hydrogen. Additionally or
alternatively, the nitriding atmosphere typically comprises
at least about 75% by volume argon and, more typically,
from about 75 to about 95% by volume argon. In certain
embodiments, the nitriding atmosphere comprises at least
about 10 liters of hydrogen per kg of carbon support per
hour (at least about 0.35 ft3 of hydrogen per Ib of carbon
support). Preferably, such a nitriding atmosphere
comprises from about 30 to about 50"liters of hydrogen per
kg of carbon support per hour (from about 1.05 to about 1.8
ft3 of hydrogen per Ib of carbon support per hour). In
various other embodiments, the nitriding atmosphere
comprises at least about 900 liters of argon per kg of
carbon support per hour (at least about 31.5 ft3 of argon
per Ib of carbon support). Preferably, such a nitriding
atmosphere comprises from about 1800 to about 4500 liters
of argon per kg of carbon support per hour (from about 63
to about 160 ft3 of argon per Ib of carbon support per
hour). In further embodiments, the nitriding atmosphere
comprises at least about 10 liters of hydrogen per kg of
carbon support per hour (at least about 0.35 ft3 of
hydrogen per Ib of carbon support) and at least about 900
liters of argon per kg of carbon support per hour (at least
about 31.5 ft3 of argon per Ib of carbon support) .
[0161] The carbon support having a precursor of the
transition metal composition thereon is typically contacted
with the nitrogen-containing compound in a nitride reaction
zone under a total pressure of no greater than about 15
psig. Typically, the nitride reaction zone is under a
pressure of from about 2 to about 15 psig. The nitrogencontaining
compound partial pressure of the nitride
reaction zone is typically no greater than about 2 psig
and, more typically, from about 1 to about 2 psig. The
partial pressure of any hydrogen present in the nitriding
zone is typically less than about 1 psig and, more
typically, from about 0.1 to about 1 psig.
[0162] When a transition metal composition comprising
a transition metal and carbon is desired, typically the
pretreated carbon support is contacted with a carbiding
atmosphere containing a carbon-containing compound
including, for example, hydrocarbons such as methane,
ethane, propane, butane, and pentane.
[0163] Typically, the carbon support having a
precursor of the transition metal composition deposited
thereon is contacted with a carbiding atmosphere which
comprises a vapor phase carbon-containing compound. In a
preferred embodiment, the carbon-containing compound
comprises methane. Typically, the carbiding atmosphere
comprises at least about 5% by volume of carbon-containing
compound and, more typically, from about 5 to about 50% by
volume of the carbon-containing compound. Generally, at
least about 100 liters of carbon-containing compound per kg
of carbon per hour (at least about 3.50 ft3 of carboncontaining
compound per Ib of carbon per hour) are
contacted with the carbon support. Preferably, from about
200 to about 500 liters of carbon-containing compound per
kg of carbon per hour (from about 7.0 to about 17.7 ft3 of
carbon-containing compound per Ib of carbon per hour) are
contacted with the carbon support.
[0164] The carbiding atmosphere optionally includes
additional components selected from the group consisting of
hydrogen and inert gases such as argon and nitrogen.
Hydrogen, where present, generally is present in a
proportion of at least about 1% by volume or, more
generally, from about I to about 50% by volume. In certain
embodiments, the carbiding atmosphere comprises at least
about 10 liters of hydrogen per kg of carbon support per
hour (at least about 0.35 ft3 of hydrogen per Ib of carbon
support). Preferably, such a carbiding atmosphere
comprises from about 30 to about 50 liters of hydrogen per
kg of carbon support per hour (from about 1.05 to about 1.8
ft3 of hydrogen per Ib of carbon support per hour).
[0165] In various other embodiments, the carbiding
atmosphere comprises at least about 900 liters of argon per
kg of carbon support per hour (at least about 31.5 ft3 of
argon per Ib of carbon support). Preferably, such a
carbiding atmosphere comprises from about 1800 to about
4500 liters of argon per kg of carbon support per hour
(from about 63 to about 160 ft3 of argon per Ib of carbon
support per hour).
[0166] In further embodiments, the carbiding
atmosphere comprises at least about 10 liters of hydrogen
per kg of carbon support per hour (at least about 0.35 ft3
of hydrogen per Ib of carbon support) and at least about
900 liters of argon per kg of carbon support per hour (at
least about 31.5 ft3 of argon per Ib of carbon support) .
[0167] In various other embodiments, the carbiding
atmosphere comprises at least about 900 liters of nitrogen
per kg of carbon support per hour (at least about 31.5 ft3
of nitrogen per Ib of carbon support). Preferably, such a
carbiding atmosphere comprises from about 1800 to about
4500 liters of nitrogen per kg of carbon support per hour
(from about 63 to about 160 ft3 of nitrogen per Ib of
carbon support per hour).
[0168] The carbon support having a precursor of the
transition metal composition thereon is typically contacted
with the carbon-containing compound in a carbide reaction
zone under a total pressure of no greater than about 15
psig. Typically, the carbide reaction zone is under a
pressure of from about 2 to about 15 psig. The carboncontaining
compound partial pressure of the carbide
reaction zone is typically no greater than about 2 psig
and, more typically, from about 1 to about 2 psig. The
partial pressure of any hydrogen present in the carbide
reaction zone is typically less than about 2 psig and, more
typically, from about 0.1 to about 2 psig.
[0169] In certain embodiments, the pretreated carbon
support, having a precursor transition metal compound
thereon, may be treated to form a transition metal
composition comprising both carbon and nitrogen and the
transition metal on the carbon support. In such
embodiments, the precursor compound on the support may be
contacted with a "carbiding-nitriding atmosphere." One
method involves contacting the pretreated carbon support
with a carbon and nitrogen-containing compound. Suitable
carbon and nitrogen-containing compounds include amines,
nitriles, nitrogen-containing heterocyclic compounds, or
combinations thereof. Such carbon and nitrogen-containing
compounds are generally selected from the group consisting
of dimethylamine, ethylenediamine, isopropylamine,
butylamine, melamine, acetonitrile, propionitrile,
picolonitrile, pyridine, pyrrole, and combinations thereof.
[0170] Typically, the carbon support having a
precursor of the transition metal composition deposited
thereon is contacted with a carbiding-nitriding atmosphere
which comprises a vapor phase carbon and nitrogencontaining
compound. Typically, the carbiding-nitriding
atmosphere comprises at least about 5% by volume of carbon
and nitrogen-containing compound and, more typically, from
about 5 to about 20% by volume of the carbon and nitrogencontaining
compound. Generally, at least about 100 liters
of carbon and nitrogen-containing compound per kg of carbon
per hour (at least about 3.50 ft3 of carbon and nitrogencontaining
compound per Ib of carbon per hour) are
contacted with the carbon support. Preferably, from about
200 to about 500 liters of carbon and nitrogen-containing
compound per kg of carbon per hour (from about 7.0 to about
17.7 ft3 of carbon and nitrogen-containing compound per Ib
of carbon per hour) are contacted with the carbon support.
[0171] The carbiding-nitriding atmosphere optionally
includes additional components selected from the group
consisting of hydrogen and inert gases such as argon.
Hydrogen, where present, is generally present in a
proportion of at least about 1% by volume or, more
generally, from about I to about 5% by volume. In certain
embodiments, the carbiding-nitriding atmosphere comprises
at least about 10 liters of hydrogen per kg of carbon
support per hour (at least about 0.35 ft3 of hydrogen per
Ib of carbon support). Preferably, such a carbidingnitriding
atmosphere comprises from about 30 to about 50
liters of hydrogen per kg of carbon support per hour (from
about 1.05 to about 1.8 ft3 of hydrogen per Ib of carbon
support per hour).
[0172] In various other embodiments, the carbidingnitriding
atmosphere comprises at least about 900 liters of
argon per kg of carbon support per hour (at least about
31.5 ft3 of argon per Ib of carbon support). Preferably,
such a carbiding-nitriding atmosphere comprises from about
1800 to about 4500 liters of argon per kg of carbon support
per hour (from about 63 to about 160 ft3 of argon per Ib of
carbon support per hour).
[0173] In further embodiments, the carbidingnitriding
atmosphere comprises at least about 10 liters of
hydrogen per kg of carbon support per hour (at least about
0.35 ft3 of hydrogen per Ib of carbon support) and at least
about 900 liters of argon per kg of carbon support per hour
(at least about 31.5 ft3, of argon per Ib of carbon
support).
[0174] The carbon support having a precursor of the
transition metal composition thereon is typically contacted
with the carbon and nitrogen-containing compound in a
carbide-nitride reaction zone under a total pressure of no
greater than about 15 psig. Typically, the carbide-nitride
reaction zone is under a pressure of from about 2 to about
15 psig. The carbon and nitrogen-containing compound
partial pressure of the carbide-nitride reaction zone is
typically no greater than about 2 psig and, more typically,
from about 1 to about 2 psig. The partial pressure of any
hydrogen present in the carbide-nitride reaction zone is
typically less than about 1 psig and, more typically, from
about 0.1 to about 1 psig.
[0175] Additionally or alternatively, a transition
metal composition comprising a transition metal, carbon,
and nitrogen may be formed by contacting the support and
precursor with a nitrogen-containing compound as described
above with the carbon of the transition metal composition
derived from the supporting structure.
[0176] In further embodiments, the support and
precursor of the transition metal composition may be
contacted with a nitrogen-containing compound (e.g.,
ammonia) and a carbon-containing compound (e.g., methane)
as set forth above to form a transition metal composition
comprising a transition metal, carbon, and nitrogen on the
carbon support.
[0177] In still further embodiments the carbon
support is contacted with a compound comprising a
transition metal, nitrogen, and carbon to form a precursor
of the transition metal composition thereon (i.e., the
source compound and carbon and nitrogen-containing compound
are provided by one composition) and heated in accordance
with the following description to form a transition metal
composition comprising a transition metal, nitrogen, and
carbon on a carbon support. Typically, such compositions
comprise a co-ordination complex comprising nitrogencontaining
organic ligands including, for example,
nitrogen-containing organic ligands including five or six
membered heterocyclic rings comprising nitrogen.
Generally, such ligands are selected from the group
consisting of porphyrins, porphyrin derivatives,
polyacrylonitrile, phthalocyanines, pyrrole, substituted
pyrroles, polypyrroles, pyridine, substituted pyridines,
bipyridyls, phthalocyanines, imidazole, substituted
imadazoles, pyrimidine, substituted pyrimidines,
acetonitrile, o-phenylenediamines, bipyridines, salen
ligands, p-phenylenediamines, cyclams, and combinations
thereof. In certain embodiments, the co-ordination complex
comprises phthalocyanine (e.g., a transition metal
phthalocyanine) or a phthalocyanine derivative. Certain of
these co-ordination complexes are also described in
International Publication No. WO 03/068387 Al and U.S.
Application Publication No. 2004/0010160 Al, the entire
disclosures of which are hereby incorporated by reference.
[0178] To deposit the transition metal composition
precursor in such embodiments, typically a suspension is
prepared comprising the carbon support and the coordination
complex which is agitated for a time sufficient
for adsorption of the co-ordination compound on the carbon
support. Typically, the suspension contains the carbon
support in a proportion of from about 5 to about 20 g/liter
and the co-ordination compound in a proportion of from
about 2 to about 5. Preferably, the carbon support and coordination
compound are present in a weight ratio of from
about 2 to about 5 and, more preferably, from about 3 to
' about 4.
[0179] Formation of a transition metal composition on
the carbon support proceeds by heating the support and
precursor in the presence of an atmosphere described above
(i.e., in the presence of a nitrogen-containing, carboncontaining,
or nitrogen and carbon-containing compound).
Typically, the carbon support having the precursor thereon
is heated using any of a variety of means known in the art
including, for example, an electrical resistance furnace or
an induction furnace.
[0180] Generally, the transition metal composition
precursor may contain a transition metal salt, partially
hydrolyzed transition metal, and/or a transition metal
oxide. For example, in the case of iron, the precursor may
comprise FeCl3/ Fe(OH)3/ Fe(OH)2
+1, Fe(OH)+2, and/or Fe2O3.
Generally, heating the carbon support having a precursor of
the transition metal composition thereon forms the
transition metal composition by providing the energy
necessary to replace the bond between the transition metal
and the other component of the precursor composition (s)
with a bond between the transition metal and nitrogen,
carbon, or carbon and nitrogen. Additionally or
alternatively, the transition metal composition may be
formed by reduction of transition metal oxide to transition
metal which combines with the carbon and/or nitrogen of the
composition present in the nitriding, carbiding, or
carbiding-nitriding atmosphere with which the carbon
support is contacted to form the transition metal
composition.
[0181] Typically, the support is heated to a
temperature of at least about 600°C, more typically to a
temperature of at least about 700°C, still more typically
to a temperature of at least about 800°C and, even more
typically, to a temperature of at least about 850°C to
produce the transition metal composition.
[0182] The maximum temperature to which the support is
heated is not narrowly critical as long as it is sufficient
to produce a transition metal nitride, transition metal
carbide, or transition metal carbide-nitride. The support
can be heated to temperatures greater than 1000°C, greater
than 1250°C, or up to about 1500°C. It has been observed,
however, that graphitization of the carbon support may
occur if the support is heated to temperatures above 900°C
or above 1000°C. Graphitization may have a detrimental
effect on the activity of the catalyst. Thus, preferably,
the support is heated to a temperature of no greater than
about 1000°C. However, active catalysts can be prepared by
heating the support and precursor to temperatures in excess
of 1000°C, regardless of any graphitization which may
occur. Preferably, the support is heated to a temperature
of from about 600°C to about 1000°C, more preferably, from
about 600 to about 975°C, more preferably from about 700 to
about 975°C, even more preferably from about 800 to about
975°C, still more preferably from about 850 to about 975°C
and especially to a temperature of from about 850°C to
about 950°C.
[0183] In the case of a carbiding atmosphere
comprising a hydrocarbon (e.g., methane), it has been
observed that heating the carbon support to temperatures
above 700°C may cause polymeric carbon to form on the
carbon support. Thus, in certain embodiments in which a
transition metal composition comprising a transition metal
and carbon is desired, it may be preferable to form such a
composition by heating the support to temperatures of from
about 600 to about 700°C. However, it should be understood
that formation of a transition metal composition comprising
a transition metal and carbon proceeds at temperatures
above 700°C and such a method produces suitable modified
carbon supports for use in accordance with the present
invention provided Tmax is sufficient for carbide formation
(e.g., at least 500°C or at least 600°C).
[0184] The rate of heating is likewise not narrowly
critical. Typically, the support having a precursor
deposited thereon is heated at a rate of at least about
2°C/minute, more typically at least about 5°C/minute, still
more typically at least about 10°C/minute and, even more
typically, at a. rate of at least about 12°C/minute.
Generally, the support having a precursor deposited thereon
is heated at a rate of from about 2 to about 15°C/minute
and, more generally, at a rate of from about 5 to about
15°C/minute.
[0185] A carbon support having a transition
metal/nitrogen and/or transition metal/carbon composition
formed thereon may serve as a modified carbon support for a
metal-containing active phase effective for promoting the
dehydrogenation of an alcohol. In various embodiments, the
metal-containing active phase comprises copper.
[0186] In certain embodiments of the present
invention it may be desired to form a transition metal
composition comprising carbon or nitrogen (i.e., a
transition metal carbide or nitride) comprising molybdenum
or tungsten (i.e., molybdenum carbide, tungsten carbide,
molybdenum nitride, or tungsten nitride). One method for
forming such carbides and nitrides involves temperature
programmed reduction (TPR) which includes contacting the
support and the transition metal precursor with a carbiding
(i.e., carbon-containing) or nitriding (i.e., nitrogencontaining)
atmosphere under the conditions described
below. It should be understood that the following
discussion regarding forming molybdenum and tungstencontaining
transition metal compositions does not limit the
discussion set forth above regarding forming catalytically
active transition metal compositions comprising at least
one of numerous transition metals (including molybdenum and
tungsten).
[0187] In embodiments in which molybdenum carbide or
tungsten carbide is desired, typically, a carbiding
atmosphere comprises a hydrocarbon having from 1 to 5
carbons. In a preferred embodiment, the carbon-containing
compound comprises methane. Typically, the carbiding
atmosphere comprises at least about 5% by volume of carboncontaining
compound and, more typically, from about 5 to
about 50% by volume of the carbon-containing compound.
Generally, at least about 100 liters of carbon-containing
compound per kg of carbon per hour (at least about 3.50 ft3
of carbon-containing compound per Ib of carbon per hour)
are contacted with the carbon support. .Preferably, from
about 200 to about 500 liters of carbon-containing compound
per kg of carbon per hour (from about 7.0 to about 17.7 ft3
of carbon-containing compound per Ib of carbon per hour)
are contacted with the carbon support.
[0188] The carbiding atmosphere optionally includes
additional components selected from the group consisting of
hydrogen and inert gases such as argon or nitrogen.
Hydrogen, where present, is generally present in a
proportion of at least about 1% by volume hydrogen or, more
generally, from about 1 to about 50% by volume hydrogen.
In one such embodiment, the carbiding atmosphere comprises
at least about 10 liters of hydrogen per kg of carbon
support per hour (at least about 0.35 ft3 of hydrogen per
Ib of carbon support per hour). Preferably, such a
carbiding atmosphere comprises from about 30 to about 50
liters of hydrogen per kg of carbon support per hour (from
about 1.05 to about 1.8 ft3 of hydrogen per Ib of carbon
support per hour).
[0189] In such embodiments in which molybdenum
nitride or tungsten nitride is desired, a nitriding
atmosphere generally comprises a nitrogen-containing
compound such as ammonia and may also include inert gases
such as argon and nitrogen. Typically, the nitriding
atmosphere comprises at least about 5% by volume of
nitrogen-containing compound and, more typically, from
about 5 to about 20% by volume of the nitrogen-containing
compound. Generally, at least about 100 liters of
nitrogen-containing compound per kg of carbon per hour (at
least about 3.50 ft3 of nitrogen-containing compound per Ib
of carbon) are contacted with the carbon support.
Preferably, from about 200 to about 500 liters of nitrogencontaining
compound per kg of carbon per hour (from about
7.1 to about 17.7 ft3 of nitrogen-containing compound per
Ib of carbon per hour) are contacted with the carbon
support. Hydrogen, where present, generally is present in
a proportion of at least about 1% by volume hydrogen or,
more generally, from about 1 to about 5% by volume
hydrogen.
[0190] In various embodiments in which a transition
metal composition comprising molybdenum or tungsten is
desired, the temperature of the atmosphere is increased to
a temperature Tx having a value of at least about 250°C,
more typically 300°C, over a period of time, ta.
Preferably, the temperature of the atmosphere is increased
to from about 250 to about 350°C and, more preferably,
increased to from about 275 to about 325°C during tx. This
period of time (tj necessary for increasing the
temperature from T0 to Tt is generally at least about 5
minutes. Typically, tj. is from about 5 to about 30 minutes
and, more typically, from about 10 to about 15 minutes.
The rate of temperature increase during tx is not narrowly
critical and generally is less than 150°C/min. Typically,
the rate of temperature increase during tx is from about 10
to about 100°C/min and, more typically, from about 20 to
about 50°C.
[0191] During t1 the source compound or derivative
transition metal carbide or nitride may be transformed to
an intermediate oxide formed on the surface of the support.
The intermediate oxide formed during t^ generally have an
empirical formula of A^Oy wherein A is molybdenum or
tungsten, depending on the desired make-up of the
transition metal composition. Typically, the ratio of x to
y is at least about 0.33:1 and preferably from about 0.33:1
to about 1:1.
[0192] For example, in the formation of a transition
metal composition comprising molybdenum, an oxide
intermediate may be formed in accordance with the following
methods:
Catalyst
Pr ecursor
from 25° C to 300-400° C in
H^ I Cm Flow
MoOilC
Catalyst
Precursor
from 25° C to 300- 400° C in ti
MoO3/C
NHi Flow
[0193] Dehydrogenations which may be promoted by
catalysts including a modified carbon support (i.e., a
carbon support having a transition metal/nitrogen and/or
transition metal/carbon composition formed thereon) having
a metal-containing (e.g., copper-containing) active phase
deposited thereon are typically conducted in an alkaline
environment. Transition metal oxide precursor unconverted
to a carbide or nitride may react with an alkaline
component of such a dehydrogenation system or alkaline
component of a metal plating solution to form a transition
metal salt due to the instability of the oxide, thus
resulting in removal of transition metal from the surface
of the carbon support. For example, Mo03 unconverted to
molybdenum carbide may react with sodium hydroxide in
accordance with the following:
2NaOH + #20
[0194] Removal of the transition metal salt from the
surface of the carbon support is undesired because it may
compromise the catalytic properties of the transition metal
composition as such, and/or result in reduced deposition of
a metal-containing active phase onto the transition metal
composition.
[0195] Thus, in accordance with the above
considerations, it is desired to convert as great a
proportion of any transition metal oxide formed during a
carbiding or nitriding operation as possible. Typically,
at least about 80% and, more typically, from about 80% to
about 95% of the transition metal oxide is converted to the
transition metal composition. Preferably, no more than
about 5% by weight of the oxide precursor remains
unconverted, more preferably, no more than about 3% by
weight of the oxide precursor remains unconverted and,
still more preferably, no more than about 1% by weight of
the oxide precursor remains unconverted.
[0196] Considerations concerning the initial
temperature (T0) , rate of increase from T0 to Tx (tx) , the
value of T17 and precursor formation are generally the same
regarding formation of carbides and nitrides from the
precursor or intermediate oxide. However, the remainder of
the temperature programmed reduction method differs in
certain important respects based on whether a carbide or
nitride is desired.
[0197] The following discussion relates to
preparation of modified carbon supports which may serve as
the support for a metal-containing active phase in a
catalyst useful for promoting the dehydrogenation of an
alcohol. After the initial period of temperature increase,
tj, which typically results in formation of transition
metal oxide precursor, the temperature of a carbiding
(i.e., carburization) atmosphere is elevated from Tx to a
maximum temperature (T^) during which time a transition
metal carbide containing molybdenum or tungsten is formed
on the surface of the carbon support by reduction of the
transition metal oxide precursor.
[0198] Typically, Tmax is at least about 500°C, more
typically at least about 600°C, still more typically at
least about 700°C and, even more typically, at least about
800°C or at least about 850°C. Preferably, Traax is from
about 600°C to about 1000°C and, more preferably, from
about 850°C to about 950°C.
[0199] In the case of a carbiding atmosphere
comprising a hydrocarbon (e.g., methane), it has been
observed that heating the carbon support to temperatures
above 700°C may cause polymeric carbon to form on the
carbon support. Thus, in certain embodiments in which a
transition metal composition comprising a transition metal
and carbon is desired, it may be preferable to form such a
composition by heating the support to temperatures of from
about 600 to about 700°C. However, it should be understood
that formation of a transition metal composition comprising
a transition metal and carbon proceeds at temperatures
above 700°C and such a method produces suitable modified
carbon supports for use in accordance with the present
invention provided Tmax is sufficient for carbide formation
(e.g., at least 500°C or at least 600°C).
[0200] In certain embodiments for carbiding
atmospheres comprising, for example, methane, the precursor
is heated to 650°C at a rate of at least about 2°C/min.
While not narrowly critical, typically the precursor is
heated to Tmax over a period of time (t2) of at least about
10 minutes and, more typically, from about 15 to about 150
minutes and, still more typically, from about 30 to about
60 minutes. The rate at which the temperature increases
from Tj_ to Tmax is not narrowly critical but generally is at
least about 2°C/min. Typically, this rate is from about 2
to about 40°C/min and, more typically, from about 5 to
about 10 °C/min.
[0201] After the atmosphere contacting the oxidecontaining
precursor reaches Tmax, the temperature of the
atmosphere is generally maintained at T^ for a time
sufficient to ensure the desired reduction of the
transition metal oxide to form the transition metal
carbide. Typically, this holding time at Tmax, t3, during
which the temperature remains at Traax is at least about 1
hour and may be from about I to about 8 hours; however,
care is preferably taken to ensure that t3 is not of a
duration such that polymeric carbon forms on the carbon
support in amounts that adversely affect catalyst activity.
Preferably, t3 is from about 1 to about 4 hours and, more
preferably, from about 2 to about 3 hours.
[0202] Generally, the intermediate transition metal
oxide is contacted with the hydrocarbon under conditions
which substantially avoid the production of polymeric
carbon on the surface of the transition metal carbide.
[0203] The transition metal oxide is typically
contacted with the hydrocarbon in a carbide reaction zone
under a total pressure of no greater than about 15 psig.
Typically, the carbide reaction zone is under a pressure of
from about 2 to about 15 psig. The hydrocarbon partial
pressure of the carbide reaction zone is typically no
greater than about 2 psig and, more typically, from about 1
to about 2 psig.
[0204] Both Tmax and the holding time at T,^, t3,
directly affect carbide formation with each condition being
controlled in order to provide sufficient carbide
formation. However, ensuring that both conditions are
within a preferred range provides even more preferred
conditions for carbide formation. Thus, in a particularly
preferred embodiment, T^ is from about 625 to about 675 °C
while t3 is from about 2 to about 3 hours.
[0205] After the initial period of temperature
increase, t-L, which typically results in formation of a
transition metal oxide, the temperature of a nitriding
(i.e., nitridation) atmosphere is elevated from Tx to a
maximum temperature (Tmax.) in order to form the transition
metal nitride containing molybdenum or tungsten. In
contrast to the method described above for carbide
formation, the temperature of a nitriding atmosphere is
then elevated from Tx to a maximum temperature (Tmax) of at
least about 700°C to produce the nitride since it has been
observed that at temperatures below 700°C the nitride
formation is not substantially complete. However, as the
nitriding atmosphere approaches temperatures of from about
900°C and above the metal nitride may be reduced by
hydrogen produced by decomposition of the nitriding gas.
Thus, Tmax is preferably from about 700 to about 900°C, more
preferably from about 700 to about 850°C and, still more
preferably, from about 725 to about 800°C. While not
narrowly critical, typically the oxide-containing precursor
is heated to Tmax over a period of time (t2) of at least
about 15 minutes, more typically from about 15 to about 250
minutes and, still more typically, from about 30 to about
60 minutes. The rate at which the temperature increases
from T! to Traax is not narrowly critical but generally is at
least about 2°C/min. Typically, this rate is from about 2
to about 40 °C/min and, more typically, from about 5 to
about 10 °C/min.
[0206] After the atmosphere contacting the oxidecontaining
precursor reaches Tmax, the temperature of the
atmosphere is generally maintained at Tmax for a time
sufficient to ensure the desired reduction of the
transition metal oxide to a transition metal nitride.
Typically, this period of time, t3, during which the
temperature remains at Tmax is at least about 1 hour.
Preferably, t3 is preferably from about 1 to about 5 hours
and, more preferably, from about 3 to about 4 hours.
[0207] As with carbide formation, both Tmax and the
holding time at Tmax/ t3, directly affect nitride formation
with each condition being controlled in order to provide
sufficient nitride formation. However, ensuring that both
conditions are within a preferred range provides even more
preferred conditions for nitride formation. Thus, in a
particularly preferred embodiment, Tmax is from about 725 to
about 800°C while t3 is from about 1 to about 5 hours.
[0208] It has been observed that during temperature
programmed reduction used to produce a transition metal
nitride in which the nitrogen-containing atmosphere
comprises ammonia, the transition metal nitride thus formed
(e.g., molybdenum nitride) may be reduced to form free
transition metal.
2MN + 2NH3 >. 2M2 + N2 + 2H2O
2M + 2NH3 • ^ ^ ' 2MN + 3H2
[0209] This reaction typically occurs when the
nitridation reaction is complete (i.e., substantially all
of the oxide precursor has been reduced to the nitride) and
is likely to occur when Tmax reaches higher temperatures
(i.e., above 900°C). Even though these reactions may
result in producing the desired transition metal nitride by
the forward reaction between free transition metal and
ammonia, the conditions for direct ammonia nitridation of
free transition metal are preferably avoided because of the
possibility of the reverse reduction of the nitride by
hydrogen. This is typically controlled by maintaining Tmax
during nitridation below that which accelerates
decomposition of ammonia to form hydrogen, thereby
preventing the reverse formation of free transition metal
by the reduction of the nitride by hydrogen.
[0210] The contact of either a carbiding or nitriding
atmosphere with the support may occur via a gas phase flow
within a fluid bed reaction chamber at a space velocity of
at least about 0.01 sec"1. The gas phase flow of the
carbiding or nitriding atmosphere within a fluid bed
reaction chamber is not narrowly critical and may exhibit a
space velocity of from about 0.01 to about 0.50 sec"1.
While carbide and nitride formation proceeds readily over a
wide range of gas phase flow rates, the flow rate may be
increased to initially increase diffusion of the source
compound into the pores of the support to accelerate
formation of the carbide or nitride and reduce the time
necessary to hold the temperature at Tmax to ensure
sufficient carbide or nitride formation.
[0211] In addition to temperature programmed
reduction, other methods for producing a transition metal
(e.g., molybdenum or tungsten) carbide may be used. For
example, a carbon support having a precursor formed on its
surface in accordance with the above description may be
contacted with an inert gas at temperatures ranging from
about 500 to about 1400°C. It is believed that the
precursor is reduced by the carbon support under the high
temperature conditions and the precursor reacts with the
carbon support to form a carbide on the surface of the
support. The inert gas may be selected from the group
consisting of argon, nitrogen, and helium.
[0212] Another method includes contacting a volatile
metal compound and a carbon support at temperatures ranging
from about 500 to about 1400°C to reduce the volatile metal
compound which then reacts with the carbon support to form
a carbide. The volatile metal compound is generally an
organometallic compound.
[0213] A carbon support having a precursor formed on
it's surface may also be contacted with hydrogen at a
temperature of from about 500 to about 1200°C (typically,
about 800°C) to reduce the precursor which reacts with the
carbon support to form a carbide on the surface of the
carbon support.
[0214] The time to reach the maximum temperature, the
maximum temperature itself or time for holding the
temperature at the maximum are not narrowly critical and
may vary widely in accordance with either of these methods.
[0215] It has been observed that the yield and
stability (e.g., resistance to leaching under alkaline
dehydrogenation or metal plating conditions) of a carbide
produced using the alternatives to temperature programmed
reduction described above are reduced as compared to
carbides produced using temperature programmed reduction.
Thus, temperature programmed reduction is the preferred
method for carbide formation.
[0216] Formation of a transition metal (e.g.,
molybdenum or tungsten) carbide and nitride on the surface
of a carbon support may proceed generally in accordance
with the above discussion. An exemplary preparation is
formation of a transition metal (i.e., molybdenum or
tungsten) carbide and nitride on the surface of a carbon
support having a molybdenum or tungsten-containing
precursor deposited thereon as described above. One such
method involves subjecting a carbon support to high
temperatures (e.g., from about 600 to about 1000°C) in the
presence of an organic ligand containing carbon and
nitrogen to form both a carbide and nitride on the support
surface. Possible ligands include, for example, a
transition metal porphyrin or a nitrogen-containing
molybdenum organometallic compound (e.g., a molybdenum
pyridine compound).
[0217] In a further alternative process for preparing
a modified carbon support comprising a transition metal
carbide and a transition metal nitride, a transition metalcontaining
(e.g., molybdenum or tungsten-containing)
nitride is formed according to any of the process schemes
described above for that purpose, after which the nitride
is contacted with a hydrocarbon or a mixture comprising a
hydrocarbon and hydrogen. Thus, a composition containing
both a carbide and a nitride is formed on the surface of
the carbon support by virtue of the conversion of only a
certain portion of the nitride. Remainder of a portion of
the nitride is assured by maintaining conditions under
which conversion of nitride to carbide is incomplete, for
example, by limiting Traax or limiting the hold time at Traax.
[0218] In the transition metal/nitrogen composition,
or transition metal/nitrogen/carbon composition, it is
believed that the transition metal is bonded to nitrogen
atoms by co-ordination bonds. In at least certain
embodiments of the process for preparing the catalyst, a
nitrogen-containing compound may be reacted with the carbon
substrate, and the product of this reaction further reacted
with a transition metal source compound or precursor
compound to produce a transition metal composition in which
the metal is co-ordinated to the nitrogen. Reaction of the
nitrogen-containing compound with the carbon substrate is
believed to be incident to many if not most embodiments of
the process for preparing the transition metal composition,
but can be assured by initially contacting a carbon
substrate with the nitrogen-containing compound under
pyrolysis conditions in the absence of the transition metal
or source thereof, and thereafter cooling the pyrolyzed Ncontaining
carbon, impregnating the cooled N-containing
carbon with a transition metal precursor compound, and
pyrolyzing again. According to this alternative process,
during the first pyrolysis step the carbon may be contacted
with a nitrogen-containing gas such as ammonia or
acetonitrile at greater than 700°C, typically about 900°C.
The second pyrolysis step may be conducted in the presence
of an inert or reducing gas (e.g., hydrogen and/or
additional nitrogen-containing compound) under the
temperature conditions described herein for preparation of
a transition metal/nitrogen composition or transition
metal/nitrogen/carbon composition on a carbon support.
Conveniently, both pyrolysis steps may be conducted by
passing a gas of appropriate composition through a fixed or
fluid bed comprising a particulate carbon substrate.
[0219] Where nitrogen is combined with the carbon
substrate, the nitrogen atoms on the carbon support are
understood to be typically of the pyridinic-type wherein
nitrogen contributes one n electron to carbon of the
support, e.g., to the graphene plane of the carbon, leaving
an unshared electron pair for co-ordination to the
transition metal. It is further preferred that the
concentration of transition metal on the support be not
substantially greater than that required to saturate the
nitrogen atom co-ordination sites on the carbon.
Increasing the transition metal concentration beyond that
level may result in the formation of zero valence (metallic
form) of the transition metal, which is believed to be
catalytically inactive for at least certain reactions. The
formation of zero valence transition metal particles on the
surface may also induce graphitization around the metal
particles. Although the graphite may itself possess
catalytic activity for certain reactions, graphitization
reduces effective surface area, an effect that, if
excessive, may compromise the activity of the catalyst.
[0220] In the case of catalysts further including a
metal-containing active phase formed on a modified carbon
support (i.e., a carbon support having a transition metal
composition formed thereon), a modified carbon support
having a high surface area is desired in order to provide a
high surface area suitable for metal deposition. Thus,
modified carbon supports typically have a Langmuir surface
area of at least about 500 m2/g prior to deposition of a
metal thereon. Preferably, the Langmuir surface area of a
modified carbon support is at least about 600 m2/g and,
more preferably, from about 600 to about 800 m2/g prior to
deposition of a metal thereon. Preferably, the surface
area of the modified support is at least about 30% of the
surface area of the support prior to formation of the
transition metal composition thereon and, more preferably,
from about 40 to about 70% of the surface area of the
support prior to formation of the transition metal
composition on the carbon support.
[0221] The micropore surface area of modified carbon
supports of the present invention (i.e., surface area
attributed to pores having a diameter less than 20A) is
typically at least about 200 m2/g and, more typically, from
about 200 to about 400 m2/g. Preferably, the Langmuir
micropore surface area of the modified support is at least
about 20% of the surface area of the support prior to
formation of the transition metal composition thereon, more
preferably from about 20 to about 50% and, still more
preferably, from about 30 to about 50% of the Langmuir
micropore surface area of the support prior to formation of
the transition metal composition on the carbon support.
[0222] The combined Langmuir mesopore and ma.cropore
surface area of modified carbon supports of the present
invention (i.e., surface area attributed to pores having a
diameter greater than 20A) is typically at least about 200
m2/g and, more typically, from about 200 to about 400 m2/g.
Preferably, the combined Langmuir micropore and mesopore
surface area of the modified support is at least about 40%
of the surface area of the support prior to formation of
the transition metal composition thereon and, more
preferably, from about 50 to about 70% of the surface area
of the support prior to formation of the transition metal
composition on the carbon support.
[0223] Modified carbon supports prepared in
accordance with the process of the present invention
likewise preferably exhibit pore volumes sufficient to
allow for diffusion of reactants into the pores of the
finished catalyst. Thus, preferably a modified carbon
support comprising a transition metal/carbon composition
(i.e., a transition metal carbide) has a total pore volume
of at least about 0.50 cm3/g and, more preferably, a pore
volume of at least about 0.60 cm3/g-
[0224] In addition to overall pore volume, the pore
volume distribution of modified carbon supports of the
present invention preferably conduces to diffusion of
reactants into the pores of the finished catalyst.
Preferably, pores having a diameter of less than about 20 A
make up no more than about 45% of the overall pore volume
of the modified carbon support and, more preferably, no
more than about 30% of the overall pore volume. Pores
having a diameter of greater than about 20 A preferably
make up at least about 60% of the overall pore volume of
the modified carbon support and, more preferably, at least
about 65% of the overall pore volume.
[0225] It has been observed that "mesopores" (i.e.,
pores having a diameter of from about 20 to about 50 A)
allow suitable diffusion of reactants into the pores of a
modified carbon support. Thus, preferably mesopores make
up at least about 25% of the overall pore volume and, more
preferably, at least about 30% of the overall pore volume.
Macro pores (i.e., pores having a diameter larger than
about 50 A) also allow suitable diffusion of reactants into
the pores of the modified carbon support. Thus,
preferably, these pores make up at least about 5% of the
overall pore volume and, more preferably, at least about
10% of the overall pore volume of the catalyst.
[0226] Catalysts of the present invention may include
a metal-containing active phase suitable for catalyzing
reactions such as, for example, the dehydrogenation of
primary alcohols deposited on a modified carbon support
prepared as described above. Such a metal-containing
active phase may comprise a metal selected from the group
consisting of Group IB and Group VIII. In various
embodiments, the metal is selected from the group
consisting of copper, nickel, platinum, and palladium with
nickel, platinum, or palladium acting as a support for an
active phase containing copper.
[0227] In the case of dehydrogenation of a primary
alcohol, the metal-containing active phase preferably
comprises copper. The following discussion focuses on
copper-containing catalysts. Nevertheless, it should be
recognized that this discussion generally applies to
catalysts containing other metals (e.g., nickel, platinum,
and palladium).
[0228] Copper may be deposited onto the modified
carbon support (i.e., the carbon support having a
transition metal composition as described above formed
thereon) surface via different methods including, for
example, electroless plating and electrolytic plating.
[0229] Electrolytic plating generally involves
passing an electric current through a plating solution
comprising the metal to be plated in contact with a cathode
comprising the modified carbon support. One alternative
method for electrolytic metal plating involves the use of a
"slurry electrode" such as that described by Kastening et
al. See Design of a slurry electrode reactor system,
(Journal of Applied Electrochemistry (1997), 27, 147-152).
Plating using a slurry electrode proceeds using a metal
(e.g., copper) anode and a slurry cathode comprising a
feeder electrode in a slurry of the modified carbon
support. Plating proceeds by oxidation of the copper anode
caused by release of electrons to the external circuit and
reduction of the resulting copper ions by electrons
supplied by the feeder cathode.
[0230] The following discussion focuses on
electroless plating since it is the preferred technique due
to its simplicity and low cost. Electroless plating
proceeds by the reduction of metal ions (e.g., copper ions)
to metal by an external reducing agent in a solution In
contact with the modified carbon support. In accordance
with the present invention, the plating solution generally
comprises an aqueous plating medium comprising a watersoluble
salt of the metal to be deposited, a reducing
agent, and a retardant which inhibits reduction of metal
ions (e.g., cupric ions) prior to contact with the modified
carbon support. The retardant may, for example, be a
chelating agent (i.e., a co-ordination compound) which
inhibits reduction of metal ions by forming a co-ordination
compound with the metal ions to be deposited in order to
delay their reduction by the reducing agent until the metal
salt is contacted with the modified carbon support. The
plating solution may contain other ingredients including,
for example, an alkaline hydroxide and other formulation
additives such as stabilizers, surfactants, and brightness
and wetting agents. The plating solution is typically
stable (i.e., remains as a well-dispersed mixture) for
extended periods of time (e.g., a week or longer) and,
thus, provides the advantage of being suitable for use in
multiple plating operations. Typically, the pH of the
aqueous medium is from about 7 to about 14.
[0231] In the case of copper, the water-soluble salts
of the aqueous medium are preferably selected from the
group consisting of copper chloride, copper nitrate, and
copper sulfate salts. In a preferred embodiment the watersoluble
salt comprises copper sulfate. While the
concentration of water-soluble salt in the aqueous medium
is not narrowly critical, to help ensure sufficient metal
deposition while preventing excess precipitation, typically
the salt concentration in the aqueous medium is no more
than about 20% by weight. Preferably, the salt
concentration in the aqueous medium is from about 1% to
about 10% by weight arid, more preferably, from about 8% to
about 10%. Generally, the aqueous medium comprises at
least about 0.2 g of copper salt per g of modified carbon
support contacted with the aqueous medium and no more than
about 1.5 g of copper salt per g of modified carbon support
contacted with the aqueous medium.
[0232] A wide variety of reducing agents may be used
including, for example, sodium hypophosphite (NaH2P02) ,
formaldehyde (CH20) and other aldehydes, formic acid
(HCOOH), salts of formic acid, salts of borohydride (e.g.,
sodium borohydride (NaBH4) ) , salts of substituted
borohydrides (e.g., sodium triacetoxyborohydride
(Na (CH3C02)3BH) ) , sodium alkoxides, dimethylborane (DMAS),
and hydrazine (H2NNH2)• n a preferred embodiment, the
reducing agent comprises formaldehyde. Reducing agent is
generally present in the aqueous medium in an amount
stoichiometrically required for reduction of all or a
substantial portion of the metal ions present in the
aqueous medium. The concentration of the reducing agent in
the aqueous medium is typically no more than about 1% by
weight of the overall plating solution and, more typically,
no more than about 0.5% by weight.
[0233] The reducing agent may be present in an amount
in excess of that stoichiometrically required for reduction
of all or a substantial portion of the metal ions present
in the aqueous medium. If present in an excess amount,
typically no more than about 400% excess reducing agent is
present.
[0234] Suitable retardants (i.e., chelating agents or
so-ordination ligands) for incorporation in the aqueous
medium for use in electroless plating include, for example,
aminopolycarboxylic ligands, aminopolyhydroxylic ligands,
polyhydroxylic ligands, and polycarboxy-polyhydroxylic
ligands. In particular, the retardant or, co-ordination
ligand, may be selected from the group consisting of
ethylenediaminetetraacetic acid (EDTA) ;
diethylenetriaminepentaaectic acid; N,N,N' ,N' -tetrakis- (2-
hydroxypropyl) -ethylenediamine; glycerol; and tartaric
acid. In a preferred embodiment, the retardant comprises
sodium potassium tartrate and, in another, EDTA.
[0235] In certain embodiments, the modified carbon
support is contacted with the aqueous medium comprising a
water-soluble salt of the metal to be deposited, a reducing
agent, and a retardant which inhibits reduction of metal
ions (e.g., cupric ions) prior to contact with the
transition metal composition of the modified carbon
support. The transition metal composition (e.g.,
transition metal carbide or nitride) catalyzes the
reduction reaction and overcomes the retardant effect of
the chelating agent or other retardant .
[0236] As the reducing agent reduces the metal ions
in the solution to metal, the metal forms a coating on the
surface of the supported transition metal composition which
has been formed on the modified carbon support and/or on
any transition metal free portion of the carbon support
surface. The mechanism of the electroless plating is shown
below in which the anodic reaction is the decomposition of
the reducing agent (as shown below, formaldehyde) and the
cathodic reaction is the reduction of the metal complex.
(Formula Removed)
[0237] It has been observed that a reducing agent
comprising formaldehyde functions more effectively in an
alkaline environment. This is because the formaldehyde
exists as methylene glycol in the aqueous medium. The
presence of an alkaline component facilitates the
deprotonation of methylene glycol; thus, the aqueous medium
typically also comprises an alkaline component. Typically,
the concentration of the alkaline component in the aqueous
medium is at least about 0.1% by weight. Preferably, the
concentration of the alkaline component in the aqueous
medium is from about 0.5 to about 5% by weight and, more
preferably, from about 1 to about 3% by weight.
[0238] When the aqueous medium does include an
alkaline component, care should be taken to avoid formation
of precipitates, which may result from reaction between
cations of the metal to be deposited and the hydroxide
ions. Precipitation is preferably avoided since any
precipitates formed may consume metal that may otherwise
deposit on the carbon support; and the catalytically
inactive precipitates (e.g., Cu(OH)2) may also deposit on
the surface of the modified support. Such precipitation
may prevent deposition of transition metal within the pores
of the carbon support. The presence of a retardant which
inhibits reduction of metal ions (e.g., cupric ions) prior
to contact with the transition metal composition of the
modified carbon support generally sufficiently inhibits
this precipitation. Thus, an alkaline component in the
aqueous medium is not detrimental to the plating process.
[0239] The electroless plating deposition of metal
onto the supported transition metal composition may in some
circumstances proceed too rapidly, thus preventing
sufficient diffusion of the metal into the carbon structure
(i.e., sufficient diffusion of the metal into the pores of
the carbon support) and, accordingly, preventing uniform
deposition of the metal throughout the carbon-supported
transition metal composition. The rate of plating is
directly proportional to the plating temperature; thus, one
way to control the plating rate is to control the plating
temperature. It has been discovered that operating the
plating process at moderate temperature improves diffusion
of the metal to be deposited into the pores of the
supported transition metal composition (e.g., carbide,
nitride, or carbide-nitride) and, accordingly, the
uniformity of metal deposition. Thus, typically the
plating is carried out (i.e., the modified carbon support
is contacted with the aqueous medium) at temperatures from
about 1 to about 50°C and, more typically, from about 2 to
about 25°C. Typically, the modified carbon support remains
in contact with the aqueous medium for at least about 0.5
hours and, more typically, for from about 0.5 to about 3
hours.
[0240] While plating of copper onto the transition
metal composition surface proceeds readily, unfortunately a
portion of the transition metal may be removed or, leached,
from the transition metal/nitrogen, transition metal/carbon
or transition metal/carbon/nitrogen composition on the
carbon support during the plating process.
[0241] Leaching of transition metal from the support
surface may be due to oxidation of the transition metal
composition (i.e., nitride, carbide-nitride or carbide) by
ions of the metal to be deposited on the transition metal
composition which are present in the aqueous medium/plating
solution. For example, an oxidized carbide is unstable
and, thus, transition metal is more likely to be leached
from the surface of the carbon support where the transition
metal composition comprises a significant fraction of
transition metal carbide. One explanation for the
instability of an oxidized carbide may be that it causes
oxidation of the transition metal and its removal from the
oxide matrix. The oxidation rate of the nitride, carbidenitride
or carbide is directly proportional to the plating
temperature; thus, this consideration may generally be
addressed by plating at low temperature in accordance with
the discussion set forth above regarding plating
temperature. Leaching of transition metal due to oxidation
of a carbide or nitride is also controlled, in part, by the
presence of the reducing agent which contributes to
maintaining the surface of the transition metal carbide or
nitride in a well-reduced state.
[0242] In addition to controlling and/or reducing
transition metal leaching, preventing oxidation of the
carbide or nitride is also advantageous because metal
generally does not plate onto an oxidized carbide or
nitride or, if it plates at all, does not produce a metal
phase stable under reaction (e.g., dehydrogenation)
conditions. This is believed to be due, at least in part,
to a much weaker interaction between oxidized carbide and
copper.
[0243] As stated, the retardant is present in the
aqueous medium in order to prevent reduction of metal ions
prior to contact with the metal to be plated, and where the
retardant is a chelating agent, it may perform this
function by forming a co-ordination compound with the metal
to be plated. Typically, the concentration of retardant in
the aqueous medium is at least about 3% by weight.
Preferably, the concentration of retardant in the aqueous
medium is from about 3 to about 6% by weight. However, if
too great a proportion of retardant is present in the
aqueous medium, transition metal may leach from the surface
of the carbon support due to formation of a co-ordination
compound between the retardant and transition metal.
[0244] Thus, the preferred proportion of retardant
present in the aqueous medium also depends on the
concentration of metal salt present in the aqueous medium.
It has been discovered that controlling the ratio of these
components contributes to optimal plating considerations.
That is to say, including an amount of retardant sufficient
to ensure that a sufficient portion of metal is plated
while maintaining the retardant concentration below that
which may contribute to leaching as discussed above. In
accordance with the present invention, the molar ratio of
moles of retardant to moles of metal present in the aqueous
medium is at least about'1:1, typically at least about
1.5:1, more typically at least about 2.0:1 and, still more
typically, at least about 2.5:1. However, the molar ratio
of moles of retardant to moles of metal present in the
aqueous medium is preferably no more than about 3:1 in
order to avoid formation of an excessive amount of coordination
compound between the retardant and the
transition metal.
[0245] In addition to plating temperature and
retardant concentration, the manner of introduction to the
aqueous medium of one or more of its components may be
modified to control the plating rate and leaching from the
surface of the support. Fig. 1 is a SEM image of a carbon
supported molybdenum carbide having copper deposited
thereon in accordance with the method described above in
which the reducing agent is present at the outset of the
electroless plating. As shown in Fig. 1, it has been
observed that plating in accordance with the method
described above in which the reducing agent is present at
the outset of the electroless plating in the case of a
carbon-supported molybdenum carbide results in appreciable
metal cluster formation and less than desired plating
within the pores of the carbon support. This method does,
however, result in very little transition metal leaching.
[0246] It has been discovered, for example, that
introducing the reducing agent into the aqueous medium
after the modified carbon support has been contacted with
the aqueous medium comprising a metal salt and a retardant
provides increased diffusion of the metal to be deposited
into the pores of the carbon support since the plating rate
is slowed down by virtue of the delay in introduction of
the reducing agent; thus resulting in more uniform metal
deposition as compared to that observed when the reducing
agent is present where the modified carbon support is
contacted with the aqueous medium.
[0247] Fig. 2 is a SEM image of a carbon supported
molybdenum carbide having copper deposited thereon in
accordance with this method (i.e., delaying introduction of
the reducing agent until the support has been contacted
with the aqueous medium). As shown in Fig. 2, uniform
copper plating (i.e., no appreciable formation of copper
clusters) and sufficient plating within the pores of the
carbon support are observed using this method. On the
other hand, introduction of the modified support to the
aqueous medium in the absence of the reducing agent may
result in high transition metal leaching from the support
surface due to oxidation of carbide or nitride surface due
to the instability of oxidized carbides and nitrides. For
example, molybdenum leaching of as high as 20% was observed
in the case of the copper plated carbon supported
molybdenum carbide shown in Fig. 2.
[0248] Introducing the metal salt into the aqueous
medium after the modified carbon support has been contacted
with the aqueous medium comprising a reducing agent and a
retardant has also been considered. Plating in this manner
provides reduced leaching (e.g., as low as 5% of the
transition metal formed on the carbon support) caused by
oxidation of the carbide or nitride surface since the
reducing agent is present to ensure that the carbide or
nitride surface remains well reduced. However, plating can
proceed too rapidly because the entire stoichiometric
amount of reducing agent and salt are present when the
carbon support is initially contacted with the aqueous
medium. Fig. 3 is a TEM image of a carbon supported
molybdenum carbide having copper deposited thereon in
accordance with this method (i.e., delaying introduction of
the metal salt into the aqueous medium after the modified
carbon support has been contacted with the aqueous medium).
As shown in Fig. 3, this method may not provide uniform
distribution (i.e., appreciable formation of copper
clusters occurs) or insufficient plating within the pores
of the carbon support. Thus, even though leaching may be
reduced as compared to those methods described above, this
method, while acceptable in some instances, is not
preferred. Deposition of metal per this alternative is
usually not as uniform as that achieved using the method
described above wherein introduction of a portion of the
reducing agent is delayed.
[0249] Thus, preferably, the often conflicting
considerations of plating rate, which directly affects the
uniformity and quality of plating, and oxidation of the
carbide or nitride are both addressed by controlling the
manner of introduction of each of its components and the
modified carbon support to the aqueous medium.
[0250] Having reducing agent present in an amount
stoichiometrically less than that required for reduction of
the metal ions to the metal to be plated in the aqueous
medium when the support is initially contacted with the
aqueous medium followed by introduction of additional
reducing agent to the aqueous medium solution after the
support has been contacted with the aqueous medium has also
been investigated. The slurry may be agitated as copper
metal is deposited on the support. Delaying introduction
of a portion of the reducing agent to the aqueous medium in
this manner to form a primary electroless plating slurry
comprising the less than stoichiometrically required amount
of reducing agent reduces the plating rate and,
accordingly, allows increased diffusion of the metal to be
deposited into the pores of the carbon support, resulting
in more uniform metal deposition. The initial portion of
reducing agent is sufficient to reduce metal ions while
also sufficient to provide a well-reduced carbide or
nitride surface to control leaching caused by oxidation of
carbide and nitride surface. Fig. 4 is a SEM image of a
carbon supported molybdenum carbide having copper deposited
thereon in accordance with this method (i.e., delaying
introduction of a portion of the reducing agent until the
support has been contacted with the aqueous medium). As
shown in Fig. 4, uniform deposition of copper is achieved
using this method. In addition, low molybdenum leaching
(e.g., no more than about 5% by weight) occurs with this
method. In certain embodiments, the electroless plating
slurry comprises no more than about 2% of the
stoichiometric amount of reducing agent required for
reduction of the metal ions to be plated while in others
the electroless plating slurry comprises from about 2 to
about 10% of the stoichiometric amount of reducing agent
necessary for reduction of the metal ions to be plated.
[0251] Delaying introduction of a portion of the
reducing agent to the aqueous medium also serves to
minimize decomposition of the reducing agent. For example,
in the case of a reducing agent comprising formaldehyde,
its decomposition to form hydrogen is delayed.
[0252] Even though each of the above methods provides
metal deposition on the carbide or nitride surface, the
preferred method is that in which introduction of a portion
of the reducing agent is delayed since both considerations
of plating rate and oxidation of the carbide or nitride are
most adequately addressed. As previously discussed, the
plating temperature preferably is used to control the
plating rate and, accordingly, provide uniform metal
deposition. Thus, it is further preferred to combine the
beneficial effect of a low plating temperature along with
delaying introduction of a portion of the reducing agent to
the aqueous medium. Accordingly, in a preferred embodiment
the plating temperature is no more than about 2°C and no
more than about 5% of the amount of reducing agent
stoichiometrically required for reduction of the metal ions
to be plated is introduced to the aqueous medium to form
the electroless plating slurry. In various embodiments,
however, the plating temperature may range from about 1 to
about 20°C, from about 1 to about 10°C, or from about 1 to
about 5°C.
[0253] Plating of metal on the modified carbon
support generally proceeds until the pH of the aqueous
medium reaches a predetermined pH based on consumption of
the hydroxide ion. Thus, the rate of pH drop is directly
related to the plating rate and accordingly is controlled
within a suitable range based on the considerations set
forth above for controlling the plating process.
Typically, plating begins with the aqueous medium at a pH
of about 13 and is typically discontinued when the pH of
the aqueous medium is about 8. In accordance with the
methods set forth above for controlling the plating rate
(e.g., temperature and introduction of the reducing agent),
preferably the rate of pH drop is no more than about
0.5/min.
[0254] Based on the foregoing, it can be seen that
numerous factors influence the plating operation. For
example, the concentration of metal, retardant, reducing
agent, and hydroxide component in the aqueous medium.
Thus, preferably the concentrations of each of these
components are maintained within a suitable range.
[0255] For dehydrogenation catalysts of the present
invention, metal deposited on a modified carbon support
typically makes up at least about 5% by weight of the
catalyst. Preferably, the metal deposited on the modified
carbon support makes up from about 5% to about 30% by
weight of the catalyst and, more preferably, from about 15%
to about 25% by weight of the catalyst and, still more
preferably, from about 18% to about 23% by weight of the
catalyst. In embodiments in which the catalyst comprises
copper deposited on a modified carbon support, the catalyst
typically comprises at least about 10% by weight copper
and, more typically, at least about 15% by weight copper.
Preferably, the catalyst comprises from about 10 to about
30% by weight copper, more preferably from about 15 to
about 25 % by weight copper and, still more preferably,
from about 18 to about 23% by weight copper. In certain
embodiments, preferably the copper-containing catalyst
comprises no more than about 3% by weight of a noble metal
(e.g., platinum) deposited as described below, more
preferably, no more than about 1% by weight of a noble
metal and, still more preferably, no more than about 0.5%
by weight of a noble metal. In other embodiments,
preferably the copper-containing catalyst of the present
invention comprises no more than about 1% by weight nickel,
more preferably, no more than about 1% by weight nickel
and, still more preferably, no more than about 0.5% by
weight nickel.
[0256] Oxidation catalysts of the present invention
including a transition metal composition formed on a carbon
support may further comprise a noble metal-containing
active phase. Catalysts containing an active phase
comprising a noble metal are effective for the oxidation of
a tertiary amine (e.g., N-(phosphonomethyl)iminodiacetic
acid), and also for the oxidation byproducts of this
reaction (e.g., formaldehyde and formic acid). In an
embodiment of the catalyst of the present invention
comprising a noble metal (e.g., platinum) deposited on a
modified carbon support, the noble metal is typically
deposited in accordance with a well-known method. These
include, for example, liquid phase methods such as reaction
deposition techniques (e.g., deposition via reduction of
noble metal compounds and deposition via hydrolysis of
noble metal compounds), ion exchange techniques, excess
solution impregnation, and incipient wetness impregnation;
vapor phase methods such as physical deposition and
chemical deposition; precipitation; and electrochemical
displacement deposition methods such as electroless and
electrolytic deposition.
[0257] Preferably, the noble metal is deposited onto
the surface of the modified carbon support via an
impregnation method comprising contacting the modified
carbon support with a solution comprising a salt of the
noble metal to be deposited followed by hydrolysis of the
salt. Generally, the salt of the noble metal to be
deposited is selected from the group consisting of
hydrogen, sodium, potassium, and ammonium salts. One
example of a platinum salt suitable for use in solution
deposition which is also relatively inexpensive is
hexachloroplatinic acid (H2PtCl6) .
[0258] The noble metal may also be deposited onto the
surface of the modified carbon support using a solution
comprising a salt of the noble metal in one of its more
reduced oxidation states. For example, instead of using a
salt of Pt(IV) (e.g., H2PtClJ , a salt of Pt(II) is used.
In another embodiment, platinum in its elemental state
(e.g., colloidal platinum) is used. Using these more
reduced metal precursors leads to less oxidation of the
modified carbon support and, therefore, less oxygencontaining
functional groups being formed at the surface of
the support while the noble metal is being deposited on the
surface. One example of a Pt(II) salt is K2PtCl4. Another
potentially useful Pt(II) salt is diamminedinitrito
platinum(II).
[0259] Suitable methods for deposition of the noble
metal are discussed in U.S. Patent No. 6,417,133, the
entire disclosure of which is hereby incorporated by
reference.
[0260] For oxidation catalysts of the present
invention, platinum is typically present in a proportion of
at least about 0.5% by weight of the catalyst and, more
typically, at least about 1% by weight of the catalyst.
Preferably, platinum is present in a proportion of from
about 1 to about 10% by weight of the catalyst, more
preferably from about 2 to about 8% by weight of the
catalyst and, still more preferably, from about 2 to about
5% by weight of the catalyst.
[0261] In addition to the noble metal, at least one
promoter may be at the surface of the carbon support.
Although the promoter typically is deposited onto the
surface of the carbon support, other sources of promoter
may be used (e.g., the carbon support itself may naturally
contain a promoter). A promoter tends to increase catalyst
selectivity, activity, and/or stability. A promoter
additionally may reduce noble metal leaching.
[0262] The promoter may, for example, be an
additional noble metal(s) at the surface of the carbon
support. For example, ruthenium and palladium have been
found to act as promoters on a catalyst comprising platinum
deposited at a carbon support surface. The promoter(s)
alternatively may be, for example, a metal selected from
the group consisting of tin (Sn), cadmium (Cd), magnesium
(Mg), manganese (Mn), nickel (Ni), aluminum (Al), cobalt
(Co), bismuth (Bi), lead (Pb), titanium (Ti), antimony
(Sb), selenium (Se), iron (Fe), rhenium (Re), zinc (Zn),
cerium (Ce), and zirconium (Zr). Preferably, the promoter
is selected from the group consisting of bismuth, iron,
tin, and titanium. In a particularly preferred embodiment,
the promoter is tin. In another particularly preferred
embodiment, the promoter is iron. In an additional
preferred embodiment, the promoter is titanium. In a
further particularly preferred embodiment, the catalyst
comprises both iron and tin. Use of iron, tin, or both
generally (1) reduces noble metal leaching for a catalyst
used over several cycles, and (2) tends to increase and/or
maintain the activity of the catalyst when the catalyst is
used to effect the oxidation of PMIDA. Catalysts
comprising iron generally are most preferred because they
tend to have the greatest activity and stability with
respect to formaldehyde and formic acid oxidation.
[0263] In one preferred embodiment, the promoter is
more easily oxidized than the noble metal. A promoter is
"more easily oxidized" if it has a lower first ionization
potential than the noble metal. First ionization
potentials for the elements are widely known in the art and
may be found, for example, in the CRC Handbook of Chemistry
and Physics (CRC Press, Inc., Boca Raton, Florida).
[0264] The amount of promoter at the surface of the
carbon support (whether associated with the carbon surface
itself, metal, or a combination thereof) may vary within
wide limits depending on, for example, the noble metal and
promoter used. Typically, the weight percentage of the
promoter is at least about 0.05% ([mass of promoter •*• total
mass of the catalyst] X 100%). The weight percent of the
promoter preferably is from about 0.05 to about 10%, more
preferably from about 0.1 to about 10%, still more
preferably from about 0.1 to about 2%, and most preferably
from about 0.2 to about 1.5%. When the promoter is tin, the
weight percent most preferably is from about 0.5 to about
1.5%. Promoter weight percentages less than 0.05%
generally do not promote the activity of the catalyst over
an extended period of time. On the other hand, weight
percents greater than about 10% tend to decrease the
activity of the catalyst.
[0265] The molar ratio of noble metal to promoter may
also vary widely, depending on, for example, the noble
metal and promoter used. Preferably, the ratio is from
about 1000:1 to about 0.01:1; more preferably from about
150:1 to about 0.05:1; still more preferably from about
50:1 to about 0.05:1; and most preferably from about 10:1
to about 0.05:1. For example, a catalyst comprising
platinum and iron preferably has a molar ratio of platinum
to iron of about 3:1.
[0266] In certain embodiments, the noble metal (e.g.,
platinum) is alloyed with at least one promoter (e.g., tin
or iron) to form alloyed metal particles.
[0267] One feature of a carbon support having a
transition metal composition formed thereon (i.e., a
modified carbon support) which affects the surface area of
transition metal composition available for deposition of
copper, noble metal, or other metal active phase thereon is
the resistance of the transition metal composition to
removal from the surface of the carbon support under
certain conditions (e.g., alkaline metal plating conditions
and contact with cations of the metal to be plated on the
modified carbon support). Thus, preferably no more than
about 20% by weight of a transition metal composition of
the present invention is removed from the surface of a
carbon support when contacted with an alkaline aqueous
plating medium under alkaline metal plating conditions for
at least about 3 hours. In addition, preferably no more
than about 5% by weight of a transition metal composition
of the present invention is removed from the surface of a
carbon support when contacted with cations of a metal to be
deposited on a modified carbon support for at least about 3
hours.
[0268] Generally, it is preferred for the oxidation
catalysts of the present invention to have a high surface
area. Formation of the transition metal/nitrogen,
transition metal/carbon or transition metal/carbon/nitrogen
composition typically is associated with some reduction in
Langmuir surface area. Loss of surface area may be a
result of coating of the carbon surface with a transition
metal composition of relatively lower surface area, e.g.,
in the form of an amorphous film and/or relatively large
particles of the transition metal composition. Amorphous
transition metal composition may be in the form of either
amorphous particles or an amorphous film. Preferably, the
sacrifice in surface area is not greater than about 40%.
Where the transition metal composition is formed under the
preferred conditions described above, the loss in total
Langmuir surface area is typically between about 20 and
about 40%. Thus, generally, the surface area of the
catalyst is at least about 60% of the surface area of the
carbon support prior to formation of the transition metal
composition thereon and, more generally, from about 60 to
about 80%.
[0269] Typically, the catalyst has a total Langmuir
surface area of at least about 500 m2/g, more typically at
least about 600 m2/g. Preferably, the total Langmuir
surface area of the catalyst is at least about 800 m2/g,
more preferably at least about 900 m2/g. It is generally
preferred that the total Langmuir surface area of the
catalyst remains at a value of at least about 1000 m2/g,
more preferably at least about 1100 m2/g, even more
preferably at least about 1200 m2/g, after the transition
metal composition has been formed. Generally, the catalyst
has a total Langmuir surface area of from about 600 to
about 1500 m2/g, typically from about 600 to about 1400
m2/g. In certain embodiments, the catalyst has a total
Langmuir surface area of from about 800 to about 1200 m2/g.
Preferably, the catalyst has a total Langmuir surface area
of from about 1000 to about 1400 m2/g, more preferably from
about 1100 to about 1400 m2/g and, even more preferably,
from about 1200 to about 1400 m2/g.
[0270] Where the transition metal composition is
formed in accordance with a preferred method, it is
believed that the composition comprises a substantial
fraction of very fine particles, e.g., wherein at least
about 20 wt.% of the transition metal is in amorphous form
or in the form of particles of less than 15 nm, more
typically less than 5 nm, more typically 2 nm, as
determined by X-ray diffraction.
[0271] It is further preferred that, as compared to
the carbon support, the micropore Langmuir surface area be
reduced by not more than 45%, more preferably not more than
about 40%. Thus, the micropore Langmuir surface area of
oxidation catalysts is generally at least about 55% of the
micropore Langmuir surface area of the carbon support prior
to formation of the transition metal composition thereon,
more generally at least about 60% and, still more
generally, at least about 80%. Typically, the micropore
Langmuir surface area of the catalyst is from about 55 to
about 80% of the micropore Langmuir surface area of the
carbon support prior to formation of the transition metal
composition thereon, more typically from about 60 to about
80% and, still more typically, from about 70 to about 80%.
[0272] The Langmuir surface area of an oxidation
catalyst of the present invention attributed to pores
having a diameter of less than 20A (i.e., micropores) is
typically at least about 750 m2/g, more typically at least
800 m2/g, still more typically at least about 800 m2/g and,
even more typically, at least about 900 m2/g. Preferably,
the micropore Langmuir surface area of the oxidation
catalyst is from about 750 to about 1100 m2/g and, more
preferably, from about 750 to about 1000 m2/g.
[0273] In addition to the preferred reduction in
micropore surface area, it is further generally preferred
that the combined mesopore and macropore Langmuir surface
area be reduced by not more than about 30%, more preferably
not more than about 20%, as a result of the formation of
the transition metal composition on the carbon support.
Thus, generally, the combined mesopore and macropore
Langmuir surface area of oxidation catalysts is generally
at least about 70% of the combined mesopore and macropore
Langmuir surface area of the carbon support prior to
formation of the transition metal composition thereon and,
more generally, at least about 80%. Typically, the
combined mesopore and macropore Langmuir surface area of
the catalyst is from about 70 to about 90% of the combined
mesopore and macropore Langmuir surface area of the carbon
support prior to formation of the transition metal
composition thereon.
[0274] Generally, the combined mesopore and macropore
surface area is at least about 175 m2/g and, more
generally, at least 200 m2/g. Preferably, the combined
mesopore and macropore Langmuir surface area of the
oxidation catalyst is from about 175 to about 300 m2/g and,
more preferably, from about 200 to about 300 m2/g. In
certain embodiments, the combined mesopore and macropore
surface area is from about 175 to about 250 m2/g.
[0275] Additionally or alternatively, it is preferred
that the micropore Langmuir surface area of the catalyst
remain at a value of at least about 750 m2/g, more
preferably at least about 800 m2/g, and the combined
mesopore and macropore Langmuir surface area of the
catalyst remain at a value of at least about 175 m2/g, more
preferably at least about 200 m2/g, after the transition
metal composition has been formed.
[0276] In various particularly preferred embodiments
of the invention, X-ray diffraction analysis at a detection
limit of 1 nm does not detect any significant portion of
transition metal composition particles. Thus, it is
currently believed that the transition metal composition
particles are present on the surface of the carbon support
in the form of discrete particles having a particle size of
less than 1 nm or are present on the surface of the carbon
support in the form of an amorphous film. However, based
on the decrease in surface area after formation of the
transition metal composition on the carbon support, it is
reasonable to infer the transition metal composition may be
present at least in part as an amorphous film since an
increase in surface area would be expected in the case of
deposition of crystallites having a particle size below 1
nm.
[0277] It is likewise preferred for dehydrogenation
catalysts of the present invention (i.e., modified carbon
supports having a metal-containing active phase deposited
thereon) to have a high surface area. Typically, the
catalyst has a Langmuir surface area of at least about 500
m2/g, more typically at least about 600 m2/g and, still more
typically, from about 500 to about 1200 m2/g. Generally,
the catalyst has a Langmuir surface area of from about 600
to about 1000 m2/g and, more generally, from about 600 to
about 800 mYg.
[0278] A further advantageous feature of the
oxidation and dehydrogenation catalysts of the present
invention is a pore volume sufficient to allow for
diffusion of reactants into the pores of the catalyst.
Thus, preferably, catalysts of the present invention
including a transition metal composition formed on a carbon
support typically have a pore volume of at least about 0.1
cm3/g and, more typically at least about 0.5 cm3/g-
Generally, such catalysts have a pore volume of from about
0.1 to about 2 cm3/g and, more generally, from about 0.5 to
about 1.5 cm3/g.
[0279] In addition to overall pore volume, the pore
volume distribution of the oxidation and dehydrogenation
catalysts of the present invention preferably conduces to
diffusion of reactants into the pores of the finished
catalyst. Preferably, pores having a diameter of less than
about 20 A make up no more than about 45% of the overall
pore volume of the catalyst and, more preferably, no more
than about 30% of the overall pore volume. Pores having a
diameter of greater than about 20 A preferably make up at
least about 60% of the overall pore volume of the catalyst
and, more preferably, at least about 65% of the overall
pore volume.
[0280] It has been observed that "mesopores" (i.e.,
pores having a diameter of from about 20 to about 40 A)
allow suitable diffusion of reactants into the pores of the
catalyst. Thus, preferably mesopores make up at least
about 25% of the overall pore volume and, more preferably,
at least about 30% of the overall pore volume. Macro pores
(i.e., pores having a diameter larger than about 40 A) also
allow suitable diffusion of reactants into the pores of the
catalyst. Thus, preferably, these pores make up at least
about 5% of the overall pore volume and, more preferably,
at least about 10% of the overall pore volume of the
catalyst.
[0281] It is generally preferred for the transition
metal composition (e.g., the transition metal carbide or
transition metal nitride) to be uniformly distributed
substantially over the surface of the pore walls and
interstitial passages of the catalyst particles (i.e., all
surfaces accessible to fluid with which the catalyst is
contacted). Particle size of the transition metal
composition, as determined, for example, by X-ray
diffraction, affects such uniform distribution and it has
been observed that the smaller the size of the particulate
crystals of the transition metal composition, the more
uniform its deposition.
[0282] For oxidation catalysts of the present
invention including a transition metal composition
deposited on a carbon support, generally, at least about
95% by weight of the transition metal composition particles
have a particle size, in their largest dimension, of less
than about 1000 nm. Typically, at least about 80% by
weight of the transition metal composition particles have a
particle size, in their largest dimension, of less than
about 250 nm. More typically, at least about 70% by weight
of the transition metal composition particles have a
particle size, in their largest dimension, of less than
about 200 nm. Still more typically, at least about 60% by
weight of the transition metal composition particles have a
particle size, in their largest dimension, of less than
about 18 nm. Even more typically, at least about 20% by
weight, preferably at least about 55% by weight of the
transition metal composition particles have a particle
size, in their largest dimension, of less than about 15 nm.
Preferably, at least about 20% by weight of the transition
metal composition particles have a particle size, in their
largest dimension, of less than about 5 nm, more
preferably, less than about 2 nm, and even more preferably,
less than about 1 nm. More preferably, from about 20 to
about 95% by weight of the transition metal composition
particles have a particle size, in their largest dimension,
of less than about 1 nm and, more preferably, from about 20
to about 100% by weight.
[0283] Generally, at least about 75%, on a number
basis, of the transition metal composition particles have a
particle size, in their largest dimension, of less than
about 1000 nm. Typically, at least about 60%, on a number
basis, of the transition metal composition particles have a
particle size, in their largest dimension, of less than
about 250 nm. More typically, at least about 50%, on a
number basis, of the transition metal composition particles
have a particle size, in their largest dimension, of less
than about 200 nm. Still more typically, at least about
40%, on a number basis, of the transition metal composition
particles have a particle size, in their largest dimension,
of less than about 18 nm. Even more typically/ at least
about 35%, on a number basis, of the transition metal
composition particles have a particle size, in their
largest dimension, of less than about 15 nm.
[0284] For dehydrogenation catalysts including a
metal-containing (e.g., copper-containing) active deposited
on a modified carbon support including a transition metal
composition comprising molybdenum or tungsten formed on a
carbon support, typically at least about 99% of the
particles of the transition metal composition formed on the
carbon support exhibit a particle size of less than about
100 nm, thereby contributing to uniform distribution of the
transition metal composition throughout the carbon support
since it has been observed that a greater proportion of
particles of such a size provide a uniform coating of
transition metal composition on the carbon support. More
preferably, at least about 95% of the particles of the
carbide or nitride formed on the carbon support exhibit a
particle size of from about 5 ran. to about 50 nm.
[0285] It has been observed that uniform distribution
of the transition metal composition on the carbon support
(i.e., reduced clustering of the transition metal and/or
suitable distribution of the transition metal composition
throughout the pores of the carbon support) may improve
catalytic activity of catalysts including a transition
metal composition deposited on a carbon support and/or may
allow for improved coating of a metal-containing active
phase on the modified carbon support in the case of a
dehydrogenation catalyst.
[0286] Fig. 5 is a High Resolution Transmission
Electron Microscopy (HRTEM) image of a carbon-supported
molybdenum carbide prepared in accordance with the above
methods in which molybdenum carbide is present in a
proportion of 15% by weight. As shown, a carbon support
having molybdenum carbide formed thereon prepared in
accordance with the methods described above exhibits
uniform dispersion of molybdenum carbide throughout the
carbon support.
[0287] Fig. 6 is a Scanning Electron Microscopy (SEM)
image of a carbon supported molybdenum carbide prepared in
accordance with the above methods in which the carbide is
present in a proportion of 10% by weight. As shown, a
carbon support having molybdenum carbide formed thereon in
a proportion of 10% by weight of the modified carbon
support in accordance with the methods described above
exhibits uniform distribution of molybdenum throughout the
carbon support. Fig. 7 is a Transmission Electron
Microscopy (TEM) image of a carbon supported molybdenum
carbide prepared in accordance with the above methods in
which the carbide is present in a proportion of 10% by
weight. As shown, a carbon support having molybdenum
carbide formed thereon in a proportion of 10% by weight of
the modified carbon support in accordance with the above
methods exhibits uniformity of molybdenum carbide
distribution throughout believed to be due, at least in
part, to the particle size distribution of molybdenum
carbide.
[0288] Uniform distribution may be indicated by the
percentage of surface area of the carbon support covered
with the transition metal composition. Preferably in
certain embodiments (e.g., transition metal compositions
including molybdenum or tungsten carbide or nitride), a
suitable portion of the surface area of the carbon support
is coated with transition metal composition. Generally, at
least about 20% and, more generally, at least about 50% of
the surface area of the carbon support is coated with a
transition metal composition (e.g., a transition metal
carbide or nitride). Typically, from about 20 to about 80%
and, more typically, from about 50% to about 80% of the
surface area of the carbon support is coated with a
transition metal composition (e.g., a transition metal
carbide or nitride).
[0289] Oxidation catalysts of the present invention
may exhibit one or more properties described in Ebner et
al., U.S. Patent No. 6,417,133, the entire disclosure of
which was incorporated by reference above. Such
characteristics may be found, for example, at column 3,
line 6 to column 7, line 23; column 8, line 27 to column 9,
line 24; column 10, lines 53-57; column 11, line 49 to
column 14, line 18; column 14, line 50 to column 16, line
3; column 17, line 14 to column 21, line 2; column 26
(Example 2); column 27, lines 21-34 (Example 4); and column
30, line 21 to column 40, line 61 (Examples 7 to 19).
[0290] Oxidation catalysts of the present invention
may include carbon nariotubes on the surface of the carbon
support which may contain a certain proportion of the
transition metal contained in the catalyst. Additionally
or alternatively, the carbon nanotubes may contain a
portion of the nitrogen of the transition metal
composition. Typically, any such transition metal is
present at the root or the tip of the nanotube, however,
transition metal may also be present along the length of
the nanotube. The carbon nanotubes typically have a
diameter of at least about 0.01 /an and, more typically,
have a diameter of at least about 0.1 [im. In certain
embodiments, the carbon nanotubes have a diameter of less
than about 1 /zm and, in other embodiments, have a diameter
of less than about 0.5 /zm.
[0291] Certain embodiments of the above-described
catalyst (e.g., catalysts comprising a transition metal
composition deposited on a carbon support and such
catalysts further including a noble metal) may be used for
liquid phase oxidation reactions. Examples of such
reactions include the oxidation of alcohols and polyols to
form aldehydes, ketones, and acids (e.g., the oxidation of
2-propanol to form acetone, and the oxidation of glycerol
to form glyeeraldehyde, dihydroxyacetone, or glyceric
acid); the oxidation of aldehydes to form acids (e.g., the
oxidation of formaldehyde to form formic acid, and the
oxidation of furfural to form 2-furan carboxylic acid); the
oxidation of tertiary amines to form secondary amines
(e.g., the oxidation of nitrilotriacetic acid ("NTA") to
form iminodiacetic acid ("IDA")); the oxidation of
secondary amines to form primary amines (e.g., the
oxidation of IDA to form glycine); and the oxidation of
various acids (e.g., formic acid or acetic acid) to form
carbon dioxide and water.
[0292] The oxidation catalyst disclosed herein is
particularly suited for catalyzing the liquid phase
oxidation of a tertiary amine to a secondary amine, for
example in the preparation of glyphosate and related
compounds and derivatives. For example, the tertiary amine
substrate may correspond to a compound of Formula II having
the structure:
(Figure Removed)
[Formula II]
wherein R1 is selected from the group consisting of
R5OC(O)CH2- and R5OCH2CH2-, R2 is selected from the group
consisting of R5OC(O)CH2-, RSOCH2CH2-, hydrocarbyl,
substituted hydrocarbyl, acyl, -CHR6PO3R7R8, and -CHR9SO3R10,
R6, R9 and R11 are selected from the group consisting of
hydrogen, alkyl, halogen and -N02, and R3, R4, R5, R7, R8 and
R10 are independently selected from the group consisting of
hydrogen, hydrocarbyl, substituted hydrocarbyl and a metal
ion. Preferably, R1 comprises R5OC(0)CH2-, R11 is hydrogen,
R5 is selected from hydrogen and an agronomically
acceptable cation and R2 is selected from the group
consisting of R5OC(0)CH2-, acyl, hydrocarbyl and substituted
hydrocarbyl. As noted above, the oxidation catalyst of the
present invention is particularly suited for catalyzing the
oxidative cleavage of a PMIDA substrate such as N-
(phosphonomethyl)iminodiacetic acid or a salt thereof to
form N-(phosphonomethyl)glycine or a salt thereof. In such
an embodiment, the catalyst is effective for oxidation of
byproduct formaldehyde to formic acid, carbon dioxide
and/or water.
[0293] The above-described catalysts are especially
useful in liquid phase oxidation reactions at pH levels
less than 7, and in particular, at pH levels less than 3.
One such reaction is the oxidation of PMIDA or a salt
thereof to form N-(phosphonomethyl)glycine or a salt
thereof in an environment having pH levels in the range of
from about 1 to about 2. This reaction is often carried
out in the presence of solvents which solubilize noble
metals and, in addition, the reactants, intermediates, or
products often solubilize noble metals. Certain catalysts
of the present invention avoid these problems due to the
absence of a noble metal. Advantageously, however, the
catalysts of the present invention containing a noble metal
have been found to be useful in such environments.
[0294] The description below.discloses with
particularity the use of catalysts described above
containing a transition metal composition (e.g., a
transition metal nitride, transition metal carbide or
transition metal carbide-nitride) acting as the catalyst or
further containing a noble metal-containing active phase to
effect the oxidative cleavage of PMIDA or a salt thereof to
form N-(phosphonomethyl)glycine or a salt thereof. It
should be recognized, however, that the principles
disclosed below are generally applicable to other liquid
phase oxidative reactions, especially those at pH levels
less than 7 and those involving solvents, reactants,
intermediates, or products which solubilize noble metals.
[0295] To begin the PMIDA oxidation reaction, it is
preferable to charge the reactor with the PMIDA reagent
(i.e., PMIDA or a salt thereof), catalyst, and a solvent in
the presence of oxygen. The solvent is most preferably
water, although other solvents (e.g., glacial acetic acid)
are suitable as well.
[0296] The reaction may be carried out in a wide
variety of batch, semi-batch, and continuous reactor
systems. The configuration of the reactor is not critical.
Suitable conventional reactor configurations include, for
example, stirred tank reactors, fixed bed reactors, trickle
bed reactors, fluidized bed reactors, bubble flow reactors,
plug flow reactors, and parallel flow reactors.
[0297] When conducted in a continuous reactor system,
the residence time in the reaction zone can vary widely
depending on the specific catalyst and conditions employed.
Typically, the residence time can vary over the range of
from about 3 to about 120 minutes. Preferably, the
residence time is from about 5 to about 90 minutes, and
more preferably from about 5 to about 60 minutes. When
conducted in a batch reactor, the reaction time typically
varies over the range of from about 15 to about 120
minutes. Preferably, the reaction time is from about 20 to
about 90 minutes, and more preferably from about 30 to
about 60 minutes.
[0298] In a broad sense, the oxidation reaction may
be practiced in accordance with the present invention at a
wide range of temperatures, and at pressures ranging from
sub-atmospheric to super-atmospheric. Use of mild
conditions (e.g., room temperature and atmospheric
pressure) have obvious commercial advantages in that less
expensive equipment may be used. However, operating at
higher temperatures and super-atmospheric pressures, while
increasing capital requirements, tends to improve phase
transfer between the liquid and gas phase and increase the
PMIDA oxidation reaction rate.
[0299] Preferably, the PMIDA reaction is conducted at
a temperature of from about 20 to about 180°C, more
preferably from about 50 to about 140°C, and most
preferably from about 80 to about 110°C. At temperatures
greater than about 180°C, the raw materials tend to begin
to slowly decompose.
[0300] The pressure used during the PMIDA oxidation
generally depends on the temperature used. Preferably, the
pressure is sufficient to prevent the reaction mixture from
boiling. If an oxygen-containing gas is used as the oxygen
source, the pressure also preferably is adequate to cause
the oxygen to dissolve into the reaction mixture at a rate
sufficient such that the PMIDA oxidation is not limited due
to an inadequate oxygen supply. The pressure preferably is
at least equal to atmospheric pressure. More preferably,
the pressure is from about 30 to about 500 psig, and most
preferably from about 30 to about 130 psig.
[0301] The catalyst concentration preferably is from
about 0.1 to about 10 wt. % ([mass of catalyst-^total
reaction mass] x 100%). More preferably, the catalyst
concentration preferably is from about 0.1 to about 5 wt.%,
still more preferably from about 0.2 to about 5 wt.% and,
most preferably, from about 0.3 to about 1.5 wt.%.
Concentrations greater than about 10 wt.% are difficult to
filter. On the other hand, concentrations less than about
0.1 wt.% tend to produce unacceptably low reaction rates.
[0302] The present invention is further directed to a
catalyst system comprising a combination of transition
metal composition on carbon catalysts of the present
invention, preferably substantially devoid of a noble metal
active phase, with a noble-metal containing bifunctional
catalyst (i.e., a catalyst which oxidizes PMIDA while
further providing oxidation of formaldehyde and formic acid
byproducts) as described in U.S. Patent No. 6,417,133 to
Ebner et al., the entire disclosure of which was
incorporated by reference above. Such a catalyst system
including the catalysts described by Ebner et al. and
transition metal containing catalysts of the present
invention is advantageous since it is effective for
oxidizing PMIDA, formaldehyde, and formic acid, but not all
of the catalyst available for PMIDA oxidation requires the
presence of a costly noble metal. Thus, such a catalyst
system may potentially provide a more economical process.
Typically, such a catalyst system comprises at least about
10% by weight of a catalyst as described in U.S. Patent No.
6,417,133, more typically at least about 20% by weight'and,
most typically from about 10 to about 50% by weight.
[0303] Additionally or alternatively, the catalyst
system comprises at least about 10% by weight of a
transition metal composition-containing catalyst of the
present invention, more typically at least about 20% by
weight and, most typically, from about 20 to about 50% by
weight of a transition metal composition-containing
catalyst of the present invention.
[0304] The concentration of PMIDA reagent in the feed
stream is not critical. Use of a saturated solution of
PMIDA reagent in water is preferred, although for ease of
operation, the process is also operable at lesser or
greater PMIDA reagent concentrations in the feed stream.
If the catalyst is present in the reaction mixture in a
finely divided form, it is preferred to use a concentration
of reactants such that all reactants and the -
(phosphonomethyl)glycine product remain in solution so that
the catalyst can be recovered for re-use, for example, by
filtration. On the other hand, greater concentrations tend
to increase reactor through-put. Alternatively, if the
catalyst is present as a stationary phase through which the
reaction medium and oxygen source are passed, it may be
possible to use greater concentrations of reactants such
that a portion of the N- (phosphonomethyl) glycine product
precipitates.
[0305] It should be recognized that, relative to many
commonly-practiced commercial processes, this invention
allows for greater temperatures and PMIDA reagent
concentrations to be used to prepare N-
(phosphonomethyl)glycine while minimizing by-product
formation. In the commonly practiced commercial processes
using a carbon-only catalyst, it is economically beneficial
to minimize the formation of the NMG by-product, which is
formed by the reaction of N-(phosphonomethyl)glycine with
the formaldehyde by-product. In processes based on carbon
catalysts, temperatures are typically maintained between
about 60 to 90°C, and PMIDA reagent concentrations are
typically maintained below about 9.0 wt.% ([mass of PMIDA
reagent4-total reaction mass]xlOO%) to achieve cost
effective yields and to minimize the generation of waste.
At such temperatures, the maximum N99
(phosphonomethyl)glycine solubility typically is less than
6.5%. However, with the oxidation catalyst and reaction
process of this invention, formaldehyde is effectively
oxidized, thereby allowing for reaction temperatures as
high as 180°C or greater with PMIDA reagent solutions and
slurries of the PMIDA reagent. The use of higher
temperatures and reactor concentrations permits reactor
throughput to be increased, reduces the amount of water
that must be removed before isolation of the solid N-
(phosphonomethyl)glycine, and reduces the cost of
manufacturing N-(phosphonomethyl)glycine. This invention
thus provides economic benefits over many commonlypracticed
commercial processes.
[0306] Normally, a PMIDA reagent concentration of up
to about 50 wt.% ([mass of PMIDA reagentstotal reaction
mass] x 100%) may be used (especially at a reaction
temperature of from about 20 to about 180°C). Preferably,
a PMIDA reagent concentration of up to about 25 wt.% is
used (particularly at a reaction temperature of from about
60 to about 150°C). More preferably, a PMIDA reagent
concentration of from about 12 to about 18 wt.% is used
(particularly at a reaction temperature of from about 100
to about 130°C). PMIDA reagent concentrations below 12
wt.% may be used, but are less economical because a
relatively low payload of N-(phosphonomethyl)glycine
product is produced in each reactor cycle and more water
must be removed and energy used per unit of N-
(phosphonomethyl)glycine product produced. Relatively low
reaction temperatures (i.e., temperatures less than 100°C)
often tend to be less advantageous because the solubility
of the PMIDA reagent and N-(phosphonomethyl)glycine product
are both relatively low at such temperatures.
[0307] The oxygen source for the PMIDA oxidation
reaction may be any oxygen-containing gas or a liquid
comprising dissolved oxygen. Preferably, the oxygen source
is an oxygen-containing gas. As used herein, an "oxygencontaining
gas" is any gaseous mixture comprising molecular
oxygen which optionally may comprise one or more diluents
which are non-reactive with the oxygen or with the reactant
or product under the reaction conditions.
[0308] Examples of such gases are air, pure molecular
oxygen, or molecular oxygen diluted with helium, argon,
nitrogen, or other non-oxidizing gases. For economic
reasons, the oxygen source most preferably is air, oxygenenriched
air, or pure molecular oxygen.
[0309] Oxygen may be introduced by any conventional
means into the reaction medium in a manner which maintains
the dissolved oxygen concentration in the reaction mixture
at a desired level. If an oxygen-containing gas is used,
it preferably is introduced into the reaction medium in a
manner which maximizes the contact of the gas with the
reaction solution. Such contact may be obtained, for
example, by dispersing the gas through a diffuser such as a
porous frit or by stirring, shaking, or other methods known
to those skilled in the art.
[0310] The oxygen feed rate preferably is such that
the PMIDA oxidation reaction rate is not limited by oxygen
supply. If the dissolved oxygen concentration is too high,
however, the catalyst surface tends to become detrimentally
oxidized, which, in turn, tends to lead to more leaching of
noble metal present in the catalyst and decreased
formaldehyde activity (which, in turn, leads to more NMG
being produced). Generally, it is preferred to use an
oxygen feed rate such that at least about 40% of the oxygen
is utilized. More preferably, the oxygen feed rate is such
that at least about 60% of the oxygen is utilized. Even
more preferably, the oxygen feed rate is such that at least
about 80% of the oxygen is utilized. Most preferably, the
rate is such that at least about 90% of the oxygen is
utilized. As used herein, the percentage of oxygen
utilized equals: (the total oxygen consumption rate +
oxygen feed rate) x 100%. The term "total oxygen
consumption rate" means the sum of: (1) the oxygen
consumption rate ("Ri") of the oxidation reaction of the
PMIDA reagent to form the N-(phosphonomethyl)glycine
product and formaldehyde, (ii) the oxygen consumption rate

("Rii") of the oxidation reaction of formaldehyde to form
formic acid, and (iii) the oxygen consumption rate ("Rui")
of the oxidation reaction of formic acid to form carbon
dioxide and water.
[0311] In various embodiments of this invention,
oxygen is fed into the reactor as described above until the
bulk of PMIDA reagent has been oxidized, and then a reduced
oxygen feed rate is used. This reduced feed rate
preferably is used after about 75% of the PMIDA reagent has
been consumed. More preferably, the reduced feed rate is
used after about 80% of the PMIDA reagent has been
consumed. Where oxygen is supplied as pure oxygen or
oxygen-enriched air, a reduced feed rate may be achieved by
purging the reactor with (non-enriched) air, preferably at
a volumetric feed rate which is no greater than the
volumetric rate at which the pure molecular oxygen or
oxygen-enriched air was fed before the air purge. The
reduced oxygen feed rate preferably is maintained for from
about 2 to about 40 minutes, more preferably from about 5
to about 20 minutes, and most preferably from about 5 to
about 15 minutes. While the oxygen is being fed at the
reduced rate, the temperature preferably is maintained at
the same temperature or at a temperature less than the
temperature at which the reaction was conducted before the
air purge. Likewise, the pressure is maintained at the
same or at a pressure less than the pressure at which the
reaction was conducted before the air purge. Use of a
reduced oxygen feed rate near the end of the PMIDA reaction
allows the amount of residual formaldehyde present in the
reaction solution to be reduced without producing
detrimental amounts of AMPA by oxidizing .the N-
(phosphonomethyl)glycine product.
[0312] In embodiments in which the catalyst includes
a noble metal, reduced losses of noble metal may be
observed with this invention if a sacrificial reducing
agent is maintained or introduced into the reaction
solution. Suitable reducing agents include formaldehyde,
formic acid, and acetaldehyde. Most preferably, formic
acid, formaldehyde, or mixtures thereof are used.
Experiments conducted in accordance with this invention
indicate that if small amounts of formic acid,
formaldehyde, or a combination thereof are added to the
reaction solution, the catalyst will preferentially effect
the oxidation of the formic acid or formaldehyde before it
effects the oxidation of the PMIDA reagent, and
subsequently will be more active in effecting the oxidation
of formic acid and formaldehyde during the PMIDA oxidation.
Preferably from about 0.01 to about 5.0 wt.% ([mass of
formic acid, formaldehyde, or a combination thereof -*- total
reaction mass] x 100%) of sacrificial reducing agent is
added, more preferably from about 0.01 to about 3.0 wt.% of
sacrificial reducing agent is added, and most preferably
from about 0.01 to about 1.0 wt.% of sacrificial reducing
agent is added.
[0313] In certain embodiments, unreacted formaldehyde
and formic acid are recycled back into the reaction mixture
for use in subsequent cycles. In this instance, an aqueous
recycle stream comprising formaldehyde and/or formic acid
also may be used to solubilize the PMIDA reagent in the
subsequent cycles. Such a recycle stream may be generated
by evaporation of water, formaldehyde, and formic acid from
the oxidation reaction mixture in order to concentrate
and/or crystallize product N-(phosphonomethyl)glycine.
Overheads condensate containing formaldehyde and formic
acid may be suitable for recycle.
[0314] As noted above, the oxidation catalysts of the
present invention including a transition metal composition
comprising a transition metal, nitrogen, and carbon formed
on a carbon support as described herein, preferably
substantially devoid of a noble metal active phase, are
effective for the oxidation of formaldehyde to formic acid,
carbon dioxide and water. In particular, oxidation
catalysts of the present invention are effective for the
oxidation of byproduct formaldehyde produced in the
oxidation of N-(phosphonomethyl)iminodiacetic acid. More
particularly, such catalysts are characterized by their
effectiveness for catalyzing the oxidation of formaldehyde
such that when a representative aqueous solution containing
about 0.8% by weight formaldehyde and having a pH of about
1.5 is contacted with an oxidizing agent in the presence of
said catalyst at a temperature of about 100°C, at least
about 5%, preferably at least about 10%, more preferably at
least about 15%, even more preferably at least about 20% or
even at least about 30% by weight of said formaldehyde is
converted to formic acid, carbon dioxide and/or water.
[0315] The oxidation catalysts of the present
invention including a transition metal composition
comprising a transition metal, nitrogen, and carbon formed
on a carbon support as described herein, preferably
substantially devoid of a noble metal active phase, is
particularly effective in catalyzing the liquid phase
oxidation of formaldehyde to formic acid, carbon dioxide
and/or water in the presence of a PMIDA reagent such as N-
(phosphonomethyl)iminodiacetic acid. More particularly,
such catalyst is characterized by its effectiveness for
catalyzing the oxidation of formaldehyde such that when a
representative aqueous solution containing about 0.8% by
weight formaldehyde and about 6% by weight of N-
(phosphonomethyl)iminodiacetic acid and having a pH of
about 1.5 is contacted with an oxidizing agent in the
presence of said catalyst at a temperature of about 100°C,
at least about 50%, preferably at least about 60%, more
preferably at least about 70%, even more preferably at
least about 80%, and especially at least about 90% by
weight of said formaldehyde is converted to formic acid,
carbon dioxide and/or water.
Typically, the concentration of N-
(phosphonomethyl)glycine in the product mixture may be as
great as 40% by weight, or greater. Preferably, the N-
(phosphonomethyl)glycine concentration is from about 5 to
about 40%, more preferably from about 8 to about 30%, and
still more preferably from about 9 to about 15%.
Concentrations of formaldehyde in the product mixture are
typically less than about 0.5% by weight, more preferably
less than about 0.3%, and still more preferably less than
about 0.15%.
[0316] Following the oxidation, the catalyst
preferably is subsequently separated by filtration. The N-
(phosphonomethyl)glycine product may then be isolated by
precipitation, for example, by evaporation of a portion of
the water and cooling.
[0317] In certain embodiments (e.g., those in which
the catalyst includes a noble metal), it should be
recognized that the catalyst of this invention has the
ability to be reused over several cycles, depending on how
oxidized its surface becomes with use. Even after the
catalyst becomes heavily oxidized, it may be reused by
being reactivated. To reactivate a catalyst having a
heavily oxidized surface, the surface preferably is first
washed to remove the organics from the surface. It then
preferably is reduced in the same manner that a catalyst is
reduced after the noble metal is deposited onto the surface
of the support, as described above.
[0318] A process incorporating a catalyst of the
present invention which includes a transition metal
composition formed on a carbon support and further
including a copper-containing active phase may generally be
used to convert any primary alcohol to a carboxylic acid
salt. As used herein, a "primary alcohol" is any alcohol
comprising a hydroxy group attached to a carbon which is
bound to two hydrogen atoms, i.e., R-CH2OH. Such a process
dehydrogenates a primary alcohol to yield both a carboxylic
acid salt and hydrogen gas. Typically, this reaction is
carried out in a heated reaction zone containing an
alkaline medium containing the primary alcohol, a base, and
a catalyst prepared in accordance with the present
invention. An example of this reaction is the
dehydrogenation of monoethano1amine in a heated reaction
zone containing KOH to form hydrogen gas and the potassium
salt of glycine:
(Formula Removed)
[0319] Another example of this reaction is the
dehydrogenation of diethanolamine (sometimes described in
the art as WDEA" ) in a heated reaction zone containing NaOH
to form hydrogen gas and disodium iminodiacetic acid
(sometimes described in the art as "DSIDA") :
(Formula Removed)
[0320] An additional example is the dehydrogenation of an
N-alkyl-monoethanolamine to form a salt of an N-alkylglycine.
The alkyl group can be, for example, methyl (-
CH3) . In that instance, the dehydrogenation product would
be a salt of N-methyl-glycine (i.e., a salt of sarcosine) :
(Formula Removed)
[0321] A further example is the dehydrogenation of
triethanolamine to form a salt of nitrilotriacetic acid:
(Formula Removed)
[0322] Although effective and useful in the
dehydrogenation of essentially any primary alcohol, the
process of the invention is particularly advantageous for
primary alcohols which contain amino groups or other
functionalities which are reactive and susceptible to side
reactions. In particular, (3-amino alcohols are susceptible
to dehydrogenation of the C-N bond and subsequent
dealkylation, consequently leading to the formation of
usually undesirable side products. In various preferred
embodiments of this invention, the primary alcohol is an
alkanolamine (i.e., a compound wherein the nitrogen of an
amine functionality is bonded directly to the carbon of an
alkyl alcohol). In this embodiment, the primary alcohol
preferably has formula (I) :
(Formula Removed)
wherein n is an integer ranging from 2 to 20; and R1 and R2
are independently hydrogen, hydrocarbyl, or substituted
hydrocarbyl.
[0323] A hydrocarbyl may be any group consisting
exclusively of carbon and hydrogen. The hydrocarbyl may be
branched or unbranched, may be saturated or unsaturated,
and may comprise one or more rings. Suitable hydrocarbyl
groups include alkyl, alkenyl, alkynyl, and aryl groups.
They also include alkyl, alkenyl, alkynyl, and aryl groups
substituted with other aliphatic or cyclic hydrocarbyl
groups, such as alkaryl, alkenaryl, and alkynaryl.
[0324] A substituted hydrocarbyl may be any
hydrocarbyl wherein a carbon atom of the hydrocarbyl group
has been substituted with an atom other than hydrogen or a
group of atoms containing at least one atom other than
hydrogen. For example, a hydrogen atom may be substituted
with a halogen atom, such as a chlorine or fluorine atom.
Alternatively, one or more hydrogen atoms may be replaced
with a substituent comprising an oxygen atom or a group
containing an oxygen atom to form, for example, a hydroxy
group, an ether, an ester, an anhydride, an aldehyde, a
ketone, or a carboxylic acid. The hydrogen atom also may
be replaced with a group containing a nitrogen atom to
form, for example, an amide or a nitro group. In addition,
a hydrogen atom may be replaced with a substituent group
containing a sulfur atom to form, for example, -SO3H.
[0325] Typically, R1 and R2 are independently either:
hydrogen; - (CH2)X- (CH3)ra, x being an integer ranging from 0
to about 19 (particularly from 1 to 6, and even more
particularly 1) , m being 1; -(CH2)y-OH, y being an integer
ranging from 1 to about 20 (especially from 2 to 6); (CH2)ZCOOH,
z being an integer ranging from 1 to about 19
(especially from 1 to '5); or phosphonomethyl.
[0326] In some preferred embodiments, R1 and R2 are
both hydrogen (i.e., the amine functionality shown in
formula (I) is a primary amine). An example of such an
alcohol is monoethanolamine.
[0327] In other preferred embodiments, R1 is hydrogen
and R2 is hydrocarbyl or substituted hydrocarbyl (i.e., the
amine functionality shown in formula (I) is a secondary
amine) . Examples of primary alcohols in which R2 is
hydrocarbyl include N-methylethanolamine,
N-ethylethanolamine, N-isopropylethanolamine,
N-butylethanolamine, and N-nonylethanolamine. Examples of
primary alcohols in which R2 is a substituted hydrocarbyl
include primary alcohols wherein R2 is -(CH2)y-OH and y is
an integer ranging from 1 to about 20 (more preferably from
1 to 6). An example of such an alcohol is diethanolamine.
Other examples of primary alcohols wherein R2 is a
substituted hydrocarbyl include
N-(2-aminoethyl)ethanolamine,
N-(3-aminopropyl)ethanolamine,
N-(carboxymethyl)ethanolamine, and
N-(phosphonomethyl)ethanolamine. N-substituted
ethanolamines, for example, may be prepared using the
various methods known in the art. For example, a ketone
may be condensed with monoethanolamine in the presence of
H2, a solvent, and a noble metal catalyst. This reaction
is described in, for example, Cope, A.C. and Hancock, E.M.
J. Am. Chem. Soc.. 64, 1503-6 (1942). N-substituted
ethanolamines also may be prepared by combining a monosubstituted
amine (such as methylamine) and ethylene oxide
to form the mono-substituted ethanolamine. This reaction
is described by, for example, Y. Yoshida in Japanese Patent
Application No. 95-141575.
[0328] In yet other preferred embodiments, both R1
and R2 are independently hydrocarbyl or substituted
hydrocarbyl (i.e., the amine functionality shown in formula
(I) is a tertiary amine). Examples of primary alcohols in
which R1 and R2 are independently hydrocarbyl include
N,N-dimethylethanolamine, N,N-diethylethanolamine, and
N,N-dibutylethanolamine. Examples of primary alcohols in
which R1 is hydrocarbyl and R2 is substituted hydrocarbyl
include primary alcohols wherein R2 is -(CH2)y-OH and y is
an integer ranging from 1 to about 20 (more preferably from
1 to 6). Such alcohols include, for example,
N-methyldiethanolamine, N-ethyldiethanolamine,
N-isopropyldiethanolamine, and N-butyldiethanolamine.
Other examples of primary alcohols in which R1 is
hydrocarbyl and R2 is substituted hydrocarbyl include
N-ethyl, N-(2-aminoethyl)ethanolamine; N-ethyl,
N-(2-aminoethyl)ethanolamine; and N-methyl,
N-(3-aminopropyl)ethanolamine. Examples of primary
alcohols in which R1 and R2 are independently substituted
hydrocarbyl include primary alcohols wherein R1 and R2 are
independently -(CH2)y-OH and y is an integer ranging from 1
to about 20 (more preferably from 1 to 6). An example of
such an alcohol is triethanolamine. Other examples of
primary alcohols in which R1 and R2 are independently
substituted hydrocarbyl include
tetra(2-hydroxyethyl)ethylenediamine and N-
(phosphonomethyl)-N-(carboxymethyl)ethanolamine.
[0329] In a particularly preferred embodiment, the
primary alcohol comprises diethanolamine and the
dehydrogenation proceeds as set forth above to form
disodium iminodiacetic acid and hydrogen. One important
consideration in this embodiment is the formation of
unwanted byproducts such as sarcosine (i.e., N-methylglycine)
which tend to impact downstream processes
incorporating the dehydrogenation product (e.g., a process
in which disodium iminodiacetic acid is converted to N-
(phosphonomethyl)iminodiacetic which is then converted to
N-(phosphonomethyl)glycine) . It has been discovered that
use of the catalyst of the present invention for the
dehydrogenation of diethanolamine to disodium iminodiacetic
produces no significant amount of sarcosine due to absence
of nickel in the catalyst. For example, typically the
product of the dehydrogenation of diethanolamine using the
catalyst of the present invention contains no more than
about 10% by weight of byproducts including sarcosine,
glycine and oxalic acid. As an added benefit, the catalyst
of the present invention does not require the presence of
an expensive noble metal.
[0330] The dehydrogenation reaction is conducted in
an alkaline environment (i.e., a basic environment) by
contacting the primary alcohol with a catalyst in a heated
reaction (i.e., dehydrogenation) zone containing an
alkaline medium containing the catalyst. More
specifically, this reaction is typically conducted in the
presence of a strong base having a pKa value of at least
about 11, more preferably at least about 12, and even more
preferably at least about 13. Suitable bases include, for
example, alkali metal hydroxides (LiOH, NaOH, KOH, RbOH, or
CsOH), alkaline-earth metal hydroxides (e.g., Mg(OH)2 or
Ca(OH)2), NaH, and tetramethyl ammonium hydroxide. Of
these bases, alkali metal hydroxides (particularly NaOH and
KOH, and even more particularly NaOH) are often preferred
because of their solubility in water under the reaction
conditions, as well as their ready commercial availability
and ease of handling.
[0331] The preferred amount of base introduced into
the reaction zone depends on, for example, the moles of
primary alcohol groups introduced into the reaction zone.
Preferably, at least about one molar equivalent of base is
introduced per mole of primary alcohol hydroxy groups.
Thus, for example, if the base is NaOH and the primary
alcohol is monoethanolamine, preferably at least about 1
mole of NaOH is introduced per mole of monoethanolamine.
If, on the other hand, the primary alcohol is
diethanolamine, preferably at least 2 moles of NaOH are
introduced per mole of diethanolamine. In a particularly
preferred embodiment, from about 1.05 to about 2.0 molar
equivalents of base per alcohol hydroxyl group are
introduced. The hydroxide may, for example, be in the form
of flakes, powder, pellets, or an aqueous solution.
[0332] The reaction is normally conducted in a liquid
medium comprising the alcohol and usually a solvent for the
alcohol and/or the base. Alcohol, base and catalyst are
introduced into the liquid medium, and reaction proceeds in
the liquid medium within the reaction zone. An alkali
metal or alkaline earth metal hydroxide may be introduced
into the reaction medium in various forms, for example, be
in the form of flakes, powder, pellets, or an aqueous
solution.
[0333] Preferably, the solvent is present in the
liquid reaction medium in a proportion sufficient to
dissolve essentially all (more preferably, all) the base.
The solvent also preferably is present in a proportion
sufficient to maintain the primary alcohol substrate and
carboxylic acid salt product in a solubilized form.
[0334] Water is normally the preferred solvent due to
its low cost, widespread availability, and ease of
handling. Alcohol, base and solvent are preferably
combined in relative proportions such that, at the outset
of a batch reaction cycle or the upstream end of a flow
reactor, the reaction medium contains at least about 1
moles of alcohol per liter of reaction medium, typically
between about 1.8 and about 2.5 moles of alcohol per liter
of reaction medium, and at least about 3 moles of base per
liter of reaction medium, typically between about 4 and
about 5 moles of alcohol per liter of base. The molar
ratio of solvent to base and solvent to alcohol•is
typically between about 0.7 and about 1.2 and between about
0.8 and about 2.0, respectively, more typically between
about 0.85 and about 1 and between about 1 and about 1.8,
respectively. In a continuous back mixed reaction system,
solvent, base and alcohol are preferably introduced into
the reaction medium in relative proportions equivalent to
the above concentrations and ratios.
[0335] Conveniently, the catalyst is slurried in the
liquid reaction medium. Alternatively, the reaction medium
containing base and alcohol can flow through a fixed bed of
catalyst bodies. In a slurry catalyst system, the
preferred catalyst loading (i.e., the preferred
concentration of catalyst in the liquid reaction medium)
depends on, for example, the initial concentration of the
primary alcohol substrate therein or the relative rates at
which solvent, catalyst and base are introduced into the
reaction zone. Typically, the catalyst loading in a batch
or continuous flow reactions system is at least about 1% by
weight relative to the initial primary alcohol substrate
content of the reaction medium (i.e., [mass of catalyst -smass
of primary alcohol substrate] x 100%) . More
preferably, the catalyst loading is from about 1% to about
70% (still more preferably from about 10% to about 40%) by
weight of the primary alcohol substrate. In a continuous
back mixed reaction system, catalyst and primary alcohol
are preferably introduced into the reactor in these same or
similar relative proportions.
[0336] The preferred catalyst loading also depends
on, for example, the total mass of the alkaline liquid
medium in which the catalyst is slurried. Typically, the
catalyst loading is at least about 0.1% by weight of the
total mass of the alkaline medium (i.e., [mass of catalyst
H- total mass of alkaline medium] x 100%) and, more
typically, at least about 5% by weight of the total mass of
the alkaline liquid medium. More preferably, the catalyst
loading is from about 0.1% to about 10% (even more
preferably from about 3.5% to about 10%, and still even
more preferably from about 3.5% to about 5%) by weight of
the total mass of the alkaline liquid medium.
Concentrations of greater than about 10 wt.% can be
difficult to filter. On the other hand, concentrations of
less than about 0.1 wt.% tend to produce less than optimal
reaction rates.
[0337] In a preferred embodiment of the invention,
particulate catalyst may be charged to an aqueous alkaline
medium to form a slurry for contacting diethanolamine with
the catalyst to produce a dehydrogenation reaction product
slurry comprising catalyst and disodium iminodiacetic acid.
Typically, in such an embodiment, the slurry comprises at
least about 3.5 % by weight of catalyst and, more
typically, from about 3.5% to about 10% by weight.
Disodium iminodiacetic acid is then recovered from the
reaction product slurry.
[0338] Regardless of whether the reaction is
conducted in a batch or continuous mode, it is preferably
driven substantially to completion, e.g., to a conversion
of at least about 90%, more preferably at least about 95%,
more preferably at least about 98%. Alternatively,
however, the reaction system may be operated at lower
conversions, with unreacted alcohol separated from the
reaction mixture, e.g., by distillation, and recycled as
part of the feed to the reactor. Where the reactor is
operated at significantly less than quantitative conversion
of alcohol, it may be preferable to seek a higher
conversion of base, since it may be less feasible to
separate and recycle the base, especially an inorganic base
such as NaOH or KOH. In such instance the ratio of base to
alcohol introduced into the reactor may be significantly
less than 1.0. For example if conversion is only 60%, the
ratio of base to alcohol may be only 0.55 to 0.65.
[0339] The reaction typically is conducted at a
temperature of at least about 70°C, preferably from about
120° to about 220°C, more preferably from about 140° to
about 200°C, even more preferably from about 145° to about
155°C, and still even more preferably at about 150°C
(particularly when the primary alcohol is diethanolamine
and the desired product is the salt of iminodiacetic acid).
Although reaction temperatures outside of these ranges may
be used, the results are typically less than optimal. For
example, at temperatures of less than about 120°C, the
reaction rate tends to be slow. And at temperatures
greater than about 220°C, the catalyst normally begins to
lose selectivity. To illustrate, as the reaction
temperature exceeds about 150°C (and particularly as the
temperature exceeds about 220°C), the dehydrogenation
reaction of diethanolamine will tend to form more glycine
salt byproduct, and, therefore, be less selective toward
forming the desired iminodiacetic acid salt product.
[0340] The reaction is preferably conducted under
pressure. More specifically, the reaction is normally
conducted under a pressure which is sufficient to prevent
boiling of the mixture at the reaction temperature. At
reaction temperatures of from about 120° to about 220°C,
the pressure preferably is at least about 5 kg/cm2, more
preferably from about 5 to about 30 kg/cm2, even more
preferably from about 5 to about 20 kg/cm2, still even more
preferably from about 8 to about 11 kg/cm2 (i.e., from
about 115 to about 155 psig), and most preferably about 9.4
kg/cm2 (i.e., 135 psig). Although greater pressures may be
used, they are normally less desirable because pressures
above about 30 kg/cm2 tend to reduce the reaction rate. In
certain embodiments, the dehydrogenation reaction zone is
under a total pressure of not greater than about 9.5 kg/cm2
(135 psig) with the hydrogen partial pressure being from
about 0 kg/cm2 (0 psig) at the outset of the reaction to
about 9.5 kg/cm2 (135 psig) (i.e., the total pressure) at
the peak of the reaction.
[0341] The dehydrogenation reaction preferably is
conducted under a non-oxidizing atmosphere (preferably, an
atmosphere containing a noble gas and/or N2, and more
preferably N2 when the reaction is conducted on a
commercial level) to avoid oxidation of the catalyst
surface (the atmosphere will also contain H2 which evolves
during the dehydrogenation). This preference stems from
the fact that oxidation of the copper near the surface of
the catalyst tends to reduce the activity and selectivity
of the catalyst.
[0342] The dehydrogenation reaction may be carried
out in a wide variety of batch, semi-batch, and continuous
reactor systems. The configuration of the reactor is not
critical. Suitable conventional reactor configurations
include, for example, stirred-tank reactors, fixed bed
reactors, trickle bed reactors, fluidized bed reactors,
bubble flow reactors, plug flow reactors, and parallel flow
reactors. Often, the more preferred reactor configurations
are stirred-tank reactors. However, for when the hydrogen
produced in the dehydrogenation reaction is fed to a fuel
cell, the preferred reactor configuration comprises a fixed
bed reactor followed by gas-liquid adsorption.
[0343] During a batch reaction cycle, typically at
least about 200 g of diethanolamine per kg of alkaline
medium are introduced to a dehydrogenation reaction zone
for each reaction cycle. Preferably, at least about 225 g
of diethanolamine per kg of alkaline medium are introduced
to a dehydrogenation reaction zone for each reaction cycle.
Typically, at least about 5% of the diethanolamine present
in the dehydrogenation reaction zone is converted to
disodium iminodiacetic acid.
[0344] Generally, a primary alcohol will be converted
to a salt of a carboxylic acid at an ultimate turnover
ratio of at least about 2 moles of salt produced per mole
of copper. Preferably, diethanolamine is converted to
disodium iminodiacetic acid within the dehydrogenation
reaction zone at an ultimate turnover ratio of at least
about 1 mole of diethanolamine per mole of copper.
[0345] In a slurry reaction system the reaction
mixture is preferably filtered for separation of the
catalyst from the liquid medium. Preferably the separated
catalyst is recycled to the reactor for further conversion
of alcohol to carboxylic acid. In a slurried catalyst
reaction system, the turnover ratio per cycle or pass
through the reactor is generally at least about 1 mole of
diethanolamine per mole of copper. Typically, the turnover
ratio per cycle or pass through the reactor is at least
about 10 moles of diethanolamine per mole of copper, more
typically at least about 15 moles of diethanolamine per
mole of copper and, still more typically, from about 15 to
about 20 moles of diethanolamine per mole of copper. The
preferred turnover ratios described hereinabove are
realized by multiple recycles of catalyst mass or multiple
passes of catalyst through the reactor. In a fixed or
fluid bed reaction system, the ultimate turnover ratio
reflects the frequency with which the catalyst mass or
catalyst bodies are removed from the reaction system and/or
regenerated for further use, and the volume of reactants
and products flowing through the bed between successive
catalyst regeneration or removal operations.
[0346] Diethanolamine may be introduced to the
dehydrogenation reaction zone continuously or
intermittently to be contacted with the catalyst to form a
product mixture comprising disodium iminodiacetic acid.
Likewise, product mixture my be continuously or
intermittently withdrawn from the product mixture.
[0347] When the catalyst is recycled and/or reused
through multiple reaction cycles or passes, migration of
the metal deposited on the carbon support tends to occur
during one or more of the initial reaction cycles or
passes. In a continuous fixed or fluid bed system, such
migration tends to occur during the early hours of
operation. Generally, deposited metal particles tend to
migrate from less stable to more stable portions of the
surface of the carbon support. This migration due to
instability of one or more sites is generally complete
after the initial (i.e., first and second) reaction cycles
of a batch system, or the early passes or other operation
of a continuous system, thereby providing a catalyst which
exhibits suitable stability throughout multiple reaction
cycles, passes, etc.
[0348] When the dehydrogenation is conducted in a
continuous reactor system, the residence time in the
reaction zone can vary widely depending on the specific
catalyst and conditions employed. Likewise, when the
dehydrogenation is conducted in a batch reactor, the
reaction time typically will also vary widely - depending on
such factors. Normally, the dehydrogenation behaves as a
first order reaction, particularly toward the end of the
reaction. Thus, the preferred residence time in a
continuous reaction zone (or the preferred reaction time in
a batch reaction zone) will also depend on the desired
degree of conversion.
[0349] Various iminodiacetic acid compounds
(preferably alkali metal salts of iminodiacetic acid, and
even more preferably a sodium salt of iminodiacetic acid)
produced using the dehydrogenation catalyst of this
invention may be used as raw materials to prepare N-
(phosphonomethyl)glycine and agronomically acceptable salts
of N-(phosphonomethyl)glycine. Salts of iminodiacetic
acid, for example, may be phosphonomethylated in a reaction
zone containing HCl, phosphorous acid (H3PO3) , and
formaldehyde (CH2O) to form N-
(phosphonomethyl)iminodiacetic acid as disclosed for
example in U.S. Patent No. 4,775,498 (Gentilcore). The N-
(phosphonomethyl)iminodiacetic acid may, in turn, be
contacted with oxygen in the presence of the oxidation
catalyst disclosed herein to oxidatively cleave a
carboxymethyl group to form N~(phosphonomethyl)glycine.
Moreover, N-(phosphonomethyl) glycine prepared in accordance
with the present invention may be further processed in
accordance with many well-known methods in the art to
produce agronomically acceptable salts of N-
(phosphonomethyl)glycine commonly used in herbicidal
glyphosate compositions. As used herein, an "agronomically
acceptable salt" is defined as a salt which contains a
cation(s) that allows agriculturally and economically
useful herbicidal activity of an N-(phosphonomethyl)glycine
anion. Such a cation may be, for example, an alkali metal
cation (e.g., a sodium or potassium ion), an ammonium ion,
an isopropyl ammonium ion, a tetra-alkylammonium ion, a
trialkyl sulfonium ion, a protonated primary amine, a
protonated secondary amine, or a protonated tertiary amine.
[0350] The present invention is illustrated by the
following examples which are merely for the purpose of
illustration and not to be regarded as limiting the scope
of the invention or the manner in which it may be
practiced.
EXAMPLES
Example 1 Electroless copper plating on bulk metal carbides
and nitrides
[0351] This example details electroless copper
plating on bulk metal carbides and nitrides.
[0352] Bulk molybdenum carbide (20.0 g) (Aldrich
Chemical Co., Milwaukee, WI) was added to a 2 1 flask
containing deionized water (200 ml) and a magnetic stirring
bar to form a slurry.
[0353] A copper plating solution was prepared by
adding reagent grade sodium potassium tartrate
(NaKC4H4O6'4H20) (29.99 g) (Aldrich Chemical Co., Milwaukee,
WI) , copper sulfate (CuS04-5H20) (11.79 g) (Aldrich Chemical
Co., Milwaukee, WI), a 50 wt.% solution of sodium hydroxide
(NaOH) (13.60 g) (Aldrich Chemical Co., Milwaukee, WI) and
37 wt.% formaldehyde (CH2O) (11.35 ml) (Aldrich Chemical
Co., Milwaukee, WI) to deionized water (950 ml) to form
approximately 1 liter of plating solution in a 2 liter
flask.
[0354] Plating solution was added to the carbide
slurry incrementally over the course of about 40 minutes
with approximately 60 ml of the plating solution added to
the slurry every 2.5 minutes. Addition of plating solution
to the carbide slurry and the plating reaction were carried
out in a nitrogen atmosphere formed by flowing N2 above the
reaction solution.
[0355] The pH of the plating solution was monitored
using a pH meter to detect reductions in the pH of the
plating slurry caused by consumption of sodium hydroxide.
Plating was allowed to proceed until the pH of the slurry
reached approximately 8.0. After plating was complete, the
slurry was filtered under the nitrogen atmosphere and the
resulting wet cake was dried in a nitrogen purged vacuum
for approximately 8 hours.
[0356] The wet cake was then weighed to determine the
plating of copper on the bulk molybdenum carbide. The
weight gain of the bulk molybdenum carbide indicated copper
plating of from 90% to approximately 100% of the copper
present in the plating solution.
Example 2 Synthesis of a precursor for use in preparing
carbon-supported molybdenum carbides (Mo2C/C) and carbonsupported
molybdenum nitrides (Mo2N/C)
[0357] This example details the preparation of a
precursor for use in preparing carbon-supported molybdenum
carbides and nitrides.
[0358] A carbon support (20.0 g) having a B.E.T.
surface area of 1067 m2/g (Degussa Corporation) was added
to a 1 1 beaker containing deionized water (300 ml) and a
magnetic stirring bar to form a slurry.
[0359] A solution (60 ml) containing ammonium
molybdate ((NH4)2Mo04) (4.236 g) (Aldrich Chemical Co.,
Milwaukee, WI) in deionized water was added to the carbon
slurry using a MasterFlex® meter pump (MasterFlex® L/S®)
manufactured by Cole-Farmer Instrument Company (Vernon
Hills, IL). The slurry was agitated by a mechanical
stirrer while the molybdenum solution was added to the
carbon slurry at a rate of 2.0 ml/min over the course of
about 30-40 minutes. During addition of the molybdenum
solution to the carbon slurry, the pH of the resulting
mixture was maintained at approximately 4.0 by co-addition
of diluted nitric acid (approximately 5-10 ml) (Aldrich
Chemical Co., Milwaukee, WI). The carbon slurry was
agitated during the deposition process and acid was added
in 5-10 ml increments when the pH of the slurry was above
4.0.
[0360] After addition of the molybdenum solution to
the carbon slurry was complete, the slurry was agitated for
approximately 30 minutes. The pH of the mixture was then
adjusted to around 3.0 by addition of diluted nitric acid
(2-5 ml) (Aldrich Chemical Co., Milwaukee, WI) and once
again agitated for approximately 30 minutes.
[0361] The resulting mixture was filtered and washed
with approximately 800 ml of deionized water and the wet
cake was dried in a nitrogen purged vacuum oven at 120°C
overnight.
Example 3 Synthesis of carbon-supported molybdenum carbide
containing 15% by weight molybdenum carbide (15% Mo.2C/C)
[0362] This example details preparation of a carbonsupported
molybdenum carbide using a carbon-supported
molybdenum carbide precursor prepared in accordance with
the procedure set forth above in Example 2.
[0363] The carbide precursor (8.0 g) was charged into
a Hastelloy C tube reactor packed with high temperature
insulation material which was purged with argon introduced
to the reactor at 100 cm3/min at about 20°C for
approximately 15 minutes. A thermocouple was inserted into
the center of the reactor for charging of the precursor
material.
[0364] The temperature of the reactor was then raised
to about 300°C over the course of 30 minutes during which
time a 50%/50% (v/v) mixture of methane and hydrogen
(Airgas Co., St. Louis, MO) was introduced to the reactor
at a rate of about 100 cm3/min.
[0365] The temperature of the reactor was then
increased to approximately 650°C at a rate of approximately
2°C/min. The reactor was maintained at this temperature
and under a flow of 50%/50% (v/v) mixture of methane and
hydrogen (Airgas Co., St. Louis, MO) was introduced to the
reactor at a rate of about 100 cm3/min for approximately 4
hours. During this period of constant temperature a
molybdenum carbide composition was formed on the carbon
support.
[0366] The resulting carbide was then cleaned by
contact with a 20%/80% (v/v) flow of a mixture of hydrogen
and argon introduced to the reactor at a rate of about 100
cm3/min. The temperature of the reactor was maintained at
about 650°C for approximately another 30 minutes after
which time the reactor was cooled to approximately 20°C
over the course of 90 minutes under a flow of argon at 100
cm3/min.
Example 4 Synthesis of carbon-supported molybdenum nitride
containing 15% by weight molybdenum nitride (15% Mo2N/C)
[0367] This example details preparation of a carbonsupported
molybdenum nitride using a 15% carbon-supported
molybdenum nitride precursor prepared in accordance with
the procedure set forth above in Example 2.
[0368] The nitride precursor (10.0 g) was charged
into a Hastelloy C tube reactor packed with high
temperature insulation material which was purged with argon
introduced to the reactor at 100 cm3/min at about 20°C for
approximately 15 minutes.
[0369] The temperature of the reactor was then raised
to about 300°C over the course of 30 minutes during which
time ammonia (Airgas Co., St. Louis, MO) was introduced to
the reactor at a rate of about 100 cm3/min.
[0370] The temperature of the reactor was then
increased to approximately 800°C at a rate of approximately
2°C/min. The reactor was maintained at this temperature
and under a flow of ammonia at a rate of about 100 cm3/min
for approximately 4 hours. During this period of constant
temperature, the reactor was maintained under flow of
ammonia introduced to the reactor at a rate of about 100
cm3/min.
[0371] A molybdenum nitride composition was formed on
the carbon support. The reactor was cooled to
approximately 20°C over the course of 90 minutes under flow
of 100 cm3/min of argon.
Example 5 Quality of plating of copper on carbon supported
nitride
[0372] The quality of plating of copper on carbon
supported metal nitride prepared in accordance with the
method set forth above in Example 4 was examined as
determined by the percent of molybdenum leaching from the
carbon support. The carbon supported nitride prepared
contained 10% by weight nitride. A nitriding operation as
described above in Example 4 was performed using different
maximum temperatures (Tmax) at a constant holding time of 1
hour. The results are summarized below in Table 1.
Table 1 Results of Cu plating and Mo leaching at varying
Tma3C and a holding time of 1 hour
(Table Removed)
Example 6 Quality, of copper plating on carbon supported
nitride
[0373] The quality of plating of copper on a carbonsupported
metal nitride prepared in accordance with the
method set forth above in Example 4 was examined as
determined by the percent of molybdenum leaching from the
carbon support. The carbon supported metal nitride
prepared contained 10% by weight nitride. A nitriding
operation as described above in Example 4 was carried out
using a maximum temperature (Tmax) of 800°C and a holding
time of 4 hours. The results are summarized below in Table
2.
Table 2 Results of Cu plating and Mo leaching at
800°C and a holding time of 4 hours
of
(Table Removed)
Example 7 Quality of copper plating on carbon supported
carbide
[0374] The quality of plating of copper on carbonsupported
metal carbides prepared in accordance with the
method set forth above in Example 3 was examined as
determined by the percent of molybdenum leaching from the
carbon support. The carbon supported carbide prepared
contained 10% by weight carbide. A carbiding operation as
described above in Example 3 was performed using different
maximum temperatures (Tmax) at a constant holding time of 1
hour. The results are summarized below in Table 3.
Table 3 Results of Cu plating and Mo leaching at varying
Tmax and a holding time of 1 hour
(Table Removed)
Example 8 Quality of copper plating on carbon supported
carbide
[0375] The quality of plating of copper on a carbonsupported
metal carbide prepared in accordance with the
method set forth above in Example 3 was examined as
determined by the percent of molybdenum leaching from the
carbon support. The carbon supported carbide contained 10
% by weight carbide. A carbiding operation as described
above in Example 3 was carried out using a maximum
temperature (Tmax) of 650°C and a holding time of from 1 to
8 hours. -The results are summarized below in Table 4.
Table 4 Results of Cu plating and Mo leaching at Tn
650°C and varying holding times
of
Holding Time
(Table Removed)
Example 9 Stability of carbon-supported carbides under
conditions suitable to dehydrogenate diethanolamirie to, form
disodium iminodiacetic acid
[0376] Carbon-supported carbides prepared in
accordance with the methods set forth above using each of
four carbon supports were tested in accordance using the
procedure set forth below.
[0377] The supports may be described as follows:
(Table Removed)
[0378] Dehydrogenation of diethanolamine was
conducted in a 300 ml autoclave reactor constructed of
Hastelloy C (high strength nickel-based alloy) and equipped
with a back pressure regulator, H2 mass flow meters, and a
charge pot which allowed reagents and rinse water to be
added to the reactor under inert gas.
[0379] To test the stability of the various carbonsupported
carbide compositions during the dehydrogenation
conditions, a catalyst containing 22% Cu by weight, 3% Pt
by weight on a carbon support was charged to the reactor
along with the carbon-supported carbide compositions.
[0380] The reactor was first flushed with argon (when
conducting this reaction on a commercial scale, N2 would be
preferred). A mixture containing a 50 wt.% solution of
sodium hydroxide (99.81 g) (Aldrich Chemical Co.,
Milwaukee, WI) , diethanolamine (62.50 g) (Huntsman
Chemicals) and deionized water (75 ml) was sparged with N2
and introduced into the reactor along with N2-sparged
deionized water (40 ml). The reactor was then sealed and
flushed with N2. During the reaction, the mixture was
continuously stirred, the pressure was maintained at 135
psig using the back pressure regulator, and the temperature
was maintained at about 150°C.
[0381] The reaction was allowed to proceed for
approximately 3 hours and samples were removed from the
reactor at the outset, after the reaction was allowed to
proceed for 1.5 hours, and after the reaction had proceeded
for 3 hours.
[0382] The samples were analyzed to determine the
stability of the carbon-supported carbide under the
dehydrogenation conditions based on the amount of
molybdenum leached from the carbide as determined by the
amount of molybdenum present in the samples removed from
the reactor determined using Inductively Coupled Plasma-
Mass Spectrometry.
[0383] The carbon-supported carbide catalysts are
referred to according to its support. For example,
Catalyst No. 1 refers to a carbon-supported carbide
catalyst including Support No. 1. One dehydrogenation
cycle was run to test each of Catalyst No. 1, Catalyst No.
2, and Catalyst No. 3 while two dehydrogenation cycles were
run to test Catalyst No. 4. The first run to test the
stability of Catalyst No. 4 was carried out using only the
carbon-supported carbide catalyst while the second run
included the 22% Cu by weight, 3% Pt by weight on a carbon
support.
[0384] The results are shown in Table 5. The
percentage of leaching measured at a reaction time of 0 is
substantially due to reaction of unconverted molybdenum
oxide with sodium hydroxide. The percentage of leaching at
a reaction time of 90 minutes and 3 hours includes that
present at reaction time of 0 along with possible leaching
from the carbide formed during the reaction. For example,
as shown below in Table 5 for Catalyst No. 1, molybdenum
leaching corresponding to 2.1% of the weight percent of
total molybdenum during the first 90 minutes of reaction
was from the surface of the carbide formed during that
time. While in certain instances the leaching at a
reaction time of 3 hours appears to be reduced, based on
experimental error these results indicate that the amount
of leaching remained substantially constant after a
reaction time of 1.5 hours.
Table 5 Stability of carbon-supported molybdenum carbides
under dehydrogenation. conditions
Catalyst Molybdenum Leaching (wt.% of total Mo)
(Table Removed)
[0385] Table 6 shows the composition of the reactor
at the sampling times.
Table 6
(Table Removed)
Reactor sample components:
Diethanolamine (DBA)
N-(2-hydroxyethyl)glycine (HEG)
Iminodiacetic acid (IDA)
Disodium iminodiacetic acid (DSIDA)
Example 10 Stability _p£ carbon-supported nitrides under
conditions suitable to dehydrogenate diethanolamine to _f orm
disodium iminodiacetic acid
[0386] Carbon-supported nitrides prepared in
accordance with the methods set forth above using two
different carbon supports were tested in accordance with
the procedure set forth below. The supports may be
described as follows:
(Table Removed)
[0387] Dehydrogenation of diethanolamine was
conducted in a 300 ml autoclave reactor constructed of
Hastelloy C (high strength nickel-based alloy) and equipped
with a back pressure regulator, H2 mass flow meters, and a
charge pot which allowed reagents and rinse water to be
added to the reactor under inert gas.
[0388] To test the stability of the carbon-supported
nitride compositions during the dehydrogenation conditions,
a catalyst containing 22% Cu by weight, 3% Pt by weight on
a carbon support was charged to the reactor along with the
carbon-supported carbide compositions.
[0389] The reactor was first flushed with argon (when
conducting this reaction on a commercial scale, N2 would be
preferred). A mixture containing a 50 wt.% solution of
sodium hydroxide (99.81 g) (Aldrich Chemical Co.,
Milwaukee, WI) , diethanolamine (62.50 g) (Huntsman
Chemicals) and deionized water (75 ml) was sparged with M2
and introduced into the reactor along with N2~sparged
deionized water (40 ml). The reactor was then sealed and
flushed with N2. During the reaction, the mixture was
continuously stirred, the pressure was maintained at 135
psig using the back pressure regulator and the temperature
was maintained at about 150°C. When the H2 generation from
the reaction decreased to cnvVmin, the reactor was cooled,
and N2-sparged deionized water (80 ml) was added to the
reactor.
[0390] The reaction was allowed to proceed for
approximately 3 hours and samples were removed from the
reactor at the outset, after the reaction was allowed to
proceed for 1.5 hours, and after the reaction had proceeded
for 3 hours.
[0391] The samples were analyzed to determine the
stability of the carbon-supported nitrides under the
dehydrogenation conditions based on the amount of
molybdenum leached from the nitride as determined by the
amount of molybdenum present in the samples removed from
the reactor.
[0392] The carbon-supported nitride catalysts are
referred to according to its support. For example,
Catalyst No. 1 refers to a carbon-supported nitride
catalyst including Support Wo. 1. One dehydrogenation
cycle was run to test Catalyst No. 1 and No. 2. The
results are shown in Table 7.
Table 7 Stability of carbon-supported molybdenum nitrides
under dehydrocrenation conditions
Nitride Molybdenum Leaching (wt.% of total Mo)
(Table Removed)
[0393] The percentage of leaching measured at a
reaction time of 0 is substantially due to reaction of
unconverted molybdenum oxide with sodium hydroxide. The
percentage of leaching at a reaction time of 90 minutes and
3 hours includes that present at reaction time of 0 along
with possible leaching from the nitride formed during the
reaction. For example, as shown for Catalyst No. 1,
molybdenum leaching corresponding to approximately 0.9% of
the weight percent of total molybdenum during the first 90
minutes of reaction was from the surface of the carbide
formed during that time. While in certain instances the
leaching at a reaction time of 3 hours appears to be
reduced, based on experimental error these results indicate
that the amount of leaching remained substantially constant
after a reaction time of 1.5 hours.
Example 11 Preparation of.._ catalyst containing copper on
carbon-supported, molybdenum carbide
[0394] This example details preparation of a catalyst
containing a carbon-supported molybdenum carbide and
copper.
[0395] A carbon-supported molybdenum carbide (6.70 g)
prepared in accordance with the method set forth above in
Example 3 and containing 15% by weight molybdenum carbide
was added to deionized water (200 ml) in a 1 liter flask
containing a magnetic stirring bar to form a slurry.
[0396] A copper plating solution (total volume
approximately 500 ml) was prepared by adding reagent grade
sodium potassium tartrate (NaKC4H4O6«4H2O) (15 g) (Aldrich
Chemical Co., Milwaukee, WI) , copper sulfate (CuS04«5H2O)
(5.90 g) (Aldrich Chemical Co., Milwaukee, WI), a 50 wt.%
solution of sodium hydroxide (NaOH) (6.80 g) (Aldrich
Chemical Co., Milwaukee, WI) and 37 wt.% formaldehyde
(CH20) (5.70 ml) (Aldrich Chemical Co., Milwaukee, WI) to
deionized water (450 ml) in a 1 liter flask.
[0397] The carbide slurry and plating solution were
both cooled to about 2°C in a nitrogen (N2) atmosphere
while stirred with a magnetic stirring bar. After cooling,
plating solution was added to the carbide slurry under the
nitrogen atmosphere incrementally over the course of
approximately 30 minutes with 16 ml of plating solution
being added to the carbide slurry every minute. After
addition of the plating solution to the carbide slurry was
complete, the resulting mixture was agitated for about 2
hours at approximately 3°C using a magnetic stirring bar.
Plating was monitored using by the drop in pH of the
mixture caused by consumption of sodium hydroxide. The pH
of the mixture is monitored using a pH meter and plating
continued until the pH of the mixture dropped below 8. The
mixture was filtered under the nitrogen atmosphere which
produced a wet cake. The resulting wet cake was washed
with water (200 ml), packed, and dried in a nitrogen purged
vacuum oven at 120°C for approximately 8 hours.
[0398] Based on metal analysis of the resulting
filtrate, the resulting solid was determined to have a
composition of 18wt.% copper, 11 wt.% carbide with the
balance consisting of the carbon support. (18%Cull%
Mo2C/C) .
Example 12 Preparation of catalyst containing copper on
carbon-supported molybdenum carbide
[0399] This example details preparation of a catalyst
containing a carbon-supported molybdenum carbide and
copper.
[0400] A carbon-supported molybdenum carbide
(6.97 g)prepared in accordance with the method set forth
above in Example 3 and containing 15% by weight molybdenum
carbide was added to deionized water (200 ml) in a 1 liter
flask containing a magnetic stirring bar to form a slurry.
[0401] A copper plating solution (total volume
approximately 500 ml) was prepared by adding reagent grade
sodium potassium tartrate (NaKC4H406-4H20) (15 g) (Aldrich
Chemical Co., Milwaukee, WI) , copper sulfate (CuS04-5H20)
(5.90 g) (Aldrich Chemical Co., Milwaukee, WI), and a 50
wt.% solution of sodium hydroxide (NaOH) (6.80 g) (Aldrich
Chemical Co., Milwaukee, WI) to deionized water (450 ml) in
a 1 liter flask.
[0402] The carbide slurry and plating solution were
both cooled to from about 0-2°C in a nitrogen (N2)
atmosphere. After cooling, the plating solution and
carbide slurry were mixed under the nitrogen atmosphere and
agitated for approximately 30 minutes using a magnetic
stirring bar. Following the agitation, a mixture of 37
wt.% formaldehyde (CH2O) (5.70 ml) (Aldrich Chemical Co.,
Milwaukee, WI) in 20 ml deionized water was added to the
slurry at approximately 3°C for approximately 30 minutes
using MasterFlex® meter pump.
[0403] The temperature of the mixture was then raised
to approximately 13°C over the course of approximately one
hour and maintained at this temperature until the mixture
became substantially colorless. This took from 10 to 15
minutes after which time the mixture was filtered under the
nitrogen atmosphere which produced a wet cake. The
resulting wet cake was washed with water (200 ml) , packed
wet, and dried in a nitrogen purged vacuum oven at 120°C
for approximately 8 hours.
[0404] Based on metal analysis of the resulting
filtrate, the resulting solid was determined to have a
composition of 19wt.% copper, 10 wt.% carbide with the
balance consisting of the carbon support. (19%Cu-10%Mo2C/C)
Example 13 Preparation of catalyst containing copper on
carbon-supported molybdenum carbide
[0405] This example details preparation of a catalyst
containing a carbon-supported molybdenum carbide and
copper.
[0406] A carbon-supported molybdenum carbide
(6.30 g) prepared in accordance with the method set forth
above in Example 3 and containing 13% by weight molybdenum
carbide was added to deionized water (200 ml) in a 1 liter
flask containing a magnetic stirring bar to form a slurry.
[0407] A copper plating solution (total volume
approximately 500 ml) was prepared by adding reagent grade
ethylenediaminetetraacetic acid (EDTA, C10H16O8N2) (13.74 g)
(Aldrich Chemical Co., Milwaukee, WI), copper sulfate
(CuS04-5H2O) (5.90 g) (Aldrich Chemical Co., Milwaukee, WI) ,
and a 50 wt.% solution of sodium hydroxide (NaOH) (6.80 g)
(Aldrich Chemical Co., Milwaukee, WI) and 37 wt.%
formaldehyde (CH20) (0.15 ml) to deionized water (450 ml)
in a 1 liter flask.
[0408] The carbide slurry and plating solution were
both cooled to from about 0-2°C in a nitrogen (N2)
atmosphere. After cooling, the plating solution and
carbide slurry were mixed under the nitrogen atmosphere and
agitated for approximately 15 minutes using a magnetic
stirring bar. Following the agitation, a mixture of 37
wt.% formaldehyde (CH20) (5.70 ml) (Aldrich Chemical Co.,
Milwaukee, WI) in deionized water was added to the mixture
which was agitated at approximately 2°C for approximately
10 minutes using a magnetic stirring bar.
[0409] The temperature of the mixture was then raised
to approximately 18°C over the course of approximately 20
minutes and maintained at this temperature until the
mixture became substantially colorless. This took from
about 10 to 15 minutes after which time the mixture was
filtered under the nitrogen atmosphere which produced a wet
cake. The resulting wet cake was washed with water (200
ml), packed wet, and dried in a nitrogen purged vacuum oven
at 120°C for approximately 8 hours.
[0410] Based on metal analysis of the resulting
filtrate, the resulting solid was determined to have a
composition of 19wt.% copper, 10 wt.% carbide with the
balance consisting of the carbon support. (19%Cu-
10%Mo2C/C)
Example 14 Use of a catalyst containing_copper deposited on
a carbon-supported molybdenum carbide for the
dehydrogenation of diethanolamine to disodium iminodiacetic
acid
[0411] This example details use of the catalyst
prepared in accordance with the procedure set forth above
in Example 11 for the dehydrogenation of diethanolamine to
produce disodium iminodiacetic acid over the course of 8
reaction cycles
[0412] The dehydrogenation was conducted in a 300 ml
Parr autoclave continuous stirred tank reactor able to be
operated in a batch or continuous manner. The reactor was
operated batch-wise for each of the 8 reaction cycles of
the present example. The reactor was constructed of
Hastelloy C (high strength nickel-based alloy) and equipped
with a back pressure regulator, H2 mass flow meters, and a
charge pot which allowed reagents and rinse water to be
added to the reactor under inert gas.
[0413] Catalyst (7.0 g) prepared in accordance with
the method set forth above in Example 7, 50 wt.% sodium
hydroxide (55.90 g) (Aldrich Chemical Co., Milwaukee, WI),
diethanolamine (35.11 g) (Huntsman Chemicals) and water
(42.44 g) were charged in this sequence to the reactor to
form a mixture.
[0414] The reactor was set at a maximum volume of
approximately 170 ml and the total amount of mixture
charged (140.45 g) provided proper hydrogen disengagement.
High-pressure bottle N2 at a pressure of 3000 psig was used
to inert the reaction headspace and bring the reaction to
the starting pressure of approximately 135 psig.
[0415] During the reaction, the mixture was
continuously stirred and the pressure maintained at
approximately 135 psig using a control valve manufactured
by Badger Research. Reaction temperature was maintained at
about 150°C during the entire reaction.
[0416] The reaction was allowed to proceed for
approximately 3 hours during which time a Brooks onstream
thermal mass flow sensor (Model No. 5860IA13VB2EA) was used
to monitor the reaction based on the amount of hydrogen
generated in the reaction mixture.
[0417] After the reaction was allowed to proceed for
approximately 3 hours, the reaction mass was cooled to
approximately 90°C and the reactants were separated from
the catalyst in situ using a 0.5 /im metal sintered frit
(Mott Corporation, Hartford, CT). Samples of the reaction
mass were analyzed using high pressure liquid
chromatography ("HPLC").
[0418] Seven additional dehydrogenation cycles were
conducted in.accordance with the above conditions with
similar amounts of diethanolamine being charged to the
reactor.
[0419] The extent of reaction in terms of hydroxide
conversion was determined for reaction cycles 1-7 by
comparing the actual amount of hydrogen generated to the
theoretical amount of hydrogen to be generated in the
reaction mixture based on the amount of diethanolamine
charged to the reactor. The results are shown below in
Table 8.
[0420] The compositions of the product samples from
reaction cycles 1 and 2 analyzed using HPLC are summarized
below in Table 9.
Table 8
(Table Removed)
Table 9 Composition of Dehydrogenation Product Samples
Cycle No.
(Table Removed)
Product Sample Components:
Diethanolamine (DEA)
N-(2-Hydroxyethyl)glycine (HEG)
Iminodiacetic acid (IDA)
Example 15 Use of a catalyst containing copper on a carbonsupported
molybdenum carbide for the dehydrogenation of
diethanolamine to disodium iminodiacetic acid
[0421] Catalyst (7.2 g) prepared in accordance with
the method set forth above in Example 12, 50 wt.% sodium
hydroxide (54.95 g) (Aldrich Chemical Co., Milwaukee, WI),
diethanolamine (35.04 g) (Huntsman Chemicals) and water
(46.74 g) were charged in this sequence to the reactor
described above in Example 14 to form a mixture.
Dehydrogenation of diethanolamine was conducted using the
same reaction conditions as in Example 14.
[0422] 6 dehydrogenation cycles were conducted with
similar amounts of diethanolamine charged to the reactor
during each cycle. The results for the extent of reaction
during each of the 6 reaction cycles were determined based
on the hydroxide conversion in accordance with the method
set forth above in Example 14 and are summarized below in
Table 10.
Table 10
(Table Removed)
Diethanolamine (DBA)
Example 16 Use of a catalyst containing copper on a carbonsupported
molybdenum carbide for the dehydrocfenation of
diethanolamine to disodium iminodiacetic acid
[0423] Catalyst (7.0 g) prepared in accordance with
the method set forth above in Example 13, 50 wt.% sodium
hydroxide (60.52 g) (Aldrich Chemical Co., Milwaukee, WI),
diethanolamine (39.16 g) (Huntsman Chemicals) and water
(49.40 g) were charged in this sequence to the reactor
described above in Example 14 to form a mixture.
[0424] Dehydrogenation of diethanolamine was
conducted using the same reaction conditions as in Example
10. 3 dehydrogenation cycles during which the reaction was
allowed to proceed for about 4, 4.5 and 6 hours,
respectively. Similar amounts of diethanolamine charged to
the reactor during each cycle. The results for the extent
of reaction during each of the 3 reaction cycles were
determined based on the hydroxide conversion in accordance
with the method set forth above in Example 13 and are
summarized below in Table 11.
Table 11
Cycle No.
(Table Removed)
Example 17 Use of a. catalyst containing copper deposited on
a carbon-supported molybdenum carbide for the
dehydrogenation of diethanolamine to disodium iminodiacetic
acid
[0425] This example details use of 12%Cu-
13%Mo2C/D1015 catalyst prepared in accordance with the
procedure set forth above in Example 14 for the
dehydrogenation of diethanolamine to produce disodium
iminodiacetic acid over the course of 3 reaction cycles.
[0426] The dehydrogenation was conducted in a 300 ml
Parr autoclave continuous stirred tank reactor able to be
operated in a batch or continuous manner. The reactor was
operated batch-wise for each of the 3 reaction cycles of
the present example. The reactor was constructed of
Hastelloy C (high strength nickel-based alloy) and equipped
with a back pressure regulator, H2 mass flow meters, and a
charge pot which allowed reagents and rinse water to be
added to the reactor under inert gas.
[0427] Catalyst (7.5 g) prepared in accordance with
the method set forth above in Example 7 (12% by weight
copper and 13% by weight molybdenum carbide and the balance
support having a surface area of 1067 m2/g), 50 wt. % sodium
hydroxide (59.6 g) (Aldrich Chemical Co., Milwaukee, WI),
diethanolamine (37.45 g) (Huntsman Chemicals) and deionized
water (36.10 g) were charged in this sequence to the
reactor to form a mixture.
[0428] The reactor was set at a maximum volume of
approximately 170 ml and the total amount of mixture
charged (140.64 g) provided proper hydrogen disengagement.
High-pressure bottle N2 at a pressure of 3000 psig was used
to inert the reaction headspace and bring the reaction to
the starting pressure of approximately 135 psig.
[0429] During the reaction, the mixture was
continuously stirred and the pressure maintained at
approximately 135 psig using a control valve manufactured
by Badger Research. Reaction temperature was maintained at
about 150°C during each of the reaction cycles.
[0430] The reaction was allowed to proceed for
approximately 3 hours during which time a Brooks onstream
thermal mass flow sensor (Model No. 5860IA13VB2EA) was used
to monitor the reaction based on the amount of hydrogen
generated in the reaction mixture.
[0431] The extent of reaction in terms of hydroxide
conversion was determined by comparing the actual amount of
hydrogen generated to the theoretical amount of hydrogen to
be generated in the reaction mixture based on the amount of
diethanolamine charged to the reactor. The results for the
extent of reaction during each of the 3 reaction cycles are
summarized below in Table 12.
Table 12
(Table Removed)
Example 18 Use of molybdenum carbide in the oxidation of N-
(phosphonomethvl)iminodiacetic acid
[0432] A 8.2% by weight solution of N-
(phosphonomethyl)iminodiacetic acid (PMIDA) (11.48g) in
water (127.8 ml) was charged to a 1L Parr reactor together
with molybdenum carbide at a loading of 1.3% (1.84 g) .
Prior to being charged to the reactor the molybdenum
carbide was subjected to a helium atmosphere at a
temperature of approximately 800°C for approximately 1
hour.
[0433] The reactor was pressurized to 60 psig in the
presence of a nitrogen atmosphere and the reaction mixture
was heated to 100°C. The reaction was allowed to proceed
for approximately 1 hour under a flow of 100 cc/min of pure
oxygen.
[0434] Samples of the reaction product were removed
from the reactor and analyzed to determine the conversion
of N-(phosphonomethyl)iminodiacetic acid. HPLC analysis
indicated a conversion of PMIDA to N-
(phosphonomethyl)glycine of approximately 18.2% and a
conversion of formaldehyde to formic acid of approximately
33.9%.
Example 19 Preparation of Carbon-supported molybdenum
catalyst
[0435] This example details preparation of a carbonsupported
molybdenum catalyst.
[0436] Activated carbon (10.2g) was added to water
(160 ml) at a temperature of approximately 20°C. The
mixture was stirred for approximately 40 minutes to form a
slurry of the carbon support.
[0437] Phosphomolybdic acid (H3Mo12O40P) (0.317 g) was
dissolved in water (30 ml) to form a solution which was
added to the support slurry. The mixture containing the
phosphomolybdic acid was then stirred for 30 minutes after
which time the solid was filtered, washed with deionized
water and dried in a vacuum at 120°C for approximately 8
hours.
[0438] The dried carbon-supported molybdenum compound
was then subjected to a reduction operation in a 5%
hydrogen in helium atmosphere at a temperature of from
about 800 or 900°C.
Example 20 Use of a carbon-supported molybdenum carbide
catalyst in the oxidation of N-
(phosphonomethyl) iminodiacet'ic acid
[0439] This example details use of a carbon-supported
molybdenum catalyst prepared in accordance with the method
set forth above in Example 19 in the oxidation of N-
(phosphonomethyl)iminodiacetic acid.
[0440] A 4.1% by weight solution of N-
(phosphonomethyl)iminodiacetic acid (PMIDA) (5.74 g) in
water (133.8 g) was charged to a 1 L Parr reactor together
with the carbon-supported molybdenum catalyst at a loading
of 0.309% (0.432 g). The reactor was pressurized to 60
psig in a nitrogen atmosphere and the reaction mixture was
heated to approximately 100°C.
[0441] The reaction was allowed to proceed for
approximately 80 minutes under a flow of 100 cc/min of pure
oxygen. Four reaction cycles were performed and catalyst
from the previous cycle was used in each of the final 3
cycles.
[0442] Samples from the reaction mixtures produced
during the third and fourth reaction cycles were analyzed.
HPLC analysis of these samples indicated conversions of
PMIDA to N- (phosphonomethyl)glycine during the third and
fourth cycles were approximately 86.2% and 86.9%,
respectively. The conversions of formaldehyde to formic
acid during the third and fourth cycles were approximately
30.0% and 34.4%, respectively.
Example 21 Use of carbon-supported molybdenum in the
oxidation of N-(phosphonomethyl)iminodiacetic acid
[0443] This example details the use of carbonsupported
molybdenum catalyst prepared in accordance with
the method set forth above in Example 19 in the oxidation
of N-(phosphonomethyl)iminodiacetic acid.
[0444] A 4.11% by weight solution of N-
(phosphonomethyl)iminodiacetic acid (PMIDA) (5.74 g) in
water (133.8 g) was charged to a 1 L Parr reactor together
with the carbon-supported molybdenum catalyst at a loading
of 0.155% (0.216 g).
[0445] The reactor was pressurized to 60 psig in a
nitrogen atmosphere and the reaction mixture was heated to
approximately 100°C. The reaction was allowed to proceed
for approximately 15 minutes under a flow of 100 cc/min of
pure oxygen.
[0446] A sample was removed from the reaction mixture
and analyzed. HPLC analysis indicated a conversion of
PMIDA to N-(phosphonomethyl)glycine of approximately 6.8%
and a conversion of formaldehyde to formic acid of
approximately 17.4%.
Example 22
[0447] This example details the preparation of a
carbon-supported iron-containing catalyst precursor.
[0448] A particulate carbon support (10.0 g) having a
Langmuir surface area of approximately 1500 m2/g was added
to a 1 liter flask containing deionized water (400 ml) to
form a slurry. The pH of the slurry was approximately 8.0
and the temperature approximately 20°C.
[0449] Iron chloride (FeCl3«6H20) (0.489 g) was added
to a 100 ml beaker containing deionized water (30 ml) to
form a clear solution. The iron solution was added
incrementally over the course of 15 minutes (i.e., at a
rate of approximately 2 ml/minute). The pH of the carbon
slurry was maintained at from about 4 to about 4.4 by coaddition
of a 0.1 wt.% solution of sodium hydroxide
(Aldrich Chemical Co., Milwaukee, WI). Approximately 5 ml
of 0.1 wt.% sodium hydroxide solution was added to the
carbon slurry during addition of the iron solution. The pH
of the slurry was monitored using a pH meter (Thermo Orion
Model 290).
[0450] After addition of the iron solution to the
carbon slurry was complete, the slurry was stirred for 30
minutes using a mechanical stirring rod (at 50% output)
(IKA-Werke RW16 Basic) with pH of the slurry monitored
using the pH meter and maintained at approximately 4.4 by
dropwise addition of 0.1 wt.% sodium hydroxide or 0.1 wt.%
HN03.
[0451] The slurry was then heated under a nitrogen
blanket to 70°C at a rate of about 2°C per minute while its
pH was maintained at 4.4. Upon reaching 70°C, the slurry
pH was slowly raised by addition of 0.1 wt.% sodium
hydroxide (5 ml) according to the following pH profile: the
pH was maintained at approximately 5.0 for 10 minutes,
increased to 5.5, maintained at 5.5 for approximately 20
minutes at pH 5.5, and stirred for approximately 20 minutes
during which time a constant pH of 6.0 was reached.
[0452] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1.0% by weight iron.
Example 23
[0453] This example details the preparation of a
carbon-supported iron-containing catalyst using a precursor
prepared in accordance with the procedure set forth above
in Example 22.
[0454] Iron-containing precursor (5.0 g) was charged
into a Hastelloy C tube reactor packed with high
temperature insulation material. The reactor was purged
with argon introduced to the reactor at a rate of
approximately 100 cm3/min at approximately 20°C for
approximately 15 minutes. A thermocouple was inserted into
the center of the reactor for charging the precursor
material.
[0455] The temperature of the reactor was then raised
to approximately 300°C over the course of approximately 15
minutes during which time a 10%/90% (v/v) mixture of
acetonitrile and argon (Airgas, Inc., Radnor, PA) was
introduced to the reactor at a rate of approximately 100
cm3/minute. The temperature of the reactor was then
increased to approximately 950°C over the course of 30
minutes during which time the 10%/90% (v/v) mixture of
acetonitrile and argon flowed through the reactor at a rate
of approximately 100 cm3/minute. The reactor was
maintained at approximately 950°C for approximately 120
minutes. The reactor was cooled to approximately 20°C over
the course of 90 minutes under a flow of argon at
approximately 100 cm3/minute.
[0456] The resulting catalyst contained approximately
1% by weight iron.
Example 24
[0457] This example details the use of various of
various noble-metal and non-noble-metal-containing
catalysts in the oxidation of PMIDA to N-
(phosphonomethyl)glycine.
[0458] A 0.5% by weight iron containing catalyst was
prepared in accordance with the procedure set forth above
in Example 23 . Its precursor was prepared in accordance
with the procedure set forth above in Example 22
(FeCl3»6H20) using a solution containing iron- chloride
(FeCl3»6H2O) (0.245 g) in deionized water (GO ml) which was
contacted with the carbon support slurry.
[0459] The 0.5% by weight iron catalyst was used to
catalyze the oxidation of PMIDA to glyphosate (curve 6 of
Fig. 8). Its performance was compared to: (1) 2 samples of
a 5% platinum, 0.5% iron particulate carbon catalyst
prepared in accordance with Ebner et al., U.S. Patent No.
6,417,133, Samples 1 and 2 (curves 1 and 4, respectively,
of Fig. 8); (2) a particulate carbon catalyst designated
MC-10 prepared in accordance with Chou, U.S. Patent No.
4,696,772 (curve 3 of Fig. 8); (3) a 1% Fe containing
catalyst precursor prepared in accordance with the
procedure set forth above in Example 22 treated in
accordance with the catalyst preparation procedure
described in Example 23 using argon in place of
acetonitrile (curve 2 of Fig. 8); and (4) a particulate
carbon support having a Langmuir surface area of
approximately 1500 m2/g which was treated with acetonitrile
in accordance with the procedure set forth above in Example
23 used to prepare the 1% by weight iron catalyst (curve 5
of Fig. 8) .
[0460] In each instance, the PMIDA oxidation was
conducted in a 200 ml glass reactor containing a total
reaction mass (200 g) which included 5.74% by weight PMIDA
(11.48 g) and 0.11% catalyst (0.22 g) . The oxidation was
conducted at a temperature of 100°C, a pressure of 60 psig,
a stir rate of 100 revolutions per minute (rpm), and an
oxygen flow rate of 150 cm3/minute for a run time of 50
minutes.
[0461] The maximum C02 percentage in the exit gas and
cumulative CO2 generated were used as indicators of the
degree of oxidation of PMIDA, formaldehyde, and formic acid
during the reaction.
[0462] Fig. 8 shows the percentage of CO2 in the exit
gas during a first reaction cycle carried out using the six
different catalysts.
[0463] As shown in Fig. 8, the 0.5% by weight iron
catalyst exhibited greater activity than the MC10 catalyst
and exhibited comparable activity as compared to
5%Pt/0.5%Fe/C catalysts. Also shown in Fig. 8, the
acetonitrile-treated carbon support and argon-treated
precursor showed little activity. Table 13 shows the C02
in the exit gas and cumulative C02 generated in the
reaction cycle using each of the 6 catalyst samples.
Table 13 Cumulative CO,' number after 50 minute runtime
(Table Removed)
Example 25
[0464] The performance of iron containing catalysts
of varying iron loadings (0.5%, 0.75%, 1%, and 2% by weight
iron) was tested in the oxidation of PMIDA to N-
(phosphonomethyl)glycine.
[0465] The 0.5% by weight iron catalyst prepared in
accordance with Example 24 and the 1% by weight iron
catalyst prepared in accordance with Example 23 were tested
along with a 0.75% by weight iron catalyst and 2% by weight
iron catalyst.
[0466] The precursors of the 0.75% and 2% iron
catalysts were prepared in accordance with the procedure
set forth above in Example 22 using varying amounts of iron
chloride (FeCl3»6H2O) , depending on the desired catalyst
loading. For the catalyst containing 0.75% by weight iron,
a solution containing iron chloride (0.366 g) in deionized
water (60 ml) was prepared and contacted with the carbon
support slurry.
[0467] For the catalyst containing 2.0% by weight
iron, a solution containing iron chloride (0.988 g) in
deionized water (60 ml) was prepared and contacted with the
carbon support slurry.
[0468] Each of the catalysts was tested under the
PMIDA oxidation reaction conditions as set forth in Example
24.
[0469] Fig. 9 shows the first cycle CO2 profiles for
the various catalysts. Curve 1 of Fig. 9 corresponds to
the first cycle using the 2% Fe catalyst, curve 2 of Fig. 9
corresponds to the first cycle using the 1% Fe catalyst,
curve 3 of Fig. 9 corresponds to the first cycle using the
0.75% Fe catalyst, and curve 4 of Fig. 9 corresponds to the
first cycle using the 0.5% Fe catalyst. As shown, the
catalyst containing 0.5% by weight iron demonstrated the
highest activity.
[0470] Table 14 shows HPLC results for the product
mixtures of the reactions carried out using the 1% by
weight iron catalyst prepared as in Example 23 and a 5%
platinum, 0.5% iron catalyst prepared in accordance with
Ebner et al., 6,417,133. The table shows the N-
(phosphonomethyl)iminodiacetic acid (PMIDA), N-
(phosphonomethyl)glycine (Gly), formaldehyde (FM), formic
acid (FA), iminodiacetic acid (IDA), aminomethylphosphonic
acid and methyl aminomethylphosphonic acid ( (M)AMPA) , Nmethy-
N-(phosphonomethyl)glycine (NMG), imino-bis-
(methylene)-bis-phosphonic acid (iminobis), and phosphate
ion (P04) content of the reaction mixture.
Table 14 HPLC results for 5% platinum, Q.S% iron 6,417,133
catalyst and !%FeCN/C catalyst after 50 minute runtime
(Table Removed)
Example 26
[0471] This example details preparation of a carbonsupported
cobalt-containing catalyst precursor containing
1% by weight cobalt.
[0472] A particulate carbon support (10.0 g) having a
Langmuir surface area of approximately 1500 m2/g was added
to a 1 liter flask containing deionized water (400 ml) to
form a slurry. The pH of the slurry was approximately 8.0
and the temperature approximately 20°C.
[0473] Cobalt chloride (CoCl2*2H2O) (0.285 g) (Sigma-
Aldrich, St. Louis, MO) was added to a 100 ml beaker
containing deionized water (60 ml) to form a clear
solution. The cobalt solution was added to the carbon
slurry incrementally over the course of 30 minutes (i.e.,
at a rate of approximately 2 ml/minute). The pH of the
carbon slurry was maintained at from about 7.5 and about
8.0 during addition of the cobalt solution by co-addition
of a 0.1 wt% solution of sodium hydroxide (Aldrich Chemical
Co., Milwaukee, WI) . Approximately 1 ml of 0.1 wt.% sodium
hydroxide solution was added to the carbon slurry during
addition of the cobalt solution. The pH of the slurry was
monitored using a pH meter (Thermo Orion, Model 290).
[0474] After addition of the cobalt solution to the
carbon slurry was complete, the slurry was stirred using a
mechanical stirring rod operating at 50% of output (Model
IKA-Werke RW16 Basic) for approximately 30 minutes; the pH
of the slurry was monitored using the pH meter and
maintained at about 8.0 by dropwise addition of 0.1 wt.%
sodium hydroxide (1 ml) or 0.1 wt.% HNO3 (1 ml) . The
slurry was then heated under a nitrogen blanket to 45°C at
a rate of about 2°C per minute while maintaining the pH at
8.0 by dropwise addition of 0.1 wt.% sodium hydroxide (1
ml) or 0.1 wt.% HNO3 (1 ml). Upon reaching 45°C, the
slurry was stirred using the mechanical stirring bar
described above for 20 minutes at constant temperature of
45°C and a pH of 8.0. The slurry was then heated to 50°C
and its pH was adjusted to 8.5 by addition of 0.1 wt.%
sodium hydroxide solution (5 ml); the slurry was maintained
at these conditions for approximately 20 minutes. The
slurry was then heated to 60 °C, its pH adjusted to 9.0 by
addition of 0.1 wt.% sodium hydroxide solution (5 ml) and
maintained at these conditions for approximately 10
minutes.
[0475] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °G. The precursor contained
approximately 1.0% by weight cobalt.
Example 27
[0476] This example details the preparation of a
carbon-supported cobalt-containing catalyst using a
precursor prepared in accordance with the procedure set
forth above in Example 26.
[0477] Cobalt-containing catalyst precursor prepared
as described above in Example 26 (5.0 g) was charged into a
Hastelloy C tube reactor packed with high temperature
insulation material. The reactor was purged with argon
introduced to the reactor at a rate of approximately 100
cm3/niin at approximately 20°C for approximately 15 minutes.
A thermocouple was inserted into the center of the reactor
for charging the precursor material.
[0478] The temperature of the reactor was then raised
to approximately 700°C during which time a 50%/50% (v/v)
mixture of hydrogen and methane (Airgas, Inc., Radnor, PA)
was introduced to the reactor at a rate of approximately 20
cm3/minute and argon at a rate of approximately 100 cm3/min.
The reactor was maintained at approximately 700°C for
approximately 120 minutes.
[0479] The reactor was cooled to approximately 20°C
over the course of 90 minutes under a flow of argon at
approximately 100 cm3/minute.
[0480] The resulting catalyst contained approximately
1% by weight cobalt.
[0481] A 1% cobalt-containing catalyst from the
precursor prepared as described in Example 26 was also
prepared as described in Example 23 using acetonitrile.
Example 28
[0482] The performance of cobalt containing catalysts
of varying cobalt loadings (0.75%, 1%, 1.5%, and 2%) were
tested in the oxidation of PMIDA under the conditions
described above in Example 24. The 1% cobalt-containing
catalyst was prepared as described in Example 27 using
acetonitrile.
[0483] The precursors of the 0.5%, 0.75%, and 2% by
weight cobalt catalysts were prepared in accordance with
the procedure set forth above in Example 26 using varying
amounts of cobalt chloride (CoCl2«2H2O) , depending on the
desired catalyst loading. The catalysts were then prepared
in accordance with the procedure described in Example 27
using acetonitrile.
[0484] For the catalyst containing 0.75% by weight
cobalt, a solution containing cobalt chloride (0.214 g) in
deionized water (60 ml) was prepared and contacted with the
carbon support slurry.
[0485] For the catalyst containing 1.5% by weight
cobalt, a solution containing cobalt chloride (0.428 g) in
deionized water (60 ml) was prepared and contacted with the
carbon support slurry.
[0486] For the catalyst containing 2.0% by weight
cobalt, a solution containing cobalt chloride (0.570 g) was
prepared and contacted with the carbon support slurry.
[0487] Fig. 10 shows the first cycle CO2 profiles
using the various catalysts. Curve 1 of Fig. 10
corresponds to the first cycle using the 0.75% Co catalyst,
curve 2 of Fig. 10 corresponds to the first cycle using the
1% Co catalyst, curve 3 of Fig. 10 corresponds to the first
cycle using the 1.50% Co catalyst, and curve 4 of Fig. 10
corresponds to the first cycle using the 2.0% Co catalyst.
[0488] As shown in Fig. 10, catalysts containing from
1-1.5% cobalt demonstrated the highest activity.
[0489] The HPLC results for the product streams of
the four PMIDA reaction cycles using the 1% cobalt catalyst
and first four reaction cycles using the 5%Pt/0.5%Fe/C
catalyst prepared in accordance with Ebner et al., U.S.
Patent No. 6,417,133 described are summarized below in
Table 15.
[0490] The table shows the N-
(phosphonomethyl)iminodiacetic acid (GI), N-
(phosphonomethyl)glycine (Gly), formaldehyde (FM), formic
acid (FA), iminodiacetic acid (IDA), aminomethylphosphonic
acid and methyl aminomethylphosphonic acid ((M)AMPA), Nmethy-
N-(phosphonomethyl)glycine (NMG) , imino-bis-
(methylene)-bis-phosphonic acid (iminobis), and phosphate
ion (PO4) content of the reaction mixture for the various
cycles.
Table 15 HPLC results for 5%Pt/0.5%Fe/C and !%CoCN/C
catalysts after 50 minute runtime
(Table Removed)
Example _29
[0491] This example compares the stability of a 1%
iron catalyst prepared as described in Example 23, a 1%
cobalt catalyst prepared as described in Example 27 using
acetonitrile, a particulate carbon catalyst containing 5%
by weight Pt, 0.5% by weight iron prepared in accordance
with Ebner et al., U.S. Patent No. 6,417,133, and a
particulate carbon catalyst designated MC-10 prepared in
accordance with Chou, U.S. Patent No. 4,696,772.
[0492] Each of the •catalysts were used in PMIDA
oxidation under the conditions described above in Example
24 for multiple reaction cycles.
[0493] Fig. 11 shows the C02 percentage in the exit
gas during each of four reaction cycles (labeled
accordingly) carried out using the 1% iron catalyst.
[0494] Fig. 12 shows the CO2 percentage in the exit
gas during each of four reaction cycles (labeled
accordingly) carried out using the 1% cobalt catalyst.
[0495] Fig. 13 shows the C02 percentage in the exit
gas during each of six reaction cycles (labeled
accordingly) carried out using the 5%Pt/0.5%Fe/C catalyst.
[0496] Pig. 14 shows the C02 percentage in the exit
gas during each of two reaction cycles (labeled
accordingly) carried out using the MC-10 catalyst.
[0497] The iron-containing catalyst exhibited a drop
in activity after the first cycle, possibly due to
overoxidation of the catalyst. Minor deactivations were
observed in later cycles where the catalyst was not
overoxidized. The 5%Pt/0.5%Fe/C was the most stable. The
1% cobalt catalyst showed similar stability to the
5%Pt/0.5%Fe/C catalyst. The MC10 catalyst exhibited the
worst stability, even in the absence of overoxidation of
the catalyst.
Example 30.
[0498] This example details the preparation of
various carbon-supported metal-containing catalysts.
[0499] Precursors were prepared for catalysts
containing vanadium, tellurium, molybdenum, tungsten,
ruthenium, and cerium generally in accordance with Example
22 disclosure detailing preparation of an iron-containing
catalyst precursor with variations in the pH and heating
schedule depending the metal to be deposited.
[0500] Preparation of vanadium precursor: Na3VO4»10H20
(0.721 g) was added to a 100 ml beaker containing deionized
water (60 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 3.4 to about 3.7 by coaddition
of a 0.1 wt.% solution of nitric acid.
Approximately 5 ml of nitric acid was added to the carbon
slurry during addition of the vanadium solution. After
addition of the vanadium solution to the carbon slurry was
complete, the slurry was stirred for 30 minutes using
mechanical stirring rod operating at 50% of output (Model
IKA-Werke RW16 Basic) with pH of the slurry monitored using
the pH meter described above and maintained at
approximately 3.6 by addition of nitric acid (0.1 wt.%
solution) (2 ml).
[0501] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight vanadium.
[0502] Preparation of tellurium precursor: Te(OH)6
(0.092 g) was added to a 100 ml beaker containing deionized
water (60 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 6.5 to about 6.9 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 2 ml of 0.1 wt.% sodium hydroxide solution
was added to the carbon slurry during addition of the
tellurium solution. After addition of the tellurium
solution to the carbon slurry was complete, the slurry was
stirred for 30 minutes with pH of the slurry monitored
using the pH meter and maintained at approximately 6.7 by
addition of 0.1 wt.% sodium hydroxide solution (1-2 ml).
[0503] The pH was maintained at pH of 6.0, 5.0, 4.0,
3.0, 2.0, and 1.0 for 10 minutes each.
[0504] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight tellurium.
[0505] Preparation of molybdenum precursor:
(NH4)2MoO4 (0.207 g) was added to a 100 ml beaker containing
deionized water (50 ml) to form a solution which was
contacted with the carbon support slurry. The pH of the
carbon support slurry was maintained at from about 1.5 to
about 2.0 by co-addition of a 0.1 wt.% solution of nitric
acid. Approximately 5 ml of 0.1 wt.% nitric acid was added
to the carbon slurry during addition of the molybdenum
solution. After addition of the molybdenum solution to the
carbon slurry was complete, the slurry was stirred for 30
minutes with pH of the slurry monitored using the pH meter
and maintained at approximately 2 .0 by addition of 0.1 wt.%
nitric acid. The pH was then increased to 3.0 by addition
of 0.1 wt.% sodium hydroxide, maintained at 3.0 for 20
minutes, increased to 4.0 by addition of 0.1 wt.% sodium
hydroxide solution, and maintained at 4.0 for 20 minutes.
[0506] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight molybdenum.
[0507] Preparation of tungsten precursor:
(NH4) 6W12039«2H2O (0.135 g) was added to a 100 ml beaker
containing deionized water (60 ml) to form a solution which
was contacted with the carbon support slurry. The pH of
the carbon support slurry was maintained at from about 3.0
to about 3.2 by co-addition of a 0.1 wt.% solution of
sodium hydroxide. Approximately 2 ml of nitric acid was
added to the carbon slurry during addition of the tungsten
solution. After addition of the tungsten 'solution to the
carbon slurry was complete, the slurry was stirred for 30
minutes with pH of the slurry monitored using the pH meter
and maintained at approximately 3.0 by addition of 0.1 wt.%
nitric acid solution.
[0508] The pH was then decreased to 2.5 by addition
of 0.1 wt.% nitric acid solution, maintained at 2.5 for 10
minutes, decreased to 2.0 by addition of 0.1 wt.% nitric
acid solution, and maintained at 2.0 for 10 minutes.
[0509] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight tungsten.
[0510] Preparation of ruthenium precursor: RuCl3»2H20
(0.243 g) was added to a 100 ml beaker containing deionized
water (50 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 3.0 to about 3.5 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 1 ml of sodium hydroxide was added to the
carbon slurry during addition of the ruthenium solution.
After addition of the ruthenium solution to the carbon
slurry was complete, the slurry was stirred for 30 minutes
with pH of the slurry monitored using the pH meter and
maintained at approximately 3.5 by addition of 0.1 wt.%
nitric acid solution.
[0511] The pH was then increased to 4.2 by addition
of 0.1 wt.% sodium hydroxide (1 ml), maintained at 4.2 for
10 minutes, increased to 5.0 by addition of 0.1 wt.% sodium
hydroxide solution (1 ml), maintained at 5.0 for 10
minutes, increased to 5.7 by addition of 0.1 wt.% sodium
hydroxide (1 ml), and maintained at 5.7 for 10 minutes.
[0512] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight ruthenium.
[0513] Preparation of cerium precursor: Ce (N03) 3«6H2O
(0.117 g) was added to a 100 ml beaker containing deionized
water (50 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 7.0 to about 7.5 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 1 ml of sodium hydroxide was added to the
carbon slurry during addition of the cerium solution.
After addition of the cerium solution to the carbon slurry
was complete, the slurry was stirred for 30 minutes with pH
of the slurry monitored using the pH meter and maintained
at approximately 7.5 by addition of 0.1 wt.% sodium
hydroxide solution (1 ml).
[0514] The pH was then increased to 8.0 by addition
of 0.1 wt.% sodium hydroxide (1 ml), maintained at 8.0 for
20 minutes, increased to 9.0 by addition of 0.1 wt.% sodium
hydroxide (1 ml), maintained at 9.0 for 20 minutes,
increased to 10.0 by addition of 0.1 wt.% sodium hydroxide
solution (1 ml), and maintained at 10.0 for 20 minutes.
[0515] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight cerium.
[0516] Precursors were also prepared for catalysts
containing nickel, chromium, manganese, magnesium, copper,
and silver generally in accordance with Example 26
disclosure detailing preparation of a cobalt-containing
catalyst precursor with variations in the pH and heating
schedule depending on the metal to be deposited.
[0517] Preparation of nickel precursor: NiCl2«6H20
(0.409 g) was added to a 100 ml beaker containing deionized
water (60 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 7.5 to about 8.0 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 2 ml of sodium hydroxide was added to the
carbon slurry during addition of the nickel solution.
After addition of the nickel solution to the carbon slurry
was complete, the slurry was stirred for 30 minutes with pH
of the slurry monitored using the pH meter and maintained
at approximately 8.0 by addition of 0.1 wt.% sodium
hydroxide solution (1 ml). The slurry was then heated
under a nitrogen blanket to 40°C at a rate of about 2°C per
minute while maintaining its pH at 8.5 by addition of 0.1
wt.% sodium hydroxide solution. Upon reaching 60°C, the
slurry was stirred for 20 minutes at constant temperature
of 40°C and a pH of 8.5. The slurry was then heated to
50°C and its pH was adjusted to 9.0 by addition of sodium
hydroxide solution (2 ml); the slurry was maintained at
these conditions for approximately 20 minutes. The slurry
was then heated to 60°C, its pH adjusted to 10.0 by
addition of sodium hydroxide solution (2 ml) and maintained
at these conditions for approximately 20 minutes.
[0518] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight nickel.
[0519] Preparation of chromium precursor: CrCl3«6H2O
(0.517 g) was added to a 100 ml beaker containing deionized
water (50 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 7.0 to about 7.5 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 1 ml of sodium hydroxide was added to the
carbon slurry during addition of the chromium solution.
After addition of the chromium solution to the carbon
slurry was complete, the slurry was stirred for 30 minutes
with pH of the slurry monitored using the pH meter and
maintained at approximately 7.5 by addition of sodium
hydroxide. The slurry was then heated under a nitrogen
blanket to 60°C at a rate of about 2°C per minute while
maintaining its pH at 8.0 by addition of 2 ml of 0.1 wt.%
sodium hydroxide.
[0520] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight chromium.
[0521] Preparation of manganese precursor: MnCl2»4H20
(0.363 g) was added to a 100 ml beaker containing deionized
water (60 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 7.5 to about 8.0 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 1 ml of sodium hydroxide solution was added
to the carbon slurry during addition of the manganese
solution. After addition of the manganese solution to the
carbon slurry was complete, the slurry was stirred for 30
minutes with pH of the slurry monitored using the pH meter
and maintained at approximately 7.4 by addition of sodium
hydroxide. The slurry was then heated under a nitrogen
blanket to 45°C at a rate of about 2°C per minute while
maintaining its pH at 8.0 by addition of 2 ml of 0.1 wt.%
sodium hydroxide solution. Upon reaching 60°C, the slurry
was stirred for 20 minutes at constant temperature of 50°C
and a pH of 8.5. The slurry was then heated to 55°C and
its pH was adjusted to 9.0 by addition of sodium hydroxide
solution (2 ml); the slurry was maintained at these
conditions for approximately 20 minutes. The slurry was
then heated to 60°C, its pH adjusted to 9.0 by addition of
sodium hydroxide solution (1 ml) and maintained at these
conditions for approximately 20 minutes.
[0522] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight manganese.
[0523] Preparation of magnesium precursor: MgCl2»6H2O
(0.420 g) was added to a 100 ml beaker containing deionized
water (50 ml) to form a solution which was contacted with
the carbon support slurry. The pH of the carbon support
slurry was maintained at from about 8.5 to about 9.0 by coaddition
of a 0.1 wt.% solution of sodium hydroxide.
Approximately 5 ml of sodium hydroxide solution was added
to the carbon slurry during addition of the magnesium
solution. After addition of the magnesium solution to the
carbon slurry was complete, the slurry was stirred for 30
minutes with pH of the slurry monitored using the pH meter
and maintained at approximately 8.5 by addition of 0.1 wt.%
sodium hydroxide solution (1 ml) .
[0524] The pH of the slurry was then increased to 9.0
by addition of 0.1 wt.% sodium hydroxide solution (1 ml)
and maintained at 9.0 for 30 minutes.
[0525] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight magnesium.
[0526] Preparation of copper precursor: CuCl2 (1.11
g) was added to a 100 ml beaker containing deionized water
(60 ml) to form a solution which was contacted with the
carbon support slurry. The pH of the carbon support slurry
was maintained at from about 6.0 to about 6.5 by co158
addition of a 0.1 wt.% solution of sodium hydroxide.
Approximately 1 ml of sodium hydroxide was added to the
carbon slurry during addition of the copper solution.
After addition of the copper solution to the carbon slurry
was complete, the slurry was stirred for 30 minutes with pH
of the slurry monitored using the pH meter and maintained
at approximately 6,5 by addition of sodium hydroxide. The
slurry was then heated under a nitrogen blanket to 40 °C at
a rate of about 2°C per minute while maintaining its pH at
7.0 by addition of 0.1 wt. % sodium hydroxide solution.
Upon reaching 40°C, the slurry was stirred for 20 minutes
at constant temperature of 40°C and a pH of 7.0 The slurry
was then heated to 50°C and its pH was adjusted to 7.5 by
addition of 0.1 wt.% sodium hydroxide solution (1 ml); the
slurry was maintained at these conditions for approximately
20 minutes. The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 5% by weight copper.
[0527] Preparation of silver precursor: AgN03 (0.159
g) was added to a 100 ml beaker containing deionized water
(60 ml) to form a solution which was contacted with the
carbon support slurry. The pH of the carbon support slurry
was maintained at from about 4,0 to about 4.5 by coaddition
of a 0.1 wt.% solution of nitric acid.
Approximately 2 ml of nitric acid solution was added to the
carbon slurry during addition of the silver solution.
After addition of the silver solution to the carbon slurry
was complete, the slurry was stirred for 30 minutes with pH
of the slurry monitored using the pH meter and maintained
at approximately 4.5 by addition of nitric acid solution (2.
ml) .
[0528] The resulting mixture was filtered and washed
with a plentiful amount of deionized water (approximately
500 ml) and the wet cake was dried for approximately 16
hours in a vacuum oven at 120 °C. The precursor contained
approximately 1% by weight silver.
[0529] Metal-containing catalysts containing 1% by
weight metal (in the case of copper, 5% by weight) were
prepared from each of the catalyst precursors as described
above in Example 23.
Example 31
[0530] Each of the catalysts prepared as described in
Example 30 was tested in PMIDA oxidation under the
conditions described in Example 24.
[0531] The maximum C02 percent composition in the
exit gas and the total C02 generated during the 50 minutes
of reaction were used to measure the catalysts' activity.
The results are shown below in Table 16.
Table 16 First cycle reaction results for various _MCN
catalysts
(Table Removed)
[0532] The carbon-supported cobalt-containing
catalyst and chromium-containing catalysts showed the
highest PMIDA oxidation activity.
160
Example 32
[0533] This example details the effectiveness of
various carbon-supported catalysts for the oxidation of
formaldehyde and formic acid during PMIDA oxidation under
the conditions described in Example 24.
[0534] Two methods were employed to evaluate the
activity of various carbon-supported metal carbide-nitride
catalysts in the oxidation of formaldehyde and formic acid:
HPLC analysis of the reaction product and the C02 droppoint
measurement. The drop-point measurement is the total
amount of C02 that has passed through the exit gas at the
moment a sudden reduction in exit gas CO2 composition is
observed. As shown in Fig. 15, a particulate carbon
catalyst containing 5%Pt/l% Fe prepared in accordance with
Ebner et al., U.S. Patent No. 6,417,133 produces a C02
drop-point around 1500-1600 cm3 of total CO2 under the PMIDA
oxidation conditions of Example 24 (curve 1 of Fig. 15).
Also shown in Fig. 15, a 1% cobalt-containing catalyst
prepared as described above in Example 27 using
acetonitrile, exhibits a CO2 drop point around 1300 cm3
under the PMIDA oxidation conditions of Example 24 (curve 2
of Fig. 15).
[0535] The 200-300 cm3 increase in total CO2 of the
5%Pt/l% Fe catalyst prepared in accordance with Ebner et
al'., U.S. Patent No. 6,417,133 may be due to greater
oxidation of formic acid as compared to the 1% cobalt
catalyst.
[0536] Table 17 shows the HPLC results of the PMIDA
oxidation product using various catalysts prepared as
described above in Example 31: 1% by weight cobalt, 1% by
weight manganese, 5% by weight copper, 1% by weight
magnesium, 1% by weight chromium, 1% by weight molybdenum,
and 1% by weight tungsten. The carbon-supported cobalt
carbide-nitride catalyst showed the highest formaldehyde
oxidation activity.
Table 17 HPLC results for various MCN catalysts after 50
minute runtime
(Table Removed)
[0537] Catalyst mixtures containing 50% by weight of
the 1% by weight cobalt catalyst prepared as described in
Example 27 using acetonitrile and 50% by weight of one of
the 1% nickel, 1% vanadium, 1% magnesium, and 1% tellurium
catalysts prepared in accordance with Example 31 were
prepared and tested under the PMIDA oxidation conditions
described in Example 24 to further test the activity toward
oxidation of formaldehyde and formic acid. A drop point of
approximately 1300 cm3 was observed for each of the 4
catalyst mixtures.
Example,33
[0538] This example details use of various promoters
in combination with a 1% cobalt catalyst prepared as
described above in Example 27 using acetonitrile in PMIDA
oxidation under the conditions described in Example 24.
[0539] The promoters tested were: bismuth nitrate
(Bi(NO3)3), bismuth oxide (Bi203) , tellurium oxide (TeO2)
iron chloride (FeCl3) , nickel chloride (NiCl2) , copper
sulf ate (CuSO4) , ammonium rnolybdate ( (NH4) 2Mo04) , and
ammonium tungstate ( (NH4) 10W12O41) .
[0540] The promoters were introduced to the reaction
mixture at the outset of the reaction cycle. The promoters
were introduced to the reaction mixture at varying loadings
as shown in Table 18.
[0541] The maximum C02 concentration in the exit gas
stream and the cumulative CO2 number were measured to
determine the catalytic activity and the CO2 drop-point
measurement was recorded to determine the catalytic formic
acid oxidation activity. Table 18 shows the maximum C02 in
the exit gas and the total CO2 generated during a first 50
minute reaction cycle. The CO2 drop points for each of the
catalysts were between about 1300 and 1350 cm3.
Table 18 First cycle reaction results from l%CoCN/C
(0.021g) catalysts doped with promoters
Promoter
(Table Removed)
Example 34
[0542] This example details preparation of bimetallic
carbon-supported carbide-nitride catalysts and
their use in PMIDA oxidation.
[0543] A catalyst containing 1% by weight cobalt and
0.5% by weight iron was prepared in accordance with the
process described above in Example 27 using acetonitrile.
The precursor for the 1% cobalt and 0.5% iron catalyst was
prepared by sequential deposition of each of the metals in
accordance with the methods described above in Examples 26
and 22, respectively.
[0544] Similarly, a catalyst containing 1% cobalt and
0.5% cerium was prepared in accordance with the process
described above in Example 27 using acetonitrile. The
precursor for the 1% cobalt and 0.5% cerium catalyst was
prepared by sequential deposition of each of the metals in
accordance with the methods described above in Examples 26
and 30, respectively.
[0545] A catalyst containing 1% cobalt and 0.5%
copper was prepared in accordance with the process
described above in Example 27. The precursor for the 1%
cobalt and 0.5% copper catalyst was prepared by sequential
deposition of each of the metals in accordance with the
methods described above in Examples 26 and 30,
respectively,
[0546] Each of the catalysts were tested in PMIDA
oxidation under the conditions described in Example 24 over
the course of four cycles. The time required to generate
1300 cm3 of CO2 was determined for each of the cycles using
each of the catalysts. For comparison purposes, a 1% by
weight cobalt and 1.5% by weight cobalt catalyst, each
prepared as described in Example 28, were also tested in
this manner. The results are shown in Fig. 16. As shown
in Fig. 16, the 1.5% cobalt catalyst had lower activity
than the 1% cobalt catalyst but exhibited greater
stability. The cobalt-cerium catalyst exhibited improved
stability as compared to each of the cobalt catalysts but
lower activity. Overall, the results indicated that the
cobalt, cobalt-iron, and cobalt-cerium catalysts had
similar formaldehyde oxidation activity.
[0547] HPLC results for the product when using the
1.5% cobalt catalyst and 1.5% cobalt/0.5% copper catalyst
are set forth in Table 19. The carbon-supported cobaltcopper
catalyst converted more formaldehyde to formic acid
than the carbon-supported cobalt carbide-nitride catalyst.
Table 19 HPLC results from 1.5% CO/C and 1.5%Cu/C catalysts
after 50 min runtime
(Table Removed)
Example 35
[0548] This example details the use of a 1:1 mixture
of 5%Pt/0.5%Fe catalyst prepared in accordance with Ebner
et al. , U.S. Patent No. 6,417,133, and carbon-supported
catalysts containing 1% by weight cobalt in the oxidation
of N-(phosphonomethyl)iminodiacetic acid prepared as
described above in Example 27 using acetonitrile.
[0549] A mixture (0.210 g) was prepared containing
50% by weight of a particulate carbon catalyst containing
5% by weight platinum and 0.5% by weight iron prepared in
accordance with Ebner et al., U.S. Patent No. 6,417,133 and
the 1% by weight cobalt catalyst (0.105 g). The catalyst
mixture was tested in PMIDA oxidation under the conditions
set forth above in Example 24 over the course of six
reaction cycles. A particulate carbon catalyst 5% by
weight platinum and 0.5% by weight iron prepared in
accordance with Ebner et al., U.S. Patent No. 6,417,133 was
also tested in PMIDA oxidation under the conditions set
forth above in Example 24 over the course of six reaction
cycles.
[0550] The maximum C02 proportion in the exit gas,
total CO2 generated during each of the reaction cycles,
remaining formaldehyde content in the reaction, formic acid
content in the reaction mixture, and platinum leaching are
summarized below in Table 20.
Table 20
(Table Removed)
[0551] The catalyst mixture performed similarly to
the 5%Pt/l%Fe catalyst in the first cycle except the
catalyst mixture exhibited a lower cumulative C02 number
possibly due to less oxidation of formic acid. During the
remaining cycles, the catalyst mixture performed in a
similar manner as the 1% by weight cobalt catalyst and
exhibited deactivation with the accumulation of formic
acid. Metal analysis showed minimal Pt leaching,
indicating the platinum had been deactivated.
Example 36
[0552] This example details deposition of platinum
onto a. catalyst containing 1% by weight cobalt prepared as
described above in Example 27 using acetonitrile.
[0553] A sample of the 1% by weight cobalt catalyst
prepared in accordance with the method described above in
Example 27 (4.72 g) was added to a 1 liter flask containing
deionized water (400 ml) to form a slurry.
[0554] H2PtCl6»2H2O (0.282) was dissolved in deionized
water (80 ml) to form a clear solution. The platinum
solution was added to the slurry incrementally over the
course of 40 minutes (i.e., at a rate of approximately 2
ml/minute). The pH of the slurry was maintained at from
approximately 3.8-4.4 by co-addition of a 0.1 wt.% sodium
hydroxide solution. Approximately 2 ml of 0.1 wt% sodium
hydroxide solution was added to the slurry during addition
of the platinum solution.
[0555] After addition of the solution to the slurry
was complete, the slurry was stirred for 30 minutes with
the pH of the slurry maintained at approximately 4.4 by
addition of 0.1 wt.% sodium hydroxide solution.
[0556] The slurry was then heated under a nitrogen
blanket to 70 °C at a rate of about 2°C per minute while its
pH was maintained at 4.4. Upon reaching 70°C, the slurry
pH was increased by addition of a 0.1 wt.% sodium hydroxide
solution according to the following profile: the pH was
maintained at approximately 5.0 for 10 minutes after
addition of 1 ml of sodium hydroxide solution, increased to
5.5 by addition of 1 ml of sodium hydroxide solution and
maintained at that level for approximately 20 minutes, and
stirred for approximately 20 minutes, increased to 6.0 by
addition of 1 ml of 0.1 wt.% sodium hydroxide solution and
maintained for 10 minutes. A 12 wt.% solution of NaBH4
(0.38g) in deionized water (10 ml) was added to the slurry
at a rate of 2 ml/minute. The slurry was then heated to
70°C under a nitrogen blanket while agitated.
[0557] The resulting mixture was filtered and washed
with a plentiful amount of deionized water and the wet cake
was dried for approximately 16 hours in a vacuum oven at
120 °C.
[0558] After precursor deposition, platinumcontaining
catalyst (5.0 g) was charged into the tube
reactor described above in Example 23. The reactor was
purged with argon introduced to the reactor at a rate of
approximately 100 cm3/min at approximately 20°C for
approximately 15 minutes. A thermocouple was inserted into
the center of the reactor for charging the catalyst.
[0559] The temperature of the reactor was then
increased to approximately 850°C over the course of 120
minutes during which time a 5%/95% (v/v) mixture of
hydrogen and argon was introduced to the reactor at a rate
of approximately 100 cm3/minute.
[0560] The catalyst contained approximately 2.5% by
weight platinum and 1% by weight cobalt.
Example 37
[0561] This example details deposition of platinum
and iron onto a catalyst containing 1% by weight cobalt
prepared as described above in Example 27 using
acetonitrile.
[0562] A sample of the 1% by weight cobalt catalyst
(4.72 g) was added to a 1 liter flask containing deionized
water (400 ml) to form a slurry.
[0563] H2PtCl6«2H20 (0.282) and FeCl3«6H2O (0.071 g)
were dissolved in deionized water (80 ml) to form a clear
solution. The iron and platinum solution was added to the
slurry incrementally over the course of 40 minutes (i.e.,
at a rate of approximately 2 ml/minute). The pH of the
slurry was maintained at from approximately 4.0-4.4 by coaddition
of a 0.1 wt.% sodium hydroxide solution.
Approximately 2 ml of sodium hydroxide solution was added
to the slurry during addition of the platinum and iron
solution.
[0564] After addition of the solution to the slurry
was complete, the slurry was stirred for 30 minutes with
the pH of the slurry maintained at approximately 4.4.
[0565] The slurry was then heated under a nitrogen
blanket to 70°C at a rate of about 2°C per minute while its
pH was maintained at 4.4. Upon reaching 70°C, the slurry
pH was increased by addition of a 0.1 wt.% sodium hydroxide
solution according to the following profile: the pH was
maintained at approximately 5.0 for 10 minutes after
addition of 1 ml of 0.1 wt.% sodium hydroxide solution,
increased to 5.5 by addition of 2 ml of 0.1 wt.% sodium
hydroxide solution and maintained at that level for
approximately 20 minutes, and stirred for approximately 20
minutes during which time a constant pH of 6.0 was reached.
A 12 wt.% solution of NaBH4 (0.38g) in deionized water (10
ml) was added to the slurry at a rate of 2 ml/minute. The
slurry was then heated to 70°C under a nitrogen blanket
while agitated.
[0566] The resulting mixture was filtered and washed
with a plentiful amount of deionized water and the wet cake
was dried for approximately 16 hours in a vacuum oven at
120 °C.
[0567] After precursor deposition, platinum/iron -
containing catalyst (5.0 g) was charged into the tube
reactor described above in Example 22 and treated in a
hydrogen/argon atmosphere as described in Example 36.
[0568] The catalyst contained approximately 2.5% by
weight platinum, 0.3% by weight iron, and 1% by weight
cobalt.
Example 38
[0569] This example details deposition of platinum
and cobalt onto a catalyst containing 1% by weight cobalt
prepared as described above in Example 27 using
acetonitrile.
[0570] A sample of the 1% by weight cobalt catalyst
(5.055 g) was added to a 1 liter flask containing deionized
water (400 ml) to form a slurry.
[0571] H2PtCl6«2H20 (0.302) and CoCl2»2H20 (0.044 g)
were dissolved in deionized water (80 ml) to form a clear
solution. The platinum solution was added to the slurry
incrementally over the course of 40 minutes (i.e., at a
rate of approximately 2 ml/minute). The pH of the slurry
was maintained at from approximately 3.5-4.0 by co-addition
of a 0.1 wt.% sodium hydroxide solution. Approximately 2
ml of sodium hydroxide was added to the slurry during
addition of the platinum solution.
[0572] After addition of the solution to the slurry
was complete, the slurry was stirred for 30 minutes with
the pH of the slurry maintained at approximately 4.4 by
addition of 1 ml of a 0.1 wt.% sodium hydroxide solution.
[0573] The slurry was then heated under a nitrogen
blanket to 70°C at a rate of about 2°C per minute while its
pH was maintained at 4.4. Upon reaching 70°C/ the slurry
pH was increased by addition of a 0.1 wt.% sodium hydroxide
solution according to the following profile-, the pH was
maintained at approximately 5.0 for 10 minutes after
addition of 1 ml of 0.1 wt.% sodium hydroxide solution,
increased to 5.5 by addition of 2 ml of 0.1 wt.% sodium
hydroxide solution and maintained at that level for
approximately 20 minutes, and stirred for approximately 20
minutes during which time a constant pH of 6.0 was reached.
The pH was then increased to approximately 8.0 by addition
of 1 ml of 0.1 wt.% sodium hydroxide solution and heated to
70°C under a nitrogen blanket.
[0574] The resulting mixture was filtered and washed
with a plentiful amount of deionized water and the wet cake
was dried for approximately 16 hours in a vacuum oven at
120 °C.
[0575] After precursor deposition, platinum/cobalt -
containing catalyst (5.0 g) was charged into the tube
reactor described above in Example 27 and treated in a
hydrogen/argon atmosphere as described in Example 36.
[0576] The catalyst contained approximately 2.5% by
weight platinum and 1.3% by weight cobalt (1% from the
preparation procedure described above in Example 27 and
0.3% from the deposition procedure detailed in the present
example) .
Example 39
[0577] This example details use of the catalysts
prepared in Examples 36 to 38 in PMIDA oxidation under the
conditions described in Example 24.
[0578] The 2.5% platinum, 1% cobalt catalyst prepared
in Example 36 was tested under the PMIDA oxidation
conditions described above in Example 24 over the course of
3 reaction cycles.
[0579] The 2.5% platinum, 1% cobalt catalyst also
containing an additional 0.3% by weight cobalt prepared in
Example 38 was tested under the PMIDA oxidation conditions
described above in Example 24 over the course of 3 reaction
cycles.
[0580] The 2.5% platinum, 0.3% iron, 1% cobalt
catalyst prepared in Example 37 was tested under the PMIDA
oxidation conditions described above in Example 24 over the
course of 2 reaction cycles. -
[0581] The 2.5% platinum, 0.3% iron, 1% cobalt
catalyst prepared in Example 37 was also tested under the
PMIDA oxidation conditions described above in Example 24
during a reaction cycle in which a bismuth oxide promoter
(Bi203) (10 mg) was added to the reaction mixture.
[0582] The 2.5% platinum, 0.3% iron, 1% cobalt
catalyst prepared in Example 37 was also tested under the
PMIDA oxidation conditions described above in Example 24
during 4 reaction cycles in which a bismuth oxide promoter
(Bi203) (10 mg) was added to the reaction mixture during the
fourth cycle.
[0583] The maximum CO2 proportion in the exit gas,
total C02 generated during each of the reaction cycles,
remaining formaldehyde content in the reaction, formic acid
content in the reaction mixture, and platinum leaching for
each of the testings are summarized below in Table 21.
Table 21 Reaction results from different catalysts
Catalyst
(Table Removed)
[0584] The performance of each of the catalysts was
similar to that of the catalyst mixture prepared and tested
in Example 35. The first cycle performance of each of the
catalysts was similar to the performance of the platinum
and iron catalyst prepared in accordance with Ebner et al.,
6,417,133 tested above in Example 35, even though the
catalysts tested in the present example contained half the
platinum loading. However, the catalysts tested in the
present example declined in subsequent cycles in both
stability and activity toward formaldehyde and formic acid
oxidation. Eventually the catalysts tested in the present
example behaved similar to the 1% cobalt-containing
catalysts described and tested above in Example 28 in terms
of an increase in formic acid content without its further
oxidation to CO2. Each of the catalysts exhibited minimal
platinum leaching, evidence that the Pt had become
inactive.
[0585] The bismuth promoter was introduced in certain
reaction cycles to determine if the platinum was initially
inactive in the fresh mixed catalyst or whether it became
inactive in subsequent cycles.
[0586] When bismuth was introduced to the reaction
mixture in the 1st reaction cycle, catalyst performance was
at least equal to that of the platinum and iron-containing
catalyst prepared in accordance with Ebner et al. ,
6,417,133 described and tested above in Example 35 in terms
of formaldehyde and formic acid oxidation. This indicated
that the Pt was active in the first reaction cycle.
[0587] When bismuth was added in the 4th reaction
cycle', catalyst performance was not affected. The
platinum/iron-containing catalyst responded to inclusion of
a bismuth promoter the same manner as the 1% cobalt
catalyst described and tested above in Example 28. This
suggested that the initially active Pt in the
platinum/iron-containing catalyst was rendered inactive in
subsequent reaction cycles.
Example 40
[0588] Various carbon-supported cobalt carbidenitride
catalysts were prepared in accordance with the
process described above in Example 27 generally by varying
the atmosphere introduced to the reactor.
[0589] Methane/hydrogen environment: A carbonsupported
cobalt carbide-nitride catalyst containing 1% by
weight cobalt was prepared as described in Example 27 under
a methane/hydrogen environment from the precursor prepared
in accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 100 cm3/minute of a 50%/50% (v/v) mixture
of methane and hydrogen.
[0590] Ammonia reactor environment: A carbonsupported
cobalt carbide-nitride catalyst containing 1% by
weight cobalt was prepared as described in Example 27 under
an NH3 environment from the precursor prepared in
accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 50 cm3/minute NH3 and 100 cm3/minute of
argon.
[0591] Ammonia reactor environment: A carbonsupported
cobalt carbide-nitride catalyst containing 1% by
weight cobalt was prepared as described in Example 27 under
an NH3 environment from the precursor prepared in
accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 50 cm3/minute NH3, 20 cm3/minute hydrogen,
and 100 cm3/minute of argon.
[0592] Ammonia/methane reactor environment: A carbonsupported
cobalt carbide-nitride catalyst containing 1% by
weight cobalt was prepared as described in Example 27 under
an NH3/CH4 environment from the precursor prepared in
accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 25 cm3/minute NH3, 25 cm3/minute of a
50%/50% (v/v/) mixture of hydrogen/methane, and 100
cm3/minute of argon.
[0593] Acetonitrile reactor environment: A carbonsupported
cobalt carbide-nitride catalyst containing 1% by
weight cobalt was prepared as described in Example 27 under
an acetonitrile-containing environment from the precursor
prepared in accordance with the procedure set forth above
in Example 26. Catalyst precursor (5.0 g) was treated in
the reactor using a flow of 100 cm3/minute argon and
approximately 10 cm3/minute of acetonitrile vapor.
[0594] Butylamine environment: A carbon-supported
cobalt carbide-nitride catalyst containing 1% by weight
cobalt was prepared as described in Example 27 under a
butylamine-containing environment from the precursor
prepared in accordance with the procedure set forth above
in Example 26. Catalyst precursor (5.0 g) was treated in
the reactor using a flow of 100 cm3/rninute argon and
approximately 15 cm3/minute of butylamine vapor.
[0595] Pyridine environment: A carbon-supported
cobalt carbide-nitride catalyst containing 1% by weight
cobalt was prepared as described in Example 27 under a
pyridine-containing environment from the precursor prepared
in accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 100 cm3/minute argon and approximately 3
cm3/minute of pyridine vapor.
[0596] Pyrrole environment: A carbon-supported cobalt
carbide-nitride catalyst containing 1% by weight cobalt was
prepared as described in Example 27 under a pyrrolecontaining
environment from the precursor prepared in
accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) was treated in the reactor
using a flow of 100 cm3/minute argon and approximately 2
cm3/minute of pyrrole vapor.
[0597] Picolonitrile environment: A carbon-supported
cobalt carbide-nitride catalyst containing 1% by weight
cobalt was prepared as described in Example 27 under a
picolonitrile-containing environment from the precursor
prepared in accordance with the procedure set forth above
in Example 26. Catalyst precursor (5.0 g) and
picolonitrile (3 g) were treated in the reactor using a
flow of 100 cm3/minute argon.
[0598] Melamine environment: A carbon-supported
cobalt carbide-nitride catalyst containing 1% by weight
cobalt was prepared as described in Example 27 under a
melamine-containing environment from the precursor prepared
in accordance with the procedure set forth above in Example
26. Catalyst precursor (5.0 g) and melamine (1 g) were
treated in the reactor using a flow of 100 cm3/minute
argon.
[0599] A carbon-supported cobalt containing catalyst
was prepared using an organometallic compound
(cobalt(II)phthalocyanine).
[0600] A particulate carbon support (5.0 g) having a
Langmuir surface area of approximately 1500 m2/g and
acetone (200 ml) (Aldrich, Milwaukee, WI) were added to a 1
liter flask to form a slurry. Cobalt(II)phthalocyanine
(0.490 g) was dissolved in acetone (200 ml) contained in a
1 liter flask. The cobalt-containing solution was added to
the carbon support slurry over the course of approximately
30 to 40 minutes.
[0601] The slurry was stirred using a mechanical
stirring rod at 50% output at approximately 20°C for 48
hours under a nitrogen blanket. The slurry was filtered
and dried in a vacuum oven for approximately 16 hours at
120°C under a small nitrogen flow of approximately 20
cm3/minute. The resulting precursor contained
approximately 1% by weight cobalt.
[0602] Dried catalyst precursor (5.0 g) was charged
to the Hastelloy C tube reactor described in Example 23.
The reactor was purged with argon introduced at a rate of
approximately 100 cm3/niinute at approximately 20°C for
approximately 15 minutes. A thermocouple was inserted into
the center of the reactor for charging the precursor
material.
[0603] The temperature of the reactor was then
increased to approximately 950°C over the course of
approximately 45 minutes under a flow of argon of 100
cc/min. The temperature of the reactor was maintained at
approximately 950°C for approximately 120 minutes. The
resulting catalyst contained approximately 1% by weight
cobalt.
Example 41
[0604] This example details the results of PMIDA
oxidations carried out under the conditions described above
in Example 24 using each of the catalysts prepared
described above in Example 40 using the various
environments. The results are shown in Table 22.
Table 22 Reaction results from catalysts synthesized at
950°C under different environments
(Table Removed)
[0605] As shown in Table 22, catalysts prepared from
CH4/H2/ NH3, (NH3 and H2) , and (CH4/H2 and NH3) exhibited
lower activity as compared to catalysts made from CH3CN,
butylamine, pyridine, pyrrole, picolinonitrile, melamine,
and cobalt phthalocyanine. Each cobalt catalyst exhibited
formaldehyde oxidation activity when the reaction was
driven to greater than 80% PMIDA conversion.
Example 42
[0606] This example details preparation of cobaltcontaining
catalysts having varying metal loadings and
their use in PMIDA oxidation to N- (phosphonoinethyl) glycine.
[0607] Each of the catalysts were synthesized using
an acetonitrile environment in accordance with the
procedure set forth above in Example 40. Each of the
catalysts was then tested in PMIDA oxidation under the
conditions described above in Example 24. The results of
each of the PMIDA oxidations are set out below in Table 23.
Table 23 Reaction results from CoCN/C synthesized by CH3CN
(Table Removed)
[0608] As shown in Table 23, all carbon-supported
cobalt carbide-nitride catalysts exhibited good PMIDA
oxidation activity. The catalysts also demonstrated higher
formaldehyde oxidation activity and much better stability
compared to the carbon-supported iron carbide-nitride
catalyst. The carbon-supported cobalt carbide-nitride
catalyst containing 1-2% by weight cobalt exhibited the
best overall reaction performance.
Example 43
[0609] This example details the preparation of a
carbon-supported iron carbide-nitride precursor from
tetraphenylporphyrin (FeTPP) precursor.
[0610] A carbon support (8.0 g) was added to a 1 liter
flask and charged with 400 ml of acetone to form a slurry.
A solution (200 ml) containing iron (III)
tetraphenylporphyrin chloride (FeTPP) (2.0 g) in acetone
was added drop wise to the carbon slurry for 30-40 minutes.
The slurry was then stirred at room temperature for 48
hours under a nitrogen blanket.
[0611] The resulting mixture was filtered and dried
overnight in a vacuum oven at 120 °C under a small nitrogen
flow. The resulting precursor contained approximately 1.1%
by weight iron.
Example 44
[0612] This example details subjecting catalysts
prepared in accordance with the procedures set forth above
25 in Example 23 and 43 to the PMIDA oxidation conditions
described in Example 24. Results are shown in Table 24.
Table 24 Reaction results from iron catalysts synthesized
under different environment
(Table Removed)
[0613] All of the carbon-supported iron carbidenitride
catalysts suffered from catalyst deactivation.
Both the maximum CO2 concentration and the cumulative C02
decreased with subsequent reaction cycles. The catalyst
synthesized from iron (III) tetraphenylporphyrin showed
high PMIDA oxidation activity but produces a large amount
of formaldehyde, aminomethylphosphonic acid, and N-methylaminophosphonic
acid and exhibited little activity toward
the oxidation of formaldehyde and formic acid. The
catalyst synthesized from CH3CN exhibited PMIDA oxidation
activity and formaldehyde oxidation activity.
Example 45
[0614] This examples details preparation of molybdenum
and tungsten-containing catalysts in different carbiding
environments and their use in PMIDA oxidation under the
conditions described in Example 24.
[0615] Molybdenum and tungsten-containing catalysts
were prepared as described above in Example 3 from
precursors prepared as described in Example 2 using a flow
of approximately 100 cm3/min in place of the 50%/50% (v/v)
mixture of methane and hydrogen as described in Example 3.
[0616] Catalysts containing 1% by weight molybdenum
and 1% by weight tungsten prepared in accordance with the
present Example were tested under the PMIDA oxidation
conditions described in Example 24. A catalyst containing
10% by weight molybdenum carbide prepared as described in
Example 3 and catalysts containing 10% by weight tungsten
nitride prepared as described in Example 3 at varying
temperatures were also tested.
[0617] The results are shown in Table 25.
Table 25 Reaction results from catalysts synthesized under
different environment
(Table Removed)
[0618] The catalysts prepared using CH3CN treatment
had superior PMIDA oxidation activity and formaldehyde
oxidation activity as compared to the catalysts prepared by
CH4/H2 treatment.
Example 46
[0619] This example details electroless copper plating
on a 1% by weight cobalt catalyst prepared as described
above in Example 27 prepared using acetonitrile.
[0620] 1% by weight cobalt catalyst (15.5 g) was added
to a 1 liter flask containing nitrogen-sparged water (364
ml) to form a slurry. The flask was fitted with a
thermocouple, a nitrogen flow inlet, and mechanical
stirrer.
[0621] A copper plating solution was prepared by
adding reagant grade copper sulfate (CuSO4«5H2O) (20.65 g)
(Aldrich Chemical Co., Milwaukee, WI) and 91.2% tetrasodium
ethylenediamine tetraacetate (EDTANaJ (41.82 g) to
nitrogen-sparged water (950 ml). The mixture was cooled to
approximately 10°C and plating solution was added to the
catalyst-containing slurry. A solution of 37% by weight
formalin (20.13) in nitrogen-sparged water (305 ml) was
prepared and added dropwise to the plating mixture over the
course of 90 minutes.
[0622] The pH of the plating solution was monitored
using a pH meter during addition of the formalin-containing
solution. During the 90 minutes of addition of formalincontaining
solution, the pH of the plating mixture changed
from 13.65 (at 9.4°C), to 13.4 (at 10.8°C) and finally to
13.2 (at 11.7°C). The plating mixture was agitated for
approximately 30 minutes.
[0623] Plated catalyst was allowed to settle out of
the plating mixture and the catalyst was recovered from the
mixture by filtration under a nitrogen atmosphere. A
filtrate (1533 g) was recovered from the mixture. The
resulting wet cake was dried in nitrogen purged vacuum for
approximately 8 hours. The dried catalyst weighed
approximately 20.21 grams and Inductively Coupled Plasma
(ICP) analysis provided a copper content of approximately
22.5% by weight.
Example 47
[0624] The example details use of the coppercontaining
catalyst prepared as described in Example 46 for
the dehydrogenation of diethanolamine.
[0625] Dehydrogenation of diethanolamine was conducted
in a 300 ml autoclave reactor constructed of Hastelloy C
(high strength nickel-based alloy) and equipped with a back
pressure regulator, H2 mass flow meters, and a charge pot
which allowed reagents and rinse water to be added to the
reactor under inert gas.
[0626] The reactor was first flushed with argon (when
conducting this reaction on a commercial scale, N2 would be
preferred). A mixture containing a 50 wt.% solution of
sodium hydroxide (99.81 g) (Aldrich Chemical Co.,
Milwaukee, WI), diethanolamine (62.50 g) (Huntsman
Chemicals), 22.5% copper/1% cobalt catalyst prepared as
described in Example 46 (12.4 g), and deionized water (75
ml) to produce a total reaction mixture of 250 grams. The
reactor was purged with nitrogen and pressurized to 135
psig with nitrogen. The reaction mixture was then heated
to 150°C while agitated over the course of two hours.
Based on the amount of hydrogen generated during the
reaction, conversion of diethanolamine to disodium
iminodiacetic was approximately 1%.
Example 48
[0627] Various carbon-supported transition metalcontaining
catalysts and their supports were analyzed to
determine their Langtnuir surface areas. Catalysts and
supports tested included: the carbon support described
above in Example 22, a !%FeCN/C catalyst prepared in
accordance with Example 23, a 1% CoCN/C catalyst prepared
in accordance with Example 27, a carbon support having a
surface area of approximately 1600 m2/g, and a 1% FeTPP/C
catalyst prepared in accordance with Coleman et al.,
International Publication No. WO 03/068387 Al. The overall
surface area, surface area attributed to pores having a
diameter less than 20A (i.e., micropores), and surface area
attributed to pores having a diameter greater than 20A
(i.e., mesopores and micropores) were determined. The
results of the surface area measurements are shown in Table
26.
Table 26
(Table Removed)
[0628] Fig. 17 shows a comparison of the pore surface
area of the of the 1% Fe, 1% Co catalysts, and the carbon
support. Fig. 18 compares the pore surface area of the
1.1% FeTPP catalyst and its carbon support. As shown in
Fig. 17, the 1% Fe catalyst has a surface area
approximately 80% the total surface area of its carbon
support while the 1% Co catalyst has a surface area
approximately 72% the total surface area of the catalyst
support. As shown in Fig. 18, the 1.1% FeTPP catalyst has
a surface area approximately 55% of the total surface area
of its carbon support.
Example 49
[0629] 1% CoCN/C and 1.5% CoCN/C catalysts prepared as
described in Example 28 were analyzed by Inductively
Coupled Plasma (ICP) analysis to determine their nitrogen
and transition metal content. The results are shown in
Table 27.
Table 27
(Table Removed)
Example 50
[0630] This example details X-ray powder diffraction
analysis (XRD) analysis of various catalysts prepared under
different conditions. The catalysts were generally
prepared in accordance with the procedure set forth above
in Example 23, 27, 40, or 43 above. The samples and
conditions for their preparation are described below in
Table 28.
Table 28
(Table Removed)
[0631] The powder samples were analyzed by placing
them directly onto a zero background holder and then
placing them directly into a Philips PW 1800 8/6
diffractometer using Cu radiation at 40 KV/BOmA and
equipped with a diffracted beam monochromator to remove the
floursecent radiation from the cobalt.
[0632] The resulting diffraction patterns for samples
1-8 are shown in Figs. 19-26, respectively. The
diffraction patterns for samples 1-4, and 6 (Figs. 19-22,
and 24) detected graphite and the face centered cubic (FCC)
form of cobalt. Particle size analysis of the cobalt and
graphite phases was performed through broadening of the
diffraction lines which is sensitive to particles in the
100 A to 2000 A range. The results are summarized below in
Table 29.
Table 29
(Table Removed)
[0633] The diffraction patterns for sample 7 (Fig. 25)
detected graphite and iron carbide (Fe3C) Particle size
analysis provided a particle size of the graphite of >1000
A and approximately 505 A. The diffraction patterns for
sample 8 (Fig. 26) detected graphite, chromium nitride
(CrN), iron nitide (FeN), chromium, and iron carbide
(Fe3C) . Particle size analysis provided a particle size of
graphite of approximately 124 A, chromium nitride of
approximately 183 A, and iron nitride of approximately 210
A.
[0634] Quantitative analysis was carried out on
Samples 1 and 2. The preferred internal standard was ZnO
since it is well characterized and has no lines that
overlap the peaks of interest. Approximately 100 mg of
samples 1 and 2 were mixed with 10.7% ZnO (Sample 1) and
4.89% ZnO (Sample 2) and tested using the XRD procedure
described above. The resulting diffraction for patterns
for Samples 1 and 2 are provided in Figs. 27 and 28,
respectively.
[0635] Quantitative analysis was then carried out on
Samples 1 and 2 using Rivetfeld refinement to determine the
amount of each phase. The Rivetfeld refinement is a whole
pattern-fitting program that computes a diffraction pattern
based on first principles, compares it to the experimental
pattern, computes an error between the two patterns, and
then modifies the theoretical pattern until the residual
error is minimized. In both cases, the Rivetfeld
refinement gave loq residual errors in the 5-7% range. The
results of the Rivetfeld refinement are set forth below in
Table 30.
Table 30
(Table Removed)
[0636] An estimate of the weight fractions of Samples
3 and 6 are provided in Table 31.
Table 31
(Table Removed)
[0637] Figs. 29 and 30 provide comparisons of the
diffraction patterns of Samples 2 and 3, and Samples 3 and
6, respectively.
Example 51
[0638] This example details scanning electron
microscopy (SEM) and transmission electron microscopy (TEM)
analysis of Samples 1, 2, 4, 7, and 8 described above in
Example 50. The SEM analysis was performed using a JEOL
JSM 6460LV scanning electron microscope operated at 30kV.
The TEM characterizations were carried out using a JEOL
1200 EX TEM operated at 120 keV and/or JEOL 2000 EX TEM
operated at 200 keV.
[0639] Figs. 31 and 32 are SEM images showing a view
of the powder of Sample 1 and a cross-sectional view,
respectively. Figs. 33 and'34 are SEM images showing the
distribution of carbon nanotubes on the surface of the
carbon substrate and the morphology of the carbon
nanotubes, respectively. Figs. 35 and 36 are SEM images
showing the carbon nanoutubes of the powder sample of
Sample 1.
[0640] Figs. 37 and 38 are SEM images showing a view
of the powder of Sample 2 and a cross-sectional view,
respectively. Figs. 39 and 40 are SEM images showing the
distribution of the cobalt particles on the powder sample
of Sample 2 and cross-sectional view, respectively. Fig.
41 is an SEM image showing the carbon nanotubes on the
surface of the carbon support. Fig. 42 is an Energy
dispersive X-ray analysis spectroscopy (EDS) spectrum of
the powder sample of Sample 2. The EDS spectrum of Sample
2 was determined using an Oxford energy dispersive X-ray
spectroscopy system.
[0641] Figs. 43 and 44 are TEM image images of Sample
4 at low and high magnification, respectively.
[0642] Fig. 45 is an SEM image of a powder sample of
Sample 7. Fig. 46 is a backscattered electron image of the
powder sample of Sample 7.
[0643] Figs. 47 and 48 are TEM images showing a crosssectional
view of Sample 7.
[0644] Fig. 49 is an SEM image of a powder sample of
Sample 8. Fig. 50 is a backscattered electron image of the
powder sample of Sample 8. Figs. 51 and 52 are high
magnification SEM images of powder sample 8 showing the
growth of carbon nanotubes on the carbon support. Figs. 53
and 54 are TEM images providing a cross-sectional view of
Sample 8.
Example 52
[0645] This examples details X-ray Photoelectron
Spectroscopy Analysis (XPS) of the samples described above
in Example 50 (detailed in Table 28).
[0646] The XPS analysis was performed under the
analytical conditions set forth in Table 32.
Table 32
(Table Removed)
[0647] Surface concentration results (area comment)
for Samples 1-6 in terms of Atomic % and Weight % are
detailed below in Tables 33 and 34, respectively.
Table 33
(Table Removed)
[0648] The cobalt 2p3 curve fit results for samples 1-
4 and 6 are summarized below in Table 35.
Table 35
(Table Removed)
[0649] Surface concentration results (area comment)
for Samples 7-8 in terms of Atomic % and Weight % are
detailed below in Tables 36 and 37, respectively.
Table 36
(Table Removed)
[0650] The iron curve fit results (% of Fe) for
samples 7-8 are summarized below in Table 38.
Table 38
(Table Removed)
[0651] Fig. 54 is the XPS spectra for samples 1-6,
Fig. 55 shows the XPS spectra for samples 7 and 8.
* * * * * * * *
The present invention is not limited to the above
embodiments and can be variously modified. - The above
description of the preferred embodiments, including the
Examples, is intended only to acquaint others skilled in
the art with the invention, its principles, and its
practical application so that others skilled in the art may
adapt and apply the invention in its numerous forms, as may
be best suited to the requirements of a particular use.
With reference to the use of the word(s) comprise or
comprises or comprising in this entire specification
(including the claims below), unless the context requires
otherwise, those words are used on the basis and clear
understanding that they are to be interpreted inclusively,
rather than exclusively, and applicants intend each of
those words to be so interpreted in construing this entire
specification.
















We Claim:
1. A process for oxidizing
N-(phosphonomethyl)iminodiacetic acid or a salt thereof, the process comprising
contacting
N-(phosphonomethyl)iminodiacetic acid or a salt thereof with an oxidizing agent in the
presence of a transition metal containing oxidation catalyst comprising a carbon support
having formed thereon a transition metal composition comprising a transition metal and
nitrogen, wherein the process is characterized in that:
the oxidation catalyst is substantially devoid of a noble metal active phase, and
the oxidation catalyst comprises carbon nanotubes at the surface of the carbon support.
2. A process as claimed in claim 1 wherein said carbon nanotubes contain a portion of the transition metal of said transition metal composition.
3. A process as claimed in claim 1 or 2 wherein said carbon nanotubes contain a portion of the nitrogen of said transition metal composition.
4. A process as claimed in any of claims 1 to 3 wherein said transition metal composition comprises a transition metal selected from the group consisting of copper, silver, vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, ruthenium, cerium, and combinations thereof.
5. A process as claimed in claim 4 wherein said transition metal composition comprises a transition metal selected from the group consisting of chromium, iron, cobalt and combinations thereof.
6. A process as claimed in claim 4 wherein said transition metal composition comprises cobalt.
7. A process as claimed in any of claims 1 to 3 wherein said transition metal composition comprises a transition metal other than cobalt selected from the group consisting of copper, silver, vanadium, chromium, molybdenum, tungsten, manganese, iron, nickel, ruthenium, cerium, and combinations thereof.

8. A process as claimed in claim 6 wherein said transition metal composition comprises a transition metal other than cobalt selected from the group consisting of chromium, iron, and a combination thereof.
9. A process as claimed in any of claims 1 to 3 wherein said transition metal composition comprises a plurality of transition metals, wherein the plurality of transition metals comprises cobalt and a transition metal selected from the group consisting of copper, silver, vanadium, chromium, molybdenum, tungsten, manganese, nickel, ruthenium, cerium, and combinations thereof.
10. A process as claimed in any of claims 1 to 9 wherein the transition metal composition comprises a transition metal nitride, transition metal carbide-nitride, or a combination thereof.
11. A process as claimed in claim 10 wherein the transition metal composition comprises a transition metal nitride.
12. A process as claimed in any of claims 1 to 11 wherein said transition metal containing oxidation catalyst comprises a particulate carbon support.
13. A process as claimed in any of claims 1 to 12 wherein the total Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon is at least 1000 m2/g.
14. A process as claimed in claim 13 wherein the total Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon is from 1000 to 1600 m2/g.
15. A process as claimed in any of claims 1 to 14 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is at least 600 m2/g.
16. A process as claimed in claim 15 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is at least 1000 m2/g.

17. A process as claimed in claim 15 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is at least 1200 m2/g.
18. A process as claimed in claim 15 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is from 1000 to 1400 m2/g.
19. A process as claimed in any of claims 1 to 18 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is at least 60% of the total Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon.
20. A process as claimed in claim 19 wherein the total Langmuir surface area of said transition metal containing oxidation catalyst is from 60 to 80% of the total Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon.
21. A process as claimed in any of claims 1 to 20 wherein the micropore Langmuir surface area of said transition metal containing oxidation catalyst is at least 750 m2/g.
22. A process as claimed in claim 21 wherein the micropore Langmuir surface area of said transition metal containing oxidation catalyst is from 750 to 1100 m2/g.
23. A process as claimed in any of claims 1 to 22 wherein the micropore Langmuir surface area of said transition metal containing oxidation catalyst is at least 55% of the micropore Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon.
24. A process as claimed in claim 23 wherein the micropore Langmuir surface area of said transition metal containing oxidation catalyst is from 55% to 80% of the micropore Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon.
25. A process as claimed in any of claims 1 to 24 wherein the combined mesopore and macropore Langmuir surface area of said transition metal containing oxidation catalyst is at least 175m2/g.

26. A process as claimed in claim 25 wherein the combined mesopore and macropore Langmuir surface area of said transition metal containing oxidation catalyst is from 175 to 300 m2/g.
27. A process as claimed in any of claims 1 to 26 wherein the combined mesopore and macropore Langmuir surface area of said transition metal containing oxidation catalyst is at least 70% of the combined mesopore and macropore Langmuir surface area of said carbon support prior to formation of said transition metal composition thereon.
28. A process as claimed in any of claims 1 to 27 wherein said transition metal composition formed on said carbon support constitutes at least 0.1% by weight of said transition metal containing oxidation catalyst.
29. A process as claimed in claim 28 wherein said transition metal composition formed on said carbon support constitutes from 0.1% to 20% by weight of said transition metal containing oxidation catalyst.
30. A process as claimed in any of claims 1 to 29 wherein transition metal of said transition metal composition formed on said carbon support constitutes at least 0.1% by weight of said transition metal containing oxidation catalyst.
31. A process as claimed in claim 30 wherein transition metal of said transition metal composition formed on said carbon support constitutes from 0.1% to 20% by weight of said transition metal containing oxidation catalyst.
32. A process as claimed in any of claims 1 to 31 wherein said nitrogen of said transition metal composition formed on said carbon support constitutes at least 0.1% by weight of said transition metal containing oxidation catalyst.
33. A process as claimed in claim 32 wherein said nitrogen of said transition metal composition formed on said carbon support constitutes from 0.1% to 5% by weight of said transition metal containing oxidation catalyst.

34. A process as claimed in any of claims 1 to 33 wherein said transition metal composition on said carbon support comprises discrete particles.
35. A process as claimed in claim 34 wherein at least 95% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 1000 nm.
36. A process as claimed in claim 34 wherein at least 80% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 250 nm.
37. A process as claimed in claim 34 wherein at least 60% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 18 nm.
38. A process as claimed in claim 34 wherein at least 20% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 1 nm.
39. A process as claimed in claim 34 wherein from 20 to 100% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 1 nm.
40. A process as claimed in claim 34 wherein from 20 to 95% by weight of said transition metal composition particles have a particle size, in their largest dimension, of less than 1 nm.
41. A process as claimed in any of claims 1 to 40 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that when a representative aqueous solution containing 0.8% by weight formaldehyde and a pH of 1.5 is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C, at least 5% of said formaldehyde is converted to formic acid, carbon dioxide and/or water.

42. A process as claimed in claim 41 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 10% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
43. A process as claimed in claim 41 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 15% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
44. A process as claimed in claim 41 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 20% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
45. A process as claimed in claim 41 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 30% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
46. A process as claimed in any of claims 1 to 45 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that when a representative aqueous solution containing 0.8% by weight formaldehyde and 6% by weight of N-(phosphonomethyl)iminodiacetic acid and having a pH of 1.5 is contacted with an oxidizing agent in the presence of said transition

metal containing oxidation catalyst at a temperature of 100°C, at least 50% of said formaldehyde is converted to formic acid, carbon dioxide and/or water.
47. A process as claimed in claim 46 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 60% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
48. A process as claimed in claim 46 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 70% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
49. A process as claimed in claim 46 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 80% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
50. A process as claimed in claim 46 wherein said transition metal containing oxidation catalyst is characterized by its effectiveness for catalyzing the oxidation of formaldehyde such that at least 90% of said formaldehyde in said representative aqueous solution is converted to formic acid, carbon dioxide and/or water when said representative aqueous solution is contacted with an oxidizing agent in the presence of said transition metal containing oxidation catalyst at a temperature of 100°C.
51. A process as claimed in any of claims 1 to 50 wherein said N-(phosphonomethyl)iminodiacetic acid or a salt thereof is oxidized to form N-(phosphonomethyl)glycine or a salt thereof.

52. A process as claimed in any of claims 1 to 51 wherein said transition metal containing oxidation catalyst is effective for oxidation of byproduct formaldehyde produced in the oxidation of N-(phosphonomethyl)iminodiacetic acid or a salt thereof.
53. A process as claimed in any of claims 1 to 52 wherein N-(phosphonomethyl) iminodiacetic acid or a salt thereof is contacted with the oxidizing agent in the presence
. of a catalyst system comprising the transition metal containing oxidation catalyst and a noble metal containing catalyst.

Documents:

713-DELNP-2006-Abstract-(11-06-2010).pdf

713-delnp-2006-Abstract-(28-10-2010).pdf

713-delnp-2006-abstract.pdf

713-DELNP-2006-Assignment-(11-06-2010).pdf

713-DELNP-2006-Claims-(11-06-2010).pdf

713-delnp-2006-Claims-(28-10-2010).pdf

713-delnp-2006-claims.pdf

713-DELNP-2006-Correspondence-Others-(06-01-2011).pdf

713-DELNP-2006-Correspondence-Others-(10-05-2006).pdf

713-DELNP-2006-Correspondence-Others-(11-06-2010).pdf

713-DELNP-2006-Correspondence-Others-(18-06-2010).pdf

713-DELNP-2006-Correspondence-Others-(21-12-2010).pdf

713-DELNP-2006-Correspondence-Others-(23-12-2010).pdf

713-delnp-2006-Correspondence-Others-(28-10-2010).pdf

713-delnp-2006-correspondence-others-1.pdf

713-delnp-2006-correspondence-others.pdf

713-DELNP-2006-Description (Complete)-(11-06-2010).pdf

713-delnp-2006-description (complete).pdf

713-DELNP-2006-Drawings-(11-06-2010).pdf

713-delnp-2006-drawings.pdf

713-DELNP-2006-Form-1-(11-06-2010).pdf

713-DELNP-2006-Form-1-(18-06-2010).pdf

713-delnp-2006-form-1.pdf

713-delnp-2006-form-18.pdf

713-DELNP-2006-Form-2-(11-06-2010).pdf

713-delnp-2006-form-2.pdf

713-DELNP-2006-Form-3-(06-01-2011).pdf

713-DELNP-2006-Form-3-(11-06-2010).pdf

713-DELNP-2006-Form-3-(21-12-2010).pdf

713-delnp-2006-Form-3-(28-10-2010).pdf

713-delnp-2006-form-3.pdf

713-DELNP-2006-Form-5-(18-06-2010).pdf

713-delnp-2006-form-5.pdf

713-DELNP-2006-GPA-(10-05-2006).pdf

713-DELNP-2006-GPA-(11-06-2010).pdf

713-delnp-2006-pct-101.pdf

713-delnp-2006-pct-210.pdf

713-delnp-2006-pct-220.pdf

713-delnp-2006-pct-237.pdf

713-delnp-2006-pct-304.pdf

713-delnp-2006-pct-401.pdf

713-delnp-2006-pct-409.pdf

713-delnp-2006-pct-416.pdf

713-DELNP-2006-Petition 137-(11-06-2010)-1.pdf

713-DELNP-2006-Petition 137-(11-06-2010).pdf


Patent Number 245635
Indian Patent Application Number 713/DELNP/2006
PG Journal Number 05/2011
Publication Date 04-Feb-2011
Grant Date 28-Jan-2011
Date of Filing 13-Feb-2006
Name of Patentee MONSANTO TECHNOLOGY, LLC.
Applicant Address 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
Inventors:
# Inventor's Name Inventor's Address
1 FUCHEN LIU C/O MONSANTO TECHNOLOGY LLC, 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
2 JUAN ARHANCET C/O MONSANTO TECHNOLOGY LLC, 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
3 ROBERT MCCALL C/O MONSANTO TECHNOLOGY LLC, 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
4 DAVID A. MORGENSTERN C/O MONSANTO TECHNOLOGY LLC, 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
5 KAM-TO WAN C/O MONSANTO TECHNOLOGY LLC, 800 NORTH LINDBERGH BLVD., ST. LOUIS, MO 63167, USA
PCT International Classification Number B01J 27/22
PCT International Application Number PCT/US2004/026550
PCT International Filing date 2004-08-16
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/495,481 2003-08-14 U.S.A.