Title of Invention

A METHOD OF PRODUCING A CATALYST OR PRE-CATALYST SUITABLE FOR ASSISTING IN THE PRODUCTION OF ALKENYL ALKANOATES

Abstract The present invention addresses at least four different aspects relating to catalyst structure, methods of making those catalysts and methods of using those catalysts for making alkenyl alkanoates. Separately or together in combination, the various aspects of the invention are directed at improving the production of alkenyl alkanoates and VA In particular, including reduction of by-product and improved production efficiency. A first aspect of the present invention pertains to a unique palladium/gold catalyst or pre- catalyst (optionally calcined) that includes rhodium or another metal. A second aspect pertains to a palladium/gold catalyst or pre-catalyst that is based on a layered support material where on layer of the support material is substantially free of catalytic component. A third aspect pertains to a palladium/gold catalyst or pre-catalyst on a zirconia containing support material. A fourth aspect pertains to a patiadium/goid catalyst or pre-catalyst that is produced from substantially chloride fi'ee catalytic components.
Full Text Halide Free Precursors for Catalysts
Claim of Priority
[0001] This application claims the benefit of U.S. Provisional Application No. 60/530,937,
filed December 19,2003, which is hereby incorporated by reference.
Field of the Invention
[0002] The present invention relates to catalysts, methods of making the catalysts, and
methods of making alkenyl alkanoates. More particularly, the invention relates to methods of
making vinyl acetate.
Background of the Invention
[0003] Certain alkenyl alkanoates, such as vinyl acetate (VA), are commodity chemicals in
high demand in their monomer form. For example, VA is used to make polyvinyl acetate
(PVAc), which is used commonly for adhesives, and accounts for a large portion of VA use.
Other uses for VA included polyvinyl alcohol (PVOH), ethylene vinyl acetate (EVA)i vinyl
acetate ethylene (VAE), polyvinyl butyral (PVB), ethylene vinyl alcohol (EVOH), polyvinyl
formal (PVF), and vinyl chloride-vinyl acetate copolymer. PVOH is typically used for textiles,
films, adhesives, and photosensitive coatings. Films and wire and cable insulation often employ
EVA in some proportion. Major applications for vinyl chloride-vinyl acetate copolymer include
coatings, paints, and adhesives often employ VAE having VA in some proportion. VAE, which
contains more than 50 percent VA, is primarily used as cement additives, paints, and cufhesives.
PVB is mainly used for under layer in laminated screens, coatings, and inks. EVOH is used for
barrier films and engineering polymers. PVF is used for wire enamel and magnetic tape.
[0004] Because VA is the basis for so many commercially significant materials and products,
the demand for VA is large, and VA production is fi-equently done on a relatively large scale, e.g.
50,000 metric tons or more per year. This large scale production means that significant
economies of scale are possible and relatively subtle changes in the process, process conditions

or catalyst characteristics can have a significant economic impact on the cost of the production of
VA.
[0005] Many techniques have been reported for the production of alkenyl alkanoates. For
example, in making VA, a widely used technique includes a catalyzed gas phase reaction of
ethylene with acetic acid and oxygen, as seen in the following reaction:
I
side reactions may take place, including, such as, the formation of CO2. The results of this
reaction are discussed in terms of the space-time yield (STY) of the reaction system, where the
STY is the grams of VA produced par litw of catalyst per hour of reaction time (g/l*h).
[0006] The composition of the starting miUerial feed can be varied within wide limits.
Typically, the starting material feed includes 30-70% ethylene, 10-30% acetic acid and 4-16%
oxygen. The feed may also include inert materials such as CO2, nitrogen, methane, ethane,
propane, argon and'or helium. The primary restriction on feed composition is the oxygen level in
the effluent stream exiting the reactor must be sufiBciently low such that the stream is outside the
flammability zone. The oxygen level in the ef&uent is affected by the oxygen level in the starting
material stream, O2 conversion rate of the reaction and the amount of any inert material in the
effluent.
[0007] The gas phase reaction has been carried out where a feed of the starting materials is
passed over or through fixed bed reactors. Successful results have been obtained through the use
of reaction temperatures in the range of- 125'C to 200*'C, while reaction pressures of 1-15
atmospheres are typical.
[0008] While these systems have provided adequate yields, there continues to be a need for
reduced production of by-products, higher rates of VA ou^ut, and lower energy use during
production. One approach is to improve catalyst characteristics, particularly as to CO2 selectivity
and/or activity of the catalyst. Another ^proach is to modify reaction conditions, such as the
ratio of starting materials to each other, the O2 conversion of the reaction, the space velocity (SV)
of the starting material feed, and operating temperatures and pressures.
[0009] Tlie formation of CO2 is one aspect which may be reduced through the use of
improved catalysts. The CO2 selectivity is the percentage of the ethylene converted that goes to
CO2. Decreasing the CO2 selectivity permits a larger amount of VA per unit volume and unit
time in existing plants, even retaining all other reaction conditions.
[0010] VA output of a particular reaction system is affected by several other factors
including the activity of the catalyst, the ratio of starting materials to each other, the O2
conversion of the reaction, the space velocity (SV) of the starting material feed, and operating
temperatures and pressures. All these factors cooperate to determine the space-time yield (STY)
of the reaction system, where the STY is discussed m terms of grams.of VA produced per liter of
catalyst per hour of reaction time or g/l*h.
[0011] Generally, activity is.a significant factor in determining the STY, but other factors
may still have a significant impact on the STY. Typically, the higjher the activity of a catalyst,
the higher the S'rY the catalyst is able to produce.
[0012] The 02 conversion is a measure of how much oxygen reacts in the presence of the
catalyst. The O2 conversion rate is temperature dependent such that the conversion rate gaierally
climbs with the reaction temperature. However, the amount of CO2 produced also increases
along with the O2 conversion. Thus, the O2 conversion rate is selected to give the desired VA
output balanced against the amount of CO2 produced. A catalyst with a higher activity means
that the overall rejiction temperature can be lowered while maintaining the same 02 conversion.
Altematively, a catalyst with a higher activity will give a higher O2 conversion rate at a given
temperature and space velocity.
[0013] It is common that catalysts employ one or more catalytic components earned on a
relatively inert support material. In the case of VA catalysts, the catalytic components are
typically a mixture of metals that may be distributed uniformly throughout the support material
("all through-out catalysts"), just on the surface of the support material ("shell catalysts"), just
below a shell of support material ("egg white catalysts") or in the core of the support material
("egg yolk catalysts").
[0014] Numerous different types of support materials have been suggested for use in VA
catalyst including silica, ceriimi doped silica, alumina, titania, ziiconia and oxide mixtures. But
very little investigation of tibe differences between the suf^ort materials has been done. For the
most part, only silica and alumina have actually been commercialized as support materials.
[0015] One useful combination of metals for VA catalysis is palladiimi and gold. Pd/Au
catalysts provide adequate CO2 selectivity and activity, but there continues to be a need for
improved catalysts given the economies of scale that are possible in the production of VA.
[0016] One process for making Pd/Au catalysts typically includes the steps of itnpregnating
the siqjport with aqueous solutions of wato'-soluble salts of palladiimi and gold; reacting the
impregnated water-soluble salts with an appropriate alkaline compound e.g., sodium hydroxide,
to precipitate (of1:en called fixing) the metallic elements as water-insoluble compounds, e.g. the
hydroxides; wastung the fixed support matoial to remove un-fixed compounds and to otherwise
cleanse the catalyst of any potential poisons, e.g. chloride; reducing the water insoluble
compounds with a typical reductant such as hydrogen, ethylene or hydrazine, and adding an
alkali metal compound such as potassium or sodium acetate.
[0017] Various modifications to this basic process have been suggested. For example, in
U.S. Patent No. 5,990,344, it is suggested that sintering of the palladium be undotaken after the
reduction to its fiee metal form.. In U.S. Pat^it No. 6,022,823, it suggested that calcining the
support in a non-reducing atmosphere after impregnation with both palladium and gold salts
might be advantageous. In W094/21374, it is suggested that after reduction and activation, but
before its first use, the catalyst may be pretreated by successive heating in oxidizing, inert, and
reducing atmospheres.
[0018] In U.S. Patent No. 5,466,652, it is suggested that salts of palladium and gold that are
hydroxyl-, halide- and barium-free and soluble in acetic acid may be useful to impregnate the
support material. A similar suggestion is made in U.S. Patent No. 4,902,823, i.e. use of halide-
and sulfur-free salts and complexes of palladium soluble in unsubstituted carboxylic acids having
two to ten carbons.
[0019] Li U.S. Patent No. 6,486,370, it suggested that a layered catalyst may be used in a
dehydrogenation process where the iimw laya: support material differs fiom the outer layer
support material. Similarly, U.S. Patent No. 5,935,889 suggests that a layered catalyst may
useful as acid catalysts. But neither suggests the use of layered catalysts in the production of
alkenyl alkanoates.
[0020] Taken together, the inventors have recognized and addressed the need for continued
improvements in the field of VA catalysts to provide improved VA production at lower costs.
Sumnuuy of the laveatioD
[0021 ] The present invention addresses at least four different aspects relating to catalyst
structure, methods of making those catalysts and methods of using those catalysts for making
alkenyl alkanoates. Separately or together in combination, the various aspects of the invention
are directed at improving the production of alkenyl alkanoates and VA in particular, including
reduction of by-products and improved production efficiency. A first aspect of the present
invention pertains to a unique palladium/gold catalyst or pre-catalyst (optionally calcined) that
includes rhodium or another metal. A second aspect pertains to a palladium/gold catalyst or pre-
catalyst that is based on a layered support material where one layer of the support material is
substantially free of catalytic components. A third aspect pertains to a palladium/gold catalyst or
pre-catalyst on a zirconia containing support material. A fourth aspect pertains to a
palladium/gold catalyst or pre-catalyst that is produced firom substantially chloride free catal>^ic
components.
Detailed Descriptioa
. [0022] Catalysts
[0023] For present purposes, a catalyst is any support material that contains at least one
catalytic component and that is capable of catalyzing a reaction, whereas a pre-catalyst is any
material that results from any of the catalyst preparation steps discussed herein.
[0024] Catalysts and pre-catalysts oflbc present invention may include those having at least
one of the following attributes: 1) the catalyst will be a palladium and gold containing catalyst
that includes at least another catalytic componoit, e.g. rhodium where the one or more of the
catalytic components have been calcined; 2) the catalyst will be carried on a layored support, 3)
the catalyst will be carried on a zirconia containing support matsial; 4) the catalyst will be
produced with chloride free precursors or any amibination of the foregoing. Effective use of the
catalyst accordingly should help improve CO2 selectivity, activity or both, particularly as
pertaining to VA production.
[0025] It should be appreciated that the present invention is described in the context of
certain illustrative embodiments, but may be varied in any of a number of aspects d^oiding on
the needs of a particular i^phcation. By way of example, without limitation, the catalysts may
have the catalytic components uniformly distributed throughout the support material or they may
be shell catalysts where the catalytic components 'are found in a relatively thin shell around a
support material core. Egg white catalysts may also be suitable, where the catalytic components
reside substantially away from the center of support material. Egg yolk catalysts may also be
suitable.
[0026] Catalytic Components
[0027] In general, the catalysts and pre-catalysts of the present invention include metals and
particularly include a combination of at least two metals. In particular, the combination of metals
includes at least one from Group VniB and at least one from Group IB. It will be appreciated
that "catalytic component" is used to signify the metal that ultimately provides cataljrtic
funciionally to the catalyst, but also includes the metal in a variety of states, such as salt,
solution, sol-gel, suspensions, colloidal suspensions, free metal, alloy, or combinations thereof
Preferred catalj'sts include palladium and gold as the catalytic components.
[0028] One embodiment of the catalyst includes a combination of catalytic components
having palladium and gold combined with a third catalytic component. The third catalytic
component is preferably selected from Group VHIB, with Rh being the most preferred. Other
preferred catalysts include those wh«e the third catalytic componeat is selected from W, Ni, Nb,
Ta, Ti, Zr, Y, Re, Os, Fe, Cu, Co, Zn, fa. So, Ce, Ge, Ga and combinations thereof.
[0029] Anotlier embodiment of the catalyst includes a combination of catalytic components
including proportions of palladium, gold, and rhodium. Optionally a third catalytic component
(as listed above) may also be included in this embodiment in place of Rh. In anotiier
embodiment, two or more catalytic componoits from the above list may be employed.
[0030] In one example, palladium and gold may be combined with Rh to form a catalyst that
shows improved CO2 selectively (i.e. decreased formation of CO2) compared to Pd/Au catalysts
that lack Rh. Also, the addition of Rh does not appear to adversely affect the activity of the
catalyst. The CO2 selectivity of the palladium, gold, rhodium catal}«t may also be iinproved
through calcining during the catalyst preparation and/or &rough the use of water-soluble halide
free precursors (both disciissed below), althoa^ these are not necessary to observe the Rh effect.
[0031] The atomic ratio of the third catalytic componoit to palladium may be in the range of
about 0.005 to about 1.0, more preferably about 0.01 to about 1.0. In one embodiment, the
catalyst contains between about O.OI and about S.O g of the third catalytic component per liter of
catalyst.
[0032] Another preferred embodiment of the catalyst includes between about 1 to about 10
grams of palladium, and about 0.5 to about 10 grams of gold per liter of catalyst, llie amount of
gold is preferably from about 10 to about 125 wt % based on the weight of palladium.
[0033] In one embodiment for ground catalysts, Au to Pd atomic ratios between about 0.5
and about 1.00 may be preferred for ground catalysts. The atomic ratio can be adjusted to
balance the activity £ind CO2 selectivity. Employment of higher Au/Pd weight or atomic ratios
tends to favor more jictive, more selective catalysts. Stated alternatively, a catalyst with an
atomic ratio of about 0.6 is less selective for CO2, but also has less activity than a catalyst with a
ratio of about 0.8. The effect of the high Au/Pd atomic ratio on ground support mateaial may
also be enhanced through the use of relatively high excess of hydroxide ion, as discussed below
with respect to the fixing step. A ground catalyst may be one where the catalytic components are
contacted to the support material followed by a reduction in the particle size (e.g. by grinding or
ball milling) or one where the catalytic components are contacted to the siq)port material after the
support material has been reduced in size.
[0034] For shell catalysts, the thickness of the shell of catalytic components on the support
material ranges fh)m about 5 y.m to about 500 fim. More preferred ranges include fixjm about 5
HID to about 300 nm.
[0035) gupttort Materials
[0036] As indicated, in one aspect of the invoition, the catalytic components of the present
invention generally will be carried by a support material. Suitable support materials typically
include materials that are substantially uniform in identity or a mixture of materials. Oveiall, the
support materials are typically inert in the reaction being performed. Siqiport materials may be
composed of any suitable substance prefisrably selected so that the support materials have a
relatively high surface area per unit mass or volume, such as a porous structure, a molecular sieve
structure, a honeycomb structure, or other suitable structure. For example, the support material
may contain silica, alumina, silica-alumina, titania, zirconia, niobia, silicates, aluminosilicates,
titanates, spinel, silicon carbide, silicon nitride, carbon, cortherite, steatite, bentonite, clays,
metals, glasses, quartz, pumice, zeolites, non-zeolitic molecular sieves combinations thereof and
the like. Any of the different crystalline form of the matoials may also be suitable, e.g. alpha or
gamma alumina. Silica and zirconia containing support materials are the most preferred. In
addition, multilayer support materials are also suitable for use in the present invention.
[0037] The support matoial in the catalyst of this invention may be composed of particles
having any of vaiious regular or irregular shapes, such as spheres, tablets, cylinders, discs, rings,
stars, or other shapes. The support material may have dimensions such as diameter, length or
width of about 1 to about 10 mm, preferably about 3 to about 9 mm. In particular having a
regular shape (e.g. spherical) will have as its preferred largest dimension of about 4 mm to about
8 mm. In addition, a ground or powder support material may be suitable such that the support
material has a reg\ilar or irregular shape with a diameter of between about 10 microns and about
1000 micron, with preferred sizes being between about 10 and about 700 microns, with most
preferred sizes being between about 180 microns and about 450 microns. Larger or smaller sizes
8
may be employed, as well as polydi^Msrse collections of particles sizes. For example, for a fluid
bed catalyst a preferred size range would include 10 to ISOinicrons. For precursors used in
layered catalysts, a size range of 10 to 250 microns is preferred.
[0038] Surface areas available for su{q>oiting catalytic components, as measured by the BET
(Brunauer, Emmett, and Teller) method, may generally be between about 1 m^/g and about 500
m^/g, preferably about 100 mVg to about 200 m^/g. For example, for a porous support, the pore
volume of the support material may generally be about 0.1 to about 2 ml/g, and preferably about
0.4 to about 1.2 ml/g. An average pore size in the range, for example, of about 50 to about 2000
angstroms is desirable, but not required.
(0039] Examples of suitable silica containing si4)port materials include KA160 fix)m Sud
Chemie, Aeroly!it350 from Degussa and other pyrogenic or microporous-free silicas with a
particle size of about 1 mm to about 10 mm.
[0040] Examples of suit^le zitconia containing support materials include those from
NorPro, Zirconia Sales (America), Inc., Daichi Kigenso Kagaku Kogyo, and Magnesium
Elektron Inc (MEI). Suitable zirconia support materials have a wide range of surface areas from
less than about 5 m^/g to more than 300 mVg. Preferred zirconia support materials have surface
areas from about 10 m^/g to about 135 m^/g. Support materials may have their surfaces treated
through a calcining step in which the virgin support matoial is heated. The heating reduces the
surface area of the support material (e.g. calcining). This provides a method of creating support
materials with specific surface areas that may not otherwise be readily available from suppliers.
[0041] In another embodiment, it is contemplated to enyjloy at least a plural combination of
support materials., each with a different characteristic. For example, at least two support
materials (e.g. zirconia) with different characteristics may exhibit different activities and CO2
selectivities, thus permitting preparation of catalysts with a desired set of characteristics, i.e.
activity of a catalj'st may be balanced against the CO2 selectivity of the catalyst.
[0042] In one embodiment, plural different supports are employed in a layered configuration.
Layering may be achieved in any of a number of different approaches, such as a plurality of
lamella that are generally flat, undulated or a combination thereof One particular approach is to
utilize successively enveloping layns leh^ve to an initial core layer. In general, herein, layered
support materials typically include at least an inner layer and an outer layer at least partially
surrounding the inner layer. The outer layer preferably contains substantially more of catalytic
components than i^ie inner layer. In one aabodiment, the inner and outer layers are made of
different materials; but the materials may be the same. While the inner layer may be non-porous,
other embodiments include an inner layer that is porous.
[0043] The layered support mat«ial prefierably results in a form of a shell catalyst. But the
layered support material offers a well defined boundary between the areas of the support material
that have catalytic components and the areas that do not. Also, the outer layer can be constructed
consistently with a. desired thickness. Together the boundary and the uniform thickness of the
outer layer result in a shell catalyst that is a sheU of catalytic components that is of a uniform and
known thickness.
[0044] Several techniques are known for creating layoed support materials includes those
described in U.S. Patent Nos. 6,486,370; 5,935,889; and 5,200,382, each of which is
incorporated by reference. In one embodiment, the materials of the ixmer layer are also not
substantially penetrated by liquids, e.g., metals including but not limited to aluminum, titanium
and zirconium. Examples of other materials for the inner layer include, but are not limited to,
alumina, silica, silica-alumina, titania, zirconia, niobia, silicates, aluminosilicates, titanates,
spinel, silicon carbide, silicon nitride, caibon, cortherite, steatite, bentonite, clays, metals,
glasses, quartz, pumice, zeolites, non-zeolitic molecular sieves and combinations thereof A
preferred inner layer is silica and KA160, in particular.
[0045] These materials which make up the inner layer may be in a variety of forms such as
regularly shaped particulates, irregularly shi^ied particulates, pellets, discs, rings, stars, wagon
wheels, honeycombs or other shaped bothes. A spherical particulate inner layer is preferred. The
inner layer, whether spherical or not, has an effective diameter of about 0.02 mm to about 10.0
mm and preferably from about 0.04 mm to about 8.0 mm.
[0046] The outermost layer of any multilayer structure is one which is porous, has a surface
area in the range of about 5 m^/g to about 300 mVg. The material of the outer layer is a metal,
10
ceramic, or a combination thereof, and in one «nbodim«at it is selected from alumina, silica,
silica-alumina, titania, zirconia, niobia, silicates, aluminosilicates, titanates, spinel, silicon
carbide, silicon nitride, carbon, cortherite, steatite, bentooite, clays, metals, glasses, quartz,
pumice, zeolites:, non-zeolitic molecular sieves and combinations thereof and preferably include
alumina, silica, silica/alumina, zeolites, non-zeolite molecular sieves (N2MS), titania, zirconia
and mixtures tiiereof Specific examples include zirconia, silica and alumina or combinations
thereof.
[0047] While the outer layer typically surrounds substantially the mtire inner layer, this is not
necessarily the case and a selective coating on the inner layer by the outer layer may be
employed.
[0048] The outer layer may be coated on to the underlying layer in a suitable maimer. In one
embodiment, a slurry of the outer layer matoial is employed. Coating of the iimer layer with the
slurry may be accomplished by methods such as rolling, dipping, spraying, wash coating, other
slurry coating techniques, combinations thereof or the like. One prefisrred technique involves
using a fixed or fluidized bed of iimer layer particles and spraying the slurry into the bed to coat
the particles evenly. The slurry may be applied repeatedly in small amounts, with intervening
drying, to provide an outer layer that is highly uniform in thickness.
[0049] The slurry utilized to coat the innor layer may also include any of a number of
additives such as a surfactant, an organic or inorganic bonding agent that aids in the adhesion of
the outer layer to an underlying layer, or combinations thereof Examples of this organic bonding
agent include but are not limited to PVA, hydroxypropylcellulose, methyl cellulose, and
carboxymethylcelluiose. The amount of organic bonding agent which is added to the slurry may
vary, such as from about I wt % to about 15 wt % of the combination of outer layer and the
bonding agent. Examples of inorganic bonding agents are selected from an alumina bonding
agent (e.g. Bohmite), a silica bonding agrait (e.g. Ludox, Teos), zirconia bonding agent (e.g.
zirconia acetate or colloidal zirconia) or combinations thereof Examples of silica bonding
agents include silica sol and silica gel, while examples of alumina bonding agents include
alumina sol, ben tonite, Bohmite, and aluminum nitrate. The amount of inorganic bonding agent
11
may range from about 2 wt % to about 15 wt % of the combination of the outer layer and the
bonding agent. The thickness of the outer layer may range from about 5 microns to about SOO
microns and preferably between about 20 microns and about 250 microns.
[0050] Once the inner layer is coated with the outer layer, the resultant layered support will
be dried, such as by heating at a temperature of about lOO^C to about 320°C (e.g. for a time of
about 1 to about 24 hours) and then may optionally be calcined at a temperature of about 300°C
to about 900°C (e.g. for a time of about O.S to about 10 hours) to enhance bonding the outer layer
to it underlying layer over a least a portion of its sur&ce and provide a layered catalyst support.
The drying and adcining steps can be combined into one stq). The resultant layered support
material may be contacted with catalj^c components just as any other support material in the
production of catalysts, as described below. Alternately, the outer layw support material is
contacted to catalytic components before it is coated onto the underlying layer.
[0051] In another embodiment of the layered support, a second outer li^er is added to
surround the initial outer layer to form at least three layers. The material for the second outer
layer may be the same or different than the first outer layer. Suitable materials include those
discussed with respect to the first outer layer. The method for applying the second outer layer
may be the same or different than the method used to apply the middle layer and suitable
methods include those discussed with respect to the first outer layer. Organic or inorganic
bonding agents as described may suitably used in the formation of the second outer layer.
[0052] The initial outer layer may or may not contain catalytic components. Similarly, the
second outer layer may or may not contain catalytic components. If both outer layers contain
catalytic component, then preferably different catalytic components are used in each layer,
although this is not necessarily the case. In one preferred embodiment, the initial outer layer
does not contain a catalytic component. Contacting catalytic component to the outer layers may
be accomplished by impregnation or spray coating, as described below.
[0053] hi embodiments whwe the initial outer layer contains catalytic component, one
method of achieving this is to contact the catalytic component to the material of the initial outer
layer before the material is applied to the inner layer. The second outer layer may be applied to
the initial outer layer neat or containing catalytic component.
[0054] Other suitable techniques may be used to achieve a three layered support material in
which one or more of the outer layers contain catalytic components. Indeed, the layered support
material is not limited to three layars, but may include four, five or more layers, some or all of
which may contain catalytic conqranents.
[0055] In acldition, the number and type of catalytic components that vary between the layers
of the layered support material, other characteristics (e.g. porosity, particle size, surface area,
pore voliune, or the like) of the si^port material may vary between the layers.
[0056] Methods Of Making Catalysts
[0057] In general the method includes contacting support matc^al catalytic componoits and
reducing the catalytic components. Preferred methods of the present invention include
impregnating the catalytic components into the support material, calcining the catalytic
component containing support material, reducing the catalytic components and modifying the
reduced catalytic components on the support material. Additional stq>s such as fixing the
catalytic components on the support material and washing the fixed catalytic components may
also be included in the method of making the catalyst or pre-catalyst. Some of the steps listed
above are optional and others may be eliminated (e.g. the washing and/fixing steps). In addition,
some steps may be repeated (e.g. multiple impregnation or fix steps) and the order of the steps
may be different fiom that listed above (e.g. the reducing step precedes the calcining stqp). To a
certain extent, the contacting step will determine what later steps are needed for the formation of
the catalyst.
[0058] Contacting Step
[0059] One particular approach to contacting is one pursuant to which an egg yolk catalyst or
pre-catalyst is formed, an egg white catalyst or pre-catalyst is formed, an all throughout catalyst
or pre-catalyst is formed or a shell catalyst or pre-catalyst is formed, or a combination thereof. In
one embodiment, techniques that form shell catalysts are preferred.
[0060] The contacting step may be carried out using any of the support materials described
above, with siUai, zirconia and layered stq^rt materials containing zirconia being the most
favored. The contacting step is preferably earned out at ambient temperature and pressure
conditions; however, reduced or elevated trnnpentfures or pressures may be en^)loyed.
[0061] In one preferred contacting step, a support material is impregnated with one or more
aqueous solutions of the catalytic components (referred to as precursor solutions). The physical
state of the support material during the contacting stq} may be a dry solid, a slurry, a sol-gel, a
colloidal suspension or the like.
[0062] In one embodiment, the catalytic components contained in the precursor solution are
water soluble salts made of the catalytic components, including but not limited to, chlorides,
other halides, nitrates, nitrites, hydroxides, oxides, oxalates, acetates (OAc), and amines, with
halide free salts being preferred and chloride free salts being more preferred. Examples of
palladium salts suitable for use in precursor solutions include PdCb, NazPdCU, Pd(NH3)20^O2)2,
Pd(NH3)4(OH)2, Pd(NH3)4(N03)2, Pd(N03)2. Pd(NH3MOAc)2, Pd(NH3)2(OAc)2, Pd(OAc)2 in
KOH and/or NMe40H and/or NaOH, Pd(NH3)4(HCO3)2 and palladium oxalate. Of the chloride-
containing palladium precursors, Na2PdCl4 is most preferred. Of the chloride free palladium
precursor salts, the following four are the most preferred: Pd(NH3)4(N03)2, Pd(N03)2,
Pd(NH3)2(N02)2, Pd(NH3)4(OH)2. Examples of gold salts suitable for use in precursor solution
include AuCb, HAuCU, NaAuCU, KAUO2, NaAu02, NMe4Au02, Au(0Ac)3 in KOH and/or
NMe40H as well as HAu(N03)4 in nitric acid, with KAUO2 being the most preferred of the
chloride free gold precursors. Examples of rhodium salts suitable for use in precursor solutions
include RhCb, RJli(0Ac)3, and Rh(N03)2. Similar salts of the above described third catalytic
components may also be selected.
[0063] Furthermore, more than one salt may be used in a given precursor solution. For
example, a palladium salt may be combined with a gold salt or two different palladium salts may
be combined together in a single precursor solution. Precursor solutions typically may be made
by dissolving the selected salt or salts in water, with or without solubility modifiers such as acids,
bases or other solvents. Other non-aqueous solvents may also be suitable.

[0064] The precursor solutions may be impregnated onto the support material simultaneously
(e.g. co-impregnation) or sequentially and may be impregnated throu^ the use of one or multiple
precursor solutions. With three or more catalytic components, a combination of simultaneous
and sequential impregnation may be used. For example, palladium and riiodium may be
impregnated througji the use of a single precursor solution (referred to as a co-impregnation),
followed by impregnation witii a precursor solution of the gold. In addition, a catalytic
component may be impregnated on to support material in multiple steps, such that a portion of
the catalytic com]:>onent is contacted each time. For example, one suitable protocol may include
impregnating witli Pd, followed by impregnating vfifh Au, followed by impregnating again with
Au.
[0065] The order of impregnating the support material with the precursor solutions is not
critical; although there may be some advantages to certain orders, as discussed below, with
respect to the calcining step. Preferably, the palladium catalytic component is impregnated onto
the support material first, with gold being impregnated after palladium, or last. Rhodium or other
third catalytic component, when used, may be impregnated with the palladium, with the gold or
by itself Also, the support material may be impregnated multiple times with the same catalytic
component. For example, a portion of the overall gold contained in the catalyst may be first
contacted, followed by contacting of a second portion of the gold. One more other stq>s may
intervene between the steps in which gold is contacted to the support material, e.g. calcining,
reducing, and/or fixing.
[0066] The acid-base profile of the precursor solutions may influence whether a co-
impregnation or a sequential impregnation is utilized. Thus, only precursor solutions with
similar acid-base profile should be used together in a co-impregnating st^; this eliminates any
acid-base reactions that may foul the precursor solutions.
[0067] For the impregnating step, the volume of precursor solution is selected so that it
corresponds to between about 85% and about 110% of the pore volimie of the support material.
Volumes between about 95% and about 100% of the pore volume of the support material are
preferred, and more preferably between about 98% and about 99% of the pore volume.

[0068] Typically, the precursor solution is added to the siq>p material is allowed absorb the precursor solution. This may be done drop wise until incipient
wetness of the support material is substantially achieved. Alternatively, the support matorial may
be placed by aliquots or batch wise into the precursor solution. A loto-immersion or other
assistive appanfitus may be used to achieve thorou^ contact between the siqpport material and the
precursor solution. Fiuther, a spray device may be used such that the precursor solution is
sprayed through a nozzle onto the support matoial, where it absorbed. Optionally, decanting,
heat or reduced, pressure may be used to r«nove any excess liquid not absorbed by the support
material or to dry the support material after impregnati [0069] For the impregnating step, the volume of precursor solution is selected so that it
corresponds to between about 85% and about 110% of the pore volume of the support material.
Volumes between about 95% and about 100% of the pore volume of the siq>port material are
preferred, andrnore preferably between about 98% and about 99% of the pore volume.
[0070] Typically, the preciu^or solution is added to the support material and the support
material is allowed absorb the precursor solution. This may be done drop wise until incipient
wetness of the support material is substantially achieved. Alternatively, the support material may
be placed by aliquots or batch wise into the precursor solution. A roto-immersion or other
assistive apparatus may be used to achieve thorough contact between the support material and the
precursor solution. Further, a spray device may be used such that the precursor solution is
sprayed through a nozzle onto the support material, where it absorbed. Optionally, decanting,
heat or reduced pressure may be used to remove any excess liquid not absorbed by the support
material or to diy the support material after impregnation.
[0071] Other contacting techniques may be used to avoid a fixing step while still achieving a
shell catalyst. For example, catalytic components may be contacted to a support material through
a chemical v^or deposition process, such as described in US2001/0048970, which is
incorporated by reference. Also, spray coating or otherwise layering a uniformly pre-
impregnited support material, as an outer layer, on to an iimer layer effectively forms sh6ll
catalyst that may also be described as a layered support material. In another technique,

organometallic precursors of catalytic con^neats, particularly with respect to gold, may be used
to form shell catalysts, as described in U.S. Pat«it No. 5,700,753, which is incorporated by
reference.
[0072] A phy!;ical shell formation technique may also be suitable for the production of shell
catalysts. Here, the precursor solution may be sprayed onto a heated support material or a
layered support material, where the solvent of the precursor solution evaporates upon contact
with the heated support material, thus depositing the catalytic components in a shell on the
support material. Preferably, tonperatures b^ween about 40 and 140°C may be used. The
thickness of the shell may be controlled by selecting the temperature of the support material and
the flow rate of the solution through the spray nozzle. For example, with temperatures above
about 100°C, a relatively thin shell is formed. This embodim«it may be particularly useiul when
chloride free precursors are utilized to help enhance the shell formation on the support material.
[0073] One skilled in the art will understand that a combination of the contacting steps may
be an appropriate method of forming a contacted support material.
[0074] Fixing Step
[0075] It may be desirable to transform at least a portion of the catalytic components on the
contacted support material from a water-soluble form to a water-insoluble form. Such a step may
be referred to as a liixing step. This may be accomplished by applying a fixing agent (e.g.
dispersion in a liquid, such as a solution) to the impregnated support material which causes at
least a portion of the catalytic components to precipitate. This fixing step helps to form a shell
catalyst, but is no!: required to form shell catalysts.
[0076] Any suii^bie fixing agent may be used, with hydroxides (e.g. alkali metal hydroxides),
silicates, borates, carbonates and bicarbonates in aqueous solutions being preferred. The
preferred fixing agent is NaOH. Fixing may be accomplished by adding the fixing agent to the
support material before, during or after the precursor solutions are impregnated on the support
material. Typically, the fixing agent is used subsequent to the contacting step such that the
contacted support material is allowed to soak in the fixing agent solution for about 1 to about 24
hours. The specific time depends upon the combination of the precursor solution and the fixing

agent. Like the impregnating stqi, an assistive device, such as a roto immo^ion q^aratus as
described in U.S. Patent No. 5,332,710, which is itMxirporated horein by reference, may
advantageously be used in the fixing stqj.
[0077] The fixing step may be accomplished in one or multiple st^s, referred as a co-fix or a
separate fix. In a co-fix, one or more volumes of a fixing agmt solution is q>plied to the
contacted support material after all the relevant precursor solutions have been contacted to the
support material, whether the contact was accomplished through the use of one or multiple
precursor solutions. For example, fixing after sequential inq>regnation with a palladium
precursor solution, a gold precursor soluti as would fixing after a co-impregnation with a palladium/rfaodium precursor solution followed by
impregnation with a gold precursor solution. An example of co-fixing may be foimd in U.S.
Patent No. 5,314,888, which is incorporated by reference.
[0078] A septarate fix, on the other hand, would include applying a fixing agent solution
during or after eiich impregnation with a precursor solution. For example, the following
protocols would be a separate fix: a) impregnating palladium followed by fixing followed by
impregnating with gold followed by fixing; or b) co-impregnating with palladium and rhodium
followed by fixing followed by impregnating wi& gold followed by fixing. Between a fix and
subsequent impregnation, any excess liquid may be removed and the support material dried,
although this is not necessarily the case. An example of sq)arate fixing may be found in U.S.
Patent No. 6,034,030, which is incorporated by reference.
[0079] In another embodiment, the fixing step and the contacting step are conducted
simultaneously, one example of which is described in U.S. Patent No. 4,048,096, which is
incorporated by reference. For example, a simultaneous fix might be: impregnating with
palladium followed by fixing followed by in:^)regnating with gold and fixing agent. In a
variation on this embodiment, the fix may be conducted twice for a catalytic component. A
catalytic component may be partially fixed when it is contacted to the support material (called a
"pre- fix"), followed an additional, final fix. For example: impregnating with palladium
followed by impregnating with gold and a pre-fixing agent followed by fixing with a final fixing

agent. This technique may be used to help insure the fonnation of shell type catalyst as opposed
to an all throughout catalyst.
[0080] In another embodiment, particularly suitable for use with chloride free precursors, the
siq)port material is pre-treated with a fixing agmt to adjust the properties of the support material.
In this embodiment, the support material is first in:q>regnated with either an acid or base solution,
typically free of rnetals. After drying, the siq)port matoial is impregnated with a precursor
solution that has the opposite acidity/alkalinity as the dried support material. The ensuing acid-
base reaction fonns a shell of catalytic components on the support matorial. For example, nitric
acid may be used to pre-treat a support material that in turn is impregnated with a basic precursor
solution such as Pd(0H)2 or Au(0H)3. This formation technique may be considered as using a
fixing step followed by a contacting step.
[0081 ] The concentration of fixing agent in the solution is typically a molar excess of the
amount of catalytic components impregnated on the support material. The amount of fixing
agent should be between about 1.0 to about 2.0, preferably about 1.1 to about 1.8 times the
amount necessar}' to react with the catalytically active cations present in the water-soluble salt.
In one embodiment using a high Au/Pd atomic or weight ratio, an increased molar excess of
hydroxide ion enliances the CO2 selectivity and activity of the resultant catalyst.
[0082] The volume of fixing agent solution supplied generally should be an amount
sufficient to cover the available fi^e surfaces of the impregnated support material This may be
accomplished by introducing, for example, a volume that is greater than the pore volume of the
contacted support: material.
[0083] The combination of impregnating and fixing steps can form a shell type catalyst. But,
the use of halide free precursor solutions also permits the fonnation of a shell catalyst while
optionally eliminating the fixing step. In the absence of a chloride precursor, a washing step, as
discussed below, may be obviated. Further, the process can be free of a step of fixing catalytic
components that would otherwise be needed to survive the washing step. Because no washing
step is needed, the catalytic components need not be fixed to survive the washing step.
Subsequent steps in the method making the catalyst do not require the catalytic components be

fixed and thus tfie remainder of the step maybe carried out without additional preparatory steps.
Overall, the use of chloride free precursors permits a catalyst or pre-catalyst production method
that is free of a step of washing, thus reducing the number of steps needed to produce the catalyst
and eUminating the need to dispose of chloride containing waste.
[OOfM] Washing Step
[0085] Particularly, when halide containing precursor solutions are utilized and in other
applications as desired, after the fixing stq), the fixed support material may be washed to remove
any halide residue on the support or otherwise treated to eliminate the potential negative effect of
a contaminant on the support material. The washing st^ included rinsing the fixed support
material in water, preferably deionized wato*. Washing may be done in a batch or a continuous
mode. Washing at room temperature should continue until the effluent wash water has a haUde
ion content of less than about 1000 ppm, and more preferably until the final effluent gives a
negative result to a silver nitrate test. The washing step may be carried out after or
simultaneously with the reducing step, discussed below, but preferably is carried out before. As
discussed above, the use of halide free precursor solutions permits the elimination of the washing
step.
[0086] Calcining Step
[0087] After at least one catalytic component has been contacted to the support material, a
calcining step may be employed. The calcining step typically is before the reducing step and
after the fixing step (if such a step is used) but may take place elsewhere in the process. In
another embodiment, the calcining step is carried out after the reducing step. The calcining step
includes heating the support material in a non-reducing atmosphere (i.e. oxidizing or inert).
Diring calcination, the catalytic components on the support material are at least partially
decomposed from their salts to a mixture of their oxide and free metal form.
[0088] For example, the calcining step is carried out at a temperature in the range of about
lOO^C to about 700°C, preferably between about 200'C and about 500°C. Non-reducing gases
used for the calcination may included one or more inert or oxidizing gases such as helium,
nitrogen, argon, neon, nitrogen oxides, oxygen, air, carbon dioxide, combinations thereof or the

like. In one embodiment, the calcining stq) is carried out in an atmosphrae of substantially pure
nitrogen, oxygen, air or combinations thereof. Calcination times may vary but preferably are
between about 1 aad 5 hours. The degree of decomposition of the catalytic component salts
depends on the temperature used and length of time the impregnated catalyst is calcined and can
be followed by monitoring volatile decomposition products.
[0089] One or more calcining stqjs may be used, such that at any point after at least one
catalytic component is contacted to the support material, it may be calcined. Preferably, the last
calcining step occurs before contact of tiie gold catalytic component to a zirconia support
material. Alternately, calcining of a zirconia support material containing gold is conducted at
temperatures below about 300°C. By avoiding calcining the gold containing zirconia support
material at temperatures above about 300°C, the risk that the CO2 selectivity of the resultant
catalyst will be detrimentally affected is reduced.
[0090] Exemplary protocols including a calcining st^ include: a) impregnating with
palladium followed by calcining followed by impregnating with gold; b) co-impregnating
palladium and rhodium followed by calcining followed by impregnating with Au; c)
impregnating with palladium followed by calcining followed by impregnating with rhodium
followed by calcining followed by impregnating with gold; or d) impregnating with palladium
and rhodium, followed by impregnating with gold, followed by calcination.
[0091] Reducing Step
[0092] Another step employed generally herein to at least partially transform any remaining
catalytic components from a salt or oxide form to a catalytically active state, such as by a
reducing step. Tyi)ically this is done by exposure of salts or oxides to a reducing agent, examples
of which include ammonia, carbon monoxide, hydrogen, hydrocarbons, olefins, aldehydes,
alcohols, hydrazine, primary amines, carboxylic acids, carboxylic acid salts, carboxylic acid
esters and combinations thereof Hydrogen, ethylene, propylene, alkaline hydrazine and alkaline
formaldehyde and combinations thereof are preferred reducing agents with ethylene and
hydrogen blended with inert gases particularly preferred. Although reduction employing a
gaseous environme;nt is preferred, a reducing step carried with a liquid environment may also be

used (e.g. employing a reducing solution). The tenq)aature selected for the reduction can range
from ambient up to about 550°C. Reduction times will typically vary from about 1 to about 5
hours.
[0093] Since the process used to reduce the catalytic components may influences the
characteristics of the final catalyst, conditions enqjloyed for the reduction may be varied
depending on whether high activity, high selectivity or some balance of these properties is
desired.
[0094] In one embodiment, palladium is contacted to the siqiport material, fixed and reduced
before gold is contacted and reduced, as described in U.S. Patent Nos. 6,486,093, 6,015,769 and
related patents, all of which are incorporated by reference.
[0095] Exemplaiy protocols including a reducing stq) include: a) impregnating with
palladium followed by optionally calcining followed by impregnating with gold followed by
reducing; b) co-impregnating with palladium and gold followed by optionally calcining followed
by reducing; or c) impregnating with palladium followed by qptionally calcining followed by
reducing followed by impregnating with gold.
[0096] Modifidng Step
[0097] Usually after the reducing stq) and before the catalyst is used, a modifying step is
desirable. While the catalyst may be used with the modifying step, the stq) has several beneficial
results, including lengthening the operational life time of the catalyst. The modifying step is
sometimes called an activating step and may be accomplished in accordance with conventional
practice. Namely, the reduced support material is contacted with a modifying agent, such as an
alkali metal csirboxylate and/or alkali metal hydroxide, prior to use. Conventional alkali metal
carboxylates such as the sodium, potassium, lithium and cesium salts of Cz^ aliphatic carboxylic
acids are employed for this purpose. A preferred activating agent in the production of VA is an
alkali acetate, with potassium acetate (KOAc) being the most preferred.
[0098] The support material may optionally be impregnated with a solution of the modifying
agent. After drying, the catalyst may contain, for example, about 10 to about 70, preferably about
20 to about 60 grams of modifying agent per liter of catalyst.

[0099] Methods of Making Alkmvl Alkanoates
[00100] The present inventioa may be utilized to produce alkoiyl atkaooates from an alkraie,
alkanoic acid and an oxygen containing gas in the ptesoice of a catalyst. Prefeired alkene
starting materials contain from two to four carbon atoms (e.g. ethylene, propylene and n-butene).
Preferred alkanoic acid starting materials used in the process of this invention for producing
alkenyl alkanoates contain from two to four carbon atoms (e.g., acetic, propionic and butyric
acid). Prefened products of the process are VA, vinyl propionate, vinyl butyrate, and allyl
acetate. The most preferred starting materials are ethylene and acetic acid with the VA being the
most preferred product. Thus, the present invention is useful in the production of olefinically
unsaturated carboxylic esters from an olefinically unsaturated coinpound, a carboxylic acid and
oxygen in the presence of a catalyst. Although the rest of the specification discusses VA
exclusively, it should be understood that the catalysts, method of making the catalysts and
production methods are equally applicable to other alkenyl alkanoates, and the description is not
intended as hmiting the application of the invention to VA.
[001011 When VA is produced using the catalyst of the preseat invention, a stream of gas,
which contains ethylene, oxygen or air, and acetic acid is passed over the catalyst. The
composition of the gas stream can be varied within wide limits, taking in account the zone of
flammability of the effluent. For example, the molar ratio of ethylene to oxygen can be about
80:20 to about 98:2, the molar ratio of acetic acid to eth>dene can be about 100:1 to about 1:100,
preferably about 10:1 to 1:10, and most preferably about 1:1 to about 1:8. The gas stream may
also contain gaseous alkali metal acetate and/or inert gases, such as nitrogen, carbon dioxide
and/or saturated hydrocarbons. Reaction temperatures which can be used are elevated
temperatures, preferably those in the range of about 125-220*'C. The pressure employed can be a
somewhat reduced pressure, norinal pressure or elevated pressure, preferably a pressure of up to
about 20 atmospheres gauge.
[00102] In addition to fixed bed reactors, the methods of producing alkenyl alkanoates and the
catalyst of the present invention may also be suitably employed in other types of reaction, for
example, fluidized bed reactors.

[00103] Examples
[00104] The following examples are provided for illustration only and not intended to be
limiting. The amounts solvents and reactants are a{q>roximate. The Au/Pd atomic ratio may be
converted to the Au/IM weight ratio and vice versa by the following equations: Au/Pd atomic
ratio = 0.54*(Au/Pd weight ratio) and Au/Pd wdg^t ratio = 1.85(Au/Pd atomic ratio. Reduction
may be abbreviated 'R' followed by the tonponture in "C at which the reduction was carried out.
Likewise, calcination may be abbreviated 'C followed by the temperature in "C at which the
calcination was carried out, whereas a drjdng step may be abbreviated as 'dry*.
[00105] The catal;/st of examples 1-11 may be prepared as described in the example and tested
according to the following procedure, where catalyst fh>m Examples 1-7 may be cort^ared to
each other and catalyst from 8-11 may be compared to each other. Results are provided where
available.
[00106] The catalysts of the examples were tested for their activity and selectivity to varioiis
by-products in the production of vinyl acetate by reaction of ethylene, oxygen and acetic acid. To
accomplish this, about 60 ml of the catalyst prqpared as described were placed in a stainless steel
basket with the temperature capable of being measured by a thermocoiq>le at both the top and
bottom of the basket. The basket was placed in a Berty continuously stirred tank reactor of the
recirculating type and was maintained at a temperature which provided about 45% oxygen
conversion with an electric heating mantle. A gas mixture of about SO normal liters (measured at
N.T.P.) of ethylene, about 10 normal liters of oxygen, about 49 normal liters of nitrogen, about
SO g of acetic acid, and about 4 mg of potassium acetate, was caused to travel imder pressure at
about 12 atmospheres through the basket, and the catalyst was aged under these reaction
conditions for at least 16 hours prior to a two hour run, after which the reaction was terminated.
Analysis of the products was accomplished by on-line gas chromatographic analysis combined
with off-line liquid product analysis by condensing the product stream at about 10°C to obtain
optimum analysis of the end products carbon dioxide (CO2), heavy ends (HE) and ethyl acetate
(EtOAc), the results of which may be used to calculate the percent selectivities (CO2 Selectivity)
of these materials for each example. The relative activity of the reaction expressed as an activity

factor (Activity) may be computer calculated using a series of equations that correlates the
activity factor witli the catalyst temperature (during the reaction), oxygen conversion, and a series
of kinetic parameters for the reactions that take place diuing VA synthesis. More generaUy, the
activity factor typically is inversely related to the tonperature required to achieve constant
oxygen conversion.
[00107] Rhodium Catalyst Examples
[00108] Example 1: A support material containing palladium and rhodium metal was pr^ared
as follows: The support material in an amount of 2S0 ml consisting of Sud Chemie KA-160 silica
spheres having a nominal diameter of 7 mm., a density of about 0.569 g/ml, in absorptivity of
about 0.568 g H20/g support, a surface area of about 160 to 175 mVg, and a pore volume of
about 0.68 ml/g., was first impregnated by incipient wetness with 82.5 ml of an aqueous solution
of sodium tetrachloropalladium (II) (Na2PdCU) and rhodium chloride trihydrite (RhCl3»3H20)
sufficient to provide about 7 grams of elemmtal palladium and about 0.29 grams of elemental
rhodium per liter of catalyst. The support was shaken in the solution for 5 minutes to ensure
complete absorption of the solution. The palladium and liiodium were then fixed to the support
as palladium (11) and rhodium (m) hydroxides by contacting the treated sqiport by roto-
immersion for 2.5 hours at approximately 5 rpm with 283 ml of an aqueous sodium hydroxide
solution prepared fiom 50% w/w NaOH/H20 in an amount of 120% of that needed to convert the
palladium and riiodium to their hydroxides. The solution was drained fix)m the treated support
and the support was: then rinsed with deionized water and dried at 100°C in a fluid bed drier for
1.2 hours. The support material containing palladium and rhodium hydroxides was then
impregnated with an aqueous solution (81 ml) containing 1.24 g Au fi-om NaAuCU and 2.71g
50% NaOH solution (1.8 equivalents with respect to Au) using the incipient wetness method.
The NaOH treated pills were allowed to stand overnight to aisure precipitation of the Au salt to
the insoluble hydroxide. The pills were thoroughly washed with deionized water (~5 hours) to
remove chloride ions and subsequently dried at 100°C in a fluid bed drier for 1.2 hours. The
palladium, rhodium, and gold containing support was then calcined at 400°C for 2 hours under
air and then allowed to naturally cool to room temperature. The palladium, rhodium, and gold

were reduced by contacting the support with C2H4 (1% in nitrogen) in the vs^r phase at ISO^C
for 5 hours. Finally the catalyst was in^)regDated by incipient wetness with an aqueous solution
of lOg of potassium acetate in 81 ml H2O and dried in a fluid bed drier at 100°C for 1.2 hours.
[00109] Example 2: A support material utilizing palladium and riiodium hydroxides was
prepared as described in Example 1. The palladium and rhodium containing support was then
calcined at 400°C for 2 hours under air and tiien allowed to naturally cool to room temperature.
The calcined support material containing palladium and ibodium hydroxides was then
impregnated with an aqueous solution (81 ml) containing 1.24g Au from NaAuCU and 2.71g
50% NaOH solution (1.8 equivalents with respect to Au) using the incipient wetness method.
The NaOH treated pills were allowed to stand overnight to ensure precipitation of the Au salt to
the insoluble hydnixide. The pills were thoroughly washed with deionized water (~5 hoius) to
remove chloride ions and subsequently dried at lOO'HIJ in a fluid bed drio: for 1.2 hours. The
palladium, rhodium, and gold were then reduced by contacting the support with C2H4 (1% in
nitrogen) in the vapor phase at IS0°C for 5 hours. Finally the catalyst was impregnated by
incipient wetness with an aqueous solution of lOg of potassium acetate in 81 ml H2O and dried in
a fluid bed drier at 100°C for 1.2 hours.
[00110] Example 3: A support material containing palladium and rhodium hydroxides was
prepared as described in Example 1. The palladiiun and rhodium containing support was then
calcined at 400°C for 2 hours under air and then allowed to naturally cool to room temperature.
The calcined support material containing palladium and rhodium hydroxides was then reduced by
contacting the support with C2H4 (1% in nitrogen) in the vapor phase at 150°C for 5 hours. The
support containing palladium and rhodium metal was subsequently impregnated with an aqueous
solution (81 ml) containing 1.24g Au from NaAuCU and 2.7Ig 50% NaOH solution (1.8
equivalents with respect to Au) using the incipient wetness method. The NaOH treated pills
were allowed to stand overnight to ensure precipitation of the Au salt to the insoluble hydroxide.
The pills were thoroughly washed with deionized water (~5 hours) to remove chloride ions and
subsequently dried at 100°C in a fluid bed drier for 1.2 hours. The palladium, rhodium, and gold
were then reduced by contacting the support with C2H4 (1% in nitrogen) in the vapor phase at

1 SO°C for 5 hours. Finally the catalyst was impregnated by incipioit wetness with an aqueous
solution of lOg of potassium acetate in 81 mi H2O and dried in a fluid bed drier at 100°C for 1.2
hours.
[00111] Example 4: A support material containing palladium and rhodium hydroxides was
prepared as described in Example 1. The palladium and liiodium containing support was then
calcined at 400'C for 2 hours imder air and then allowed to naturally cool to room temperature.
The calcined support material containing palladium and rhodium hydroxides was then reduced by
contacting the support with C2H4 (1% in nitrogen) in the vapor phase at 150°C for 5 hours. The
support containing palladium and rhodium metal was subsequently impregnated with an aqueous
solution (81 ml) containing 1. Ig Au from KAuOi using the incipient wetness method. The pills
were subsequently dried at 100°C in a fluid bed drier for 1.2 hours. The palladium, rhodium, and
gold were then reduced by contacting the support with C2H4 (1% in nitrogen) in the vapor phase
at 1S0°C for 5 hours. Finally the catalyst was impregnated by incipient wetness widi an aqueous
solution of lOg of potassium acetate in 81 ml HjO and dried in a fluid bed drier at IOO°C for 1.2
hours.
[00112] Example S: A si4>port material containing palladium and rhodium hydroxides was
prepared as described in Example 1. The palladiiun and rhodium containing support was then
calcined at 400'C for 2 hours under air and then allowed to naturally cool to room temperature.
The calcined support containing palladium and rhodium hydroxides was subsequently
impregnated with an aqueous solution (81 ml) containing l.lg Au from KAuOi using the
incipient wetness method. The pills were then dried at 100°C in a fluid bed drier for 1.2 hours. •
The palladium, rhodium, and gold were then reduced by contacting the support with C2H4 (1% in
nitrogen) in the vapor phase at 150°C for 5 hours. Finally the catalyst was impregnated by
incipient wetness with an aqueous solution of lOg of potassium acetate in 81 ml H2O and dried in
a fluid bed drier at 100°C for 1.2 hours.
[001131 Example 6: A support material containing palladium and rhodium hydroxides was
prepared as described in Example 1. The palladium and rhodium containing support was then
calcined at 400°C for 2 hours under air and then allowed to naturally cool to room temperature.

The calcined support material containing palladium and rhodium hydroxides was then reduced by
contacting the support with C2H4 (1% in nitrogen) in the vapor phase at 150°C for 5 hours. The
support containing palladium and rhodium metal was subsequently impregnated with an aqueous
solution (81 ml) containing 1.1 g Au from KAUO2 and lOg potassiimi acetate using the incipient
wetness method. The pills were subsequmtly dried at 100°C in a fluid bed drier for 1.2 hoiu°s.
[00114] Example 7 (Reference Catalyst): A si^port material containing palladium metal was
prepared as follows: The support material in an amount of 250 ml consisting of Sud Chemie KA-
160 silica spheres having a nominal diameter of 7 mm., a density of about 0.569 g/ml, in
absorptivity of about 0.568 g HjO/g support, a surface area of about 160 to 175 mVg, and a pore
volxime of about 0.68 ml/g., was first impregnated by incipient wetness with 82.5 ml of an
aqueous solution of sodium tetrachloropalladium (II) (Na2PdCU) sufficient to provide about 7
grams of elemental palladium per liter of catalyst. The support was shaken in the solution for 5
minutes to ensure complete absoiption of the solution. The palladium was then fixed to the
support as palladium (II) hydroxides by contacting the treated support by roto-immersion for 2.5
hours at ^proximately 5 rpm with 283 ml of an aqueous sodium hydroxide solution prepared
from 50% w/w NaOH/H20 in an amount of 110% of that needed to convwt the palladium to its
hydroxide. The solution was drained from the treated support and the support was then rinsed
with deionized water and dried at lOO^C in a fluid bed drier for 1,2 hours. The support material
containing palladium hydroxide was then impregnated with an aqueous solution (81 ml)
containing 1.24 g Au from NaAuCU and 2.71g 50% NaOH solution (1.8 equivalents with respect
to Au) using the incipient wetness method. The NaOH treated pills were allowed to stand
overnight to ensure precipitation of the Au salt to the insoluble hydroxide. The pills were
thoroughly washed with deionized water (~5 hours) to remove chloride ions and subsequently
dried at lOO^C in a fluid bed drier for 1.2 hours. The palladium and gold containing support was
then reduced by contacting the support with C2H4 (1% in nitrogen) in the vapor phase at 150°C
for 5 hours. Finally the catalyst was impregnated by incipient wetness with an aqueous solution
of lOg of potassium acetate in 81 ml H2O and dried in a fluid bed drier at 100°C for 1.2 hours.
Table 1 shows comparison CO2 selectivity and activity for the catalyst of Examples 1 and 7.

[00116] Layered Support Examples
[00117] Example 8: 40 g of Zr02 (RC-100, supplied by DKK) was calcined at 650°C for 3 h.
Resulting material has a BET surface area 38 mVg. The material was ball milled with 120 ml of
DI water for 6 h. The sol was mixed with 22.5 g of the binder zirconium acetate supplied by
DKK (ZA-20) and sprayed onto 55 g of spheres of bentonite KA-160 with OD~7.5mm. Coated
beads were calcined for 3 h at 600°C. Examination under microscope has shown uniform shell
formation with thickness of 250 ^un.
[00118] Example 9: 20 g of ZrOa (XZ16075, BET surface area 55 m^/g) were impregnated
with Pd(N03)2 solution (Aldrich) to give Pd loading of 39 mg/g of Zr02. Impregnated material
was dried and calcined at 450*0 for 4 h. The material was ball milled with 60 ml of DI water for
4h, mixed with 11 g of a binder (21A-20) and sprayed onto 30 g of bentonite KA-160 spheres.
The beads were calcined at 450°C for 3h. This procedure results in formation of a strong uniform
shell with 160 urn thickness.
[00119] Example 10: The beads from Example 8 were impregnated with solution of potassium
acetate to give loading of 40 mg KOAc/ml of KA-160, dried and calcined at 300'C for 4 h. After
that the solution, containing 9.4 mM of Pd(from Pd(NH3)4(OH)2 supplied by Heraeus) and 4.7
mM of Au (from a 1 M solution, Au{0H)3 "Alfa" dissolved in 1.6 M KOH) was sprayed onto
these beads. Material was reduced with the mixture: 5% H2, 95 % N2 at 200°C for 4 h. The beads
were crushed and tested in fix bed micro reactor under conditions described in the experimental
section. CO2 selectivity of ~ 6% at 45% oxygen conversion was achieved.
[00120] Example 11 (reference catalyst): The same catalyst prepared in Example 7 was used
as a reference catalyst here. Table 2 shows comparison CO2 selectivity and activity for the
catalyst of Examples 9-11.
[00121] Table 2

COa Selectivity Activity
Example 9 9.33 2.08
Example 10 9.03 1.69
Example 11 (Reference Catalyst) 11.13 2.36
[00122] Zirconia Support Material and Chloride Free Precursor Examples
[00123] The following general procedure was used for this set of examples. Zirconia support
material catalysts were made as follows: various shaped catalyst carriers were crushed and
sieved. Zirconia support materials were supplied by NorPro (XZ16052 and XZ16075), DKK and
MEL Silica support materials were suppUed by Degussa and Sud Chemie. The sieve fiaction of
180-425um was impregnated (either simultaneously or sequentially with an intermediate drying
step at 110°C and optionally with an intermediate calcination step) to incipi«it wetness with a Pd
and Au precursor solution, optionally calcined in air, reduced with 5%H2/N2 formation gas, post-
impregnated with KOAc solution, dried at lOO'C under N2, and screraied in a 8x6 multi channel
fixed bed reactor. A solution of Au(0H)3 in KOH was used as the Au precursor. Aqueous
solutions of Pd(NH3)4(OH)2, Pd(NH3)2(N02)2, Pd(NH3)4(N03)2 and Pd(N03)2 were used as the
Pd precursors.
[00124] A silica support material catalyst reference was made as follows: A support material
containing palladium and rhodium metal was prqpared as follows: The support material in an
amount of 250 ml consisting of Sud Chemie KA-160 silica spheres having a nominal diameter of
7 mm, a density of about 0.569 g/ml, an absorptivity of about 0.568 g H20/g support, a surface
area of about 160 to 175 m^/g, and a pore volume of about 0.68 ml/g., was first impregnated by
incipient wetness with 82.5 mi of an aqueous solution of sodium tetrachloropalladium (II)
(Na2PdCl4) sufficient to provide about 7 grams of elemental palladium per liter of catalyst. The
support was shaken in the solution for 5 minutes to ensure complete absorption of the solution.
The palladium was then fixed to the support as palladium(II) hydroxides by contacting the treated
support by roto-immersion for 2.5 hours at approximately 5 rpm wath 283 ml of an aqueous
sodium hydroxide solution prepared firora 50% w/w NaOH/H20 in an amount of 110% of that
needed to convert ttie palladium to its hydroxide. The solution was drained from the treated
support and the support was then rinsed with deionized water and dried at 100°C in a fluid bed

drier for 1.2 hours. The support material containiag palladium hydroxide was then impregnated
with an aqueous solution (81 ml) containing 1.24 g Au from NaAuCU and 2.71g 50% NaOH
solution (1.8 equivalents with respect to Au) using the incipient wetness me1iu>d. The NaOH
treated pills were allowed to stand ovemi^t to ensure precipitation of the Au salt to the insoluble
hydroxide. The pills wwe thorou^ly washed with deionized water (~5 hours) to remove
chloride ions and subsequently dried at lOO^C in a fluid bed drier for 1.2 hours. The palladium
and gold containing support was then reduced by contacting the support with C2H4 (1% in
nitrogen) in the vapor phase at 150°C for 5 hours. Finally the catalyst was impregnated by
incipient wetness with an aqueous solution of lOg of potassium acetate in 81 ml H2O and dried in
a fluid bed drier at 100°C for 1.2 hours. Before testing, the catalyst was crushed and sieved. The
sieved fraction in the size range of 180-425um was used.
[00125] Catalyst libraries of arrays of 8 rows x 6 columns in glass vials were designed and a
rack of 36 glass viah; was mounted on a vortexer and agitated while dispensing metal precursor
solutions using Cavro^™* liquid dispensing robots. 0.4ml of support was used for each library
elemrait, for the glass vial synthesis as well as loaded to each reactor vessel.
[00126] KOAc loading is reported as grams KOAc p&: liter catalyst volume or as fimol KOAc
on 0.4ml support. For the specification of Au loading, the relative atomic ratio of Au to Pd is
reported as Au/Pd. Pd loading is specified as mg Pd per 0.4ml support voliune (i.e. absolute
amount of Pd in reactor vessel).
[00127] The screening protocol used a temperature ramp from 145°C to 165°C in 5°C
increments, at a fixed space velocity of 175% (with 1.5mg Pd on 0.4ml support). 100% space
velocity is defined as the following flows: 5.75 seem of Nitrogen, 0.94 seem of Oxygen, 5.94
seem of Ethylene, and 5.38 microliters per minute of Acetic Acid through each of the 48 catalyst
vessels (all of which had an inner diameter of approximately 4 mm). CO2 selectivity was plotted
versus oxygen conversion, a linear fit performed, and the calculated (interpolated in most eases)
CO2 selectivity at 45% oxygen conversion reported in the performance summary tables below.
The temperature at 45% oxygen conversion calculated fixsm the T ramp (linear fits of CO2
selectivity and oxygen conversion versus reaction temperature is also reported). The lower this

calculated temperatun; the higher the activity of the catalyst. The space time yield (STY; g VA
produced per ml catalyst volume per h) at 45% oxygen conversion is a measure of the
productivity of the catalyst.
[00128] Example 12: 400ul of ZrOz carriers XZi6075 (55m^/g as supplied) and XZ16052
(precalcined at 650°C/2h to lower the surface area to 42mVg) were impregnated with 3 different
Pd solutions to incipient wetness, dried at 1 ICC for 5h, impregnated with KAu02 (0.97M Au
stock solution) to incipient wetness, dried at 11CC for 5h, reduced at SSCC for 4h in 5%H2/N2
formation gas, post-impregnated with KOAc and dried at 1 lO'C for 5h. The Pd/Au/ZrOa samples
(shells) were then diluted 1/9.3 with KA160 diluter (preloaded with 40g/l KOAc), i.e. 43ul
Pd/Au/ZrOa shell and 357ul diluter (400ul total fixed bed volume) were charged to the reactor
vessels. The Pd loading was 14 mg Pd in 400ul Zr02 shell (or 14*43/400=14/9.3=1.5mg Pd in
reactor vessel for all library elements. The Pd precursors were Pd(NH3)2CN02)2 in columns 1 and
4, Pd(NH3)4(OH)2 in columns 2 and 5, Pd(NH3)4(N03)2 in columns 3 and 6. Au/Pd=0.3 in row 2
and row 5, Au/Pd=0.6 in row 3, Au/Pd=0.9 in row 4, row 6 and row 7. The KOAc loading was
114umol in rows 2, 3, 5 and 147umol in rows 4,6, 7. The silica reference catalyst was loaded
into Row 1. The library was screened using the T ramp screening protocol at fixed SV.
Screening results are summarized in Table 3
[00129] Table 3
*Data shown is taken from average of two Au/Pd atomic ratios (namely 0.3 and 0.6) and two
different ZrOz supports.
[00130] Example 13: 400ul of Zr02 carriers XZ16075 (55mVg as supplied) and XZ16052
(precalcined at 650°C/2h to lower the surface area to 42mVg) were impregnated with
Pd(NH3)4(OH)2 (1.117M Pd stock solution) to incipient wetness, calcined at 350°C for 4h in air,
impregnated with KAUO2 (0.97M Au stock solution) to incipient wetness, dried at 110°C for 5h,
reduced at 350°C for 4h in 5%H2/N2 formation gas, post-impregnated with KOAc and dried at

1 ICC for 5h. The Pd/Au/Zr02 san^iles (shells) were then diluted 1/12 with KA160 diluter
(preloaded with 40g/l KOAc), i.e. 33.3ul Pd/Au/ZiOz catalyst and 366.7ul diluter (400ul total
fixed bed volume) were charged to flie reactor vessels. The library design and library element
compositions were as follows: ZrOz XZ16075 in colunms 1-3 (left half of library) and ZtOi
XZI6052 (650°C) in columns 4-6 (ri^it half of library). The Pd loading was 18 mg Pd in 400ul
ZrOa shell (or 18*33/400=18/12 mg Pd in reactor vessel) in cell G2, column 3 (cells B3-G3), cell
G5. column 6 (cells B6-G6); 10 mg Pd in 400ul ZrOa shell (or 10*33/400=10/12 mg Pd in
reactor vessel) in column 1 (cells Al-Gl) and column 4 (cells A4-G4)j 14 mg Pd in 400ul Zr02
shell (or 14*33/400=14/12 mg Pd in reactor vessel) in column 2 (ceils B2-F2) and column 5
(cells B5-F5). Au/l?d=0.3 in row 2 and row 5, Au/Pd=0.5 in row 3 and row 6, Au/Pd=0.7 in row
4 and row 7 (except cells Al, A4, G2, G5 where Au/Pd was 0.3). The KOAc loading was
1 Mumol (except cells D3, G3, D6, G6 whore KOAc loading was 147umol). The silica reference
catalyst was loaded into Row 1. The library was screened u^g the T ramp screening protocol at
fixed SV. Screening results are siunmarized in Table 4.
100131} Table 4 ____________________________________________________
[00132J Example 14: Zr02 carrier (supplied by NorPro, XZl6075, sieve fraction 180-425um,
density 1.15g/ml, pore volume 475ul/g, BET surface area 55m2/g) was impregnated with
Pd(N03)2 precursor solution to incipient wetness, dried at 110°C, calcined at 250'C (columns 1-
2), BSCC (columns 3-4), 450'C (colunms 5-6) in air, impregnated with KAuOz solution
(prepared by dissolution of Au(0H)3 in KOH), dried at llO^C, reduced with SVoHi/Nz formation
gas at ZSO^C for 4h, and post-impregnated with KOAc solution. The library has a KOAc grathent
from 25 to 50g/l in row 2 to row 7. The Pd loading amounts to l.Smg Pd on 0.4ml support. Two
different Au loadings were chosen (Au/Pd=0.5 in columns 1, 3, 5 and Au/Pd=0.7 in columns 2,
4, 6). The silica reference catalyst was loaded in row 1. The library was screened using the T

ramp screening protocol in MCFB48 VA reactor at fixed SV. Screening results are summarized
in Table 5.
[00133J Table 5
*Data shown is tak:en firom average of two Au/Pd atomic ratios (namely 0.5 and 0.7) at 40g/L
KOAc, calcination at 450°C, and reduction at SSO^C.
[00134] Example 15: ZrOa carrier (supplied by NorPro, XZ16075, sieve fiaction 180-425um,
density I.15g/ml, pore volume 575ul/g, BET surface area 55m2/g) was impregnated with
Pd(N03)2 precursor solution to incipient wetness, dried at 1 ICC, calcined at 450°C in air,
impregnated with KlAuOa solution (prepared by dissolution of Au(OH)3 in KOH), dried at 1 lO'C,
reduced with 5%H2/N2 formation gas at 20O'C (columns 1-2), 300°C (columns 3-4), or 400'C
(columns 5-6), and post-impregnated with KOAc solution. The library has a KOAc grathent from
15 to 40g/l in row 2 to row 7. The Pd loading amounts to 1.5mg Pd on 0.4ml support. Two
different Au loadings were chosen (Au/Pd=0.5 in columns 1,3, 5 and Au/Pd=0.7 in columns 2,
4, 6). The silica reference catalyst was loaded in row 1. The library was screened in MCFB48
VA reactor using the T ramp screening protocol at fixed SV. Screening results are summarized
in Table 6.
[00135J Table 6
*Data shown is taken fi-om average of two Au/Pd atomic ratios (namely 0.5 and 0.7) at 40g/L
KOAc, calcination at 450°C, and reduction at 400°C.
[00136] It will be further ^preciated that functions or structures of a plurality of components
or steps may be combined into a single component or step, or the functions or structures of one
step or component may be split among plural steps or components. The present invention
contemplates all of these combinations. Unless stated otherwise, dimensions and geometries of
the various structures depicted herein are not intended to be restrictive of the invention, and other

dimensions or geometries are possible. Plural structural components or st^s can be provided by
a single integrated structure or step. Alternatively, a single integrated structure or stq) might be
divided into sqparate plural components or st invention may have been described in the context of only one of the illustrated embodiments,
such feature may be combined with one or more other features of other onbodiments, for any
given application. It will also be appreciated fiom the above that the fabrication of the unique
structures herein and the operation thereof also constitute methods in accordance with the pres|pnt
invention.
[00137] The explanations and illustrations presented herein are intended to acquaint others
skilled in the art with the invention, its principles, and its practical f^jplication. Those 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. Accordingly, the specific embodiments of the present invention
as set forth are not intended as being exhaustive or limiting of the invention. The scope of the
invention should, therefore, be determined not with reference to the above description, but should
instead be determineci with reference to the impended claims, along with the full scope of
equivalents to which such claims are entitled. The disclosures of all articles and references,
including patent applications and publications, are incorporated by reference for all piuposes.
WE CLAIM;
1. A method of producing a catalyst or pre-catalyst suitable for assisting
in the production of alkenyl alkanoates, comprising:
contacting at least one catalytic precursor solution comprising
palladium and gold in amounts such as herein described, to a support
material wherein the at least one
catalytic precursor solution is an aqueous solution that comprises one
or more of Pd(NH3)2(N02)2, Pd(NH3)4(OH)2, Pd(NH3)4(N03)2,
Pd(NH3)4(OAc)2, Pd{NH3)2(OAc)2, Pd(NH3)4(HCO3)2, NaAu02, NMe4Au02,
HAu(N03)4 in nitric acid or combinations thereof; and
reducing the palladium or gold by contacting a reducing
environment to the support material in a manner such as herein
described.
2. The method as claimed in claim 1, wherein the palladium catalytic
precursor solution comprises Pd(NH3)2(NO2)2, Pd(NH3)4(OH)2,
Pd(NH3)4(N03)2, Pd(NH3)4(OAc)2, Pd{NH3)2(OAc)2, Pd(NH3)4(HCO3)2 and a
gold catalytic precursor solutions comprises NaAu02, NMe4AuO2,
HAu{N03)4 in nitric acid.

3. The method as claimed in claim 1 wherein the palladium catalytic
precursor solution comprises Pd(NH3)2(N02)2, Pd(NH3)4(OH)2,
Pd(NH3)4(N03)2, Pd(NH3)4(OAc)2, Pd(NH3)2(OAc)2, Pd(NH3)4{HCO3)2, and a
gold catalytic precursor solutions comprises NaAu02.
4. The method as claimed in claim 1 wherein a gold catalytic precursor
solutions comprises NaAu02, NMe4Au02, HAu(N03)4 in nitric acid and a
palladium catalytic precursor solution comprises Pd{N03)2 or palladium
oxalate.
5. The method as claimed in any of claims 1-4, wherein the support
material comprises silica, alumina, silica-alumina, titania, zirconia,
niobia, silicates, aluminosilicates, titanates, spinel, silicon carbide,
silicon nitride, cairbon, steatite, bentonite, clays, metals, glasses, quartz,
pumice, zeolites, non-zeolitic molecular sieves, or combinations thereof.
6. The method as claimed in any of claims 1-5, wherein the support
material comprises zirconia.
7. The method as claimed in any of claims 1-6, wherein the support
material comprises a layered support material.
8. The method as claimed in any of claims 1-7, wherein the layered
support material comprises an inner layer and an outer layer, wherein
the inner layer is substantially free of palladium and gold.
9. The method as claimed in any of claims 1-8, wherein the
contacting step comprises contacting between 1 to 10 grams of
palladium, and 0.5 to 10 grams of gold per liter of catalyst to the
support material, with the amount of gold being from 10 to 125 wt %
based on the weight of palladium.
10. The method as claimed in any of claims 1-9, wherein the catal5rtic
precursor solution comprises at least a third component containing
rhodium.
11. The method as claimed in any of claims 1-10, further comprising
contacting potassium acetate to the support material.
12. The method as claimed in any of claims 1-11, wherein the potassium
acetate is present in an amount of between 10 and 70 grams per liter of
catalyst.
13. A composition for catalyzing the production of an alkenyl
alkanoates, comprising:
a support materisLl selected from support materials as herein described
with at least palladium and gold in amounts as herein described,
contacted thereon to form a catalyst or pre-catalyst, wherein catalyst or
pre-catalyst is formed
from one or more precursors comprising one or more of Pd(NH3)2(N02)2,
Pd(NH3)4(OH)2, Pd(NH3)4(N03)2, Pd(NH3)4(OAc)2, Pd(NH3)2(OAc)2,
Pd(NH3)4(HCO3)2, NaAu02, NMe4Au02, HAu(N03)4 in nitric acid or
combinations thereof.
14. The composition as claimed in claim 13 wherein a palladium
catalytic precursor solution comprises Pd{NH3)2(N02)2, Pd(NH3)4(OH)2,
Pd(NH3)4(N03)2, Pd(NH3)4(OAc)2, Pd(NH3)2(OAc)2, Pd(NH3)4{HCO3)2 and a
gold catalytic precursor solutions comprises NaAu02, NMe4Au02,
HAu(N03)4 in nitric acid.
15. The composition as claimed in claim 13 wherein a palladium
catalytic precursor solution comprises Pd(NH3)2(N02)2, Pd(NH3)4(OH)2,
Pd(NH3)4(N03)2, Pd(NH3)4(OAc)2, Pd(NH3)2(OAc)2, Pd(NH3)4(HCO3)2 and a
gold catalytic precursor comprises KAUO2.
16.The composition as claimed in claim 13 wherein a gold catalytic
precursor solutions comprises NaAu02, NMe4Au02, HAu(N03)4 in niti-ic
acid and a palladiiam catalytic precursor solution comprises Pd(N03)2 or
palladium oxalate.
17. The composition as claimed in any of claims 13-16, wherein the
support material comprises zirconia.
18. The composition as claimed in any of claims 13-17, wherein the
support material comprises a layered support material.
19. The composition as claimed in any of claims 13-18, wherein the
catalyst or pre-catalyst comprises a third component containing
rhodium.
20. The composition as claimed in any of claims 13-19, wherein the
catalyst or pre-catalyst comprises between 1 to 10 grams of palladium,
and 0.5 to 10 grams of gold per liter of catalyst, with the amount of gold
being from 10 to 125 wt% based on the weight of palladium.
21. The composition as claimed in any of claims 13-20, wherein the
catalyst or pre-catalyst comprises potassium acetate.
22. The composition as claimed in any of claims 13-21, wherein the
potassium acetate is present in an amount of between 10 and 70 grams
per liter of catalyst.
23. The composition as claimed in any of claims 13-22, wherein the
support material comprises particle support material or a ground
support material.


The present invention addresses at least four different aspects relating to catalyst
structure, methods of making those catalysts and methods of using those catalysts for
making alkenyl alkanoates. Separately or together in combination, the various aspects
of the invention are directed at improving the production of alkenyl alkanoates and VA
In particular, including reduction of by-product and improved production efficiency. A
first aspect of the present invention pertains to a unique palladium/gold catalyst or pre-
catalyst (optionally calcined) that includes rhodium or another metal. A second aspect
pertains to a palladium/gold catalyst or pre-catalyst that is based on a layered support
material where on layer of the support material is substantially free of catalytic
component. A third aspect pertains to a palladium/gold catalyst or pre-catalyst on a
zirconia containing support material. A fourth aspect pertains to a patiadium/goid
catalyst or pre-catalyst that is produced from substantially chloride fi'ee catalytic
components.

Documents:

01284-kolnp-2006 abstract.pdf

01284-kolnp-2006 claims.pdf

01284-kolnp-2006 correspondence others-1.1.pdf

01284-kolnp-2006 correspondence others.pdf

01284-kolnp-2006 description (complete).pdf

01284-kolnp-2006 form-1.pdf

01284-kolnp-2006 form-2.pdf

01284-kolnp-2006 form-26.pdf

01284-kolnp-2006 form-3.pdf

01284-kolnp-2006 form-5.pdf

01284-kolnp-2006 international publication.pdf

01284-kolnp-2006 international search report.pdf

01284-kolnp-2006 pct form.pdf

01284-kolnp-2006 priority document-1.1.pdf

01284-kolnp-2006 priority document.pdf

1284-KOLNP-2006-ABSTRACT.pdf

1284-KOLNP-2006-CANCELLED DOCUMENT.pdf

1284-KOLNP-2006-CLAIMS.pdf

1284-KOLNP-2006-CORRESPONDENCE 1.1.pdf

1284-KOLNP-2006-DESCRIPTION COMPLATE.pdf

1284-KOLNP-2006-FORM 1.pdf

1284-KOLNP-2006-FORM 2.pdf

1284-kolnp-2006-form 27 1.1.pdf

1284-kolnp-2006-form 27.pdf

1284-KOLNP-2006-FORM 3.pdf

1284-KOLNP-2006-FORM 5.pdf

1284-kolnp-2006-granted-abstract.pdf

1284-kolnp-2006-granted-assignment.pdf

1284-kolnp-2006-granted-claims.pdf

1284-kolnp-2006-granted-correspondence.pdf

1284-kolnp-2006-granted-description (complete).pdf

1284-kolnp-2006-granted-examination report.pdf

1284-kolnp-2006-granted-form 1.pdf

1284-kolnp-2006-granted-form 18.pdf

1284-kolnp-2006-granted-form 2.pdf

1284-kolnp-2006-granted-form 26.pdf

1284-kolnp-2006-granted-form 3.pdf

1284-kolnp-2006-granted-form 5.pdf

1284-kolnp-2006-granted-reply to examination report.pdf

1284-kolnp-2006-granted-specification.pdf

1284-KOLNP-2006-OTHERS-1.1.pdf

1284-KOLNP-2006-OTHERS.pdf

1284-KOLNP-2006-PETITION UNDER SECTION 8(1).pdf

1284-KOLNP-2006-REPLY TO EXAMINATION REPORT.pdf


Patent Number 236247
Indian Patent Application Number 1284/KOLNP/2006
PG Journal Number 42/2009
Publication Date 16-Oct-2009
Grant Date 13-Oct-2009
Date of Filing 16-May-2006
Name of Patentee CELANESE INTERNATIONAL CORPORATION
Applicant Address 1601 WEST LBJ FREEWAY, DALLAS, TX
Inventors:
# Inventor's Name Inventor's Address
1 WANG, TAO 15811 EI DORADO OAKS DRIVE, HOUSTON, TX 77059
2 WADE, LESLIE, E. 1310 SENTOR DR., PEARLAND, TX 77581
3 WONG, VICTOR 3229 GATELAND COURT, SAN JOSE, CA 95148
4 HAN, JUN 865 CARLISLE WAY, APT. 44, SUNNYVALE, CA 94087
5 HAGEMEYER, ALFRED 655 FAIR OAKS AVENUE, APT. J-302, SUNNYVALE, CA 94086
6 LOWE, DAVID 992 BELMONT TERRACE, APT. 8, SUNNYVALE, CA 94086
7 SOKOLOVSKII, VALERY 578 IRONWOOD TERRACE, APT.4, SUNNYVALE, CA 94086
PCT International Classification Number B01J 23/52
PCT International Application Number PCT/US2004/038815
PCT International Filing date 2004-11-19
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/530/937 2003-12-19 U.S.A.