Title of Invention

A METHOD FOR THE MANUFACTURE OF A NOBLE METAL CATALYST

Abstract There is disclosed a method for the manufacture of a noble metal catalyst for hydrocarbon conversion, characterized in that the method comprises the following steps: a) Pre-treatment of a support comprising a zeolite selected from medium and large pore zeolite having acid sites, at a temperature between 323 to 1173 K, and optional modification of the support; b) Deposition of a noble metal, as_described herein before, selected from platinum, palladium, ruthenium, rhodium, iridium and mixtures and combinations thereof by gas phase deposition technique comprising vaporisation of the noble metal precursor selected from β-diketonates and metallocenes and reaction with the support, and c) Heat treatment at oxidising or reducing conditions.
Full Text A METHOD FOR THE MANUFACTURE OF A NOBLE METAL CATALYST
Field of the invention
The present invention relates to a noble metal catalyst, to a method for the preparation
thereof based on gas phase technique, to the use of the catalyst in reactions such as ring-
opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming, hydrogena-
tion and dehydrogenation reactions, and to a method for the manufacture of middle dis-
tillates.
Background of the invention
It is well known in the state of the art that noble metal catalysts are active in hydrocar-
bon reforming, isomerisation, isodewaxing, dehydrogenation and hydrogenation reac-
tions. Commercially available noble metal catalysts typically consist of platinum, palla-
dium, ruthenium, rhodium, iridium or mixtures thereof.
Supported noble metal catalysts are traditionally prepared in liquid phase by impregna-
tion or ion-exchange technique. Only a few reports on the deposition of noble metals
from gas phase on porous support materials, in the preparation of heterogeneous cata-
lysts, are known from the literature. Vaporised noble metal precursors are most com-
monly deposited intact, usually by physisorption/condensation, on the support surface
and afterwards decomposed to form metallic particles, or they are thermally or chemi-
cally decomposed during deposition.
Dossi et al. (J. Catal. 145 (1994) 377-383) have introduced reductive decomposition of
volatile organometallic precursors inside zeolites, a two-step process where the or-
ganometallic precursor was first deposited intact inside zeolite cages and then decom-
posed under controlled reduction conditions to metal particles. When Pt/KL catalysts

were prepared from platinum hexafluoro acetylacetonate, small metal particles (maxi-
mum diameter 7-8 Å) were formed inside the zeolite cages. In Pd/NaY catalysts pre-
pared from Pd(C3H5)(C5H5) large Pd particles filling zeolite supercages were formed (J.
Catal 149 (1994) 92-99). An advantage of this organometallic chemical vapour deposi-
tion (CVD) procedure, when compared to ion-exchange procedures, is that no acidic
sites are formed in the zeolite upon reduction.
A method for producing Pd/Au shell catalysts by a CVD process is disclosed in WO
99/67022. Evaporable Pd/Au precursors form metal particles on the support surface
either during the deposition or afterwards by thermal or chemical reduction. The thick-
ness of the shell containing the metal particles is controlled by process parameters.
Lashdaf et al. (Appl. Catal. A241 (2003) 51-63) present a different approach, where
vaporised Pd and Ru beta-diketonates were deposited on alumina and silica supports in
gas-solid reactions. In this technique, the reaction temperature was kept high enough to
ensure chemisorption of the metal precursor, and me reactions were allowed to proceed
until saturation of the surface was achieved. This reactive interaction with the support
surface generally leads to well-dispersed species. The reactive interaction of a vaporis-
able noble metal precursor with a support has also been utilized by Mu et al. (Appl.
Catal A248 (2003) 85-95).
The use of saturating gas-solid reactions in a gas phase process, for the manufacture of a
heterogeneous catalyst, is disclosed in WO 91/10510. Said process comprises an op-
tional pre-treatment step wherein the support, which may be an inorganic oxide, such as
alumina or silica, or a zeolite, is thermally and/or chemically treated in order to provide
the desired binding sites for the catalytically active component that is to be bound to the
support. Then the surface activated support is contacted and allowed to interact with
vapour containing the catalytically active species or its precursor at conditions ensuring
that saturating gas-solid reactions take place, i.e. by providing the precursor in an excess
relative to the amount of binding sites on the support and by maintaining the reaction
temperature at a sufficiently high level to attain chemisorption of the precursor to the

binding sites of the support. Then an optional post-treatment follows, which may com-
prise a heat-treatment step carried out at oxidizing or reducing conditions. Zeolite-
supported zinc, alumina-supported rhenium and silica-supported chromium are men-
tioned as main groups.
A similar, improved gas phase memod for the manufacture of a heterogeneous catalyst,
based on saturating gas-solid reactions, is presented in FI 913438. It discloses control
methods that can be employed in saturating reactions to attain a desired content of the
active metal species. Said process comprises an optional pre-treatment step wherein the
support is thermally and/or chemically treated. The chemical treatment may comprise
treating the support with an inhibiting reagent, such as hexamethyl disilazane, which
deactivates a portion of the available surface bonding sites, or a reagent, such as water,
which increases the number of available surface bonding sites.
Noble metal catalysts are chemically stable, easy to store and handle. Mechanical stabil-
ity and formability lie mainly on the support used in the catalyst. Noble metal catalysts
are widely used in oil refining and in chemical and pharmaceutical industry in several
reactions like hydrocarbon reforming, isomerisation, isodewaxing, dehydrogenation,
hydrogenation and dry reforming processes.
Said reactions are defined generally in the following. Hydrocarbon reforming reactions
typically comprise aromatics and hydrogen formation as well as isomerisation. In olefin
isomerisation processes double bond isomerisation and skeletal isomerisation take
place, in addition to side reactions such as cracking and dimerisation. The desired reac-
tion in n-paraffin isomerisation processes is isomerisation of n-paraffins to isoparaffins.
Isodewaxing processes comprise isomerising of wax molecules, and in dehydrogenation
reactions olefins are produced from paraffins. Hydrogenation processes comprise addi-
tion of hydrogen into a molecule, and thus olefins and diolefins are hydrogenated to
paraffins and olefins, respectively, and aromatics to naphthenes. In dry reforming reac-
tions methane and carbon dioxide react to produce hydrogen and carbon monoxide.

Carbon monoxide is an important reactant in many processes, such as the Fischer-
Tropsch synthesis and the process for the manufacture of methanol. The required car-
bon monoxide and hydrogen may be prepared by dry reforming technique utilizing car-
bon dioxide and paraffins as reactants and by steam reforming technique using water
and paraffins as reactants and a catalyst for said carbon monoxide activating reactions
comprises nickel, rhodium, rumenium, palladium, platinum or mixtures thereof on a
support.
Various ring-opening catalysts and processes have been proposed in the state of the art.
A catalyst for ring-opening reactions of cyclic organic compounds is presented in US
6,235,962. The catalyst comprises a catalytically active metal selected from platinum,
palladium, rhodium, rhenium, iridium, ruthenium, nickel, cobalt and mixtures or com-
binations thereof, a metal modifier selected from tungsten, molybdenum, lanthanum and
rare earth metals and mixtures and combinations thereof, on a carrier selected from
alumina, silica, zirconia and mixtures thereof. Said catalysts are efficient heterogeneous
catalysts for ring-opening reactions of cyclic compounds in the presence of hydrogen.
Cyclic compounds include derivatives of cyclopentane, cyclohexane, decalin, indane,
indene, benzene and naphthalene present in diesel fuel.
A naphthalene ring-opening catalyst for forming high cetane number distillates having
high degree of linear paraffins is disclosed in WO 00/08156. The catalyst comprises
iridium and an effective amount of metals of group VIII, such as platinum, rhodium
and/or ruthenium. The catalyst composition is especially effective in opening com-
pounds containing C6 naphthene rings to C5 naphthene rings bearing at least one. tertiary
carbon.
WO 00/08157 discloses a catalyst system comprising naphthene ring-isomerising cata-
lyst (50-90 %) and naphthene ring-opening catalyst (50-10 %). The isomerising catalyst
contains a specific metal supported on a first catalyst support for isomerising com-
pounds containing C6 naphthene rings to C5 naphthene rings, preferably platinum or
palladium on alumina. The naphthene ring-opening catalyst contains another specific

metal on a second catalyst support, for ring-opening compound containing naphthene
rings, preferably iridium on alumina.
WO 00/08158 teaches the use of a catalyst for naphthenic ring-opening of distillates,
comprising group VIII metal e.g. iridium, platinum, palladium, rhodium and/or ruthe-
nium, supported on a substrate (e.g. alumina modified with magnesium) having at least
one group IB, IIB and IVA metal in an amount effective to moderate cracking of naph-
thene ring containing feed to form methane. The catalyst also suppresses dealkylation of
any pendant substituents optionally present in the ring structure. The catalyst exhibits
desirable tertiary bond cleavage activity. Said method provides relatively high contents
of linear and less branched paraffins and the preferred ring-opening catalyst composi-
tions are Ir-Cu, Ir-Sn, Pt-Ir-Sn, Pt-Cu and Pt-Sn.
The use of a catalyst composition comprising iridium is disclosed in WO 02/07881. Said
catalyst composition is useful for altering the range of tertiary carbon sites in naphthene
or naphthenic ring containing distillates, in order to form products with a higher degree
of linear paraffin functionality. Particularly the composition is effective in ring-opening
compounds containing C5 and C6 naphthene rings bearing at least one tertiary carbon.
The catalyst composition comprises iridium, which is supported on a composite support
of an alumina component and acidic silica alumina molecular sieve component. Alter-
natively, at least one other or second group VIII metal selected from platinum, ruthe-
nium and rhodium can be added to the iridium containing catalyst.
A two-stage process for producing diesel fuel with increased cetane number and par-
ticularly for selective naphthenic ring-opening reactions is disclosed in US
2002/0121457. In said process the first stage comprises a hydro-treating stage for re-
moving sulphur from the feed and the second stage is the selective ring-opening stage.
The ring-opening catalyst is an extremely low acidic catalyst having a high selectivity
to middle distillate, containing highly dispersed platinum. Preferably the catalyst con-
tains a crystalline molecular sieve material component and a group VIII noble metal
component. The crystalline molecular sieve component is a large pore zeolite having an

alpha-acidity of less than 1, and zeolite USY is mentioned as the preferred crystalline
molecular sieve material. The group VIE noble metal component can be platinum, pal-
ladium, iridium, rhodium or a combination thereof. The ultra low acidity of the catalysts
permits the cracking of only carbon-carbon bonds without secondary cracking and hy-
droisomerisation of desired paraffins for diesel fuel.
It is known from the state of the art relating to diesel fuels that the quality can be im-
proved and the volume can be increased by ring-opening of naphthenes and further, the
production of diesel fuels from naphthenic crude oils can be increased. The general re-
action for converting naphthenes to paraffins is referred to herein as a ring-opening re-
action. The cetane number of n-paraffins and slightly branched paraffmic components
in the diesel region is higher and the density is lower than that of the corresponding
naphthenic components. Although the hydrogenation of aromatics of middle distillates
increases remarkably the cetane number and effects also in some extent on particle
emissions, the opening of naphthenic rings brings additional advantage.
Middle distillate is a mixture of different hydrocarbons comprising typically molecules
with carbon numbers C9 - C21 and the typical boiling range of middle distillate is be-
tween 432 - 623 K. Middle distillate contains usually aromatics, paraffins and naphte-
nes.
The reaction from naphthenes to paraffins can also be applied in the production of base
oils and in the improvement of the quality of solvents. The quality of crude oils used in
oil refineries in the production of base oils effects on the viscosity index and on the vis-
cosity of the obtained products. By opening of naphthenic rings the viscosity index of
lube oils can also be increased. Further, as naphthenic components may cause undesired
odours in solvents, by opening naphthenic rings it is possible to decrease the odour and
improve the quality of solvents.
WO 00/40676 teaches a process for producing of diesel fuel with increased cetane num-
ber from hydrocarbon feedstock. The process includes contacting the feedstock with a

catalyst, which has large pore crystalline molecular sieve material component having
faujasite structure and alpha acidity of less than 1. The catalyst contains a dispersed
Group VIII noble metal component which catalyses the hydrogenation/hydrocracking of
the aromatic and naphthenic species in the feedstock and the preferred catalyst combi-
nation is platinum/USY. The cetane number of the fraction boiling above 477 K was
improved from 63 to 65-69.
WO 02/07877 discloses a process for opening naphthenic rings of naphthenic ring con-
taining compounds with catalysts comprising at least one group VIII metal selected
from iridium, platinum, rhodium and ruthenium wherein these metals are supported on
an alkali metal or alkaline earth metal modified support. Said catalysts can be used to
provide a reduced number of ring structures in the product stream, to minimize dealky-
lation of any pendant substituents optionally present in the ring structure and to increase
the volume of the product. The catalyst is particularly beneficial in converting
naphthene feed containing C6 naphthene ring containing composition, wherein the C6
ring contains at least one tertiary carbon site, to a product containing a substantial quan-
tity of linear and less branched paraffin compounds. The group VIII metal is supported
on a substrate containing an effective amount of an alkali metal or alkaline-earth metal
and the substrate is desirably a refractory inorganic oxide, preferably with lower acidity,
such as alumina.
The distribution and dispersion of metal particles on a support material are important
properties, which affect the behaviour of noble metal catalysts in hydrocarbon reactions.
Mostly, highly dispersed metal particles on suitable support materials are a prerequisite
for highly active noble metal catalysts. However, well-dispersed metal particles may
show different behaviour due to variations in their electronic and/or geometric proper-
ties. Since noble metals are commonly present in very low concentrations in heteroge-
neous catalysts, said properties are difficult to measure directly.
Indirect measurements using probe molecules are in many cases more sensitive and they
can be used for monitoring even small variations in the properties of metal particles.

Formation of carbon dioxide during adsorption of carbon monoxide at a temperature
below 300 K is a reaction, which so far has not been observed to be activated on noble
metal catalysts, as was confirmed by Bourane and Bianchi (J. Catal. 218 (2003) 447-
452).
From the state of the art it can be seen that the cleavage of carbon-carbon bond inside
the naphthene ring is not an easy reaction and it leads very readily to secondary crack-
ing reactions. Thus there is an evident need for a selective noble metal catalyst with
improved performance in the process involving the cleavage of carbon-carbon bond
inside the naphthene ring. There is also an increasing demand for paraffinic solvents,
arising from their low toxicity and biodegradability.
Object of the invention
An object of the invention is to provide a selective noble metal catalyst for hydrocarbon
conversion reactions such as ring-opening, isomerisation, alkylation, hydrocarbon re-
forming, dry reforming, hydrogenation and dehydrogenation reactions, and particularly
for ring-opening of naphthenic molecules.
A further object of the invention is a method for the manufacture of a selective noble
metal catalyst for hydrocarbon conversion reactions such as ring-opening, isomerisa-
tion, alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydroge-
nation reactions, and particularly for ring-opening of naphthenic molecules.
A further object of the invention is the use of a selective noble metal catalyst in hydro-
carbon conversion reactions such as ring-opening, isomerisation, alkylation, hydrocar-
bon reforming, dry reforming, hydrogenation and dehydrogenation reactions, and par-
ticularly in ring-opening of naphthenic molecules.
A still further object of the invention is a process for the manufacture of middle distil-
late diesel fuel using a selective noble metal catalyst for ring-opening of naphthenes

with two and multiple rings in middle distillate, particularly to manufacture correspond-
ing isoparaffins, n-paraffins and mononaphthenes in the middle distillate region.
The characteristic features of the catalysts, of the method for the manufacture of the
catalyst, of the use of the catalyst and of the process for the manufacture of middle dis-
tillate diesel fuel are provided in the claims.
Summary of the invention
The present invention relates to a selective noble metal catalyst comprising a noble
metal catalyst on a support, wherein the noble metal and the support are active, or the
noble metal is active. The method for the manufacture of said selective noble metal
catalyst comprises use of gas phase technique. The selective noble metal catalyst ac-
cording to the invention can be used as a catalyst in hydrocarbon conversion reactions,
such as ring-opening, isomerisation, alkylation, hydrocarbon reforming, dry reforming,
hydrogenation and dehydrogenation reactions. The method for the manufacture of mid-
dle distillate diesel fuels comprises the use of the selective noble metal catalyst in the
process.
Detailed description of the invention
Surprisingly it has been found that a selective noble metal catalyst can be obtained,
comprising a noble metal catalyst on a support, wherein the noble metal and the support
are active, or the noble metal is active, using gas phase technique. According to the in-
vention the selective noble metal catalyst comprises a group VIII metal selected from
platinum, palladium, ruthenium, rhodium, iridium or mixtures or combinations thereof,
preferably platinum, on a support and the catalyst activates carbon monoxide at tem-
perature below 323 K.

The support is selected from zeolites, inorganic oxides, carbon related materials and
mixtures and combinations thereof. Acidic support materials are also catalytically ac-
tive.
The zeolite is selected from medium or large pore zeolites having acid sites, preferably
large pore zeolites having weak or medium strength of acid sites. Particularly suitable
zeolite materials are mesoporous aluminosilicates, such as MCM-41, crystalline alurni-
nosilicates, such as Y- and beta-zeolites, and mordenites, crystalline aluminophos-
phates, such as AIPO-5 and AIPO-11, as well as crystalline aluminosilicophosphates,
such as SAPO-5 and SAPO-11.
The inorganic oxide is selected from silicon oxide, aluminum oxide, titanium oxide,
zirconium oxide, tungsten oxide, magnesium oxide and any mixtures thereof and pref-
erably from silicon oxide and aluminum oxide.
The carbon related material is selected from activated carbon, graphite and carbon
nano tubes.
The method for the manufacture of the noble metal catalyst comprises the following
steps:
a) pre-treatment of the support at a temperature between 423 - 1173 K and op-
tional modification of the support;
b) deposition of the noble metal comprising vaporisation of the noble metal precur-
sor and reaction with the support, and
c) final handling.
The noble metal is deposited on the support by gas phase deposition technique. As a
preferable embodiment, the gas phase technique is based on gas-solid reactions. The
selection of the noble metal precursor is an important feature, as the noble metal precur-
sor should not decompose thermally during the vaporisation and it should also be stable

enough to withstand heating to the reaction temperature. The volatile metal compounds
used as precursors in the gas phase preparation are selected from a wide range of com-
pounds including metal chlorides, oxychlorides, beta-diketonates, metallocenes, such as
(CH3)3(CH3C5H4)Pt, and oxides. The precursor may be a liquid, solid, or gas at room
temperature.
Accordingly, the metal is deposited on the support by gas phase deposition using a cor-
responding metal precursor. The processing is carried out at ambient or reduced pres-
sure depending on the precursor, in the presence of an inert carrier gas, such as nitrogen,
helium, argon, methane or the like.
In the first process step the support is pre-treated at a temperature of 423 - 1173 K. A
pressure in the range of ambient to reduced pressure may be used. When saturating gas-
solid reactions are utilised, the amount of the metal deposited can be minimised in the
optional modification step by blocking part of the available surface sites on the support.
The optional modification to modify the support surface can be carried out by deposit-
ing a blocking agent on the support using gas phase or liquid phase technique, such as
impregnation from an organic solution, preferably gas phase technique. Any blocking
agents known in the art may be used and me suitable ones are selected from com-
pounds, which during final handling can be completely removed from the support sur-
face, preferably such as alcohols, acetylacetone (acacH) or 2,2,6,6-tetramethyl-3,5-
heptanedione (thdH), or the blocking agents may leave elements on the surface of the
support, common with the support material itself, preferably such as precursors of sili-
con oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide and mag-
nesium oxide. The preferable silicon oxide, aluminum oxide, titanium oxide, zirconium
oxide, tungsten oxide and magnesium oxide precursors are presented in the following.

Silicon oxide
Preferable silicon compounds are, for example, silicon tetrachloride SiCl4, silicon
alkoxides, such as tetramethoxysilane Si(OMe)4 and tetraethoxysilane Si(OEt)4, and
compounds formed by silicon and organic compounds, such as hexamethyldisilazane
(HMDS) (CH3)3Si-NH-Si(CH3)3 or hexamethyldisiloxane (HMDSO) (CH3)3Si-O-
Si(CH3)3.
Aluminum oxide
Preferable aluminum compounds are, for example, aluminum chloride A1C13 or meta-
lorganic compounds, such as aluminum ethoxide Al(OEt)3, aluminum (III) acetyl-
acetonate Al(C5H7O2)3, tris(2,2,6,6,-tetemaemyl-3,5-heptanedlonato)aluminum
Al(C11H19O2)3, or organometallic compounds, such as trimethylaluminum (TMA)
A1(CH3)3 and triethylaluminum Al(C2H5)3.
Titanium oxide
Preferable titanium compounds are titanium tetrachloride TiCl4 and titanium isopropox-
ideTi(OCH(CH3)2)4.
Zircnninm oxide
A preferable zirconium compound is zirconium tetrachloride ZrCl4.
Tungsten oxide
Preferable tungsten compounds are tungsten oxychloride WOCUand tungsten hexachlo-
ride WCl6.
Magnesium oxide
A preferable magnesium compound is tris(2,2,6,6-tetramethyl-3,5-heptanedionato)-
magnesium Mg(C11H19O2)2.

In the second process step the precursor selected from volatile metal compounds, pref-
erably (trimethyl)methyl cyclopentadienyl platinum (CH3)3(CH3C5H4)Pt, is vaporised at
a temperature of 323-573 K, preferably 343-473 K and it is allowed to react with the
support, preferably as a fixed or fluidised bed of the support, and the support has been
stabilised at a temperature of 323-573 K, preferably 373-573 K. The precursor is va-
porised in amounts sufficiently high to ensure the desired noble metal content on the
support. The amount of the noble metal deposited on the support varies between
0.01-20 wt%, preferably 0.01-5 wt%.
In the third process step final handling is carried out by a heat-treatment performed at
oxidising or reducing conditions.
After the final handling the formulation of the catalyst material with a carrier and/or
binder can be performed using methods known in the state of the art, such as grinding,
tabletting, granulating or extruding.
The gas phase processing of the catalyst material can be carried out in a conventional
fixed bed reactor, in a fluidised bed reactor or in any other reactors known in the state of
the art. The gas phase reaction can be performed in closed reactor systems or in open
reactor systems.
The obtained noble metal catalyst exhibits the following characteristic features: the
catalyst activates carbon monoxide at temperatures below 323 K and it is highly dis-
persed which is illustrated in example 19. The noble metal content in the catalyst ac-
cording to the invention is low.
The catalyst according to the invention performs well in hydrocarbon conversion reac-
tions such as ring-opening, isomerisation, alkylation, hydrocarbon reforming, dry-
reforming and dehydrogenation reactions, and particularly it is suitable for ring-opening
of naphthenic molecules.

The noble metal catalyst according to the invention has several further advantages. It is
stable, more effective and selective in reactions such as ring-opening, isomerisation,
alkylation, hydrocarbon reforming, dry reforming, hydrogenation and dehydrogenation
reactions, and it can be used in smaller amounts to achieve high conversions. Addition-
ally it causes less cracking than catalysts according to the state of the art and it can be
easily regenerated.
The method according to the present invention, for the manufacture of the noble metal
catalyst, is simpler, it requires less process steps than conventional liquid phase meth-
ods, it can be performed in a single apparatus and the manufacture is less expensive as
less noble metal is needed. Further, this is a novel method for the manufacture of ring-
opening catalysts, as earlier catalysts have not been prepared by gas phase technique.
The noble metal catalyst is particularly suitable for the process for the manufacture of
middle distillates. In the process for the manufacture of middle distillate diesel fuel a
middle distillate feedstock is transferred to a reactor wherein it is allowed to react at a
temperature of 283 - 673 K and under a pressure of 10 - 200 bar with hydrogen in the
presence of the noble metal catalyst according to the invention to accomplish opening
of naphthenes with two and multiple rings to produce isoparaffins, n-paraffms and
mononaphthenes in the middle distillate region. The volume of middle distillate diesel
fuels can be increased and higher cetane numbers can be achieved when the catalyst
according to the invention is used in a reaction where multi-ring naphthenes are con-
verted into mono-ring naphthenes and paraffins.
The invention is illustrated in more detail with the following examples, however to
which the scope of the invention is not meant to be limited.
Examples
For the manufacture of noble metal catalysts by impregnation (comparative examples)
and by gas phase technique (examples according to the invention) the supports, com-

mercial beta-zeolite and MCM-41, which was supplied by Abo Akademie University,
Finland, were sieved to a particle size of 75-150 µm and dried overnight at 423 K. The
platinum contents of the catalysts were determined by ICP (Inductively coupled plasma
emission). The prepared catalysts were characterised by dispersion measured by CO-
adsorption analysis. In the analysis the sample (100-200 mg) was inserted in a quartz U-
tube and reduced in H2 stream (20 ml/min). A ramp rate of 10 K/min was applied and
the temperature was linearly raised to a final temperature of 573 K, where it was held
for 120 min. Then the specimen was cooled to 300 K under flowing He (purity 99.9999
%), and when the baseline was stable the experiment was started. Pulses of CO (purity
99.997 %) were repeated until the adsorption was saturated. The exhaust gas was ana-
lysed with infrared spectroscopy (IR) and with mass spectrometry (MS).
Example 1 (comparative example)
Manufacture of platinum loaded beta-zeolite catalyst (Pt-beta-1) by conventional incipi-
ent wetness impregnation
Platinum loaded beta-zeolite catalyst (Pt-beta-1) was prepared by conventional incipient
wetness impregnation of standardised metal solutions. The platinum precursor was
tetraammineplatinum(II) nitrate [Pt(NH3)4](NO3 )2]. The catalyst was calcined at 623 K
in air and reduced under hydrogen at 573 K. The platinum content was 0.5 wt%. The
dispersion measured by CO adsorption was 45 %.
Example 2 (comparative example)
Manufacture of platinum loaded beta-zeolite catalyst (Pt-beta-2) by conventional incipi-
ent wetness impregnation
Platinum loaded beta-zeolite catalyst (Pt-beta-2) was prepared by conventional incipient
wetness impregnation of standardised metal solutions. The platinum precursor was
tetraamrnineplatinum(II) nitrate [Pt(NH3)4](NO3 )2]. The catalyst was calcined at 623 K
in air and reduced under hydrogen at 573 K. The platinum content was 4.7 wt%. The
dispersion measured by CO adsorption was 24 %.

Example 3 (comparative example)
Manufacture of platinum loaded beta-zeolite catalyst (Pt-beta-3) by conventional incipi-
ent wetness impregnation
Platinum loaded beta-zeolite catalyst (Pt-beta-3) was prepared by conventional incipient
wetness impregnation of standardised metal solutions. The platinum precursor was
tetrammineplatinum(n) chloride [Pt(NH3)4]Cl2]. The catalyst was calcined at 623 K in
air and reduced under hydrogen at 573 K. The platinum content was 0.5 wt%.
Example 4 (comparative example)
Manufacture of platinum loaded beta-zeolite by conventional ion-exchange procedure
Platinum loaded beta-zeolite was prepared by an ion-exchange procedure as follows. 10
g of H-beta-zeolite was weighed to a 2 1 flask and 11 of ion-exchanged water was ad-
ded. 52 ml of 0.01 M Pt-solution was measured to a drop funnel and the Pt-solution was
dropped slowly (about 15 drops/min) to the flask at a temperature of 343 K and with
shaking. The mixture was filtered. The impregnated zeolite was washed with ion-
exchanged water, refiltered and placed into an oven at a temperature of 353 K for 16
hours. The obtained catalyst was calcined in an oven at 573 K. The platinum content of
the catalyst was 0.11 wt%.
Examples 5-7
Manufacture of platinum catalysts on beta-zeolite and mesoporous MCM-41 by gas
phase deposition technique according to the invention
Platinum catalysts were prepared on beta-zeolite and mesoporous MCM-41 by gas pha-
se deposition using (trimethyl)methyl cyclopentadienyl platinum (TV) as the precursor
(purity 99 %). The processing was carried out in a flow-type reactor at reduced pressure
of about 5-10 kPa with nitrogen as carrier gas. Before the deposition the supports were
preheated at 673 K in a muffle furnace under atmospheric pressure for 16 hours. Addi-
tionally, they were heated in situ in the reactor at 473 - 673 K for 3 hours to remove

water adsorbed during their transfer to the reactor. The precursor (CH3)3(CH3C5H4)Pt
was vaporised at 343 K and allowed to react at 373 K with a fixed bed of the support
that had been stabilised to the same temperature. The reaction was completed with a
nitrogen purge at the reaction temperature. In the final handling step the catalysts were
calcined in air at 623 K.
In the following table 1 the properties of the platinum catalysts prepared from gas phase
using (CH3)3(CH3C5H4)Pt are presented (examples 5 - 7). Saturated deposition in the
table means that the metal precursor was allowed to react with all available adsorption
sites on the support

Examples 8-11
Manufacture of Pt/Al2O3 catalysts by saturating gas-solid reactions using Pt(acac)2 ac-
cording to the invention and effect of blocking
When saturating gas-solid reactions were utilised, the amount of the required metal
could be reduced by blocking part of the available surface sites. The nature of the block-
ing agent influenced the extent of blocking. This can be seen from following table 2,
wherein the blocking reaction conditions and Pt content of the obtained Pt catalysts are
presented (examples 8 - 11). The catalysts were prepared by saturating gas-solid reac-
tions using Pt(acac)2.


The processing was carried out in a flow-type reactor at reduced pressure of about 5-10
kPa with nitrogen as carrier gas. Before the deposition the supports (zeolites) were pre-
heated at 873 K in a muffle furnace under atmospheric pressure for 16 hours. Addition-
ally, they were heated in situ in the reactor at 453 - 473 K for 3 hours to remove water
adsorbed during their transfer to the reactor. The reaction of the blocking reagent and
the reaction of Pt(acac)2 were carried out as successive reactions, each reaction step
being completed with a nitrogen purge at the reaction temperature concerned. The va-
porisation and reaction temperatures of the blocking reagents are given in Table 2. The
platinum precursor, Pt(acac)2, was vaporised and allowed to react with the modified
support at 453 K. The amount of vaporised blocking/platinum reagent was kept suffi-
ciently high to ensure saturation of the surface. The ligands were removed by a post-
treatment in synthetic air at 623 or 723 K. The blocking reagents were totally removed
(thdH) or formed silicon oxide (from HMDS) or aluminum oxide (from Al(acac)3) were
left on the support surface.

Examples 12 -17
Decalin ring-opening reaction using noble metal catalysts
The performance of the catalysts in decalin ring-opening reaction was tested in a 50 ml
autoclave at 523 K under 20 bar hydrogen pressure. Decalin (10 ml -9.0 g) was added
to a reactor containing 1 g at 523 K reduced catalyst at room temperature. The pressure
was increased with hydrogen to 10 bar. Then the reactor was put into an oil bath at 523
K and when the temperature of the reactor reached 523 K, the hydrogen pressure was
adjusted to 20 bar. The reaction time was five hours. Then the reactor was cooled rap-
idly to a temperature of 263 K and the reactor was weighted after the cooling. The pres-
sure in autoclave was released and the product with catalyst was taken to a sample ves-
sel for GC testing. The results of the test runs are summarized in following table 3. The
conversion, selectivity and yield were calculated with the following formula:



Example 18
Formation of carbon dioxide on the catalyst according to the invention
Carbon dioxide was formed on the catalyst prepared according to example 6 during CO
adsorption at 300 K. In Figure 1 the mass spectrum of exhaust gas in CO adsorption is
shown. The x-axis is the mass number and y-axis the abundance of the component. Fig-
ure 2 presents the IR spectrum of the exhaust gas in CO adsorption. The x-axis is the
wave number and the y-axis the signal intensity.
Example 19
Deactivation of the catalysts
The deactivation of the catalysts from examples 6 and 7 was tested with a hydrodesul-
phurised refinery feed sample (total aromatics content 30.6 wt%, sulphur The results in the following table 4 show that the deactivation of the catalysts manufac-
tured by the method according to the invention (6.4Pt/H-beta example 6 and

4.9Pt/MCM-41 example 9) is much slower than with comparative catalyst, Pt-beta-1
(example 1), prepared by dry impregnation method.

Example 20
Product analysis
The product analysis of test runs with 4.9Pt/MCM-41 (from example 7) and 6.4Pt/H-
beta (from example 6), from the previous example 19, compared to the feed are pre-
sented in me following table 5. The gasoline fractions (bp before analysis. The amounts of distilled fractions were 2.2 wt% for 4.9Pt/MCM-41 at
553 K, 2.6 wt% for 4.9Pt/MCM-41 at 573 K and 2.5 wt% for 6.4Pt/H-beta at 503 K,
respectively. The results reveal that nearly complete hydrogenation of aromatics was
achieved. The other changes in product quality were very similar with both catalysts
tested.


The applicant hereby asserts that the "method", as described and claimed herein, is not a
method useful for, or relates to, the production, control, use or disposal of atomic energy or the
prospecting, mining, extraction, production, physical and chemical treatment, fabrication,
enrichment, canning, nor the use of the method has relation, in any manner whatsoever, to the use or
production of atomic energy or research onto matters connected therewith or for atomic energy
operations.

We Claim:
1. A method for the manufacture of a noble metal catalyst for hydrocarbon conversion,
characterized in that the method comprises the following steps:
a) Pre-treatment of a support comprising a zeolite selected from medium and large pore
zeolite having acid sites, at a temperature between 423 to 1173 K, and optional modification of the
support;
b) Deposition of a noble metal, as described herein before, selected from platinum, palladium,
ruthenium, rhodium, iridium and mixtures and combinations thereof by gas phase deposition
technique comprising vaporisation of the noble metal precursor selected from p-diketonates and
metallocenes and reaction with the support, and
c) Heat treatment at oxidising or reducing conditions.

2. The method as claimed in claim 1, wherein the noble metal is platinum.
3. The method as claimed in any one of claims 1 to 3, wherein the the zeolite is selected from
large pore zeolites having weak or medium strength of acid sites.
4. The method as claimed in any one of claims 1 to 3, wherein the zeolite is selected from the
mesoporous aluminosilicates, crystalline aluminosilicates, crystalline aluminophosphates and
crystalline aluminosilicophosphates.
5. The method as claimed in any one of claims 1 to 4, wherein the zeolite is selected from
MCM-41, Y- and beta-zeolites, mordenites, AIPO-5 and AIPO-11, SAPO-5 and SAPO-11.
6. The method as claimed in any one of claims 1 to 5, wherein the support further comprises
inorganic oxide, carbon related material or mixtures or combinations thereof.
7. The method as claimed in claim 6, wherein the inorganic oxide is selected from silicon oxide,
aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide and magnesium oxide, preferably
from silicon oxide and aluminum oxide.

8. The method as claimed in claim 6, wherein the carbon related material is selected from
activated carbon, graphite and carbon nanotubes.
9. The method as claimed in any one of claims 1 to 8, wherein the noble metal precursor is
(CH3)3(CH3C5H4)Pt.
10. The method as claimed in any one of claims 1 to 9, wherein the zeolite is MCM-41.
11. The method as claimed in any one of claims 1 to 10, wherein in the first process step a) the
support is pre-treated at a temperature of 423-1173 K, and in the second step b) the deposition is
carried out in the presence of an inert carrier gas.
12. The method as claimed in claim 11, wherein the inert carrier gas is nitrogen, helium, argon or
methane.
13. The method as claimed in any one of claims 1 to 12, wherien the modification in the firs step
a) is carried out by blocking part of available surface sites on the support with a blocking agent
selected from alcohols, acetyl acetone, 2,2,6,6-tetramethyl-3,5-heptanedione, precursors of silicon
oxide, aluminum oxide, titanium oxide, zirconium oxide, tungsten oxide and magnesium oxide, and
nitrates.
14. The method as claimed in claim 13, wherein the blocking agent is silicon tetrachloride,
tetramethoxysilane, tetraethoxysilane, hexamethyldisilazane, hexamethyldi-siloxane, aluminum
chloride, aluminum ethoxide, aluminum (III) acetylacetonate, tris(2,2,6,6-tetramethyl-3,5-
heptanedionato) aluminum, trimethyl aluminum, triethyl aluminum, titanium tetrachloride, titanium
isopropoxide, zirconium tetrachloride, tungsten oxy-chloride, tungsten hexachloride or tris(2,2,6,6-
tetramethyl-3,5-heptanedionato) magnesium.
15. A noble metal catalyst manufactured according to the method as claimed in any one of claims
1-14 for its application in ring-opening, isomerisation, alkylation, hydrocarbon reforming, dry
reforming, hydrogenation and dehydrogenation reactions, and preferably in ring-opening of
naphthenic molecules.

16. A process for the manufacture of the manufacture of middle distillate diesel fuel, wherein the
middle distillate feedstock is transferred to a reactor wherein it is allowed to react at a temperature of
283-673 K and under a pressure of 10 to 200 bar with hydrogen in the presence of a noble metal
catalyst manufactured acording to the method as claimed in any one of claims 1-14 to accomplish
opening of naphthenes with two and multiple rings to produce isoparaffins, n-paraffins and
mononaphthenes in the middle distillate region.

There is disclosed a method for the manufacture of a noble metal catalyst for hydrocarbon
conversion, characterized in that the method comprises the following steps: a) Pre-treatment of a
support comprising a zeolite selected from medium and large pore zeolite having acid sites, at a
temperature between 323 to 1173 K, and optional modification of the support; b) Deposition of a
noble metal, as_described herein before, selected from platinum, palladium, ruthenium, rhodium,
iridium and mixtures and combinations thereof by gas phase deposition technique comprising
vaporisation of the noble metal precursor selected from β-diketonates and metallocenes and reaction
with the support, and c) Heat treatment at oxidising or reducing conditions.

Documents:

01172-kolnp-2006-abstract.pdf

01172-kolnp-2006-assignment.pdf

01172-kolnp-2006-claims.pdf

01172-kolnp-2006-correspondence others-1.1.pdf

01172-kolnp-2006-correspondence others.pdf

01172-kolnp-2006-description complete.pdf

01172-kolnp-2006-drawings.pdf

01172-kolnp-2006-form 1.pdf

01172-kolnp-2006-form 3.pdf

01172-kolnp-2006-form 5.pdf

01172-kolnp-2006-form-3-1.1.pdf

01172-kolnp-2006-international publication.pdf

01172-kolnp-2006-international search authority report.pdf

01172-kolnp-2006-pct form.pdf

1172-kolnp-2006-abstract.pdf

1172-kolnp-2006-assignment.pdf

1172-kolnp-2006-assignment1.1.pdf

1172-kolnp-2006-claims.pdf

1172-kolnp-2006-correspondence.pdf

1172-kolnp-2006-correspondence1.1.pdf

1172-kolnp-2006-description (complete).pdf

1172-kolnp-2006-drawings.pdf

1172-kolnp-2006-examination report.pdf

1172-kolnp-2006-examination report1.1.pdf

1172-kolnp-2006-form 1.pdf

1172-kolnp-2006-form 18.1.pdf

1172-kolnp-2006-form 18.pdf

1172-kolnp-2006-form 3.1.pdf

1172-kolnp-2006-form 3.pdf

1172-kolnp-2006-form 5.1.pdf

1172-kolnp-2006-form 5.pdf

1172-kolnp-2006-gpa.pdf

1172-kolnp-2006-gpa1.1.pdf

1172-kolnp-2006-granted-abstract.pdf

1172-kolnp-2006-granted-claims.pdf

1172-kolnp-2006-granted-description (complete).pdf

1172-kolnp-2006-granted-drawings.pdf

1172-kolnp-2006-granted-form 1.pdf

1172-kolnp-2006-granted-specification.pdf

1172-kolnp-2006-others.pdf

1172-kolnp-2006-others1.1.pdf

1172-kolnp-2006-reply to examination report.pdf

1172-kolnp-2006-reply to examination report1.1.pdf

1172-kolnp-2006-specification.pdf


Patent Number 248226
Indian Patent Application Number 1172/KOLNP/2006
PG Journal Number 26/2011
Publication Date 01-Jul-2011
Grant Date 28-Jun-2011
Date of Filing 05-May-2006
Name of Patentee NESTE OIL OYJ
Applicant Address KEILARANTA 8, FI-02150 ESPOO
Inventors:
# Inventor's Name Inventor's Address
1 TIITA, MARJA VIIKINTIE 11 C 102, FI-06150 PORVOO
2 LINBLAD, MARINA KANKURINKATU 4 A 14, FI-00150, HELSINKI
3 NIEMI, VESA OHRATIE 2, FI-06400 PORVOO
PCT International Classification Number B01J 23/40
PCT International Application Number PCT/FI2004/000713
PCT International Filing date 2004-11-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 20031734 2003-11-27 Finland