USOO6268522B1

(12) United States Patent (10) Patent No.: US 6,268,522 B1

Hagemeyer et al. (45) Date of Patent: Jul. 31, 2001

(54) CATALYST, PROCESS FOR ITS 4.264,421 4/1981 Bard et al. .

PRODUCTION AND ITS USE FOR 5,185,308 2/1993 Bartley et al..
PREPARING WINYLACETATE 5,260,108 11/1993 Braren et al..

(75) Inventors: Alfred Hagemeyer, Sunnyvale, CA * cited by examiner

(US); Uwe Dingerdissen,
Seeheim-Jugenheim; Klaus Kihlein, Primary Examiner-Gary Geist
Kelkheim, both of (DE); Johannes ASSistant Examiner Robert W. Deemie
Heitz, Linz (AT); Dieter Bäuerle, (74) Attorney, Agent, or Firm-Frommer Lawrence &
Altenberg (AT) Haug LLP
(73) Assignee: Celanese GmbH, Frankfurt (DE) (57) ABSTRACT
The invention relates to a process for producing Supported
(*) Notice: Subject to any disclaimer, the term of this shell catalysts comprising noble metals by UV photoreduc
patent is extended or adjusted under 35 tion of noble metal Salt precursors fixed to a Support. For this
U.S.C. 154(b) by 0 days. purpose, the shaped Supported body is impregnated with
Suitable noble metal salts which are then reduced to the
(21) Appl. No.: 09/089,627 metals in a Zone close to the surface by means of UV
(22) Filed: Jun. 3, 1998 radiation, preferably in the absence of a chemical reducing
agent. The metal salts in the interior of the pellets which
(30) Foreign Application Priority Data have not been irradiated and therefore have not been reduced
Jun. 5, 1997 (DE) .............................................. 19723,591 are extracted using a Solvent.
(51) Int. CI.7. ... C07C 67/05; B01J 31/00 The noble metal shell catalysts produced in this way can be
(52) U.S. Cl. .......................... 560/245; 502/330, 502/170; used for many heterogeneously catalyzed reactions Such as
204/157.41 hydrogenations and oxidations.
(58) Field of Search ..................................... 502/170,330; According to the invention, Pd/Au Shell catalysts on porous
560/245; 207/157.41
ceramic Supports, e.g. SiO2 shaped bodies, produced by this
(56) References Cited process can be used in the Synthesis of Vinyl acetate.
U.S. PATENT DOCUMENTS
3,627,821 * 12/1971 Sennewald et al.. 20 Claims, No Drawings
 US 6,268,522 B1
1 2
CATALYST, PROCESS FOR ITS glass or Si. It is pointed out that the commencement of the
PRODUCTION AND ITS USE FOR deposition is attributable to the photoreduction of an
PREPARING WINYLACETATE adsorbed Ni(CO) layer. This photoreduction is significantly
more efficient when ultraviolet (UV) light is used than when
The present invention relates to a proceSS for producing 5 visible light is used.
a catalyst by UV photoreduction of metal Salts on a Support, Y.-F. Lu, M. Takai, S. Nagatomo, K. Kato and S. Namba,
to the catalyst produced in this way and to its use for Appl. Phys. A 54, 51-56 (1992) describe the deposition of
preparing Vinyl acetate. Ag from an adsorbed Silver acetate layer on a manganese
It is known that Vinyl acetate can be prepared in the gas Zinc ferrite Substrate. An argon ion laser having a wave
phase from ethylene, acetic acid and oxygen. The Supported length of 514.5 nm was used for the irradiation.
catalysts used for this Synthesis comprise Pd and an alkali R. C. Sausa, A. Gupta and J. R. White, J. Electrochem.
metal, preferably K. Further additives used are Cd, Au or Ba. Soc. 134, 2707-2713 (1987) describe the deposition of Pt
The metal Salts can be applied to the Support by Steeping, onto quartz from an organometallic layer, likewise by irra
Spraying on, Vapor deposition, impregnation, dipping or diation using an argon ion laser. The layer was produced by
precipitation. 15 evaporation of the Solvent from a Solution containing the
In the case of the Pd/Au/K catalysts it has been found to organometallic compound (Bright Platinum-05X, Engelhard
be advantageous to apply the two noble metals in the form Corporation) plus varnish-like binders and solvents. The
of a shell on the Support, i.e. the noble metals are distributed deposited Pt was used as nucleating layer for electroless
only in a Zone close to the Surface while the regions lying deposition of copper.
further inside the shaped supported body are virtually free of H. Esrom, J. Demmy and U. Kogelschatz, Chemtronics
noble metal. The thickness of these catalytically active shells 4, 202-208 (1989) report the use of an Xe excimer lamp
is generally about 0.1-2 mm. Shell catalysts make it possible (wavelength 172 nm) for depositing Pd nuclei on aluminum
to carry out the process more Selectively than in the case of oxide Substrates for the electroless deposition of copper. The
catalysts in which the Support particles are impregnated adsorbed layer used was palladium acetate.
through to the core (“fully impregnated') or make it possible 25 Y. Zhang and M. Stuke, Chemtronics 4, 212-215 (1989)
to increase the capacity. Here, the reaction conditions can be also describe the deposition of Pd from a palladium acetate
kept unchanged compared to the fully impregnated catalysts layer on aluminum oxide ceramics, quartz Substrates and
and more vinyl acetate can be produced for a given reactor Silicon wafers. The Synchrotron radiation having a wave
volume and time. This makes the work-up of the crude vinyl length range of 40-400 nm from an electron synchrotron
acetate obtained easier, Since the vinyl acetate content of the was used for irradiation.
gas leaving the reactor is higher, which leads to an energy H. Esrom and G. Wahl, Chemtronics 4, 216–223 (1989)
Saving in the work-up Section. Suitable work-ups are describe the photoreduction of palladium acetate by irradia
described, for example, in U.S. Pat. No. 5,066,365, DE-34 tion with light from an ArF excimer laser (wavelength 193
22575, DE-34 08 239, DE-29 45 913, DE-26 10 624 and nm) and a KrF excimer laser (wavelength 248 nm). This
U.S. Pat. No. 3,840,590. On the other hand, if the plant 35 process was used to deposit Pd nuclei for the electroleSS
capacity is kept constant, the reaction temperature can be deposition of copper on quartz and aluminum oxide ceram
lowered and the reaction can thus be carried out more CS.
Selectively at the same total output, resulting in raw material A. G. Schrott, B. Braren and R. Saraaf, Appl. Phys. Lett.
Savings. This also reduces the amount of the carbon dioxide 64, 1582–1584 (1994) report the photoreduction of PdSO
which is formed as by-product and therefore has to be 40 to metallic Pd using an excimer laser. Here too, it could be
discharged and consequently reduces the loSS of entrained shown that nucleated substrates (SiO) could be used for
ethylene associated with this discharge. In addition, this electroleSS deposition of copper.
method of operation leads to a lengthening of the operating P. B. Comita, E. Kay, R. Zhang and W. Jacob, Appl. Surf.
life of the catalyst. Sci. 79/80,196-202 (1994) describe the laser-induced coa
Many documents disclose catalysts and processes for 45 lescence of gold clusters in a thin fluorocarbon layer which
preparing vinyl acetate and processes for their production. has been produced by plasma polymerization. During the
These are fully impregnated catalysts or shell catalysts production of this layer, gold was embedded by ion Sput
which are generally Subjected to a chemical reduction of the tering. The polymer matrix was broken up and vaporized by
noble metal compounds applied to the Support to deposit the irradiation with an argon ion laser to leave coherent gold
noble metals on the catalyst Support. It has Surprisingly been 50 StructureS.
found that the catalytically active metals can also be depos None of these publications discloses a process for pro
ited on the Support by photoreduction. ducing catalysts.
The deposition of a metal on the Surface of a Support can The photoinduced deposition of noble metals from
be carried out from a gas, a liquid or an adsorbed Surface adsorbed surface layers has been carried out using both UV
layer. Such processes are described for many metals 55 light Sources and light Sources which emit visible light.
(including Ni, Ag, Au, Pd, Pt, Os and Ir) in the publications Since the absorption coefficients of the materials used in the
“Laser Processing and Chemistry” (Springer-Verlag, Berlin process of the invention are significantly higher in the
Heidelberg-N.Y., 1996) and “Chemical Processing with ultraViolet spectral region than in the visible spectral region,
Lasers” (Springer-Verlag, Berlin-Heidelberg-N.Y., 1986) by correspondingly lower power densities can be employed if
D. Bauerle. 60 UV light Sources are used. Since a significantly higher
In terms of the process of the invention, the deposition of throughput is achieved in this way, the use of UV light
catalytically active metals from adsorbed Surface layerS is of Sources is preferred. The Sources having the shortest wave
particular interest. lengths generally display the highest efficiency and their use
W. Krauter, D. Bauerle, F. Fimberger, Appl. Phys. A 31, is therefore particularly preferred.
13 (1983) describe the laser-induced deposition of Ni from 65 The UV radiation sources used for the photoreduction are
the gas phase (Ni(CO)) using a krypton ion laser having prior art. They are lamps, laserS or other radiation Sources
wavelengths of from 476 to 647 nm. The substrate used was Such as Synchrotrons or plasma discharger. Lamps which can
 US 6,268,522 B1
3 4
be used are, in particular, Hg vapor lamps (with Strong Solution and time and temperature of the photoreduction. In
emission lines at wavelengths of 185 nm and 254 nm) and the process of the invention, the reduction and fixing in the
narrow-spectrum excimer lamps in which the UV radiation shell occur Simultaneously in one step.
arises from the disintegration of excimerS or exciplexes. Such Preference is given to catalysts having a shell thickness
as Kra (wavelength 146 nm), Xe (172 nm), KrCl* (222 of from 5 to 5000 um. Furthermore, preference is given to
nm) or XeCl* (308 nm). As high-power UV lasers, use is those catalysts which comprise Pd and/or Au.
made of pulse excimer lasers. Here too, the light arises from The photoreduction according to the invention takes only
the disintegration of excimers or exciplexes Such as F* (157 a few minutes, while the conventional base fixing requires
about 20 hours.
nm), ArF* (193 nm), KrF* (248 nm), XeCl* (308 nm) and Owing to the properties mentioned, the shell catalysts
XeF (351 nm). It is also possible to use frequency produced according to the invention have high activities and
multiplied Nd-YAG lasers (wavelength 1064 nm/n; n=3, 4, Selectivities.
5, . . . ). Further sources of UV radiation are synchrotrons AS active metals which can be concentrated in the shell,
which produce broad-band radiation extending into the all metals for which photoreducible precursors exist are
X-ray region and the light of a plasma discharge at low suitable. A prerequisite for this is sufficient UV absorption
preSSure. 15
by the precursors at the wavelength used for irradiation.
It is an object of the present invention to provide a Appropriate Selection of the wavelength used for the irra
proceSS for producing shell catalysts which comprise noble diation enables UV absorption to be achieved for many
metals, which process does not use chemical reducing Simple and readily available metal Salts. Such as acetates,
agents and allows the shell thickness to be adjusted in a formates, propionates, butyrates, nitrates, Sulfates or chlo
Simple way. It is a further object of the present invention to rides. The impregnated Supports can also be treated with
produce an active and Selective vinyl acetate shell catalyst sensitizers before irradiation with UV light. Owing to their
based on Pd/Au quickly and inexpensively using few pro ready photoreducibility, all noble metals and their mixtures
ceSS Steps while making it possible to control the shell are particularly suitable. Preference is given to Pd, Au, Pt,
thickness in a simple manner. Ag, Rh, Ru, Os and Ir. Particular preference is given to Pd
and Au.
According to the invention, these objects are achieved by Supports used are inert materials such as SiO, Al-O,
noble metal Salts on a Support being reduced to the metal and 25
fixed in an outer shell of the shaped Support body by means TiO, ZrO or mixtures of these oxides in the form of
of photoreduction using UV radiation. The shell thickness Spheres, pellets, rings, StarS or other shaped bodies. The
can be adjusted via the penetration depth of the UV radia diameter or the length and thickness of the Support particles
tion. In this way, good uniformity of the catalytically active is generally from 3 to 9 mm. The Surface of the Support is
metal particles, a narrow particle size distribution and high generally 10–500 m/g, preferably 20–250 m/g, as mea
dispersion of metal in the shell are achieved. sured by the BET method. The pore volume is generally
The present invention provides a process for producing from 0.3 to 1.2 ml/g.
shell catalysts comprising noble metals on a porous Support, The reduction and fixing to the Support of the noble metal
which comprises impregnating the Support with Salt Solu precursors is, according to the invention, carried out by
tions of the nobel metals and Subsequently exposing it to UV 35
means of UV light. It is possible to use, for example, the
radiation So that the metal Salts in the Zone close to the following UV radiation sources: UV excimer lasers,
Surface are reduced to the metals. frequency-multiplied Nd:YAG laser, UV excimer lamps, Hg
The photoreduction is preferably carried out using mono Vapor lamps, Synchrotrons or low-pressure plasma discharg
chromatic UV excimer radiation. The process is preferably erS. Preference is given to using UV excimer radiation which
carried out in the absence of chemical reducing agents. is monochromatic and has high power peakS. Suitable wave
The metal salts in the interior of pellet which have not 40 lengths are in the range from 40 to 400 nm. Preferred
been irradiated and therefore have not been reduced are wavelengths are from 140 to 360 nm, in particular 172 nm
extracted by means of a Solvent after irradiation of the (Xe lamp), 193 nm (ArF* laser), 222 nm (KrCl* lamp),
Support. The nanosize particles of nobel metal fixed in the 248 nm (KrF* laser) and 308 nm (XeCl* lamp). Preferred
shell are, owing to their insolubility, not washed out and UV power densities are from 0.01 to 100 W/cmi, particu
remain fixed in position. 45 larly preferably UV power densities of from 0.1 to 20
The invention further provides the shell catalysts which W/cm.
can be produced by this process. When pulsed lasers are used, Suitable pulse frequencies
The shell catalysts produced in this way can be used for are generally in the range from 0.1 to 5000 pulses/s. The
many heterogeneously catalyzed reactions Such as hydroge irradiation times are generally from 0.01 s to 3600 s.
nations and oxidations. 50
Preferred pulse frequencies are from 1 to 1000 pulses/s and
Pd/Au Shell catalysts produced by this proceSS are Suit preferred irradiation times are from 0.01 to 1000 s, in
able for use in the Synthesis of vinyl acetate. Compared to particular from 0.1 to 300 s.
conventional preparation techniques for Supported noble When using UV lamps which are not pulsed and can have
metal catalysts (impregnation with metal salts and chemical Significantly greater Spatial and Spectral irradiation windows
reduction thereof), the photoreduction according to the than UV lasers, Suitable irradiation times are from 1 S and 10
55 h. Preferred irradiation times are from 0.1 min to 100 min.
invention makes it possible to omit the chemical reducing As a result of the limited penetration depth of the UV
agent and thus avoid the associated disadvantages Such as radiation, the thickness of the shell can be set and controlled
contamination of the Support with extraneous metals, dis easily.
posal of the Salt formed, multistage operation and energy If a plurality of noble metals are to be fixed to the Support
intensive and time-consuming handling of often toxic Solu 60 (e.g. Pd and Au), these can be photoreduced simultaneously
tions.
Compared to the conventional processes for producing a according to the process of the invention by means of
shell (fixing by means of base precipitation followed by appropriate Selection of the physical parameters significant
chemical reduction), the process of the invention has the in the deposition. This generally results in alloy particles. AS
advantage that the shell thickneSS can be readily controlled an alternative, it is also possible to carry out Sequential
and monitored via the the physical parameters significant in 65 photoreduction under irradiation conditions optimized for
the deposition, e.g. wavelength and power of the UV radia each of the individual metals, which can lead to Structured
tion Source, and also concentration of the impregnation noble metal particles.
 US 6,268,522 B1
S 6
The photoreduction can also be combined with conven of the three elements. The necessary amount of Salt can be
tional chemical reduction. For example, the photoreduction applied in one Step or by multiple impregnation. The Salts
can be used only for preliminary creation of the nuclei in the can be applied to the Support by known methods Such as
shell, which is then reinforced by renewed impregnation Steeping, Spraying on, Vapor deposition, dipping, impregna
with the same or other metal Salts and chemical reduction of 5 tion or precipitation.
these. Likewise, it is also possible to photoreduce only one In the process of the invention, only the noble metal Salts,
of the two metals and Subsequently to apply and reduce the i.e. Pd and Au Salts, are reduced to the corresponding
other metal using conventional methods. For example, the nanosize noble metal particles and the “base' constituents
Support can first be impregnated with palladium acetate K, Cd, Ba are not reduced. The latter can be applied to the
which is then phototreduced in a shell to give Pd metal. The Support together with the noble metal Salts or else before
Support can then be further impregnated with Au Salts which hand or afterwards. In the process of the invention, it is usual
can be reduced wet chemically or else in Situ in the reactor to first produce a shell of Pd/Au and then to impregnate the
using gaseous reducing agents Such as H2 or ethylene. This Support with potassium acetate Solution, giving a uniform
ensures that the actual active metal for the vinyl acetate distribution of K over the pellet cross section.
process, i.e. the Pd, is fixed in a shell, while the distribution Vinyl acetate is generally prepared by passing acetic
of the activator, i.e. the Au, is leSS critical and it can therefore 15 acid, ethylene and oxygen or oxygen-containing gases at
be fixed using conventional chemical methods. temperatures of from 100 to 220 C., preferably from 120 to
The noble metal salts in the interior of the pellet which 200 C., and at pressures of from 1 to 25 bar, preferably from
have not been irradiated and therefore have not been reduced
are extracted by means of a Solvent. Suitable Solvents are, 1 to 20 bar, over the finished catalyst, with unreacted
for example, chloroform, acetic acid or aqueous Solutions of components being able to be circulated. The oxygen con
citric acid or oxalic acid. centration is advantageously kept below 10% by volume
The process of the invention is particularly suitable for (based on the gas mixture without acetic acid). Dilution with
producing vinyl acetate shell catalysts. There are 3 types of inert gases Such as nitrogen or carbon dioxide may also be
these, which are composed essentially of Pd/Cd/K, Pd/Ba/K advantageous under Some circumstances. Carbon dioxide is
or Pd/Au/K. The finished vinyl acetate catalysts have the particularly Suitable for dilution Since it is formed in Small
following compositions: 25 amounts during the reaction.
The Pd content of the Pd/K/Cd and the Pd/K/Ba catalysts The following examples illustrate the invention.
is generally from 0.6 to 3.5% by weight, preferably from 0.8 EXAMPLE 1.
to 3.0% by weight, in particular from 1.0 to 2.5% by weight. a) Impregnation of porous SiO2 pellets with palladium
The Pd content of the Pd/Au/K catalysts is generally from acetate:
0.5 to 2.0% by weight, preferably from 0.6 to 1.5% by 50 ml (about 25 g) of Aerosil 200 pellets (5.5x6 mm,
weight. Degussa) are placed in a flask. 530 mg of palladium acetate
The K content of all three types of catalysts is generally (Aldrich) are dissolved in 30 ml of glacial acetic acid
from 0.5 to 4.0% by weight, preferably from 1.5 to 3.0% by (corresponds to 1% by weight of Pd). The solution is filtered
weight.
The Cd content of the Pd/K/Cd catalysts is generally 35
through a fluted filter paper. The clear Pd solution is added
from 0.1 to 2.5% by weight, preferably from 0.4 to 2.0% by to the Aerosil pellets and the glacial acetic acid is taken off
weight. again over a period of 2 hours on a rotary evaporator with
The Ba content of the Pd/K/Ba catalysts is generally continuous rotation. Remaining acetic acid is Subsequently
from 0.1 to 2.0% by weight, preferably from 0.2 to 1.0% by taken off in an oil pump vacuum at 0.2 mbar/60° C.
weight. b) Photoreduction:
The Au content of the Pd/K/Au catalysts is generally 40 The end faces of the pellets were irradiated in air by
from 0.2 to 1.0% by weight, preferably from 0.3 to 0.8% by means of a KrF* laser (wavelength 248 nm) using 500 laser
weight. pulses in each case. The energy density of the laser on the
Suitable Salts are all Salts of palladium, cadmium, specimen surface was 350 ml/cm. The pulse frequency of
barium, gold and potassium which are Soluble and contain the laser was 10 pulses/s. After cutting a representative
no constituents which act as catalyst poisons, e.g. Sulfur. 45 number of pellets, the shell thickneSS was measured by
Preference is given to the acetates and the chlorides. means of optical microscopy and XPS line scans. The shell
thickness is about 0.5 mm.
However, in the case of the chlorides, it has to be ensured c) Conversion into the industrial catalyst:
that the chloride ions are removed before the catalyst is used. 20 ml of irradiated Aerosil pellets are washed with 2 1 of
This is achieved by Washing the doped Support, e.g. with
water, after Pd and, if desired, Au have been fixed on the 50 acetic acid, 40%+10% of potassium acetate, in a Soxhlet
Support by reduction to the metal particles. extractor and dried at 110° C. Since the pellets already
Suitable Solvents for the impregnation are all compounds contain 1% of Pd, only Au is applied here: 125.4 mg of
in which the salts selected are soluble and which can be Au(CH-COO) (corresponds to 66 mg of Au), prepared by
easily removed again by drying after the impregnation. the method of U.S. Pat. No. 4,933,204, are dissolved in 1
Suitable solvents for the acetates are first and foremost 55
Omi of H2O and added to the pellets. The solution is
unsubstituted carboxylic acids, in particular acetic acid. For evaporated on a rotary evaporator with rotation and under a
the chlorides, water is especially Suitable. The additional use stream of N. The pellets are then dried at 110° C. 0.8 g of
of a further Solvent is advantageous when the Salts are not potassium acetate is dissolved in 15 ml of HO and applied
sufficiently soluble in the acetic acid or in the water. Suitable to the pellets as above, dried at 110° C. for 4 hours then
additional Solvents are those which are inert and miscible additionally dried overnight under reduced pressure.
with acetic acid or water. Examples of additives for acetic 60 d) Reactor tests
acid are ketones Such as acetone and acetylacetone, also Reactor tests on the gas phase oxidation of ethylene and
etherS Such as tetrahydrofuran or dioxane, acetonitrile, dim acetic acid to give vinyl acetate:
ethylformamide and also hydrocarbons Such as benzene. The catalysts are tested in a fixed-bed tube reactor having
In general, at least one Salt of each of the elements a tube diameter of 2 cm. The reactor is heated externally by
(Pd/K/Au, Pd/K/Cd, Pd/K/Ba) to be applied to the support 65 means of oil jacket heating. 15 ml of the shaped catalyst
particles is applied. It is possible to apply a plurality of Salts bodies are placed in the reactor. The reactor Volume
of one element, but it is usual to apply only one Salt of each upstream and downstream of the catalyst bed is filled with
 US 6,268,522 B1
7 8
glass spheres. The test apparatus is controlled by a proceSS XPS line scans. The number of pulses is selected so that the
control System and is operated continuously. The catalyst is shell thickness is about 0.9 mm.
first activated and then tested under constant reaction con The color change from yellow to black/brown induced by
ditions. the irradiation could be seen clearly. In contrast to Example
Activation comprises a plurality of Steps: heating under 5 1 (preimpregnation only with palladium acetate), a color
N, addition of ethylene, pressure increase, addition of acetic change could be achieved more easily in the case of the
acid, holding of the conditions, addition of oxygen. Pd/Au preimpregnation.
The reaction conditions during the test are 160-170° C. c) Conversion into the industrial catalyst
reaction temperature, 8-9 bar gauge pressure. The feed is The irradiated tablets are washed in a Soxhlet extractor
composed of 64.5% by volume of ethylene, 16.1% by first with 2000 ml of 40% acetic acid and then with 1000 ml
volume of N, 14.3% by volume of acetic acid and 5.1% by of water, dried overnight at 110° C. under atmospheric
Volume of O. A full analysis of the reactor output is carried preSSure and then dried for another 1 hour under reduced
out directly at the reactor outlet by means of on-line GC (2 preSSure. 2 g of potassium acetate are dissolved in 30 ml of
column arrangement). water and added all at once to the pellets. The Solution and
The test results are shown in the following table. The 15 pellets are mixed for 15 min with continual rotation and are
concentration ratioS of the components are given in GC again dried at 110° C. under atmospheric pressure, finally for
percentage areas. another 1 hour under reduced pressure.
TABLE 1.
GC analysis of the reactor Output
T p Vinyl Acetic
Catalyst ( C.) (bar) CO, CH, O, N, HO acetate acid
Example 1 160 9 O.85 55.7 3.25 19.5 O.8 1.27 18.5
Example 2 170 9 1.4 53.8 2.59 23.1 1.18 1.15 16.8

EXAMPLE 2 d) Reactor tests

a) Impregnation of porous SiO pellets with palladium 30
acetate and gold acetate: The preparation of vinyl acetate was carried out under the
50 ml (about 25 g) of Aerosil 200 pellets (5.5x6 mm, same conditions as indicated under d) in Example 1. The test
Degussa) are placed in a flask. 530 mg of palladium acetate results are shown in the following table. The concentration
(Aldrich) (corresponds to 1% by weight of Pd) are dissolved ratioS of the components are given in GC percentage areas:

TABLE 2
GC analysis of the reactor Output
T p Vinyl Acetic
Catalyst ( C.) (bar) CO, CH, O, N, HO acetate acid
Example 2 160 9 O.O1 56.8 4.3 19.5 O.O6 O.34 19.0

5
in 30 ml of glacial acetic acid. 290 mg of gold acetate 4 What is claimed is:
(corresponds to 0.6% by weight of Au), prepared by the 1. A process for producing shell catalysts comprising
method of U.S. Pat. No. 4,933,204, are dissolved in 10 ml noble metals on a porous Support, which comprises:
of glacial acetic acid. The two Solutions are combined and impregnating the Support with Salt Solutions of the noble
filtered through a fluted filter paper. The clear Pd/Au Solu- 50 metals,
tion is added to the Aerosil pellets and the glacial acetic acid exposing the Support to UV radiation So that the noble
metals in the Zone close to the Surface are reduced to
is taken off again over a period of 2 hours on a rotary metals, and
evaporator with continual rotation. Remaining acetic acid is extracting the pellets in a Solvent in order to remove the
Subsequently taken off in an oil pump vacuum at 0.2 noble metal salts in the interior of the pellet which have
mbar/60° C. The final weight of the impregnated pellets is 55 not been irradiated.
25.8 g. 2. The proceSS as claimed in claim 1, wherein the noble
metals are Selected from the group consisting of Pd, Au, Pt,
b) Photoreduction: Ag, Rh, Ru, Os and Ir.
3. The process as claimed in claim 1 wherein the noble
The impregnated tablets were irradiated on both end faces 60 metals are Au and Pd and the salts thereof which are used are
in air by means of a KrF* laser (wavelength 248 nm) using the acetates.
150 laser pulses in each case. The energy density (flux) of 4. The process as claimed in one of claims 1 to 3, wherein
the laser light on the specimen surface was 350 m.J/cm. The the Support material used is SiO, Al-O, TiO, ZrO or a
pulse frequency of the laser was 10 pulses/s. mixture thereof.
65 5. The process as claimed in one of claims 1 to 3, wherein
After cutting a representative number of pellets, the shell the UV photoreduction is carried out by irradiation with light
thickneSS was measured by means of optical microscopy and having a wavelength of from 40 to 400 nm.
 US 6,268,522 B1
9 10
6. The process as claimed in claim 5, wherein the UV 14. A shell catalyst obtainable by the process of claim 8,
photoreduction is carried out by irradiation with light having wherein the shell thickness is from 5 to 5000 um.
a wavelength of from 140 to 360 nm. 15. A shell catalyst obtainable by the process of claim 10,
7. The process as claimed in one of claims 1 to 3, wherein wherein the shell thickness is from 5 to 5000 um.
the photoreduction of the Pd and/or Au is carried out by 16. A process for hydrogenation or oxidation reactions in
irradiation with UV light having a power density of from the presence of a catalyst obtainable by a process as claimed
0.01 to 100 W/cm from a lamp or a pulsed laser, where, in one or more of claims 1 to 3.
when a pulsed laser is used, the pulse frequency is from 1 to 17. A process for preparing vinyl acetate in the gas phase
1000 pulses/s and the irradiation time is from 0.01 to 1000 from ethylene, acetic acid and oxygen or oxygen-containing
S, while when a lamp is used the irradiation time is from 0.1 gases in the presence of a catalyst obtainable by a proceSS as
min to 100 min. claimed in one of claims 1 to 3.
8. The process as claimed in claim 7, wherein the UV light 18. A process for preparing vinyl acetate in the gas phase
has a power density of from 0.1 to 20 W/cm. from ethylene, acetic acid and oxygen or oxygen-containing
9. The process as claimed in one or more of claims 1 to gases in the presence of a catalyst obtainable by a proceSS as
3, wherein the impregnated catalyst Support is treated with 15 claimed in claim 11.
UV sensitizers before irradiation. 19. A process for preparing vinyl acetate in the gas phase
10. The process as claimed in one of claims 1 to 3 carried from ethylene, acetic acid and oxygen or oxygen-containing
out without using a chemical reducing agent. gases in the presence of a catalyst obtainable by a proceSS as
11. A Shell catalyst obtainable by the process as claimed claimed in claim 8.
in one of claims 1 to 3, wherein the shell thickness is from 20. A process for preparing Vinyl acetate in the gas phase
5 to 5000 um. from ethylene, acetic acid and oxygen or oxygen-containing
12. A shell catalyst as claimed in claim 11, wherein the gases in the presence of a catalyst obtainable by a proceSS as
noble metals present are Pd and/or Au. claimed in claim 10.
13. A shell catalyst obtainable by the process of claim 9,
wherein the shell thickness is from 5 to 5000 um.
 UNITED STATES PATENT AND TRADEMARK OFFICE
CERTIFICATE OF CORRECTION
PATENT NO. : 6,268,522 Bl Page 1 of
DATED : July 31, 2001
INVENTOR(S) : Hagemeyer et al.

It is certified that error appears in the above-identified patent and that said Letters Patent is
hereby corrected as shown below:

Column 8,
Line 54, insert -- at elevated temperatures -- after "in a solvent'.
Column 9,
Line 24, "claim 9' should read -- claim 7 --.

Signed and Sealed this

Twenty-sixth Day of March, 2002

Attest.

JAMESE. ROGAN
Attesting Officer Director of the United States Patent and Trademark Office