Integrated Process For The Production of Vinyl Acetate From Acetic Acid Via Ethyl Acetate

1
INTEGRATED PROCESS FOR THE PRODUCTION OF VINYL ACETATE FROM
ACETIC ACID VIA ETHYL ACETATE
DETAILED DESCRIPTION
TECHNICAL FIELD
5 The present invention relates generally to an integrated process for the production of
vinyl acetate monomer (VAM) from acetic acid via ethyl acetate. More specifically, the
present invention relates to an integrated process first involving hydrogenating acetic acid
utilizing a catalyst composed of a supported bimetal catalyst, such as for example, platinum or
palladium and copper or cobalt supported on a suitable catalyst support optionally containing
10one or more additional hydrogenating metals to form ethyl acetate with high selectivity. In a
subsequent second step, ethyl acetate thus formed is subjected to a pyrolysis step to form
ethylene and in a final step the thus formed ethylene is combined with additional amounts of
acetic acid and molecular oxygen to form vinyl acetate over a suitable catalyst.
TECHNICAL BACKGROUND
15 There is a long felt need for an economically viable process to form VAM directly
from acetic acid. VAM is an important monomer in the production of polyvinyl acetate and
polyvinyl alcohol products among other important uses. VAM is currently produced from two
key raw materials, ethylene and acetic acid. Ethylene is predominantly produced from
petroleum based raw materials although acetic acid can be produced to a lesser extent from
20petroleum based raw materials. Therefore, fluctuating natural gas and crude oil prices
contribute to fluctuations in the cost of conventionally produced petroleum or natural gas-
sourced VAM, making the need for alternative sources of VAM all the greater when oil prices
rise.
25 It has now been found that VAM can be produced essentially from a mixture of carbon
monoxide and hydrogen (commonly known as synthesis gas) involving a few industrially
viable steps. For example, it is well know that synthesis gas can be reduced to methanol,
which is in fact the industrially preferred way to manufacture methanol. Methanol thus
formed can then be converted selectively to acetic acid under catalytic carbonylation
30conditions which is again the industrially preferred process for the manufacture of acetic acid.
The acetic acid thus formed then can be selectively converted to ethyl acetate under suitable
2
catalytic conditions. Although there are no known preferred processes for such a conversion,
the prior art does provide certain processes for such a conversion of acetic acid to ethyl
acetate albeit at low conversions and yields thus making it industrially unsuitable.
5 For instance, one such process involves first hydrogenation of carboxylic acids over
heterogeneous catalysts to produce alcohols, which can then be converted to the
corresponding acetates by an esterification reaction. For example, United States Patent No.
2,607,807 to Ford discloses that ethanol can be formed from acetic acid over a ruthenium
catalyst at extremely high pressures of 700-950 bar in order to achieve yields of around 88%,
10whereas low yields of only about 40% are obtained at pressures of about 200 bar. However
such extreme reaction conditions are unacceptable and uneconomical for a commercial
operation.
More recently, even though it may not still be commercially viable it has been reported
15that ethanol can be produced from hydrogenating acetic acid using a cobalt catalyst at
superatmospheric pressures such as about 40 to 120 bar. See, for example, United States
Patent No. 4,517,391 to Shuster et al.
On the other hand, United States Patent No. 5,149,680 to Kitson et al. describes a
20process for the catalytic hydrogenation of carboxylic acids and their anhydrides to alcohols
and/or esters utilizing a platinum group metal alloy catalyst. The catalyst is comprised of an
alloy of at least one noble metal of Group VIII of the Periodic Table and at least one metal
capable of alloying with the Group VIII noble metal, admixed with a component comprising
at least one of the metals rhenium, tungsten or molybdenum. Although it has been claimed
25therein that improved selectivity to a mixture of alcohol and its ester with the unreacted
carboxylic acid is achieved over the prior art references it was still reported that 3 to 9 percent
of alkanes, such as methane and ethane are formed as by-products during the hydrogenation
of acetic acid to ethanol under their optimal catalyst conditions.
30 A slightly modified process for the preparation of ethyl acetate by hydrogenating

acetic acid has been reported in EP 0 372 847. In this process, a carboxylic acid ester, such as
for example, ethyl acetate is produced at a selectivity of greater than 50% while producing the
corresponding alcohol at a selectivity less than 10% from a carboxylic acid or anhydride
thereof by reacting the acid or anhydride with hydrogen at elevated temperature in the
3
presence of a catalyst composition comprising as a first component at least one of Group VIII
noble metal and a second component comprising at least one of molybdenum, tungsten and
rhenium and a third component comprising an oxide of a Group IVb element. However, even
the optimal conditions reported therein result in significant amounts of by-products including
5methane, ethane, acetaldehyde and acetone in addition to ethanol. In addition, the conversion
of acetic acid is generally low and is in the range of about 5 to 40% except for a few cases in
which the conversion reached as high as 80%.
Similarly, it has been reported in the literature that ethyl acetate can be converted to
10ethylene under a variety of conditions. Although some of the processes reported in the art
may not be suitable for a commercial operation, certain modifications thereof maybe suitable
for selective conversion of ethyl acetate to ethylene such that it can be employed industrially
as further described herein in the detailed description of the instant invention.
15 For example, it has been reported that ethylene can be produced from various ethyl
esters in the gas phase in the temperature range of 150-300°C over zeolite catalysts. The
types of ethyl esters that can be employed include ethyl esters of formic acid, acetic acid and
propionic acid. See, for example, United States Patent No. 4,620,050 to Cognion et al., where
selectivity is reported to be acceptable.
20
United States Patent No. 4,270,015 to Knifton describes obtaining ethylene involving a
two-step process in which a mixture of carbon monoxide and hydrogen is reacted with a
carboxylic acid containing 2 to 4 carbon atoms to form the corresponding ethyl ester of said
carboxylic acid which is subsequently pyrolyzed in a quartz reactor at elevated temperatures
25in the range of about 200º to 600ºC to obtain ethylene. The ethylene thus produced contains
other hydrocarbons, particularly, ethane as an impurity. It was also reported therein that the
concentration of ethane can reach high values, near 5% by pyrolyzing pure ethyl propionate at
460ºC. More importantly, the conversion of the esters and yield of ethylene are reported to be
very low.
30
United States Patent No. 4,399,305 to Schreck describes obtaining high purity ethylene
from ethyl acetate employing a cracking catalyst composed of a perfluorosulfonic acid resin
commercially sold under the trademark NAFION® by E.I. DuPont de Nemours & Co.
4
On the other hand, Malinowski et al., Bull. Soc. Chim. Belg. (1985), 94(2), 93-5,
disclose the reaction of acetic acid on low-valent titanium heterogenized on support materials
such as silica (SiO2) or titania (TiO2) resulted in a mixture of products including diethyl ether,
ethylene and methane where selectivity is poor.
5
WO 2003/040037 discloses that crystalline microporous metalloalumino-phosphates
(ELAPO), particularly, SAPO-type zeolites, such as SAPO-5, SAPO-11, SAPO-20, SAPO-18
and SAPO-34, having Si/Al ratio of 0.03-017 are useful as adsorbent or as a catalyst for the
production of olefins from an oxygenated feedstock containing methanol, ethanol, n-propanol,
10isopropanol, C4-C20 alcohols, methyl ethyl ether, di-methyl ether, di-ethyl ether, di-isopropyl
ether, formaldehyde, dimethyl carbonate, dimethyl ketone and/or acetic acid. A similar
disclosure utilizes a silicoaluminophosphate molecular sieves comprising at least one
intergrown phase of molecular sieve. It is reported that in this process a feedstock containing
an oxygenate contacts a catalyst comprising the molecular sieve in a reaction zone of a reactor
15at conditions effective to produce light olefins, particularly ethylene and propylene. See
United States Patent No. 6,812,372 to Janssen et al. It is mentioned that such oxygenated
feedstocks include acetic acid, but the disclosure appears to be limited to either methanol or
dimethyl ether. See, also, United States Patent No. 6,509,290 to Vaughn et al., which further
discloses conversion of oxygenated feedstocks to olefins.
20
Bimetallic ruthenium-tin/silica catalysts have been prepared by reaction of tetrabutyl
tin with ruthenium dioxide supported on silica. It has been reported that these catalysts
exhibit different selectivities based on their content of tin/ruthenium ratio (Sn/Ru).
Specifically, it has been reported that the selectivity for the hydrogenolysis of ethyl acetate is
25quite different, which depends upon the Sn/Ru ratio in the catalyst. For instance, with
ruthenium alone on SiO2, the reaction is not selective: methane, ethane, carbon monoxide,
carbon dioxide as well as ethanol and acetic acid are produced. Whereas, with low tin
content, it has been reported that the catalysts are fairly selective for the formation of acetic
acid, while at higher Sn/Ru ratios, ethanol is the only detected product. See Loessard et al.,
30Studies in Surface Science and Catalysis (1989), Volume Date 1988, 48 (Struct. React. Surf.),
591-600.
The catalytic reduction of acetic acid has also been studied. For instance, Hindermann
et al., J. Chem. Res., Synopses (1980), (11), 373, have disclosed the catalytic reduction of
5
acetic acid on iron and on alkali-promoted iron. In their study they found that the reduction of
acetic acid on alkali-promoted iron, followed at least two different routes depending on the
temperature. For example, they found that at 350°C, the Piria reaction was predominant and
gave acetone and carbon dioxide, as well as the decomposition products methane and carbon
5dioxide, whereas the decomposition products were reduced at lower temperatures. On the
other hand, at 300°C a normal reduction reaction was observed resulting in the formation of
acetaldehyde and ethanol.
In addition, it should also be noted that there are industrially viable processes for the
10production of VAM from ethylene and acetic acid. For example, United States Patent No.
6,696,596 to Herzog et al., which is incorporated herein by reference in its entirety, discloses
that VAM can be produced in the gas phase from ethylene, acetic acid and oxygen or oxygen
containing gases over a catalyst comprising palladium and/or its compounds, gold and/or its
compounds and alkali metal compounds on a support, wherein the catalyst further comprises
15vanadium and/or its compounds.
There are also reports in the literature of integrated processes for the manufacture of
VAM involving oxidation of an alkane such as ethane or an alkene such as ethylene to acetic
acid and in a subsequent step reaction of so formed acetic acid with additional amounts of
20ethylene in the presence of oxygen to form VAM. See for instance, United States Patent No.
6,040,474 to Jobson et al., which describes the manufacture of acetic acid and/or vinyl acetate
using two reaction zones wherein the first reaction zone comprises ethylene and/or ethane for
oxidation to acetic acid with the second reaction zone comprising acetic acid and ethylene
with the product streams being subsequently separated thereby producing vinyl acetate. See
25also, United States Patent No. 6,476,261 to Ellis et al. which describes an oxidation process
for the production of alkenes and carboxylic acids such as ethylene and acetic acid which are
reacted to form vinyl acetate demonstrating that more than one reaction zone can be used to
form the vinyl acetate.
30 United States Patent No. 6,852,877 to Zeyss et al., describes another integrated
process wherein ethane is reacted with molecular oxygen in the presence of a suitable
oxidation catalyst in first reaction zone; concurrently, in a second reaction zone another batch
of ethane is oxidatively dehydrogenated to ethylene in the presence of a suitable catalyst and
subsequently in a third reaction zone, the acetic acid formed in reaction zone 1 is reacted with
6
ethylene produced from a second reaction zone in the presence of additional amounts of
molecular oxygen and a suitable catalyst to form VAM.
From the foregoing it is apparent that existing processes do not have the requisite
5selectivity to form ethyl acetate from acetic acid and/or its direct conversion to ethylene and
then to convert the resulting products to VAM in an integrated process thus making them
industrially adoptable to produce VAM essentially from synthesis gas and/or synthesis gas
based products.
DISCLOSURE OF THE INVENTION
10 Surprisingly, it has now been unexpectedly found that VAM can be produced on an
industrial scale involving an integrated process by which ethyl acetate is first formed directly
from acetic acid with very high selectivity and yield, which is subsequently pyrolyzed to form
ethylene and acetic acid. In a final step the mixture of ethylene and acetic acid so formed in
second step is mixed with molecular oxygen and optionally with more acetic acid to form
15VAM in the presence of a suitable catalyst. More particularly, this invention provides a
process for the selective formation of VAM from acetic acid comprising: (a) hydrogenating
acetic acid in the first reaction zone in the presence of hydrogen over a hydrogenating catalyst
comprising at least one metal selected from the group consisting of nickel, platinum and
palladium and at least one metal selected from molybdenum, rhenium, zirconium, copper and
20cobalt with the proviso that platinum may be used without molybdenum, rhenium, zirconium,
copper or cobalt to produce a first gaseous product stream; (b) enriching said first gaseous
product stream with ethyl acetate at least up to 50 mole percent; (c) reacting said enriched
first gaseous product stream from step (b) over a suitable cracking catalyst in a second
reaction zone to form a second gaseous product stream consisting essentially of ethylene and
25acetic acid; (d) reacting said second gaseous product stream from step (c) with molecular
oxygen and optionally additional amounts of acetic acid in the presence of a catalyst to form a
third gaseous product stream comprising vinyl acetate; and (e) separating the vinyl acetate
from said third gaseous product stream.
30 In addition, the catalyst employed in step (a) is comprised of a suitable catalyst

support optionally including one or more metal catalysts selected from the group consisting of
ruthenium, iridium, chromium, tin, tungsten, vanadium and zinc. More specifically, the
catalyst suitable for the process of step (a) of this invention is typically comprised of a
7
combination of platinum and copper supported on a suitable catalyst support or palladium and
cobalt supported on a suitable catalyst support. Suitable catalyst supports include without any
limitation, silica, alumina, calcium silicate, carbon, zirconia, zirconia-silica, titania, titania-
silica, iron oxide and zeolite catalysts such as, for example,
5H-ZSM-5. Similarly, various supports as described herein may also be employed in steps (c)
and (d) of this invention.
PREFERRED EMBODIMENTS OF THE INVENTION
The invention is described in detail below with reference to numerous embodiments

for purposes of exemplification and illustration only. Modifications to particular
10embodiments within the spirit and scope of the present invention, set forth in the appended
claims, will be readily apparent to those of skill in the art.
Unless more specifically defined below, terminology as used herein is given its
ordinary meaning. Mole percent (mole % or %) and like terms refer to mole percent unless
15otherwise indicated. Weight percent (wt % or %) and like terms refer to weight percent unless
otherwise indicated.
Typically, the catalyst metal loadings are expressed as weight percent of a catalyst
metal based on the total dry weight of the metal and catalyst support. Thus, for example, one
20(1) weight percent of metal on a support means that one gram of pure metal is present in 100
grams of supported metal catalyst, i.e., the combined weight of support (99 grams) and the
metal (1 gram).
“Conversion” is expressed as a mole percentage based on acetic acid in the feed. The
25conversion of acetic acid (AcOH) is calculated from gas chromatography (GC) data using the
following equation:
30 “Selectivity” is expressed as a mole percent based on converted acetic acid. For

example, if the conversion is 50 mole % and 50 mole % of the converted acetic acid is
8
converted to ethyl acetate (EtOAC), we refer to the ethyl acetate selectivity as 50%.
Selectivity is calculated from gas chromatography (GC) data using the following equation:
5
wherein “Total mmol C out (GC)” refers to total mmols of carbon from all of the products
analyzed by gas chromatograph.
The reaction proceeds in accordance with the following chemical equations:

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9
(a) Hydrogenation of Acetic Acid to Ethyl Acetate
O O
2H2 H2
2
C C + 2 H2O
CH3 O CH3
H3C OH
5
(b) Cracking of Ethyl Acetate to Ethylene and Acetic Acid
O
O
+ H2C CH2
H2
C C
H3C OH
CH3 O CH3
(c) Oxidative Addition of Acetic Acid to Ethylene to form VAM

10
O O
H + H2O
+ 1/2 O2 + H2C CH2
C C
CH3 O CH2
H3C OH
Step (a): Hydrogenation of Acetic Acid to Ethyl Acetate

In accordance with the invention, conversion of acetic acid to ethyl acetate can be
15carried out in a variety of configurations, such as for example in a single reaction zone which
may be a layered fixed bed, if so desired. An adiabatic reactor could be used, or a shell and
tube reactor provided with a heat transfer medium could be used. The fixed bed can comprise
a mixture of different catalyst particles or catalyst particles which include multiple catalysts as
further described herein. The fixed bed may also include a layer of particulate material
20making up a mixing zone for the reactants. A reaction mixture including acetic acid,
hydrogen and optionally an inert carrier gas is fed to the bed as a stream under pressure to the
mixing zone. The stream is subsequently supplied (by way of pressure drop) to the reaction
zone or layer. Reaction zone comprises a catalytic composition including a suitable
hydrogenating catalyst where acetic acid is hydrogenated to produce ethyl acetate. Any
25suitable particle size may be used depending upon the type of reactor, throughput
requirements and so forth.
10
Although various metal supported hydrogenating catalysts known to one skilled in the
art can be employed in hydrogenating acetic acid to form ethyl acetate in step (a) of the
process of this invention, it is preferred that the hydrogenating catalyst employed is comprised
of at least one metal selected from the group consisting of nickel, platinum and palladium and
5at least one metal selected from molybdenum, rhenium, zirconium, copper and cobalt. In
addition, the catalyst is comprised of a suitable catalyst support optionally including one or
more metal catalysts selected from the group consisting of ruthenium, iridium, chromium, tin,
tungsten, vanadium and zinc. However, single supported metal catalyst such as platinum
alone supported on a suitable catalyst support such as titania may also be employed in the
10process of this invention.
Preferably, the catalyst suitable for the process of this invention is comprised of a
combination of platinum and copper supported on a suitable catalyst support or palladium and
cobalt supported on a suitable catalyst support. Typically, it is preferred that a suitable weight
15ratio of a combination of metals on a suitable support can be used as a hydrogenating catalyst.
Thus, for example, a combination of platinum and copper (Pt/Cu) or palladium and cobalt
(Pd/Co) in the weight ratio of about 0.1 – 1 are particularly preferred. More preferably, a
weight ratio of Pt/Cu or Pd/Co is about 0.2 -0.5 and most preferably the weight ratio of Pt/Cu
or Pd/Co is about 0.2.
20
The other catalysts suitable in the process of this invention include a bimetallic
combination of nickel/molybdenum (Ni/Mo), palladium/molybdenum (Pd/Mo) or
platinum/molybdenum (Pt/Mo) supported on H-ZSM-5, silica or carbon. In this aspect of the
invention the loading levels of a bimetallic combination of Ni/Mo may be any level to affect
25the selective hydrogenation of acetic acid to ethyl acetate and typically it is about 1 weight
percent nickel and 5 weight percent molybdenum (1 wt% Ni/5 wt% Mo) supported on carbon.
In another aspect, the loading levels of a bimetallic combination of Pd/Mo is about 1

weight percent palladium and 5 weight percent molybdenum (1 wt% Pd/5 wt% Mo)
30supported on H-ZSM-5 or silica. Similarly, a bimetallic combination of Pt/Mo with a loading
of about 1 weight percent platinum and 5 weight percent molybdenum (1 wt% Pt/5 wt% Mo)
supported on silica or carbon can also be employed.
11
In another aspect of this invention, the catalyst is chosen from a bimetallic
combination of nickel/rhenium (Ni/Re) or palladium/rhenium (Pd/Re) supported on titania.
Again, in this aspect of the invention any suitable metal loadings can be employed to bring
about the selective hydrogenation of acetic acid to ethyl acetate. For instance a bimetallic
5combination of 1 weight percent nickel and 5 weight percent rhenium (1 wt% Ni/5 wt% Re)
supported on titania or a bimetallic combination of 1 weight percent palladium and 5 weight
percent rhenium (1 wt% Pd/5 wt% Re) supported on titania can be employed.
In another embodiment of this invention, there is also provided a process for selective
10and direct formation of ethyl acetate from acetic acid comprising: contacting a feed stream
containing acetic acid and hydrogen at an elevated temperature with a suitable hydrogenating
catalyst containing about 0.5 weight percent to about 1 weight percent of palladium and 2.5
weight percent to about 5 weight percent of rhenium on a suitable catalyst support. More
specifically, the catalyst support contains palladium at a loading level of about one (1) weight
15percent and rhenium at a loading level of about five (5) weight percent and the catalyst
support is titania.
In this aspect of the invention, the reactants consist of acetic acid and hydrogen with a
molar ratio in the range of about 1:10 to 1:5, the temperature of the reaction zone is in the
20range of about 225ºC to 275ºC, and the pressure of the reaction zone is in the range of about
10 to 20 atmospheres absolute.
Various catalyst supports known in the art can be used to support the catalysts of this
invention. Examples of such supports include without any limitation, zeolite, such as H-
25ZSM-5, iron oxide, silica, alumina, titania, zirconia, magnesium oxide, calcium silicate,
carbon, graphite and a mixture thereof. Preferred supports are silica, alumina, calcium
silicate, carbon, zirconia and titania. More preferably silica is used as a catalyst support in the
process of this invention. It is also important to note that higher the purity of silica, the better
it functions as a support.
30
In another aspect of the process of this invention, any of known zeolite catalysts can
also be employed as a catalyst support. While any zeolite having a pore diameter of at least
about 0.6 nm can be used, preferably employed among such zeolites are the catalyst supports
selected from the group consisting of mordenites, ZSM-5, a zeolite X and a zeolite Y.
12
The preparation of large-pore mordenites is described, for example, in United States

Patent No. 4,018,514 to Plummer and in Mol. Sieves Pap. Conf., 1967, 78, Soc. Chem. Ind.
London, by D. DOMINE and J. QUOBEX.
5
Zeolite X is described, for example, in United States Patent No. 2,882,244 to Milton
and zeolite Y in United States Patent No. 3,130,007 to Breck.
Various zeolites and zeolite-type materials are known in the art for the catalysis of
10chemical reactions. For example, United States Patent No. 3,702,886, to Argauer, discloses a
class of synthetic zeolites, characterized as "Zeolite
ZSM-5", which are effective for the catalysis of various hydrocarbon conversion processes.
The zeolites suitable for the procedure of the invention can be in the basic form, in the
15partially or totally acidified form, or in the partially dealuminated form.
Preferably, the zeolite catalyst support in the process of the present invention are in the
protic form, characterized as "H-ZSM-5" or “H-mordenite” zeolites, which are prepared from
a corresponding "ZSM-5" zeolite or “mordenite” zeolite by replacing most, and generally at
20least about 80% of the cations of the latter zeolite with hydrogen ions using techniques well-
known in the art. These zeolite catalysts are essentially crystalline aluminosilicates or in the
neutral form a combination of silica and alumina in a well defined crystalline structure. In a
particularly preferred class of zeolite catalysts for purposes of the present invention, the molar
ratio of SiO2 to Al2O3 in these zeolites is within the ratio of about 10 to 60.
25
In another aspect of this invention, the combination of catalyst metals, palladium and
cobalt or a combination of platinum and copper are supported on a high purity low surface
area silica or H-ZSM-5 using the procedures well known in the art or the procedures further
described herein. Other preferred catalyst supports for platinum or palladium based metal
30catalysts are carbon, titania and zirconia.
In another embodiment of this invention, the preferred catalyst support is carbon.

Various forms of carbon known in the art that are suitable as catalyst support can be used in
the process of this invention. Particularly preferred carbon support is a graphitized carbon,
13
particularly the high surface area graphitized carbon as described in Great Britain Patent No.
2,136,704. The carbon is preferably in particulate form, for example, as pellets. The size of
the carbon particles will depend on the pressure drop acceptable in any given reactor (which
gives a minimum pellet size) and reactant diffusion constraint within the pellet (which gives a
5maximum pellet size).
The carbon catalyst supports that are suitable in the process of this invention are
preferably porous carbon catalyst supports. With the preferred particle sizes the carbon will
need to be porous to meet the preferred surface area characteristics.
10
The catalyst supports, including the carbon catalyst supports, may be characterized by
their BET, basal plane, and edge surface areas. The BET surface area is the surface area
determined by nitrogen adsorption using the method of Brunauer Emmett and Teller, J. Am.
Chem. Soc., 60,309 (1938). The basal plane surface area is the surface area determined from
15the heat of adsorption on the carbon of n-dotriacontane from n-heptane by the method
described in Proc. Roy. Soc. A314 pages 473-498, with particular reference to page 489. The
edge surface area is the surface area determined from the heat of adsorption on the carbon of
n-butanol from n-heptane as disclosed in the Proc. Roy. Soc. article mentioned above with
particular reference to page 495.
20
The preferred carbon catalyst supports for use in the present invention have a BET
surface area of at least 100 m2/g, more preferably at least 200 m2/ g, most preferably at least
300 m2 /g. The BET surface area is preferably not greater than 1000 m2/g, more preferably
not greater than 750 m2/g.
25
It is possible to use carbon catalyst supports with ratios of basal plane surface area to
edge surface area of at least 10:1, preferably at least 100:1. It is not believed that there is an
upper limit on the ratio, although in practice it will not usually exceed 200:1.
30 The preferred carbon support may be prepared by heat treating a carbon-containing

starting material. The starting material may be an oleophillic graphite e.g. prepared as
disclosed in Great Britain Patent No. 1,168,785 or may be a carbon black.
14
However, oleophillic graphites contain carbon in the form of very fine particles in
flake form and are therefore not very suitable materials for use as catalyst supports. We prefer
to avoid their use. Similar considerations apply to carbon blacks which also have a very fine
particle size.
5
The preferred materials are activated carbons derived from vegetable materials, e.g.
coconut charcoal, or from peat or coal or from carbonizable polymers. The materials
subjected to the heat treatment preferably have particle sizes not less than these indicated
above as being preferred for the carbon support.
10
The preferred starting materials have the following characteristics: BET surface area
of at least 100 m2/g, more preferably at least 500 m2/g.
One preferred heat treatment procedure for preparing carbon supports having the
15defined characteristics, comprise successively (1) heating the carbon in an inert atmosphere at
a temperature of from 900ºC to 3300ºC, (2) oxidizing the carbon at a temperature between
300ºC and 1200ºC, (3) heating in an inert atmosphere at a temperature of between 900ºC and
3000ºC.
20 The oxidation step is preferably carried out at temperatures between 300º and 600ºC
when oxygen (e.g. as air) is used as the oxidizing agent.
The duration of the heating in inert gas is not critical. The time needed to heat the
carbon to the required maximum temperature is sufficient to produce the required changes in
25the carbon.
The oxidation step must clearly not be carried out under conditions such that the
carbon combusts completely. It is preferably carried out using a gaseous oxidizing agent fed
at a controlled rate to avoid over-oxidation. Examples of gaseous oxidizing agents are steam,
30carbon dioxide, and gases containing molecular oxygen, e.g. air. The oxidation is preferably
carried out to give a carbon weight loss of at least 10 weight percent based on the weight of
carbon subjected to the oxidation step, more preferably at least 15 weight percent.
15
The weight loss is preferably not greater than 40 weight percent of the carbon
subjected to the oxidation step, more preferably not greater than 25 weight percent of the
carbon.
5 The rate of supply of oxidizing agent is preferably such that the desired weight loss
takes place over at least 2 hours, more preferably at least 4 hours.
Where an inert atmosphere is required it may be supplied by nitrogen or an inert gas.
10 As noted above, the loading levels of a combination of two metal catalysts are
generally referenced with the content of main catalyst metal and the weight ratio of the
combination. For instance, the weight ratio of Pt/Cu or Pd/Co is in the range of about 0.1 to
2. Thus, when the weight ratio of Pt/Cu or Pd/Co is 0.1, the amount of platinum or palladium
can be 0.1 or 1 weight percent and thus 1 or 10 weight percent of copper or cobalt is present
15on the catalyst support. More preferably, the weight ratio of Pt/Cu or Pd/Co is about 0.5, and
thus the amount of platinum or palladium on the catalyst support can be either 0.5 or 1 weight
percent and that of copper or cobalt is either one or two weight percent. More preferably, the
weight ratio of Pt/Cu or Pd/Co is one or 0.2. Thus the amount of platinum or palladium on a
support is 0.5, one or two weight percent and that of copper or cobalt is also 0.5, one or two
20weight percent when the weight ratio is one. Similarly, when a weight ratio of Pt/Cu or Pd/Co
is 0.2, the amount of platinum or palladium on the support can be 0.5 or one weight percent
and of copper or cobalt is either 2.5 or five weight percent.
The amount of third metal loading if present on a support is not very critical in this
25invention and can vary in the range of about 0.1 weight percent to about 10 weight percent. A
metal loading of about 1 weight percent to about 6 weight percent based on the weight of the
support is particularly preferred.
The metal impregnation can be carried out using any of the known methods in the art.
30Typically, before impregnation the supports are dried at 120ºC and shaped to particles having
size distribution in the range of about 0.2 to 0.4 mm. Optionally the supports may be pressed,
crushed and sieved to a desired size distribution. Any of the known methods to shape the
support materials into desired size distribution can be employed.
16
For supports having low surface area, such as, for example, alpha-alumina, the metal
solutions are added in excess until complete wetness or excess liquid impregnation so as to
obtain desirable metal loadings.
5 As noted above, the hydrogenation catalysts used in the process of this invention are at
least bimetallic containing platinum/copper, palladium/cobalt and so on. Generally, without
intending to be bound by any theory, it is believed that one metal acts as a promoter metal and
another metal is the main metal. For instance, in the instant process of the invention, of the
above noted combinations respectively platinum, palladium, and copper are considered as
10main metals for preparing hydrogenation catalysts of this invention. The other metals, copper
with platinum, cobalt with palladium are considered to be the promoter metals depending
upon various reaction parameters including, but not limited to, catalyst support employed,
reaction temperature and pressure, etc. The catalysts may include other promoter metals, such
as tungsten, vanadium, molybdenum, chromium or zinc.
15
The bimetallic catalysts are generally impregnated in two steps. Each impregnation
step is followed by drying and calcination. The bimetallic catalysts may also be prepared by
co-impregnation. In most cases, the impregnation may be carried out using metal nitrate
solutions. However, various other soluble salts which upon calcination release metal ions can
20also be used. Examples of other suitable metal salts for impregnation include metal oxalate,
metal hydroxide, metal oxide, metal acetate, ammonium metal oxide, such as ammonium
heptamolybdate hexahydrate, metal acids, such as perrhenic acid solution, and the like.
Thus in one embodiment of this invention, there is provided a hydrogenation catalyst

25wherein the catalyst support is silica with a bimetallic loading of platinum and copper. In this
aspect of the invention, the loading of platinum is about 0.5 weight percent to about 1 weight
percent and the loading of copper is about 2.5 weight percent to about 5 weight percent.
Specifically, platinum/copper loading levels of 1/1, 1/5, 0.5/0.5, and 0.5/2.5 weight percent on
silica can be used.
30
In another embodiment of this invention, there is further provided a hydrogenation
catalyst wherein the catalyst support is high purity low surface area silica with a bimetallic
loading of platinum and copper or palladium and cobalt. In this aspect of the invention, the
loading of platinum or palladium is about 0.5 weight percent to about 1 weight percent and
17
the loading of copper or cobalt is about 0.1 weight percent to about 5 weight percent.
Specifically, platinum/copper or palladium/cobalt loading levels of 1/1, 1/5, 0.5/0.5, and
0.5/2.5 weight percent on high purity low surface area silica can be used. Other preferred
supports in this aspect of the invention include H-ZSM-5, graphitized carbon, zirconia, titania,
5iron oxide, silica-alumina and calcium silicate.
In a further embodiment of this invention, there is provided a hydrogenation catalyst

wherein the bimetallic catalyst is copper and chromium supported on silica, zirconia,
graphitized carbon, H-ZSM-5, titania-silica and zirconia-silica. In this aspect of the
10invention, the loading level of copper and chromium is about 3 weight percent to about 10
weight percent each. Specifically, copper/chromium loading levels of 5 weight percent each
on any of the aforementioned catalyst support is preferred.
In general, by the practice of this invention, acetic acid can selectively be converted to
15ethyl acetate at very high rates. The selectivity to ethyl acetate in general is very high and
may be at least 60 percent. Under preferred reaction conditions, acetic acid is selectively
converted to ethyl acetate at a selectivity of greater than 85 or 87.5 percent or more preferably
at a selectivity of 90 percent or more. Most preferably ethyl acetate selectivity is at least 95
percent.
20
The conversion of acetic acid using the catalysts of this invention is at least 20% and
can be up to 70% with selectivity to ethyl acetate at least 60%, preferably 80% and most
preferably 95%.
25 Generally, the active catalysts of the invention are the single metal or the bimetallic
catalysts as described herein. More specifically, a bimetallic catalyst containing platinum and
copper supported on silica with a platinum loading of 1 weight percent and copper loading of
5 weight percent is preferred. In accordance with the practice of this invention, acetic acid
can be converted using this catalyst at conversions of around 70% with ethyl acetate
30selectivity of at least 80%, more preferably selectivity to ethyl acetate of at least 90% can be
achieved.
Similar conversions and selectivities are achieved using zirconia, graphite or titania as
a support and with loadings of platinum and copper of one weight percent and five weight
18
percent respectively. Other promoter metals can also be used in conjunction with palladium
or platinum as noted above.
In another aspect of this invention, it is also possible to obtain high levels of

5conversions in the order of at least 25% and high selectivity to ethyl acetate of at least about
90% using palladium loading of one weight percent and cobalt loading of five weight percent
on silica or H-ZSM-5 as catalyst supports. In this aspect of the invention, other preferred
catalyst supports include graphitized carbon, titania, zirconia, iron oxide, silica-alumina and
calcium silicate.
10
In another aspect of the process of this invention, the hydrogenation is carried out at a
pressure just sufficient to overcome the pressure drop across the catalytic bed.
The reaction may be carried out in the vapor or liquid state under a wide variety of
15conditions. Preferably, the reaction is carried out in the vapor phase. Reaction temperatures
may be employed, for example in the range of about 200ºC to about 300ºC, preferably about
225ºC to about 275ºC. The pressure is generally uncritical to the reaction and
subatmospheric, atmospheric or superatmospheric pressures may be employed. In most cases,
however, the pressure of the reaction will be in the range of about 5 to 30 atmospheres
20absolute, most preferably the pressure of reaction zone is in the range of about 8 to 20
atmospheres absolute.
Although the reaction consumes a mole of hydrogen per mole of acetic acid to
produce a ½ mole of ethyl acetate, the actual molar ratio of acetic acid to hydrogen in the feed
25stream may be varied between wide limits, e.g. from about 100:1 to 1:100. It is preferred
however that such ratio be in the range of about 1:20 to 1:2. More preferably the molar ratio
of acetic acid to hydrogen is about 1:5.
The raw materials used in connection with the process of this invention may be
30derived from any suitable source including natural gas, petroleum, coal, biomass and so forth.
It is well known to produce acetic acid through methanol carbonylation, acetaldehyde
oxidation, ethylene oxidation, oxidative fermentation, and anaerobic fermentation and so
forth. As petroleum and natural gas have become more expensive, methods for producing
acetic acid and intermediates such as methanol and carbon monoxide from alternate carbon
19
sources have drawn more interest. Of particular interest is the production of acetic acid from
synthesis gas (syngas) that may be derived from any suitable carbon source. United States
Patent No. 6,232,352 to Vidalin, the disclosure of which is incorporated herein by reference,
for example teaches a method of retrofitting a methanol plant for the manufacture of acetic
5acid. By retrofitting a methanol plant the large capital costs associated with CO generation
for a new acetic acid plant are significantly reduced or largely eliminated. All or part of the
syngas is diverted from the methanol synthesis loop and supplied to a separator unit to
recover CO and hydrogen, which are then used to produce acetic acid. In addition to acetic
acid, the process can also be used to make hydrogen which is utilized in connection with this
10invention.
United States Patent No. RE 35,377 to Steinberg et al., also incorporated herein by
reference, provides a method for the production of methanol by conversion of carbonaceous
materials such as oil, coal, natural gas and biomass materials. The process includes
15hydrogasification of solid and/or liquid carbonaceous materials to obtain a process gas which
is steam pyrolyzed with additional natural gas to form synthesis gas. The syngas is converted
to methanol which may be carbonylated to acetic acid. The method likewise produces
hydrogen which may be used in connection with this invention as noted above. See also,
United States Patent No. 5,821,111 to Grady et al., which discloses a process for converting
20waste biomass through gasification into synthesis gas as well as United States Patent No.
6,685,754 to Kindig et al., the disclosures of which are incorporated herein by reference.
The acetic acid may be vaporized at the reaction temperature, and then it can be fed
along with hydrogen in an undiluted state or diluted with a relatively inert carrier gas, such as
25nitrogen, argon, helium, carbon dioxide and the like.
Alternatively, acetic acid in vapor form may be taken directly as crude product from
the flash vessel of a methanol carbonylation unit of the class described in United States Patent
No. 6,657,078 to Scates et al., the disclosure of which is incorporated herein by reference.
30The crude vapor product may be fed directly to the reaction zones of the present invention
without the need for condensing the acetic acid and light ends or removing water, saving
overall processing costs.
20
Contact or residence time can also vary widely, depending upon such variables as the
amount of acetic acid, catalyst, reactor, temperature and pressure. Typical contact times range
from a fraction of a second to more than several hours when a catalyst system other than a
fixed bed is used, with preferred contact times, at least for vapor phase reactions, between
5about 0.5 and 100 seconds.
Typically, the catalyst is employed in a fixed bed reactor e.g. in the shape of an
elongated pipe or tube where the reactants, typically in the vapor form, are passed over or
through the catalyst. Other reactors, such as fluid or ebullient bed reactors, can be employed,
10if desired. In some instances, it is advantageous to use the hydrogenation catalysts in
conjunction with an inert material to regulate the pressure drop, flow, heat balance or other
process parameters in the catalyst bed including the contact time of the reactant compounds
with the catalyst particles.
15 In one of the preferred embodiments there is also provided a process for selective and
direct formation of ethyl acetate from acetic acid comprising: contacting a feed stream
containing acetic acid and hydrogen at an elevated temperature with a suitable hydrogenating
catalyst containing about 0.5 weight percent to about 1 weight percent of platinum or
palladium and about 2.5 weight percent to about 5 weight percent of copper or cobalt on a
20suitable catalyst support. The preferred catalyst support is either silica or H-ZSM-5.
In this embodiment of the process of this invention, the preferred hydrogenation

catalyst contains about one (1) weight percent platinum and about five (5) weight percent
copper or about one (1) weight percent palladium and about five (5) weight percent cobalt. It
25is preferred that the hydrogenation catalysts are layered in a fixed bed and the reaction is
carried out in the vapor phase using a feed stream of acetic acid and hydrogen in the molar
range of about 1:20 to 1:5 and at a temperature in the range of about 225ºC to 275ºC and at a
pressure of reaction zones in the range of about 8 to 20 atmospheres absolute, and the contact
time of reactants is in the range of about 0.5 and 100 seconds.
30
Step (b): Enriching of Ethyl Acetate in the First Gaseous Product Stream
In the second step of the process of this invention, the ethyl acetate formed in the first
reaction zone, step (a) of the process of this invention as described herein is further enriched
so as to result in a stream containing at least 50 mole percent of ethyl acetate. Any of the
21
methods known in the art can be employed for this purpose. For example, one can employ a
suitable distillation column to remove the volatile gaseous byproducts at the overhead and the
bottom column to separate the high boiling fractions. Various other cryogenic methods and/or
temperature controlled trapping devices can also be employed, such as a scrubber to remove
5either the impurities or other byproducts having either low or high boiling points such that the
resulting stream contained at least 50 mole percent of ethyl acetate.
Preferably the enriched product stream from the first reaction zone contained at least
60 mole percent of ethyl acetate. More preferably the enriched gaseous product stream from
10the first reaction zone contained at least 70 mole percent of ethyl acetate. Even more
preferably the enriched gaseous product stream from the first reaction zone contained at least
80 mole percent of ethyl acetate.
Step (c): Cracking of Ethyl Acetate to Ethylene and Acetic Acid

15 The enriched gaseous product stream is then contacted in a second reaction zone at an
elevated temperature with a cracking catalyst. Typically such cracking reactions are carried
out at an elevated temperature in the range of about 300ºC to about 550ºC without any
catalyst. The yields of ethylene and acetic acid can generally be high. See, for example,
DePuy and King, Chem. Rev., 60, 431-445 (1960), incorporated herein by reference in its
20entirety. However, such reactions can be catalyzed if desired utilizing a cracking catalyst.
More importantly by the employment of a cracking catalyst in this step (b) of the process of
this invention, it is possible to dramatically reduce the cracking temperature yet obtain high
selectivity and conversions to cracking products.
25 Suitable cracking catalysts include sulfonic acid resins such as perfluorosulfonic acid
resins disclosed in United States Patent No. 4,399,305 to Schreck, noted above, the disclosure
of which is incorporated herein by reference. Zeolites are also suitable as cracking catalysts
as noted in United States Patent No. 4,620,050 to Cognion et al, the disclosure of which is
also incorporated herein by reference. Thus, a zeolite catalyst may be used to concurrently
30support a hydrogenating catalyst as described hereinabove and then to crack the resulting
ethyl acetate to form ethylene and acetic acid.
Thus in accordance with one aspect of the process of this invention there is also
provided a consolidated fixed bed reactor wherein the front end of the reactor is loaded with
22
the hydrogenation catalyst as described hereinabove and the rear end of the reactor is loaded
with a suitable cracking catalyst as described hereinabove thereby both steps (a) and (b) of the
process of this invention can effectively be carried out in a single stage. Any of the known
fixed bed reactors that can bring about such results can be employed for this purpose.
5Preferably a tubular reactor designed to contain two different catalyst layers as described
herein is employed to achieve this task.
Typically, cracking of ethyl acetate in the presence of a cracking catalyst can be

carried out in the temperature range of from about 150ºC to about 300ºC, preferably in the
10range of from about 160ºC to about 250ºC and more preferably in the range of from about
170ºC to 225ºC. Again, as described above, any of the zeolites can be used as cracking
catalyst. Preferably, the cracking is carried out in the presence of a zeolite having a pore
diameter above about 0.6 nm. Specific examples of such zeolites include, without any
limitation, mordenites, zeolite X and zeolite Y as described herein.
15
As noted above, another preferred cracking catalyst that can be employed in step (c) of
the process of this invention is perfluorosulfonic acid resin, which is commercially available
under the trademark NAFION® from the duPont de Nemours Company at Wilmington,
Delaware. Suitable variations of these resins are described in United States Patent No.
204,065,512 to Cares and in duPont “Innovation,” Volume 4, number 3, Spring 1973.
Step (d): Formation of VAM from the Second Gaseous Product Stream
Containing Ethylene and Acetic Acid
In a third reactor zone, the gaseous product stream from the cracking reactor is
25contacted further with a catalyst and a second feed containing molecular oxygen and
optionally additional amount of acetic acid, if desired, in order to balance the stoichiometry of
the reaction. It is preferable that equal mole ratio of ethylene and acetic acid is fed into the
third reactor zone.
30 Any of the known catalysts for oxidative reaction of ethylene with acetic acid to form
VAM can be employed in step (d) of the process of this invention, for example, as described
in GB 1 559 540; United States Patent Nos. 5,185,308; 5,691,267; 6,114,571; and WO
99/08791, the equivalent to United States Patent No. 6,603,038. EP-A 0 330 853 describes
impregnated catalysts for the production of VAM containing palladium, potassium,
23
manganese and cadmium as additional promoter instead of gold. All of the references
mentioned herein are incorporated herein by reference in their entirety.
GB 1 559 540 describes suitable catalysts that can be employed in the preparation of
5VAM by the reaction of ethylene, acetic acid and oxygen, as used in step (d) of the process of
this invention. The catalyst is comprised of: (1) a catalyst support having a particle diameter
of from 3 to 7 mm and a pore volume of from about 0.2 to 1.5 ml/g, a 10% by weight water
suspension of the catalyst support having a pH from about 3.0 to 9.0, (2) a palladium-gold
alloy distributed in a surface layer of the catalyst support, the surface layer extending less than
100.5 mm from the surface of the support, the palladium in the alloy being present in an amount
of from about 1.5 to 5.0 grams per liter of catalyst, and the gold being present in an amount of
from about 0.5 to 2.25 grams per liter of catalyst, and (3) from 5 to 60 grams per liter of
catalyst of alkali metal acetate.
15 United States Patent No. 5,185,308 describes a shell impregnated catalyst active for
the production of VAM from ethylene, acetic acid and an oxygen containing gas, the catalyst
consisting essentially of (1) a catalyst support having a particle diameter from about 3 to
about 7 mm and a pore volume of 0.2 to 1.5 ml per gram, (2) palladium and gold distributed
in the outermost 1.0 mm thick layer of the catalyst support particles, and (3) from about 3.5 to
20about 9.5% by weight of potassium acetate wherein the gold to palladium weight ratio in said
catalyst is in the range 0.6 to 1.25.
United States Patent No. 5,691,267 to Nicolau et al. describes a two step gold addition
method for making a catalyst used in the gas phase formation of VAM from the reaction of
25ethylene, oxygen, and acetic acid. The catalyst is formed by (1) impregnating a catalyst
carrier with aqueous solutions of a water-soluble palladium salt and a first amount of a water-
soluble gold compound such as sodium-palladium chloride and auric chloride, (2) fixing the
precious metals on the carrier by precipitating the water-insoluble palladium and gold
compounds by treatment of the impregnated carriers with a reactive basic solution such as
30aqueous sodium hydroxide which reacts with the palladium and gold compounds to form
hydroxides of palladium and gold on the carrier surface, (3) washing with water to remove the
chloride ion (or other anion), and (4) reducing all the precious metal hydroxides to free
palladium and gold, wherein the improvement comprises (5) impregnating the carrier with a
second amount of a water-soluble gold compound subsequent to fixing a first amount of
24
water-soluble gold agent, and (6) fixing the second amount of a water-soluble gold
compound.
United States Patent No. 6,114,571 to Abel et al. describes a catalyst for forming vinyl
5acetate in the gas phase from ethylene, acetic acid, and oxygen or oxygen-containing gases
wherein the catalyst is comprised of palladium, gold, boron, and alkali metal compounds on a
support. The catalyst is prepared by a) impregnating the support with soluble palladium and
gold compounds; b) converting the soluble palladium and gold compounds on the support into
insoluble compounds by means of an alkaline solution; c) reducing the insoluble palladium
10and gold compounds on the support by means of a reducing agent in the liquid phase; d)
washing and subsequently drying the support; e) impregnating the support with a soluble
alkali metal compound; and f) finally drying the support at a maximum of 150°C, wherein
boron or boron compounds are applied to the catalyst prior to the final drying.
15 WO 99/08791, the equivalent of United States Patent 6,603,038 to Hagemeyer et al.,

describes a method for producing catalysts containing metal nanoparticles on a porous
support, especially for gas phase oxidation of ethylene and acetic acid to form VAM. The
invention relates to a method for producing a catalyst containing one or several metals from
the group of metals comprising the sub-groups Ib and VIIIb of the periodic table on porous
20support particles, characterized by a first step in which one or several precursors from the
group of compounds of metals from sub-groups Ib and VIIIb of the periodic table is or are
applied to a porous support, and a second step in which the porous, preferably nanoporous
support to which at least one precursor has been applied is treated with at least one reduction
agent, to obtain the metal nanoparticles produced in situ in the pores of said support.
25
Typically, step (d) of the process of the present invention is carried out
heterogeneously with the reactants being present in the gas phase.
The molecular oxygen-containing gas used in step (d) of the process of the present
30invention may comprise other inert gases such as nitrogen. Preferably, molecular oxygen
used in step (d) of the process of the present invention is air.
Step (d) of the process of the present invention may suitably be carried out at a
temperature in the range of from about 140ºC to 220ºC and a pressure in the range of from
25
about 1 to 100 atmospheres absolute. Step (d) of the process of the present invention can be
carried out in any suitable reactor design capable of removing the heat of reaction in an
appropriate way; preferred technical solutions are fixed or fluidized bed reactors as described
herein.
5
Acetic acid conversions in the range of about 5 to 50% may be achieved in step (d) of
the process of the present invention. Oxygen conversions in the range of about 20 to 100%
may be achieved in step (d) of the present invention. In step (d) of the process of the present
invention, the catalyst suitably has a productivity (space time yield, STY) in the range of
10about 100 to 2000 grams of vinyl acetate per hour per liter of catalyst, but >10,000 grams of
vinyl acetate per hour per liter of catalyst is also suitable.
As already noted above, the third gaseous product stream from step (d) of the process
comprises VAM and water and optionally also unreacted acetic acid, ethylene, ethyl acetate,
15ethane, nitrogen, carbon monoxide, carbon dioxide and possibly traces of other byproducts.
Intermediate between step (d) and step (e) of the process of the invention it is preferred to
remove ethylene, and ethane, carbon monoxide and carbon dioxide, if any, from the third
product stream, suitably as an overhead gaseous fraction from a scrubbing column, in which a
liquid fraction comprising vinyl acetate, water and acetic acid is removed from the base.
20
The third product stream from step (d) comprising VAM, water and acetic acid, with
or without the intermediate scrubbing step, is separated in step (e) by distillation into an
overhead azeotrope fraction comprising vinyl acetate and water and a base fraction
comprising acetic acid.
25
VAM is recovered from the azeotrope fraction separated in step (d), suitably for
example by decantation. The recovered VAM may, if desired, be further purified in a known
manner. The base fraction comprising acetic acid separated in step (d) is preferably recycled,
with or preferably without further purification, to step (a) or, if desired, to step (d) of the
30process.
METHOD OF INDUSTRIAL APPLICATION OF THE INVENTION
The following Examples A-V describe the procedures used for the preparation of
various catalysts employed in the Examples 1-15 which follow:
26
Example A
Preparation of 1 weight percent platinum and 5 weight percent copper
on high purity low surface area silica
5 Powdered and meshed high purity low surface area silica (94 g) of uniform particle
size distribution of about 0.2 mm is dried at 120ºC in an oven under nitrogen atmosphere
overnight and then cooled to room temperature. To this is added a solution of platinum nitrate
(Chempur) (1.64 g) in distilled water (16 ml). The resulting slurry is dried in an oven
gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst mixture is then
10calcined at 500ºC (6 hours, 1ºC/min). To this calcined and cooled material is added a solution
of copper nitrate trihydrate (Alfa Aesar) (19 g) in distilled water (19 ml). The resulting slurry
is dried in an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst
mixture is then calcined at 500ºC (6 hours, 1ºC/min).
15Example B
Preparation of 1 weight percent palladium and 5 weight percent cobalt on high purity low
surface area silica
Powdered and meshed high purity low surface area silica (94 g) of uniform particle
20overnight and then cooled to room temperature. To this is added a solution of palladium
nitrate (Heraeus) (2.17 g) in distilled water (22 ml). The resulting slurry is dried in an oven
calcined at 500ºC (6 hours, 1ºC/min). To this calcined and cooled material is added a solution
of cobalt nitrate hexahydrate (24.7 g) in distilled water (25 ml). The resulting slurry is then
25dried in an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst
Example C
Preparation of 1 weight percent palladium and 5 weight percent cobalt on H-ZSM-5
30 The procedures of Example B are substantially repeated except for utilizing H-ZSM-5
as the catalyst support.
Example D
27
Preparation of 5 weight percent copper and 5 weight percent chromium on high purity low
surface area silica
5overnight and then cooled to room temperature. To this is added a solution of copper nitrate
trihydrate (Alfa Aesar) (19 g) in distilled water (19 ml). The resulting slurry is then dried in
an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst mixture is
then calcined at 500ºC (6 hours, 1ºC/min). To this calcined and cooled material is added a
solution of chromium nitrate nonahydrate (Alfa Aesar) (32.5 g) in distilled water (65 ml). The
10resulting slurry is dried in an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The
impregnated catalyst mixture is then calcined at 500ºC (6 hours, 1ºC/min).
Example E
Preparation of 5 weight percent molybdenum carbide (MoC2) on high purity low surface area
15silica
overnight and then cooled to room temperature. To this is added a solution of ammonium
heptamolybdate hexahydrate (Sigma) (9.5 g) in distilled water (63 ml). The resulting slurry is
20dried in an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst
mixture is then calcined at 500ºC (6 hours, 1ºC/min). This results in molybdenum oxide on
silica. It is then treated in a flow of methane at 500ºC to afford the titled catalyst.
Example F
25Preparation of 1 weight percent platinum and 5 weight percent molybdenum on titania
Powdered and meshed titania (94 g) of uniform particle size distribution of about 0.2
mm was dried at 120ºC in an oven under nitrogen atmosphere overnight and then cooled to
room temperature. To this is added a solution of platinum nitrate (Chempur) (1.64 g) in
distilled water (16 ml). The resulting slurry is dried in an oven gradually heated to 110ºC (>2
30hours, 10ºC/min). The impregnated catalyst mixture is then calcined at 500ºC (6 hours,
1ºC/min). To this calcined and cooled material was added a solution of ammonium
heptamolybdate hexahydrate (Sigma) (9.5 g) in distilled water (63 ml). The resulting slurry is
dried in an oven gradually heated to 110ºC (>2 hours, 10ºC/min). The impregnated catalyst
28
Example G
Preparation of 1 weight percent palladium on high purity low surface area silica
5size distribution of about 0.2 mm is dried at 120ºC in an oven under nitrogen atmosphere
overnight and then cooled to room temperature. To this is added a solution of palladium
nitrate (Heraeus) (2.17 g) in distilled water (22 ml). The resulting slurry is dried in an oven
calcined at 500ºC (6 hours, 1ºC/min).
10
Example H
Preparation of 1 weight percent palladium and 5 weight percent molybdenum on H-ZSM-5
The procedures of Example A are substantially repeated except for utilizing a solution
of palladium nitrate (Heraeus) (2.17 g) in distilled water (22 ml), a solution of ammonium
15heptamolybdate hexahydrate (Sigma) (9.5 g) in distilled water (65 ml) and 94 grams of H-
ZSM-5. The catalyst is sequentially impregnated first with molybdenum and then with
palladium.
Example I
20Preparation of 1 weight percent nickel and 5 weight percent molybdenum on carbon
of nickel nitrate hexahydrate (Alfa Aesar) (4.96 g) in distilled water (5 ml), a solution of
ammonium heptamolybdate hexahydrate (Sigma) (9.5 g) in distilled water (65 ml) and 94
grams of carbon. The catalyst is sequentially impregnated first with molybdenum and then
25with nickel.
29
Example J
Preparation of 1 weight percent platinum on titania
of platinum nitrate (Chempur) (1.64 g) in distilled water (16 ml) and 99 grams of titania.
5
Example K
Preparation of 1 weight percent palladium and 5 weight percent rhenium on titania
of palladium nitrate (Heraeus) (2.17 g) in distilled water (22 ml), a solution of perrhenic acid
10(7 g) in distilled water (14 ml) and 94 grams of titania. The catalyst is sequentially
impregnated first with rhenium and then with palladium.
Example L
Preparation of 1 weight percent platinum and 5 weight percent molybdenum on carbon
15 The procedures of Example F are substantially repeated except for utilizing 94 grams
of carbon.
Example M
Preparation of 1 weight percent palladium and 5 weight percent zirconium on silica
20 The procedures of Example A are substantially repeated except for utilizing a solution
of palladium nitrate (Heraeus) (2.17 g) in distilled water (22 ml), a solution of zirconium
nitrate pentahydrate (23.5 g) in distilled water (100 ml) and 94 grams of silica. The catalyst is
sequentially impregnated first with zirconium and then with palladium.
30
Example N
Preparation of 1 weight percent platinum and 5 weight percent copper on titania
The procedures of Example A are substantially repeated except for utilizing 94 grams
of titania.
5
Example O
Preparation of 1 weight percent nickel and 5 weight percent rhenium on titania
of nickel nitrate hexahydrate (Alfa Aesar) (4.96 g) in distilled water (5 ml), a solution of
10perrhenic acid (7 g) in distilled water (14 ml) and 94 grams of titania. The catalyst is
sequentially impregnated first with rhenium and then with nickel.
Example P
Preparation of 1 weight percent platinum and 5 weight percent molybdenum on silica
15 The procedures of Example F are substantially repeated except for utilizing 94 grams
of silica.
Example Q
Preparation of 1 weight percent palladium and 5 weight percent molybdenum on silica
20 The procedures of Example H are substantially repeated except for utilizing 94 grams
of silica.
Example R
Preparation of 5 weight percent copper and 5 weight percent zirconium on silica
25 The procedures of Example A are substantially repeated except for utilizing a solution
of copper nitrate trihydrate (Alfa Aesar) (19 g) in distilled water (19 ml), a solution of
zirconium nitrate pentahydrate (23.5 g) in distilled water (100 ml) and 94 grams of silica. The
catalyst is sequentially impregnated first with copper and then with zirconium.
30Example S
Preparation of K, Pd, Au/TiO2
The title catalyst is prepared in accordance with the procedures set forth in United
States Patent No. 6,852,877 to Zeyss et al.
31
Example T
Preparation of Pd and Au
A vinyl acetate catalyst containing Pd and Au for converting a stream of gas
containing ethylene, oxygen or air, and acetic acid into VAM is prepared generally as follows:
5
The catalyst is prepared on spherical silica supports with diameters of about 5 mm.
The silica supports are impregnated with an aqueous solution containing sodium palladium
tetrachlorate and sodium tetracholroaurate in sufficient amounts such that the catalysts would
have about 7 gm/l of palladium metal and about 7 gm/l of gold metal each.
10
After impregnation, the carrier is placed in a roto-evaporator, without vacuum, and
treated with 283 ml of a 50% w/w aqueous solution of sodium hydroxide. The supports are
rotated at about 5 rpm for about 2.5 hours in a sodium hydroxide solution at a temperature of
70°C by rotation in a hot water bath. The resulting catalysts are reduced in a gas blend of 5%
15ethylene in nitrogen for about 5 hours at a temperature of about 150°C at a flow rate of about
0.5 SCFH (standard cubic feet per hour) at atmospheric pressure to reduce the metal salts to
metal.
The catalysts are then impregnated again with an aqueous solution of sodium
20tetrachloroaurate and 1.65 gm of a 50% w/w aqueous sodium hydroxide fixing solution. The
resulting catalysts are reduced in a gas blend of 5% ethylene in nitrogen for about 5 hours at a
temperature of about 150°C at a flow rate of about 0.5 SCFH (standard cubic feet per hour) at
atmospheric pressure to reduce the gold salts to gold metal.
25Example U
Preparation of Pd, Au, and K
A catalyst for preparing vinyl acetate in the gas phase from ethylene, acetic acid, and
oxygen or oxygen-containing gases wherein the catalyst is prepared generally as follows:
30 250 ml of silicon dioxide catalyst sphere supports having a diameter of 7.3 mm are
impregnated with 85 ml of an aqueous solution containing 4.6 g of Na2PdCl4 and 1.4 g of
NaAuCl4. The precipitation of the insoluble metal compounds is achieved by the addition of
283 ml of an aqueous solution of 17 g of borax. The vessel is then immediately rotated by
means of a rotary evaporator, without vacuum, for 2.5 hours at 5 revolutions per minute
32
(rpm). The reduction is achieved by the addition of 7 ml of hydrazine hydrate in 20 ml of
water and immediate rotation of the vessel at 5 rpm for 1 hour.
The pellets thus obtained are dried for 1 hour at 1000°C. The reduced catalyst is
5impregnated with an aqueous solution containing 10 g of potassium acetate and having a
volume corresponding to the absorption capacity of the dry support material. The catalyst is
then dried again.
Example V
10Preparation of Pd, Au, and B
A catalyst containing nanosize metal particles on a porous support for the gas phase
oxidation of ethylene and acetic acid to give vinyl acetate is prepared as follows:
200 g of SiO2 supports having a BET surface area of 300 m2/g are sprayed
15discontinuously at a temperature of 30-32°C with a hydrochloric acid solution of 3.33 g (18.8
mmol) of palladium chloride and 1.85 g (4.7 mmol) of auric acid in 500 ml of water over a
period of 35 minutes in a coating unit.
The support spheres are subsequently dried and sprayed with 20 g of tripotassium
20citrate hydrate dissolved in 200 ml of water over a period of 25 minutes. At a drum rotation
speed of 10 rpm, spraying is carried out discontinuously at 1 bar. The inlet temperature
(warm air temperature) is 60°C and the product temperature was 32-30° C. This gave a
homogeneously impregnated coated catalyst having a shell thickness of 400 µm. The
diameter of the nanosize particles is determined by means of TEM. The mean particle
25diameter is 30 nm.
Gas Chromatographic (GC) analysis of the Products

The analysis of the products was carried out by online GC. A three channel compact
GC equipped with one flame ionization detector (FID) and 2 thermal conducting detectors
30(TCDs) was used to analyze the reactants and products. The front channel was equipped with
an FID and a CP-Sil 5 (20 m) + WaxFFap (5 m) column and was used to quantify:
Acetaldehyde
Ethanol
33
Acetone
Methyl acetate
Vinyl acetate
Ethyl acetate
5 Acetic acid
Ethylene glycol diacetate
34
Ethylene glycol
Ethylidene diacetate
Paraldehyde
5 The middle channel was equipped with a TCD and Porabond Q column and was used
to quantify:
CO2
Ethylene
10 Ethane
The back channel was equipped with a TCD and Molsieve 5A column and was used to
quantify:
15 Helium
Hydrogen
Nitrogen
Methane
Carbon monoxide
20
Prior to reactions, the retention time of the different components was determined by
spiking with individual compounds and the GCs were calibrated either with a calibration gas
of known composition or with liquid solutions of known compositions. This allowed the
determination of the response factors for the various components.
25
Examples 1-10 describe procedures for the hydrogenation of acetic acid to ethyl
acetate as described in step (a) of the process of the present invention.
Example 1
30 The catalyst utilized was 1 weight percent platinum and 5 weight percent copper on
silica prepared in accordance with the procedure of Example A.
In a tubular reactor made of stainless steel, having an internal diameter of 30 mm and

capable of being raised to a controlled temperature, there are arranged 50 ml of 1 weight
35
percent platinum and 5 weight percent copper on silica. The length of the catalyst bed after
charging was approximately about 70 mm. Prior to the reaction the catalyst was reduced in
situ by heating at a rate of 2ºC/min to a final temperature of 400ºC. Then, 5 mol% hydrogen
in nitrogen was introduced to the catalyst chamber at a gas hourly space velocity (GHSV) of
57500 h-1. After reduction, the catalyst was cooled to reaction temperature of 275ºC by
continuing the gas flow of 5 mol% hydrogen in nitrogen. Once the reaction temperature was
stabilized at 275ºC the hydrogenation of acetic acid was begun as follows.
A feed liquid was comprised essentially of acetic acid. The reaction feed liquid was
10evaporated and charged to the reactor along with hydrogen and helium as a carrier gas with an
average combined gas hourly space velocity (GHSV) of about 1250 hr-1 at a temperature of
about 275ºC and pressure of 15 bar. The resulting feed stream contained a mole percent of
acetic acid from about 4.4% to about 13.8% and the mole percent of hydrogen from about
14% to about 77%. A portion of the vapor effluent was passed through a gas chromatograph
15for analysis of the contents of the effluents. The selectivity to ethyl acetate was 88.5% at a
conversion of acetic acid of 37%.
Example 2
The catalyst utilized was 1 weight percent palladium and 5 weight percent cobalt on
20silica prepared in accordance with the procedure of Example B.
The procedure as set forth in Example 1 was substantially repeated with an average
combined gas hourly space velocity (GHSV) of 2,500 hr-1 of the feed stream of the vaporized
acetic acid and hydrogen (H2 to acetic acid mole ratio of 5) at a temperature of 250ºC and
25pressure of 8 bar. A portion of the vapor effluent is passed through a gas chromatograph for
analysis of the contents of the effluents. The acetic acid conversion was 26% and ethyl
acetate selectivity was 91%.
Example 3
30 The catalyst utilized was 1 weight percent palladium and 5 weight percent cobalt on
H-ZSM-5 prepared in accordance with the procedure of Example C.
The procedure as set forth in Example 1 was substantially repeated with an average
36
pressure of 15 bar. A portion of the vapor effluent is passed through a gas chromatograph for
acetate selectivity was 93%.
5
Example 4
The catalyst utilized was 1 weight percent palladium and 5 weight percent cobalt on
H-ZSM-5 prepared in accordance with the procedure of Example C.
10 The procedure as set forth in Example 1 was substantially repeated with an average
combined gas hourly space velocity (GHSV) of 10,000 hr-1 of the feed stream of the
vaporized acetic acid and hydrogen (H2 to acetic acid mole ratio of 5) at a temperature of
250ºC and pressure of 1 bar. A portion of the vapor effluent is passed through a gas
chromatograph for analysis of the contents of the effluents. The acetic acid conversion was
156% and ethyl acetate selectivity was 96%. The other products formed were ethane (1.8%) and
ethanol (0.3%).
37
Example 5
The catalyst utilized was 1 weight percent palladium and 5 weight percent
molybdenum on H-ZSM-5 prepared in accordance with the procedure of Example H.
5 The procedure as set forth in Example 1 was substantially repeated with an average
10acetate selectivity was 93%. The other products formed were ethane (4.3%) and ethanol
(0.2%).
Example 6
The catalyst utilized was 1 weight percent nickel and 5 weight percent molybdenum
15on carbon prepared in accordance with the procedure of Example I.
The procedure as set forth in Example 1 is substantially repeated with an average

analysis of the contents of the effluents. The acetic acid conversion was 6% and ethyl acetate
selectivity was 88%. The other products formed were ethane (3.3%) and ethanol (4.9%).
Example 7
25 The catalyst utilized was 1 weight percent platinum on titania prepared in accordance
with the procedure of Example J.

30acetic acid and hydrogen (H2 to acetic acid mole ratio of 5) at a temperature of 250ºC and
acetate selectivity was 88%. The other products formed were ethane (4.8%) and methane
(1.7%).
38
Example 8
The catalyst utilized was the same catalyst used in Example 7 which was reused in this
Example 8.
5
10analysis of the contents of the effluents. The acetic acid conversion was 41% and ethyl
acetate selectivity was 87%. The other products formed were ethane (5%) and methane
(1.7%).
Example 9
15 The catalyst utilized was 1 weight percent palladium and 5 weight percent rhenium on
titania prepared in accordance with the procedure of Example K.

acetate selectivity was 87%. The other products formed were ethanol (11%) and acetaldehyde
(1.3%).
25
39
Example 10A
The catalyst utilized was 1 weight percent platinum and 5 weight percent molybdenum
on carbon prepared in accordance with the procedure of Example L.
5 The procedure as set forth in Example 1 is substantially repeated with an average

10acetate selectivity was 85%. The other products formed were ethane (7.1%) and ethanol
(5.2%).
Example 10B
The catalyst utilized was 1 weight percent palladium and 5 weight percent zirconium
15on silica prepared in accordance with the procedure of Example M.

analysis of the contents of the effluents. The acetic acid conversion was 8.3% and ethyl
acetate selectivity was 84%. The other products formed were methane (7.9%) and ethane
(1%).
25Example 10C
The catalyst utilized was 1 weight percent platinum and 5 weight percent copper on
titania prepared in accordance with the procedure of Example N.

30combined gas hourly space velocity (GHSV) of 2,500 hr-1 of the feed stream of the vaporized
40
acetate selectivity was 84%. The other products formed were acetone (8.4%) and
acetaldehyde (7.1%).
Example 10D
5 The catalyst utilized was 1 weight percent nickel and 5 weight percent rhenium on
titania prepared in accordance with the procedure of Example O.

acetate selectivity was 83%. The other products formed were ethanol (10.4%) and ethane
(2%).
15
Example 10E
on silica prepared in accordance with the procedure of Example P.

25acetate selectivity was 82.4%. The other products formed were ethane (6.6%) and ethanol
(5.7%).
41
Example 10F
The catalyst utilized was 1 weight percent palladium and 5 weight percent
molybdenum on silica prepared in accordance with the procedure of Example Q.

10acetate selectivity was 82%. The other products formed were ethanol (8.3%) and ethane
(3.5%).
Example 10G
The catalyst utilized was 5 weight percent copper and 5 weight percent zirconium on
15silica prepared in accordance with the procedure of Example R.

acetate selectivity was 81.4%. The other products formed were ethane (3.3%) and
acetaldehyde (10%).
25Example 10H
The catalyst utilized was 5 weight percent copper and 5 weight percent chromium on
silica prepared in accordance with the procedure of Example D.

30combined gas hourly space velocity (GHSV) of 2,500 hr-1 of the feed stream of the vaporized
acetic acid and hydrogen at a temperature of 250ºC and pressure of 15 bar. A portion of the
vapor effluent is passed through a gas chromatograph for analysis of the contents of the
effluents. The acetic acid conversion is 25% and ethyl acetate selectivity is about 75%.
42
Example 10I
The catalyst utilized was 5 weight percent molybdenum carbide (MoC2) on High
Purity Low Surface Area Silica prepared in accordance with the procedure of Example E.

effluents. The acetic acid conversion is 25% and ethyl acetate selectivity is 75%.
10
Example 10J
on titania prepared in accordance with the procedure of Example F.

effluents. The acetic acid conversion is about 50% and ethyl acetate selectivity is 85%.
20
Example 10K
The catalyst utilized was 1 weight percent palladium on silica prepared in accordance
with the procedure of Example G.

effluents. The acetic acid conversion is about 65% and ethyl acetate selectivity is 85%.
30
Example 11 describes cracking of ethyl acetate to ethylene and acetic acid as
described in step (b) of the present invention.
Example 11
43
The procedure as set forth in United States Patent No. 4,399,305 to Schreck is used to
crack ethyl acetate to ethylene and acetic acid using NAFION as the cracking catalyst at
185ºC in step (c) of the process of the present invention using the ethyl acetate enriched feed
stream from step (b) of the process of the present invention..
5
Example 12
The catalyst utilized is K, Pd, Au/TiO2 prepared in accordance with the procedure of
Example S. The procedure as set forth in United States Patent No. 6,852,877 to Zeyss et al. is
used to carry out step (d) of the process of the present invention using the feed stream from
10step (c) of the process of the present invention and molecular oxygen in combination with
additional amounts of acetic acid, if desired, to balance the stoichiometry of the product
stream.
Example 13
15 The catalyst utilized is Pd and Au prepared in accordance with the procedure of
Example T. The procedure as set forth in U. S. Patent No. 5,691,267 to Nicolau et al. is used
to carry out step (d) of the process of the present invention using the feed stream from step (c)
of the process of the present invention and molecular oxygen in combination with additional
amounts of acetic acid, if desired, to balance the stoichiometry of the product stream.
20
Example 14
The catalyst utilized is Pd, Au, and K prepared in accordance with the procedure of
Example U. The procedure as set forth in U. S. Patent No. 6,114,571 to Abel et al. is used to
carry out step (d) of the process of the present invention using the feed stream from step (c) of
25the process of the present invention and molecular oxygen in combination with additional
amounts of acetic acid, if desired, to balance the stoichiometry of the product stream.
Example 15
The catalyst utilized is Pd, Au, and B prepared in accordance with the procedure of
30Example S. The procedure as set forth in U. S. Patent No. 6,603,038 to Hagemeyer et al. is
used to carry out step (d) of the process of the present invention using the feed stream from
step (c) of the process of the present invention and molecular oxygen in combination with
additional amounts of acetic acid, if desired, to balance the stoichiometry of the product
stream.
44
While the invention has been illustrated in connection with particular examples,
modifications to these examples within the spirit and scope of the invention will be readily
apparent to those of skill in the art. In view of the foregoing discussion, relevant knowledge
5in the art and references discussed above in connection with the Background and Detailed
Description, the disclosures of which are all incorporated herein by reference, further
description is deemed unnecessary.

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1

INTEGRATED PROCESS FOR THE PRODUCTION OF VINYL ACETATE FROM

ACETIC ACID VIA ETHYL ACETATE

30 A slightly modified process for the preparation of ethyl acetate by hydrogenating

DISCLOSURE OF THE INVENTION

30 In addition, the catalyst employed in step (a) is comprised of a suitable catalyst

PREFERRED EMBODIMENTS OF THE INVENTION

The invention is described in detail below with reference to numerous embodiments

30 “Selectivity” is expressed as a mole percent based on converted acetic acid. For

The reaction proceeds in accordance with the following chemical equations:

(c) Oxidative Addition of Acetic Acid to Ethylene to form VAM

Step (a): Hydrogenation of Acetic Acid to Ethyl Acetate

In another aspect, the loading levels of a bimetallic combination of Pd/Mo is about 1

The preparation of large-pore mordenites is described, for example, in United States

In another embodiment of this invention, the preferred catalyst support is carbon.

30 The preferred carbon support may be prepared by heat treating a carbon-containing

Where an inert atmosphere is required it may be supplied by nitrogen or an inert gas.

Thus in one embodiment of this invention, there is provided a hydrogenation catalyst

In a further embodiment of this invention, there is provided a hydrogenation catalyst

In another aspect of this invention, it is also possible to obtain high levels of

In this embodiment of the process of this invention, the preferred hydrogenation

Step (c): Cracking of Ethyl Acetate to Ethylene and Acetic Acid

Typically, cracking of ethyl acetate in the presence of a cracking catalyst can be

15 WO 99/08791, the equivalent of United States Patent 6,603,038 to Hagemeyer et al.,

METHOD OF INDUSTRIAL APPLICATION OF THE INVENTION

Gas Chromatographic (GC) analysis of the Products

In a tubular reactor made of stainless steel, having an internal diameter of 30 mm and

The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

5 The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

20 The procedure as set forth in Example 1 is substantially repeated with an average

5 The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

The procedure as set forth in Example 1 is substantially repeated with an average

5 The procedure as set forth in Example 1 is substantially repeated with an average

15 The procedure as set forth in Example 1 is substantially repeated with an average

25 The procedure as set forth in Example 1 is substantially repeated with an average

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