US 20100197959A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2010/0197959 A1
Johnston et al.
(54)

PROCESSES FOR MAKING ETHYL ACETATE

Aug. 5, 2010

(43) Pub. Date:

(22)

Filed:

Feb. 2, 2010

FROM ACETIC ACID

Related U.S. Application Data

(75)

Inventors:

Victor J. Johnston, Houston, TX

(US); Laiyuan Chen, Houston, TX

(63) Continuation-in-part of application No. 12/588,727,

?led on Oct. 26, 2009, Continuation-in-part of appli

(US); Barbara F. Kimmich,

Bernardsville, N] (U S); Jose?na T.

cation No. 12/221 ,209, ?led on Jul. 31, 2008, Continu

ation-in-part of application No. 12/221,141, ?led on
Jul. 31, 2008.

Chapman, Houston, TX (US);

James H. Zink, League City, TX
(US); Heiko Weiner, Pasadena, TX
(US); John L. Potts, Angleton, TX
(US); Radmila Jevtic, Houston, TX

(Us)

Publication Classi?cation

(51)

C07C 1/213
C07C 67/00
C09K 3/00

Correspondence Address:
KATTEN MUCHIN ROSENMAN LLP

(C/O PATENT ADMINISTRATOR)

Int. Cl.

(52)

(2006.01)
(2006.01)
(2006.01)

U.S. Cl. ................... .. 560/265; 585/640; 252/182.11

2900 K STREET NW, SUITE 200

WASHINGTON, DC 20007-5118 (US)

(73) Assignee:

CELANESE INTERNATIONAL

CORPORATION, Dallas, TX (US)

(21) Appl. No.:

12/699,024

(57)

ABSTRACT

A process for hydrogenating acetic acid to form of ethyl

acetate and mixtures of ethyl acetate and ethanol. The hydro
genation is done in the presence of catalyst, preferably on a
support that optionally includes a support modi?er.

Patent Application Publication

Aug. 5, 2010 Sheet 1 of3

US 2010/0197959 A1

FIG. 1A - Selectivity PtISn Catalyst

100

SiO2-PtmSn1_m

80

(Sel%ctiv)y

60

40
20
0

/....
0

0.2

0.4

0.6

0.8

FIG. 1B - Productivity of PtISn Catalyst

2500

(Pr)rgodlucktivhy

2000

SiO2-PtmSn1 A

1500

+ EtOH
I EtOAC

FIG. 1C - Conversion of HOAc

100
80

C(onve%rsio)n

SiO') PtmSHl -m

60

40
20

0.2

0.4

0.6

0.8

Patent Application Publication

Aug. 5, 2010 Sheet 2 0f 3

US 2010/0197959 A1

FIG. 2A - Selectivity of ReIPd

100

SiO2-RenPd1_n

80

(Sel%ctiv)y

6O
4O
2O

+EtOH

+ EtOAc

0.2

0.4

0.6

0.8

I!

FIG. 2B - Productivity of ReIPd

400
350

(Prgoldkuctihv)y

Si

(,0 O O
250
200
150
100

+ EtOH
-I EtOAC

FIG. 2C - Conversion of HOAc

12
10

C(onve%rsio)n

ON-biCD

/
SiO2-RenPd1_n
/
i/

\\
0.2

0.4

0.6

0.8

Patent Application Publication

Aug. 5, 2010 Sheet 3 0f 3

US 2010/0197959 A1

FIG. 3

~EtOH O -HAc a
1200

- EtOAc

280 "C

|IF

0lI|iL
r

\5293.835
TOSIh

FIG. 4

T||I|

5g.__.58am

TOSIh

296 "C

Aug. 5, 2010

US 2010/0197959 A1

PROCESSES FOR MAKING ETHYL ACETATE

FROM ACETIC ACID
CROSS REFERENCE TO RELATED
APPLICATIONS

[0001] This is a continuation-in-part of US. application

Ser. No. 12/588,727, ?led Oct. 26, 2009, entitled Tunable

Catalyst Gas Phase Hydrogenation of Carboxylic Acids, of

US. application Ser. No. 12/221,209, ?led Jul. 31, 2008,
entitled Direct and Selective Production of Ethyl Acetate
from Acetic Acid Utilizing a Bimetal Supported Catalyst,
and of US. application Ser. No. 12/221,141, ?led Jul. 31,
2008, entitled Direct and Selective Production of Ethanol
from Acetic Acid Utilizing a Platinum/Tin Catalyst, the
entireties of Which are incorporated herein by reference.
FIELD OF THE INVENTION

[0002]

The present invention relates generally to processes

for hydrogenating acetic acid to form ethyl acetate or a mix

ture of ethyl acetate and ethanol and to novel catalysts for use

nium, tungsten or molybdenum. Although it has been claimed

therein 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.
[0007] A slightly modi?ed 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 anhy

dride thereof by reacting the acid or anhydride With hydrogen

at elevated temperature in the presence of a catalyst compo
sition comprising as a ?rst 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 com
ponent comprising an oxide of a Group IVB element. HoW
ever, even the optimal conditions reported therein result in

signi?cant amounts of by-products including methane,

in such processes, the catalysts having high selectivities for

ethyl acetate.

ethane, acetaldehyde and acetone in addition to ethanol. In

addition, the conversion of acetic acid is generally loW and is

BACKGROUND OF THE INVENTION

in the range of about 5 to 40% except for a feW cases in Which

the conversion reached as high as 80%.

[0003] There is a long felt need for an economically viable

process to convert acetic acid to ethyl acetate. Ethyl acetate is
an important commodity feedstock for a variety of industrial
products and is also used as an industrial solvent in the manu
facture of various chemicals. For instance, ethyl acetate can

readily be converted to ethylene by subjecting it to a cracking

process, Which can then be converted to a variety of other

[0008]

and/or ethanol, employ highly expensive catalysts or produce

undesirable by-products such as methane and ethane. Thus,

the need exists for forming ethyl acetate (and optionally etha
nol) at high selectivity using a more economical catalyst,
While minimiZing the formation of undesirable byproducts.

products. Ethyl acetate is conventionally produced from feed

stocks Where price ?uctuations are becoming more signi?
cant. That is, ?uctuating natural gas and crude oil prices
contribute to ?uctuations in the cost of conventionally pro

duced, petroleum or natural gas-sourced ethyl acetate, mak

ing the need for alternative sources of ethyl acetate all the

From the foregoing it is apparent that existing pro

cesses do not have the requisite selectivity to ethyl acetate

SUMMARY OF THE INVENTION

[0009]

The present invention relates to a process for pro

ducing ethyl acetate at high selectivities. In one embodiment,

the process comprises hydrogenating acetic acid in the pres

[0004] Ethanol is another important commodity chemical,

ence of a catalyst under conditions effective to form ethyl

acetate, Wherein the catalyst comprises a ?rst metal, a second
metal and a support, Wherein the ?rst metal is selected from

Which may be used in its oWn right, for example as a fuel, or

the group consisting of nickel, palladium and platinum, and is

greater When oil prices rise.

as a feedstock for forming ethylene, vinyl acetate, ethyl
acetate, or other chemical products. The hydrogenation of
carboxylic acids over heterogeneous catalysts to produce
alcohols is Well reported. For instance, US. Pat. No. 2,607,
807 discloses that ethanol canbe formed from acetic acid over

a ruthenium catalyst at extremely high pressures of 700-950

bar in order to achieve yields of around 88%, Whereas loW
yields of only about 40% are obtained at pressures of about
200 bar. HoWever such extreme reaction conditions are unac

ceptable and uneconomical for a commercial operation.

[0005] More recently, even though it may not still be com
mercially viable it has been reported that ethanol can be
produced from hydrogenating acetic acid using a cobalt cata
lyst at superatmospheric pressures such as about 40 to 120
bar. See, for example, US. Pat. No. 4,517,391 to Shuster et al.
[0006] On the other hand, US. Pat. No. 5, 149,680 to Kitson
et al. describes a process 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 rhe

present in an amount greater than 1 Wt %, based on the total

Weight of the catalyst. The second metal may be selected from

the group consisting of molybdenum, rhenium, Zirconium,

copper, cobalt, tin, and Zinc. The ?rst metal may be present,
for example, in an amount of from 0.1 to 10 Wt. % and the
second metal may be present in an amount of from 0.1 to 10

Wt. %, based on the total Weight of the catalyst.

[0010] In another embodiment, the present invention

relates to a process for producing ethyl acetate, comprising
hydrogenating acetic acid in the presence of a catalyst under
conditions effective to form ethyl acetate, Wherein the cata
lyst comprises a ?rst metal, a second metal and a support,
Wherein the ?rst metal is selected from group consisting of
nickel and palladium, and Wherein the second metal is
selected from the group consisting of tin and Zinc. In one
embodiment, the ?rst metal is present in an amount from 0.1
to 25 Wt. %, based on the total Weight of the catalyst.

[0011]

In another embodiment, the present invention

relates to a process for producing ethyl acetate comprising

hydrogenating acetic acid in the presence of a catalyst under
conditions effective to form ethyl acetate, Wherein the cata
lyst comprises a ?rst metal, a support, and at least one support
modi?er selected from the group of oxides of Group IVB

Aug. 5, 2010

US 2010/0197959 A1

metals, oxides of Group VB metals, oxides of Group VIB

metals, iron oxides, aluminum oxides and mixtures thereof.
As an example, the ?rst metal may be present in an amount
from 0.1 to 25 Wt %, based on the total Weight of the catalyst.
In one aspect, the ?rst metal is selected from the group con

sisting of Group IB, IIB, IIIB, IVB, VB, VIIB, VIIB, or VIII
transitional metal, a lanthanide metal, an actinide metal or a

metal from any of Groups IIIA, IVA, VA, or VIA. As another

option, the ?rst metal may be selected from the group con

sisting of copper, iron, cobalt, nickel, ruthenium, rhodium,

palladium, osmium, iridium, platinum, titanium, Zinc, chro

5 to 75 Wt. %; (d) Water in an amount offrom 5 to 50 Wt %; and

(e) any other compounds in an amount less than 10 Wt %,

Wherein all Weight percents are based on the total Weight of

the crude product. A preferred crude ethanol product com

prises (a) ethyl acetate in an amount from 15 to 50 Wt. %; (b)
ethanol in an amount from 5 to 70 Wt. %; (c) acetic acid in an
amount from 10 to 60 Wt. %; (d) Water in an amount of from
10 to 45 Wt %; and (e) any other compounds in an amount less
than 6 Wt %, Wherein all Weight percents are based on the total

Weight of the crude product.

BRIEF DESCRIPTION OF DRAWINGS

mium, rhenium, molybdenum, and tungsten. In another

embodiment, the catalyst further comprises a second metal
(optionally different from the ?rst metal). In embodiments
Where a second metal is present, the second metal may be
different from the ?rst metal and may be selected from the

group consisting of copper, molybdenum, tin, chromium,

iron, cobalt, vanadium, tungsten, palladium, platinum, lan

thanum, cerium, manganese, ruthenium, rhenium, gold, and
nickel. Preferably, the ?rst metal is platinum and/ or the sec

ond metal is tin. In another preferred combination, the ?rst

metal is palladium and the second metal is rhenium. Option
ally, the catalyst further comprises a third metal different
from the ?rst and second metals. The third metal may be

selected from the group consisting of cobalt, palladium,

ruthenium, copper, Zinc, platinum, tin, and rhenium and/or
may be present in an amount of 0.05 and 4 Wt. %, based on the

total Weight of the catalyst.

[0012] As noted above, the catalysts may, generally, be
suitable for use as a hydrogenation catalyst in converting
acetic acid to ethyl acetate and at least 10% of the acetic acid

may be converted during hydrogenation. Also, the hydroge

nation may be performed in a vapor phase at a temperature of
from 1250 C. to 3500 C., a pressure of 10 KPa to 3000 KPa,
and a hydrogen to acetic acid mole ratio of greater than 4: 1. In

addition, the catalysts may have a selectivity to ethyl acetate

of at least 40% and/or a selectivity to methane, ethane, and
carbon dioxide of less than 4%. In one embodiment, the
catalyst has a productivity that decreases less than 6% per 100

hours of catalyst usage.

[0013] In one embodiment, the support is present in an
amount of 25 Wt. % to 99 Wt. %, based on the total Weight of
the catalyst and is selected from the group consisting of iron

[0015] The invention is described in detail beloW With ref

erence to the appended draWings, Wherein like numerals des

ignate similar parts.

[0016]

FIG. 1A is a graph of the selectivity to ethanol and

ethyl acetate using a SiOZiPtMSnLM catalyst;

[0017]

FIG. 1B is a graph of the productivity to ethanol and

ethyl acetate of the catalyst of FIG. 1A;

[0018]

FIG. 1C is a graph of the conversion of the acetic

acid of the catalyst of FIG. 1A;

[0019] FIG. 2A is a graph of the selectivity to ethanol and

ethyl acetate using a SiOziRenPdm catalyst;

[0020]

FIG. 2B is a graph of the productivity to ethanol and

ethyl acetate of the catalyst of FIG. 2A;

[0021]

FIG. 2C is a graph of the conversion of the acetic

acid of the catalyst of FIG. 2A;

[0022]

FIG. 3 is a graph of the activity of a catalyst com

pared to the productivity of the catalyst to a mixture of ethyl

acetate and ethanol at various temperatures according to one

embodiment of the invention; and

[0023] FIG. 4 is a graph of the activity of a catalyst com
pared to the selectivity of the catalyst to a mixture of ethyl
acetate and ethanol at various temperatures according to one
embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION

Introduction

[0024]

The present invention relates to processes for pro

ducing ethyl acetate by hydrogenating acetic acid in the pres

ence of a catalyst. The hydrogenation reaction may be repre
sented as follows:

oxide, silica, alumina, silica/aluminas, titania, Zirconia, mag

nesium oxide, calcium silicate, carbon, graphite, high surface
area graphitiZed carbon, activated carbons, and mixtures

thereof. As one option, the catalyst may comprise at least one

support modi?er selected from the group consisting of (i)

alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alka
line earth metal metasilicates, (iv) alkali metal metasilicates,
(v) Group IIB metal oxides, (vi) Group IIB metal metasili

cates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal
metasilicates, and mixtures thereof preferably being CaSiO3.
In another option the support modi?er is selected from the
group consisting of oxides of Group IVB metals, oxides of

Group VB metals, oxides of Group VIB metals, iron oxides,

aluminum oxides and mixtures thereof. The support modi?er
may be present in an amount of 0.1 Wt. % to 50 Wt. %, based

on the total Weight of the catalyst.

[0014] In another embodiment, the invention relates to a

CH3

+ 2 H2O

CH3

Depending on the catalyst and process conditions employed,

the hydrogenation reaction may produce ethanol in addition
to ethyl acetate. Embodiments of the present invention ben

e?cially may be used in industrial applications to produce

ethyl acetate and/or ethanol on an economically feasible
scale.

[0025] The processes of the invention employ various cata

lysts that may be used to form ethyl acetate and optionally
ethanol. Typically, the catalyst Will comprises a ?rst metal

crude product (optionally obtained from the hydrogenation of

acetic acid, as discussed herein), Which comprises (a) ethyl

and optionally one or more of a second metal, a third metal,

and optionally additional metals. The one or more metals
preferably are disposed on a support, such as silica or titania.

acetate in an amount from 5 to 70 Wt. %; (b) ethanol in an

amount from 5 to 70 Wt. %; (c) acetic acid in an amount from

In a ?rst embodiment, the process employs a catalyst that

includes a high loading of nickel, palladium or platinum. In a

Aug. 5, 2010

US 2010/0197959 A1

second embodiment, the process employs a catalyst that com

prises a ?rst metal selected from nickel and palladium and a
second metal selected from tin and Zinc. In a third embodi
ment, the process employs a catalyst that comprises one or

[0031]

The preferred metal ratios may vary someWhat

depending on the metals used in the catalyst. In some embodi

ments, the mole ratio of the ?rst metal to the second metal is
from 10:1 to 1:10, e.g., from 4:1 to 1:4, from 2:1 to 1:2, from

more metals on a support that has been modi?ed With an

1.5:1 to 1:1.5 orfrom1.1:1 to 1:1.1.

acidic support modi?er or a redox support modi?er. It has

[0032] Molar ratios other than 1:1 may be preferred

depending on the composition of the catalyst employed. It has
noW surprisingly and unexpectedly been discovered, for

noW been discovered that these catalyst compositions surpris

ingly and unexpectedly can be formulated to be selective for

the formation of ethyl acetate, optionally in combination With

example, that for platinum/tin catalysts, platinum to tin molar

ethanol.

ratios less than 04:06, or greater than 06:04 are particularly

preferred in order to form ethyl acetate from acetic acid at

High Loading Nickel, Palladium and Platinum Catalysts

high selectivity, conversion and productivity, as shoWn in

FIGS. 1A, 1B and 1C. More preferably, the Pt/ Sn ratio is

[0026] In a ?rst embodiment, the invention is to hydroge

nation processes using catalysts that comprise one or more of

greater than 0.65:0.35 or greater than 07:03, e.g., from 0.65:

0.35 to 1:0 or from 07:03 to 1:0. Selectivity to ethyl acetate

nickel, palladium or platinum at high metal loadings. For

example, the catalyst may comprise a ?rst metal selected
from the group consisting of nickel, palladium, and platinum

may be further improved by incorporating modi?ed supports

on a support in an amount greater than 1 Wt. %, e.g., greater

than 1.1 Wt. %, or greater than 1.2 Wt. %, based on the total

[0033] With rhenium/palladium catalysts, as shoWn in

FIGS. 2A, 2B and 2C, preferred rhenium to palladium molar
ratios for forming ethyl acetate in terms of selectivity, con

Weight of the catalyst. In terms of ranges, the amount of the

?rst metal on the support preferably is from 1 to 25 Wt. %, e. g.,
from 1.2 to 15 Wt. %, or from 1.5 Wt. % to 10 Wt. %. For

purposes of the present speci?cation, unless otherWise indi

cated, Weight percent is based on the total Weight the catalyst

including metal and support.

[0027] The metal(s) in the catalyst may be present in the
form of one or more elemental metals and/or one or more

metal oxides. For purposes of determining the Weight percent

of the metal(s) in the catalyst, the Weight of any oxygen that
is bound to the metal is ignored. In a more preferred aspect,

the ?rst metal is selected from platinum and palladium. When

the ?rst metal comprises platinum, it is preferred that the
catalyst comprises the platinum in an amount greater than 1
Wt. %, but less than 10 Wt. %, e.g., less than 5 Wt. % or less

as described herein.

version and production are less than 07:03 or greater than

0.85 : 0. 1 5. A preferred Re/Pd ratio for producing ethyl acetate
in the presence ofa Re/Pd catalyst is from 02:08 to 04:06.

Again, selectivity to ethyl acetate may be further improved by

incorporating modi?ed supports as described herein.
[0034] In embodiments When the catalyst comprises a third
metal, the third metal may be selected from any of the metals
listed above in connection With the ?rst or second metal, so

long as the third metal is different from the ?rst and second
metals. In preferred aspects, the third metal is selected from

the group consisting of cobalt, palladium, ruthenium, copper,

Zinc, platinum, tin, and rhenium. More preferably, the third
metal is selected from cobalt, palladium, and ruthenium.
When the third metal is present, the catalyst composition

than 3 Wt. %, due to the availability of platinum.

[0028] In addition to the ?rst metal, the catalyst optionally

preferably comprises the third metal in an amount from 0.05

further comprises one or more of a second metal, a third metal

[0035] In addition to the metal, the catalysts of the ?rst

embodiment further comprise a support, optionally a modi

or additional metals. In this context, the numerical terms

and 4 Wt. %, e.g., from 0.1 to 3 Wt. %, or from 0.1 to 2 Wt. %.

?rst, second, third, etc., When used to modify the Word

?ed support. As Will be appreciated by those of ordinary skill

metal, are meant to indicate that the respective metals are

in the art, support materials are selected such that the catalyst
system is suitably active, selective and robust under the pro
cess conditions employed for the formation of ethyl acetate or
a mixture of ethyl acetate and ethanol. Suitable support mate
rials may include, for example, stable metal oxide-based sup

different from one another. If present, the second metal pref

erably is selected from the group consisting of molybdenum,

rhenium, Zirconium, copper, cobalt, tin, and Zinc. More pref
erably, the second metal is selected from the group consisting
of molybdenum, rhenium, tin and cobalt. Even more prefer
ably, the second metal is selected from tin and rhenium.
[0029] Where the catalyst includes tWo or more metals, one
metal may act as a promoter metal and the other metal is the

ports or ceramic-based supports as Well as molecular sieves,

such as Zeolites. Examples of suitable support materials

include Without limitation, iron oxide, silica, alumina, silica/

num may be considered to be the main metal and tin may be

aluminas, titania, Zirconia, magnesium oxide, calcium sili

cate, carbon, graphite, high surface area graphitiZed carbon,
activated carbons, and mixtures thereof. Exemplary preferred

considered the promoter metal. For convenience, the present

speci?cation refers to the ?rst metal as the primary catalyst
and the second metal (and optional metals) as the promoter

aluminas, titania, and Zirconia. The total Weight of the support

in the catalyst, based on the total Weight of the catalyst,

(s). This should not be taken as an indication of the underlying

preferably is from 25 Wt % to 99 Wt %, e.g., from 30 Wt % to

mechanism of the catalytic activity.

[0030] In the ?rst embodiment, When the catalyst includes

98.5 Wt %, or from 35 Wt % to 98 Wt %.

main metal. For instance, With a platinum/tin catalyst, plati

tWo or more metals, e.g., a ?rst metal and a second metal, the

?rst metal optionally is present in the catalyst in an amount

from 1 to 10 Wt. %, e.g., from 1.2 to 5 Wt. %, or from 1.5 to 3
Wt. %. The second metal optionally is present in an amount
from 0.1 and 20 Wt. %, e.g., from 0.1 to 10 Wt. %, or from 0.1
to 5 Wt. %. For catalysts comprising tWo or more metals, the

supports are selected from the group consisting of silica/

[0036] A preferred silica/ alumina support material is

KA-160 (Sud Chemie) silica spheres having a nominal diam
eter of about 5 mm, a density of about 0.562 g/ml, in absorp
tivity of about 0.583 g H2O/ g support, a surface area of about
160 to 175 m2/g, and a pore volume of about 0.68 ml/g.

[0037]

In one embodiment, the support material comprises

a silicaceous support material selected from the group con

tWo or more metals may be alloyed With one another or may

sisting of silica, silica/alumina, a Group IIA silicate such as

comprise a non-alloyed metal solution or mixture.

calcium metasilicate, pyrogenic silica, high purity silica and

Aug. 5, 2010

US 2010/0197959 A1

mixtures thereof. In one embodiment silica may be used as

support modi?er adjusts effects of the acidity of the support

the silicaceous support, and the amount of aluminum, Which

is a common contaminant for silica, may be loW, preferably

material. The acid sites, e.g. Bronsted acid sites, on the sup

under 1 Wt. %, e.g., under 0.5 Wt. % or under 0.3 Wt. %, based

on the total Weight of the support. In this regard, pyrogenic

silica is preferred as it commonly is available in purities
exceeding 99.7 Wt. %. High purity silica, as used throughout
the application, refers to silica in Which acidic contaminants
such as aluminum are present, if at all, at levels of less than 0.3
Wt. %, e.g., less than 0.2 Wt. % or less than 0.1 Wt. %.

[0038] The surface area of the support may vary Widely

depending on the type of support. In some aspects, the surface
area of the support material, e.g., silicaceous material, may be
at least about 50 m2/g, e.g., at least about 100 m2/g, at least
about 150 m2/ g, at least about 200 m2/g or most preferably at
least about 250 m2/ g. In terms of ranges, the support material
preferably has a surface area of from 50 to 600 m2/g, e.g.,
from 100 to 500 m2/g or from 100 to 300 m2/ g. High surface
area silica, as used throughout the application, refers to silica
having a surface area of at least about 250 m2/g. High surface
area silica/alumina, as used throughout the application, refers

port material may be adjusted by the support modi?er, for

example, to favor selectivity to ethyl acetate and mixtures of
ethyl acetate during the hydrogenation of acetic acid. Unless
the context indicates otherWise, the acidity of a surface or the

number of acid sites thereupon may be determined by the

technique described in F. Delannay, Ed., Characterization of
Heterogeneous Catalysts; Chapter III: Measurement of
Acidity of Surfaces, p. 370-404; Marcel Dekker, Inc., NY.
1984, the entirety of Which is incorporated herein by refer
ence.

[0043] In some aspects, the support material may be unde

sirably too acidic for formation of ethyl acetate at high selec
tivity. In this case, the support material may be modi?ed With
a basic support modi?er. Suitable basic support modi?ers
may be selected, for example, from the group consisting of:

(i) alkaline earth oxides, (ii) alkali metal oxides, (iii) alkaline
earth metal metasilicates, (iv) alkali metal metasilicates, (v)
Group IIB metal oxides, (vi) Group IIB metal metasilicates,
(vii) Group IIIB metal oxides, (viii) Group IIIB metal meta

to silica/alumina having a surface area of at least about 150

silicates, and mixtures thereof. In addition to oxides and

m2/g. For purposes of the present speci?cation, surface area

metasilicates, other types of modi?ers including nitrates,

refers to BET nitrogen surface area, meaning the surface area

as determined by ASTM D6556-04, the entirety of Which is

nitrites, acetates, and lactates may be used in embodiments of

the present invention. Preferably, the basic modi?ers have a
loW volatility or are non-volatile. LoW volatility modi?ers
have a rate of loss that is loW enough such that the acidity of
the support modi?er is not reversed during the life of the

incorporated herein by reference.

[0039]

The support material, e. g. silicaceous material, also

preferably has an average pore diameter of from 5 to 100 nm,

e.g., from 5 to 30 nm, from 5 to 25 nm or from about 5 to 10
nm, as determined by mercury intrusion porosimetry, and an
average pore volume of from 0.5 to 2.0 cm3/g, e.g., from 0.7

to 1.5 cm3/g or from about 0.8 to 1.3 cm3/g, as determined by

mercury intrusion porosimetry.

[0040] The morphology of the support material, and hence
of the resulting catalyst composition, may vary Widely. In
some exemplary embodiments, the morphology of the sup
port material and/or of the catalyst composition may be pel

catalyst. For example, the support modi?er may be selected

from the group consisting of oxides and metasilicates of any

of sodium, potassium, magnesium, calcium, scandium,

yttrium, and Zinc, and mixtures of any of the foregoing. A
particularly preferred basic support modi?er is calcium meta

silicate (CaSiO3).
[0044]

In some aspects, the support material is too basic or

is not acidic enough for formation of ethyl acetate at high

selectivity. In this case, the support may be modi?ed With a

lets, extrudates, spheres, spray dried microspheres, rings,

support modi?er that adjusts the support material by increas

pentarings, trilobes, quadrilobes, multi-lobal shapes, or ?akes

although cylindrical pellets are preferred. Preferably, the sup
port material, e.g., silicaceous material, has a morphology

ing the number or availability of acid sites by using a redox

support modi?er or an acidic support modi?er. Suitable redox

and acidic support modi?ers may be selected from the group

that alloWs for a packing density of from 0.1 to 1.0 g/cm3 , e. g.,
from 0.2 to 0.9 g/cm3 or from 0.5 to 0.8 g/cm3. In terms of

consisting of: oxides of Group IVB metals, oxides of Group

VB metals, oxides of Group VIB metals, iron oxides, alumi

siZe, the support material, eg silicaceous material, prefer

num oxides, and mixtures thereof. These support modi?ers

ably has an average particle siZe, meaning the diameter for

spherical particles or equivalent spherical diameter for non

redox support modi?ers include those selected from the

spherical particles, offrom 0.01 to 1.0 cm, e.g., from 0.1 to 0.5

group consisting of W03, M003, Fe2O3, and Cr2O3. Pre

are redox or acid non-volatile support modi?ers. Preferred

cm or from 0.2 to 0.4 cm. Since the one or more metal(s) that

ferred acidic support modi?ers include those selected from

are disposed on or Within the modi?ed support are generally

the group consisting of TiO2, ZrO2, Nb2O5, Ta2O5, and

very small in siZe, they should not substantially impact the

siZe of the overall catalyst particles. Thus, the above particle
siZes generally apply to both the siZe of the modi?ed supports

A1203. Without being bound by theory, it is believed that an

increase in acidity of the support may favor ethyl acetate
formation. HoWever, increasing acidity of the support may

as Well as to the ?nal catalyst particles.

also form ethers and basic modi?ers may be added to coun

[0041] A preferred silica support material is SS61138 High

Surface Area (HSA) Silica Catalyst Carrier from Saint

teract the acidity of the support.

Gobain N or Pro. The Saint-Gobain N or Pro SS61138 silica

contains approximately 95 Wt % high surface area silica; a

surface area of about 250 m2/g; a median pore diameter of
about 12 nm; a total pore volume of about 1.0 cm3/g as

measured by mercury intrusion porosimetry and a packing

density of about 0.352 g/cm3 (22 lb/ft3).

[0042] The supports for the ?rst embodiment may further
comprise a support modi?er. A support modi?er is added to
the support and is not naturally present in the support. A

Catalysts Comprising Nickel or Palladium and Tin or Zinc

[0045]

In a second embodiment of the present invention,

the invention is to a hydrogenation process that employs a

catalyst for making ethyl acetate or optionally a mixture of

ethyl acetate and ethanol, in Which the catalyst comprises a
?rst metal selected from the group consisting of nickel and
palladium, a second metal selected from the group consisting
of tin and Zinc, and a support, optionally a modi?ed support.
In contrast to the above-described ?rst embodiment, in the

Aug. 5, 2010

US 2010/0197959 A1

second embodiment, lower loadings of the ?rst metal may be

employed. For example, the catalyst may comprise the ?rst

metal in an amount from 0.1 to 10 Wt. %, e.g., from 0.1 to 5 Wt.

%, or from 0.1 to 3 Wt. %. The second metal preferably is

present in an amount from 0.1 and 20 Wt. %, e.g., from 0.1 to
10 Wt. %, or from 0.1 to 5 Wt. %. The mole ratio ofthe ?rst
metal to the second metal preferably is from 10:1 to 1 :10, e. g.,
from 4:1 to 1:4, from 2:1 to 1:2, from 1.5:1 to 1:1.5 or from

1.1 :1 to 1:1.1. Optionally, the catalyst of the second embodi

ment may further comprise a third metal as described above in

connection With the ?rst embodiment.

[0046] In the second embodiment, the catalyst includes a
support, optionally a modi?ed support, as discussed above in
connection With the ?rst embodiment. The total Weight of the
support, based on the total Weight of the catalyst, for the
second embodiment preferably is from 25 Wt. % to 99.9 Wt.

preferably is from 10:1 to 1:10, e.g., from 4:1 to 1:4, from 2:1
to 1:2, from 1.5:1 to 1:1.5 orfrom1.1:1to1:1.1.
[0052] Molar ratios other than 1:1 may be preferred for
other catalysts. It has noW surprisingly and unexpectedly

been discovered, for example, that for platinum/tin catalysts,

platinum to tin molar ratios less than 04:06, or greater than
0.6 :0.4 are particularly preferred in order to form ethyl acetate

from acetic acid at high selectivity, conversion and produc

tivity, as shoWn in FIGS. 1A, 1B and 1C. A preferred Pt/ Sn
molar ratio for producing ethyl acetate in the presence of a
Pt/Sn catalyst is from 0.65:0.35 to 0.95:0.05, e.g., from 0.7:
0.3 to 0.95:0.05. Selectivity to ethyl acetate may be further

improved by incorporating modi?ed supports as described

throughout the present speci?cation.

[0053] With rhenium/palladium catalysts, as shoWn in
FIGS. 2A, 2B and 2C, preferred rhenium to palladium molar
ratios for forming ethyl acetate in terms of selectivity, con

%, e.g., from 30 Wt. % to 97 Wt. %, or from 35 Wt. % to 95 Wt.

%.

version and production are less than 07:03 or greater than

Catalyst on Acidic or Redox Modi?ed Support

acetate in the presence of a Re/Pd catalyst is from 02:08 to

[0047]

04:06. Again, selectivity to ethyl acetate may be further

improved by incorporating modi?ed supports as described

0.85:0.15. A preferred Re/Pd molar ratio for producing ethyl

In a third embodiment of the invention, the hydro

genation process uses a catalyst that comprises a ?rst metal

and optionally one or more of a second metal, a third metal or

additional metals, on a support that has been modi?ed With a

redox support modi?er or an acidic support modi?er. The

total Weight of all metals present in the catalyst preferably is

from 0.1 to 25 Wt. %, e.g., from 0.1 to 15 Wt. %, or from 0.1
1 to 10 Wt. %.

throughout the present speci?cation.

[0054] In embodiments When the catalyst comprises a third
metal, the third metal may be selected from any of the metals
listed above in connection With the ?rst or second metal, so
long as the third metal is different from the ?rst and second
metals. In preferred aspects, the third metal is selected from

The ?rst metal may be a Group IB, IIB, IIIB, IVB,

the group consisting of cobalt, palladium, ruthenium, copper,

Zinc, platinum, tin, and rhenium. More preferably, the third

VB, VIIB, VIIB, or VIII transitional metal, a lanthanide

metal, an actinide metal or a metal from any of Groups IIIA,
IVA, VA, orVIA. In a preferred embodiment, the ?rst metal is

metal is selected from cobalt, palladium, and ruthenium.

When present, the total Weight of the third metal preferably is

selected the group consisting of copper, iron, cobalt, nickel,

to 2 Wt. %.

[0048]

ruthenium, rhodium, palladium, osmium, iridium, platinum,

titanium, Zinc, chromium, rhenium, molybdenum, and tung
sten. Preferably, the ?rst metal is selected from the group

consisting of platinum, palladium, cobalt, nickel, and ruthe

nium. More preferably, the ?rst metal is selected from plati
num and palladium. When the ?rst metal comprises platinum,
it is preferred that the catalyst comprises the platinum in an
amount less than 5 Wt %, e.g. less than 3 Wt % or less than 1

Wt %, due to the limited availability of platinum.

[0049] The catalyst optionally further comprises a second
metal selected from the group consisting of copper, molyb

denum, tin, chromium, iron, cobalt, vanadium, tungsten, pal

ladium, platinum, lanthanum, cerium, manganese, ruthe
nium, rhenium, gold, and nickel. More preferably, the second
metal is selected from the group consisting of copper, tin,
cobalt, rhenium, and nickel. More preferably, the second
metal is selected from tin and rhenium.
[0050]

If the catalyst includes tWo or more metals, e.g., a

?rst metal and a second metal, the ?rst metal optionally is

present in the catalyst in an amount from 0.1 to 10 Wt. %, eg

from 0.05 and 4 Wt. %, e.g., from 0.1 to 3 Wt. %, or from 0.1

[0055] In one embodiment, the catalyst comprises a ?rst

metal and no additional metals (no second metal, etc.). In this
embodiment, the ?rst metal preferably is present in an amount
from 0.1 to 10 Wt. %. In another embodiment, the catalyst
comprises a combination of tWo or more metals on a support.

Speci?c preferred metal compositions for various catalysts of

this embodiment of the invention are provided beloW in Table
1. Where the catalyst comprises a ?rst metal and a second
metal, the ?rst metal preferably is present in an amount from
0.1 to 5 Wt. % and the second metal preferably is present in an
amount from 0.1 to 5 Wt. %. Where the catalyst comprises a
?rst metal, a second metal and a third metal, the ?rst metal
preferably is present in an amount from 0.1 to 5 Wt. %, the
second metal preferably is present in an amount from 0.1 to 5
Wt. %, and the third metal preferably is present in an amount
from 0.1 to 2 Wt. %. Where the ?rst metal is platinum, the ?rst
metal preferably is present in an amount from 0.1 to 3 Wt. %,
the second metal is present in an amount from 0.1 to 5 Wt. %,
and the third metal, if present, preferably is present in an
amount from 0.1 to 2 Wt. %.

from 0.1 to 5 Wt. %, or from 0.1 to 3 Wt. %. The second metal

preferably is present in an amount from 0.1 and 20 Wt. %, e.g.,

from 0.1 to 10 Wt. %, or from 0.1 to 5 Wt. %. For catalysts

TABLE 1

comprising tWo or more metals, the tWo or more metals may

EXEMPLARY METAL COMBINATIONS FOR CATALYSTS

be alloyed With one another or may comprise a non-alloyed

First Metal

Second Metal

Cu

Ag

Cu
Cu
Cu

Cr
V
W

metal solution or mixture.

[0051] As stated above in the ?rst embodiment, in the third

embodiment the preferred metal ratios may vary someWhat
depending on the metals used in the catalyst. In some embodi
ments, the mole ratio of the ?rst metal to the second metal

Third Metal

Aug. 5, 2010

US 2010/0197959 A1

from the group consisting of TiO2, ZrO2, Nb2O5, Ta2O5, and

A1203. Preferably, the support comprises a support modi?er

TABLE l-continued
EXEMPLARY METAL COMBINATIONS FOR CATALYSTS

that is an acidic or redox modi?er having a loW volatility or is

non-volatile. LoW volatility modi?ers have a rate of loss that

First Metal

Second Metal

is loW enough such that the acidity of the support modi?er is

not reversed during the life of the catalyst. As indicated above,

Cu
Ni
Ni
Ni
Ni
Ni
Ni
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pd
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Pt
Rh
Rh
Ru
Ru
Ru
Ru
Ru
Ru
Ru
Ru

Zn
Au
Re
V
W
Zn
Sn
Zn
Co
Cr
Cu
Fe
La
Mo
Ni
Re
Sn
V
W
Co
Cr
Cu
Fe
Mo
Sn
Sn
Sn
Sn
Sn
Cu
N1
Co
Cr
Cu
Fe
La
Mo
Ni
Sn

Third Metal

the support modi?er is added to the support and is not natu

rally present in the support.

[0059] The total Weight of the modi?ed support, including
the support material and the support modi?er, based on the
total Weight of the catalyst, preferably is from 25 Wt. % to 99.9
Wt. %, e.g., from 30 Wt. % to 97 Wt. %, or from 35 Wt % to 95

Wt. %. The support modi?er preferably is provided in an

amount su?icient to increase the number of active Bronsted

acid sites or availability of those acid sites. In preferred

embodiments, the support modi?er is present in an amount
from 0.1 Wt. % to 50 Wt. %, e.g., from 0.2 Wt. % to 25 Wt. %,
from 0.5 Wt. % to 15 Wt. %, or from 1 Wt. % to 8 Wt. %, based

on the total Weight of the catalyst. In preferred embodiments,

the support material is present in an amount from 25 Wt. % to
99 Wt. %, e.g., from 30 Wt. % to 97 Wt. % or from 35 Wt. % to
95 Wt. %.

[0060] If desired, the acidic or redox support modi?ers

described herein in connection With the third embodiment of
the invention may also be used to modify the supports of the
above-described ?rst embodiment or the second embodi
Co
Re
Ru
Pd

[0056] Depending primarily on hoW the catalyst is manu

factured, the metals of the catalysts of the present invention
may be dispersed throughout the support, coated on the outer
surface of the support (egg shell) or decorated on the surface
of the support.
[0057]

In addition to one or more metals, the catalysts of the

third embodiment of the present invention further comprise a

modi?ed support, meaning a support that includes a support
material and a support modi?er. In particular, the use of acidic
or redox modi?ed supports surprisingly and unexpectedly has
noW been demonstrated to favor formation of ethyl acetate

over other hydrogenation products.

[0058] Examples of suitable support materials include
those stated above in connection With the ?rst embodiment

and Without limitation include iron oxide, silica, alumina,

silica/aluminas, titania, Zirconia, magnesium oxide, calcium

silicate, carbon, graphite, high surface area graphitiZed car
bon, activated carbons, and mixtures thereof. The support
further comprises a support modi?er that, for example, may
be selected from the group consisting of: oxides of Group
IVB metals, oxides of Group VB metals, oxides of Group VIB
metals, iron oxides, aluminum oxides, and mixtures thereof.
These support modi?ers are redox or acidic support modi?
ers. Preferred redox support modi?ers include those selected

ment.

[0061] Catalysts of the present invention are particulate

catalysts in the sense that, rather than being impregnated in a
Wash coat onto a monolithic carrier similar to automotive

catalysts and diesel soot trap devices, the catalysts of the

invention preferably are formed into particles, sometimes
also referred to as beads or pellets, having any of a variety of

shapes and the catalytic metals are provided to the reaction

Zone by placing a large number of these shaped catalysts in
the reactor. Commonly encountered shapes include extru
dates of arbitrary cross-section taking the form of a general
iZed cylinder in the sense that the generators de?ning the
surface of the extrudate are parallel lines. As indicated above,

any convenient particle shape including pellets, extrudates,

spheres, spray dried microspheres, rings, pentarings, trilobes,
quadrilobes and multi-lobal shapes may be used, although
cylindrical pellets are preferred. Typically, the shapes are
chosen empirically based upon perceived ability to contact

the vapor phase With the catalytic agents effectively.

[0062] One advantage of catalysts of the present invention,
in all of the above embodiments, is the stability or activity of

the catalyst for producing ethyl acetate and mixtures of ethyl

acetate and ethanol. Accordingly, it can be appreciated that

the catalysts of the present invention are fully capable of

being used in commercial scale industrial applications for the

hydrogenation of acetic acid, particularly in the production of

ethyl acetate. In particular, it is possible to achieve such a

degree of stability such that catalyst activity Will have rate of

productivity decline that is less than 6% per 100 hours of
catalyst usage, e.g., less than 3% per 100 hours or less than
1.5% per 100 hours. Preferably, the rate of productivity
decline is determined once the catalyst has achieved steady
state conditions.

Processes for Making the Catalysts

[0063]

The catalyst compositions of the ?rst, second and

from the group consisting of W03, M003, Fe2O3, and Cr2O3.

third embodiments of the present invention preferably are

Preferred acidic support modi?ers include those selected

formed through metal impregnation of the support and/or

Aug. 5, 2010

US 2010/0197959 A1

modi?ed supports, although other processes such as chemical

vapor deposition may also be employed. Before the metals are
impregnated, it typically is desired to form the modi?ed sup

port, if necessary, through a step of impregnating the support

material With the support modi?er. In one aspect, the support
modi?er, e.g., WO3 or TiO2, or a precursor to the support
modi?er is added to the support material in an aqueous sus

pension. For example, an aqueous suspension of the support

modi?er may be formed by adding the solid support modi?er
to deioniZed Water, folloWed by the addition of colloidal
support material thereto. The resulting mixture may be stirred
and added to additional support material using, for example,
incipient Wetness techniques in Which the support modi?er is
added to a support material having the same pore volume as

the volume of the support modi?er solution. Capillary action

then draWs the support modi?er into the pores in the support
material. The modi?ed support can then be formed by drying
and calcining to drive off Water and any volatile components
Within the support modi?er solution and depositing the sup
port modi?er on the support material. Drying may occur, for
example, at a temperature offrom 50 C. to 300 C., e.g., from
100 C. to 200 C. or about 120 C., optionally for a period of
from 1 to 24 hours, e.g., from 3 to 15 hours or from 6 to 12

hours. Once formed, the modi?ed supports may be shaped

into particles having the desired siZe distribution, e.g., to form
particles having an average particle siZe in the range of from
0.2 to 0.4 cm. The supports may be extruded, pelletiZed,
tabletiZed, pressed, crushed or sieved to the desired siZe dis
tribution. Any of the knoWn methods to shape the support
materials into desired siZe distribution can be employed. Cal
cining of the shaped modi?ed support may occur, for
example, at a temperature of from 250 C. to 800 C., e.g.,
from 300 to 700 C. or about 500 C., optionally for a period
of from 1 to 12 hours, e.g., from 2 to 10 hours, from 4 to 8
hours or about 6 hours.

[0064]

In a preferred method of preparing the catalyst, the

initial phase of use of the catalyst, such compounds are con

verted into a catalytically active form of the metal or a cata

lytically active oxide thereof.

[0066] Impregnation of the ?rst and second metals (and
optional additional metals) into the support or modi?ed sup
port may occur simultaneously (co-impregnation) or sequen

tially. In simultaneous impregnation, the ?rst and second

metal precursors (and optionally additional metal precursors)
are mixed together and added to the support or modi?ed

support together, folloWed by drying and calcination to form

the ?nal catalyst composition. With simultaneous impregna
tion, it may be desired to employ a dispersion agent, surfac
tant, or solubiliZing agent, e.g., ammonium oxalate, to facili
tate the dispersing or solubiliZing of the ?rst and second metal
precursors in the event the either or both precursors are

incompatible With the desired solvent, e.g., Water.

[0067] In sequential impregnation, the ?rst metal precursor
is ?rst added to the support or modi?ed support folloWed by

drying and calcining, and the resulting material is then

impregnated With the second metal precursor folloWed by an

additional drying and calcining step to form the ?nal catalyst

composition. Additional metal precursors (e.g., a third metal
precursor) may be added either With the ?rst and/or second
metal precursor or a separate third impregnation step, fol
loWed by drying and calcination. Of course, combinations of

sequential and simultaneous impregnation may be employed

if desired.

[0068] Suitable metal precursors include, for example,

metal halides, amine solubiliZed metal hydroxides, metal
nitrates or metal oxalates of the desired metal(s). For

example, suitable compounds for platinum precursors and

palladium precursors include chloroplatinic acid, ammonium

chloroplatinate, amine solubiliZed platinum hydroxide, plati

num nitrate, platinum tetra ammonium nitrate, platinum chlo

ride, platinum oxalate, palladium nitrate, palladium tetra

ammonium nitrate, palladium chloride, palladium oxalate,
sodium palladium chloride, and sodium platinum chloride.
Generally, both from the point of vieW of economics and

metals are impregnated onto the support or modi?ed support.

environmental aspects, aqueous solutions of soluble com

A precursor of the ?rst metal (?rst metal precursor) preferably

pounds of platinum are preferred. In one embodiment, the

is used in the metal impregnation step, such as a Water soluble

?rst metal precursor is not a metal halide and is substantially

free of metal halides.
[0069] In one aspect, the promoter metal or metal precur
sor is ?rst added to the modi?ed support, folloWed by the
main or primary metal or metal precursor. Of course, the
reverse order of addition is also possible. Exemplary precur
sors for promoter metals include metal halides, amine solu
biliZed metal hydroxides, metal nitrates or metal oxalates. As

compound or Water dispersible compound/complex that

includes the ?rst metal of interest. Depending on the metal
precursor employed, the use of a solvent, such as Water,

glacial acetic acid or an organic solvent, may be preferred.

The second metal also preferably is impregnated into the
support or modi?ed support from a second metal precursor. If
desired, a third metal or third metal precursor may also be

impregnated into the support or modi?ed support.

[0065] Impregnation occurs by adding, optionally drop

Wise, either or both the ?rst metal precursor and/ or the second

metal precursor and/or additional metal precursors, prefer

ably in suspension or solution, to the dry support or modi?ed
support. The resulting mixture may then be heated, e.g.,
optionally under vacuum, in order to remove the solvent.

Additional drying and calcining may then be performed,

optionally With ramped heating to form the ?nal catalyst
composition. Upon heating and/or the application of vacuum,
the metal(s) of the metal precursor(s) preferably decompose
into their elemental (or oxide) form. In some cases, the

completion of removal of the liquid carrier, e.g., Water, may

not take place until the catalyst is placed into use and calcined,
e.g., subjected to the high temperatures encountered during
operation. During the calcination step, or at least during the

indicated above, in the sequential embodiment, each impreg

nation step preferably is folloWed by drying and calcination.
In the case of promoted bimetallic catalysts as described

above, a sequential impregnation may be used, starting With

the addition of the promoter metal folloWed by a second

impregnation step involving co-impregnation of the tWo prin

cipal metals, e.g., Pt and Sn.

Hydrogenation of Acetic Acid

[0070]

The process of hydrogenating acetic acid to form

ethyl acetate or a mixture of ethyl acetate and ethanol accord

ing to one embodiment of the invention may be conducted in
a variety of con?gurations using a ?xed bed reactor or a
?uidized bed reactor as one of skill in the art Will readily

appreciate using catalysts of the ?rst, second or third embodi

ments. In many embodiments of the present invention, an

Aug. 5, 2010

US 2010/0197959 A1

adiabatic reactor can be used; that is, there is little or no

need for internal plumbing through the reaction Zone to add or
remove heat. Alternatively, a shell and tube reactor provided
With a heat transfer medium can be used. In many cases, the
reaction Zone may be housed in a single vessel or in a series of

vessels With heat exchangers therebetWeen. It is considered

signi?cant that acetic acid reduction processes using the cata
lysts of the present invention may be carried out in adiabatic
reactors as this reactor con?guration is typically far less capi
tal intensive than tube and shell con?gurations.
[0071] Typically, the catalyst is employed in a ?xed 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 ?uid or ebullient
bed reactors, can be employed, if desired. In some instances,

[0077]

In particular, the catalysts and processes of the

present invention may achieve favorable conversion of acetic

acid and favorable selectivity and productivity to ethyl acetate

or mixtures of ethyl acetate and ethanol. For purposes of the
present invention, the term conversion refers to the amount of
acetic acid in the feed that is convert to a compound other than
acetic acid. Conversion is expressed as a mole percentage
based on acetic acid in the feed. The conversion of acetic acid

(AcOH) is calculated from gas chromatography (GC) data

using the folloWing equation:

mmol AcOH (feed stream)

mmol AcOH (GC)

the hydrogenation catalysts may be used in conjunction With

an inert material to regulate the pressure drop of the reactant
stream through the catalyst bed and the contact time of the

reactant compounds With the catalyst particles.

[0072] The hydrogenation reaction may be carried out in
either the liquid phase or vapor phase. Preferably the reaction
is carried out in the vapor phase under the folloWing condi
tions. The reaction temperature may the range from of 125 C.
to 350 C., e.g., from 200 C. to 325 C., from 225 C. to
about 300 C., or from 250 C. to about 300 C. The pressure
may range from 10 KPa to 3000 KPa (about 0.1 to 30 atmo
spheres), e.g., from 50 KPa to 2300 KPa, or from 100 KPa to
1500 KPa. The reactants may be fed to the reactor at a gas

hourly space velocities (GHSV) of greater than 500 hr_l, e.g.,

greater than 1000 hr_l, greater than 2500 hr1 and even
greater than 5000 M. In terms of ranges the GHSV may
range from 50 hr1 to 50,000 hr_l, e.g., from 500 hr1 to
30,000 M, from 1000 hr-l to 10,000 M, or from 1000 hr-l
to 6500 M.
[0073] In another aspect of the process of this invention, the
hydrogenation is carried out at a pressure just suf?cient to
overcome the pressure drop across the catalytic bed at a
suitable GHSV, although there is no bar to the use of higher

[0078] For purposes of the present invention, the conver

sion may be at least 10%, e.g., at least 20%, at least 40%, at
least 50%, at least 60%, or at least 70% or at least 80%.

Although catalysts that have high conversions are desirable,

such as at least 80% or at least 90%, a loW conversion may be

acceptable at high selectivity for ethyl acetate or mixtures of

ethyl acetate and ethanol. It is, of course, Well understood that
in many cases, it is possible to compensate for conversion by
appropriate recycle streams or use of larger reactors, but it is
more dif?cult to compensate for poor selectivity.
[0079] Selectivity is expressed as a mole percent based
on converted acetic acid. It should be understood that each

compound converted from acetic acid has an independent

selectivity and that selectivity is independent from conver
sion. For example, if 50 mole % of the converted acetic acid
is converted to ethyl acetate, We refer to the ethyl acetate

selectivity as 50%. Selectivity to ethyl acetate (EtOAc) and

mixtures of EtOAc and ethanol (EtOH) is calculated from gas

chromatography (GC) data using the folloWing equation:

pressures, it being understood that considerable pressure drop

through the reactor bed may be experienced at high space
velocities, e.g., on the order of 5000 hrl or 6,500 hr_l.
[0074] Although the reaction consumes tWo moles of
hydrogen for every tWo moles of acetic acid to produce one
mole of ethyl acetate, the actual molar ratio of hydrogen to
acetic acid in the feed stream may vary from about 100:1 to
1:100, e.g., from 50:1 to 1:50, from 20:1 to 1:2, or from 12:1
to 1: 1. Most preferably, the molar ratio of hydrogen to acetic
acid is greater than 4: 1, e.g., greater than 5:1 or greater than
10:1.
[0075] Contact or residence time can also vary Widely,
depending upon such variables as amount of acetic acid,

EtOAc s61. (%) = 100 *

mmol EtOAc (GC)

Total mmol C (GC)
f _

mmol AcOH (feed stream)

[0080] Wherein Total mmol C (GC) refers to total mmols

of carbon from all of the products analyZed by gas chromato

graph.
[0081]

For purposes of the present invention, the selectivity

to ethoxylates of the catalyst is at least 60%, e.g., at least 70%,

or at least 80%. As used herein, ethoxylates refers con
verted compounds that have at least tWo carbon atoms, such

catalyst, reactor, temperature and pressure. Typical contact

as ethanol, acetaldehyde, ethyl acetate, etc., but excludes

ethane. Preferably, the selectivity to ethyl acetate is at least

times range from a fraction of a second to more than several

40%, e.g., at least 50% or at least 60%.

hours When a catalyst system other than a ?xed bed is used,

With preferred contact times, at least for vapor phase reac
tions, from 0.1 to 100 seconds, e.g., from 0.3 to 80 seconds or
from 0.4 to 30 seconds.
[0076] The acetic acid may be vaporiZed at the reaction
temperature, and then the vaporiZed acetic acid can be fed
along With hydrogen in undiluted state or diluted With a
relatively inert carrier gas, such as nitrogen, argon, helium,
carbon dioxide and the like. For reactions run in the vapor

phase, the temperature should be controlled in the system

such that it does not fall beloW the deW point of acetic acid.

[0082]

Preferably, the selectivity to mixtures of ethyl

acetate and ethanol is at least 50%, e.g., at least 60% or at least

70%. In one embodiment of the present invention, it is pre

ferred that ethyl acetate comprises at a major component of
the product mixture, e.g., at least 50 Wt %, eg from at least 55
Wt % or from at least 60 Wt %. In addition to ethyl acetate,
ethanol also may be formed, for example, at selectivities of at
least 20%, eg least 30% or at least 40%. In another embodi
ment of the present invention, the process forms ethanol as a
major component, e.g., in an amount greater than 50 Wt %,
e.g., at least 55 Wt % or at least 60 Wt %. In this aspect, ethyl

Aug. 5, 2010

US 2010/0197959 A1

acetate may be also be formed, for example, at a selectivities

ofat least 20%, eg at least 30% or at least 40%. It should be

understood that in such mixtures, if desired, either the ethyl

acetate may be further reacted to form more ethanol, or the
ethanol may be further reacted to form more ethyl acetate.

[0083] In embodiments of the present invention, it is also

desirable to have loW selectivity to undesirable products, such
as methane, ethane, and carbon dioxide. The selectivity to

these undesirable products preferably should be less than 4%,

less than 4 Wt. %. In terms of ranges other components may be

present in an amount from 0.1 to 10 Wt. %, e.g., from 0.1 to 6
Wt. %, or from 0.1 to 4 Wt. %.

[0087] In a preferred embodiment, depending on the spe

ci?c catalyst and process conditions employed, the crude
ethyl acetate product may have any of the compositions indi
cated beloW in Table 2. Crude mixtures of ethyl acetate and
ethanol may have any of the compositions indicated beloW in
Table 3.

e.g., less than 2% or less than 1%. Preferably, no detectable

amounts of these undesirable products are formed during

hydrogenation. In several embodiments of the present inven

TABLE 2

tion, formation of alkanes is loW, usually under 2%, often

CRUDE ETHYL ACETATE

PRODUCT COMPOSITIONS

under 1%, and in many cases under 0.5% of the acetic acid

passed over the catalyst is converted to alkanes, Which have

little value other than as fuel.

[0084]

Productivity refers to the grams of a speci?ed prod

uct, e.g., ethyl acetate, formed during the hydrogenation

based on the kilogram of catalyst used per hour. In one
embodiment, a productivity of at least 200 grams of ethyl
acetate per kilogram catalyst per hour, e.g., at least 400 grams
of ethyl acetate or least 600 grams of ethyl acetate, is pre
ferred. In another embodiment, a productivity of at least 200
grams of a mixture of ethyl acetate and ethanol per kilogram
catalyst per hour, e.g., at least 400 grams of a mixture of ethyl
acetate and ethanol or least 600 grams of ethyl a mixture of

ethyl acetate and ethanol, is preferred. In terms of ranges, the

productivity preferably to ethyl acetate is from 200 to 3,000
grams of ethyl acetate per kilogram catalyst per hour, e.g.,
from 400 to 2,500 or from 600 to 2,000.

[0085]

Some catalysts of the present invention may achieve

a conversion of acetic acid of at least 10%, a selectivity to

ethyl acetate of at least 60%, and a productivity of at least 200

Component
Ethyl Acetate
Acetic Acid
Water
Other

Conc.

Conc.

Conc.

(Wt. %)

(Wt. %)

(Wt. %)

5-70
5-75

15-50
10-60

5-50
<10

10-45
<6

20-35
20-50
15-35
<4

TABLE 3
CRUDE ETHYL ACETATE/ETHANOL MIXTURE
PRODUCT COMPOSITIONS
Conc.

Conc.

Conc.

(Wt. %)

(Wt. %)

(Wt. %)

Ethyl Acetate

5-70

15-50

20-35

Ethanol
Acetic Acid
Water
Other

5-70
5-75
5-50
<10

15-50
10-60
10-45
<6

20-35
20-50
15-35
<4

Component

g of ethyl acetate per kg of catalyst per hour. A subset of

catalysts of the invention may achieve a conversion of acetic
acid of at least 50%, a selectivity to ethyl acetate of at least

70%, a selectivity to undesirable compounds of less than 4%,

and a productivity of at least 600 g of ethyl acetate per kg of
catalyst per hour.

[0088]

The raW materials used in connection With the pro

cess of this invention may be derived 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. As

Crude Ethyl Acetate Product

petroleum and natural gas prices ?uctuate becoming either

[0086]

more or less expensive, methods for producing acetic acid and

intermediates such as methanol and carbon monoxide from
alternate carbon sources have draWn increasing interest. In

In another embodiment, the invention is to a crude

ethyl acetate product formed by any of the processes of the

present invention. The crude ethyl acetate product produced
by the hydrogenation process of the present invention, before
any subsequent processing, such as puri?cation and separa

particular, When petroleum is relatively expensive compared

to natural gas, it may become advantageous to produce acetic

tion, typically Will comprise primarily unreacted acetic acid,

acid from synthesis gas (syn gas) that is derived from any

ethyl acetate and optionally ethanol. In some exemplary

embodiments, the crude product comprises ethyl acetate in an

available carbon source. US. Pat. No. 6,232,352 to Vidalin,

the disclosure of Which is incorporated herein by reference,

amount from 5 Wt % to 70 Wt. %, e.g., from 15 Wt. % to 50 Wt.

%, or from 20 Wt. % to 35 Wt. %, based on the total Weight of

for example, teaches a method of retro?tting a methanol plant

for the manufacture of acetic acid. By retro?tting a methanol

the crude product. The crude product may comprise ethanol

plant, the large capital costs associated With CO generation

in an amount from 5 Wt. % to 70 Wt. %, e.g., from 15 Wt % to

50 Wt. %, or from 20 Wt. % to 35 Wt. %, based on the total

for a neW acetic acid plant are signi?cantly reduced or largely

eliminated. All or part of the syn gas is diverted from the

Weight of the crude product. The crude product typically Will

methanol synthesis loop and supplied to a separator unit to

further comprise unreacted acetic acid, depending on conver

sion, for example, in an amount from 5 to 75 Wt. %, e.g., from

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 may be utiliZed in connection
With this invention.

10 to 60 Wt. % or from 20 to 50 Wt. %. Since Water is formed

in the reaction process, Water Will also be present in the crude

product, for example, in amounts ranging from 5 to 50 Wt. %,

e.g., from 10 to 45 Wt. % or from 15 to 35 Wt. %. Other

components, such as, for example, aldehydes, ketones,

alkanes, and carbon dioxide, if detectable, collectively may
be present in amounts less than 10 Wt. %, e.g., less than 6 or

[0089] US. Pat. 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 mate
rials such as oil, coal, natural gas and biomass materials. The
process includes hydrogasi?cation of solid and/ or liquid car

Aug. 5, 2010

US 2010/0197959 A1

bonaceous materials to obtain a process gas Which is steam

244 and ZeoliteY in Us. Pat. No. 3,130,007, the entireties of

pyroliZed With additional natural gas to form synthesis gas.

The syn gas is converted to methanol Which may be carbony
lated to acetic acid. The method likewise produces hydrogen

Which are hereby incorporated by reference. A Zeolite catalyst

may be used to concurrently dehydrate ethanol to ethylene
and decompose ethyl acetate to ethylene in a highly ef?cient

Which may be used in connection With this invention as noted

process of the invention.

[0095] In embodiments Where a mixture of ethyl acetate
and ethanol is formed, it may be desired to further react the
mixture in order to enrich the mixture in either the ethyl
acetate or ethanol. For example, if desired, the ethanol con

above. See also, U.S. Pat. No. 5,821,1 11 to Grady et al., Which
discloses a process for converting Waste biomass through
gasi?cation into synthesis gas as Well as U.S. Pat. No. 6,685,
754 to Kindig et al., the disclosures of Which are incorporated

herein by reference.
[0090] Alternatively, acetic acid in vapor form may be
taken directly as crude product from the ?ash vessel of a
methanol carbonylation unit of the class described in Us.
Pat. No. 6,657,078 to Scates et al., the entirety of Which is

incorporated herein by reference. The crude vapor product,

for example, may be fed directly to the ethanol synthesis

centration in the mixture may be increased through hydroly

sis of the ethyl acetate in the presence of an acid catalyst to
make additional ethanol and acetic acid. The acetic acid then

may be recycled back in the hydrogenation process.

[0096] The folloWing examples describe the procedures

used for the preparation of various catalysts employed in the
process of this invention.

reaction Zones of the present invention Without the need for

condensing the acetic acid and light ends or removing Water,

saving overall processing costs.
[0091] Ethyl acetate obtained by the present invention, may
be used in its oWn right, polymerized, or converted to ethylene
through a cracking process. The cracking of ethyl acetate to

ethylene is shoWn below.

0

i /CH2\

CH3

EXAMPLES

Catalyst Preparations (General)

[0097]

The catalyst supports Were dried at 1200 C. over

night under circulating air prior to use. All commercial sup

ports (i.e., SiO2, TiO2) Were used as a 14/30 mesh, or in its
original shape (1/16 inch or 1/s inch pellets) unless mentioned
otherwise. PoWdered materials Were pelletiZed, crushed and
sieved after the metals had been added. The individual cata

_>

CH2=CH2

lyst preparations of the invention, as Well as comparative

CH3

examples, are described in detail beloW.

0

anion
[0092]

The cracking may be a catalyZed reaction utiliZing a

cracking catalyst. Suitable cracking catalysts include sulfonic

acid resins such as per?uorosulfonic acid resins disclosed in
Us. Pat. No. 4,399,305, noted above, the disclosure ofWhich
is incorporated herein by reference. Zeolites are also suitable
as cracking catalysts as noted in Us. Pat. No. 4,620,050, the
disclosure of Which is also incorporated herein by reference.

[0093]

Any ethanol in the mixtures of the present invention,

Example 1

SiO2iCaSiO3(5)-Pt(3)-Sn(1.8)
[0098] The catalyst Was prepared by ?rst adding CaSiO3
(Aldrich) to the SiO2 catalyst support, folloWed by the addi
tion of Pt/ Sn. First, an aqueous suspension of CaSiO3 200
mesh) Was prepared by adding 0.52 g of the solid to 13 ml of
deioniZed H2O, folloWed by the addition of 1.0 ml of colloidal

SiO2 (15 Wt % solution, NALCO). The suspension Was stirred

for 2 h at room temperature and then added to 10.0 g of SiO2

catalyst support (14/30 mesh) using incipient Wetness tech

verted to ethylene Which is an important commodity feed

nique. After standing for 2 hours, the material Was evaporated

to dryness, folloWed by drying at 1200 C. overnight under

stock as it can be converted to polyethylene, vinyl acetate

and/ or ethyl acetate or any of a Wide variety of other chemical

circulating air and calcination at 5000 C. for 6 hours.All of the

SiO24CaSiO3 material Was then used for Pt/ Sn metal

products. For example, ethylene can also be converted to

numerous polymer and monomer products. The dehydration
of ethanol to ethylene is shoWn beloW.

impregnation.

may be used in its oWn right as a fuel or subsequently con

[0099] The catalysts Were prepared by ?rst adding

Sn(OAc)2 (tin acetate, Sn(OAc)2 from Aldrich) (0.4104 g,
1.73 mmol) to a vial containing 6.75 ml of 1:1 diluted glacial
acetic acid (Fisher). The mixture Was stirred for 15 min at

room temperature, and then, 0.6711 g (1.73 mmol) of solid

[0094]

Any of knoWn dehydration catalysts can be

Pt(NH3)4(NO3)2 (Aldrich) Were added. The mixture Was

stirred for another 15 min at room temperature, and then
added drop Wise to 5.0 g of SiO2iCaSiO3 support, in a 100

employed in to dehydrate ethanol, such as those described in

ml round-bottomed ?ask. The metal solution Was stirred con

copending applications U.S. application Ser. No. 12/221,137

tinuously until all of the Pt/ Sn mixture had been added to the

and Us. application Ser. No. 12/221,138, the entire contents

and disclosures of Which are hereby incorporated by refer
ence. A Zeolite catalyst, for example, may be employed as the
dehydration catalyst. While any Zeolite having a pore diam

addition of metal solution. After completing the addition of

the metal solution, the ?ask containing the impregnated cata

eter of at least about 0.6 nm can be used, preferred Zeolites

include dehydration catalysts selected from the group con

sisting of mordenites, ZSM-5, a Zeolite X and a Zeolite Y.
Zeolite X is described, for example, in Us. Pat. No. 2,882,

SiO24CaSiO3 support While rotating the ?ask after every

lyst Was left standing at room temperature for tWo hours. The
?ask Was then attached to a rotor evaporator (bath tempera

ture 800 C.), and evacuated until dried While sloWly rotating
the ?ask. The material Was then dried further overnight at

1200 C., and then calcined using the folloWing temperature

Aug. 5, 2010

US 2010/0197959 A1

program: 25>160 C./ramp 5.0 deg/min; hold for 2.0 hours;

160>500 C./ramp 2.0 deg/min; hold for 4 hours. Yield:

Was prepared then by impregnating the SiO24CaSiO3(5)

Example 2

(1/16 inch extrudates) With an aqueous solution containing

NH4ReO4 and Pd(NO3)2. The metal solutions Were prepared
by ?rst adding NH4ReO4 (0.7237 g, 2.70 mmol) to a vial
containing 12.0 ml of deioniZed H2O. The mixture Was stirred

KAl60-CaSiO3(8)-Pt(3)-Sn(1.8)

for 15 min at room temperature, and 0.1756 g (0.76 mmol) of

11.21 g of dark grey material.

[0100] The material Was prepared by ?rst adding CaSiO3 to

the KA160 catalyst support (SiO2-(0.05)Al2O3, Sud Chemie,
14/30 mesh), folloWed by the addition of Pt/ Sn. First, an
aqueous suspension of CaSiO3(200 mesh) Was prepared by
adding 0.42 g of the solid to 3.85 ml of deioniZed H2O,
folloWed by the addition of 0.8 ml of colloidal SiO2 (15 Wt %

solid Pd(NO3)2 Was then added. The mixture Was stirred for
another 15 min at room temperature, and then added drop

Wise to 10.0 g ofdry SiO2-(0.05)CaSiO3 catalyst support in a

100 ml round-bottomed ?ask. After completing the addition
of the metal solution, the ?ask containing the impregnated
catalyst Was left standing at room temperature for tWo hours.

All other manipulations (drying, calcination) Were carried out

solution, NALCO). The suspension Was stirred for 2 h at room

temperature and then added to 5.0 g of KA160 catalyst sup

as described in Example 1.Yield: 10.9 g of broWn material.

port (14/30 mesh) using incipient Wetness technique. After

Example 6

standing for 2 hours, the material Was evaporated to dryness,

folloWed by drying at 120 C. overnight under circulating air
and calcinations at 500 C. for 6 hours. All of the KA160

CaSiO3 material Was then used for Pt/ Sn metal impregnation.

[0101] The catalysts Were prepared by ?rst adding

Sn(OAc)2 (tin acetate, Sn(OAc)2 from Aldrich) (0.2040 g,

0.86 mmol) to a vial containing 6.75 ml of 1 :1 diluted glacial
acetic acid (Fisher). The mixture Was stirred for 15 min at
room temperature, and then, 0.3350 g (0.86 mmol) of solid
Pt(NH3)4(NO3)2 (Aldrich) Were added. The mixture Was
stirred for another 15 min at room temperature, and then

added drop Wise to 5.0 g of SiOZiCaSiO3 support, in a 100

ml round-bottomed ?ask. After completing the addition of the

metal solution, the ?ask containing the impregnated catalyst

Was left standing at room temperature for tWo hours. The ?ask
Was then attached to a rotor evaporator (bath temperature 80

SiO2iZnO(5)-Pt(1)-Sn(1)
[0105]

of about 0.2 mm Was dried at 120 C. in a circulating air oven

atmosphere overnight and then cooled to room temperature.

To this Was added a solution of Zinc nitrate hexahydrate. The
resulting slurry Was dried in an oven gradually heated to 1 10
C. (>2 hours, 10 C./min.) then calcined. To this Was added a

solution of platinum nitrate (Chempur) in distilled Water and

a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric
acid (1N, 8.5 ml) The resulting slurry Was dried in an oven

gradually heated to 110 C. (>2 hours, 10 C./min.). The

impregnated catalyst mixture Was then calcined at 500 C. (6

hours, 1 C./min).

C.), and evacuated until dried While sloWly rotating the ?ask.

Example 7

The material Was then dried further overnight at 120 C., and

then calcined using the folloWing temperature program:

25Q160 C./ramp 5.0 deg/min; hold for 2.0 hours;
160>500 C./ramp 2.0 deg/min; hold for 4 hours. Yield: 5.19
g of tan-colored material.

PoWdered and meshed high surface area silica

NPSG SS61138 (100 g) of uniform particle siZe distribution

TiO2%aSiO3(5)-Pt(3)-Sn(1.8)
[0106]

The material Was prepared by ?rst adding CaSiO3 to

the TiO2 catalyst (Anatase, 14/30 mesh) support, folloWed by

the addition of Pt/Sn as described in Example 1. First, an

[0102]

Example 3

aqueous suspension of CaSiO3 200 mesh) Was prepared by

SiO2iCaSiO3(2.5)-Pt(1.5)-Sn(0.9)

adding 0.52 g of the solid to 7.0 ml of deioniZed H2O, fol

loWed by the addition of 1.0 ml of colloidal SiO2 (15 Wt %

This catalyst Was prepared in the same manner as

solution, NALCO). The suspension Was stirred for 2 h at room

Example 1, With the folloWing starting materials: 0.26 g of

temperature and then added to 10.0 g of TiO2 catalyst support

CaSiO3 as a support modi?er; 0.5 ml ofcolloidal SiO2 (15 Wt

(14/30 mesh) using incipient Wetness technique. After stand

% solution, NALCO), 0.3355 g (0.86 mmol) of Pt(NH3)4

(NO3)2; and 0.2052 g (0.86 mmol) of Sn(OAc)2.Yield: 10.90
Example 4

ing for 2 hours, the material Was evaporated to dryness, fol

loWed by drying at 120 C. overnight under circulating air and
calcination at 500 C. for 6 hours. All of the TiO2iCaSiO3
material Was then used for Pt/Sn metal impregnation using
0.6711 g (1 .73 mmol) ofPt(NH3)4(NO3)2 and 0.4104 g (1.73

SiO2+MgSiOliPt(1.0)-Sn(1.0)

mmol) of Sn(OAc)2 folloWing the procedure described in

g of dark grey material.

[0103]

Example 1.Yield: 11.5 g of light grey material.

This catalyst Was prepared in the same manner as

Example 1, With the folloWing starting materials: 0.69 g of

Mg(AcO) as a support modi?er; 1.3 g of colloidal SiO2 (15
Wt. % solution, NALCO), 0.2680 g (0.86 mmol) of Pt(NH3)
4(NO3)2; and 0.1640 g (0.86 mmol) of Sn(OAc)2.Yield: 8.35
g. The SiO2 support is impregnated With a solution of
Mg(AcO) and colloidal SiO2. The support is dried and then
calcined to 700 C.

Example 5

SiO2iCaSiO3 (5)-Re(4.5)-Pd(1)
[0104] The SiO24CaSiO3 (5) modi?ed catalyst support
Was prepared as described in Example 1. The Re/Pd catalyst

Example 8
Pt(2)-Sn(2) on High Surface Area Silica
[0107]

PoWdered and meshed high surface area silica

NPSG SS61138 (100 g) of uniform particle siZe distribution

of about 0.2 mm Was dried at 120 C. in a circulating air oven

atmosphere overnight and then cooled to room temperature.

To this Was added a solution of nitrate hexahydrate (Chem
pur). The resulting slurry Was dried in an oven gradually
heated to 110 C. (>2 hours, 10 C./min.) then calcined. To
this Was added a solution of platinum nitrate (Chempur) in
distilled Water and a solution of tin oxalate (Alfa Aesar) in

Aug. 5, 2010

US 2010/0197959 A1

dilute nitric acid. The resulting slurry Was dried in an oven

gradually heated to 110 C. (>2 hours, 10 C./min.). The

impregnated catalyst mixture Was then calcined at 500 C. (6

hours, 1 C./min).

added dropWise to 10.0 g of SiO2 NPSGSS 61138 catalyst

support (SA:250 m2/g, 1/16 inch extrudates) in a 100 ml
round-bottomed ?ask. The ?ask Was left standing for tWo
hours at room temperature, and then evacuated to dryness

using a rotor evaporator (bath temperature 80 C.). The result

Example 9

KA160-Pt(3)-Sn(1.8)
[0108]

The material Was prepared by incipient Wetness

ing material Was dried at 120 C. overnight under circulation

air, folloWed by calcination at 500 C. for 6 hours. All of the
(light yelloW) SiOZiWO3 material Was then used for Pt/ Sn

impregnation of KAl 60 catalyst support (SiO2-(0.05) A1203,

metal impregnation using 0.6711 g (1.73 mmol) of Pt(NH3)

4(NO3)2 and 0.4104 g (1 .73 mmol) ofSn(OAc)2 folloWing the

Sud Chemie, 14/30 mesh) as described in Example 1. The

procedure described above for Example 1.Yield: 12.10 g of

metal solutions Were prepared by ?rst adding Sn(OAc)2

dark grey 1/16 inch extrudates.

(0.2040 g, 0.86 mmol) to a vial containing 4.75 ml, of 1:1

diluted glacial acetic acid. The mixture Was stirred for 15 min
at room temperature, and then, 0.3350 g (0.86 mmol) of solid
Pt(NH3)4(NO3)2 Were added. The mixture Was stirred for
another 15 min at room temperature, and then added drop

Example 13

Comparative

Wise to 5.0 g of dry KA160 catalyst support (14/30 mesh) in

[0112] Sn(0.5) on High Purity LoW Surface Area Silica.

PoWdered and meshed high purity loW surface area silica (100

a 100 ml round-bottomed ?ask. All other manipulations, dry

ing and calcination Was carried out as described in Example
16. Yield: 5.23 g of tan-colored material.

dried at 120 C. in an oven under nitrogen atmosphere over

night and then cooled to room temperature. To this Was added

g) of uniform particle siZe distribution of about 0.2 mm Was

a solution of tin oxalate (Alfa Aesar) (1.74 g) in dilute nitric

[0109]

Example 10

acid (1N, 8.5 ml). The resulting slurry Was dried in an oven

SiO2iSnO2(5)-Pt(1)-Zn(1)

gradually heated to 110 C. (>2 hours, 10 C./min.). The

impregnated catalyst mixture Was then calcined at 500 C. (6

PoWdered and meshed high surface area silica

NPSG SS61138 (100 g) of uniform particle siZe distribution

of about 0.2 mm Was dried at 120 C. in a circulating air oven

atmosphere overnight and then cooled to room temperature.

To this Was added a solution of tin acetate (Sn(OAc)2). The
resulting slurry Was dried in an oven gradually heated to 1 10
C. (>2 hours, 10 C./min.) then calcined. To this Was added a

solution of platinum nitrate (Chempur) in distilled Water and

a solution of tin oxalate (Alfa Aesar) in dilute nitric acid The
resulting slurry Was dried in an oven gradually heated to 1 10

C. (>2 hours, 10 C./min.). The impregnated catalyst mixture

Was then calcined at 500 C. (6 hours, 1 C./min).

Example 11

SiO2iTiO2(10)-Pt(3)-Sn(1.8)
[0110]

The TiO2-modi?ed silica support Was prepared as

hours, 1 C./min).
Example 14
Gas Chromatographic (GC) Analysis of the Crude
Product Hydrogenation
[0113] Catalyst of Examples 1-13 Were tested to determine
the selectivity and productivity to ethyl acetate and ethanol as
shoWn in Table 4.
[0114] 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 catalyst
listed in Table 2. The length of the combined catalyst bed after
charging Was approximately about 70 mm. The reaction feed
liquid of acetic acid Was evaporated and charged to the reactor
along With hydrogen and helium as a carrier gas With an

average combined gas hourly space velocity (GHSV), tem

folloWs. A solution of 4.15 g (14.6 mmol) of Ti{OCH(CH3)

2}4 in 2-propanol (14 ml) Was added dropWise to 10.0 g of
SiO2 catalyst support (1/16 inch extrudates) in a 100 ml round

perature, and pres sure as indicated in Table 4. The feed stream

contained a mole ratio hydrogen to acetic acid as indicated in
Table 4.

bottomed ?ask. The ?ask Was left standing for tWo hours at
room temperature, and then evacuated to dryness using a rotor

online GC. A three channel compact GC equipped With one

evaporator (bath temperature 80 C.). Next, 20 ml of deion

?ame ioniZation detector (FID) and 2 thermal conducting

detectors (TCDs) Was used to analyZe the reactants and prod

iZed H2O Was sloWly added to the ?ask, and the material Was

[0115]

The analysis of the products Was carried out by

left standing for 15 min. The resulting Water/2-propanol Was

then removed by ?ltration, and the addition of H20 Was

ucts. The front channel Was equipped With an FID and a

repeated tWo more times. The ?nal material Was dried at 120

quantify: Acetaldehyde; Ethanol; Acetone; Methyl acetate;

Vinyl acetate; Ethyl acetate; Acetic acid; Ethylene glycol
diacetate; Ethylene glycol; Ethylidene diacetate; and Paral

C. overnight under circulation air, folloWed by calcination at

500 C. for 6 hours. All of the SiOZiTiO2 material Was then

CP-Sil 5 (20 m)+WaxFFap (5 m) column and Was used to

used for Pt/ Sn metal impregnation using 0.6711 g (1.73

mmol) of Pt(NH3)4(NO3)2 and 0.4104 g (1.73 mmol) of

dehyde. The middle channel Was equipped With a TCD and

Sn(OAc)2 folloWing the procedure described above for

and ethane. The back channel Was equipped With a TCD and
Molsieve 5A column and Was used to quantify: Helium;

Example 1.Yield: 11.98 g of dark grey 1/16 inch extrudates.

Porabond Q column and Was used to quantify: CO2; ethylene;

Hydrogen; Nitrogen; Methane; and Carbon monoxide.

Example 12

SiO2iWO3(10)-Pt(3)-Sn(1.8)
[0111] The WO3-modi?ed silica support Was prepared as
folloWs. A solution of 1.24 g (0.42 mmol) of (NH4)

6H2Wl2O4On H2O, (AMT) in deioniZed H20 (14 ml) Was

[0116] Prior to reactions, the retention time of the different

components Was determined by spiking With individual com
pounds 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.

Aug. 5, 2010

US 2010/0197959 A1
13

TABLE 4
Reaction Conditions

Ratio of

Cat. Ex. Cat.

1
2
3
4
5
6
7
8
8
8
8
9
10
11
12

SiO24CaSiO3(5)-Pt(3)-Sn(1.8)
KAl60-CaSiO3(8)-Pt(3)-Sn(1.8)
SiO24CaSiO3(2.5)-Pt(1.5)-Sn(0.9)
$102 + MgSiO3iPt(1.0)Sn(1.0)
SiO24CaSiO3(5)-Re(4.5)-Pd(1)
SiO2iZnO(5)-Pt(1)-Sn(1)
TiO24CaSiO3(5)-Pt(3)-Sn(1.8)
Pt(2)-Sn(2) on $102
Pt(2)-Sn(2) on $102
Pt(2)-Sn(2) on $102
Pt(2)-Sn(2) on $102
KA160-Pt(3)-Sn(1.8)
SiO2iSnO2(5)-Pt(1)-Zn(1)
SiO2iTiO2(10)-Pt(3)-Sn(1.8)
SiO2iWO3(10)-Pt(3)-Sn(1.8)

13

Sn(0.5) on $102

Press.

Temp.

GHSV

H2:AcOH (KPa)

(0 C.)

(hrl)

[0117]

Selectivig %

AcOH (%) EtOAc EtOH

5:1
5:1
10:1
4:1
5:1
4:1
5:1
5:1
5:1
5:1
5:1
5:1
4:1
5:1
5:1

2200
2200
1400
1400
1400
1400
1400
1400
1400
1400
1400
2200
1400
1400
1400

250
250
250
250
250
275
250
296
280
250
225
250
275
250
250

2500
2500
2500
6570
6570
6570
6570
6570
6570
6570
6570
2500
6570
6570
6570

24
43
26
22
8
22
38
34
37
26
11
61
13
73
17

6
13
8
10
17
21
78
64
62
63
57
50
44
53
23

92
84
86
88
83
76
22
33
36
36
42
47
48
47
77

9:1~8:1

2200

250

2500

10

Example 15
_

Conv. of

Vaporrzed acet1c ac1d and hydrogen Were passed

over a hydrogenation catalyst of the present invention com

prising 2 Wt % Pt; and 2 Wt % Sn on high surface area silica

(NPSG SS61 138) having a surface area of approximately 250

m2/g at a ratio of hydrogen to acetic acid of about 160 sccm/

We claim:
1. A process for producing ethyl acetate, comprising

hydrogenating acetic acid in the presence of a catalyst under

conditions effective to form ethyl acetate, Wherein the cata
lyst comprises a ?rst metal, a second metal and a support,
Wherein the ?rst metal is selected from the group consisting of

min H2: 0.09 g/min HOAc, the hydrogen being diluted With

nickel, palladium and platinum and is present in an amount

greater than 1 Wt %, based on the total Weight of the catalyst.

about 60 sccm/min N2 at a space velocity of about 6570 hr1

and a pressure of 200 psig (1379 kPag). The temperature Was
increased at about 50 hrs, 70 hrs and 90 hrs as indicated in
FIG. 3 and FIG. 4. The productivity in grams of the indicated

in an amount greater than 1 Wt. % and less than 25 Wt %, based

products (ethanol, acetaldehyde, and ethyl acetate) per kilo

gram of catalyst per hour are indicated in FIG. 3, and the
selectivity of a catalyst for the various products are indicated
in FIG. 4 With the upper line indicating productivity of or

selectivity to ethyl acetate, the intermediate line indicating

ethanol and the loWer line indicating acetaldehyde. It is con

sidered especially signi?cant that production of, and selec

tivity for, acetaldehyde Were loW. FIGS. 3 and 4 demonstrate
that the relative insensitivity of the catalyst to changes in
temperature make this catalyst Well-suited for use in a so

called adiabatic reactor in Which the temperature may vary

substantially over the catalyst bed due to the loW and uneven
rate of heat removal from the reactor.

[0118] While the invention has been described in detail,

modi?cations 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 in the art and ref
erences discussed above in connection With the Background
and Detailed Description, the disclosures of Which are all

incorporated herein by reference. In addition, it should be

understood that aspects of the invention and portions of vari
ous embodiments and various features recited beloW and/or in

the appended claims may be combined or interchanged either

in Whole or in part. In the foregoing descriptions of the vari

2. The process of claim 1, Wherein the ?rst metal is present

on the total Weight of the catalyst.

3. The process of claim 1, Wherein the support is present in
an amount of 25 Wt. % to 99 Wt. %, based on the total Weight

of the catalyst.
4. The process of claim 1, Wherein the support is selected

from the group consisting of iron oxide, silica, alumina,

silica/aluminas, titania, Zirconia, magnesium oxide, calcium

silicate, carbon, graphite, high surface area graphitiZed car
bon, activated carbons, and mixtures thereof.
5. The process of claim 1, further comprising at least one

support modi?er selected from the group consisting of (i)

alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alka
line earth metal metasilicates, (iv) alkali metal metasilicates,
(v) Group JIB metal oxides, (vi) Group IIB metal metasili

cates, (vii) Group IIIB metal oxides, (viii) Group IIIB metal
metasilicates, and mixtures thereof.
6. The process of claim 1, further comprising at least one

support modi?er selected from the group consisting of oxides

of Group IVB metals, oxides of Group VB metals, oxides of
Group VIB metals, iron oxides, aluminum oxides and mix
tures thereof.

7. The process of claim 1, Wherein the second metal is

selected from the group consisting of molybdenum, rhenium,

Zirconium, copper, cobalt, tin, and Zinc.
8. The process of claim 1, Wherein the second metal is

ous embodiments, those embodiments Which refer to another

present in an amount of from 0.1 to 10 Wt. %, based on the

embodiment may be appropriately combined With other

total Weight of the catalyst.

embodiments as Will be appreciated by one of skill in the art.

Furthermore, those of ordinary skill in the art Will appreciate

that the foregoing description is by Way of example only, and

is not intended to limit the invention.

9. The process of claim 1, Wherein at least 10% of the acetic

acid is converted during hydrogenation.

10. The process of claim 1, Wherein the hydrogenation has
a selectivity to ethyl acetate of at least 40%.

Aug. 5, 2010

US 2010/0197959 A1

11. The process of claim 1, wherein the hydrogenation has

a selectivity to methane, ethane, and carbon dioxide of less
than 4%.
12. The process of claim 1, Wherein the catalyst has a
productivity that decreases less than 6% per 100 hours of

catalyst usage.
13. The process of claim 1, Wherein the catalyst has a
surface area of from 50 m2/g to 600 m2/g.
14. The process of claim 1, Wherein the acetic acid is
obtained from a coal source, natural gas source or biomass
source.

15. The process of claim 1, further comprising cracking the

ethyl acetate obtained during the hydrogenation to produce

ethylene.
16. The process of claim 1, Wherein the hydrogenation is
performed in a vapor phase at a temperature of from 125 C.
to 350 C., a pressure of 10 KPa to 3000 KPa, and a hydrogen
to acetic acid mole ratio of greater than 4:1.

17. The process of claim 1, further comprising producing

ethanol in addition to the ethyl acetate, Wherein the selectivity
to ethanol is at least 20%.

18. A crude product formed by the process of claim 1,

comprising:
(a) ethyl acetate in an amount from 15 to 50 Wt. %;
(b) ethanol in an amount from 5 to 70 Wt. %;
(c) acetic acid in an amount from 10 to 60 Wt. %;
(d) Water in an amount from 10 to 45 Wt. %; and
(e) any other compounds in an amount less than 6 Wt. %,

Wherein all Weight percents are based on the total Weight of

the crude product.

19. A crude product, comprising:
(a) ethyl acetate in an amount from 5 to 70 Wt. %;
(b) ethanol in an amount from 5 to 70 Wt. %;
(c) acetic acid in an amount from 5 to 75 Wt. %;
(d) Water in an amount from 5 to 50 Wt. %; and
(e) any other compounds in an amount less than 10 Wt. %,
Wherein all Weight percents are based on the total Weight of

the crude product.

20. A process for producing ethyl acetate, comprising
hydrogenating acetic acid in the presence of a catalyst under
conditions effective to form ethyl acetate, Wherein the cata
lyst comprises a ?rst metal, a second metal and a support,
Wherein the ?rst metal is selected from group consisting of
nickel and palladium, and Wherein the second metal is
selected from the group consisting of tin and Zinc.
21. The process of claim 20, Wherein the ?rst metal is
present in an amount from 0.1 to 25 Wt. %, based on the total

Weight of the catalyst.

22. The process of claim 20, Wherein the support is present
in an amount from 25 Wt % to 99.9 Wt %, based on the total

Weight of the catalyst.

23. The process of claim 20, Wherein the support has a
surface area of from 50 m2/g to 600 m2/g.
24. The process of claim 20, Wherein the support is selected

from the group consisting of iron oxide, silica, alumina,

silica/aluminas, titania, Zirconia, magnesium oxide, calcium

silicate, carbon, graphite, high surface area graphitiZed car
bon, activated carbons, and mixtures thereof.
25. The process of claim 20, further comprising at least one

support modi?er selected from the group consisting of (i)

alkaline earth metal oxides, (ii) alkali metal oxides, (iii) alka
line earth metal metasilicates, (iv) alkali metal metasilicates,
(v) Group HB metal oxides, (vi) Group HB metal metasili

cates, (vii) Group lllB metal oxides, (viii) Group lllB metal
metasilicates, and mixtures thereof.
26. The process of claim 20, further comprising at least one
support modi?er selected from the group of oxides of Group
lVB metals, oxides of Group VB metals, oxides of Group VlB
metals, iron oxides, aluminum oxides and mixtures thereof.
27. The process of claim 20, Wherein the second metal is
present in an amount of from 0.1 to 10 Wt. %, based on the

total Weight of the catalyst.

28. The process of claim 20, Wherein at least 10% of the

acetic acid is converted during hydrogenation.

29. The process of claim 20, Wherein the hydrogenation has
a selectivity to ethyl acetate of at least 40%.

30. The process of claim 20, Wherein the hydrogenation has

a selectivity to methane, ethane, and carbon dioxide and
mixtures thereof of less than 4%.
31. The process of claim 20, Wherein the catalyst has a
productivity that decreases less than 6% per 100 hours of

catalyst usage.
32. The process of claim 20, Wherein the acetic acid is
obtained from a coal source, natural gas source or biomass
source.

33. The process of claim 20, further comprising dehydrat

ing the ethanol obtained during the hydrogenation to produce

ethylene.
34. The process of claim 20, Wherein the hydrogenation is
performed in a vapor phase at a temperature of from 1250 C.
to 350 C., a pressure of 10 KPa to 3000 KPa, and a hydrogen
to acetic acid mole ratio of greater than 4: 1.

35. The process of claim 20, further comprising producing

ethanol in addition to the ethyl acetate, Wherein the selectivity
to ethanol is at least 20%.

36. A crude product formed by the process of claim 20,

comprising:
(a) ethyl acetate in an amount from 5 to 70 Wt. %;
(b) ethanol in an amount from 5 to 70 Wt. %;
(b) acetic acid in an amount from 5 to 75 Wt. %;
(c) Water in an amount from 5 to 50 Wt. %; and
(d) any other compounds in an amount less than 10 Wt. %,
Wherein all Weight percents are based on the total Weight of

the crude product.

37. A process for producing ethyl acetate comprising
hydrogenating acetic acid in the presence of a catalyst under
conditions effective to form ethyl acetate, Wherein the cata
lyst comprises a ?rst metal, a support, and at least one support
modi?er selected from the group of oxides of Group lVB

metals, oxides of Group VB metals, oxides of Group VlB

metals, iron oxides, aluminum oxides and mixtures thereof.
38. The process of claim 37, Wherein the ?rst metal is

selected from the group consisting of Group lB, llB, HIB,

lVB, VB, VllB, VllB, or Vlll transitional metal, a lanthanide
metal, an actinide metal or a metal from any of Groups lllA,
IVA, VA, or VIA.
39. The process of claim 37, Wherein the ?rst metal is

selected from the group consisting of copper, iron, cobalt,

nickel, ruthenium, rhodium, palladium, osmium, iridium,

platinum, titanium, Zinc, chromium, rhenium, molybdenum,
and tungsten.
40. The process of claim 37, Wherein the ?rst metal is
present in an amount of from 0.1 to 25 Wt. %, based on the

total Weight of the catalyst.

Aug. 5, 2010

US 2010/0197959 A1

41. The process of claim 37, wherein the at least one

52. The process of claim 50, Wherein the third metal is

support modi?er is selected from the group consisting of

present in an amount of 0.05 and 4 Wt. %, based on the total

W03, M003, Fe2O3, Cr2O3, TiO2, ZrO2, Nb2O5, Ta2O5, and

Weight of the catalyst.

A1203.
42. The process of claim 37, Wherein the at least one
support modi?er is present in an amount of 0.1 Wt. % to 50 Wt.

%, based on the total Weight of the catalyst.

43. The process of claim 37, Wherein the support is present
in an amount of 25 Wt. % to 99 Wt. %, based on the total Weight

of the catalyst.
44. The process of claim 37, Wherein the support is selected

from the group consisting of iron oxide, silica, alumina,

53. The process of claim 37, Wherein at least 10% of the

acetic acid is converted during hydrogenation.

54. The process of claim 37, Wherein the hydrogenation has
a selectivity to ethyl acetate of at least 40%.

55. The process of claim 37, Wherein the hydrogenation has

a selectivity to methane, ethane, and carbon dioxide and
mixtures thereof of less than 4%.
56. The process of claim 37, Wherein the catalyst has a
productivity that decreases less than 6% per 100 hours of

catalyst usage.

silica/aluminas, titania, Zirconia, magnesium oxide, calcium

57. The process of claim 37, Wherein the acetic acid is

silicate, carbon, graphite, high surface area graphitiZed car

bon, activated carbons, and mixtures thereof.
45. The process of claim 38, Wherein the catalyst further

obtained from a coal source, natural gas source or biomass

comprises a second metal different from the ?rst metal.

46. The process of claim 45, Wherein the ?rst metal is
platinum and the second metal is tin.
47. The process of claim 45, Wherein the ?rst metal is
palladium and the second metal is rhenium.
48. The process of claim 45, Wherein the second metal is

selected from the group consisting of copper, molybdenum,

tin, chromium, iron, cobalt, vanadium, tungsten, palladium,

platinum, lanthanum, cerium, manganese, ruthenium, rhe
nium, gold, and nickel.
49. The process of claim 45, Wherein the second metal is
present in an amount of from 0.1 to 10 Wt. %, based on the

total Weight of the catalyst.

50. The process of claim 45, Wherein the catalyst further
comprises a third metal different from the ?rst and second
metals.
51. The process of claim 50, Wherein the third metal is

selected from the group consisting of cobalt, palladium,

ruthenium, copper, Zinc, platinum, tin, and rhenium.

source.

58. The process of claim 37, further comprising dehydrat

ing the ethanol obtained during the hydrogenation to ethyl
ene.

59. The process of claim 37, Wherein the hydrogenation is

performed in a vapor phase at a temperature of from 1250 C.
to 3500 C., a pressure of 10 KPa to 3000 KPa, and a hydrogen
to acetic acid mole ratio of greater than 4: 1.

60. The process of claim 37, further comprising producing

ethanol in addition to the ethyl acetate, Wherein the selectivity
to ethanol is at least 20%.
61. The process of claim 37, Wherein the process forms a

crude ethyl acetate product having the folloWing composi

tion:
(a) ethyl acetate in an amount from 5 to 70 Wt. %;
(b) acetic acid in an amount from 5 to 75 Wt. %;
(c) Water in an amount from 5 to 50 Wt. %; and
(d) any other compounds in an amount less than 10 Wt. %,
Wherein all Weight percents are based on the total Weight of

the crude product.