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Johnston et a].
(54)
6,657,078 B2
12/2003
A PLATINUM/TIN CATALYST
6,693,213 B1
6,906,228
6,927,048
7,297,236
7,425,657
Notice:
7,507,562 B2
7,538,060 B2
7,553,397 B1
7,572,353 B1
B2
B2
B1
B1
TX (Us)
Jan. 4, 2011
6,685,754 B2
(75)
US 7,863,489 B2
7,608,744 B1
2003/0077771 A1
2003/0104587 A1
2004/0195084 A1
2006/0019360
2006/0127999
2008/0207953
2009/0023192
A1
A1
A1
A1
2009/0166172 A1
6/2005
8/2005
11/2007
9/2008
FiSCheT et 31~
Verser et a1.
Vander Griend
ElllOtt et a1.
Barnlckl et al.
Colley et a1.
Vander Griend
Johnston et a1.
4/2003 Verser et a1.
6/2003 Verser
Verser et a1.
Verser et a1.
Houssin et a1.
Verser et a1.
7/2009 Casey
2009/0221725 A1
2009/0318573 A1
(65)
PH Pubhcatlon Data
US 2010/0029995 A1
Feb 4, 2010
2009/0326080 A1
2010/0016454 A1
2010/0029980 A1
(51)
Int_C1_
2010/0121114 A1
C07C 29/149
(2006.01)
(52)
568/885
(58)
568/885
EP
0137749 A2
EP
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OTHER PUBLICATIONS
U.S. Appl. NO. 12/221,239, ?led Jul. 31, 2008, Johnston et al.
. . . . . . . . . . . . . . ..
SOC,
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ABSTRACT
8/1999
31. """"" u
5/2001
10/2002
12/2002
1/2003
'
16 Claims, No Drawings
US 7,863,489 B2
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OTHER PUBLICATIONS
OrdoneZ et al., The role of metal and support sites on the hydroge
nation of acetic acid on Ru-based catalysts, 21ST NAM San Fran
(USA).
nacatsoc.org/20nam/abstracts/O-S9-18.pdf>.
zeachem.com, 2008.
US 7,863,489 B2
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catalyst conditions.
US. Pat. No. 4,777,303 to Kitson et al. describes a process
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25
products.
35
commercial operation.
More recently, it has been reported that ethanol can be
produced from hydrogenating acetic acid using a cobalt cata
lyst again at superatmospheric pressures such as about 40 to
120 bar. See, for example, US. Pat. No. 4,517,391 to Shuster
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60
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US 7,863,489 B2
4
following equation:
any limitation any of the other metals listed above, such as for
following equation:
Selectivity to EIOH(%) = 100 *
f _
silicate.
In another embodiment of this invention the preferred cata
lyst support is carbon. Various forms of carbon known in the
art that are suitable as catalyst support can be used in the
25
chemical equation:
30
size).
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60
ferred that the catalysts that are suitable in the process of this
invention contain optionally a third metal supported on the
same catalyst support. The following metals may be men
least 300 m2/g. The BET surface area is preferably not greater
than 1000 m2/g, more preferably not greater than 750 m2/g.
It is preferred to use carbon catalyst supports with ratios of
basal plane surface area to edge surface area of at least 10:1,
preferably at least 100:1. It is not believed that there is an
upper limit on the ratio, although in practice it will not usually
exceed 200: 1.
carbon black.
forth.
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US 7,863,489 B2
5
employed.
the heat treatment preferably have particle sizes not less than
these indicated above as being preferred for the carbon sup
port.
The preferred starting materials have the following char
metal and the other metal is the main metal. For instance, in
the instant process of the invention, combination of platinum
and tin is considered to be main metal for preparing hydro
genation catalysts of this invention. However, it can also be
considered that platinum is the main metal and tin is the
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25
40
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50
weight percent and that of tin is also 0.5, one or two weight
percent. However, low weight ratios of Pt/ Sn can also be
employed. For instance, a weight ratio of Pt/ Sn of 0.2 can also
be employed. In such cases, the amount of platinum on the
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60
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US 7,863,489 B2
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25
percent.
above. See also, US. Pat. No. 5,821,111 Grady et al., which
discloses a process for converting waste biomass through
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herein by reference.
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US 7,863,489 B2
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10
Example C
Example D
20
(Alfa Aesar) (1.74 g) in dilute nitric acid (1N, 8.5 ml), and
utilizing calcium silicate as a catalyst support.
Example E
25
bed and the reaction is carried out in the vapor phase using a
feed stream of acetic acid and hydrogen in the molar range of
about 1:20 to 1:5 and at a temperature in the range of about
225 C. to 275 C. and at a pressure of reaction zones in the
30
(0.87 g) in dilute nitric acid (1N, 4.5 ml). The resulting slurry
Example A
45
Example F
acid (1N, 8.5 ml). The resulting slurry was dried in an oven
hours, 1 C./min).
Examples B
Preparation of 0.5 Weight Percent Platinum and 5
Weight Percent Tin on High Purity Low Surface
Area Silica
hours, 1 C./min).
60
(8.7 g) in dilute nitric acid (1N, 43.5 ml). The resulting slurry
was dried in an oven gradually heated to 110 C. (>2 hours,
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US 7,863,489 B2
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Acetaldehyde
Ethanol
Acetone
Methyl acetate
Vinyl acetate
Ethyl acetate
Comparative Example
The catalyst utilized was 1 weight percent tin on low sur
Acetic acid
Ethylene glycol
procedure of Example F.
Ethylidene diacetate
Paraldehyde
The middle channel was equipped with a TCD and Pora
CO2
Ethylene
Ethane
The back channel was equipped with a TCD and Molsieve
5A column and was used to quantify:
Helium
20
Hydrogen
Nitrogen
Methane
Carbon monoxide
Prior to reactions, the retention time of the different com
ponents 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.
25
30
Example 1
The catalyst utilized was 1 weight percent platinum and 1
weight percent tin on silica prepared in accordance with the
procedure of Example C.
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45
55
Example 2
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