Академический Документы
Профессиональный Документы
Культура Документы
Aug. 5, 2010
Filed:
Feb. 2, 2010
(75)
Inventors:
(Us)
Publication Classi?cation
(51)
C07C 1/213
C07C 67/00
C09K 3/00
Correspondence Address:
KATTEN MUCHIN ROSENMAN LLP
Int. Cl.
(52)
(2006.01)
(2006.01)
(2006.01)
(73) Assignee:
CELANESE INTERNATIONAL
12/699,024
(57)
ABSTRACT
US 2010/0197959 A1
SiO2-PtmSn1_m
80
(Sel%ctiv)y
60
40
20
0
/....
0
0.2
0.4
0.6
0.8
(Pr)rgodlucktivhy
2000
SiO2-PtmSn1 A
1500
+ EtOH
I EtOAC
C(onve%rsio)n
SiO') PtmSHl -m
60
40
20
0.2
0.4
0.6
0.8
US 2010/0197959 A1
SiO2-RenPd1_n
80
(Sel%ctiv)y
6O
4O
2O
+EtOH
+ EtOAc
0.2
0.4
0.6
0.8
I!
(Prgoldkuctihv)y
Si
(,0 O O
250
200
150
100
+ EtOH
-I EtOAC
C(onve%rsio)n
ON-biCD
/
SiO2-RenPd1_n
/
i/
\\
0.2
0.4
0.6
0.8
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
[0002]
[0008]
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.
[0009]
[0011]
Aug. 5, 2010
US 2010/0197959 A1
sisting of Group IB, IIB, IIIB, IVB, VB, VIIB, VIIB, or VIII
transitional metal, a lanthanide metal, an actinide metal or a
Introduction
[0024]
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
CH3
+ 2 H2O
CH3
Aug. 5, 2010
US 2010/0197959 A1
[0031]
ethanol.
as described herein.
long as the third metal is different from the ?rst and second
metals. In preferred aspects, the third metal is selected from
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
98.5 Wt %, or from 35 Wt % to 98 Wt %.
tWo or more metals, e.g., a ?rst metal and a second metal, the
[0037]
Aug. 5, 2010
US 2010/0197959 A1
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
(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
silicate (CaSiO3).
[0044]
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
spherical particles, offrom 0.01 to 1.0 cm, e.g., from 0.1 to 0.5
cm or from 0.2 to 0.4 cm. Since the one or more metal(s) that
[0045]
Aug. 5, 2010
US 2010/0197959 A1
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
[0047]
to 2 Wt. %.
[0048]
from 0.05 and 4 Wt. %, e.g., from 0.1 to 3 Wt. %, or from 0.1
TABLE 1
First Metal
Second Metal
Cu
Ag
Cu
Cu
Cu
Cr
V
W
Third Metal
Aug. 5, 2010
US 2010/0197959 A1
TABLE l-continued
EXEMPLARY METAL COMBINATIONS FOR CATALYSTS
First Metal
Second Metal
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
ment.
[0063]
Aug. 5, 2010
US 2010/0197959 A1
[0064]
Aug. 5, 2010
US 2010/0197959 A1
[0077]
graph.
[0081]
[0082]
Aug. 5, 2010
US 2010/0197959 A1
TABLE 2
under 1%, and in many cases under 0.5% of the acetic acid
[0084]
[0085]
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
[0088]
[0086]
acid from synthesis gas (syn gas) that is derived from any
Aug. 5, 2010
US 2010/0197959 A1
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
i /CH2\
CH3
EXAMPLES
_>
CH2=CH2
CH3
anion
[0092]
[0093]
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
impregnation.
[0094]
tinuously until all of the Pt/ Sn mixture had been added to the
ture 800 C.), and evacuated until dried While sloWly rotating
the ?ask. The material Was then dried further overnight at
Aug. 5, 2010
US 2010/0197959 A1
Example 2
KAl60-CaSiO3(8)-Pt(3)-Sn(1.8)
solid Pd(NO3)2 Was then added. The mixture Was stirred for
another 15 min at room temperature, and then added drop
Example 6
SiO2iZnO(5)-Pt(1)-Sn(1)
[0105]
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
TiO2%aSiO3(5)-Pt(3)-Sn(1.8)
[0106]
[0102]
Example 3
SiO2iCaSiO3(2.5)-Pt(1.5)-Sn(0.9)
SiO2+MgSiOliPt(1.0)-Sn(1.0)
[0103]
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]
Aug. 5, 2010
US 2010/0197959 A1
hours, 1 C./min).
Example 9
KA160-Pt(3)-Sn(1.8)
[0108]
Example 13
Comparative
[0109]
Example 10
acid (1N, 8.5 ml). The resulting slurry Was dried in an oven
SiO2iSnO2(5)-Pt(1)-Zn(1)
Example 11
SiO2iTiO2(10)-Pt(3)-Sn(1.8)
[0110]
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
bottomed ?ask. The ?ask Was left standing for tWo hours at
room temperature, and then evacuated to dryness using a rotor
iZed H2O Was sloWly added to the ?ask, and the material Was
[0115]
repeated tWo more times. The ?nal material Was dried at 120
and ethane. The back channel Was equipped With a TCD and
Molsieve 5A column and Was used to quantify: Helium;
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)
Aug. 5, 2010
US 2010/0197959 A1
13
TABLE 4
Reaction Conditions
Ratio of
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 %
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
We claim:
1. A process for producing ethyl acetate, comprising
min H2: 0.09 g/min HOAc, the hydrogen being diluted With
of the catalyst.
4. The process of claim 1, Wherein the support is selected
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
Aug. 5, 2010
US 2010/0197959 A1
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.
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.
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. %,
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
catalyst usage.
32. The process of claim 20, Wherein the acetic acid is
obtained from a coal source, natural gas source or biomass
source.
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.
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
Aug. 5, 2010
US 2010/0197959 A1
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.
of the catalyst.
44. The process of claim 37, Wherein the support is selected
catalyst usage.
source.