U.S. patent application number 15/210959 was filed with the patent office on 2016-11-10 for iridium catalysts for carbonylation.
This patent application is currently assigned to Eastman Chemical Company. The applicant listed for this patent is Eastman Chemical Company. Invention is credited to David Alan Jenkins, Mary Kathleen Moore, Gerald Charles Tustin, Zhidong George Zhu, Joseph Robert Zoeller.
Application Number | 20160325270 15/210959 |
Document ID | / |
Family ID | 48695364 |
Filed Date | 2016-11-10 |
United States Patent
Application |
20160325270 |
Kind Code |
A1 |
Zhu; Zhidong George ; et
al. |
November 10, 2016 |
IRIDIUM CATALYSTS FOR CARBONYLATION
Abstract
A solid catalyst comprising an effective amount of iridium and
at least one second metal selected from gallium, zinc, indium and
germanium associated with a solid support material is useful for
vapor phase carbonylation to produce carboxylic acids and esters
from alkyl alcohols, esters, ethers or ester-alcohol mixtures. The
iridium and at least one second metal are deposited on a support
material. In some embodiments of the invention, the catalyst is
useful for vapor phase carbonylation.
Inventors: |
Zhu; Zhidong George;
(Kingsport, TN) ; Tustin; Gerald Charles;
(Kingsport, TN) ; Zoeller; Joseph Robert;
(Kingsport, TN) ; Moore; Mary Kathleen;
(Jonesborough, TN) ; Jenkins; David Alan;
(Jonesborough, TN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Eastman Chemical Company |
Kingsport |
TN |
US |
|
|
Assignee: |
Eastman Chemical Company
Kingsport
TN
|
Family ID: |
48695364 |
Appl. No.: |
15/210959 |
Filed: |
July 15, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13716336 |
Dec 17, 2012 |
9421522 |
|
|
15210959 |
|
|
|
|
61580818 |
Dec 28, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 21/18 20130101;
B01J 31/0231 20130101; B01J 37/0215 20130101; C07C 51/12 20130101;
B01J 23/624 20130101; B01J 37/0201 20130101; B01J 37/08 20130101;
C07C 69/14 20130101; C07C 53/08 20130101; C07C 67/36 20130101; B01J
23/62 20130101; C07C 67/36 20130101; B01J 23/60 20130101; C07C
51/12 20130101; B01J 37/0236 20130101 |
International
Class: |
B01J 23/62 20060101
B01J023/62; C07C 51/12 20060101 C07C051/12; C07C 67/36 20060101
C07C067/36; B01J 23/60 20060101 B01J023/60; B01J 37/02 20060101
B01J037/02 |
Claims
1. A carbonylation catalyst comprising an effective amount of
iridium and at least one second metal selected from gallium, zinc,
indium and germanium wherein the iridium and the at least one
second metal are associated with a solid support material
comprising activated carbon.
2. (canceled)
3. (canceled)
4. The carbonylation catalyst of claim 1 wherein the catalyst
includes from about 0.01 weight percent to about 10 weight percent
each of the iridium and the at least one second metal.
5. The carbonylation catalyst of claim 1 wherein the catalyst
includes from about 0.1 weight percent to about 3 weight percent
each of the iridium and the at least one second metal.
6. The carbonylation catalyst of claim 1 wherein the molar ratio of
the at least one second metal to iridium is from about 0.1:1 to
about 10:1.
7. The carbonylation catalyst of claim 1 wherein the molar ratio of
the at least one second metal to iridium is from about 0.5:1 to
about 5:1.
8. The carbonylation catalyst of claim 1, further comprising at
least one vaporous halogen promoting component selected from
hydrogen halides, gaseous hydrogen iodide, alkyl and aryl halides
having up to 12 carbon atoms, iodine, bromine, chlorine, and
mixtures of two or more of the foregoing.
9. The carbonylation catalyst of claim 8 wherein the at least one
vaporous halogen promoting component is selected from hydrogen
iodide, methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane,
1-iodobutane, hydrogen bromide, methyl bromide, ethyl bromide,
benzyl iodide and combinations of two or more of the foregoing.
10. The carbonylation catalyst of claim 8 wherein the at least one
vaporous halogen promoting component is selected from hydrogen
iodide, methyl iodide, hydrogen bromide, methyl bromide and
combinations of two or more of the foregoing.
11. A carbonylation catalyst comprising from about 0.01 weight
percent to about 10 weight percent each of iridium and at least one
second metal selected from gallium, zinc, indium and germanium
wherein the iridium and at least one second metal are associated
with a solid support material comprising activated carbon.
12. (canceled)
13. (canceled)
14. The carbonylation catalyst of claim 11 wherein the molar ratio
of the at least one second metal to iridium is from about 0.5:1 to
about 5:1.
15. The carbonylation catalyst of claim 11 wherein the catalyst
includes from about 0.1 weight percent to about 3 weight percent
each of the iridium and the at least one second metal.
16. The carbonylation catalyst of claim 11 wherein the molar ratio
of the at least one second metal to iridium is from about 0.1:1 to
about 10:1.
17. The carbonylation catalyst of claim 11 further comprising at
least one vaporous halogen promoting component selected from
hydrogen halides, gaseous hydrogen iodide, alkyl and aryl halides
having up to 12 carbon atoms, iodine, bromine or chlorine, and
mixtures of two or more of the foregoing.
18. The carbonylation catalyst of claim 17 wherein the at least one
vaporous halogen promoting component is selected from hydrogen
iodide, methyl iodide, ethyl iodide, 1-iodopropane, 2-iodobutane,
1-iodobutane, hydrogen bromide, methyl bromide, ethyl bromide,
benzyl iodide and combinations of two or more of the foregoing.
19. The carbonylation catalyst of claim 17 wherein the at least one
vaporous halogen promoting component is selected from hydrogen
iodide, methyl iodide, hydrogen bromide, methyl bromide and
combinations of two or more of the foregoing.
20. A method for preparing a solid supported catalyst composition
useful for vapor phase carbonylation, the method comprising: a)
providing a solid support material comprising activated carbon; b)
contacting the solid support material with a solution containing
iridium and at least one second metal selected from gallium, zinc,
indium and germanium to form a solid supported catalyst
composition, wherein the iridium and the at least one second metal
are associated with the solid support material; and c) drying the
solid support material wherein from about 0.01 weight percent to
about 10 weight percent of the iridium and at least one second
metal are associated with the solid supported catalyst composition,
wherein weight percent of each metal is determined as the weight of
atoms of that particular metal based on the total weight of the
solid supported catalyst composition.
21. The method of claim 20 further comprising contacting the solid
support material with a solution having at least one second
component selected from I.sub.2, Br.sub.2, Cl.sub.2, hydrogen
iodide, methyl iodide, ethyl iodide, 1 iodopropane, 2 iodobutane, 1
iodobutane, methyl bromide, ethyl bromide, benzyl iodide and
combinations of two or more of the foregoing.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional of U.S. application Ser.
No. 13/716,336 filed Apr. 20, 2016 which claims the benefit of U.S.
Provisional Application No. 61/580,818 filed on Dec. 28, 2011, the
disclosures of which are incorporated herein by reference to the
extent it does not contradict the disclosures herein.
FIELD OF THE INVENTION
[0002] The present invention relates to a solid phase catalyst and
more particularly to a catalyst for the vapor phase carbonylation
of alkyl alcohols, ethers and ester-alcohol mixtures to produce
esters and carboxylic acids. More particularly, the present
invention relates to a catalyst having an effective amount of
iridium and at least one second metal selected from the group
gallium, zinc, indium and germanium associated with a solid support
material. The catalyst is particularly useful in the carbonylation
of methanol.
BACKGROUND OF THE INVENTION
[0003] Lower carboxylic acids and esters such as acetic acid and
methyl acetate have been known as industrial chemicals for many
years. Acetic acid is used in the manufacture of a variety of
intermediary and end-products. For example, an important derivative
is vinyl acetate which can be used as monomer or co-monomer for a
variety of polymers. Acetic acid itself is used as a solvent in the
production of terephthalic acid, which is widely used in the
container industry, and particularly in the formation of PET
beverage containers.
[0004] There has been considerable research activity in the use of
metal catalysts for the carbonylation of alkyl alcohols, such as
methanol, and ethers to their corresponding carboxylic acids and
esters, as illustrated in equations 1-3 below:
ROH+CO.fwdarw.RCOOH (1)
2ROH+CO.fwdarw.RCOOR+water (2)
ROR'+CO.fwdarw.RCOOR (3)
[0005] Carbonylation of methanol is typically carried out in the
liquid phase with a catalyst. However, there is a continuing need
for a catalyst which can be used in a vapor phase carbonylation
process for the production of carboxylic acids and their esters and
in which the catalyst is maintained in the solid phase.
SUMMARY OF THE INVENTION
[0006] Briefly, the present invention relates to solid supported
catalysts for producing esters and carboxylic acids in a vapor
phase carbonylation process, processes for making the catalyst
compositions, and carbonylation processes that use such catalysts.
Suitable reactants for contacting the solid catalyst includes alkyl
alcohols, ethers and ester-alcohol mixtures. The catalyst includes
an effective amount of iridium and at least one second metal
selected from gallium, zinc, indium and germanium, wherein the
iridium and at least one second metal are associated with a solid
support material which, desirably, is inert to the carbonylation
reaction.
[0007] The invention thus provides carbonylation catalysts
containing an effective amount of iridium and at least one second
metal selected from gallium, zinc, indium and germanium wherein the
iridium and the at least one second metal are associated with a
solid support material. The invention further carbonylation
catalyst containing from about 0.01 weight percent to about 10
weight percent each of iridium and at least one second metal
selected from gallium, zinc, indium and germanium wherein the
iridium and at least one second metal are associated with a solid
support material. In some embodiments, the solid support material
is selected from carbon, activated carbon, pumice, alumina, silica,
silica-alumina, magnesia, diatomaceous earth, bauxite, titania,
zirconia, clay, magnesium silicate, silicon carbide, zeolites,
ceramics and combinations thereof. In some embodiments, the solid
support material contains activated carbon. In some embodiments,
the molar ratio of the at least one second metal to iridium is from
about 0.5:1 to about 5:1. In some embodiments, the catalyst
includes from about 0.1 weight percent to about 3 weight percent
each of the iridium and the at least one second metal. In some
embodiments, the molar ratio of the at least one second metal to
iridium is from about 0.1:1 to about 10:1. In some embodiments, the
catalyst includes at least one vaporous halogen promoting component
selected from hydrogen halides, gaseous hydrogen iodide, alkyl and
aryl halides having up to 12 carbon atoms, iodine, bromine or
chlorine, and mixtures of two or more of the foregoing. In some
embodiments, the at least one vaporous halogen promoting component
is selected from hydrogen iodide, methyl iodide, ethyl iodide,
1-iodopropane, 2-iodobutane, 1-iodobutane, hydrogen bromide, methyl
bromide, ethyl bromide, benzyl iodide and combinations of two or
more of the foregoing. In some embodiments, the at least one
vaporous halogen promoting component is selected from hydrogen
iodide, methyl iodide, hydrogen bromide, methyl bromide and
combinations of two or more of the foregoing.
[0008] The invention further provides methods for producing at
least one carboxylic acid, ester, or combination of carboxylic acid
and ester mixtures from at least one reactant selected from alkyl
alcohols, ethers, esters and combinations of two or more of the
foregoing, which methods include contacting the at least one
reactant with carbon monoxide in a reaction zone under vapor-phase
carbonylation reaction conditions in the presence of a catalyst of
the present invention, then recovering at least one carboxylic acid
or ester from the reaction zone. In some embodiments, the reaction
zone is maintained at a pressure of from about 0.1 to about 100 bar
absolute and a temperature of from about 100.degree. C. to about
350.degree. C.
[0009] The invention further provides methods for preparing a solid
supported catalyst composition useful for vapor phase
carbonylation. The methods including: (a) providing a solid support
material selected from carbon, activated carbon, pumice, alumina,
silica, silica-alumina, magnesia, diatomaceous earth, bauxite,
titania, zirconia, clays, magnesium silicate, silicon carbide,
zeolites, ceramics and combinations of two or more of the
foregoing; (b) contacting the support material with a solution
containing iridium and at least one second metal selected from
gallium, zinc, indium and germanium wherein the iridium and the at
least one second metal are associated with the solid support
material; and (c) drying the solid support material wherein from
about 0.01 weight percent to about 10 weight percent of the iridium
and at least one second metal are associated with the solid
catalyst support material, wherein weight percent of each metal is
determined as the weight of atoms of that particular metal based on
the total weight of the solid supported catalytic material.
BRIEF DESCRIPTION OF THE DRAWING
[0010] The drawing of FIG. 1 is a plot of acetyl space time yield
vs. time on stream of Example 13 herein demonstrating the longevity
of the catalyst of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0011] The catalyst of the present invention is particularly useful
for the continuous production of carboxylic acids and esters by
reacting alkyl alcohols, ethers and ester-alcohol mixtures in a
vapor-phase carbonylation process. The catalyst includes an
effective amount of iridium and at least one second metal selected
from gallium, zinc, indium and germanium. The iridium and at least
one second metal are associated with a solid support material. The
catalyst is particularly useful in a vapor-phase carbonylation
method for the continuous production of acetic acid, methyl acetate
and combinations thereof.
[0012] As used herein, the term "effective amount" or
"catalytically effective amount" means a measurable quantity of at
least one substance, such as the primary metal, wherein the
quantity or selectivity to make a targeted or desired product is at
least 5 weight % greater in a given process than what would be
produced under the same conditions without the substance. In some
embodiments, the amount is from about 0.01 weight percent to about
10 weight percent each of iridium and at least one second metal
selected from gallium, zinc, indium and germanium wherein the
iridium and at least one second metal are associated with a solid
support material. In some embodiments, the amount is from about 0.1
weight percent to about 3 weight percent each of the iridium and
the at least one second metal.
[0013] As used herein, the term "associated with" means that one or
more substances are deposited upon or joined with another material
in such a manner that such substances are not readily removed under
vapor-phase carbonylation reaction conditions.
Making the Catalyst
[0014] The compound or form of iridium used to prepare the catalyst
generally is not critical, and the catalyst may be prepared from
any of a wide variety of iridium containing compounds. Some
examples include many combinations of halides, trivalent nitrogen,
organic compounds of trivalent phosphorous, carbonyl compounds
monoxide, hydrides, and 2,4-pentane-dione, either alone or in
combination. Such materials are available commercially and may be
used in the preparation of the catalysts utilized in the present
invention. In addition, the oxides of iridium may be used if
dissolved in the appropriate medium. In some embodiments, iridium
is used as a salt of one of its chlorides, such as iridium
trichloride or hydrated trichloride, hexacholoro-iridate and any of
the various salts of hexachloro-iridate(IV). One skilled in the art
will understand that use of the iridium complexes can be comparable
on the basis of cost, solubility, and performance.
[0015] Similarly, the compound or form of the at least one second
metal compound (gallium, zinc, indium, germanium or combinations of
two or more of the foregoing) used to prepare the catalyst
generally is not critical, and the catalyst may be prepared using
any of a wide variety of compounds containing one or more of the
second metals. A wide variety of compounds of these elements
containing various combinations of halides, acetates, nitrates,
cyclopentadiene, and 2,4-pentane-dione, either alone or in
combination, are available commercially and may be used in the
preparation of the catalysts utilized in the process of the present
invention. In some embodiments, the form of the at least one second
metal that may be used to prepare the catalyst of the present
invention includes halides, oxides, acetylacetonate, nitrate,
perchlorate, phosphide, sulfate and sulfide, either alone or in
mixtures. In addition, the oxides of these materials may be used if
dissolved in the appropriate medium. In some embodiments, the
compound is in a form selected from acetates, nitrates, and their
halides. In some embodiments, the compound used to provide the at
least one second metal is a water soluble form of the metal(s). For
example, many halides of second metals are generally commercially
available and water soluble.
[0016] The solid support useful for acting as a carrier for the
iridium and the at least one second metal contains a porous solid
of such size that it can be employed in fixed or fluidized bed
reactors. Typical support materials have a size of from about 400
mesh per inch to about 0.5 mesh per inch. The shape of the solid
support is not particularly important and can be regular or
irregular and include extrudates, rods, spheres, broken pieces and
the like disposed within the reactor.
[0017] In some embodiments, the support is carbon, including
activated carbon, having a high surface area. Activated carbon may
be derived from several sources including, but not limited to,
coal, peat having a density of from about 0.03 grams/cubic
centimeter (g/cm.sup.3) to about 2.25 g/cm.sup.3. The carbon can
have a surface area of from about 200 square meters/gram
(m.sup.2/g) to about 1200 m.sup.2/g. Other solid support materials
may be used, either alone or in combination, in accordance with the
present invention include pumice, alumina, silica, silica-alumina,
magnesia, diatomaceous earth, bauxite, titania, zirconia, clays,
magnesium silicate, silicon carbide, zeolites, and ceramics.
[0018] In some embodiments, the amount of iridium and at least one
second metal on the support (determined as metal) can independently
vary from about 0.01 weight percent to about 10 weight percent
each, as metal. In some embodiments, the amount of iridium and at
least one second metal on the support is from about 0.1 weight
percent to about 3 weight percent for each component. The weight
percent or "weight %" of each metal is determined as the weight of
atoms of that particular metal based on the total weight of the
solid components of the catalytic material.
[0019] In some embodiments, the molar ratio of the at least one
second metal to iridium in the catalytic material, is from about
0.1:1 to about 10:1. In some embodiments, the molar ratio of the at
least one second metal to iridium is from about 0.5:1 to about
5:1.
[0020] Any effective means may be used to prepare the catalyst. A
variety of methods are known in which the contacting method
provides association between iridium, the at least one second metal
and the selected support material. For example, the metal
components may be dissolved or dispersed in a suitable solvent. The
solid support material is then contacted and desirably impregnated
with the iridium and at least one second metal containing solvent.
Various methods of contacting the support material with the iridium
and at least one second metal may be employed. For example, an
iridium containing solvent can be admixed with a solvent containing
the at least one second metal prior to impregnating the support
material. Alternatively, the respective one the solvents can be
impregnated or associated with the support material separately. In
some embodiments, the support material is impregnated the support
material with a first solvent followed a second solvent. In some
embodiments, the support is dried prior to contacting the second
solvent. In some embodiments, the at least one second metal
component may be deposited on a previously prepared catalyst
support having the iridium component already incorporated thereon.
Similarly, the iridium and at least one second metal(s) may be
associated with the support material in a variety of forms. For
example, slurries of the iridium and at least one second metal can
be poured over the support material. Alternatively, the support
material may be immersed in excess solutions of the active
components with the excess being subsequently removed, for example
by using techniques known to those skilled in the art. The solvent
or liquid is evaporated, i.e. the solid support is dried so that at
least a portion of the iridium and at least one second metal is
associated with the solid support. In some embodiments, drying
temperatures can range from about 100.degree. C. to about
600.degree. C. One skilled in the art will understand that the
drying time is dependent upon the temperature, humidity, and
solvent. Generally, lower temperatures require longer heating
periods to effectively evaporate the solvent from the solid
support.
[0021] In some embodiments, the liquid used to deliver the iridium
and at least one second metal in a form a solution, dispersion, or
suspension is a liquid having a low boiling point, i.e., high vapor
pressure at a temperature of from about 10.degree. C. to about
140.degree. C. Some examples of suitable solvents include carbon
tetrachloride, benzene, acetone, methanol, ethanol, isopropanol,
isobutanol, pentane, hexane, cyclohexane, heptane, toluene,
pyridine, diethylamine, acetaldehyde, acetic acid, tetrahydrofuran
and water.
Promoting Components
[0022] In some embodiments of the present invention, a catalytic
system is used having a solid supported catalyst component as
described above, and a vaporous halogen promoting component which
can be catalytically active and which aids in the carbonylation
process. The halogen promoter may be introduced at any suitable
location, such as the catalyst preparation step or into
carbonylation reactor under vapor-phase carbonylation reaction
conditions with conjunction with the reactants. While not wanting
to be bound by any theory, it is considered that as a result of
contacting the active metal components with the halogen promoter
the ultimate active species of the iridium and at least one second
metal may exist as one or more coordination compounds or a halide
thereof.
[0023] The halide component includes one or more of chlorine,
bromine and/or iodine. In some embodiments, the halide component
includes bromine and/or iodine, which are vaporous under
vapor-phase carbonylation conditions of temperature and pressure.
Some examples of suitable halides include: hydrogen halides such as
hydrogen iodide and gaseous hydrogen iodide; and alkyl and aryl
halides having up to 12 carbon atoms such as methyl iodide, ethyl
iodide, 1-iodopropane, 2-iodobutane, 1-iodobutane, methyl bromide,
ethyl bromide, and benzyl iodide. Desirably, the halide is a
hydrogen halide or an alkyl halide having up to 6 carbon atoms. In
some embodiments, the halide is selected from hydrogen iodide,
methyl bromide and methyl iodide. In some embodiments, the halide
is a molecular halide such as I.sub.2, Br.sub.2 or Cl.sub.2.
Carbonylation Processes
[0024] In some embodiments of the present invention, a method for
producing esters and carboxylic acids from reactants including
alkyl alcohols, ethers, esters and ester-alcohol mixtures and
carbon monoxide is provided including contacting the reactants in a
reaction zone under vapor-phase carbonylation reaction conditions
with the solid supported catalyst described above and recovering
the ester or carboxylic acid from the reaction zone. In practice, a
gaseous composition containing: at least one alkyl alcohol, ether,
esters and ester-alcohol mixture, either alone or in combination;
carbon monoxide; and a halide are fed to the reaction zone of a
carbonylation reactor containing the iridium and at least one
second metal supported catalyst described above. The reactor is
maintained under vapor-phase carbonylation reaction conditions of
temperature and pressure. For example, in some embodiments in which
acetic acid is the desired product, the feedstock may contain
methyl alcohol, dimethyl ether, methyl acetate, a methyl halide or
any combination thereof. If it is desired to increase the
proportion of acid produced, in some embodiments the ester may be
recycled to the reactor together with water or introduced into a
separate reactor with water to produce the acid in a separate
zone.
[0025] As used herein, "vapor-phase carbonylation reaction
conditions" means temperature and pressure conditions suitable to
allow vapor-phase carbonylation reaction to occur. Vapor-phase
carbonylation is operated at temperatures above the dew point of
the product mixture, i.e., the temperature at which condensation
occurs. However, since the dew point is a complex function of
dilution (particularly with respect to non-condensable gases such
as unreacted carbon monoxide, hydrogen, or inert diluent gas),
product composition, and pressure, the process may still be
operated over a wide range of temperatures, provided the
temperature exceeds the dew point of the product effluent. In
practice, this generally dictates a temperature range of from about
100.degree. C. to about 500.degree. C. In some embodiments, the
temperatures are in the range of from about 100.degree. C. to about
350.degree. C. In some embodiments, the temperatures are in the
range of from about 150.degree. C. to about 275.degree. C.
Advantageously, operating in the vapor phase reduces the potential
for catalyst dissolution, i.e., metal leaching from the catalyst
support, which occurs in the known heterogeneous processes
operating in the presence of liquid compounds.
[0026] As with temperature, the useful pressure range is limited by
the dew point of the product mixture. However, provided that the
reaction is operated at a temperature sufficient to prevent
liquefaction of the product effluent, a wide range of pressures may
be used, e.g., pressures in the range of from about 0.1 to about
100 bar absolute. In some embodiments, the process is carried out
at a pressure in the range of from about 1 to about 50 bar
absolute. In some embodiments, the process is carried out at a
pressure in the range of from about 3 to about 30 bar absolute.
[0027] Suitable feedstocks for carbonylation include alkyl
alcohols, ethers, esters-alcohol mixtures and, as more fully
discussed below, esters, which may be carbonylated using the
catalyst of the present invention. Non-limiting examples of
feedstocks include alcohols and ethers in which an aliphatic carbon
atom is directly bonded to an oxygen atom of either an alcohol
hydroxyl group in the compound or an ether oxygen in the compound
and may further include aromatic moieties. In some embodiments, the
feedstock is one or more alkyl alcohols having from 1 to 10 carbon
atoms. In some embodiments the feedstock is selected from alkyl
alcohols having from 1 to 6 carbon atoms, alkane polyols having 2
to 6 carbon atoms, alkyl alkylene polyethers having 3 to 20 carbon
atoms and alkoxyalkanols having from 3 to 10 carbon atoms and
combinations of two or more of the foregoing. In some embodiments
the feedstock is selected from alkyl alcohols having from 1 to 6
carbon atoms. In some embodiments the feedstock reactant is
methanol. In some embodiments using methanol, the methanol is fed
as methanol or it is supplied in the form of a combination of
materials which generate methanol. Some examples of such materials
include: (i) methyl acetate and water and (ii) dimethyl ether and
water. During carbonylation, both methyl acetate and dimethyl ether
are formed within the reactor and, unless methyl acetate is the
desired product, they are recycled with water to the reactor where
they are converted to acetic acid. Accordingly, in some embodiments
the catalyst of the present invention is useful to produce a
carboxylic acid from an ester feed material.
[0028] While the presence of water in the gaseous feed mixture is
not essential when using methanol, the presence of some water may
be used in some embodiments to suppress formation of methyl acetate
and/or dimethyl ether. When using methanol to generate acetic acid,
the molar ratio of water to methanol in some embodiments is from
about 0:1 to about 10:1. The molar ratio of water to methanol in
some embodiments is from about 0.1:1 to about 1:1. When using an
alternative source of methanol such as methyl acetate or dimethyl
ether, the amount of water fed usually is increased to account for
the mole of water required for hydrolysis of the methanol
alternative. Accordingly, when using either methyl acetate or
dimethyl ether, the mole ratio of water to ester or ether in some
embodiments is in the range of from about 1:1 to about 10:1, in
some embodiments from about 1:1 to about 3:1. In the preparation of
acetic acid, it is apparent that combinations of methanol, methyl
ester, and/or dimethyl ether are equivalent, provided the
appropriate amount of water is added to hydrolyze the ether or
ester to provide the methanol reactant.
[0029] In some embodiments in which the catalyst is used in a
vapor-phase carbonylation process to produce methyl acetate, no
water is added and dimethyl ether is the feedstock. In some
embodiments in which methanol is used as the feedstock in the
preparation of methyl acetate, water may be removed.
[0030] The carbon monoxide can be a purified carbon monoxide or
include other gases. The carbon monoxide need not be of a high
purity and may contain from about 1% by volume to about 99% by
volume carbon monoxide, in some embodiments in the range of from
about 70% by volume to about 99% by volume carbon monoxide. The
remainder of the gas mixture can include such gases as nitrogen,
hydrogen, carbon dioxide, water, paraffinic hydrocarbons having
from one to four carbon atoms, and combinations of two or more of
the foregoing. Although hydrogen is not part of the reaction
stoichiometry, hydrogen may be useful in maintaining optimal
catalyst activity. In some embodiments, the ratio of carbon
monoxide to hydrogen generally ranges from about 99:1 to about 2:1,
but ranges with even higher hydrogen levels are also likely to be
useful.
[0031] The amount of halide present to produce an effective
carbonylation ranges from a molar ratio of from about 1:1 to about
10,000:1. In some embodiments the is from about 5:1 to about
1000:1. The foregoing molar ratios are based on methanol or
methanol equivalents to halide.
[0032] In some embodiments of the invention, the vapor-phase
carbonylation catalyst of the present invention may be used for
making acetic acid, methyl acetate or a combination thereof. The
process includes contacting a gaseous mixture containing methanol
and carbon monoxide with the iridium/second metal catalyst
described above in a carbonylation zone and recovering a gaseous
product from the carbonylation zone.
[0033] The various aspects of the present invention can be further
illustrated and described by the following Examples. It should be
understood, however, that these Examples are included merely for
purposes of illustration and are not intended to limit the scope of
the invention, unless otherwise specifically indicated.
[0034] In the examples which follow all of the catalysts were
prepared in a similar manner except as specified otherwise.
Catalyst 1
[0035] A catalyst in accordance with the present invention was
prepared by dissolving 419 milligrams (mg) of iridium trichloride
hydrate (53.2 weight % Ir) in 25 milliliters (ml) of distilled
water to form a first solution. A second solution was prepared by
dissolving 631 mg gallium iodide in 10 ml of concentrated
hydrochloric acid. The first and second solutions were then
combined and added to 20.0 grams (g) of 12.times.40 mesh activated
carbon granules using a rotary evaporator. The mixture was heated
under a water bath at a temperature of 60.degree. C. and evacuated
under 30 Torr until the granules were dry. The mixture was then
transferred to a 106 cm long.times.25 mm (outer diameter) quartz
tube containing a quartz wool support plug. The quartz tube was
placed in a Lindberg electric furnace and heated in an upward flow
of nitrogen at a flow rate of 100 standard cubic centimeters per
minute. The tube was gradually heated from room temperatures to
300.degree. C. over a 2 hour period, then held at 300.degree. C.
for 2 hours before cooling back to ambient temperature to obtain
the final catalyst for methanol carbonylation. The catalyst weighed
18.13 grams after drying. The catalyst prepared in this manner,
designated as Catalyst 1, had a nominal metal content of 1.23
weight % Ir and 0.54 weight % Ga, representing an IrGa molar ratio
of 1:1.21.
Catalyst 2
[0036] The same procedure as above was repeated except that the
amount of gallium iodide dissolved into 10 ml of concentrated
hydrochloric acid was 1.89 grams. The catalyst weighed 18.91 grams
after drying. The catalyst prepared in this manner, designated as
Catalyst 2, had a nominal metal content of 1.18 weight % Ir and
1.55 weight % Ga, representing, an IrGa molar ratio of 1:3.63.
Catalyst 3
[0037] The same procedure to prepare Catalyst 1 above was repeated
except that the amount of gallium iodide dissolved into 10 ml of
concentrated hydrochloric acid was 3.10 grams. The catalyst weighed
21.03 grams after drying. The catalyst prepared in this manner,
designated as Catalyst 3, had a nominal metal content of 1.06 wt. %
Ir and 2.28 wt. % Ga, representing, an IrGa molar ratio of
1:5.92.
Catalyst 4
[0038] A catalyst in accordance with the present invention was
prepared by dissolving 418 milligrams (mg) of iridium trichloride
hydrate (53.2 weight % Ir) in 25 milliliters (ml) of distilled
water to form a first solution. A second solution was prepared by
dissolving 449 mg zinc iodide in 10 ml of concentrated hydrochloric
acid. The first and second solutions were then combined and added
to 20.0 grams (g) of 12.times.40 mesh activated carbon granules
using a rotary evaporator. The mixture was heated under a water
bath at a temperature of 60.degree. C. and evacuated under 30 Torr
until the granules were dry. The mixture was then transferred to a
106 cm long.times.25 mm (outer diameter) quartz tube containing a
quartz wool support plug. The quartz tube was placed in a Lindberg
electric furnace and heated to 300.degree. C. over a 2 hour period
in an upward flow of nitrogen a flow rate of 100 standard cubic
centimeters per minute and held at 300.degree. C. for 2 hours
before cooling back to ambient temperature to obtain the final
catalyst for methanol carbonylation. The catalyst weighed 18.46
grams after drying. The catalyst prepared in this manner,
designated as Catalyst 4, had a nominal metal content of 1.21
weight % Ir and 0.50 weight % Zn, representing, an Ir:Zn molar
ratio of 1:1.21.
Catalyst 5
[0039] The same procedure to prepare Catalyst 4 above was repeated
except that the amount of zinc iodide dissolved into 10 ml of
concentrated hydrochloric acid was 1.344 grams. The catalyst
weighed 19.33 grams after drying. The catalyst prepared in this
manner, designated as Catalyst 5, had a nominal metal content of
1.15 weight % Ir and 1.42 weight % Zn, representing, an Ir:Zn molar
ratio of 1:3.63.
Catalyst 6
[0040] The same procedure to prepare Catalyst 4 above was repeated
except that the amount of zinc iodide dissolved into 10 ml of
concentrated hydrochloric acid was 2.24 grams. The catalyst weighed
19.86 grams after drying. The catalyst prepared in this manner,
designated as Catalyst 6, had a nominal metal content of 1.12
weight % Ir and 2.31 weight % Zn, representing, an Ir:Zn molar
ratio of 1:6.05.
Catalyst 7
[0041] A catalyst in accordance with the present invention was
prepared by dissolving 418 milligrams (mg) of iridium trichloride
hydrate (53.2 weight % Ir) in 25 milliliters (ml) of distilled
water to form a first solution. A second solution was prepared by
dissolving 695 mg indium iodide in 10 ml of concentrated
hydrochloric acid. The first and second solutions were then
combined and added to 20.0 grams (g) of 12.times.40 mesh activated
carbon granules using a rotary evaporator. The mixture was heated
under a water bath at a temperature of 60.degree. C. and evacuated
under 30 Torr until the granules were dry. The mixture was then
transferred to a 106 cm long.times.25 mm (outer diameter) quartz
tube containing a quartz wool support plug. The quartz tube was
placed in a Lindberg electric furnace and heated to 300.degree. C.
over a 2 hour period in an upward flow of nitrogen a flow rate of
100 standard cubic centimeters per minute and held at 300.degree.
C. for 2 hours before cooling back to ambient temperature to obtain
the final catalyst for methanol carbonylation. The catalyst weighed
19.15 grams after drying. The catalyst prepared in this manner,
designated as Catalyst 7, had a nominal metal content of 1.16
weight % Ir and 0.84 weight % In, representing, an Ir:In molar
ratio of 1:1.21.
Catalyst 8
[0042] The same procedure to prepare Catalyst 7 above was repeated
except that the amount of indium iodide dissolved into 10 ml of
concentrated hydrochloric acid was 2.085 grams. The catalyst
weighed 20.46 grams after drying. The catalyst prepared in this
manner, designated as Catalyst 8, had a nominal metal content of
1.09 weight % Ir and 2.36 weight % In, representing, an Ir:In molar
ratio of 1:3.63.
Catalyst 9
[0043] The same procedure to prepare Catalyst 7 above was repeated
except that the amount of indium iodide dissolved into 10 ml of
concentrated hydrochloric acid was 3.475 grams. The catalyst
weighed 21.92 grams after drying. The catalyst prepared in this
manner, designated as Catalyst 9, had a nominal metal content of
1.02 weight % Ir and 3.67 weight % In, representing, an Ir:In molar
ratio of 1:6.05.
Catalyst 10
[0044] A catalyst in accordance with the present invention was
prepared by dissolving 418 milligrams (mg) of iridium trichloride
hydrate (53.2 weight % Ir) in 25 milliliters (ml) of distilled
water to form a first solution. A second solution was prepared by
dissolving 2.438 grams of germanium iodide in 10 ml of concentrated
hydrochloric acid. The first and second solutions were then
combined and added to 20.0 grams (g) of 12.times.40 mesh activated
carbon granules using a rotary evaporator. The mixture was heated
under a water bath at a temperature of 60.degree. C. and evacuated
under 30 Torr until the granules were dry. The mixture was then
transferred to a 106 cm long.times.25 mm (outer diameter) quartz
tube containing a quartz wool support plug. The quartz tube was
placed in a Lindberg electric furnace and heated to 300.degree. C.
over a 2 hour period in an upward flow of nitrogen a flow rate of
100 standard cubic centimeters per minute and held at 300.degree.
C. for 2 hours before cooling back to ambient temperature to obtain
the final catalyst for methanol carbonylation. The catalyst weighed
20.83 grams after drying. The catalyst prepared in this manner,
designated as Catalyst 10, had a nominal metal content of 1.07
weight % Ir and 1.47 weight % Ge, representing, an IrGe molar ratio
of 1:3.62.
Comparative Catalyst 1
[0045] A catalyst was prepared by dissolving 418 milligrams (mg) of
iridium trichloride hydrate (53.2 weight % Ir) in 25 milliliters
(ml) of distilled water and 10 ml of concentrated hydrochloric acid
to form a solution. The solution was then added to 20.0 grams (g)
of 12.times.40 mesh activated carbon granules using a rotary
evaporator. The mixture was heated under a water bath at a
temperature of 60.degree. C. and evacuated under 30 Torr until the
granules were dry. The mixture was then transferred to a 106 cm
long.times.25 mm (outer diameter) quartz tube containing a quartz
wool support plug. The quartz tube was placed in a Lindberg
electric furnace and heated to 300.degree. C. over a 2 hour period
in an upward flow of nitrogen a flow rate of 100 standard cubic
centimeters per minute and held at 300.degree. C. for 2 hours
before cooling back to ambient temperature to obtain the final
catalyst for methanol carbonylation. The catalyst prepared in this
manner had a metal content of approximately one (1) weight % Ir
based on the total weight of the supported catalyst.
Comparative Catalyst 2
[0046] A catalyst in accordance with the present invention was
prepared by dissolving 418 milligrams (mg) of iridium trichloride
hydrate (53.2 weight % Ir) in 25 milliliters (ml) of distilled
water to form a first solution. A second solution was prepared by
dissolving 1.099 g ruthenium iodide hydrate (RuCl.sub.3.3H.sub.2O)
in 10 ml of concentrated hydrochloric acid. The first and second
solutions were then combined and added to 20.0 grams (g) of
12.times.40 mesh activated carbon granules using a rotary
evaporator. The mixture was heated under a water bath at a
temperature of 60.degree. C. and evacuated under 30 Torr until the
granules were dry. The mixture was then transferred to a 106 cm
long.times.25 mm (outer diameter) quartz tube containing a quartz
wool support plug. The quartz tube was placed in a Lindberg
electric furnace and heated to 300.degree. C. over a 2 hour period
in an upward flow of nitrogen a flow rate of 100 standard cubic
centimeters per minute and held at 300.degree. C. for 2 hours
before cooling back to ambient temperature to obtain the final
catalyst for methanol carbonylation. The catalyst weighed 18.79
grams after drying. The catalyst prepared in this manner had a
nominal metal content of 1.19 weight % Ir and 2.26 weight % Ru,
representing, an Ir:Ru molar ratio of 1:3.63.
Carbonylation of Methanol
[0047] In the examples which follow, the reactor included a clean
Hastelloy C alloy tubing. Reactants entered the base of the reactor
via an inside diameter (I.D.) of 0.374 of an inch. The portion
above the inlet tube expanded as a conical collar piece into a
cylindrical section having an I.D. of 0.625 of an inch and an
overall length of 2.00 inches. The top 0.38 of an inch was machined
to a diameter of 0.750 of an inch. The machined portion of the
collar had an I.D. of 0.735 of an inch. A 5 micron metal filter
acted as a gas dispersion device and a support for the catalyst.
The filter and collar were welded to a 6.25 inch long.times.0.750
inch I.D. Hastelloy C alloy reaction tube. The reaction tube was
welded to an expansion zone having a conical shape and an outer
diameter of 1.50 inches, then continuing in a cylindrical
cross-section for another 1.83 inches, then decreasing at a 45
degree angle and welded to a 4.50 inch long.times.0.375 inch
outside diameter (O.D.) loading and sensing tube. The vertical
loading and sensing tube contained a 0.375 inch O.D. pressure
transducer side arm located 2.0 inches above the expanded zone and
positioned 45 degrees from vertical from the loading and sensing
tube. Vapor product was removed from the expanded zone through a
0.250 inch O.D. product removal line connected approximately half
the vertical distance of the expanded zone. The product removal
line exited the reactor horizontally and then bent downward.
[0048] Metered gas flows were maintained by Brooks 5850 Series E
mass flow controllers interfaced with a Camile.TM. 3300 Process
Monitoring and Control System. Temperature control was also
provided by the Camile. 3300 Process Monitoring and Control System.
Liquid feed was provided by an Alltech 301 HPLC pump. Liquid and
gas feeds were vaporized by feeding to a heated Hastelloy C alloy
vaporizer maintained at 150.degree. C. and transported in the vapor
phase through a transfer line at 150.degree. C. to the base of the
reactor inlet tube. Heat to the reactor was provided by three
separate split aluminum blocks with each split aluminum block
surrounded by band heaters. Each split aluminum block heating unit
had its own temperature control provided by the Camile.TM. 3300
Process Monitoring and Control System. The bottom heater provided
heat to the reactor inlet tube and collar piece. The central heater
provided heat to the reaction tube section. The top heater provided
heat to the expansion zone.
[0049] The end of the product removal line was connected to a 60
micron filter attached to a Hastelloy C alloy condenser, which was
attached to a Hastelloy C alloy product collection tank with a
working capacity of one liter. The pressure was maintained using a
Tescom Model 44-2300 back pressure regulator (BPR) attached to a
vent line on the top of product collection tank. Liquid samples
were collected from a valve at the base of the liquid collection
tank. The carbonylation products were weighed and analyzed by gas
chromatography using a Hewlett Packard Model 6890 gas chromatograph
fitted with a 30 meter.times.0.25 millimeter DB_FFAP capillary
column (0.25 micron film thickness) programmed at 40.degree. C. for
5 minutes, 25.degree. C. per minute to 240.degree. C. and holding
at 240.degree. C. for 1 minute using a thermal conductivity
detector held at 250.degree. C. (injector temperature=250.degree.
C.). Mixtures were prepared for gas chromatographic analysis by
adding 5 ml tetrahydrofuran solution containing 2 wt % decane
internal standard to an accurately weighed sample of the product
mixture.
[0050] The vent gas samples were collected using either a small gas
bomb before the BPR or a gas bag after BPR and the gas flow rate
was measured after the BPR using a Bios flow meter with an average
over five measurements. The gas analysis was done using a micro-GC
with two modules. The module A is molecular sieve 10 m.times.320
.mu.m.times.12 .mu.m and module B is Plot U 8 m.times.320
.mu.m.times.12 .mu.m. The injection and column temperature of
module A are both 100.degree. C. The injection temperature of
module B is 100.degree. C. while the column temperature is
65.degree. C.
[0051] The reactor was loaded with 10 ml of catalyst made above
through the top of the reactor. The reactor was then pressurized to
200 psig with carbon monoxide (150 standard cubic centimeters per
minute, SCCM). Then the vaporizer was set for 220.degree. C. and
the three reactor heaters were set for 190.degree. C. with CO
flowing at 150 SCCM through the base of the reactor. After the
reactor temperature had stabilized at 190.degree. C. at 200 psig, a
solution containing methanol and methyl iodide in a weight ratio of
70 methanol/30 methyl iodide was fed to the reactor system at 0.11
ml/minute while maintaining the carbon monoxide flow at 150 SCCM.
The experimental conditions were varied for each catalyst as shown
in each example.
[0052] In the following examples "Rx temp" is the reactor
temperature; "Liquid feed rate" is the reactant methanol feed rate;
"MeOH:MeI" is the molar ratio of methanol to methyl iodide in the
feed; "CO:MeOH" is the molar ratio of carbon monoxide to methanol
in the feed. MeOH conversion is defined as (methanol from feed
minus methanol remaining)/(methanol from feed).times.100%. "Acetyl
STY" is the rate of acetyl production, which is the amount (moles)
of methyl acetate and acetic acid produced per liter of catalyst
per hour. CO conversion is defined as (CO from feed-CO
remaining)/(CO from feed).times.100%. "Methane produced vs. acetyl
produced" is defined as the methane amount (moles)/total amount
(moles) of methyl acetate and acetic acid. "Molar ratio of
HOAc:MeOAc" is defined as molar ratio of acetic acid to methyl
acetate.
Example 1
[0053] The reaction conditions in which Catalyst 1 (IrGa molar
ratio of 1:1.21) was used are set forth in Tables 1 A (feed) and 1B
(product) below.
TABLE-US-00001 TABLE 1A (Feed) liquid feed Rx temp rate MeOH:MeI
CO:MeOH Run No. (.degree. C.) (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 210 0.11 10 2.83 C 190 0.11 25 2.62 D 190 0.11
25 1.22 E 190 0.22 25 1.31
TABLE-US-00002 TABLE 1B (Product) methane % Conversion produce vs
Run % Acetyl STY acetyl HOAc:MeOAc No. MeOH % CO moles/L-hr
produced molar ratio A 97.32 34 9.33 0.02 1.48 B 99.72 17 9.97 0.05
3.90 C 98.74 26 11.64 0.08 2.05 D 99.69 51 12.13 0.02 3.46 E 99.61
66 22.10 0.12 3.13
Example 2
[0054] The reaction conditions in which Catalyst 2 (IrGa molar
ratio of 1:3.63) was used are set forth in Tables 2A (feed) and 2B
(product) below.
TABLE-US-00003 TABLE 2A (Feed) liquid feed Rx temp rate MeOH:MeI
CO:MeOH Run No. (.degree. C.) (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22
TABLE-US-00004 TABLE 2B (Product) methane % Conversion produce vs
Run % Acetyl STY acetyl HOAc:MeOAc No. MeOH % CO moles/L-hr
produced molar ratio A 100 22 12.47 0.07 14.40 B 100 55 23.75 0.04
8.25 C 100 28 12.64 0.04 26.43 D 100 27 12.71 0.07 10.26 E 100 70
12.41 0.01 9.40
Example 3
[0055] The reaction conditions in which Catalyst 3 (IrGa molar
ratio of 1:5.92) was used are set forth in Tables 3A (feed) and 3B
(product) below.
TABLE-US-00005 TABLE 3A (Feed) liquid feed Rx temp rate MeOH:MeI
CO:MeOH Run No. (.degree. C.) (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00006 TABLE 3B (Product) methane % Conversion produce vs
Run % Acetyl STY acetyl HOAc:MeOAc No. MeOH % CO moles/L-hr
produced molar ratio A 100 22 13.18 0.08 105.66 B 100 61 24.31 0.05
18.04 C 100 35 12.84 0.10 48.97 D 100 31 12.91 0.08 15.95 E 100 63
12.85 0.03 8.39 F 99.68 56 22.31 0.09 4.43
Example 4
[0056] The reaction conditions in which Catalyst 4 (Ir:Zn molar
ratio of 1:1.21) was used are set forth in Tables 4A (feed) and 4B
(product) below.
TABLE-US-00007 TABLE 4A (Feed) liquid feed Run Rx temp rate
MeOH:MeI CO:MeOH No. (.degree. C.) (ml/min) molar ratio molar ratio
A 190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00008 TABLE 4B (Product) methane % Conversion produce vs
Run % Acetyl STY acetyl HOAc:MeOAc No. MeOH % CO moles/L-hr
produced molar ratio A 99.58 32 10.04 0.08 3.27 B 99.36 53 18.21
0.14 2.61 C 99.53 69 11.52 0.11 4.61 D 99.75 36 11.93 0.09 3.90 E
98.93 58 10.37 0.04 3.08 F 97.58 89 17.13 0.12 1.99
Example 5
[0057] The reaction conditions in which Catalyst 5 (Ir:Zn molar
ratio of 1:3.63) was used are set forth in Tables 5A (feed) and 5B
(product) below.
TABLE-US-00009 TABLE 5A (Feed) liquid feed Rx temp rate MeOH:MeI
CO:MeOH Run No. (.degree. C.) (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00010 TABLE 5B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 100.00 36 12.59 0.03 15.23 B 100.00 62 22.10 0.05
5.13 C 100.00 38 13.43 0.06 18.58 D 99.97 38 13.56 0.07 9.24 E
100.00 71 12.62 0.00 5.95 F 100.00 64 24.72 0.07 7.20
Example 6
[0058] The reaction conditions in which Catalyst 6 (Ir:Zn molar
ratio of 1:6.05) was used are set forth in Tables 6A (feed) and 6B
(product) below.
TABLE-US-00011 TABLE 6A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00012 TABLE 6B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 100.00 35 12.62 0.02 51.28 B 100.00 62 22.27 0.06
17.55 C 100.00 39 12.92 0.11 65.05 D 100.00 40 13.93 0.05 36.95 E
99.51 48 11.89 0.05 3.05 F 97.83 33 20.22 0.14 1.34
Example 7
[0059] The reaction conditions in which Catalyst 7 (Ir:In molar
ratio of 1:1.21) was used are set forth in Tables 7A (feed) and 7B
(product) below.
TABLE-US-00013 TABLE 7A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00014 TABLE 7B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 99.28 28 9.89 0.01 2.30 B 98.22 48 17.54 0.02 1.01 C
99.60 33 11.06 0.03 3.18 D 99.20 24 9.89 0.02 1.78 E 99.47 53 11.36
0.01 2.64 F 99.09 44 21.78 0.05 1.77
Example 8
[0060] The reaction conditions in which Catalyst 8 (Ir:In molar
ratio of 1:3.63) was used are set forth in Tables 8A (feed) and 8B
(product) below.
TABLE-US-00015 TABLE 8A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00016 TABLE 8B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 100.00 40 13.31 0.03 170.53 B 100.00 65 25.35 0.03
18.66 C 100.00 33 11.87 0.11 20.66 D 99.52 25 8.54 0.08 3.07 E
99.15 56 9.42 0.01 2.51 F 92.45 50 17.81 0.00 1.11
Example 9
[0061] The reaction conditions in which Catalyst 9 (Ir:In molar
ratio of 1:6.05) was used are set forth in Tables 9A (feed) and 9B
(product) below.
TABLE-US-00017 TABLE 9A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00018 TABLE 9B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 100.00 49 13.47 0.03 169.93 B 99.57 42 22.88 0.07
5.56 C 98.89 31 8.50 0.14 3.10 D 71.81 20 4.03 0.05 0.71 E 80.77 16
4.07 0.03 0.50 F 61.56 11 6.08 0.07 0.29
Example 10
[0062] The reaction conditions in which Catalyst 10 (IrGe molar
ratio of 1:3.62) was used are set forth in Tables 10A (feed) and
10B (product) below.
TABLE-US-00019 TABLE 10A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31
TABLE-US-00020 TABLE 10B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 96.61 26 8.92 0.02 0.89 B 91.07 36 15.33 0.08 0.72 C
98.29 14 9.46 0.02 1.42 D 96.43 21 9.60 0.03 0.91 E 95.00 45 9.08
0.03 0.77 F 82.20 27 14.53 0.11 0.43
Example 11 (Comparative)
[0063] Comparative catalyst Ir/C was utilized in the carbonylation
of methanol according to the above-described procedure. The
reaction conditions in which comparative catalyst Ir/C was used are
set forth in Table 11. Table 11 shows that the reaction rate for
catalyst of the present invention are significantly more than the
reaction rates of the Ir/C catalyst.
TABLE-US-00021 TABLE 11A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31 G 190 0.11 10
2.83
TABLE-US-00022 TABLE 11B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 95.58 14 8.05 0.02 0.77 B 88.03 29 14.01 0.07 0.49 C
95.56 17 8.51 0.06 1.01 D 92.73 18 8.82 0.05 0.99 E 85.77 30 7.00
0.03 0.32 F 84.26 35 13.78 0.28 0.46 G 59.71 8 3.97 0.27 0.15
Example 12 (Comparative)
[0064] Comparative catalyst Ir/Ru/C (molar ratio of Ir:Ru 1:3.63)
was utilized in the carbonylation of methanol according to the
above-described procedure. The reaction conditions in which
comparative catalyst Ir/Ru/C was used are set forth in Table 12.
Table 12 shows that the rate of reaction of the catalyst of the
present invention is significantly more than the reaction rates of
the Ir/Ru/C catalyst.
TABLE-US-00023 TABLE 12A (Feed) Run Rx temp liquid feed MeOH:MeI
CO:MeOH No. (.degree. C.) rate (ml/min) molar ratio molar ratio A
190 0.11 10 2.83 B 190 0.22 10 1.42 C 210 0.11 10 2.83 D 190 0.11
25 2.62 E 190 0.11 25 1.22 F 190 0.22 25 1.31 G 190 0.11 10
2.83
TABLE-US-00024 TABLE 12B (Product) methane produce Run % Conversion
Acetyl STY vs acetyl HOAc:MeOAc No. % MeOH % CO moles/L-hr produced
molar ratio A 99.76 16 11.73 0.01 4.88 B 98.66 27 17.64 0.02 1.64 C
99.86 19 8.56 0.04 5.80 D 99.81 13 10.07 0.02 3.81 E 99.65 35 10.34
0.01 3.03 F 98.58 36 18.33 0.04 1.43 G 99.92 15 8.62 0.02 5.81
Example 13
[0065] Example 13 demonstrates the longevity of the catalyst of the
present invention. Four parallel fixed bed reactors were designed
for catalyst life time study. Each reactor system includes a gas
feed manifold, a feed pre-heater, a reactor, a condenser for
separation of liquid and gas product, and operates independently.
They were designed to operate at a maximum temperature of
400.degree. C. and a maximum pressure of 450 psig. The whole
reactor system is controlled by a distributive control system. This
system controls the temperature, feed rates, gases, and other
parameters on the system as whole.
[0066] The reactor was constructed entirely of Hastelloy C alloy.
Reactants entered the base of the reactor via a 0.375 inch (9.5 mm)
outer diameter (O.D.) inlet tube having a wall thickness of 0.035
inch. Metered gas flows were maintained by Brooks 5850 Series E
mass flow controllers interfaced with a distributive control
system. Temperature control was also provided by the distributive
control system. Liquid feed was provided by an Alltech 301 HPLC
pump. Liquid and gas feeds were vaporized by feeding to a heated
Hastelloy C alloy vaporizer maintained at 190.degree. C. and
transported in the vapor phase through a transfer line at
180.degree. C. to the base of the reactor inlet tube. Heat to the
reactor was provided by the aluminum block surrounded by the band
heater. The aluminum block heating unit had its own temperature
control provided by the distributive control system. The portion of
the product removal line above the reactor was heat traced with
heat tape at 180.degree. C.
[0067] The end of the product removal line was connected to a 60
micron filter attached to a Hastelloy C alloy condenser, which was
attached to a Hastelloy C alloy product collection tank with a
working capacity of 1 liter. The pressure was maintained using a
backpressure regulator attached to a vent line on the top of
product collection tank. Liquid samples were collected from a valve
at the base of the liquid collection tank. The carbonylation
products were weighed and analyzed by gas chromatography as in
previous examples.
[0068] One of the parallel reactors was loaded with 2 ml of
catalyst through the top of the reactor. The reactor was then
pressurized to 200 psig with carbon monoxide (150 SCCM). Then the
vaporizer was set for 190.degree. C. and the reactor heater was set
for 190.degree. C. with CO flowing at 150 SCCM through the base of
the reactor. After the reactor temperature had stabilized at
190.degree. C. at 200 psig, a solution containing 1 weight % methyl
iodide in methanol was fed to the reactor system at 0.02 ml/minute
while maintaining the carbon monoxide flow at 30 SCCM. One sample
per day was taken. The life time of Ir--Ga/C catalyst with 0.75
weight % Ir and a molar ratio of IrGa of 1.3 was examined for 700
hours. The acetyl space time yield vs. time on stream was shown in
the FIG. 1. The catalyst was tested at 200.degree. C. in the first
350 hours and then tested at 240.degree. C. for the rest time on
stream.
[0069] The preferred forms of the invention described above are to
be used as illustration only, and should not be used in a limiting
sense to interpret the scope of the present invention. Obvious
modifications to the exemplary one embodiment, set forth above,
could be readily made by those skilled in the art without departing
from the spirit of the present invention.
* * * * *