U.S. patent application number 14/585884 was filed with the patent office on 2016-06-30 for methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol.
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 William Norman, Jonathan Michael Penney, Andrew James Vetter.
Application Number | 20160185700 14/585884 |
Document ID | / |
Family ID | 56100436 |
Filed Date | 2016-06-30 |
United States Patent
Application |
20160185700 |
Kind Code |
A1 |
Penney; Jonathan Michael ;
et al. |
June 30, 2016 |
METHYL-IODIDE-FREE CARBONYLATION OF AN ALCOHOL TO ITS HOMOLOGOUS
ALDEHYDE AND/OR ALCOHOL
Abstract
Disclosed is a process for the reductive carbonylation of a low
molecular weight alcohol to produce the homologous aldehyde and/or
alcohol. The process includes conducting the reaction to produce
the aldehyde in the presence of a single component catalyst complex
composed of cobalt, an onium cation and iodide in a ratio of 1:2:4
without additional promoters. A ruthenium co-catalyst is used in
the production of the homologous alcohol. The reductive
carbonylation reaction does not require an additional iodide
promoter and produces a crude reductive carbonylation product
substantially free of methyl iodide.
Inventors: |
Penney; Jonathan Michael;
(Gray, TN) ; Norman; David William; (Cary, NC)
; Vetter; Andrew James; (Kingsport, TN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
EASTMAN CHEMICAL COMPANY |
Kingsport |
TN |
US |
|
|
Assignee: |
EASTMAN CHEMICAL COMPANY
Kingsport
TN
|
Family ID: |
56100436 |
Appl. No.: |
14/585884 |
Filed: |
December 30, 2014 |
Current U.S.
Class: |
568/487 ;
568/885 |
Current CPC
Class: |
B01J 27/128 20130101;
C07C 29/32 20130101; B01J 31/0268 20130101; C07C 51/12 20130101;
B01J 2231/321 20130101; C07C 51/12 20130101; B01J 31/20 20130101;
B01J 31/0239 20130101; C07C 45/49 20130101; B01J 2531/821 20130101;
C07C 45/49 20130101; C07C 53/08 20130101; C07C 47/06 20130101; C07C
31/08 20130101; C07C 29/32 20130101 |
International
Class: |
C07C 45/49 20060101
C07C045/49; B01J 31/24 20060101 B01J031/24; B01J 31/22 20060101
B01J031/22; C07C 29/157 20060101 C07C029/157; B01J 27/128 20060101
B01J027/128 |
Claims
1.-15. (canceled)
16. A process for the preparation of a crude reductive
carbonylation product comprising contacting hydrogen, carbon
monoxide, and an alcohol having 1 to 3 carbon atoms in the presence
of a catalyst to form said crude reductive carbonylation product
comprising homologous alcohol equivalents in a higher mole percent
than homologous aldehyde equivalents or homologous acid
equivalents, each based on the total moles of said homologous
aldehyde equivalents, said homologous acid equivalents, and said
homologous alcohol equivalents; wherein said catalyst comprises a
complex of cobalt, iodide, and an onium cation or alkali metal
cation of the general formula Y.sub.2CoI.sub.4; wherein Y is said
onium cation or alkali metal cation and said onium cation is of the
general formula (I) or (II) ##STR00012## wherein X is phosphorus
(P), R.sup.1 is methyl, and R.sup.2, R.sup.3, and R.sup.4 are
independently selected from alkyl having up to 12 carbons and aryl,
wherein said aryl is selected from only one of the group consisting
of phenyl, tolyl, xylyl, and mesityl; R.sup.5 is methyl and
R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen;
further comprising a ruthenium co-catalyst; and wherein said crude
reductive carbonylation product comprises less than 1 weight
percent of methyl iodide, based on the total weight of said crude
reductive carbonylation product.
17. The process according to claim 16, wherein said alcohol
comprises methanol, the CO:H2 molar ratio ranges from 1:1 to 1:10,
and said process is carried out at a temperature ranging from
100.degree. C. to 250.degree. C. and a pressure ranging from 100
kPa (15 psig) to 60 MPa (8700 psig), and wherein said crude
reductive carbonylation product comprises ethanol equivalents in a
higher mole percent than acetaldehyde equivalents or acetic acid
equivalents, each based on the total moles of acetaldehyde
equivalents, acetic acid equivalents, and ethanol equivalents.
18. The process according to claim 16, wherein said alcohol
comprises ethanol, the CO:H2 molar ratio ranges from 1:1 to 1:10,
said process is carried out at a temperature ranging from
100.degree. C. to 250.degree. C. and a pressure ranging from 100
kPa (15 psig) to 60 MPa (8700 psig), and wherein said crude
reductive carbonylation product comprises n-propanol equivalents in
a higher mole percent than n-propionaldehyde equivalents or
n-propionic acid equivalents, each based on the total moles of
n-propionaldehyde equivalents, n-propionic acid equivalents, and
n-propanol equivalents.
19. The process according to claim 16, wherein said alcohol
comprises n-propanol, the CO:H2 molar ratio ranges from 1:1 to 1:0,
said process is carried out at a temperature ranging from
100.degree. C. to 250.degree. C. and a pressure ranging from 100
kPa (15 psig) to 60 MPa (8700 psig) and wherein said crude
reductive carbonylation product comprises n-butanol equivalents in
a higher mole percent than n-butyraldehyde equivalents or n-butyric
acid equivalents, each based on the total moles of n-butyraldehyde
equivalents, n-butyric acid equivalents, and n-butanol
equivalents.
20. The process according to claim 16, wherein said contacting
further occurs in the presence of a solvent selected from the group
consisting of toluene, heptane, cyclohexane, ethylbenzene, diethyl
ether, and 4-methylanisole.
21. The process according to claim 17, wherein and said process is
carried out at a temperature ranging from 150.degree. C. to
230.degree. C. and a pressure ranging from 1 MPa (150 psig) to 40
MPa (5800 psig); said catalyst is selected from the group
consisting of bis(methyltriphenylphosphonium) cobalt tetraiodide,
bis(methyltributylphosphonium) cobalt tetraiodide,
bis(methyltrioctylphosphonium), and bis(1-methylpyridinium) cobalt
tetraiodide; and wherein said co-catalyst is selected from the
group consisting of triruthenium dodecacarbonyl,
1,1,1-tris(diphenylphosphinomethyl)ethane ruthenium dicarbonyl, and
ruthenium(IV)oxide hydrate.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a process for the reductive
carbonylation of a low molecular weight alcohol to produce the
homologous aldehyde and/or alcohol. For example, this invention
relates to a process for the reductive carbonylation of methanol,
hydrogen, and carbon monoxide to form acetaldehyde, and/or ethanol.
The invention relates to the reductive carbonylation of a low
molecular weight alcohol without the need to use methyl iodide as a
co-catalyst. Specifically the invention relates to a process
comprising conducting the reductive carbonylation reaction in the
presence of a single component catalyst complex composed of cobalt,
an onium cation, and iodide such that there is less than one weight
percent methyl iodide in the crude reductive carbonylation
product.
BACKGROUND OF THE INVENTION
[0002] Cobalt can catalyze the formation of acetaldehyde from
methanol, carbon monoxide, and hydrogen, a reaction known as
methanol reductive carbonylation. For example, it was disclosed by
Wender et al., Science, 113, (1951), 206-7 that a cobalt carbonyl
catalyst system could be used. However, the product of the
disclosed process was primarily ethanol, together with a small
amount of acetaldehyde. It was later shown that the addition of
iodide to a cobalt-containing catalyst system increased the amount
of acetaldehyde produced. Iodide is typically added as a
co-catalyst (also commonly referred to as a promoter) to the
reaction in a form such as hydrogen iodide (a strong acid), methyl
iodide, elemental iodine, or as an iodide salt such as lithium
iodide or sodium iodide.
[0003] Homologation of methanol to ethanol can be achieved by
addition of a hydrogenation catalyst, typically ruthenium based, to
a reductive carbonylation system. For example, Mizoroki, et al.,
Bull. Chem. Soc. Japan, 52, (1979), 479-482, have described a
catalyst system containing a cobalt compound, a ruthenium compound
and methyl iodide to convert methanol to ethanol with 77%
selectivity.
[0004] Addition of iodide co-catalysts in these reactions often
leads to formation of dimethyl ether as well as free methyl iodide
in the crude reductive carbonylation product. Methyl iodide is an
undesirable co-product due to the difficulty in separating it from
the aldehyde and/or alcohol product as well as its toxicity.
Current methanol carbonylation processes carefully balance the
amount of iodide containing compounds added to the reaction to
obtain optimized reaction rate and conversion while limiting
dimethyl ether and methyl iodide formation.
[0005] There is a need for an improved catalyst system which will
allow reasonable reductive carbonylation reaction rates as well as
little to no methyl iodide in the crude reductive carbonylation
product. Additionally there is a need to readily influence the
relative amounts of aldehyde and/or alcohol produced in a reductive
carbonylation reaction to maximize the desired product profile.
[0006] There is also a need for an inexpensive catalyst for the
reductive carbonylation of alcohol that can replace the typical
rhodium catalyst or iridium/ruthenium catalyst while producing a
substantially methyl iodide free crude reductive carbonylation
product.
SUMMARY OF THE INVENTION
[0007] The present invention provides in a first embodiment a
process for the preparation of a crude reductive carbonylation
product comprising contacting hydrogen, carbon monoxide, and an
alcohol having 1 to 3 carbon atoms in the presence of a catalyst to
form the crude reductive carbonylation product. The crude reductive
carbonylation product comprises homologous aldehyde equivalents in
a higher mole percent than homologous acid equivalents or
homologous alcohol equivalents, each based on the total moles of
the homologous aldehyde equivalents, homologous acid equivalents,
and homologous alcohol equivalents. The catalyst comprises a
complex of cobalt, iodide, and an onium cation or an alkali metal
cation of the general formula Y.sub.2CoI.sub.4, where Y represents
the onium cation or the alkali metal cation. The onium cation is of
the general formula (I) or (II)
##STR00001##
[0008] For formula (I), X can be phosphorus (P) or nitrogen (N) and
R.sup.1 is methyl. R.sup.2, R.sup.3, and R.sup.4 are independently
selected from alkyl having up to 12 carbons and aryl. When R.sup.2,
R.sup.3, and/or R.sup.4 are aryl, each aryl is the same, and can be
phenyl, tolyl, xylyl, or mesityl. For formula (II), R.sup.5 is
methyl and R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are
hydrogen. The crude reductive carbonylation product comprises less
than 1 weight percent of methyl iodide.
[0009] The present invention provides in a second embodiment a
process for the preparation of a crude reductive carbonylation
product comprising contacting hydrogen, carbon monoxide, and
methanol in the presence of a catalyst to form the crude reductive
carbonylation product. The crude reductive carbonylation product
comprises acetaldehyde equivalents in a higher mole percent than
acetic acid equivalents or ethanol equivalents, each based on the
total moles of the acetaldehyde equivalents, acetic acid
equivalents, and ethanol equivalents. The catalyst comprises a
complex of cobalt, iodide, and an onium cation or an alkali metal
cation of the general formula Y.sub.2CoI.sub.4, where Y represents
the onium cation or the alkali metal cation. The onium cation is of
the general formula (I) or (II)
##STR00002##
[0010] For formula (I), X is phosphorus (P) and R.sup.1 is methyl.
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each aryl is the same, and can be phenyl, tolyl,
xylyl, or mesityl. For formula (II), R.sup.5 is methyl and R.sup.6,
R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen. The crude
reductive carbonylation product comprises less than 1 weight
percent of methyl iodide.
[0011] The present invention provides in a third embodiment a
process for the preparation of a crude reductive carbonylation
product comprising contacting hydrogen, carbon monoxide, and an
alcohol having 1 to 3 carbon atoms in the presence of a catalyst to
form the crude reductive carbonylation product. The crude reductive
carbonylation product comprises homologous alcohol equivalents in a
higher mole percent than homologous aldehyde equivalents or
homologous acid equivalents, each based on the total moles of the
homologous aldehyde equivalents, homologous acid equivalents, and
homologous alcohol equivalents. The catalyst comprises a complex of
cobalt, iodide and an onium cation or an alkali metal cation of the
general formula Y.sub.2CoI.sub.4, where Y represents the onium
cation or the alkali metal cation. The onium cation is of the
general formula (I) or (II)
##STR00003##
[0012] For formula (I), X is phosphorus (P) and R.sup.1 is methyl.
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each will be the same, and be phenyl, tolyl,
xylyl, or mesityl. For formula (II), R.sup.5 is methyl and R.sup.6,
R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen. The process
further comprises a ruthenium co-catalyst. The crude reductive
carbonylation product comprises less than 1 weight percent of
methyl iodide.
DETAILED DESCRIPTION
[0013] The present invention provides in a first embodiment a
process for the preparation of a crude reductive carbonylation
product comprising contacting hydrogen, carbon monoxide, and an
alcohol having 1 to 3 carbon atoms in the presence of a catalyst to
form the crude reductive carbonylation product. The crude reductive
carbonylation product comprises homologous aldehyde equivalents in
a higher mole percent than homologous acid equivalents or
homologous alcohol equivalents, each based on the total moles of
the homologous aldehyde equivalents, homologous acid equivalents,
and homologous alcohol equivalents. The catalyst comprises a
complex of cobalt, iodide and an onium cation or an alkali metal
cation of the general formula Y.sub.2CoI.sub.4, where Y represents
the onium cation or the alkali metal cation. The onium cation is of
the general formula (I) or (II)
##STR00004##
[0014] For formula (I), X can be phosphorus (P) or nitrogen (N) and
R.sup.1 is methyl. R.sup.2, R.sup.3, and R.sup.4 are independently
selected from alkyl having up to 12 carbons and aryl. When R.sup.2,
R.sup.3, and/or R.sup.4 are aryl, each aryl is the same, and can be
phenyl, tolyl, xylyl, or mesityl. For formula (II), R.sup.5 is
methyl and R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are
hydrogen. The crude reductive carbonylation product comprises less
than 1 weight percent of methyl iodide.
[0015] Unless otherwise indicated, all numbers expressing
quantities of ingredients, properties such as molecular weight,
reaction conditions, and so forth used in the specification and
claims are to be understood as being modified in all instances by
the term "about." Accordingly, unless indicated to the contrary,
the numerical parameters set forth in the following specification
and attached claims are approximations that may vary depending upon
the desired properties sought to be obtained by the present
invention. At the very least, each numerical parameter should at
least be construed in light of the number of reported significant
digits and by applying ordinary rounding techniques. Further, the
ranges stated in this disclosure and the claims are intended to
include the entire range specifically and not just the endpoint(s).
For example, a range stated to be 0 to 10 is intended to disclose
all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4,
etc., all fractional numbers between 0 and 10, for example 1.5,
2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10. Also, a range
associated with chemical substituent groups such as, for example,
"C.sub.1 to C.sub.5 hydrocarbons", is intended to specifically
include and disclose C.sub.1 and C.sub.5 hydrocarbons as well as
C.sub.2, C.sub.3, and C.sub.4 hydrocarbons.
[0016] Notwithstanding that the numerical ranges and parameters
setting forth the broad scope of the invention are approximations,
the numerical values set forth in the specific examples are
reported as precisely as possible. Any numerical value, however,
inherently contains certain errors necessarily resulting from the
standard deviation found in their respective testing
measurements.
[0017] As used herein, the singular forms "a", "an", and "the"
include plural referents unless the context clearly dictates
otherwise. For example, reference to a complex of cobalt iodide and
an onium cation is intended to include multiple complexes of cobalt
iodide and onium cations.
[0018] It is to be understood that the mention of one or more
process steps does not preclude the presence of additional process
steps before or after the combined recited steps or intervening
process steps between those steps expressly identified. Moreover,
the lettering of process steps or ingredients is a convenient means
for identifying discrete activities or ingredients and the recited
lettering can be arranged in any sequence, unless otherwise
indicated.
[0019] As used herein the term "and/or", when used in a list of two
or more items, means that any one of the listed items can be
employed by itself, or any combination of two or more of the listed
items can be employed. For example, if a composition is described
as containing components A, B, and/or C, the composition can
contain A alone; B alone; C alone; A and B in combination; A and C
in combination; B and C in combination; or A, B, and C in
combination.
[0020] The term "crude reductive carbonylation product", as used
herein, refers to the reaction products of carbon monoxide, an
alcohol, and hydrogen. The crude reductive carbonylation product
comprises the many different compounds produced under carbonylation
conditions. The crude reductive carbonylation product is the liquid
effluent directly exiting the carbonylation reactor, before any
separation of the homogeneous catalyst or other liquid compounds.
The crude reductive carbonylation product comprises the homologous
aldehyde, homologous acid, and/or homologous alcohol, unreacted
feed, and other byproducts, as well as the catalyst.
[0021] The term "catalyst", as used herein, has its typical meaning
to one skilled in the art as a substance that increases the rate of
chemical reactions without being consumed.
[0022] The term "complex", "coordination complex" and "metal
complex" as used herein, are equivalent terms which have their
typical meaning to one skilled in the art as a metal ion and a
surrounding array of bound molecules.
[0023] The term "homologous aldehyde", as used herein, refers to an
aldehyde containing one more carbon atom than the alcohol used to
produce it. For example, n-propionaldehyde is the homologous
aldehyde of ethanol reductive carbonylation. The term "homologous
aldehyde equivalents", as used herein refers to the common products
and byproducts containing at least one aldehyde group. The specific
homologous aldehyde equivalents for methanol, ethanol, and propanol
reductive carbonylation are given in the specification.
[0024] The term "homologous acid", as used herein, refers to an
acid containing one more carbon atom than the alcohol used to
produce it. For example, n-propionic acid is the homologous acid of
ethanol reductive carbonylation. The term "homologous acid
equivalents", as used herein refers to the common products and
byproducts containing at least one acid group. The specific
homologous acid equivalents for methanol, ethanol, and propanol
reductive carbonylation are given in the specification.
[0025] The term "homologous alcohol", as used herein, refers to an
alcohol containing one more carbon atom than the alcohol used to
produce it. For example, n-propanol is the homologous alcohol of
ethanol reductive carbonylation. The term "homologous alcohol
equivalents", as used herein refers to the common products and
byproducts containing at least one alcohol group. The specific
homologous alcohol equivalents for methanol, ethanol, and propanol
reductive carbonylation are given in the specification.
[0026] The term "onium cation", as used herein, refers to a cation
selected from quaternary atoms or radicals such as quaternary
ammonium, quaternary phosphonium, trialkyl sulfonium, and alkylated
sulfoxide. The onium cation can also be of N-alkylated pyridinium.
The term "onium salt", as used herein refers to a salt containing
an onium cation. One skilled in the art will recognize that the
disclosure of any onium salt necessarily and simultaneously
discloses the corresponding onium cation.
[0027] The term "alkali metal cation", as used herein, refers to a
group one element of the periodic table excluding hydrogen having
at least one more proton than electron.
[0028] The term "higher mole percent" as used herein, refers to a
larger number of moles of one component than another component in a
mixture. For example, if a crude reductive carbonylation product
contains 60 mole percent acetaldehyde equivalents, 30 mole percent
acetic acid equivalents, and 10 mole percent ethanol equivalents,
on a total acetaldehyde equivalents, acetic acid equivalents, and
ethanol equivalents basis, then the crude reductive carbonylation
product has a higher mole percent of acetaldehyde equivalents than
either of acetic acid equivalents or ethanol equivalents. In the
specific example, the crude reductive carbonylation product has
(60-30) 30 mole percent higher acetaldehyde equivalents than acetic
acid equivalents and (60-10) 50 mole percent higher acetaldehyde
equivalents and ethanol equivalents.
[0029] The term "co-catalyst" as used herein, refers to a second
catalyst which impacts the reaction rate and/or the selectivity to
a given product.
[0030] The alcohol contacted with carbon monoxide and hydrogen in
the process is an alcohol having 1 to 3 carbon atoms. In one
aspect, the alcohol is selected from the group consisting of
methanol, ethanol, and n-propanol. In another aspect the alcohol
comprises methanol. In another aspect the alcohol comprises
ethanol. In yet another aspect the alcohol comprises
n-propanol.
[0031] In one aspect, the crude reductive carbonylation product
comprises homologous aldehyde equivalents in a higher mole percent
than homologous acid equivalents or homologous alcohol equivalents
from the reaction of carbon monoxide, hydrogen, and the alcohol. In
one aspect the alcohol comprises methanol and the crude reductive
carbonylation product comprises acetaldehyde equivalents in a
higher mole percent than acetic acid equivalents or ethanol
equivalents, each based on the total moles of acetaldehyde
equivalents, acetic acid equivalents, and ethanol equivalents. In
one aspect, the alcohol comprises ethanol and the crude reductive
carbonylation product comprises n-propionaldehyde equivalents in a
higher mole percent than n-propionic acid equivalents or n-propanol
equivalents, each based on the total moles of n-propionaldehyde
equivalents, n-propionic acid equivalents, and n-propanol
equivalents. In one aspect, the alcohol comprises n-propanol and
the crude reductive carbonylation product comprises n-butyraldehyde
equivalents in a higher mole percent than n-butyric acid
equivalents, or n-butanol equivalents, each based on the total
moles of n-butyraldehyde equivalents, n-butyric acid equivalents,
and n-butanol equivalents.
[0032] The total moles of homologous aldehyde equivalents are
determined as the sum of the moles of reductive carbonylation
product compounds that have at least one aldehyde group, with the
number of moles of each compound multiplied by the number of
aldehyde groups in the compound. For example, when methanol is
carbonylated, the total moles of homologous aldehyde equivalents
are the sum of the moles Acetaldehyde+3*moles Paraldehyde+moles
Acetaldehyde dimethyl acetal+moles Acetaldehyde methyl ethyl
acetal+moles Acetaldehyde diethyl acetal. The total moles of
homologous acid equivalents and homologous alcohol equivalents are
determined in the same manner. The homologous aldehyde equivalents,
homologous acid equivalents, and homologous alcohol equivalents for
methanol, ethanol, and n-propanol reductive carbonylation are
listed below.
[0033] For methanol reductive carbonylation, homologous aldehyde
equivalents, homologous acid equivalents, and homologous alcohol
equivalents--acetaldehyde equivalents, acetic acid equivalents, and
ethanol equivalents--are given below.
TABLE-US-00001 Acetaldehyde Acetic Acid Ethanol Equivalents
Equivalents Equivalents Acetaldehyde Acetic acid Ethanol
Acetaldehyde Methyl Acetaldehyde dimethyl acetal acetate diethyl
acetal Acetaldehyde Ethyl Acetaldehyde methyl ethyl acetate methyl
ethyl acetal acetal Acetaldehyde Diethyl ether diethyl acetal
Methyl ethyl Paraldehyde ether Ethyl acetate
[0034] For ethanol reductive carbonylation, homologous aldehyde
equivalents, homologous acid equivalents, and homologous alcohol
equivalents--n-propionaldehyde equivalents, n-propionic acid
equivalents, and n-propanol equivalents--are given below.
TABLE-US-00002 Propionic Propionaldehyde Acid Propanol Equivalents
Equivalents Equivalents Propionaldehyde Propionic 1-Propanol
Propionaldehyde acid Propionaldehyde diethyl acetal Ethyl
di-n-propyl Propionaldehyde propionate acetal n-propyl ethyl Propyl
Propionaldehyde acetal propionate n-propyl ethyl Propionaldehyde
acetal di-n-propyl acetal Di-n-propyl ether 2,4,6-triethyl-
n-Propyl ethyl 1,3,5-trioxane ether n-Propyl propionate
[0035] For n-propanol reductive carbonylation, homologous aldehyde
equivalents, homologous acid equivalents, and homologous alcohol
equivalents--n-butyraldehyde equivalents, n-butyric acid
equivalents, and n-butanol equivalents--are given below.
TABLE-US-00003 Butyraldehyde Butyric Acid Butanol Equivalents
Equivalents Equivalents n-Butyraldehyde n-Butyric 1-Butanol
n-Butyraldehyde acid n- di-n-propyl acetal n-Propyl Butyraldehyde
n-Butyraldehyde butyrate di-n-butyl n-butyl n-propyl n-Butyl acetal
acetal butyrate n- n-Butyraldehyde Butyraldehyde di-n-butyl acetal
n-butyl n- 2,4,6-tripropyl- propyl acetal 1,3,5-trioxane Di-n-butyl
ether n-Butyl n- propyl ether n-Butyl butyrate
[0036] The hydrogen and carbon monoxide contacted with an alcohol
can be obtained from typical sources that are well known in the
art. For example, the carbon monoxide and hydrogen can be provided
by any of a number of methods known in the art including steam or
carbon dioxide reforming of carbonaceous materials such as natural
gas or petroleum derivatives; partial oxidation or gasification of
carbonaceous materials, residuum, bituminous, sub bituminous, and
anthracitic coals and cokes; lignite; oil shale; oil sands; peat;
biomass; petroleum refining residues of cokes; and the like. For
example, the carbon monoxide can be provided to the reaction
mixture as a component of synthesis gas or "syngas", comprising
carbon dioxide, carbon monoxide, and hydrogen. The hydrogen and
carbon monoxide can be mixed together before the contacting, or a
stream of hydrogen and a separate stream of carbon monoxide can be
contacted with the alcohol.
[0037] The molar ratio of carbon monoxide to hydrogen (CO:H2) can
vary over a wide range. For example, CO:H2, can range from 50:1 to
1:50. In other examples, CO:H2 can range from 10:1 to 1:10 or 5:1
to 1:5 or 3:1 to 1:3 or 2:1 to 1:2 or 10:1 to 1:1 or 5:1 to 1:1 or
2:1 to 1:1 or 2:1 to 1:5 or 1:1 to 1:5 or 1:1 to 1:10.
[0038] The hydrogen, carbon monoxide, and alcohol are contacted in
the presence of a catalyst to form the crude reductive
carbonylation product. The catalyst comprises a complex of cobalt,
iodide, and an onium cation or an alkali metal cation of the
general formula Y.sub.2CoI.sub.4, where Y is an onium cation or an
alkali metal cation. The catalyst complex can be readily
synthesized by those skilled in the art. For example, an onium
iodide salt or alkali metal iodide salt can be reacted with
cobalt(II) iodide as illustrated in the reaction below.
2Y.sup.+I.sup.-+CoI.sub.2(Y.sup.+).sub.2[CoI.sub.4].sup.2-
[0039] When an onium salt is used to produce the catalyst, the
onium salt can comprise an onium cation selected from quaternary
atoms or radicals such as quaternary ammonium, quaternary
phosphonium, trialkyl sulfonium, and alkylated sulfoxide. The onium
salt compound can be functional and includes protonated forms of
the atoms or radicals, especially protonated forms of various
tertiary amines and tertiary phosphines. The onium salt can contain
any number of carbon atoms, e.g., up to about 60 carbon atoms, and
also can contain one or more heteroatoms. The tri- and tetra-alkyl
quaternary ammonium and phosphonium salts typically contain a total
of about 5 to 40 carbon atoms. One skilled in the art understands
that the listing of the onium salts simultaneously gives a listing
of the onium cations (e.g., if onium salt
methyltriphenylphosphonium iodide is disclosed, then onium cation
methyltriphenylphosphonium is also disclosed).
[0040] Examples of an alkali metal cation include cations of
lithium, sodium, potassium, rubidium and cesium. In one aspect, the
alkali metal cation can be lithium, sodium, potassium, rubidium, or
cesium. In another aspect, the alkali metal cation can be lithium,
sodium, or potassium.
[0041] Examples of quaternary ammonium and phosphonium salts
include salts having onium cations of the general formula (I)
##STR00005##
[0042] wherein X can be phosphorus (P) or nitrogen (N) and wherein
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected
from substituted or unsubstituted alkyl having up to 20 carbon
atoms, substituted or unsubstituted cycloalkyl having 5 to 20
carbon atoms, or substituted or unsubstituted aryl having 6 to 20
carbon atoms.
[0043] In one aspect, X is selected from phosphorus (P) and
nitrogen (N), R.sup.1 is methyl, and R.sup.2, R.sup.3, and R.sup.4
are independently selected from alkyl having up to 12 carbons and
aryl. When R.sup.2, R.sup.3, and/or R.sup.4 are aryl, the aryl is
selected from only one of the group consisting of phenyl, tolyl,
xylyl, and mesityl.
[0044] The quaternary ammonium salts can also be selected from
salts of aromatic, heterocyclic onium cations having the general
formula (II) or (III)
##STR00006##
[0045] wherein at least one ring atom is a quaternary nitrogen atom
and R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.12,
R.sup.14, and R.sup.15 are independently selected from hydrogen,
substituted or unsubstituted alkyl having up to 20 carbon atoms,
substituted or unsubstituted cycloalkyl having 5 to 20 carbon
atoms, and substituted or unsubstituted aryl having 6 to 20 carbon
atoms; and R.sup.5, R.sup.11, and R.sup.13 are independently
selected from substituted or unsubstituted alkyl having up to 20
carbon atoms, substituted or unsubstituted cycloalkyl having 5 to
20 carbon atoms, and substituted or unsubstituted aryl having about
6 to about 20 carbon atoms. In one aspect, R.sup.5 is methyl and
R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen.
[0046] Examples of specific ammonium salts include
tetrapentylammonium iodide, tetrahexylammonium iodide,
tetraoctyl-ammonium iodide, tetradecylammonium iodide,
tetradodecylammonium iodide, tetrapropylammonium iodide,
tetrabutylammonium iodide, methyltrioctylammonium iodide,
methyltributylammonium iodide, N-octyl-quinuclidinium iodide,
N,N'-dimethyl-N,N'-dihexadecylpiperazinium diiodide,
dimethyl-hexadecyl-[3-pyrrolidinylpropyl]ammonium iodide,
N,N,N,N',N',N'-hexa(dodecyl)octane-1,8-diammonium diiodide,
N,N,N,N',N',N'-hexa(do-decyl)butane-1,4-diammonium diiodide;
imidazolium iodides such as 1-butyl-3-methylimidazolium iodide,
1,3-dimethylimidazolium iodide, 1,3,4-trimethyl-imidazolium iodide,
1,2,3,4,5-pentamethylimidazolium iodide; pyridinium iodides such as
N-octylpyridinium iodide, N-methylpyridinium iodide,
N-methyl-2-picolinium iodide, N-methyl-3-picolinium iodide,
N-methyl-4-picolinium iodide, N-methyl-5-ethyl-2-methyl-pyridinium
iodide, N-methyl-3,4-lutidinium iodide; N-methyl quinolinium
iodide, N-methyl isoquinolinium iodide or mixtures thereof.
Preferred quaternary ammonium iodides include
1-butyl-3-methylimidizolium iodide, N-methyl pyridinium iodide,
N-methyl-2-methyl pyridinium iodide, N-methyl-3-methyl pyridinium
iodide, N-methyl-4-methyl pyridinium iodide, and
1,3-dimethylimidazolium iodide.
[0047] Exemplary phosphonium salts include tetraoctylphosphonium
iodide, tetrabutylphosphonium iodide, triphenyl(hexyl)phosphonium
iodide, triphenyl(octyl)phosphonium iodide,
tribenzyl(octyl)phosphonium iodide, tribenzyl(dodecyl)phosphonium
iodide, triphenyl(decyl)phosphonium iodide,
triphenyl(dodecyl)phosphonium iodide,
tetrakis(2-methylpropyl)phosphonium iodide,
tris(2-methylpropyl)(butyl)phosphonium iodide,
triphenyl(3,3-dimethylbutyl)phosphonium iodide,
triphenyl(3-methylbutyl)phosphonium iodide,
tris(2-methylbutyl)(3-methylbutyl)phosphonium iodide,
triphenyl[2-trimethylsilylethyl]phosphonium iodide,
tris(p-chlorophenyl)-(dodecyl)phosphonium iodide,
hexyltris(2,4,6-trimethylphenyl)phosphonium iodide,
tetradecyltris(2,4,6-trimethylphenyl)phosphonium iodide,
dodecyltris(2,4,6-trimethylphenyl)phosphonium iodide,
methyltrioctylphosphonium iodide, methyltributylphosphonium iodide,
methyl-tricyclohexylphosphonium iodide, and the like. Preferred
phosphonium iodides include methyltriphenylphosphonium iodide,
methyltributylphosphonium iodide, and methyltrioctylphosphonium
iodide.
[0048] In one aspect, the onium cation can be of the general
formula (I) or (II)
##STR00007##
[0049] X is phosphorus (P), R.sup.1 is methyl, and R.sup.2,
R.sup.3, and R.sup.4 are independently selected from alkyl having
up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or R.sup.4
are aryl, the aryl groups are the same and can be phenyl, tolyl,
xylyl, or mesityl. For example, the onium cation can be
methyltriphenylphosphonium and/or methyltributylphosphonium. In
another aspect, R.sup.5 is methyl and R.sup.6, R.sup.7, R.sup.8,
R.sup.9, and R.sup.10 are hydrogen.
[0050] In one aspect, the onium cation can be
methyltriphenylphosphonium, methyltributylphosphonium,
methyltrioctylphosphonium, or 1-methylpyridinium. In another
aspect, the onium cation can be methyltriphenylphosphonium,
methyltributylphosphonium, or 1-methylpyridinium. In another
aspect, the onium cation can be methyltriphenylphosphonium or
1-methylpyridinium. In one aspect, catalyst can be
bis(methyltriphenylphosphonium) cobalt tetraiodide,
bis(methyltributylphosphonium) cobalt tetraiodide, or
bis(1-methylpyridinium) cobalt tetraiodide.
[0051] In one aspect of the invention, the onium salt can be
generated from polymers containing a quaternary or quaternizable
phosphine or amine. The onium salt polymer may be derived in whole
or part from (or containing polymerized residues of) 2- or
4-vinyl-N-alkylpyridinium iodide or 4-(trialkyl-ammonium)styrene
iodide. For example, a variety of 4-vinyl pyridine polymers and
copolymers are available, and may be quaternized or protonated with
alky iodide or hydrogen iodide to generate heterogeneous onium
salts. Further, polymers of N-methyl-4-vinylpyridinium chloride are
commercially available and may be used as-is or are preferably
exchanged with iodide by well-known means to form the iodide salt.
The heterogeneous onium compound may comprise (1) an onium salt
compound deposited on a catalyst support material or (2) of a
polymeric material containing quaternary nitrogen groups. Examples
of such polymeric onium compounds include polymers and co-polymers
of vinyl monomers which contain quaternary nitrogen (ammonium)
groups. Polymers and copolymers derived from 2- and
4-vinyl-N-alkylpyridinium iodide, e.g.,
poly(4-vinyl-N-methylpyridinium iodide), are specific examples of
such polymeric onium salt compounds. In this aspect, the onium
cation would be a heterogeneous component in the reaction
mixture.
[0052] In one aspect, the catalyst is present in an amount ranging
from 0.001 moles to 50 moles of catalyst per 100 moles of alcohol.
Other examples of catalyst concentration include 0.001 moles to 10
moles of catalyst per 100 moles of alcohol, 0.01 moles to 5 moles
of catalyst per 100 moles of alcohol, 0.01 moles to 2 moles of
catalyst per 100 moles of alcohol, 0.02 moles to 5 moles of
catalyst per 100 moles of alcohol. For a batch reaction, the
catalyst concentration can be determined based on the moles of
catalyst charged per 100 moles of alcohol charged to the batch
reactor. For a continuous reaction, the catalyst concentration can
be determined based on the moles of catalyst fed per 100 moles of
alcohol fed to the reactor over a given time period. The catalyst
and the alcohol can be fed to the reactor together or
separately.
[0053] The present invention can be conducted under continuous,
semi-continuous, and batch modes of operation and can utilize a
variety of reactor types. The term "continuous" as used herein
means a process wherein reactants are introduced and products
withdrawn simultaneously in an uninterrupted manner. By
"continuous" it is meant that the process is substantially or
completely continuous in operation and is to be contrasted with a
"batch" process. "Continuous" is not meant in any way to prohibit
normal interruptions in the continuity of the process due to, for
example, start-up, reactor maintenance, or scheduled shut down
periods. The term "batch" process as used herein means a process
wherein all the reactants are added to the reactor and then
processed according to a predetermined course of reaction during
which no material is fed or removed into the reactor. The term
"semicontinuous" means a process where some of the reactants are
charged at the beginning of the process and the remaining reactants
are fed continuously as the reaction progresses. Alternatively, a
semicontinuous process may also include a process similar to a
batch process in which all the reactants are added at the beginning
of the process except that one or more of the products are removed
continuously as the reaction progresses.
[0054] Any of the known carbonylation reactor designs or
configurations may be used in carrying out the process provided by
the present invention. Examples of suitable reactor types include,
but are not limited to, stirred tank, continuous stirred tank,
tower, and tubular reactors. The process also may be practiced in a
batchwise manner by contacting the low molecular weight alcohol,
hydrogen and carbon monoxide with the present catalyst in an
autoclave.
[0055] The amount of methyl iodide in the crude reductive
carbonylation product is significantly less than in typical
methanol carbonylation processes. In one aspect, the crude
reductive carbonylation product comprises less than 1 weight
percent methyl iodide, based on the total weight of the crude
reductive carbonylation product. In other aspects, the crude
reductive carbonylation product comprises less than 0.8 weight
percent, less than 0.5 weight percent, less than 0.1 weight
percent, less than 0.05 weight percent, less than 100 ppm, less
than 50 ppm, less than 10 ppm, less than 100 ppb, less than 50 ppb,
or less than 10 ppb of methyl iodide, based on the total weight of
the crude reductive carbonylation product.
[0056] The process can be carried out over a range of temperatures.
For example, the process can be carried out at a temperature
ranging from 100.degree. C. to 250.degree. C. In other examples,
the process can be carried out at a temperature ranging from
150.degree. C. to 230.degree. C., or ranging from 170.degree. C. to
210.degree. C.
[0057] The process can be carried out over a range of pressures.
For example, the process can be carried out at a pressure ranging
from 100 kPa (15 psig) to 60 MPa bar (8700 psig). In other
examples, the process can be carried out at a pressure ranging from
1 MPa (150 psig) to 40 MPa (5800 psig) or ranging from 6.9 MPa
(1000 psig) to 34 MPA (4900 psig).
[0058] In one aspect of our invention, the contacting of the
hydrogen, carbon monoxide, and alcohol can occur in the presence of
a solvent selected from alkanes and arenes having 6 to 20 carbon
atoms, ketones having 5 to 20 carbon atoms, esters having 5 to 20
carbon atoms, ethers having 5 to 20 carbon atoms, and alkyl
carbonate esters having from 3 to 20 carbon atoms. Some
representative examples of the solvent include, but are not limited
to, hexane, heptane, octane, decane, benzene, toluene, xylenes,
methyl naphthalenes, 3-methyl-2-butanone, methyl isobutyl ketone
(also known as 4-methyl-2-pentanone), methyl isopropyl ketone,
methyl propyl ketone, diisobutyl ketone, isobutylisobutyrate, ethyl
acetate, n-butyl acetate, isobutylacetate, isopropylacetate,
n-propyl acetate, diispropylether, dibutylether, tertiary-amyl
methyl ether, tertiary-butyl methyl ether, and mixtures thereof. In
one aspect of our invention, the solvent can be toluene, heptane,
cyclohexane, ethylbenzene, diethyl ether, or 4-methylanisol.
[0059] The amount of solvent used is not critical to the subject
invention. For example, the solvent can be present in an amount
ranging from 5 vol % to 90 vol % based on the total volume of
solvent and alcohol. In other examples, the solvent can be present
in an amount ranging from 10 vol % to 80 vol %: 20 vol % to 60 vol
%: or 30 vol % to 50 vol %, each based on the total volume of
solvent and alcohol.
[0060] A second embodiment of our invention is a process for the
preparation of a crude reductive carbonylation product comprising
contacting hydrogen, carbon monoxide, and methanol in the presence
of a catalyst to form a crude reductive carbonylation product. The
crude reductive carbonylation product comprises acetaldehyde
equivalents in a higher mole percent than acetic acid equivalents
or ethanol equivalents, each based on the total moles of the
acetaldehyde equivalents, the acetic acid equivalents, and the
ethanol equivalents. The catalyst comprises a complex of cobalt,
iodide and an onium cation or an alkali metal cation of the general
formula Y.sub.2CoI.sub.4, where Y represents the onium cation or
the alkali metal cation. The onium cation is of the general formula
(I) or (II)
##STR00008##
[0061] For formula (I), X is phosphorus (P) and R.sup.1 is methyl.
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each aryl is the same, and can be phenyl, tolyl,
xylyl, or mesityl. For formula (II), R.sup.5 is methyl and R.sup.6,
R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen. The crude
reductive carbonylation product comprises less than 1 weight
percent of methyl iodide.
[0062] It is understood that the descriptions herein above
regarding methanol reductive carbonylation reactions and the
corresponding products, carbon monoxide and hydrogen feed, CO:H2,
the catalyst, the onium salts and alkali salts, the level of methyl
iodide in the crude reductive carbonylation product, pressure,
temperature, and solvent apply equally well to the second
embodiment.
[0063] For example, the molar ratio of carbon monoxide to hydrogen
(CO:H2) can range from 10:1 to 1:10, 5:1 to 1:5, or 3:1 to 1:3. The
onium cation can be methyltriphenylphosphonium or
1-methylpyridinium. The alkali metal cation can be lithium, sodium,
or potassium. The catalyst can be present in an amount ranging from
0.02 moles to 5 moles of catalyst per 100 moles of methanol, and
the process can be carried out at a temperature ranging from
150.degree. C. to 230.degree. C. and a pressure ranging from 1 MPa
(150 psig) to 40 MPa (5800 psig) or ranging from 6.9 MPa (1000
psig) to 34 MPA (4900 psig). The contacting can further occur in
the presence of a solvent. The solvents can be toluene, heptane,
cyclohexane, ethylbenzene, diethyl ether, or 4-methylanisole. In
one aspect, the catalyst can be bis(methyltriphenylphosphonium)
cobalt tetraiodide, bis(methyltributylphosphonium) cobalt
tetraiodide, or bis(1-methylpyridinium) cobalt tetraiodide.
[0064] A third embodiment of our invention is a process for the
preparation of a crude reductive carbonylation product comprising
contacting hydrogen, carbon monoxide, and an alcohol having 1 to 3
carbon atoms in the presence of a catalyst to form the crude
reductive carbonylation product. The crude reductive carbonylation
product comprises homologous alcohol equivalents in a higher mole
percent than homologous aldehyde equivalents or homologous acid
equivalents, each based on the total moles of the homologous
aldehyde equivalents, homologous acid equivalents, and homologous
alcohol equivalents. The catalyst comprises a complex of cobalt,
iodide and an onium cation or an alkali metal cation of the general
formula Y.sub.2CoI.sub.4, where Y represents the onium cation or
the alkali metal cation. The onium cation is of the general formula
(I) or (II)
##STR00009##
[0065] For formula (I), X is phosphorus (P) and R.sup.1 is methyl.
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each aryl is the same, and can be phenyl, tolyl,
xylyl, or mesityl. For formula (II), R.sup.5 is methyl and R.sup.6,
R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are hydrogen. The process
further comprises a ruthenium co-catalyst. The crude reductive
carbonylation product comprises less than 1 weight percent of
methyl iodide.
[0066] It is understood that the descriptions herein above
regarding carbon monoxide and hydrogen feed, the catalyst, the
onium salts and alkali salts, the level of methyl iodide in the
crude reductive carbonylation product, pressure, temperature, and
solvent apply equally well to the third embodiment.
[0067] The alcohol contacted with carbon monoxide and hydrogen in
the process is an alcohol having 1 to 3 carbon atoms. In one
aspect, the alcohol can be methanol, ethanol, or n-propanol. In
another aspect the alcohol comprises methanol. In another aspect
the alcohol comprises ethanol. In yet another aspect the alcohol
comprises n-propanol.
[0068] In one aspect, the crude reductive carbonylation product
comprises homologous alcohol equivalents in a higher mole percent
than homologous aldehyde equivalents or homologous acid equivalents
from the reaction of carbon monoxide, hydrogen, and the alcohol. In
one aspect the alcohol comprises methanol and the crude reductive
carbonylation product comprises ethanol equivalents in a higher
mole percent than acetaldehyde equivalents or acetic acid
equivalents, each based on the total moles of acetaldehyde
equivalents, acetic acid equivalents, and ethanol equivalents. In
one aspect, the alcohol comprises ethanol and the crude reductive
carbonylation product comprises n-propanol equivalents in a higher
mole percent than n-propionaldehyde equivalents or n-propionic acid
equivalents, each based on the total moles of n-propionaldehyde
equivalents, n-propionic acid equivalents, and n-propanol
equivalents. In one aspect, the alcohol comprises n-propanol and
the crude reductive carbonylation product comprises n-butanol
equivalents in a higher mole percent than n-butyraldehyde
equivalents, or n-butyric acid equivalents, each based on the total
moles of n-butyraldehyde equivalents, n-butyric acid equivalents,
and n-butanol equivalents.
[0069] The molar ratio of carbon monoxide to hydrogen (CO:H.sub.2)
can vary over a wide range. For example, CO:H.sub.2, can range from
1:1 to 1:10. In other examples, CO:H.sub.2 ranges from 1:1 to 1:5
or 1:1 to 1:2.
[0070] In order to increase selectivity of the reductive
carbonylation reaction from homologous aldehyde equivalents to
homologous alcohol equivalents, the addition of a co-catalyst can
be used. This co-catalyst can be chosen from any metal capable of
hydrogenating an aldehyde such as iridium, rhodium, or ruthenium,
with ruthenium being most often used. The source of ruthenium is
not particularly limiting and can be chosen from many commercially
available materials such as ruthenium(III) acetylacetonate,
ruthenium trichloride, triruthenium dodecacarbonyl,
1,1,1-tris(diphenylphosphinomethyl)ethane ruthenium dicarbonyl,
and/or ruthenium(IV)oxide hydrate. In one aspect the co-catalyst
can be triruthenium dodecacarbonyl,
1,1,1-tris(diphenylphosphinomethyl)ethane ruthenium dicarbonyl, or
ruthenium(IV)oxide hydrate. In one aspect, the co-catalyst is
present in an amount ranging from 0.0001 moles to 10 moles of
co-catalyst per 100 moles of alcohol. Other examples of co-catalyst
concentration include 0.001 moles to 5 moles of co-catalyst per 100
moles of alcohol and 0.001 moles to 2 moles of co-catalyst per 100
moles of alcohol.
Listing of Non-Limiting Embodiments
[0071] Embodiment A is a process for the preparation of a crude
reductive carbonylation product comprising contacting hydrogen,
carbon monoxide, and an alcohol having 1 to 3 carbon atoms in the
presence of a catalyst to form the crude reductive carbonylation
product. The crude reductive carbonylation product comprises
homologous aldehyde equivalents in a higher mole percent than
homologous acid equivalents or homologous alcohol equivalents, each
based on the total moles of the homologous aldehyde equivalents,
the homologous acid equivalents, and the homologous alcohol
equivalents. The catalyst comprises a complex of cobalt, iodide and
an onium cation or an alkali metal cation of the general formula
Y.sub.2CoI.sub.4, where Y represents the onium cation or the alkali
metal cation. The onium cation is of the general formula (I) or
(II)
##STR00010##
[0072] For formula (I), X can be phosphorus (P) or nitrogen (N) and
R.sup.1 is methyl. R.sup.2, R.sup.3, and R.sup.4 are independently
selected from alkyl having up to 12 carbons and aryl. When R.sup.2,
R.sup.3, and/or R.sup.4 are aryl, each aryl is the same, and can be
phenyl, tolyl, xylyl, or mesityl. For formula (II), R.sup.5 is
methyl and R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are
hydrogen. The crude reductive carbonylation product comprises less
than 1 weight percent of methyl iodide.
[0073] The process of Embodiment A wherein the onium cation is
formula (I), X is phosphorus (P), R.sup.1 is methyl and R.sup.2,
R.sup.3, and R.sup.4 are independently selected from alkyl having
up to 12 carbons and aryl, wherein when R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each aryl is the same, and can be phenyl, tolyl,
xylyl, or mesityl: or the onium cation is formula (II), R.sup.5 is
methyl and R.sup.6, R.sup.7, R.sup.8, R.sup.9, and R.sup.10 are
hydrogen: or the onium cation is selected from the group consisting
of methyltriphenylphosphonium, methyltributylphosphonium,
methyltrioctylphosphonium, and 1-methylpyridinium: or the onium
cation is selected from the group consisting of
methyltriphenylphosphonium and 1-methylpyridinium: or the onium
cation comprises methyltriphenylphosphonium: or the alkali metal
cation is selected from the group consisting of lithium, sodium,
potassium, rubidium, and cesium: or the alkali metal cation is
selected from the group consisting of lithium, sodium, potassium:
or the catalyst is selected from the group consisting of
bis(methyltriphenylphosphonium) cobalt tetraiodide,
bis(methyltributylphosphonium) cobalt tetraiodide,
bis(methyltrioctylphosphonium), and bis(1-methylpyridinium) cobalt
tetraiodide.
[0074] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the crude reductive
carbonylation product comprises homologous aldehyde equivalents in
at least 10 higher mole percent, 25 higher mole percent, 50 higher
mole percent, or 75 higher mole percent than homologous acid
equivalents; and homologous aldehyde equivalents in at least 10
higher mole percent, 25 higher mole percent, 50 higher mole
percent, or 75 higher mole percent than homologous alcohol
equivalents.
[0075] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the crude reductive
carbonylation product comprises less than 1 weight percent methyl
iodide: or less than 500 ppm methyl iodide: or less than 10 ppm
methyl iodide.
[0076] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the catalyst is present in an
amount ranging from 0.001 moles to 10 moles of the catalyst per 100
moles of the alcohol; or from 0.01 moles to 5 moles of catalyst per
100 moles of alcohol, or from 0.02 moles to 5 moles of catalyst per
100 moles of alcohol.
[0077] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the process is carried out at a
temperature ranging from 100.degree. C. to 250.degree. C.; or from
150.degree. C. to 230.degree. C.
[0078] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the process is carried out at a
pressure ranging from 100 kPa (15 psig) to 60 MPa (8700 psig); or
from 1 MPa (150 psig) to 40 MPa (5800 psig); or from 6.9 MPa (1000
psig) to 34 MPA (4900 psig).
[0079] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the molar ratio of carbon
monoxide to hydrogen, CO:H2, ranges from 10:1 to 1:10 or from 5:1
to 1:5.
[0080] The process of Embodiment A or Embodiment A with one or more
of the intervening features wherein the contacting further occurs
in the presence of a solvent selected from the group consisting of
alkanes and arenes having 6 to 20 carbon atoms, ketones having 5 to
20 carbon atoms, esters having 5 to 20 carbon atoms, ethers having
5 to 20 carbon atoms, and alkyl carbonate esters having 3 to 20
carbon atoms: or wherein the contacting further occurs in the
presence of a solvent selected from the group consisting of
toluene, heptane, cyclohexane, ethylbenzene, diethyl ether, and
4-methylanisole.
[0081] The process of Embodiment A or Embodiment A with one or more
of the intervening features and any one of the following features
(1) through (3)
[0082] (1) wherein the alcohol comprises methanol and the crude
reductive carbonylation product comprises acetaldehyde equivalents
in a higher mole percent than acetic acid equivalents or ethanol
equivalents, each based on the total moles of acetaldehyde
equivalents, acetic acid equivalents, and ethanol equivalents;
[0083] (2) wherein the alcohol comprises ethanol, and the crude
reductive carbonylation product comprises n-propionaldehyde
equivalents in a higher mole percent than n-propionic acid
equivalents or n-propanol equivalents, each based on the total
moles of n-propionaldehyde equivalents, n-propionic acid
equivalents, and n-propanol equivalents; or
[0084] (3) wherein the alcohol comprises n-propanol and the crude
reductive carbonylation product comprises n-butyraldehyde
equivalents in a higher mole percent than n-butyric acid
equivalents or n-butanol equivalents, each based on the total moles
of n-butyraldehyde equivalents, n-butyric acid equivalents, and
n-butanol equivalents.
[0085] Embodiment B is a process for the preparation of a crude
reductive carbonylation product comprising contacting hydrogen,
carbon monoxide, and an alcohol having 1 to 3 carbon atoms in the
presence of a catalyst to form the crude reductive carbonylation
product. The crude reductive carbonylation product comprises
homologous alcohol equivalents in a higher mole percent than
homologous aldehyde equivalents or homologous acid equivalents,
each based on the total moles of the homologous aldehyde
equivalents, the homologous acid equivalents, and the homologous
alcohol equivalents. The catalyst comprises a complex of cobalt,
iodide and an onium cation or an alkali metal cation of the general
formula Y.sub.2CoI.sub.4, where Y represents the onium cation or
the alkali metal cation. The onium cation is of the general formula
(I) or (II)
##STR00011##
[0086] For formula (I), X is phosphorus (P) and R.sup.1 is methyl.
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl. When R.sup.2, R.sup.3, and/or
R.sup.4 are aryl, each is the same, and is phenyl, tolyl, xylyl, or
mesityl. For formula (II), R.sup.5 is methyl and R.sup.6, R.sup.7,
R.sup.8, R.sup.9, and R.sup.10 are hydrogen. The process further
comprises a ruthenium co-catalyst. The crude reductive
carbonylation product comprises less than 1 weight percent of
methyl iodide.
[0087] The process of Embodiment B wherein the onium cation is
formula (I), X can be phosphorus (P), R.sup.1 is methyl and
R.sup.2, R.sup.3, and R.sup.4 are independently selected from alkyl
having up to 12 carbons and aryl, wherein when R.sup.2, R.sup.3,
and/or R.sup.4 are aryl, each aryl is the same, and can be phenyl,
tolyl, xylyl, or mesityl: or the onium cation is formula (II),
R.sup.5 is methyl and R.sup.6, R.sup.7, R.sup.8, R.sup.9, and
R.sup.10 are hydrogen: or the onium cation is selected from the
group consisting of methyltriphenylphosphonium,
methyltributylphosphonium, methyltrioctylphosphonium, and
1-methylpyridinium: or the onium cation is selected from the group
consisting of methyltriphenylphosphonium and 1-methylpyridinium: or
the onium cation comprises methyltriphenylphosphonium: or the
alkali metal cation is selected from the group consisting of
lithium, sodium, potassium, rubidium, and cesium: or the alkali
metal cation is selected from the group consisting of lithium,
sodium, potassium: or the catalyst is selected from the group
consisting of bis(methyltriphenylphosphonium) cobalt tetraiodide,
bis(methyltributylphosphonium) cobalt tetraiodide,
bis(methyltrioctylphosphonium), and bis(1-methylpyridinium) cobalt
tetra iodide.
[0088] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the crude reductive
carbonylation product comprises homologous alcohol equivalents in
at least 10 higher mole percent, 25 higher mole percent, 50 higher
mole percent, or 75 higher mole percent than homologous aldehyde
equivalents; and homologous alcohol equivalents in at least 10
higher mole percent, 25 higher mole percent, 50 higher mole
percent, or 75 higher mole percent than homologous acid
equivalents.
[0089] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the crude reductive
carbonylation product comprises less than 1 weight percent methyl
iodide: or less than 500 ppm methyl iodide: or less than 10 ppm
methyl iodide.
[0090] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the catalyst is present in an
amount ranging from 0.001 moles to 10 moles of the catalyst per 100
moles of the alcohol; or from 0.01 moles to 5 moles of catalyst per
100 moles of alcohol.
[0091] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the co-catalyst is present in
an amount ranging from 0.0001 moles to 10 moles of co-catalyst per
100 moles of alcohol; 0.001 moles to 5 moles of co-catalyst per 100
moles of alcohol; and 0.001 moles to 2 moles of co-catalyst per 100
moles of alcohol.
[0092] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the process is carried out at a
temperature ranging from 100.degree. C. to 250.degree. C.; or from
150.degree. C. to 230.degree. C.
[0093] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the process is carried out at a
pressure ranging from 100 kPa (15 psig) to 60 MPa (8700 psig); or
from 1 MPa (150 psig) to 40 MPa (5800 psig); or from 6.9 MPa (1000
psig) to 34 MPA (4900 psig).
[0094] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the molar ratio of carbon
monoxide to hydrogen, CO:H2, ranges from 1:1 to 1:10 or from 1:1 to
1:5 or from 1:1 to 1:2.
[0095] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the contacting further occurs
in the presence of a solvent selected from the group consisting of
alkanes and arenes having 6 to 20 carbon atoms, ketones having 5 to
20 carbon atoms, esters having 5 to 20 carbon atoms, ethers having
5 to 20 carbon atoms, and alkyl carbonate esters having 3 to 20
carbon atoms: or wherein the contacting further occurs in the
presence of a solvent selected from the group consisting of
toluene, heptane, cyclohexane, ethylbenzene, diethyl ether, and
4-methylanisole.
[0096] The process of Embodiment B or Embodiment B with one or more
of the intervening features wherein the co-catalysts is selected
from the group consisting of ruthenium(III) acetylacetonate,
ruthenium trichloride, and triruthenium dodecacarbonyl: or the
co-catalysts is selected from triruthenium dodecacarbonyl,
1,1,1-tris(diphenylphosphinomethyl)ethane ruthenium dicarbonyl, and
ruthenium(IV)oxide hydrate.
[0097] The process of Embodiment B or Embodiment B with one or more
of the intervening features and any one of the following features
(1) through (3).
[0098] (1) wherein the alcohol comprises methanol and the crude
reductive carbonylation product comprises ethanol equivalents in a
higher mole percent than acetaldehyde equivalents or acetic acid
equivalents, each based on the total moles of acetaldehyde
equivalents, acetic acid equivalents, and ethanol equivalents;
[0099] (2) wherein the alcohol comprises ethanol, and the crude
reductive carbonylation product comprises n-propanol equivalents in
a higher mole percent than n-propionaldehyde equivalents or
n-propionic acid equivalents, each based on the total moles of
n-propionaldehyde equivalents, n-propionic acid equivalents, and
n-propanol equivalents; or
[0100] (3) wherein the alcohol comprises n-propanol and the crude
reductive carbonylation product comprises n-butanol equivalents in
a higher mole percent than n-butyraldehyde equivalents or n-butyric
acid equivalents, each based on the total moles of n-butyraldehyde
equivalents, n-butyric acid equivalents, and n-butanol
equivalents.
EXAMPLES
Abbreviations
[0101]
(MePPh.sub.3).sub.2CoI.sub.4=Bis(methyltriphenylphosphonium)cobalt
tetraiodide=(CH.sub.3P(C.sub.6H.sub.5).sub.3).sub.2CoI.sub.4;
(MePBu.sub.3).sub.2CoI.sub.4=Bis(methyltributylphosphonium)cobalt
tetraiodide=(CH.sub.3P(C.sub.4H.sub.9).sub.3).sub.2CoI.sub.4;
(MePy).sub.2CoI.sub.4=Bis(1-methylpyridinium)cobalt
tetraiodide=(1-CH.sub.3(C.sub.5H.sub.5N)).sub.2CoI.sub.4;
(MePPh.sub.3)CoBr.sub.4=Bis(methyltriphenylphosphonium)cobalt
tetrabromide=(CH.sub.3P(C.sub.6H.sub.5).sub.3).sub.2CoBr.sub.4;
CoI.sub.2=cobalt(II) iodide.
[0102] MeI=methyl iodide; DME=dimethyl ether;
THF=tetrahydrofuran
[0103] dppe=1,2-bis(diphenylphosphino)ethane;
dppb=1,4-bis(diphenylphosphino)butane;
dpph=1,6-bis(diphenylphosphino)hexane:
dppbenz=1,2-bis(diphenylphosphino)benzene;
bisbi=bis(diphenylphosphinomethyl)biphenyl;
(PPh.sub.2).sub.3Me=1,1,1-tris(diphenylphosphino)methane;
dppp=1,3-bis(diphenylphosphino)propane;
Ph-triphos=1,1,1-tris(diphenylphosphinomethyl)ethane;
Et-triphos=1,1,1-tris(diethylphosphinomethyl)ethane;
PPh.sub.3=triphenylphosphine; bipy=2,2'-bipyridine;
P,N=2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl;
[0104] Ru.sub.3(CO).sub.12=triruthenium dodecacarbonyl;
(Ph-triphos)Ru(CO).sub.2=1,1,1-tris(diphenylphosphinomethyl)ethane
ruthenium dicarbonyl; RuO.sub.2xH.sub.2O=ruthenium(IV)oxide
hydrate.
[0105] STY=space time yield
[0106] For examples having a methanol feed, selectivities are
reported as selectivity to acetaldehyde equivalents, acetic acid
equivalents, ethanol equivalents, and C4 equivalents relative to
methanol carbonylated. Reported acetaldehyde equivalents include:
Acetaldehyde, Paraldehyde, Acetaldehyde dimethyl acetal,
Acetaldehyde methyl ethyl acetal, Acetaldehyde diethyl acetal.
Reported acetic acid equivalents include: Acetic acid, Methyl
acetate, and Ethyl acetate. Reported ethanol equivalents include
all ethoxy containing products including: Ethanol, Acetaldehyde
diethyl acetal, Acetaldehyde methyl ethyl acetal, Diethyl ether,
Methyl ethyl ether, and Ethyl acetate. Reported C4 equivalents
include: n-Butyl alcohol, Crotonaldehyde, n-Butyraldehyde,
Butyraldehyde acetals, and Crotyl alcohol. A summary of commonly
observed products and byproducts is provided in Table 1.
TABLE-US-00004 TABLE 1 commonly observed products incorporated into
selectivity calculations for methanol reductive carbonylation
Acetaldehyde Acetic Acid Ethanol Equivalents Equivalents
Equivalents C4 Equivalents Ethanol Acetaldehyde Acetic acid n-Butyl
alcohol Acetaldehyde diethyl Acetaldehyde Methyl Crotonaldehyde
acetal dimethyl acetal acetate n-Butyraldehyde Acetaldehyde methyl
Acetaldehyde methyl Ethyl acetate Butyraldehyde acetals ethyl
acetal ethyl acetal Crotyl Alcohol Diethyl ether Acetaldehyde
diethyl Methyl ethyl ether acetal Ethyl acetate Paraldehyde
[0107] The phosphonium salts and ammonium salts used in these
examples are easily prepared by alkylation of the parent tertiary
phosphine or amine with an alkyl halide, a process well known to
practitioners of the art. Complexes of the type Y.sub.2CoI.sub.4
and Y.sub.2CoBr.sub.4 where Y=MePPh.sub.3
(methyltriphenylphosphonium), Y=MePBu.sub.3
(methyltributylphosphonium), Y=MePy (1-methylpyridinium) were
prepared by the method of Wegman et al., J. Mol. Cat., 32, (1985),
125-136.
[0108] Phosphine ligands, solvents, and alcohols were purchased and
used without further processing.
[0109] The contents of the examples were analyzed by gas
chromatography. When the reaction products formed two liquid phases
at room temperature, an additional component, such as THF, was
added to ensure a one-phase liquid sample was fed to the gas
chromatograph. Catalyst was not removed from the reaction product
before analysis. Selectivities are reported based upon detection of
the components listed in Table 1. The detection limit for methyl
iodide (MeI) was 100 ppm. MeI listed as n/d indicates that no
methyl iodide was detected.
[0110] Methanol Conversion was calculated as the difference between
the initial amount of methanol and the recovered amount of free
methanol divided by the initial amount of methanol. Methanol is
converted to carbonylated produces and non-carbonylated
methoxy-containing products. As the non-carbonylated
Methoxy-containing products would be readily recycled in a
commercial process, the effective selectivities are based upon the
moles of Methanol Carbonlyated. The moles of Methanol Carbonylated
were calculated as the sum of homologated products.
[0111] Moles of Methanol Carbonylated=moles Acetaldehyde+3*moles
Paraldehyde+moles Acetaldehyde dimethyl acetal+moles Acetaldehyde
methyl ethyl acetal+moles Acetaldehyde diethyl acetal)+moles Acetic
acid+moles Methyl acetate+moles Ethyl acetate+moles Ethanol+2*moles
Acetaldehyde diethyl acetal+moles Acetaldehyde methyl ethyl
acetal+2*moles Diethyl ether+moles Methyl ethyl ether+moles Ethyl
acetate+2*moles n-Butyl alcohol+2*moles Crotonaldehyde+2*moles
n-Butyraldehyde+2*moles Butyraldehyde acetals+2*moles Crotyl
alcohol.
[0112] Selectivities to one of the product equivalents, as detailed
in equations 1-4 below, are reported as the sum of methanol
carbonylated to the product equivalent divided by the total amount
of methanol carbonylated.
[0113] (1) % Acetaldehyde Equivalents Selectivity=100*(moles
Acetaldehyde+3*moles Paraldehyde+moles Acetaldehyde dimethyl
acetal+moles Acetaldehyde methyl ethyl acetal+moles Acetaldehyde
diethyl acetal)/moles Methanol Carbonylated.
[0114] (2) % Acetic Acid Equivalents Selectivity=100*(moles Acetic
acid+moles Methyl acetate+moles Ethyl acetate)/moles Methanol
Carbonylated
[0115] (3) % Ethanol Equivalents Selectivity=100*(moles
Ethanol+2*moles Acetaldehyde diethyl acetal+moles Acetaldehyde
methyl ethyl acetal+2*moles Diethyl ether+moles Methyl ethyl
ether+moles Ethyl acetate)/moles Methanol Carbonylated.
[0116] (4) % C4 Equivalents Selectivity=100*(2*moles n-Butyl
alcohol+2*moles Crotonaldehyde+2*moles n-Butyraldehyde+2*moles
Butyraldehyde acetals+2*moles Crotyl alcohol)/moles Methanol
Carbonylated.
[0117] Yield of Carbonylated Products was calculated as the Moles
of Methanol Carbonylated divided by the initial amount of
methanol.
[0118] Space Time Yield (STY), for a methanol feed and with
acetaldehyde equivalents as the desired product, was calculated as
the moles of acetaldehyde equivalents produced per liter of initial
reaction mixture per hours of reaction (moles per liter per hour,
Mh.sup.-1). One skilled in the art can readily calculate the STY
when ethanol equivalents are the desired product.
[0119] Mole percent (Mole %) of methyl iodide (MeI) or dimethyl
ether (DME) were calculated as the percentage of moles of species
produced compared to the initial amount of methanol (or other
alcohol) charged to the reactor.
Example 1
[0120] A 100-mL Hastelloy.RTM. C autoclave was charged with a
solution of (MePPh.sub.3).sub.2CoI.sub.4 (1.236 mmol) in 25 mL of
methanol, sealed and purged 3 times with N.sub.2. The reactor was
pressurized to 6.9 MPa (1000 psig) with 1:1 CO:H.sub.2 and heated
to 190.degree. C. Upon reaching 190.degree. C., the reactor was
pressurized to a total pressure of 27.6 MPa (4000 psig) with 1:1
CO:H.sub.2. After 30 minutes the reactor was cooled to 5.degree. C.
and the gas was vented. The contents were analyzed by gas
chromatography and the results are shown in Table 2.
Examples 2-6 and Comparative Example C1
[0121] Example 1 was repeated except the catalyst used and the
amount of catalyst were as given in Table 2. Example 2 is a
duplicate of Example 1 with the other examples varying the amount
and/or type of catalyst. While Comparative Example C1 shows a Space
Time Yield comparable to Examples 1-6, the crude reductive
carbonylation product contains 0.23 mole % methyl iodide and 3.4
mole % dimethyl ether, each based on the amount of methanol
charged. Examples 1-6 show no detectable methyl iodide and 0.8 mole
% as the highest level of DME.
Examples 7-14 and Comparative Examples C2-C5
[0122] Example 1 was repeated with the addition of a solvent used
at a 50 vol % level. The solvent used and the amount of catalyst,
as well as the results, are given in Table 2. One skilled in the
art would recognize that the Space Time Yield would be lower for
systems with 50 vol % solvent compared to systems with no solvent.
For example, comparing Examples 1 and 7 which were run under the
same conditions except that Example 7 had 50 vol % toluene, the STY
for Example 1 was 13.8 while the STY for Example 7 was 8.4. The use
of solvent does, however, improve selectivity to acetaldehyde
equivalents. For Example 7, the selectivity to acetaldehyde
equivalents was 89% compared to 74% for Example 1. Each of Examples
7-14 produced products which separated into two distinct liquid
phases at room temperature. Advantageously, the catalyst, which
would be recycled in a continuous process, partitioned to the
aqueous phase, while the desired products partitioned to the
organic phase (see Examples 87-90). Comparative Examples C2-C5 did
not form two distinct liquid phases at room temperature.
Furthermore, Comparative Example C5, with acetonitrile as the
solvent, showed the lowest STY of 4.8.
TABLE-US-00005 TABLE 2 Reductive carbonylation of methanol to
acetaldehyde equivalents at 190.degree. C., 4000 psig, carbon
monoxide to hydrogen ratio of 1:1 for 30 minutes. Catalyst Conc.
Yield of (mole % relative Methanol Carbonylated Ex Catalyst to
Methanol) Solvent Conversion Products 1 (MePPh3)2CoI4 0.2% -- 75%
38% 2 (MePPh3)2CoI4 0.2% -- 73% 40% 3 (MePPh3)2CoI4 0.4% -- 77% 47%
4 (MePPh3)2CoI4 0.025% -- 55% 19% 5 (MePBu3)2CoI4 0.2% -- 71% 36% 6
(MePy)2CoI4 0.2% -- 72% 37% C1 CoI2 0.2% -- 69% 26% MeI 0.4% 7
(MePPh3)2CoI4 0.2% Toluene 83% 38% 8 (MePPh3)2CoI4 0.4% Toluene 81%
47% 9 (MePPh3)2CoI4 0.4% Heptane 80% 38% 10 (MePPh3)2CoI4 0.2%
Cyclohexane 78% 33% 11 (MePPh3)2CoI4 0.4% Ethylbenzene 83% 47% 12
(MePPh3)2CoI4 0.2% Diethyl ether 70% 32% 13 (MePPh3)2CoI4 0.4%
Diethyl ether 80% 43% 14 (MePPh3)2CoI4 0.4% 4-Methylanisole 83% 53%
C2 (MePPh3)2CoI4 0.4% THF 83% 54% C3 (MePPh3)2CoI4 0.4% Dioxane 78%
55% C4 (MePPh3)2CoI4 0.2% Acetone 74% 42% C5 (MePPh3)2CoI4 0.2%
Acetonitrile 62% 25% Acetal- Mole % Mole % dehyde Ethanol Acetic
Acid C4 STY MeI in DME in Ex Selectivity Selectivity Selectivity
Selectivity (Mh.sup.-1) product product 1 74% 2% 15% 9% 13.8 n/d
0.5% 2 73% 2% 15% 10% 14.5 n/d 0.6% 3 65% 2% 20% 13% 15.3 n/d 0.8%
4 88% 3% 7% 2% 8.4 n/d 0.5% 5 76% 2% 12% 10% 13.4 n/d 0.6% 6 72% 2%
13% 13% 13.2 n/d 0.7% C1 79% 2% 9% 10% 10.2 0.23% 3.4% 7 89% 4% 5%
2% 8.4 n/d 0.3% 8 86% 3% 7% 4% 9.8 n/d 0.3% 9 79% 2% 16% 3% 5.4 n/d
0.2% 10 88% 5% 4% 2% 7.2 n/d 0.2% 11 86% 2% 8% 3% 10 n/d 0.3% 12
86% 5% 6% 2% 6.8 n/d 0.2% 13 78% 5% 13% 4% 8.25 n/d 0.2% 14 81% 2%
10% 7% 10.5 n/d 0.4% C2 77% 2% 14% 7% 10.3 n/d 0.2% C3 82% 2% 13%
3% 11.1 n/d 0.3% C4 84% 2% 9% 5% 8.7 n/d 0.3% C5 76% 3% 15% 6% 4.8
n/d 0.2%
The results of Example 9, with heptane as the solvent, show an
unexpectedly low STY compared to other solvent examples with the
(MePPh.sub.3).sub.2CoI.sub.4 catalyst level of 0.4 mole % (e.g.,
Examples 8, 11, 13, and 14). This is believed to be an anomaly of
the analysis, as this was the only Example in which each of the two
liquid phases was analyzed separately.
Example 15
[0123] Example 1 was repeated at a temperature of 195.degree. C.
and 0.025 mole % (MePPh.sub.3).sub.2CoI.sub.4 catalyst as shown
with the corresponding results in Table 3.
Comparative Examples C6-C8
[0124] Example 15 was repeated using the same total amount of
catalyst, but varying the relative amounts of
(MePPh.sub.3).sub.2CoI.sub.4 and (MePPh.sub.3).sub.2CoBr.sub.4 as
given in Table 3. At the same total catalyst concentration, the
Space Time Yield decreased from 9.8 with all
(MePPh.sub.3).sub.2CoI.sub.4 (Example 15) down to 2.5 with all
(MePPh.sub.3).sub.2CoBr.sub.4 (Comparative Example C8). These
examples show that an iodide cation for catalyzing the reductive
carbonylation of methanol to acetaldehyde equivalents produces a
higher STY than a bromide cation.
Example 16
[0125] Example 1 was repeated at a temperature of 195.degree. C.
and 0.2 mole % (MePPh.sub.3).sub.2CoI.sub.4 catalyst as shown with
the corresponding results in Table 3.
Examples 17-26
[0126] Example 16 was repeated with the amount of
(MePPh.sub.3).sub.2CoI.sub.4 catalyst shown and varying amounts of
phosphine ligand, 1,3-bis(diphenylphosphino)propane (dppp), as
shown in Table 3. The amount of phosphine ligand is given in mole %
phosphine ligand relative to the initial amount of methanol.
Examples 25 and 26 were run for 1 hour. Results are shown in Table
3.
Examples 27-31
[0127] Example 16 was repeated with 50 vol % toluene as a solvent
and the amounts of (MePPh.sub.3).sub.2CoI.sub.4 and dppp as shown
in Table 3. Examples 27 and 28 were run for one hour. The contents
were analyzed by gas chromatography and the results are shown in
Table 3.
[0128] Examples 16, 17, and 29 were each run at 195.degree. C.,
4000 psig, CO:H.sub.2 of 1:1, and 0.2 mole %
(MePPh.sub.3).sub.2CoI.sub.4 for 30 min. The STY increased from
11.8 with no phosphine ligand present (Example 16) to 16.4 with 0.1
mole % dppp present (Example 17). Comparison of the selectivity to
acetaldehyde equivalents shows that the addition of a toluene
solvent gave an acetaldehyde equivalents selectivity of 84%
(Example 29) which is higher than the catalyst alone or catalyst
with phosphine ligand values of 73% (Example 16) and 63% (Example
17), respectively.
TABLE-US-00006 TABLE 3 Reductive carbonylation of methanol to
acetaldehyde equivalents at 195.degree. C., 4000 psig, carbon
monoxide to hydrogen ratio of 1:1 for 30 minutes. Catalyst Conc.
(mole % relative Ex Time Catalyst to Methanol) Phosphine ligand
Solvent 15 0.5 (MePPh3)2CoI4 0.025% -- -- C6 0.5 (MePPh3)2CoI4
0.0125% -- -- (MePPh3)2CoBr4 0.0125% C7 0.5 (MePPh3)2CoI4 0.00625%
-- -- (MePPh3)2CoBr4 0.01875% C8 0.5 (MePPh3)2CoBr4 0.025% -- -- 16
0.5 (MePPh3)2CoI4 0.2% -- -- 17 0.5 (MePPh3)2CoI4 0.2% dppp(0.1%)
-- 18 0.5 (MePPh3)2CoI4 0.4% dppp(0.2%) -- 19 0.5 (MePPh3)2CoI4
0.6% dppp(0.3%) -- 20 0.5 (MePPh3)2CoI4 0.2% Et-tripohs(0.1%) -- 21
0.5 (MePPh3)2CoI4 0.2% Et-tripohs(0.2%) -- 22 0.5 (MePPh3)2CoI4
0.2% Et-tripohs(0.3%) -- 23 0.5 (MePPh3)2CoI4 0.2% Et-tripohs(0.4%)
-- 24 0.5 (MePPh3)2CoI4 0.4% Et-tripohs(0.2%) -- 25 1 (MePPh3)2CoI4
0.4% dppp(0.2%) -- 26 1 (MePPh3)2CoI4 0.6% dppp(0.3%) -- 27 1
(MePPh3)2CoI4 0.4% dppp(0.2%) Toluene 28 1 (MePPh3)2CoI4 0.6%
dppp(0.3%) Toluene 29 0.5 (MePPh3)2CoI4 0.2% dppp(0.1%) Toluene 30
0.5 (MePPh3)2CoI4 0.4% dppp(0.2%) Toluene 31 0.5 (MePPh3)2CoI4 0.6%
dppp(0.3%) Toluene Yield of Acetal- Methanol Carbonylated dehyde
Ethanol Acetic Acid C4 Space Time Yield Ex Conversion Products
Selectivity Selectivity Selectivity Selectivity (Mh.sup.-1) 15 67%
24% 83% 6% 8% 3% 9.8 C6 39% 13% 86% 3% 8% 3% 5.4 C7 35% 10% 87% 2%
8% 3% 4.1 C8 34% 6% 86% 2% 8% 4% 2.5 16 68% 33% 73% 3% 16% 8% 11.8
17 76% 53% 63% 9% 18% 10% 16.4 18 89% 49% 58% 10% 21% 11% 14.1 19
94% 62% 41% 14% 28% 17% 12.7 20 78% 51% 72% 4% 16% 8% 18.2 21 83%
57% 72% 4% 17% 7% 20.1 22 79% 48% 76% 3% 17% 4% 17.9 23 30% 10% 79%
0.8%.sup. 17% 3% 3.7 24 90% 62% 65% 4% 22% 9% 19.8 25 95% 64% 45%
15% 23% 17% 7.2 26 95% 64% 33% 10% 39% 18% 5.2 27 93% 72% 71% 7%
11% 11% 6.3 28 96% 66% 56% 8% 17% 19% 4.6 29 82% 42% 84% 4% 10% 2%
8.6 30 86% 52% 80% 5% 10% 5% 10.3 31 94% 66% 64% 6% 14% 15%
10.3
The Examples and Comparative Examples of Table 3 each showed no
detectable amount of MeI. The amount of DME ranged from 0.3 mole %
to 0.8 mole % for Examples 15-19 and 25-31 and from 0.4 mole % to
1.9 mole % for Examples 20-24.
Examples 32-42
[0129] Example 1 was repeated at the temperature, carbon monoxide
to hydrogen ratio, dppp at 0.1 mole % if present, and toluene at 50
vol % if present as shown in Table 4. All examples had 0.2 mole %
(MePPh.sub.3).sub.2CoI.sub.4 as the catalyst except for example 42
which had 0.4 mole %.
[0130] Selectivity to acetaldehyde equivalents improved as the
ratio of carbon monoxide to hydrogen went from 2:1 to 1:1 to 1:2.
Examples 36, 17, and 37 were each run at a temperature of
195.degree. C., 4000 psig, 0.2 mole % (MePPh.sub.3).sub.2CoI.sub.4
and 0.1 mole % dppp. These Examples show that acetaldehyde
equivalents selectivities increased from 48% (Example 36,
CO:H.sub.2 of 2:1) to 63% (Example 17, CO:H.sub.2 of 1:1) to 70%
(Example 37 CO:H.sub.2 of 1:2).
TABLE-US-00007 TABLE 4 Reductive carbonylation of methanol to
acetaldehyde equivalents at 4000 psig and 0.2 mole %
(MePPh.sub.3).sub.2CoI.sub.4 for 30 minutes. Ex Temp. C. .degree.
CO:H.sub.2 Phosphine ligand Solvent 32 190 2:1 -- -- 33 190 1:2 --
-- 34 190 2:1 -- Toluene 35 190 1:2 -- Toluene 36 195 2:1
dppp(0.1%) -- 37 195 1:2 dppp(0.1%) -- 38 195 2:1 dppp(0.1%)
Toluene 39 195 1:2 dppp(0.1%) Toluene 40 195 1:2 Et-tripohs(0.1%)
-- 41 195 1:2 Et-tripohs(0.2%) -- 42 195 1:2 Et-tripohs(0.2%) --
Yield of Acetal- Methanol Carbonylated dehyde Ethanol Acetic Acid
C4 Space Time Yield Ex Conversion Products Selectivity Selectivity
Selectivity Selectivity (Mh.sup.-1) 32 78% 45% 66% 1% 28% 5% 14.5
33 61% 25% 84% 3% 7% 6% 10.2 34 83% 35% 81% 1% 16% 2% 7 35 65% 22%
91% 4% 3% 2% 5 36 87% 55% 48% 3% 43% 6% 12.9 37 78% 33% 70% 14% 7%
9% 11.6 38 77% 31% 72% 3% 20% 5% 5.5 39 70% 23% 89% 4% 4% 3% 5 40
79% 28% 79% 6% 6% 9% 11.1 41 88% 35% 81% 8% 6% 5% 14.0 42 83% 40%
73% 9% 8% 10% 14.6
The Examples of Table 4 each showed no detectable amount of MeI.
The amount of DME ranged from 0.2 mole % to 0.8 mole % for Examples
32-39 and from 0.6 mole % to 1.8 mole % for Examples 40-42, based
on the initial amount of methanol charged. Examples 42 was run with
0.4 mole % (MePPh.sub.3).sub.2CoI.sub.4.
Examples 43a-43c
[0131] This Example illustrates the effect of recycling the cobalt
catalyst. For Example 43a, Example 1 was repeated at a temperature
of 175.degree. C., pressure of 2400 psig, and 0.05 mole %
(MePPh.sub.3).sub.2CoI.sub.4 as the catalyst. A total amount of 60
mL methanol was charged. The contents were analyzed by gas
chromatography. The catalyst was recovered for recycling by
removing volatiles from the reaction mixture by rotary evaporation,
leaving a green crystalline solid. For Example 43b, the solid
catalyst was dissolved in enough methanol to maintain 0.05 mole %
(MePPh.sub.3).sub.2CoI.sub.4 catalyst concentration. Example 43b
was run under the same conditions as Example 43a. For Example 43c,
volatiles were again removed by rotary evaporation and the green
crystalline solid was again dissolved in enough methanol to
maintain 0.05 mole % (MePPh.sub.3).sub.2CoI.sub.4 catalyst
concentration. The solution was then run under the same conditions
as Example 43a. Results are shown in Table 5. Comparison of
Examples 43a-43c show similar values for methanol conversion,
acetaldehyde equivalents selectivity, and STY after the
(MePPh.sub.3).sub.2CoI.sub.4 catalyst was recycled a first and
second time.
Examples 44-52 and Comparative Examples C9 and C10
[0132] For Examples 44 and 45, Example 1 was repeated at a
temperature of 175.degree. C. and a pressure of 2400 psig. Examples
46-52 and Comparative Examples C9 and C10 repeated Example 44 with
0.1 mole % of the phosphine ligand listed in Table 5. The STY for
Examples 44 and 45, which had no phosphine ligand, were 6.7 and
7.8, respectively. The STY for Examples 46-52, which had inventive
catalyst/phosphine ligand combinations ranged from 7.6-11.0. The
STY for Comparative Examples C9 and C10 was 5.4 and 7.5,
respectively.
Examples 53-57 and Comparative Examples C11-C13
[0133] Example 53 repeated Example 1 at a temperature of
190.degree. C. and a pressure of 2400 psig. Examples 54-57 and
Comparative Examples C11-C13 repeated Example 53 with 0.1 mole % of
the phosphine ligand listed in Table 5. The STY for Example 53,
which had no phosphine ligand, was 6.0. The STY for Examples 54-57,
which had inventive catalyst/phosphine ligand combinations ranged
from 9.4-11.2. The STY for Comparative Example C11 and C12 which
did not have an inventive catalyst/phosphine ligand combination was
8.9 and 6.9, respectively. Comparative Example C13 repeated Example
53 using a catalyst of 0.2 mole % CoI.sub.2 and 0.2 mole % MeI with
0.1 mole % dppp in place of the 0.2 mole %
(MePPh.sub.3).sub.2CoI.sub.4 with 0.1 mole % dppp for the
catalyst/phosphine ligand combination. Comparative Example C13 had
a STY of 10.2, but also had 0.08 mole % MeI and 1.4 mole % DME in
the crude reductive carbonylation product as compared to
non-detectable MeI and 0.7 mole % DME for Example 53.
TABLE-US-00008 TABLE 5 Reductive carbonylation of methanol to
acetaldehyde equivalents at 2400 psig a carbon monoxide to hydrogen
ratio of 1:1 for 30 minutes. Catalyst Conc. Yield of (mole %
relative Methanol Carbonylated Ex. Temp C. .degree. Catalyst to
Methanol) Phosphine ligand Conversion Products 43a 175
(MePPh3)2CoI4 0.05% -- 37% 11% 43b 175 (MePPh3)2CoI4 0.05% -- 36%
11% 43c 175 (MePPh3)2CoI4 0.05% -- 43% 11% 44 175 (MePPh3)2CoI4
0.2% -- 50% 17% 45 175 (MePPh3)2CoI4 0.2% -- 53% 20% 46 175
(MePPh3)2CoI4 0.2% dppp(0.1%) 72% 30% 47 175 (MePPh3)2CoI4 0.2%
dppp(0.1%) 73% 31% 48 175 (MePPh3)2CoI4 0.2% Ph-triphos(0.1%) 64%
23% 49 175 (MePPh3)2CoI4 0.2% Ph-triphos(0.1%) 62% 25% 50 175
(MePPh3)2CoI4 0.2% bisbi(0.1%) 61% 25% 51 175 (MePPh3)2CoI4 0.2%
dpph(0.1%) 55% 20% 52 175 (MePPh3)2CoI4 0.2% dppb(0.1%) 56% 19% C9
175 (MePPh3)2CoI4 0.2% bipy(0.1%) 41% 14% C10 175 (MePPh3)2CoI4
0.2% P, N(0.1%) 57% 19% 53 190 (MePPh3)2CoI4 0.2% -- 45% 14% 54 190
(MePPh3)2CoI4 0.2% dppp(0.1%) 70% 32% 55 190 (MePPh3)2CoI4 0.2%
dppe(0.1%) 66% 26% 56 190 (MePPh3)2CoI4 0.2% dppbenz(0.1%) 70% 31%
57 190 (MePPh3)2CoI4 0.2% Ph-triphos(0.1%) 62% 25% C11 190
(MePPh3)2CoI4 0.2% (PPh2)3Me 59% 23% (0.1%) C12 190 (MePPh3)2CoI4
0.2% PPh3(0.2%) 53% 18% C13 190 CoI2 0.2% dppp(0.1%) 69% 27% MeI
0.2% Acetal- Mole % Mole % dehyde Ethanol Acetic Acid C4 Space Time
Yield MeI in DME in Ex. Selectivity Selectivity Selectivity
Selectivity (Mh.sup.-1) Product Product 43a 88% 1% 11% 0% 4.7 n/d
0.4% 43b 83% 1% 12% 4% 4.4 n/d 0.3% 43c 85% 1% 14% 0% 4.5 n/d 0.3%
44 80% 1% 18% 1% 6.7 n/d 0.3% 45 78% 1% 19% 2% 7.8 n/d 0.5% 46 73%
4% 20% 3% 10.7 n/d 0.6% 47 72% 4% 20% 3% 11.0 n/d 0.6% 48 77% 2%
19% 2% 8.8 n/d 0.4% 49 77% 2% 19% 2% 9.7 n/d 0.4% 50 78% 3% 16% 4%
9.4 n/d 0.3% 51 79% 2% 16% 2% 7.8 n/d 0.2% 52 80% 3% 16% 2% 7.6 n/d
0.2% C9 80% 1% 19% 1% 5.4 n/d 0.3% C10 77% 1% 21% 1% 7.3 n/d 0.2%
53 84% 1% 14% 1% 6.0 n/d 0.7% 54 71% 4% 20% 4% 11.1 n/d 0.7% 55 74%
3% 21% 2% 9.4 n/d 0.5% 56 72% 5% 20% 2% 11.2 n/d 0.7% 57 77% 2% 19%
2% 9.7 n/d 0.4% C11 77% 1% 19% 2% 8.9 n/d 0.5% C12 78% 1% 19% 2%
6.9 n/d 0.2% C13 76% 3% 17% 4% 10.2 0.08% 1.4%
Examples 58-61
[0134] For Example 58, a 100-mL Hastelloy.RTM. C autoclave was
charged with a solution of (MePPh.sub.3).sub.2CoI.sub.4 (1.34 mmol)
in 25 mL of n-propanol. The autoclave was sealed and purged 3 times
with nitrogen. The reactor was pressurized to 6.9 MPa (1000 psig)
with 1:1 CO:H.sub.2 and heated to 195.degree. C. Upon reaching the
desired temperature, the reactor was pressurized to a total
pressure of 27.6 MPa (4000 psig) with 1:1 CO:H.sub.2. After 30
minutes the reactor was cooled to 5.degree. C. and the gas was
vented. The contents were analyzed by gas chromatography and the
amount of n-butyraldehyde produced is shown in Table 6. Examples
59-61 were run at the conditions shown in Table 6 and show the
production of n-butyraldehyde by the reductive carbonylation of
n-propanol. Table 6 shows weight percent of n-butyraldehyde in the
crude reductive carbonylation product; it does not include any
other components that could be an n-butyraldehyde equivalents.
TABLE-US-00009 TABLE 6 reductive carbonylation of n-propanol to
n-butyraldehyde at 195.degree. C., 4000 psig and a carbon monoxide
to hydrogen ratio of 1:1 Catalyst Conc. (mole % relative Wt % Time
to n- Phosphine n- Ex. (hr) Catalyst propanol) ligand butyraldehyde
58 0.5 (MePPh3)2Col4 0.2% -- 1.4% 59 1 (MePPh3)2Col4 0.2% -- 2.6%
60 0.5 (MePPh3)2Col4 0.2% dppp (0.1%) 1.4% 61 1 (MePPh3)2Col4 0.2%
dppp (0.1%) 3.0%
Examples 62-77 and C14-C15
[0135] These examples illustrate the ability to selectively produce
ethanol equivalents with the use of a ruthenium co-catalyst. For
Example 62, a 100-mL Hastelloy.RTM. C autoclave was charged with a
solution of (MePPh.sub.3).sub.2CoI.sub.4 (1.236 mmol), dppp (0.618
mmol), and Ru.sub.3(CO).sub.12 (0.206 mmol) in 25 mL of methanol.
The autoclave was sealed and purged 3 times with nitrogen. The
reactor was pressurized to 6.9 MPa (1000 psig) with 1:1 CO:H.sub.2
and heated to 195.degree. C. Upon reaching the desired temperature,
the reactor was pressurized to a total pressure of 16.5 MPa (2400
psig) with 1:1 CO:H.sub.2. After 30 minutes the reactor was cooled
to 5.degree. C. and the gas was vented. The contents were analyzed
by gas chromatography. The results are given in Table 7. Examples
63-77 and Comparative Examples C14 and C15 repeated Example 62 at
the conditions shown in Table 7; all runs were conducted with a
CO:H2 ratio of 1:1 and for 30 minutes, except Example 75 was
conducted for one hour. If toluene was present, it was present at
50 vol. %. No methyl iodide was detected in any of the crude
reductive carbonylation products listed in Table 7.
TABLE-US-00010 TABLE 7 reductive carbonylation of methanol to
ethanol with CO:H.sub.2 1:1 for 30 min. catalyst conc. Pres. (mol %
relative Ex. Temp. C. (psig) Catalyst to Methanol) ligand solvent
62 195 2400 (MePPh3)2CoI4 0.2% dppp -- Ru3(CO)12 0.03% (0.1%) 63
195 2400 (MePPh3)2CoI4 0.2% dppp -- Ru3(CO)12 0.03% (0.2%) 64 195
2400 (MePPh3)2CoI4 0.2% -- Ru3(CO)12 0.07% 65 195 2400
(MePPh3)2CoI4 0.2% dppp -- Ru3(CO)12 0.07% (0.1%) 66 195 2400
(MePPh3)2CoI4 0.2% Ph- -- Ru3(CO)12 0.07% triphos (0.1%) 67 190
4000 (MePPh3)2CoI4 0.4% -- -- Ru3(CO)12 0.133% 68 190 4000
(MePPh3)2CoI4 0.4% dppp -- Ru3(CO)12 0.133% (0.2%) 69 190 4000
(MePPh3)2CoI4 0.4% -- Toluene Ru3(CO)12 0.133% 70 195 4000
(MePPh3)2CoI4 0.2% -- Ru3(CO)12 0.07% 71 195 4000 (MePPh3)2CoI4
0.2% dppp -- Ru3(CO)12 0.07% (0.1%) 72 195 4000 (MePPh3)2CoI4 0.2%
Ph- -- Ru3(CO)12 0.07% triphos (0.1%) 73 195 4000 (MePPh3)2CoI4
0.4% dppp -- Ru3(CO)12 0.133% (0.2%) 74 195 4000 (MePPh3)2CoI4 0.4%
dppp Ru3(CO)12 0.133% (0.2%) 75 195 4000 (MePPh3)2CoI4 0.4% dppp
Ru3(CO)12 0.133% (0.2%) 76 195 4000 (MePPh3)2CoI4 0.4% dppp (Ph-
0.2% (0.2%) Triphos)Ru(CO)2 77 195 4000 (MePPh3)2CoI4 0.4% dppp
Toluene (Ph- 0.2% (0.2%) Triphos)Ru(CO)2 C14 175 4000 CoI2 0.2%
dppp -- MeI 0.2% (0.1%) Ru3(CO)12 0.07% C15 175 4000 CoI2 0.2% dppp
-- MeI 0.2% (0.1%) Ru3(CO)12 0.07% Yield of Acetal- Mol % Methanol
Carbonylated dehyde Ethanol Acetyls C4 Space Time Yield DME in Ex.
Conversion Products selectivity Selectivity Selectivity Selectivity
(Mh.sup.-1) product 62 39% 15% 23% 62% 13% 3% 4.2 0.2% 63 38% 14%
54% 33% 9% 4% 2.2 0.2% 64 24% 10% 7% 76% 13% 4% 2.3 0.1% 65 28% 11%
7% 75% 15% 4% 3.2 0.1% 66 28% 10% 7% 75% 13% 5% 7.7 0.1% 67 70% 43%
8% 68% 21% 3% 13.0 0.2% 68 64% 38% 5% 74% 20% 1% 12.2 0.3% 69 55%
20% 16% 75% 8% 1% 3.6 0.0% 70 43% 24% 2% 88% 8% 2% 8.2 0.3% 71 44%
25% 4% 85% 10% 2% 8.7 0.2% 72 38% 22% 4% 87% 8% 2% 7.7 0.2% 73 58%
33% 4% 85% 11% 1% 12.4 0.2% 74 48% 27% 3% 90% 7% 1% 10.5 0.2% 75
57% 36% 2% 92% 6% 1% 7.2 0.3% 76 76% 40% 45% 41% 8% 6% 7.7 0.3% 77
75% 40% 45% 43% 7% 6% 4.0 0.4% C14 48% 28% 4% 82% 14% 0% 9.6 0.8%
C15 52% 31% 4% 82% 14% 0% 10.3 1.1%
All Examples were conducted for 30 minutes except Example 75 was
conducted for one hour.
Examples 78-83
[0136] For Example 78, Example 67 was repeated with a carbon
monoxide to hydrogen (CO:H.sub.2) ratio of 1:2. The contents were
analyzed by gas chromatography. Results are given in Table 8.
Examples 79-83 repeated Example 78 at the conditions noted in Table
8. All of the Examples in Table 8 were conducted at 4000 psig and
CO:H.sub.2 ratio of 1:2.
TABLE-US-00011 TABLE 8 reductive carbonylation of methanol to
ethanol at 4000 psig and a CO:H.sub.2 of 1:2 catalyst conc. (mol %
relative Ex. Temp. C. Time (h) Catalyst to Methanol) ligand solvent
78 190 0.5 (MePPh3)2CoI4 0.4% -- -- Ru3(CO)12 0.133% 79 195 0.5
(MePPh3)2CoI4 0.4% dppp Toluene Ru3(CO)12 0.133% (0.2%) 80 195 1
(MePPh3)2CoI4 0.4% dppp Toluene Ru3(CO)12 0.133% (0.2%) 81 195 0.5
(MePPh3)2CoI4 0.6% dppp Ru3(CO)12 0.2% (0.3%) 82 195 0.5
(MePPh3)2CoI4 0.4% RuO2.cndot.xH2O 0.019% 83 195 2 (MePPh3)2CoI4
0.4% RuO2.cndot.xH2O 0.019% Yield of Acetal- Mol % Methanol
Carbonylated dehyde Ethanol Acetyls C4 Space Time Yield DME in Ex.
Conversion Products selectivity Selectivity Selectivity Selectivity
(Mh.sup.-1) product 78 44% 28% 1% 91% 8% 0% 10.3 0.3% 79 33% 16% 9%
78% 7% 6% 2.6 0.1% 80 41% 29% 5% 87% 5% 4% 2.7 0.1% 81 61% 34% 3%
86% 9% 3% 12.4 0.2% 82 33% 9% 23% 60% 13% 4% 2.0 0.5% 83 51% 28% 5%
87% 7% 1% 2.6 1.1%
Examples 84-87
[0137] The reductive carbonylation reaction of Example 1 was
repeated twice using 0.4 mole % (MePPh.sub.3).sub.2CoI.sub.4 and 50
vol % toluene. The cooled reductive carbonylation product for
Examples 84 and 86 partitioned into two layers. The relative
partitioning of selected components are given in Tables 9
(organics) and 10 (catalyst). The reductive carbonylation of
Example 1 was again repeated twice using 0.4 mole %
(MePPh.sub.3).sub.2CoI.sub.4 and 50 vol % hexane. The cooled
reductive carbonylation products for Examples 85 and 87 partitioned
into two layers. The relative partitioning of selected components
are given in Tables 9 and 10. The results shown in Table 9, the
partitioning of the organic compounds, were calculated based upon
gas chromatography analysis. The partitioning of the catalyst
component was determined using XRF. One skilled in the art, based
on these preliminary results, can expect that the desired products
could be extracted using a non-polar solvent, such as toluene,
while the catalyst would remain in the polar phase and be readily
recycled to the carbonylation reactor.
TABLE-US-00012 TABLE 9 Partitioning of components in the crude
reductive carbonylation product Yield of Co- MeOH Carbonylated
Product Ex. solvent Conv. Products Layer Water MeOH AcH
(MeO).sub.2Et EtOH HOAc MeOAc HBu 84 Toluene 84% 49% Non-polar 4%
17% 25% 77% 26% 34% 75% 69% Polar 96% 83% 75% 23% 74% 66% 25% 31%
85 Heptane 80% 41% Non-polar 2% 4% 5% 51% 7% 12% 34% 22%
TABLE-US-00013 TABLE 10 Partitioning of catalyst in the crude
reductive carbonylation product Cobalt Iodine Phosphorus Co-
content content content Ex. solvent Product Layer (ppm) (ppm) (ppm)
86 Toluene Non-polar <10.0 1288 272 (upper) Polar (lower) 1564
45923 3623 87 Heptane Non-polar <10.0 92 <10.0 (upper)
[0138] The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *