CA1157453A - Process for the selective production of ethanol and methanol directly from synthesis gas - Google Patents
Process for the selective production of ethanol and methanol directly from synthesis gasInfo
- Publication number
- CA1157453A CA1157453A CA000384412A CA384412A CA1157453A CA 1157453 A CA1157453 A CA 1157453A CA 000384412 A CA000384412 A CA 000384412A CA 384412 A CA384412 A CA 384412A CA 1157453 A CA1157453 A CA 1157453A
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- Prior art keywords
- ruthenium
- hydrogen
- charged
- promoter
- reaction
- Prior art date
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- Expired
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1512—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
- C07C29/1514—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions the solvents being characteristic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0211—Metal clusters, i.e. complexes comprising 3 to about 1000 metal atoms with metal-metal bonds to provide one or more all-metal (M)n rings, e.g. Rh4(CO)12
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF THE INVENTION
Alkanols are selectively produced as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalyst, a halogen or halide promoter and a phosphine oxide compound as solvent.
Alkanols are selectively produced as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalyst, a halogen or halide promoter and a phosphine oxide compound as solvent.
Description
~ ~7~
BACKGROUND OF THE INVENTION
Within the past decade the price of crude oil, the basis for most petroleum products, has increased significantly;
in addition its availability in needecl quantities has at times been severely curtailed. This has created many problems to the manufacturers and consumers leading to attempts to reduce reliance on crude oil as the basic starting material. A
maior product dependent on adequate supplies of crude oil is ethanol, which has ~een manufactured in significant quantities by the hydration of ethylene derived from petroleum or crude oil. The increased costs of crude oil are3 however, making this process less economical at a time when the demand for ethanol for use in fuels, such as gasohol, or as an inter-mediate for producing other organic compounds, such as ethylene Cfrom dehydration), is increasing at an unpredictable rate. Thus, much effort is being expended to the development of alternate processes for the production of ethanol at economically acceptable costs from otl~er sources.
While the production of ethanol by the well known fermentation process is well established, this process competes with the use of the s~arting materials generally used, grains and sugars, as foodstuffs. Further, in many instances the feedstocks are not readily available at the plant site and the processes are multi-step procedures re-quiring provisions for fermentation, distillation and disposal of residual solid wastes. To attempt to supp'y the antici-pated demand for ethanol solely by additional :Eermentation plants could result in a significant ~isru~tion in the amount of feed grain availa~le or human needs. As a result methods which do not severely disrupt these needs are preferred.
BACKGROUND OF THE INVENTION
Within the past decade the price of crude oil, the basis for most petroleum products, has increased significantly;
in addition its availability in needecl quantities has at times been severely curtailed. This has created many problems to the manufacturers and consumers leading to attempts to reduce reliance on crude oil as the basic starting material. A
maior product dependent on adequate supplies of crude oil is ethanol, which has ~een manufactured in significant quantities by the hydration of ethylene derived from petroleum or crude oil. The increased costs of crude oil are3 however, making this process less economical at a time when the demand for ethanol for use in fuels, such as gasohol, or as an inter-mediate for producing other organic compounds, such as ethylene Cfrom dehydration), is increasing at an unpredictable rate. Thus, much effort is being expended to the development of alternate processes for the production of ethanol at economically acceptable costs from otl~er sources.
While the production of ethanol by the well known fermentation process is well established, this process competes with the use of the s~arting materials generally used, grains and sugars, as foodstuffs. Further, in many instances the feedstocks are not readily available at the plant site and the processes are multi-step procedures re-quiring provisions for fermentation, distillation and disposal of residual solid wastes. To attempt to supp'y the antici-pated demand for ethanol solely by additional :Eermentation plants could result in a significant ~isru~tion in the amount of feed grain availa~le or human needs. As a result methods which do not severely disrupt these needs are preferred.
2.
1~7~3 1~835 Such procedures involve the use of synthesis gas, a mixture of carbon monoxide and hydrogen. This is an alternate feedstock which is inexpensive and increasingly desirable ~ecause it can be derived from n~n-petroleum sources such as coal.
Among the references relating to the production of or~anic compounds, including ethanol, of particular interest are those using complexes containing cobalt or osmium or ruthenium compounds as a component of the catalyst complex in the r~action of synthesis gas. Basically the known processes ~nvolve the catalytic homologation of methanol with synthesis gas at elevated temperatures and pressures, with most processes yielding a mixture of products that are subsequently separated.
To our present knowledge there is no single reference that can be said to individually teach how to selectively produce ethanol at commercially significant efficiencies directly from synthesis gas.
The direct, homogeneous con~ersion of synthesis gas to produce some ethanol is discussed in U.S. 2,534,018 issued ; 20 to W.F. Gresham on December 12, 1950. In this disclosure a cobalt-based catalyst and high pressures are used.
In U.S. 2,535,060 issued to W.F. Gresham on December 26, 1950, there is described a process for preparing mixtures of monohydric alcohols by the reaction of a mixture of carbon monoxide, hydrogen and a hydroxylated solvent at a temperature of from 150C to 300G and a pressure of from 200 to 1,000 atmospheres using a ruthenium-containing catalyst and an alkaline reagent to control pH within the range of 7 to 11.5. The reference clearl~ states that it is essential that the reac~ion take place in ~he liquid phase and that
1~7~3 1~835 Such procedures involve the use of synthesis gas, a mixture of carbon monoxide and hydrogen. This is an alternate feedstock which is inexpensive and increasingly desirable ~ecause it can be derived from n~n-petroleum sources such as coal.
Among the references relating to the production of or~anic compounds, including ethanol, of particular interest are those using complexes containing cobalt or osmium or ruthenium compounds as a component of the catalyst complex in the r~action of synthesis gas. Basically the known processes ~nvolve the catalytic homologation of methanol with synthesis gas at elevated temperatures and pressures, with most processes yielding a mixture of products that are subsequently separated.
To our present knowledge there is no single reference that can be said to individually teach how to selectively produce ethanol at commercially significant efficiencies directly from synthesis gas.
The direct, homogeneous con~ersion of synthesis gas to produce some ethanol is discussed in U.S. 2,534,018 issued ; 20 to W.F. Gresham on December 12, 1950. In this disclosure a cobalt-based catalyst and high pressures are used.
In U.S. 2,535,060 issued to W.F. Gresham on December 26, 1950, there is described a process for preparing mixtures of monohydric alcohols by the reaction of a mixture of carbon monoxide, hydrogen and a hydroxylated solvent at a temperature of from 150C to 300G and a pressure of from 200 to 1,000 atmospheres using a ruthenium-containing catalyst and an alkaline reagent to control pH within the range of 7 to 11.5. The reference clearl~ states that it is essential that the reac~ion take place in ~he liquid phase and that
3.
~ ~7~3 12835 water and any alcohol can be used as the liquid reaction medium; it also mentions that experimental evidence indicates that the liquid reaction medium may participate in the reaction. The chief products obtained are hydroxyalkanes having from 2 to lO carbon atoms but there does not seem to be any indication of selectivity to any one specific alkanol.
A closely relatPd reference is U.S. 2,549,470 issued to B.W. Howk et al on April 17, 1951, which claims a process for selectively producing straight chain alkanols having from 3 ~o 50 carbon atoms by the liquid phase reaction of a mixture of carbon monoxide, hydrogen and a hydroxylated sol~ent at a temperaturP of from 100C ~o 250C and a pressure of from 200 to l,000 atmospheres using a ruthenium-containing catalyst. These examples do show the production of small amounts of methanol and ethanol but the process essentially selectively produces the higher alkanols.
In U.S. 2,636,046 issued to W.F. Gresham on April 21, 1953 there is discussed a dîrect, homogeneous process for producing ethanol from synthesis gas at low selectivities using cobalt-based catalysts and high pressures.
A cobalt-based catalyst is used in U.S. 3,248,432 issued to A.D. Rlley et al on April 26, 1966, to produce ethanol. In this reference methanol is reacted with carbon monoxide and hydrogen at a pressure in excess of 3,000 to
~ ~7~3 12835 water and any alcohol can be used as the liquid reaction medium; it also mentions that experimental evidence indicates that the liquid reaction medium may participate in the reaction. The chief products obtained are hydroxyalkanes having from 2 to lO carbon atoms but there does not seem to be any indication of selectivity to any one specific alkanol.
A closely relatPd reference is U.S. 2,549,470 issued to B.W. Howk et al on April 17, 1951, which claims a process for selectively producing straight chain alkanols having from 3 ~o 50 carbon atoms by the liquid phase reaction of a mixture of carbon monoxide, hydrogen and a hydroxylated sol~ent at a temperaturP of from 100C ~o 250C and a pressure of from 200 to l,000 atmospheres using a ruthenium-containing catalyst. These examples do show the production of small amounts of methanol and ethanol but the process essentially selectively produces the higher alkanols.
In U.S. 2,636,046 issued to W.F. Gresham on April 21, 1953 there is discussed a dîrect, homogeneous process for producing ethanol from synthesis gas at low selectivities using cobalt-based catalysts and high pressures.
A cobalt-based catalyst is used in U.S. 3,248,432 issued to A.D. Rlley et al on April 26, 1966, to produce ethanol. In this reference methanol is reacted with carbon monoxide and hydrogen at a pressure in excess of 3,000 to
4,000 psi and a temperature of from about 150C to 250C in the presence of a modified catalyst complex containing cobalt, an iodine promoter and a phosphorus compound as defined. In essence this is an homologation process using a cobalt-based catalyst.
4.
I :~57~53 Another homologation process is disclosed in .S. 3,2~5,94,~ issued to C.N. Butter et al on November 15, 1966. Thls patent discloses the use of halides of ruthenium and osmium as second promoters in conjunction with cobalt and iodine for the production of ethanol by the homologation reaction of methanol with carbon mono~ide and hydrogen.
The in~ention claimed in U.S. 3,387,043 issued to M. Kuraishi et al on June 4, 1968 is the improvemPnt of adding water to the homologation reaction of ethanol, n-propanol or n-butanol with carbon monoxide and hydrogen using a catalyst containing cobalt and iodine.
The heterogeneous reaction of synthesis gas to produce ethanol at selectivities of less than 40 mole percent is discussed in U.S. 2,490,488 issued to S.G. Stewart on December 6, 1949. In this patent the catalyst was molybdenum disulfide and an alkaline compound of an alkali metal.
A solid, heterogeneous catalyst is used in the homologation reaction disclosed in U.S. 3,972,952 issued to R T. Clark on August 3, 1976. The catalytic agent :is a base pr~moter such as an oxide, hydroxide or salt of the alkali and alkaline earth metals and a metal of the group ruthenium, rhodium, palladlum, osmi~lm, iridium and platin~m on an inert solid support material comprising alumina. In this process an alkanol is converted to a higher alkanol.
In. U.S. 4,111,837 issued to P.D. Taylor on September 5, 1978, methanol is reacted in liquid phase with carbon monoxide and hydrogen at a temperature of from 100C
to 350G. and a pressure of from 1,000 to 15,000 psi in the presence of a heterogeneous catalyst containing a cobalt
4.
I :~57~53 Another homologation process is disclosed in .S. 3,2~5,94,~ issued to C.N. Butter et al on November 15, 1966. Thls patent discloses the use of halides of ruthenium and osmium as second promoters in conjunction with cobalt and iodine for the production of ethanol by the homologation reaction of methanol with carbon mono~ide and hydrogen.
The in~ention claimed in U.S. 3,387,043 issued to M. Kuraishi et al on June 4, 1968 is the improvemPnt of adding water to the homologation reaction of ethanol, n-propanol or n-butanol with carbon monoxide and hydrogen using a catalyst containing cobalt and iodine.
The heterogeneous reaction of synthesis gas to produce ethanol at selectivities of less than 40 mole percent is discussed in U.S. 2,490,488 issued to S.G. Stewart on December 6, 1949. In this patent the catalyst was molybdenum disulfide and an alkaline compound of an alkali metal.
A solid, heterogeneous catalyst is used in the homologation reaction disclosed in U.S. 3,972,952 issued to R T. Clark on August 3, 1976. The catalytic agent :is a base pr~moter such as an oxide, hydroxide or salt of the alkali and alkaline earth metals and a metal of the group ruthenium, rhodium, palladlum, osmi~lm, iridium and platin~m on an inert solid support material comprising alumina. In this process an alkanol is converted to a higher alkanol.
In. U.S. 4,111,837 issued to P.D. Taylor on September 5, 1978, methanol is reacted in liquid phase with carbon monoxide and hydrogen at a temperature of from 100C
to 350G. and a pressure of from 1,000 to 15,000 psi in the presence of a heterogeneous catalyst containing a cobalt
5.
~ 3 12835 derivative and a me~hanol-insoluble rhenium derivative.
Another heterogeneous reaction using a mixture of four essential elements Cl~ copper, (2) cobalt, ~3~ chromium, iron, vanadi~n or maganese, and (4) an alkali metal in the catalyst to convert synthesis gas to ethanol is described in .S. 4,122,110 issued to A. Sugier et al on October 24, 1978.
In this process the selectivity is below 40 weight percent.
The homologation of methanol with carbon monoxide and hydrogen to produce ethanol is described in U.S. 4,133,966 issued to W.R. Pretzer et al on January 9, 1979. In the process disclosed the catalyst system is cobalt acetylacetonate, a tertiary organo Group VA - compound, an iodine compound as a first promoter and a ruthenium compound as a second pro-moter. ~hile the reaction is said to be selective to the production o~ ethanol, the experimental data fails to show any selectivity values greater than 60 mole percent.
The use of rhodium in co~bination with thorium and/or uranium to produce two-carbon atom oxygenated products from synthesis gas using a heterogeneous catalyst is disclosed in U.S. 4,162,262 issued to P.C. Ellgen et al on July 24~
1979. This patent stresses the minimization of methanol co-production.
The ho~ologation of methanol wi~h synthesis gas in the liquid phase using a cobalt carbonyl catalyst is disclosed in U.S. 4,168,391 issued to W.E. Slinkard et al on September 18, 1979. The improvement claimed in this patent is the use of a non-polar, substantially inert, oxygenated hydrocarbon solvent that does not coordinate strongly with cobalt carbonyl as the solvent during the reaction.
~ 3 12835 derivative and a me~hanol-insoluble rhenium derivative.
Another heterogeneous reaction using a mixture of four essential elements Cl~ copper, (2) cobalt, ~3~ chromium, iron, vanadi~n or maganese, and (4) an alkali metal in the catalyst to convert synthesis gas to ethanol is described in .S. 4,122,110 issued to A. Sugier et al on October 24, 1978.
In this process the selectivity is below 40 weight percent.
The homologation of methanol with carbon monoxide and hydrogen to produce ethanol is described in U.S. 4,133,966 issued to W.R. Pretzer et al on January 9, 1979. In the process disclosed the catalyst system is cobalt acetylacetonate, a tertiary organo Group VA - compound, an iodine compound as a first promoter and a ruthenium compound as a second pro-moter. ~hile the reaction is said to be selective to the production o~ ethanol, the experimental data fails to show any selectivity values greater than 60 mole percent.
The use of rhodium in co~bination with thorium and/or uranium to produce two-carbon atom oxygenated products from synthesis gas using a heterogeneous catalyst is disclosed in U.S. 4,162,262 issued to P.C. Ellgen et al on July 24~
1979. This patent stresses the minimization of methanol co-production.
The ho~ologation of methanol wi~h synthesis gas in the liquid phase using a cobalt carbonyl catalyst is disclosed in U.S. 4,168,391 issued to W.E. Slinkard et al on September 18, 1979. The improvement claimed in this patent is the use of a non-polar, substantially inert, oxygenated hydrocarbon solvent that does not coordinate strongly with cobalt carbonyl as the solvent during the reaction.
6.
~ 1~7~3 1~835 A ruthenium based ca~alys~ is disclosed in U.S.
4,170,605 issued to R.C. Williamson et al on October 9, 1979; however, ~he process is one which selectively produces ethylene gl~col, not alkanols.
Homologation is also disclosed in U.S. 4,190,72~
issued to D. Foster on Tebruary 26, 1980, in which a tertiary phosphine oxide is used as a stabilizer during the homologation reaction of me~hanol to ethanol, acetaldehyde and methyl acetate employing a cobalt-based catalyst.
The selective production of ethanol by the homologa-tion of methanol with carbon ~onoxide and hydrogen under selected ratios and reaction conditions catalyzed by cobalt, ruthenium~ an iodine promoter, and a phosphine ligand is shown in commonly assigned paten~ application Serial No.
91,241,filed on November 15, 1979 by R.A. Fiato.
CQ~1 ~ .(~ C~ ~
In another commonly assigned~patent application 3~ 7 ~ec ~
Serial No.-9~iY~ filed on-~eYe~ee-~r, 1979 by B.D. Dombek, there is disclosed a process for selectively converting s~nthesis gas to ethylene glycol, ethanol and methanol using a homogeneous ruthenium carbonyl complex as the catalyst and a solvent which has a dielectric constant of at least 2 determined at 25C or at its melting point, whichever is higher; the process also contemplates the use of a Lewis ba~e promoter.
As is evident from the above, there is little existing prior art concerned with the direct selective pro-duction of ethanol from synthesis gas. In most instances ethanol is produced by homologation reactions, not directly, and in t~ose instances in which a direct process is clisclosed
~ 1~7~3 1~835 A ruthenium based ca~alys~ is disclosed in U.S.
4,170,605 issued to R.C. Williamson et al on October 9, 1979; however, ~he process is one which selectively produces ethylene gl~col, not alkanols.
Homologation is also disclosed in U.S. 4,190,72~
issued to D. Foster on Tebruary 26, 1980, in which a tertiary phosphine oxide is used as a stabilizer during the homologation reaction of me~hanol to ethanol, acetaldehyde and methyl acetate employing a cobalt-based catalyst.
The selective production of ethanol by the homologa-tion of methanol with carbon ~onoxide and hydrogen under selected ratios and reaction conditions catalyzed by cobalt, ruthenium~ an iodine promoter, and a phosphine ligand is shown in commonly assigned paten~ application Serial No.
91,241,filed on November 15, 1979 by R.A. Fiato.
CQ~1 ~ .(~ C~ ~
In another commonly assigned~patent application 3~ 7 ~ec ~
Serial No.-9~iY~ filed on-~eYe~ee-~r, 1979 by B.D. Dombek, there is disclosed a process for selectively converting s~nthesis gas to ethylene glycol, ethanol and methanol using a homogeneous ruthenium carbonyl complex as the catalyst and a solvent which has a dielectric constant of at least 2 determined at 25C or at its melting point, whichever is higher; the process also contemplates the use of a Lewis ba~e promoter.
As is evident from the above, there is little existing prior art concerned with the direct selective pro-duction of ethanol from synthesis gas. In most instances ethanol is produced by homologation reactions, not directly, and in t~ose instances in which a direct process is clisclosed
7.
a~57~L~3 12835 the process was not a homogeneous process or the ethanol selectivities and efficiencies achieved are not commercially acceptable.
SUMMA~Y OF THE II~VENTION
It ~s now been found that ethanol can be produced selectively as the major product directly from synthesis gas under mild conditions using a homogeneous catalyst. The catalyst system contains a ruthenium compound, an halogen or halide promoter Cpreferably based on iodine or bromine) and a phosphine oxide compound as solYen~. One can also include other promoters, if desired.
DES~RIPTION OF THE INVENTION
In the catalytic reactions of synthesis gas to produce organic compounds~ there are basically three signifi-cant parameters or criteria by which the catalysts are judged;
namely, stability, activity and selectivity. Stability re-lates to how long the catalyst remains functional before either breaking down or losing catalytic effect; activity relates to the amount of reactants the catalysts converts per unit of time; selectivity relates to the quantity of desired product produced, as compared to undesired compounds, during the catalytic reaction. The ideal situation is to have high values for all of these parameters, but this ideal is seldom, if ever, achieved. In fact, experience has shown that an improvement in one of the parameters often tends to have a detrimental effect on one or both of the other parameters and the ultimate result is usually an o~erall less efficient process.
The present invention is directed to a catalytic
a~57~L~3 12835 the process was not a homogeneous process or the ethanol selectivities and efficiencies achieved are not commercially acceptable.
SUMMA~Y OF THE II~VENTION
It ~s now been found that ethanol can be produced selectively as the major product directly from synthesis gas under mild conditions using a homogeneous catalyst. The catalyst system contains a ruthenium compound, an halogen or halide promoter Cpreferably based on iodine or bromine) and a phosphine oxide compound as solYen~. One can also include other promoters, if desired.
DES~RIPTION OF THE INVENTION
In the catalytic reactions of synthesis gas to produce organic compounds~ there are basically three signifi-cant parameters or criteria by which the catalysts are judged;
namely, stability, activity and selectivity. Stability re-lates to how long the catalyst remains functional before either breaking down or losing catalytic effect; activity relates to the amount of reactants the catalysts converts per unit of time; selectivity relates to the quantity of desired product produced, as compared to undesired compounds, during the catalytic reaction. The ideal situation is to have high values for all of these parameters, but this ideal is seldom, if ever, achieved. In fact, experience has shown that an improvement in one of the parameters often tends to have a detrimental effect on one or both of the other parameters and the ultimate result is usually an o~erall less efficient process.
The present invention is directed to a catalytic
8.
~ ~ ~7~53 12835 process in which the three basic parameters are maximized to a significant degree and in wllich ethanol is directly and selectively produced in a homogeneous process, and to the catalyst compositions used in such process; In the process of this invention ethanol is ohtained as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalys~. Methanol propanol, ethylene glycol and methane are the significant by-products, all of which can be separated and recovered, or recycled, if desired.
Alternately, the mixture of products could be used with a minimum of separation as a fuel.
Best resul~s are achieved in the process of this invention, leading to high selectivities and rates to ethanol and the above mentioned alkanols, when using a ruthenium catalyst, a halide or halogen promoter and a phosphine oxide compound as the solvent. The advantages observed by the instant process in t~e production of ethanol, as compared to other known processes, include the fact that it is a homogeneous process, it uses synthesis gas as a feedstock rather than petroleum based feedstocks, it produces a maJor amount of ethanol directly in a single step, the selectivity to ethanol is unexpectedly high and the selectivity to ethanol plus methanol ~which can be recycles to retard fur~her formation of methanol) is even higher, the reaction can be conducted at what are considered mild conditions by those skilled in this art, and the number of significant by-products produced are few, but useful. The method has significant economic and process advantages due to the fact that since it is a homogeneous reaction there is greater efficiency in removing heat of 1~57~3 1~835 reaction and thus a corresponding ease of heat control;
further, there is greater ease in charac~erizing the catalytic and related species present in the reactio~, which helps in controlling the process, analyzing the process and products, and opt~nizing the final results.
The invention is ad~antageous when compared to other known processes when the intent is to produce a mixture of compounds, e.g. alkanols, for fuel use in that it is a one-step, h~mogeneous, direct process from synthesis gas to yield a mixture ~igh in alcohols that can be used wLth a minimum of purification. Thus the use of this înven~ion for the manufacture of compositions useful as fuels is of significant importance in today's ecomony.
The ruthenium component of the catalyst can be supplied from any number of sources and those skilled in the art are full~ familiar with tlle many classes of ruthenium compounds that can be used to supply the rutheni~n component.
Thus, any of th~ ruthenium compounds such as the ruthenium salts, oxides, carbonyls, organic carboxylic acid salts, or ruthenium metal its~lf, which may form soluble rutheniurn carbonyl or hydrocarbonyl compounds under the reaction conditions can be used. The ruthenium complexes which catalyze the reaction are not speci~ically known; they can be monorutheni~m or polyruthenium complexes. Arnong the ruthenium compounds that can be used as the source for the ruthenium component one can mention ruthenium dioxide, rutheniurn ses-quioxide, ruthenium tetraoxide, rutheniurn trichloride or tri~romide or triiodide, ruthenium acetate, ruthenium acetyl-acetonate, ruthenium propionate, ruthenium octanoate, 10 .
~ 157~53 12835 ruthenium pentacarbonyl, triruthenium dodecacarbonyl, ruthenium carbonyl hydride, diruthenium nonacarbonyl, ruthenium C2,4-pentanedionate~, or any other ruthenlum compound wllich can generate a soluble ruthenium complex under th~ reaction conditions. They can be used individually or as mix~ures of two or more ruthenium compounds.
The concentration of ruthenium compound charged to the reaction can be from 0.01 to 30 weight percent of the total weight of the reaction mixture, based on contained ruthenium, it is preferably from 0.2 to 10 weight percent and most preferably from 0.5 to 5 weight percent.
The preferred promoters are those halogen con~aining compounds capable of genera~ing HI or HBr during the reaction, including elemental iodine and bromine, i.e., HI or HBr precursors. ~ome stable halide salts, e.g. KI, CsI, were also found to be good promoters to selectively produce mixtures of ethanol plus methanol, and under certain conditions produce ethanol as the major product. Illustrative of suitable halogen promoters, or HI or HBr precursors, one can mention iodine, bromine, potassium iodide, tetramethylammonium iodide, trimethylsulfonium iodide, methyl iodide, butyl iodide, tetrabutylammonium iodide, hydrogen iodide, tetramethyl-phosphonium iodide, cesium iodide, tetraethylammonium iodide, cobalt iodide, as well as the corresponding bromide compounds. Any source of iodine or bromine capable of generating HI or HBr in situ can be used; these are well known to those of average skill in this art. Also among the useful compounds are the alkyl iodides and bromides having from 1 to about 10 carbon atoms, as well as any other organic 11 .
~1~7~3 12835 iodine or bromine compound capable of producing HI or HBr in situ. Furth~r, one can use mixtures of the elemental halogens and/or the halogen compounds. As used in this application the term "halogen promoter" incl`udes the elemental forms of iodine and bromine as well as the compounds containing these elements.
The amoun~ of halogen promoter charged ~o the reac~ion will vary from an amount sufficien~ to produce an HI and/or HBr/~u atom mole ratio of O.OUl:l to S:l, prefer-ahly ~rom 0.01:1 to 3:1, most preferably from 0.1:1 to 2:1,in situ during the reaction. It has been observed, however, that at ratios above about 3:1 the reaction will not proceed at a substantial rate even though it will selectively prodwce alkanols in major amounts. Care must be exercised in selection of a particular promoter compound. Thus, it was found that when the organic quarternary halide salts were used as promotars, even at high promoter to ruthenium levels Cgreater than 3:1~ the reaction proceeded well at low temperatures, e.g. below about 2~0C, but at higher tempera-tures, e.g. above about 240C, decomposi~ion of such promotersto generate the hydrogen halide proceeds to such a degree that the hydrogen halide to ruthenium ratio becomes greater than 3:1 and the reaction will not proceed as well.
The preferred halogen promoters can also be supple-mented, if desired, by the inclusion of other promoters that are known in the art. Thus, it has been found that the inclusion of selected promoters, in amounts known to those skilled in the art, such as the Lewls bases ~e.g. R3N, R3P, R2S t~pe compounds and zinc iodide) did not harm the reaction and in certain instances were beneficial.
12.
~57453 12$35 Xt was also noted that promoter combinations containing an alkali metal halide as one of the components of the comhination were effective and that ~hen used in metal halide to ruthenium atom ratios of about less than 1:1 served to pr~mote the ra~e at which ethanol was selec~ively produced.
At high levels of alkali metal halide t:o ru~henium atom, methanol and ethanol are produced at a faster rate but me~hanol may ~e the major product. In addition it was observed that the use of an alkali metal halide as the sole promoter at a ratio to ruthenium greater than ~:l and as high as 20:1 results in good rates to mixtures of ethanol plus methanol hut that ethanol was produced at a lower selectivity than when the alkali me~al halide to ruthenium ratio was less ~han 2:1.
Also present in the reaction is an organic phosphine oxide compound as solvent, which can be represented by the general formula:
R'3P=0 in which R' is an organic radical such as an unsubstituted or substituted alkyl group having from 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms or an unsubstituted or sub-stituted aryl group having from 6 to 10 ring carbon atoms.
The alkyl or aryl groups can be substi~uted with oxygen, sulfur, phosphorus or nitrogen containing groups which do not unduly interfere with the reaction. These co~pounds are well known to those skilled in the art and illustrative thereof one can ~ention tripropylphosphine oxide, di(2-methoxyethoxymethyl~
methylphosphine oxide, triphenylphosphine oxide, trioctylphos-phlne oxide, di-n-n-propyl-n-butylphosphine oxide, triallyl-phosphine oxide, tricyclohexylphosphine oxide, and ~he like.
13.
1 ~57~3 The phosphine oxides can be used alone or in combination with otller sol~ents kno~n to be useful to tho~e skilled in the art.
The amount of phosphine oxide used can be from 1 to 100 weight percent; preferably from lO to lO0, of the total weight of solvent charged to the reactor wi~h the balance being a conventional solvent known to those skilled in the art, e~g. 1,4,7,10,13,]6-hexaoxacyclooc~adecane, di-phenyl ether, sulfolane, M-methylpyrollidone, tetraglyme, and the like.
The reaction is carried out at a temperature of from about 100C to 350C, preferably from 160C to 2.~0~C. The preferred range is more satis~actory with the onium salts in order to obtain better control of the hydrogen halide to ruthenium ratio.
~ le reaction can be carried out at total pressures of from 500 psi to 20,000 psi or more; preXerably from l,000 psi to 12,500 psi; and most preferably from 2,500 psi to 8,000 psi. Variations in pressure can affect the rate and selectivity to ethanol and those skilled in the art can readily ascertain the best conditions to employ with each particular catalyst, promoter and solvent system employed by routine procedures. While higher pressures tend to result in greater productivities, they may not be justified economically since they require higher capital investment and since, generally, good rates can be achieved at the lower pressures indicated.
The xatio of carbon monoxide to hydrogen (CO:H2) in the s~nthesis gas feed mixture can range from 0.1:1 to 10:1; preferably from 0.25:1 to 4:1; and most preferably from 0.33:1 to 2:1.
14.
` ~57453 The improved process and catalyst of this invention result in the selective production of ethanol or mixtures containing ethanol directly from synthesis gas at significantly better yields than heretofore achieved. By use of this in~ention ethanol or synthetic fuel mixtures can be produced directly under what are technlcally considered relatively mild reaction conditions using a homogeneous catalyst s~stem. The results achieved and the advantages noted were completely unexpected and unpredictable from the published knowledge.
In the examples the product yields are reported in values o weight of product produced, the rates are reported in moles/liter/hour and the selectivity in weight percent, unless otherwise indicated. Carbon dioxide produced by the water gas shift reaction is ignored in the selectivity cal culations. Standard analytical procedures were used to analyze for gaseous and liquid components present in the final reaction product.
Three standard procedures were used for the reactions described in the examples.
Standard Procedure A
_ _ Triruthenium dodecacarbonyl, promoter and 75 ml of tripropylphosphine oxide were placed in a back-~ixed autoclave having a net vol~e of 128 ml and heated, with stirring, to 55C. ~he reactor was pressured to 500 psi with C0, heated to the desired te-mperature and pressurized wi~h a H2/C0 mixture chaving the desired ratio of H2:C0) to the total desired pressure plus 250 psi. As the reaction proceeded the pressure ~as allowea to drop 500 psi and then repressured to 15.
~ ~ S7~3 12~35 the original total pressure with the synthesis gas. After a total of 2,000 psi of synthesis gas had reacted, or two hours had passed, whichever occurred first, the reactor was rapidly cooled to 40C. The gaseous components in the reactor were vented to and collected in a 3 liter stainless steel bomb and vapor phase chroma~ographic analyses were performed to determine hydrogen, carbon monoxide, carbon dioxide and Cl to C~ carbon, hydrogen and oxygen containing gaseous organic compounds. The liquid components in the reactor were weighed and analyzed by vapor phase chromatograph and other conventional analytical methods to ascertain their identity and concentration.
Standard Procedure B
-Triruthenium dodecacarbonyl, promoter and 50 ml of tripropylphosphine oxide were placed in a glass lined rocker autoclave having a net volume of 500 ml and pressurized with a H2/C0 mixture ~having the desired ratio~ to a pressure such that after the desired temperature has been attained, the preæsure in the autoclave was at 4,600 psi to 5,000 psi.
The autoclave wasrepressurized with synthesis gas when the pressure had dropped to about 4,000 psi. Two hours after the initial attainment of the desired temperature, the autoclave and its contents were cooled to 0 to 40C, ~aseous components vented to the atmosphere and the liquid components were weighed and analyzed by vapor phase chro~atograph methods using at least two difEerent columns The total pressure is reported as t~e average pressure for the run.
S'tandard ~rocedure C
This procedur~ is identical to Standard Procedure A
except that the reaction proceeded until 6,000 psi of synthesis gas had reacted or four hours had passed, whichever occurred 16.
1 ~57453 first, and that the gaseous components were vented and not an~lyzed; therefore, seIectivities reported are based on the ~eight percen~ of liquid products analyzed by the vapor phase chromatographic methods.
The following examples serve to rurther illustrate the in~ention.
Example 1 Ethanol was selectively produced using Standard Procedure A. In this experiment 16 mgram atoms of Ru, as triruthenium dodecacarbonyl, 5.6 mmoles of elemental iodine and 75 ml of tripropylphosphine oxide were used; the H~/C0 ratio was 2:1 and the reaction was carried ou~ at a ~otal pressure of 6,000 psi at 240C. There were produced as determined by vapor phase chromatograph analysis, 2.12 g of ethanol, 1.03 g of methanol, 0.12 g of propanol, 0.82 g of methane and 0.17 g of other liquid products; slight traces of gaseous or other liquid produc~s were also detected. Ethanol was produced at the rate of 2.05 moles/liter/hour at a selectivity of 50 weight percent; the selectivity to ethanol plus methanol was 74 weight percent. The results show that ethanol or mixtures of alkanols can be produced at high selectivity directly from synthesis gas by this invention.
_ample 2 Standard Procedure A was again employed using 8 mgram atoms of Ru, as ruthenium dodecacarbonyl, 4 mmoles of elemental iodine and 75 ml o tripropylphosphine oxide; the /CO ratio was 2:1. Th2 reaction was carried out at a total pressure of 6,000 psi at 240C. There were produced 2.46 g o~ ethanol, 0.97 g of methanol, 0.19 g of propanol, 0.95 grams of methane and 0.18 g of other liquid produc~s;
17.
1~57~3 12835 slight traces o~ gaseous or other liquid products were also detected Ethanol was produced at a rate of 1.9 moles/liter/
hour at a selectivit~ of 52 weight percent; the selectivlty to ethanol plus methanol was 72 weight percent; illustrating the ability to directly produce alkanols at high selectivity from synthesis gas.
Example 3 Standard Procedure A was employed using 24 mgram atoms of Ru, as ruthenium dodecacarbonyl, 15.6 mmoles of elemental iodine a~d 75 ml of tripropylphosphine oxide; the H2/C0 ratio was 1:1. The reaction was carried out at a total pressure of 6,000 psi at 195~C. There were produced 2.48 g of ethanol, 1.03 g of methanol, 0.1 g of propanol, 0.62 g of methane and 0.27 g of other liquid products;
slight traces of gaseous or other liqui.d products were also detected. Ethanol was produced at the rate of 0.6 molel liter/hour at a selectivity to e~hanol plus methanol o 78 weight percent. The results show that at lower temperatures high selectivity -to alkanols is still achieved though at a lower rate.
Examples 4 to 23 Standard Procedure A was followed in these examples in which ethanol and mix~ures of ethanol with other alkanols were selectively produced directly from synthesis gas. The reaction conditions and results are summarized in Table I.
In the table the partial pressures of H2 and C0 present in the synthesls gas mixture charged are recorded, from which the total pressure is readily ascertained. Elemental iodine ~as used as promoter and the ratio stated is the L/Ru ratio, 18.
~ ~157~3 1~835 not the l2/Ru ratio. Selectivity (Sel.) values reported are the area percent ethanol divided by the total area for all vapor phase chromatograph peaks other than water, air and solvent.
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~ 4~3 12835 Examples _24 to _ Table II shows the selective production of ethanol or eth~nol plus methanol mixtures directly from synthesis gas ~y the process of this invention. It illu`strates the use of dif~erent promoters and solvents as well as variations in the temperature and pressure reaction conditions employable.
~nless otherwise indicated all of the examples used 75 ml of tripropylphosphine oxide ~Pr3PO), 9 mgram atoms of Ru as tri-ruthenium dodecacarbonyl and a H2/~O ratio of 1:1, and were run at 210C. Selectivities were determined by vapor phase chromatographic analysis of the liquid products produced and are reported in weight percent.
The proceclure ~sed in Examples 55, 56 and 70 through 76 was identical to Standard Procedure A except that the reaction proceeded until 6,00G psi of synthesis gas had reacted or two hours had passed, whichever occurred first.
In all 76 eEamples the designation moles/liter/
hour, indicating the formation rates of produc~s, is based on the reaction solution in the reactor or moles/liter of solution/hour.
21.
1 1~7~3 TABLE II
F~ atio-ll Selectiviti~.s Total P p~moter M~leslL/Hr. Etn~ F~n~ 5tandard Ex pSI Cmmoles~ MeOH EtOH Wt,~--- Proce~ure 24 12,500 MerNI(18~ 3.042.56 44.982.6 C
25 12,500 I~ ~4~1.20 2.25 63.490.4 C
26 6,000 I2(2) .11 .37 68.784.3 C
27 6,000 I2(3~ .07 .32 67.379.0 C
28 6,000 KI (18~.46 .56 52.984.9 C
29 6,000 I2(4~ .28 .59 57.176.8 C
30 4,300r Me4NI(18).55.76 63.591.8 B
31 4~300 Me3SI~9).16 .52 72.187.3 B
32 4,300r KI (9~ .94 .83 52.294.2 B
33 4,300r MeI (3).17 .49 71.387.5 B
34 4,300r MeI (3).26 .62 _ _ B
35 4,300r KI (9) .86 .76 52.893.9 B
BuI (3) 36 4,300r KI (18)1.12 .68 44.596.4 B
37 12,500b ~u~Nl (18) .17.74 51 50.3 C
38 6,000 I2 ~6) .08 .38 _ - C
39 6,0~0 I2 (1) .11 .27 _ _ C
6,000 I2 (9) 04 .18 - - C
41 12,500q KI (18)2.S52.25 _ _ C
42 12,500q KI ~13)1.722.26 _ _ C
HI 6) 43 12,500q KI ~18).47 1.53 - C
HI (12) 1~7~3 1~83 TABLE II CContinued) F~ io~l Selectivitie~
Total P Prc)moter Mole~./Hr. EtO~ tml~ Standard Ex PSI Cmm~les~P~eO~ EtOH ~ ~/ eOHProcedure 4412,500q'e KI ~18~ 2.91 1,71 - - C
HI C2 ~
45 4,300r Me4Br(18) .44 .57 - - B
46 6, ooOd Me~PI(36)~ 40 . 39 - - C
474,300e~P Me4PCl(9) .07 .0~ - - B
4~4, 300~ ~ P KI (9) . 99 . 43 - - B
4912,500b~e CsI(18) 1.5 .32 _ _ C
5012,500b~e KI(18) 2.1 .32 - _ C
51 12,500b'e'fBu4NI(18) .45 .12 - _ C
5 212, 500b ~ ' gBP4NI (18). 43 .18 - - C
53 6, 000 I2(4 . 5) .15 . 34 - - C
KI (183 Bu3P (3) 54 6, 000 I2 (4 . 5). 22 . 36 ~ ~ C
5~ 1~,500 Bu4NI(6) .52 1.04 - - C
MeI (1) 56 " Bu4NI (6). 75 1. 3 - _ C
MeI (~) Bu3N (1 . 5 ) 5712,500b lKI~18) .96 1.04 - C
MeI (3) 5812, 500b KI C18) 1. 7 . 81 - - C
MeI (3 ) Bu3N C4~
59S, 000 I2 ~4~ . 09 . 3S - C
606, 000 I2 C4~ . 28 . 59 ~u4N C6 ) 23 .
~7~3 ~2835 TABLE II (Continued) Formation Rates Selectivi~ies To~al PPromoter Moles/L/Hr. EtOH~ Standard Ex. PSI_(mmoles) MeOH EtOH Wt. ~ Procedure 61 69000 I2~4) ~19 .41 - C
Bu3N~8) 62 6,000 I2l4) .27 ~40 _ _ C
Bu3N~12) 10 63 6,000 I2~) 3 .40 - C
Bu3N(18) 64 4,300 Bu4NI(6) .4 .59 4,300 Bu4NI(6) .009 .002 - _ MeI(35.2) 66 12,500b ZnI2(1.5) .71 1.25 - - C
67 6,000i'J'mI2(4) .98 1.~4 - - A
68 6,000i9g'i'mI2(4) .02 - _ _ A
69 6 0OOi,k~m I2(4) .60 .72 - _ A
20 70 6,000~ 'mI2(4) 1.04 .93 - - A
71 6,000i9i~ CsI(~) .99 .73 - - A
72 6,000i~J~m CsI(2) .41 .47 _ _ A
73 6~000i~i~m CsI(8) .93 .58 - _ A
74 6,000m~n' CsI(6.4) .21 47 ~ ~ A
6,000m'n' CsI(3.2) .26 .43 - - A
76 6,000~ m KI(4) 1.0 .90 - - A
b 3 mgram atoms Ru as Ru3~CO)12 d 13 mgram-atoMs ~u as RU3~CO)12 e Some of these examples are for comparative purposes. They do not represent preferred conditions of this invention.
f 75 ml of 18 Crown~6 as solvent g 75 ml of ~ulfolane as solvent i 8 mgram-atoms Ru as Ru3(CO)12 j H~/CO = 2 k 37.5 ml of Pr3PO and 37.5 ml 18-C-6 as solvent 1 37.5 ml of Pr3PO and 37.5 ml oE ~lolane as solvent m Run at 240C
n H2/CO = 2.33 o 16 mgram-atoms Ru as Ru3(CO)12 p ~un at ~30C
q 6 mgram atoms Ru aæ Ru3(COa12 r 50 ml Pr3PO a~ 601vent 24.
~,
~ ~ ~7~53 12835 process in which the three basic parameters are maximized to a significant degree and in wllich ethanol is directly and selectively produced in a homogeneous process, and to the catalyst compositions used in such process; In the process of this invention ethanol is ohtained as the major product directly from synthesis gas under mild conditions using a homogeneous ruthenium catalys~. Methanol propanol, ethylene glycol and methane are the significant by-products, all of which can be separated and recovered, or recycled, if desired.
Alternately, the mixture of products could be used with a minimum of separation as a fuel.
Best resul~s are achieved in the process of this invention, leading to high selectivities and rates to ethanol and the above mentioned alkanols, when using a ruthenium catalyst, a halide or halogen promoter and a phosphine oxide compound as the solvent. The advantages observed by the instant process in t~e production of ethanol, as compared to other known processes, include the fact that it is a homogeneous process, it uses synthesis gas as a feedstock rather than petroleum based feedstocks, it produces a maJor amount of ethanol directly in a single step, the selectivity to ethanol is unexpectedly high and the selectivity to ethanol plus methanol ~which can be recycles to retard fur~her formation of methanol) is even higher, the reaction can be conducted at what are considered mild conditions by those skilled in this art, and the number of significant by-products produced are few, but useful. The method has significant economic and process advantages due to the fact that since it is a homogeneous reaction there is greater efficiency in removing heat of 1~57~3 1~835 reaction and thus a corresponding ease of heat control;
further, there is greater ease in charac~erizing the catalytic and related species present in the reactio~, which helps in controlling the process, analyzing the process and products, and opt~nizing the final results.
The invention is ad~antageous when compared to other known processes when the intent is to produce a mixture of compounds, e.g. alkanols, for fuel use in that it is a one-step, h~mogeneous, direct process from synthesis gas to yield a mixture ~igh in alcohols that can be used wLth a minimum of purification. Thus the use of this înven~ion for the manufacture of compositions useful as fuels is of significant importance in today's ecomony.
The ruthenium component of the catalyst can be supplied from any number of sources and those skilled in the art are full~ familiar with tlle many classes of ruthenium compounds that can be used to supply the rutheni~n component.
Thus, any of th~ ruthenium compounds such as the ruthenium salts, oxides, carbonyls, organic carboxylic acid salts, or ruthenium metal its~lf, which may form soluble rutheniurn carbonyl or hydrocarbonyl compounds under the reaction conditions can be used. The ruthenium complexes which catalyze the reaction are not speci~ically known; they can be monorutheni~m or polyruthenium complexes. Arnong the ruthenium compounds that can be used as the source for the ruthenium component one can mention ruthenium dioxide, rutheniurn ses-quioxide, ruthenium tetraoxide, rutheniurn trichloride or tri~romide or triiodide, ruthenium acetate, ruthenium acetyl-acetonate, ruthenium propionate, ruthenium octanoate, 10 .
~ 157~53 12835 ruthenium pentacarbonyl, triruthenium dodecacarbonyl, ruthenium carbonyl hydride, diruthenium nonacarbonyl, ruthenium C2,4-pentanedionate~, or any other ruthenlum compound wllich can generate a soluble ruthenium complex under th~ reaction conditions. They can be used individually or as mix~ures of two or more ruthenium compounds.
The concentration of ruthenium compound charged to the reaction can be from 0.01 to 30 weight percent of the total weight of the reaction mixture, based on contained ruthenium, it is preferably from 0.2 to 10 weight percent and most preferably from 0.5 to 5 weight percent.
The preferred promoters are those halogen con~aining compounds capable of genera~ing HI or HBr during the reaction, including elemental iodine and bromine, i.e., HI or HBr precursors. ~ome stable halide salts, e.g. KI, CsI, were also found to be good promoters to selectively produce mixtures of ethanol plus methanol, and under certain conditions produce ethanol as the major product. Illustrative of suitable halogen promoters, or HI or HBr precursors, one can mention iodine, bromine, potassium iodide, tetramethylammonium iodide, trimethylsulfonium iodide, methyl iodide, butyl iodide, tetrabutylammonium iodide, hydrogen iodide, tetramethyl-phosphonium iodide, cesium iodide, tetraethylammonium iodide, cobalt iodide, as well as the corresponding bromide compounds. Any source of iodine or bromine capable of generating HI or HBr in situ can be used; these are well known to those of average skill in this art. Also among the useful compounds are the alkyl iodides and bromides having from 1 to about 10 carbon atoms, as well as any other organic 11 .
~1~7~3 12835 iodine or bromine compound capable of producing HI or HBr in situ. Furth~r, one can use mixtures of the elemental halogens and/or the halogen compounds. As used in this application the term "halogen promoter" incl`udes the elemental forms of iodine and bromine as well as the compounds containing these elements.
The amoun~ of halogen promoter charged ~o the reac~ion will vary from an amount sufficien~ to produce an HI and/or HBr/~u atom mole ratio of O.OUl:l to S:l, prefer-ahly ~rom 0.01:1 to 3:1, most preferably from 0.1:1 to 2:1,in situ during the reaction. It has been observed, however, that at ratios above about 3:1 the reaction will not proceed at a substantial rate even though it will selectively prodwce alkanols in major amounts. Care must be exercised in selection of a particular promoter compound. Thus, it was found that when the organic quarternary halide salts were used as promotars, even at high promoter to ruthenium levels Cgreater than 3:1~ the reaction proceeded well at low temperatures, e.g. below about 2~0C, but at higher tempera-tures, e.g. above about 240C, decomposi~ion of such promotersto generate the hydrogen halide proceeds to such a degree that the hydrogen halide to ruthenium ratio becomes greater than 3:1 and the reaction will not proceed as well.
The preferred halogen promoters can also be supple-mented, if desired, by the inclusion of other promoters that are known in the art. Thus, it has been found that the inclusion of selected promoters, in amounts known to those skilled in the art, such as the Lewls bases ~e.g. R3N, R3P, R2S t~pe compounds and zinc iodide) did not harm the reaction and in certain instances were beneficial.
12.
~57453 12$35 Xt was also noted that promoter combinations containing an alkali metal halide as one of the components of the comhination were effective and that ~hen used in metal halide to ruthenium atom ratios of about less than 1:1 served to pr~mote the ra~e at which ethanol was selec~ively produced.
At high levels of alkali metal halide t:o ru~henium atom, methanol and ethanol are produced at a faster rate but me~hanol may ~e the major product. In addition it was observed that the use of an alkali metal halide as the sole promoter at a ratio to ruthenium greater than ~:l and as high as 20:1 results in good rates to mixtures of ethanol plus methanol hut that ethanol was produced at a lower selectivity than when the alkali me~al halide to ruthenium ratio was less ~han 2:1.
Also present in the reaction is an organic phosphine oxide compound as solvent, which can be represented by the general formula:
R'3P=0 in which R' is an organic radical such as an unsubstituted or substituted alkyl group having from 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms or an unsubstituted or sub-stituted aryl group having from 6 to 10 ring carbon atoms.
The alkyl or aryl groups can be substi~uted with oxygen, sulfur, phosphorus or nitrogen containing groups which do not unduly interfere with the reaction. These co~pounds are well known to those skilled in the art and illustrative thereof one can ~ention tripropylphosphine oxide, di(2-methoxyethoxymethyl~
methylphosphine oxide, triphenylphosphine oxide, trioctylphos-phlne oxide, di-n-n-propyl-n-butylphosphine oxide, triallyl-phosphine oxide, tricyclohexylphosphine oxide, and ~he like.
13.
1 ~57~3 The phosphine oxides can be used alone or in combination with otller sol~ents kno~n to be useful to tho~e skilled in the art.
The amount of phosphine oxide used can be from 1 to 100 weight percent; preferably from lO to lO0, of the total weight of solvent charged to the reactor wi~h the balance being a conventional solvent known to those skilled in the art, e~g. 1,4,7,10,13,]6-hexaoxacyclooc~adecane, di-phenyl ether, sulfolane, M-methylpyrollidone, tetraglyme, and the like.
The reaction is carried out at a temperature of from about 100C to 350C, preferably from 160C to 2.~0~C. The preferred range is more satis~actory with the onium salts in order to obtain better control of the hydrogen halide to ruthenium ratio.
~ le reaction can be carried out at total pressures of from 500 psi to 20,000 psi or more; preXerably from l,000 psi to 12,500 psi; and most preferably from 2,500 psi to 8,000 psi. Variations in pressure can affect the rate and selectivity to ethanol and those skilled in the art can readily ascertain the best conditions to employ with each particular catalyst, promoter and solvent system employed by routine procedures. While higher pressures tend to result in greater productivities, they may not be justified economically since they require higher capital investment and since, generally, good rates can be achieved at the lower pressures indicated.
The xatio of carbon monoxide to hydrogen (CO:H2) in the s~nthesis gas feed mixture can range from 0.1:1 to 10:1; preferably from 0.25:1 to 4:1; and most preferably from 0.33:1 to 2:1.
14.
` ~57453 The improved process and catalyst of this invention result in the selective production of ethanol or mixtures containing ethanol directly from synthesis gas at significantly better yields than heretofore achieved. By use of this in~ention ethanol or synthetic fuel mixtures can be produced directly under what are technlcally considered relatively mild reaction conditions using a homogeneous catalyst s~stem. The results achieved and the advantages noted were completely unexpected and unpredictable from the published knowledge.
In the examples the product yields are reported in values o weight of product produced, the rates are reported in moles/liter/hour and the selectivity in weight percent, unless otherwise indicated. Carbon dioxide produced by the water gas shift reaction is ignored in the selectivity cal culations. Standard analytical procedures were used to analyze for gaseous and liquid components present in the final reaction product.
Three standard procedures were used for the reactions described in the examples.
Standard Procedure A
_ _ Triruthenium dodecacarbonyl, promoter and 75 ml of tripropylphosphine oxide were placed in a back-~ixed autoclave having a net vol~e of 128 ml and heated, with stirring, to 55C. ~he reactor was pressured to 500 psi with C0, heated to the desired te-mperature and pressurized wi~h a H2/C0 mixture chaving the desired ratio of H2:C0) to the total desired pressure plus 250 psi. As the reaction proceeded the pressure ~as allowea to drop 500 psi and then repressured to 15.
~ ~ S7~3 12~35 the original total pressure with the synthesis gas. After a total of 2,000 psi of synthesis gas had reacted, or two hours had passed, whichever occurred first, the reactor was rapidly cooled to 40C. The gaseous components in the reactor were vented to and collected in a 3 liter stainless steel bomb and vapor phase chroma~ographic analyses were performed to determine hydrogen, carbon monoxide, carbon dioxide and Cl to C~ carbon, hydrogen and oxygen containing gaseous organic compounds. The liquid components in the reactor were weighed and analyzed by vapor phase chromatograph and other conventional analytical methods to ascertain their identity and concentration.
Standard Procedure B
-Triruthenium dodecacarbonyl, promoter and 50 ml of tripropylphosphine oxide were placed in a glass lined rocker autoclave having a net volume of 500 ml and pressurized with a H2/C0 mixture ~having the desired ratio~ to a pressure such that after the desired temperature has been attained, the preæsure in the autoclave was at 4,600 psi to 5,000 psi.
The autoclave wasrepressurized with synthesis gas when the pressure had dropped to about 4,000 psi. Two hours after the initial attainment of the desired temperature, the autoclave and its contents were cooled to 0 to 40C, ~aseous components vented to the atmosphere and the liquid components were weighed and analyzed by vapor phase chro~atograph methods using at least two difEerent columns The total pressure is reported as t~e average pressure for the run.
S'tandard ~rocedure C
This procedur~ is identical to Standard Procedure A
except that the reaction proceeded until 6,000 psi of synthesis gas had reacted or four hours had passed, whichever occurred 16.
1 ~57453 first, and that the gaseous components were vented and not an~lyzed; therefore, seIectivities reported are based on the ~eight percen~ of liquid products analyzed by the vapor phase chromatographic methods.
The following examples serve to rurther illustrate the in~ention.
Example 1 Ethanol was selectively produced using Standard Procedure A. In this experiment 16 mgram atoms of Ru, as triruthenium dodecacarbonyl, 5.6 mmoles of elemental iodine and 75 ml of tripropylphosphine oxide were used; the H~/C0 ratio was 2:1 and the reaction was carried ou~ at a ~otal pressure of 6,000 psi at 240C. There were produced as determined by vapor phase chromatograph analysis, 2.12 g of ethanol, 1.03 g of methanol, 0.12 g of propanol, 0.82 g of methane and 0.17 g of other liquid products; slight traces of gaseous or other liquid produc~s were also detected. Ethanol was produced at the rate of 2.05 moles/liter/hour at a selectivity of 50 weight percent; the selectivity to ethanol plus methanol was 74 weight percent. The results show that ethanol or mixtures of alkanols can be produced at high selectivity directly from synthesis gas by this invention.
_ample 2 Standard Procedure A was again employed using 8 mgram atoms of Ru, as ruthenium dodecacarbonyl, 4 mmoles of elemental iodine and 75 ml o tripropylphosphine oxide; the /CO ratio was 2:1. Th2 reaction was carried out at a total pressure of 6,000 psi at 240C. There were produced 2.46 g o~ ethanol, 0.97 g of methanol, 0.19 g of propanol, 0.95 grams of methane and 0.18 g of other liquid produc~s;
17.
1~57~3 12835 slight traces o~ gaseous or other liquid products were also detected Ethanol was produced at a rate of 1.9 moles/liter/
hour at a selectivit~ of 52 weight percent; the selectivlty to ethanol plus methanol was 72 weight percent; illustrating the ability to directly produce alkanols at high selectivity from synthesis gas.
Example 3 Standard Procedure A was employed using 24 mgram atoms of Ru, as ruthenium dodecacarbonyl, 15.6 mmoles of elemental iodine a~d 75 ml of tripropylphosphine oxide; the H2/C0 ratio was 1:1. The reaction was carried out at a total pressure of 6,000 psi at 195~C. There were produced 2.48 g of ethanol, 1.03 g of methanol, 0.1 g of propanol, 0.62 g of methane and 0.27 g of other liquid products;
slight traces of gaseous or other liqui.d products were also detected. Ethanol was produced at the rate of 0.6 molel liter/hour at a selectivity to e~hanol plus methanol o 78 weight percent. The results show that at lower temperatures high selectivity -to alkanols is still achieved though at a lower rate.
Examples 4 to 23 Standard Procedure A was followed in these examples in which ethanol and mix~ures of ethanol with other alkanols were selectively produced directly from synthesis gas. The reaction conditions and results are summarized in Table I.
In the table the partial pressures of H2 and C0 present in the synthesls gas mixture charged are recorded, from which the total pressure is readily ascertained. Elemental iodine ~as used as promoter and the ratio stated is the L/Ru ratio, 18.
~ ~157~3 1~835 not the l2/Ru ratio. Selectivity (Sel.) values reported are the area percent ethanol divided by the total area for all vapor phase chromatograph peaks other than water, air and solvent.
19 .
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~ 4~3 12835 Examples _24 to _ Table II shows the selective production of ethanol or eth~nol plus methanol mixtures directly from synthesis gas ~y the process of this invention. It illu`strates the use of dif~erent promoters and solvents as well as variations in the temperature and pressure reaction conditions employable.
~nless otherwise indicated all of the examples used 75 ml of tripropylphosphine oxide ~Pr3PO), 9 mgram atoms of Ru as tri-ruthenium dodecacarbonyl and a H2/~O ratio of 1:1, and were run at 210C. Selectivities were determined by vapor phase chromatographic analysis of the liquid products produced and are reported in weight percent.
The proceclure ~sed in Examples 55, 56 and 70 through 76 was identical to Standard Procedure A except that the reaction proceeded until 6,00G psi of synthesis gas had reacted or two hours had passed, whichever occurred first.
In all 76 eEamples the designation moles/liter/
hour, indicating the formation rates of produc~s, is based on the reaction solution in the reactor or moles/liter of solution/hour.
21.
1 1~7~3 TABLE II
F~ atio-ll Selectiviti~.s Total P p~moter M~leslL/Hr. Etn~ F~n~ 5tandard Ex pSI Cmmoles~ MeOH EtOH Wt,~--- Proce~ure 24 12,500 MerNI(18~ 3.042.56 44.982.6 C
25 12,500 I~ ~4~1.20 2.25 63.490.4 C
26 6,000 I2(2) .11 .37 68.784.3 C
27 6,000 I2(3~ .07 .32 67.379.0 C
28 6,000 KI (18~.46 .56 52.984.9 C
29 6,000 I2(4~ .28 .59 57.176.8 C
30 4,300r Me4NI(18).55.76 63.591.8 B
31 4~300 Me3SI~9).16 .52 72.187.3 B
32 4,300r KI (9~ .94 .83 52.294.2 B
33 4,300r MeI (3).17 .49 71.387.5 B
34 4,300r MeI (3).26 .62 _ _ B
35 4,300r KI (9) .86 .76 52.893.9 B
BuI (3) 36 4,300r KI (18)1.12 .68 44.596.4 B
37 12,500b ~u~Nl (18) .17.74 51 50.3 C
38 6,000 I2 ~6) .08 .38 _ - C
39 6,0~0 I2 (1) .11 .27 _ _ C
6,000 I2 (9) 04 .18 - - C
41 12,500q KI (18)2.S52.25 _ _ C
42 12,500q KI ~13)1.722.26 _ _ C
HI 6) 43 12,500q KI ~18).47 1.53 - C
HI (12) 1~7~3 1~83 TABLE II CContinued) F~ io~l Selectivitie~
Total P Prc)moter Mole~./Hr. EtO~ tml~ Standard Ex PSI Cmm~les~P~eO~ EtOH ~ ~/ eOHProcedure 4412,500q'e KI ~18~ 2.91 1,71 - - C
HI C2 ~
45 4,300r Me4Br(18) .44 .57 - - B
46 6, ooOd Me~PI(36)~ 40 . 39 - - C
474,300e~P Me4PCl(9) .07 .0~ - - B
4~4, 300~ ~ P KI (9) . 99 . 43 - - B
4912,500b~e CsI(18) 1.5 .32 _ _ C
5012,500b~e KI(18) 2.1 .32 - _ C
51 12,500b'e'fBu4NI(18) .45 .12 - _ C
5 212, 500b ~ ' gBP4NI (18). 43 .18 - - C
53 6, 000 I2(4 . 5) .15 . 34 - - C
KI (183 Bu3P (3) 54 6, 000 I2 (4 . 5). 22 . 36 ~ ~ C
5~ 1~,500 Bu4NI(6) .52 1.04 - - C
MeI (1) 56 " Bu4NI (6). 75 1. 3 - _ C
MeI (~) Bu3N (1 . 5 ) 5712,500b lKI~18) .96 1.04 - C
MeI (3) 5812, 500b KI C18) 1. 7 . 81 - - C
MeI (3 ) Bu3N C4~
59S, 000 I2 ~4~ . 09 . 3S - C
606, 000 I2 C4~ . 28 . 59 ~u4N C6 ) 23 .
~7~3 ~2835 TABLE II (Continued) Formation Rates Selectivi~ies To~al PPromoter Moles/L/Hr. EtOH~ Standard Ex. PSI_(mmoles) MeOH EtOH Wt. ~ Procedure 61 69000 I2~4) ~19 .41 - C
Bu3N~8) 62 6,000 I2l4) .27 ~40 _ _ C
Bu3N~12) 10 63 6,000 I2~) 3 .40 - C
Bu3N(18) 64 4,300 Bu4NI(6) .4 .59 4,300 Bu4NI(6) .009 .002 - _ MeI(35.2) 66 12,500b ZnI2(1.5) .71 1.25 - - C
67 6,000i'J'mI2(4) .98 1.~4 - - A
68 6,000i9g'i'mI2(4) .02 - _ _ A
69 6 0OOi,k~m I2(4) .60 .72 - _ A
20 70 6,000~ 'mI2(4) 1.04 .93 - - A
71 6,000i9i~ CsI(~) .99 .73 - - A
72 6,000i~J~m CsI(2) .41 .47 _ _ A
73 6~000i~i~m CsI(8) .93 .58 - _ A
74 6,000m~n' CsI(6.4) .21 47 ~ ~ A
6,000m'n' CsI(3.2) .26 .43 - - A
76 6,000~ m KI(4) 1.0 .90 - - A
b 3 mgram atoms Ru as Ru3~CO)12 d 13 mgram-atoMs ~u as RU3~CO)12 e Some of these examples are for comparative purposes. They do not represent preferred conditions of this invention.
f 75 ml of 18 Crown~6 as solvent g 75 ml of ~ulfolane as solvent i 8 mgram-atoms Ru as Ru3(CO)12 j H~/CO = 2 k 37.5 ml of Pr3PO and 37.5 ml 18-C-6 as solvent 1 37.5 ml of Pr3PO and 37.5 ml oE ~lolane as solvent m Run at 240C
n H2/CO = 2.33 o 16 mgram-atoms Ru as Ru3(CO)12 p ~un at ~30C
q 6 mgram atoms Ru aæ Ru3(COa12 r 50 ml Pr3PO a~ 601vent 24.
~,
Claims (14)
1. A process for the selective, direct production of ethanol or mixtures thereof with other alkanols containing up to three carbon atoms, which method comprises the reaction of carbon monoxide and hydrogen in contact with a homogeneous ruthenium catalyst, a halogen or halide promoter and an organic phosphine oxide compound, wherein said process is carried out at:
(a) a total pressure of from 500 to 20,000 psi, (b) a temperature of from 100°C to 350°C, (c) the carbon monoxide to hydrogen ratio of the gas mixture charged is from 0.1:1 to 10:1, (d) the ruthenium compound charged is capable of generating a soluble ruthenium complex under the reaction conditions and it is charged at a concentration of from 0.01 to 30 weight percent based on the total weight of the reaction mixture, (e) said promoter is (i) elemental iodine or bromine or a compound thereof which is or is capable of generating hydrogen iodide or hydrogen bromide during the reaction and is charged at an amount sufficient to generate a hydrogen halide to ruthenium atom mole ratio of from 0.001:1 to 5:1 in the reaction mixture, or (ii) an alkali metal halide at a ratio to ruthenium atom as high as 20:1, or (iii) a mixture thereof, (f) said organic phosphine oxide is charged at a concentration of from 1 to 100 weight percent of total solvent charged to the reactor.
25.
(a) a total pressure of from 500 to 20,000 psi, (b) a temperature of from 100°C to 350°C, (c) the carbon monoxide to hydrogen ratio of the gas mixture charged is from 0.1:1 to 10:1, (d) the ruthenium compound charged is capable of generating a soluble ruthenium complex under the reaction conditions and it is charged at a concentration of from 0.01 to 30 weight percent based on the total weight of the reaction mixture, (e) said promoter is (i) elemental iodine or bromine or a compound thereof which is or is capable of generating hydrogen iodide or hydrogen bromide during the reaction and is charged at an amount sufficient to generate a hydrogen halide to ruthenium atom mole ratio of from 0.001:1 to 5:1 in the reaction mixture, or (ii) an alkali metal halide at a ratio to ruthenium atom as high as 20:1, or (iii) a mixture thereof, (f) said organic phosphine oxide is charged at a concentration of from 1 to 100 weight percent of total solvent charged to the reactor.
25.
2. A process as claimed in claim 1 wherein the pressure is from 1,000 to 12,500 psi, the temperature is from 160°C to 230°C, the carbon monoxide to hydrogen ratio is from 0.25:1 to 4:1, the concentration of ruthenium compound charged is from 0.2 to 10 weight percent, said component (e) promoter which is or is capable of generating hydrogen iodide or hydrogen bromide is present at a halide to ruthenium atom mole ratio of from 0.01:1 to 3:1, the organic phosphine oxide is a trialkylphosphine oxide having from 1 to 20 carbon atoms in each alkyl group and it is charged at a concentration of from 1 to 100 weight percent of the total weight of solvent charged to the reactor.
3. A process as claimed in claim 2 wherein the pressure is from 2,500 to 8,000 psi, the carbon monoxide to hydrogen ratio is from 2:1 to 0.33:1, the concentration of ruthenium compound charged is from 0.5 to 5 weight percent, said component (e) promoter which is or is capable of generating hydrogen iodide or hydrogen bromide is present at a halide to ruthenium atom mole ratio is from from 0.1:1 to 2:1.
4. A process as claimed in claim 3 wherein said ruthenium compound is triruthenium dodecacarbonyl.
5. A process as claimed in claim 3 wherein the halogen promoter initially charged is elemental iodine.
6. A process as claimed in claim 3 wherein the halogen promoter initially charged is hydrogen iodide.
26.
26.
7. A process as claimed in claim 1 wherein said organic phosphine oxide is charged at a concentration of from 20 to 100 weight percent.
8. A process as claimed in claim 1 wherein methanol is recycled to the reaction mixture.
9. A catalyst for the direct production of ethanol or mixtures thereof with other alkanols containing up to three carbon atoms by the reaction of carbon monoxide and hydrogen comprising (a) a ruthenium compound, (b) a promoter, and (c) an organic phosphine oxide solvent wherein said ruthenium compound (a) is a compound capable of generating a soluble ruthenium complex under the reaction conditions, said promoter (b) is (i) elemental iodine or bromine or a compound thereof which is capable of generating hydrogen iodide or hydrogen bromide during said reaction and is charged at an amount sufficient to generate a hydrogen halide to ruthenium atom mole ratio of from 0.001:1 to 5:1 in said reaction mixture, or (ii) an alkali halide at a ratio to ruthenium atom as high as 20:1, or (iii) mixture thereof, and said organic phosphine oxide solvent (c) is present at a concentration of from 1 to 100 weight percent of the total solvent charged.
10. A catalyst as claimed in claim 9 wherein said promoter component (b) which is capable of generating hydrogen iodide or hydrogen bromide is present at a halide to ruthenium atom mole ratio is from 0.01:1 to 3:1.
11. A catalyst as claimed in claim 9 wherein said promoter component (b) which is capable of generating hydrogen 27.
iodide or hydrogen bromide is present at a halide to ruthenium atom mole ratio is from 0.1:1 to 2:1.
iodide or hydrogen bromide is present at a halide to ruthenium atom mole ratio is from 0.1:1 to 2:1.
12. A catalyst as claimed in claim 9 wherein said ruthenium compound is triruthenium dodecacarbonyl.
13. A catalyst as claimed in claim 9 wherein said halogen promoter is elemental iodine.
14. A catalyst as claimed in claim 9 wherein said halogen promoter is hydrogen halide.
28.
28.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US190,905 | 1980-09-25 | ||
| US06/190,905 US4301253A (en) | 1980-09-25 | 1980-09-25 | Process for the selective production of ethanol and methanol directly from synthesis gas |
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| US (1) | US4301253A (en) |
| EP (1) | EP0048918B1 (en) |
| JP (2) | JPS5782327A (en) |
| AU (1) | AU7552781A (en) |
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| US4703064A (en) * | 1979-11-15 | 1987-10-27 | Union Carbide Corporation | Process for producing alcohols |
| US4301253A (en) * | 1980-09-25 | 1981-11-17 | Union Carbide Corporation | Process for the selective production of ethanol and methanol directly from synthesis gas |
| CA1179315A (en) * | 1981-06-30 | 1984-12-11 | Union Carbide Corporation | Process for producing alcohols |
| JPS6027651B2 (en) * | 1981-08-13 | 1985-06-29 | 工業技術院長 | Method for producing alkanpolyol |
| US4362821A (en) * | 1981-10-29 | 1982-12-07 | Texaco Inc. | Process for preparing alkanols from synthesis gas |
| JPS617221A (en) * | 1984-06-20 | 1986-01-13 | Agency Of Ind Science & Technol | Preparation of oxygen-containing compound |
| US4590216A (en) * | 1984-09-07 | 1986-05-20 | Union Carbide Corporation | Process for the manufacture of alcohols using ruthenium and lanthanide catalysts |
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| US2490488A (en) * | 1947-03-28 | 1949-12-06 | Phillips Petroleum Co | Hydrocarbon synthesis catalyst |
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| US4301253A (en) * | 1980-09-25 | 1981-11-17 | Union Carbide Corporation | Process for the selective production of ethanol and methanol directly from synthesis gas |
| JPS621929A (en) * | 1985-06-27 | 1987-01-07 | Fujita Corp | Foundation structure for machine |
-
1980
- 1980-09-25 US US06/190,905 patent/US4301253A/en not_active Expired - Lifetime
-
1981
- 1981-08-19 ZA ZA815738A patent/ZA815738B/en unknown
- 1981-08-21 CA CA000384412A patent/CA1157453A/en not_active Expired
- 1981-09-21 DE DE8181107492T patent/DE3170617D1/en not_active Expired
- 1981-09-21 BR BR8106002A patent/BR8106002A/en unknown
- 1981-09-21 EP EP81107492A patent/EP0048918B1/en not_active Expired
- 1981-09-21 AU AU75527/81A patent/AU7552781A/en not_active Abandoned
- 1981-09-22 JP JP56148907A patent/JPS5782327A/en active Granted
-
1986
- 1986-07-21 JP JP61169953A patent/JPS6226242A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0048918A1 (en) | 1982-04-07 |
| AU7552781A (en) | 1982-04-01 |
| DE3170617D1 (en) | 1985-06-27 |
| JPS5782327A (en) | 1982-05-22 |
| BR8106002A (en) | 1982-06-08 |
| EP0048918B1 (en) | 1985-05-22 |
| JPS6226242A (en) | 1987-02-04 |
| ZA815738B (en) | 1982-08-25 |
| US4301253A (en) | 1981-11-17 |
| JPS621929B2 (en) | 1987-01-16 |
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