Carbon Monoxide Or Metal Carbonyl Reactant Patents (Class 562/890)
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Publication number: 20140051885Abstract: A method for stabilizing a carbonylation catalyst with carbon monoxide recovered from a gaseous stream derived from a carbonylation reaction. The carbon monoxide enriched stream is fed downstream of the carbonylation reactor, preferably to a flasher or light ends column, to enhance catalyst stability throughout the process.Type: ApplicationFiled: August 17, 2012Publication date: February 20, 2014Applicant: Celanese International CorporationInventors: Mark O. Scates, Ronald D. Shaver, Gregory Blanchard
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Publication number: 20130197267Abstract: In one embodiment, the invention is to a process for producing acetic anhydride. The process includes at least a step of carbonylating methanol and/or a methanol derivative with carbon monoxide to form acetic acid, and contacting ketene with the acetic acid to form a crude acetic anhydride product stream and a vent stream having unreacted ketene. The process further comprises a step of directing at least a portion of the vent stream to a liquid ring vacuum compressor having a ring seal fluid comprising acetic acid The unreacted ketene in the portion of the vent stream contacts the ring seal fluid to form supplemental acetic anhydride.Type: ApplicationFiled: January 26, 2012Publication date: August 1, 2013Applicant: CELANESE INTERNATIONAL CORPORATIONInventors: R. Jay Warner, Melchoir Meilchen
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Patent number: 7737298Abstract: Disclosed is a process for the production of acetic acid or mixtures of acetic acid and acetic anhydride in a carbonylation process wherein a mixture comprising methyl acetate and/or dimethyl ether and methyl iodide is contacting in the liquid phase with carbon monoxide in the presence of a carbonylation catalyst at elevated pressures and temperatures. Methanol, water, or a mixture thereof is added to an acetic anhydride-containing stream within a flash evaporation zone to convert some or all of the acetic anhydride to acetic acid and optionally methyl acetate and to provide heat for the evaporation of a portion of the product effluent produced by the carbonylation process.Type: GrantFiled: June 9, 2006Date of Patent: June 15, 2010Assignee: Eastman Chemical CompanyInventors: Robert Sterling Kline, Gregory Abbott Wellman, Jr., Brandon Tyler Earls, Jerry Lee Bewley
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Publication number: 20090299092Abstract: A process for the carbonylation of an alcohol and/or reactive derivative thereof, in which one or more reaction zone feed streams are fed to a reaction zone in which exothermic carbonylation takes place to produce one or more product streams. Heat from at least a portion of the one or more product streams is fed to a first heat-exchange stream, such as a supply of pressurised steam. The process is characterised by heat from a second heat-exchange stream, having a temperature lower than that of the one or more product streams, being transferred to a reaction zone feed stream, so that the one or more product streams comprise heat originating from the second heat-exchange stream and heat generated by the exothermic carbonylation reaction. Thus, heat originating from the second heat-exchange stream can be transferred to the first heat-exchange stream, resulting in reduced heat loss and greater process efficiency.Type: ApplicationFiled: November 22, 2006Publication date: December 3, 2009Applicant: BP CHEMICALS LIMITEDInventors: Richard Beavis, Sean Anthony Hennigan, Michael James Muskett
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Publication number: 20070293695Abstract: Disclosed is a carbonylation process for the production of carboxylic acids, carboxylic acid esters and/or carboxylic acid anhydrides wherein a carbonylation feedstock compound selected from one or more organic oxygenates such as alcohols, ethers, and esters is contacted with carbon monoxide in the presence of a carbonylation catalyst and one or more onium compounds. The carbonylation process differs from known carbonylation processes in that a halide compound such as a hydrogen halide, typically hydrogen iodide, and/or alkyl halide, typically methyl iodide, extraneous or exogenous to the carbonylation process is not fed or supplied separately to the process.Type: ApplicationFiled: June 15, 2006Publication date: December 20, 2007Applicant: EASTMAN CHEMICAL COMPANYInventors: Joseph Robert Zoeller, Mary Kathleen Moore, Andrew James Vetter
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Patent number: 7253304Abstract: Disclosed is a carbonylation process wherein a mixture of a dialkyl carbonate and halide compound is contacted with carbon monoxide in the presence of a metal selected from Group VIII of the Periodic Table to co-produce carbon dioxide and a carbonyl compound selected from a carboxylic acid, an alkyl carboxylate ester, a carboxylic acid anhydride or a mixture of any two or more thereof. The carbon dioxide co-product of the process may be recovered, and sold or further reacted with a suitable substrate to produce useful chemicals such as urea or cyclic carbonates.Type: GrantFiled: June 20, 2006Date of Patent: August 7, 2007Assignee: Eastman Chemical CompanyInventor: Gerald Charles Tustin
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Patent number: 6984755Abstract: A process for the preparation of an carboxylic anhydride by reaction of an ethylenically unsaturated compound with carbon monoxide and an carboxylic acid in the presence of a catalyst involving: a) a source of a group VIII metal; b) a bidentate diphosphine of formula I, ?wherein R1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1 {3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R2 and R3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and ?wherein R represents a bivalent organic bridging group; and, c) a complexing anion; wherein the complexing anion is the anion of the carboxylic acid. A process wherein the carboxylic acid is prepared in-situ and use of the carboxylic anhydride as an acylation agent.Type: GrantFiled: February 18, 2003Date of Patent: January 10, 2006Assignee: Shell Oil CompanyInventors: Eit Drent, Renata Helena Van Der Made, Robert Ian Pugh
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Patent number: 6916951Abstract: Disclosed is a continuous process wherein carbon monoxide, a carbonylatable reactant, and a halide in the gas phase are contacted with a non-volatile catalyst solution comprising an ionic liquid and a Group VIII metal to produce a carbonylation product in the gas phase. The process is useful for the continuous preparation of acetic acid by the carbonylation of methanol.Type: GrantFiled: May 9, 2003Date of Patent: July 12, 2005Assignee: Eastman Chemical CompanyInventors: Gerald Charles Tustin, Regina Michelle Moncier
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Patent number: 6596781Abstract: An integrated process for carrying out the production of Fischer-Tropsch products and acetic acid made using the methanol and carbonylation route which utilizes the hydrogen recovered from the methanol production to upgrade the Fischer-Tropsch products.Type: GrantFiled: May 2, 2002Date of Patent: July 22, 2003Assignee: Chevron U.S.A. Inc.Inventor: William L. Schinski
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Patent number: 6541666Abstract: A process for the co-production of acetic anhydride and acetic acid which process comprises introducing a carbonylatable feedstock comprising methyl acetate and/or dimethyl ether and optionally also comprising methanol and/or water, to a carbonylation reactor in which there is maintained a liquid reaction composition comprising acetic anhydride, acetic acid, rhodium carbonylation catalyst, alkyl iodide co-catalyst and an iodide salt promoter consisting essentially of an alkali metal iodide and/or alkaline earth metal iodide, contacting said carbonylatable feedstock with carbon monoxide in said liquid reaction composition to produce acetic anhydride and acetic acid, and introducing to the carbonylation reactor methyl formate and/or formic acid in the range from 0.1 to 20% by weight of the total feed of liquid components to the reactor.Type: GrantFiled: December 26, 2000Date of Patent: April 1, 2003Assignee: BP Chemicals LimitedInventors: Robert Edward Allan, Derrick John Watson
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Patent number: 6521783Abstract: This invention relates in part to a processes for the conversion of a feedstock stream comprising carbon monoxide and hydrogen to a product stream comprising at least one of an ester, acid, acid anhydride and mixtures thereof. This invention also relates in part to processes for converting an alcohol and/or ether feedstock to oxygenated products, e.g., esters, acids, acid anhydrides and mixtures thereof. The processes and catalysts are especially suitable for the production of acetic acid and methyl acetate from a synthesis gas feedstock or from an alcohol and/or ether feedstock.Type: GrantFiled: July 10, 2000Date of Patent: February 18, 2003Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Richard William Wegman, David McNeill Somerville, Barry Brent Fish, Raymond Edwin Rooks, Chinsoo Stephen Lee, Paul Frank Bryan, William J. Bartley, David Michael Anthony Minahan, Fungau Ho
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Patent number: 6420304Abstract: The invention relates to a polymer-supported carbonylation catalyst and its use in a process for preparing organic carboxylic acid or anhydride having n+1 carbon atoms. The invention relates also to a process for preparing organic carboxylic acid or anhydride having n+1 carbon atoms by carbonylating with monoxide, in the presence of the above-mentioned carbonylation catalyst, on alcohols having n carbon atoms, ethers having 2n carbon atoms or esters formed from said alcohols and acids. In particular, the invention relates to a process for preparing acetic acid by carbonylating methanol with carbon monooxide in the presence of said carbonylation catalyst. By using said carbonylation catalyst, the temperature for carbonylation can be lowered to about 160° C. with a reaction rate better than that of a traditional process, while the tendency of catalyst precipitation in the course of carbonylation can be improved also.Type: GrantFiled: April 20, 2000Date of Patent: July 16, 2002Assignee: China Petrochemical Development CorporationInventors: Chia-Jung Tsai, Yao-Lung Liu, Hsi-Chin Tsai
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Patent number: 6222070Abstract: In a liquid phase carbonylation process for the production of acetic anhydride by reacting a feed stream which includes methyl acetate, methanol and carbon monoxide using a Group VIII metal-containing catalyst, and preferably a rhodium containing material, a liquid reaction product is continuously withdrawn from the carbonylation zone and fed to an evaporation/separation zone for separating volatile constituents of the reaction from the non-volatile constituents which, includes a portion of the Group VIII metal catalyst from the carbonylation reactor. The Group VIII metal catalyst is contacted with a gas stream which includes hydrogen for a period of from about 0.001 seconds to about 200 seconds as it is being returned to the carbonylation zone.Type: GrantFiled: September 7, 1999Date of Patent: April 24, 2001Assignee: Eastman Chemical CompanyInventors: Joseph Nathaniel Bays, Joseph Robert Zoeller, Michael Roy Cushman, Brent Alan Tennant
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Patent number: 6211405Abstract: The present invention provides a process for the carbonylation of an alcohol, ether or ester to products comprising a carboxylic acid, the anhydride thereof or coproduction of the carboxylic acid and anhydride. More particularly, the present invention provides a process for the carbonylation of methanol to produce acetic acid by reacting methanol with carbon monoxide in a liquid reaction medium containing a catalyst comprising rhodium, iridium, iodide ion, and said reaction medium further comprising water, acetic acid, methyl iodide, and methyl acetate and subsequently recovering acetic acid from the resulting reaction product.Type: GrantFiled: October 23, 1998Date of Patent: April 3, 2001Assignee: Celanese International CorporationInventors: Hung-Cheun Cheung, Elaine C. Sibrel, Robin S. Tanke, G. Paull Torrence
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Patent number: 6087533Abstract: A process for the carbonylation of allylic butenol or butenyl ester of a carboxylic acid (e.g., crotyl acetate, 3-acetoxybutene-1 and mixtures thereof) in an anhydrous carboxylic acid solvent and production of beta-gamma unsaturated carboxylic acid anhydride (e.g., 3-pentenoic acid anhydride) utilizing a rhodium-containing catalyst (e.g., dicarbonylacetylacetonate rhodium(I)) promoted with a metal iodide (e.g., dicarbonylacetylacetonate rhodium(I), or the like). The following representative reaction showing a crotyl ester (i.e., a carboxylic acid ester of 2-buten-1-ol) as the reactant producing a corresponding pentenoic acid anhydride is illustrative of the overall carbonylation. ##STR1## Suitable allylic compounds are of the form ##STR2## where one of the groups R.sup.1, R.sup.2, and R.sup.3 is methyl and the other two groups are H and wherein R.sub.4 is selected from the group consisting of H and ##STR3## wherein R.sup.5 is selected from the group consisting of a C.sub.1 to C.sub.10 alkyl.Type: GrantFiled: December 18, 1998Date of Patent: July 11, 2000Assignees: E I. du Pont de Nemours and Company, DSM Desotech Inc.Inventor: Patrick Michael Burke
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Patent number: 6049005Abstract: Process to prepare a pentenoic acid anhydride in the pressence of a catalyst comprising palladium and an organic phosphine ligand, wherein the corresponding alkoxycarbonyl butene is reacted with carbon monoxide at a temperature between 50 and 130.degree. C. and that the phosphine is a monodentate phosphine or a bidentate phosphine.Type: GrantFiled: October 7, 1997Date of Patent: April 11, 2000Assignees: DSM N.V., E. I. du Pont de NemoursInventor: Patrick M. Burke
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Patent number: 5936117Abstract: Disclosed is a process for the preparation of aliphatic carbonyl compounds selected from aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by the carbonylation of olefins in the presence of a catalyst system comprising (1) a primary component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a secondary component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester.Type: GrantFiled: July 28, 1995Date of Patent: August 10, 1999Assignee: Eastman Chemical CompanyInventors: Joseph Robert Zoeller, Elizabeth MacGowan West, Horace Lawrence Browning, Jr., George Geiger Mayfield
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Patent number: 5760284Abstract: Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein.Type: GrantFiled: April 10, 1997Date of Patent: June 2, 1998Assignee: Eastman Chemical CompanyInventor: Joseph Robert Zoeller
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Patent number: 5705683Abstract: The process for carbonylating olefins with carbon monoxide in the presence of water, an alcohol or a carboxylic acid and a halogen-free catalyst comprises using a catalyst comprising nickel or a nickel compound and at least one of the metals of the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, or a compound of these metals.Type: GrantFiled: January 13, 1997Date of Patent: January 6, 1998Assignee: BASF AktiengesellschaftInventors: Ferdinand Lippert, Arthur Hohn, Martin Schafer, Leopold Hupfer
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Patent number: 5648531Abstract: A process for continuously producing acetic anhydride alone or acetic anhydride and acetic acid by reacting methyl acetate and/or dimethyl ether and, optionally, water and/or methanol, with carbon monoxide alone or carbon monoxide and hydrogen in the presence of a rhodium compound and methyl iodide as principal catalysts. Trace impurities causative of tar formation are distilled and separated in an evaporator and/or a subsequent refining step to remove the same. The removal of the trace impurities causative of tar formation serves to decrease the amount of tar formed as an impurity.Type: GrantFiled: March 22, 1995Date of Patent: July 15, 1997Assignee: Daicel Chemical Industries, Ltd.Inventors: Yoshiaki Morimoto, Hiroto Tanigawa, Kazuyuki Akita
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Patent number: 5380929Abstract: To prepare acetic acid and acetic anhydride, methanol and methyl acetate are reacted under anhydrous conditions with carbon monoxide in the presence of a catalyst system containing carbonyl complexes of group VIII noble metals, methyl iodide, an alkali metal acetate or iodide, or quaternary organophosphonium or organoammonium acetate or iodide, The hot carbonylation mixture is decompressed, the evaporated components are fed to a first distillation zone, and the catalyst solution which remains is fed back to the reaction zone. In the first distillation zone, the volatile carbonylation products are subjected to fractional distillation; the low-boiling methyl iodide and methyl acetate pass back into the reaction zone, and the bottom product produced is a mixture of acetic acid and acetic anhydride, which is split into the pure components in a second distillation zone and a third distillation zone.Type: GrantFiled: May 2, 1994Date of Patent: January 10, 1995Assignee: Hoechst AktiengesellschaftInventors: Heinz Erpenbach, Klaus Gehrmann, Erhard Jagers, Georg Kohl
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Patent number: 5360929Abstract: A process for the production of a carboxylic acid anhydride comprises contacting a reaction composition comprising a carboxylic acid ester, a hydrocarbyl halide and/or a hydrocarbyl ether reactant and a hydrocarbyl halide promoter with carbon monoxide in the presence of a catalyst comprising an insoluble polymer support having pendant quaternised N-base or alkylated N-oxide pyridine groups supporting a rhodium species in which process the rhodium species is prevented from leaching from the polymer support by maintaining throughout the process a finite concentration of carboxylic acid anhydride in the reaction composition.Type: GrantFiled: February 10, 1994Date of Patent: November 1, 1994Assignee: BP Chemicals LimitedInventors: Derrick J. Watson, Bruce L. Williams, John G. Sunley, Robert J. Watt
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Patent number: 5214205Abstract: The invention relates to a process for the preparation of acetic anhydride, characterized in that a gas containing essentially CO, at a pressure of at least 1 MPa, is reacted with methyl formate in the presence ofa) a rhodium-based catalyst,b) two iodine-containing promoters of different kind, successively ionic and covalent, andc) an N-substituted cyclic amide as solvent.Type: GrantFiled: April 14, 1992Date of Patent: May 25, 1993Assignee: Sollac, A French Body CorporateInventors: Yves Castanet, Bruno Seuillet, Andre Mortreux, Francis Petit
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Patent number: 5189203Abstract: The present invention relates to a process for preparing acetic acid, acetic acid methyl ester or acetic anhydride or mixtures thereof by converting a synthesis gas mainly containing hydrogen and carbon oxides, by first converting the synthesis gas catalytically into a gas mixture containing methanol and dimethyl ether and then carbonylating this mixture catalytically into acetic acid and/or methyl acetate and/or acetic anhydride.Type: GrantFiled: June 30, 1988Date of Patent: February 23, 1993Assignee: Haldor Topsoe A/SInventors: John B. Hansen, Finn H. Joensen, Haldor F. A. Topsoe
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Patent number: 5177253Abstract: A process for the preparation of an alpha,beta-olefinically unsaturated compound, which comprises reacting an acetylenically unsaturated compound with monoxide and a hydroxyl-containing compound in the presence of a catalyst system comprising:(a) a source of a Group VIII metal cation,(b) a source of an organic diphosphine having at least one of the phosphorus atoms substituted by an aromatic substituent containing an imino nitrogen atom, and(c) a source of an anion.Type: GrantFiled: March 13, 1991Date of Patent: January 5, 1993Assignee: Shell Oil CompanyInventors: Eit Drent, Petrus H. M. Budzelaar, Willem W. Jager
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Patent number: 5028576Abstract: A catalyst system which comprises:a) a group VIII metal compound, andb) a monophosphine of formula ##STR1## where R.sup.1 represents an aliphatic hydrocarbyl group, R.sup.2 represents an optionally substituted aromatic heterocyclic group having 5 or 6 ring atoms of which at least one is nitrogen, which may form part of an optionally substituted larger condensed ring structure, and R.sup.3 independently has the meaning of R.sup.2 or represents an optionally substituted aryl group or an acid addition salt thereof, and their use in the carbonylation of unsaturated compounds.Type: GrantFiled: March 1, 1990Date of Patent: July 2, 1991Assignee: Shell Oil CompanyInventors: Eit Drent, Petrus H. M. Budzelaar
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Patent number: 5028734Abstract: A process for the selective carbonylation of a conjugated diene by contacting with carbon monoxide in the presence of a hydroxyl-group-containing compound such as water, alcohol, phenol or carboxylic acid in liquid phase using a catalyst system formed by the combination of:(a) a palladium compound and(b) at least one organic bidentate phosphine.Type: GrantFiled: January 27, 1989Date of Patent: July 2, 1991Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 5002914Abstract: A process for purifying and recovering the contaminated catalyst solution arising from the carbonylation of methanol, methyl acetate and/or dimethyl ether. The solution contains carbonyl complexes of rhodium, quaternary organophosphorus compounds as organic promoters, undistillable organic impurities, and acetic acid, acetic anhydride and ethylidene diacetate. The carbonyl complex of rhodium together with acetic acid, acetic anhydride and ethylidene diacetate are extracted from the contaminated catalyst solution by using a tri-C.sub.3 - to C.sub.8 -alkylphosphine. The trialkylphosphine phase is separated from the promoter phase and is separated into the volatile constituents acetic acid, acetic anhydride and ethylidene diacetate as well as trialkylphosphine. The rhodium carbonyl complex remaining as the residue and the recovered trialkylphosphine is used for further extraction.Type: GrantFiled: March 9, 1990Date of Patent: March 26, 1991Assignee: Hoechst AktiengesellschaftInventors: Heinz Erpenbach, Winfried Lork, Norbert Weferling, Peter Prinz
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Patent number: 4985383Abstract: In a process for removing the metallic corrosion products from a contaminated catalyst solution produced on carbonylation of methanol and/or methyl acetate and/or dimethyl ether and containing carbonyl complexes of noble metals from group VIII of the Periodic Table of the elements, quaternary organo-phosphorus compounds as organic promoters, metallic corrosion products and acetic acid, acetic anhydride, ethylidene diacetate and, in some cases, undistillable organic compounds, the catalyst solution is treated with water, the noble metal carbonyl complex and the undistillable organic compounds, if present, being precipitated, while the organic promoter and the metallic corrosion products remain in solution; the aqueous phase is separated from the precipitated noble metal carbonyl complex and the organic promoter is extracted from the aqueous phase using C.sub.4 -C.sub.Type: GrantFiled: January 26, 1990Date of Patent: January 15, 1991Assignee: Hoechst AktiengesellschaftInventors: Heinz Erpenbach, Winfried Lork, Andreas Seidel, Peter Prinz
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Patent number: 4960926Abstract: Process for the carbonylation of olefinically unsaturated compounds with carbon monoxide in the presence of a hydroxyl-group-containing compound, a palladium catalyst, an organic phosphine, an acid with a pKa value <2, with the exception of halogen acids and carboxylic acids as promoter, and a catlayst stabilizer selected from the group consisting of compounds of the general formula; ##STR1## wherein X represents an element of group Va with a valency greater than 3, selected from P. As or Sb, where Y represents an element of group VIa, selected from O, S or Se, and where either a, b and c are 0 or 1, where R.sub.4, R.sub.5 and R.sub.6 are the same or different and represent hydrocarbon groups, or a and b=0 and c=0 or 1 and R.sub.4 and R.sub.5 together with X form a heterocyclic group, or a, b and c=0 and R.sub.4, R.sub.5 R.sub.6 together with X form a heterocyclic group, compounds of the general formula: ##STR2## wherein R.sub.7 is a hydrocarbon group and where R.sub.8 and R.sub.Type: GrantFiled: July 27, 1989Date of Patent: October 2, 1990Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4940787Abstract: A method for the preparation of alpha,beta-olefinic unsaturated compounds by means of carbonylation of acetylenic unsaturated compounds with carbon monoxide in the presence of a hydroxy-containing compound in liquid phase, accomplished in the presence of a catalytic system that can be formed from:(a) a palladium compound,(b) a protonic acid, and(c) an organic phosphine according to the formula: ##STR1## wherein R.sub.1 represents a heterocyclic five- or six-atom ring, comprising, at least as hetero atom, nitrogen, which may be optionally substituted and/or may form part of a larger condensed ring structure that may be optionally substituted, and wherein R.sub.2 and R.sub.3 each have the aforesaid meaning of R.sub.1 or may represent an optionally substituted aryl group.The invention further comprises novel organic phosphines and compositions containing said phosphines as wel as the catalytic systems containing said phosphines.Type: GrantFiled: November 25, 1987Date of Patent: July 10, 1990Assignee: Shell Oil CompanyInventor: Eit Drent