Of Olefins Patents (Class 560/233)
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Patent number: 5237097Abstract: A process is disclosed for the carbonylation of an organic compound selected from the group consisting of an olefin, an alcohol, an acid and an ester. In this process the organic compound is reacted with carbon monoxide in the presence of a Group VIII metal-containing catalyst. The liquid carbonylation product solution of this reaction is conveyed to a separation zone maintained at a lower total pressure than is the pressure in the reaction zone. Simultaneously with the conveyance of the liquid product solution to the separation zone is the introduction therein of a carbon monoxide-containing gaseous stream, the carbon monoxide therein contributing a partial pressure of up to 30 psia of the total pressure in said separation zone. A portion of the liquid carbonylation product solution is flashed and removed from the separation zone. The unflashed liquid carbonylation product solution is recycled back into the reaction zone.Type: GrantFiled: December 22, 1992Date of Patent: August 17, 1993Assignee: Quantum Chemical CorporationInventors: David W. Smith, Ronnie M. Hanes
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Patent number: 5218145Abstract: In the manufacture of isobutyric acid or its precursors or esters by the Koch synthesis from propylene, carbon monoxide, and, optionally, water or an alcohol in liquid hydrogen fluoride, the reaction mixture is maintained at a constant reaction temperature in a heat exchanger using an addition product of at least two of the aforementioned materials, preferably isopropanol, as a coolant.Type: GrantFiled: October 20, 1988Date of Patent: June 8, 1993Assignee: Rohm GmbHInventors: Wolfgang Ruppert, Hermann-Josef Siegert
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Patent number: 5206396Abstract: Octyl ethers and octadienyl ethers of glucose, sucrose, bisphenol A, 4-substituted-2,2,6,6-tetramethylpiperidines are disclosed. Compositions comprised of a mixture of octyl ethers of glucose and sucrose and those containing octadienyl ethers of sugar acids and ring-opened epoxidized octadienyl ethers are also disclosed as are telomerization processes.Type: GrantFiled: July 25, 1990Date of Patent: April 27, 1993Assignee: Henkel Research CorporationInventors: Bert Gruber, Kenneth J. Weese, Steven M. Hoagland, Hans-Peter Mueller, Karlheinz Hill, Arno Behr, James R. Tucker
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Patent number: 5194676Abstract: Saturated carboxylic esters are produced from alkyl formate and an olefin, without the presence of substantial amounts of carbon monoxide, at a temperature of 120.degree. to 280.degree. C., under a pressure of 1 to 3,000 bars, in the presence of a catalyst based on ruthenium coordinated by ligands selected from carbon monoxide, halogen atoms and amines, and in the presence of an amide as a solvent. The catalyst is selected from catalysts consisting essentially of RuCl.sub.3.3H.sub.2 O; catalysts consisting essentially of the combination of an RuCl.sub.3.3H.sub.2 O together with at least one stabilizer selected from iodine, covalent iodides and quaternary ammonium halides; catalysts comprising Ru.sub.3 (CO).sub.12 together with at least one stabilizer such as is mentioned above; and catalysts selected from RuI.sub.3, [RuCl.sub.2 (CO).sub.3 ].sub.2, Ru(NH.sub.3).sub.6 Cl.sub.3 and [Ru(NH.sub.3).sub.5 Cl]Cl.sub.2, comprising, where appropriate, in addition, at least one stabilizer such as is mentioned above.Type: GrantFiled: March 26, 1991Date of Patent: March 16, 1993Assignee: AtochemInventors: Yves Castanet, Christophe Legrand, Andre Mortreux, Francis Petit
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Patent number: 5179224Abstract: Disclosed herein is a process for preparing a corresponding cinnamate ester by reacting a styrene compound, carbon monoxide, an alcohol and oxygen by the use of (1) metallic palladium or a compound thereof, (2) a copper compound, (3) a compound of at least one metal selected from Groups 4A, 5A, 7A, 8A (the iron group only) and 2B in the Periodic Table and (4) a halogen compound as a catalyst which comprises treating the catalyst components recovered from the reaction liquid after completion of the reaction with an oxidizing agent in the presence of an organic acid to regenerate their catalytic activity, using the resulting catalyst components again in the reaction as a catalyst and repeating the foregoing procedure.The regenerated catalyst is recovered in catalytic activity to the extent of that of a fresh catalyst and thus gives a high reaction performance in the subsequent reaction. Thus, the catalyst containing expensive metal can be used circulatively.Type: GrantFiled: October 1, 1991Date of Patent: January 12, 1993Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Usaji Takaki, Yoshihiro Yamamoto, Toshio Matsuhisa, Isamu Sudo, Shinobu Aoki
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Patent number: 5169985Abstract: Methods of improving the yield in the continuous preparation of isobutyric acid from propene, carbon monoxide, and water under pressure in liquid hydrogen fluoride as a Koch catalyst by mixing the propene with excess carbon monoxide, preferably carbon monoxide reintroduced from the process and freed of HF, and introducing the mixture into the reactor.Type: GrantFiled: April 24, 1992Date of Patent: December 8, 1992Assignee: Rohm GmbHInventors: Wolfgang Ruppert, Willi Ploesser
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Patent number: 5158921Abstract: A catalyst system, which containsa) a source of a group VIII metal, andb) a phosphine of general formula: ##STR1## in which R.sup.1, R.sup.2 and R.sup.3 are independently selected from an optionally substituted aryl group and a group of general formula: ##STR2## wherein eachh of A, X, Y and Z is independently selected from a nitrogen atom, a CH group and a group of formula CR wherein R represents a hydroxyl group, an amino group, an amido group, a cyano group, an aryl group, an aryloxy group, a halogen atom, an optionally substituted hydrocarbyl group or an optionally substituted hydrocarbyloxy group, it also being possible for two adjacent CR groups to form a ring, provided that at least one of R.sup.1, R.sup.2 and R.sup.3 represents a group of formula (II) in which at least one of A and Z represents a group of formula CR; or an acid addition salt thereof.Also disclosed is the use of the catalyst system in the selective carbonylation of unsaturated hydrocarbons.Type: GrantFiled: February 28, 1990Date of Patent: October 27, 1992Assignee: Shell Oil CompanyInventors: Eit Drent, Petrus H. M. Budzelaar, Willem W. Jager
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Patent number: 5124300Abstract: A catalyst system, which comprises:a) a source of a Group VIII metal;b) a phosphine having an aromatic substituent which contains an imino nitrogen atom;c) a source of protons; andd) a tertiary amine.Type: GrantFiled: February 4, 1991Date of Patent: June 23, 1992Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 5041623Abstract: A continuous process for the preparation of an alkyl propionate, which comprises reacting an alkanol in a liquid phase with ethene in a reaction vessel in the presence of a carbonylation catalyst, and removing alkyl propionate from the reaction vessel in a stream of vapor.Type: GrantFiled: May 15, 1990Date of Patent: August 20, 1991Assignee: Shell Oil CompanyInventors: Willem G. Reman, Gerben B. J. de Boer, Simon A. J. van Langen, Antonie Nahuijsen
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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: 5003104Abstract: This invention involves a process for the carbonylation of a carbonylatable reactant, e.g., an alkyl ester, a dialkyl ether or mixtures thereof by reacting the same with carbon monoxide. The process comprises effecting the carbonylation in the presence of a solution of a catalyst system containing a rhodium compound, an iodide and a lithium component at a temperature of from 50.degree. C. to 400.degree. C. at a carbon monoxide partial pressure of 1 psig to 15,000 psig. Hydrogen may also be present. The invention also concerns a carbonylation catalyst system effective for the addition of carbon monoxide to a carbonylatable reactant which comprises a solution containing as essential components a rhodium containing active component, an iodide and a lithium component.Type: GrantFiled: October 31, 1988Date of Patent: March 26, 1991Assignee: BP Chemicals LimitedInventors: Frank E. Paulik, Arnold Hershman, Walter R. Knox, Robert G. Schultz, James F. Roth
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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: 4945179Abstract: Process for the preparation of esters of carboxylic acids by contacting an olefinically unsaturated compound with CO and an alcohol, in the presence of (a) a ruthenium compound and (b) an iodide salt, LiBr and/or an onium bromide, with a molar ratio of CO to olefinically unsaturated compound.ltoreq.2.0 being applied when "b" is an iodide salt.Type: GrantFiled: August 15, 1988Date of Patent: July 31, 1990Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4902822Abstract: A process for the preparation of carboxylic acids or of esters thereof by contacting an olefinically unsaturated compound with CO in the presence of water or an alcohol, respectively, and of a catalytic system prepared by combining a ruthenium compound and a compound having a non-coordinating anion of an acid with a pK.sub.a below 0.5; compositions comprising a ruthenium compound and a salt having a non-coordinating anion of an acid with a pK.sub.a below 0.5 are novel.Type: GrantFiled: May 11, 1988Date of Patent: February 20, 1990Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4894188Abstract: Fatty acid and their derivatives are simply produced by reacting an olefin, carbon monoxide and water or reacting an alcohol or its derivative and carbon monoxide in the presence of a hydrogen fluoride catalyst and thermally decomposing the resulting reaction product in the presence of a lower hydrocarbon or a lower halogenated hydrocarbon.Type: GrantFiled: February 13, 1985Date of Patent: January 16, 1990Assignee: Mitsubishi Gas Chemical Company, Inc.Inventors: Takehiko Takahashi, Makoto Takagawa, Tomiyoshi Furuta, Toshio Hidaka, Kazuo Takada
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Patent number: 4791227Abstract: What is disclosed is the use of metallic vessels having particularly high corrosion resistance which are made of(a) aluminum or alloys containing more than 95% aluminum, or of(b) nickel-chromium-iron alloys containing from 30 to 50% of nickel, from 20 to 30% of chromium, and from 18 to 50% of iron, by weight, in reacting or working up mixtures containing substantial amounts of hydrogen fluoride in addition to organic carboxylic acids and/or carbon monoxide and/or water.Type: GrantFiled: September 23, 1982Date of Patent: December 13, 1988Assignee: Rohm GmbHInventors: Alfred Neumann, Willi Ploesser, Hermann-Josef Siegert
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Patent number: 4777284Abstract: Carbalkoxy-containing aliphatic compounds are prepared continuously by reacting an olefinically unsaturated aliphatic compound with carbon monoxide and an alkanol in the presence of a cobalt carbonyl catalyst and a tertiary nitrogen base at from 80.degree. to 200.degree. C. and under from 100 to 1,200 bar by an improved process in which carbon monoxide is circulated, and a carbon dioxide content of from 0.1 to 2% by volume is maintained in the carbon monoxide fed to the reaction.Type: GrantFiled: November 5, 1987Date of Patent: October 11, 1988Assignee: BASF AktengesellschaftInventors: Robert Maerkl, Werner Bertleff, Gebhard Kuehn, Paul Panitz, Peter Stops, Rudolf Kummer, Guenter Schuch
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Patent number: 4681707Abstract: Carboxylic acid esters are produced by reacting an unsaturated hydrocarbon, for example an olefin or an alkyne, with carbon monoxide and an alcohol in the presence of a protonic acid and as catalyst (a) at least one of the metals palladium, rhodium, ruthenium, iridium and cobalt, and (b) copper. In a modification of the invention carboxylic acids are produced by omitting the alcohol reactant and replacing it with water in an amount up to 8 mole equivalents based on the unsaturated hydrocarbon and a solvent other than an alochol, for example tetrahydrofuran.Type: GrantFiled: April 23, 1984Date of Patent: July 21, 1987Assignee: The British Petroleum Company p.l.c.Inventors: Howard Alper, Bertrand Despeyroux, David J. H. Smith, James B. Woell
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Patent number: 4670582Abstract: Process for the preparation of carboxylate esters of alpha-ethylenically unsaturated alcohols by reacting an ethylenically unsaturated compound with carbon monoxide and an enolizable ketone in the presence of a catalytic system formed by combining a palladium catalyst, a triarylphosphine and a protonic acid having a pK.sub.a below 1.5, except hydrohalogenic acids and carboxylic acids.Type: GrantFiled: August 15, 1986Date of Patent: June 2, 1987Assignee: Shell Oil CompanyInventor: Eit Drent
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Patent number: 4668816Abstract: High yields of aromatic, aromatic acetic and olefinic acids, esters, amides and the like are derived from a process wherein a halo-hydrocarbon is carbonylated in the presence of a palladium catalyst, a hindered amine base and phosphine in excess. The hindered amine base can comprise C.sub.3 -C.sub.10 branched alkyls, cyclic compounds, or mixtures of the above. The preferred amine is N,N-diisopropylethyl amine. The preferred catalyst is PdCl.sub.2 (PPH.sub.3).sub.2 with the excess phosphine generally supplied by a compound of the formula PR.sup.1 R.sup.2 R.sup.3 where R.sup.1, R.sup.2 and R.sup.3 are preferably phenyl.Type: GrantFiled: November 12, 1985Date of Patent: May 26, 1987Assignee: Stauffer Chemical CompanyInventor: Ronald A. Epstein
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Patent number: 4665213Abstract: Carboxylic acid esters are produced by reacting an olefinic hydrocarbon with an ester of formic acid in the presence of both carbon monoxide and oxygen at a temperature of up to 200.degree. and a pressure of up to 300 bar in the presence of water, typically in an amount of from 0.01 to 5% w/w, a source of protons, which is preferably a mineral acid or a tectometallosilicate in the hydrogen form, and as catalyst (a) a source of palladium, and (b) a source of copper.Type: GrantFiled: August 25, 1986Date of Patent: May 12, 1987Assignee: The British Petroleum Company p.l.c.Inventors: Howard Alper, David J. H. Smith
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Patent number: 4625055Abstract: A carboxylic acid, such as propionic acid, is prepared by carbonylation of an olefin, such as ethylene in the presence of water by the use of a molybdenum-nickel-alkali metal, tungsten-nickel alkali metal, or chromium-nickel-alkali metal co-catalyst in the presence of a halide.Type: GrantFiled: June 3, 1985Date of Patent: November 25, 1986Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4619790Abstract: Alkylcarboxylic acids (where alkyl is of 6 to 20 carbon atoms) are manufactured by hydrocarboxylating the corresponding olefins by means of cobalt carbonyl compounds in the presence of from 0.5 to 1.5 kg of N-methylpyrrolidone, per kg of the olefin, as the solvent.Type: GrantFiled: February 1, 1978Date of Patent: October 28, 1986Assignee: BASF AktiengesellschaftInventors: Rudolf Kummer, Kurt Schwirten
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Patent number: 4612390Abstract: A novel method for producing branched carboxylic acids or esters from alpha-unsaturated olefins is disclosed. Such olefins are reacted with a novel, sterically hindered, ortho substituted phenylphosphine palladium halide catalysts in the presence of water or primary or secondary alcohols to produce high branched end product yields. Such catalysts have phosphine ligand cone angles of between about 170.degree. and 180.degree.. Tris(o-methoxyphenyl)phosphine palladium halide and o-trifluoromethylphenyldiphenylphosphine palladium halide catalysts are preferred.Type: GrantFiled: March 24, 1982Date of Patent: September 16, 1986Assignee: Atlantic Richfield CompanyInventors: Wilfred P. Shum, John F. White
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Patent number: 4590293Abstract: An exothermic reaction's heat of a low-temperature reaction is used for further processing of the product mixture, for example, to separate the product from the reaction mixture.Type: GrantFiled: March 23, 1984Date of Patent: May 20, 1986Assignee: Ashland Oil, Inc.Inventor: Ralph F. Pascoe
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Patent number: 4588834Abstract: Carboxylic acids, for example n-butyric and isobutyric are prepared from an olefin such as propylene in a process comprising passing a liquid feed consisting of an olefin, an alkyl halide or heterocyclic amine promoter, a protonic coreactant, and a low concentration of a soluble metal catalyst, optionally in the presence of a solvent, and a gas consisting essentially of carbon monoxide over a carbon bed maintained at a temperature of from about 200.degree. C. to about 400.degree. C. and a pressure of from about 500 psi to about 4000 psi or greater.Type: GrantFiled: October 4, 1984Date of Patent: May 13, 1986Assignee: Texaco Inc.Inventor: John M. Larkin
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Patent number: 4578367Abstract: The catalytic cobalt compound used in the reaction of olefins with carbon monoxide and water or alkanols which employs an oxidizing treatment is reprocessed according to the present invention. This reprocessing includes in a first embodiment treating the cobaltic residue obtained as the distillation sump product with water and a carboxylic acid having 1 to 4 C atoms. The phases generated are separated and cobalt is recovered from the carboxylic acid/water phase in the form of the corresponding carboxylic acid salt. Where appropriate, the corresponding carboxylic acid salt is transformed into another carboxylic-acid salt.A second embodiment includes the steps of hydrogenating the cobalt containing residue obtained as the distillation sump product, separating the metallic cobalt which is obtained, reacting the metallic cobalt with an acid and where appropriate converting the cobalt salt so obtained into another cobalt salt.Type: GrantFiled: February 19, 1985Date of Patent: March 25, 1986Assignee: Chemische Werke Huls AktiengesellschaftInventor: Peter Hofmann
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Patent number: 4568653Abstract: Reaction mixtures which are obtained on hydroformylation or carbonylation of olefinically unsaturated compounds and which contain dissolved non-volatile complex compounds of metals of group VIII of the periodic table are worked up by a method wherein the products, after distillative removal of low-boiling constituents alone, or of these constituents plus a part of the high-boiling residue, or a part of the high-boiling residue after distillative removal of the desired products, are or is extracted with carbon dioxide, a C.sub.2 -C.sub.4 -paraffin, a C.sub.2 -C.sub.4 -olefin or a normally gaseous halohydrocarbon at above the critical temperature and above the critical pressure of these (extractant) compounds.Type: GrantFiled: January 6, 1981Date of Patent: February 4, 1986Assignee: BASF AktiengesellschaftInventors: Kurt Schwirten, Rudolf Kummer, Wolfgang Richter
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Patent number: 4540811Abstract: A carboxylic acid esters, such as methyl propionate, is prepared by carbonylation of an olefin, such as ethylene, in the presence of an alcohol by the use of a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium nickel-alkali metal co-catalyst and in the presence of a halide.Type: GrantFiled: September 30, 1982Date of Patent: September 10, 1985Assignee: The Halcon SD Group, Inc.Inventor: Nabil Rizkalla
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Patent number: 4536340Abstract: A mixture of 1,3-butadiene, carbon monoxide and a monoalkanol of the general formula ROH in which R is a straight or branched chain alkyl group of from 1 to about 12 carbon atoms is reacted in the presence of catalyst to provide alkyl nonadienoate ester at high levels of productivity and little, if any, catalyst decomposition, employing as catalyst, a palladium-ligand complex comprising:(a) a member selected from the group consisting of zerovalent palladium, a palladium-containing composition which provides zerovalent palladium under reaction conditions and palladium (II) salt;(b) a strong ligand selected from the group consisting of tertiary phosphine having a pKa in water of not greater than about 6, a phosphite of the general formula (R.sup.1 O) (R.sup.2 O) (R.sup.3 O)P in which each of R.sup.1, R.sup.2 and R.sup.3 is an alkyl group having at least 9 carbon atoms, an aryl group or an alkaryl group, an arsine of the general formula R.sup.1 R.sup.2 R.sup.3 As in which each of R.sup.1, R.sup.2 and R.sup.Type: GrantFiled: May 24, 1983Date of Patent: August 20, 1985Assignee: National Distillers and Chemical CorporationInventor: Ronnie M. Hanes
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Patent number: 4536597Abstract: A process for the selective hydrocarboxylation of propylene to produce predominantly isobutyric acid in the liquid phase is provided. The reaction of propylene, carbon monoxide and water wherein a water to propylene ratio is maintained of from about 0.01 to a value less than 1.0 is effected at a temperature of about 75.degree. C. to about 150.degree. C. and at a pressure of about 250 psi to about 5000 psi in the presence of a carboxylic acid solvent and a catalyst comprising a coordinating palladium compound, an organo-arsine and a hydrogen halide.Type: GrantFiled: December 31, 1979Date of Patent: August 20, 1985Assignee: The Standard Oil Company (Ohio)Inventors: Frederick A. Pesa, Thomas A. Haase
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Patent number: 4522760Abstract: Palladium values are separated from the products of reaction resulting from the carbonylation of a conjugated diene with carbon monoxide in the presence of an alcohol, a halogenated hydracid and a palladium catalyst, by (i) contacting the carbonylation reaction medium with a nitrogen, phosphorus or arsenic quaternary onium salt, a polar alcohol and an apolar, aliphatic or cycloaliphatic hydrocarbon solvent, and permitting the resulting admixture to phase separate into an alcohol phase and an organic phase; (ii) decanting/separating said alcohol phase from said organic phase; (iii) recovering the palladium values and the quaternary onium salt from said alcohol phase; and (iv) recovering the products of carbonylation from said organic phase.Type: GrantFiled: July 23, 1982Date of Patent: June 11, 1985Assignee: Rhone-Poulenc Chimie de BaseInventor: Jean Jenck
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Patent number: 4521526Abstract: The catalytic cobalt compound used in the reaction of olefins with carbon monoxide and water or alkanols which employs an oxidizing treatment is reprocessed according to the present invention. This reprocessing includes in a first embodiment treating the cobaltic residue obtained as the distillation sump product with water and a carboxylic acid having 1 to 4 C atoms. The phases generated are separated and cobalt is recovered from the carboxylic acid/water phase in the form of the corresponding carboxylic acid salt. Where appropriate, the corresponding carboxylic acid salt is transformed into another carboxylic-acid salt.A second embodiment includes the steps of hydrogenating the cobalt containing residue obtained as the distillation sump product, separating the metallic cobalt which is obtained, reacting the metallic cobalt with an acid and where appropriate converting the cobalt salt so obtained into another cobalt salt.Type: GrantFiled: July 25, 1983Date of Patent: June 4, 1985Assignee: Chemische Werke Huls AGInventor: Peter Hofmann
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Patent number: 4521614Abstract: Esters, e.g., alkyl adipates, are facilely prepared by carbonylation among an alcohol, carbon monoxide and a monoolefin, e.g., an alkyl pentenoate, in the presence of a catalytically effective amount of cobalt and a tertiary nitrogen base, and optionally hydrogen, said reaction being carried out in an aromatic hydrocarbon reaction medium bearing from 1 to 3 nuclear substituents, and said substituents comprising cyano or a radical of the formula R--Y-- having up to 20 carbon atoms, wherein Y is a direct valence bond, an oxygen atom, a sulfur atom, a carbonyl group or a carbonyloxy group (--CO--O--), with R being bonded to the oxygen of the group --CO--O--, and R is alkyl, aralkyl or or aryl, or a cyano substituted such R--Y-- radical, or a radical R--Y-- which includes one of the divalent bridges --O--, --CO-- or --CO--O-- along its skeletal carbon chain, with the proviso that at least one of said substituents is either cyano or a radical R--Y-- wherein Y is other than a direct valence bond.Type: GrantFiled: May 3, 1983Date of Patent: June 4, 1985Assignee: Rhone-Poulenc Chimie De BaseInventor: Jean Jenck
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Patent number: 4518798Abstract: Esters or carboxylic acids are prepared from olefins containing at least two carbon atoms by reacting the olefin with carbon monoxide in the presence of:(i) a first complex of a selected Lewis acid with the ester or carboxylic acid, whichever is the reaction product recovered;(ii) a second complex of the Lewis acid with an alcohol, if an ester is being prepared, or with water, if a carboxylic acid is being prepared; and(iii) a metal carbonyl compound containing a Group IB transition metal in the first oxidation state; andby recovering the reaction product(s).The preferred olefin is propylene, the preferred ester to be prepared is methylisobutyrate, the preferred metal is copper and the preferred Lewis acid is boron trifluoride.Type: GrantFiled: September 30, 1982Date of Patent: May 21, 1985Assignee: Exxon Research & Engineering Co.Inventors: George M. Kramer, Walter Weissman, Herbert C. Brown, Rowland Pettit, deceased
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Patent number: 4508660Abstract: Process using selected sulfones, e.g., tetramethylenesulfone as solvents in the carbonylation of nitriles, e.g., 3-pentenenitrile and acids, e.g., 3-pentenoic acid to produce highly linear products.Type: GrantFiled: March 14, 1983Date of Patent: April 2, 1985Assignee: E. I. Du Pont de Nemours and CompanyInventor: James B. Sieja
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Patent number: 4504675Abstract: What is disclosed is a process for the continuous production of isobutyric acid or an alkyl ester thereof by the Koch synthesis, which process comprises reacting propylene, carbon monoxide, and water or an alkanol in the presence of hydrogen fluoride in at least one reaction space containing a liquid phase and a gas phase under high pressure, releasing said pressure at least partially, whereby a gas containing organic compounds from said synthesis evolves from said liquid phase, adding oxygen to said evolved gas and at least partially combusting the organic compounds contained therein, then contacting the evolved gas containing the at least partially combusted organic compounds with at least a portion of the water or alkanol to be reacted with said propylene and carbon monoxide, whereby at least a portion of said combusted organic compounds are absorbed by said water or alkanol, returning said water or alkanol containing the absorbed combusted organic compounds to said reaction space, and discharging any unabType: GrantFiled: October 25, 1982Date of Patent: March 12, 1985Assignee: Rohm GmbHInventors: Siegmund Besecke, Hermann-Josef Siegert, Gunter Schroder
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Patent number: 4500727Abstract: A process for producing methyl lactate by (I) hydroformylating vinyl acetate or vinyl propionate with a gaseous mixture of hydrogen and carbon monoxide in an organic solvent in the presence of a substantially water-insoluble rhodium complex and a tri-substituted phosphine to form .alpha.-acetoxy- or propionyloxy-propionaldehyde, (II) subjecting at least part of the reaction mixture obtained in step (I) to extraction with an aqueous medium to obtain an aqueous layer containing .alpha.-acetoxy- or propionyloxy-propionaldehyde and an extraction residue containing the catalyst components, and recycling the extraction residue to the hydroformylation step (I), (III) separating .alpha.-acetoxy- or propionyloxy-propionaldehyde from the aqueous layer containing the same as obtained in step (II), (IV) oxidizing .alpha.-acetoxy- or propionyloxy-propionaldehyde obtained in step (III) in the liquid phase with oxygen gas or an oxygen-containing gas in the presence of an oxidation catalyst to form .alpha.Type: GrantFiled: March 18, 1982Date of Patent: February 19, 1985Assignee: Kuraray Co., Ltd.Inventors: Takanori Kitamura, Mitsuo Matsumoto, Masuhiko Tamura
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Patent number: 4495359Abstract: Described is the genus of compounds defined according to the structure: ##STR1## wherein one of the dashed lines represents a carbon-carbon double bond and each of the other of the dashed lines represent carbon-carbon single bonds; wherein the wavy line represents a carbon-carbon single bond or no bond; wherein when the wavy line represents a carbon-carbon single bond, Z represents methylene and when the wavy line represents no bond, Z represents hydrogen or C.sub.2 -C.sub.Type: GrantFiled: May 5, 1983Date of Patent: January 22, 1985Assignee: International Flavors & Fragrances Inc.Inventor: Richard M. Boden
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Patent number: 4481147Abstract: Alkylesters of saturated aliphatic carboxylic acids are prepared by reacting aliphatic monoolefins containing internal double bonds and having 6 to 20 carbon atoms with carbon monoxide and an alkanol having one hydroxyl function in the presence of a catalyst of a cobalt compound and a promoter where the promoter is pyridine, a non-ortho-substituted alkylpyridine or a mixture thereof.The monoolefins can possibly contain paraffins and the reaction is carried out with:(a) a promoter to cobalt ratio of 3/1 to 25/1;(b) a cobalt concentration from 0.02 to 0.2 gram-atom of cobalt per mole of monoolefin;(c) a temperature between 165.degree. and 195.degree. C.;(d) a pressure from 150 to 300 bars;(e) a molar ratio of alkanol to monoolefin from 1/1 to 10/1; and(f) a dwell time exceeding 15 minutes.Type: GrantFiled: July 11, 1983Date of Patent: November 6, 1984Assignee: Chemische Werke Huls AGInventor: Peter Hofmann
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Patent number: 4452999Abstract: What is disclosed is a continuous one-step method for the preparation of isobutyric acid or a lower alkyl ester thereof by the Koch synthesis, which method comprises reacting propylene, carbon monoxide, and water or a lower alcohol, in the gaseous and liquid phases, in the presence of hydrogen fluoride as a Koch catalyst, at a temperature between 80.degree. C. and 160.degree. C., at a dwell time of the liquid phase of less than 20 minutes, and with a high degree of backmixing, while maintaining the content of propylene in the reaction mixture at less than one percent by weight of the liquid phase, wherein all or part of the propylene, carbon monoxide, and water or lower alcohol can be replaced by binary addition compounds formed pairwise between these materials. In the alternative, isopropylformiate can be continuously rearranged in the presence of hydrogen fluoride to produce isobutyric acid.Type: GrantFiled: May 21, 1982Date of Patent: June 5, 1984Assignee: Rohm GmbHInventors: Siegmund Besecke, Guenter Schroeder, Hermann-Josef Siegert, Wolfgang Gaenzler
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Patent number: 4451407Abstract: Oxygenated organic compounds, e.g. esters, aldehydes, and amides, are prepared by reacting an olefinically unsaturated compound with carbon monoxide and a compound containing a replaceable hydrogen atom in the presence of a catalyst comprising cobalt or ruthenium carbonyl and a promoter ligand. The promoter ligand is selected from the group consisting of heterocyclic nitrogen oxide compounds and phosphorus or sulfur oxides. These reactions are carried out under relatively mild conditions of temperature and pressure.Type: GrantFiled: December 18, 1981Date of Patent: May 29, 1984Assignee: The Standard Oil CompanyInventors: Frederick A. Pesa, Thomas A. Haase
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Patent number: 4433165Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system that contains (a) a rhodium component, and (b) an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer component selected from N,N,N',N'-tetramethyl-o-phenylenediamine and 2,3'-dipyridyl.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventor: Thomas C. Singleton
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Patent number: 4433166Abstract: The present invention provides for an improved process wherein an olefin, an alcohol, or an ester, halide or ether derivative of said alcohol is reacted with carbon monoxide in a liquid phase in the presence of a catalyst system containing a rhodium component and an iodine or bromine component. By passing at least a portion of the liquid reaction mass from the reaction zone to a separation zone of substantially lower CO partial pressure, at least a portion of the carbonylation products, as well as unreacted carbon monoxide, inert gases, and unreacted olefin, alcohol, or alcohol derivatives are vaporized and can be withdrawn from the separation zone. Precipitation of the rhodium catalyst under carbon monoxide deficient conditions is prevented or retarded by addition to the system of a stabilizer which is a tin component which may be tin or a tin compound.Type: GrantFiled: December 29, 1980Date of Patent: February 21, 1984Assignee: Monsanto CompanyInventors: Thomas C. Singleton, Frank E. Paulik
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Patent number: 4431593Abstract: Organic esters, e.g., linear esters, including diesters, are prepared by carbonylating a monoolefin with carbon monoxide and an alcohol in the presence of a catalytically effective amount of a catalyst comprising cobalt, a tertiary amine base and ruthenium.Type: GrantFiled: September 21, 1981Date of Patent: February 14, 1984Assignee: Rhone-Poulenc IndustriesInventor: Jean Jenck
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Patent number: 4424375Abstract: Improvement in the process of producing carboxylic acid esters or salts involving contacting a halogen alkyl compound with carbon monoxide and a basic substance in the presence of a carbonylation catalyst for carbonylation of the halogen alkyl and production of the corresponding ester or salt of the basic substance. The improvement involves performing the contacting in a reaction vessel, circulating a liquid mass of the halogen alkyl, basic substance and carbonylation catalyst through the vessel and maintaining a carbon monoxide atmosphere in the vessel, injecting the circulating liquid mass into the vessel with a nozzle to spray the liquid mass into the vessel and intimately mixing the liquid mass with carbon monoxide in the nozzle for injection of carbon monoxide into the vessel with the sprayed liquid mass.Type: GrantFiled: June 16, 1981Date of Patent: January 3, 1984Assignee: Dynamit Nobel AGInventors: Moustafa El-Chahawi, Uwe Prange, Hermann Richtzenhain, Wilhelm Vogt
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Patent number: 4421691Abstract: A process for preparing fatty acid esters by reacting olefins, alkanols and carbon monoxide in the presence of a compound of cobalt and a promoter consisting of pyridine, non-orthosubstituted alkylpyridines or mixtures thereof. The reaction output is at first treated with a gas containing oxygen in a non-damaging manner and then reprocessed in two distillation stages. The first distillation stage is operated at a higher pressure than the second. In the first distillation stage there is produced a distillate free of cobalt and a sump product containing all of the cobalt used as catalyst. In the second distillation stage the sump product of the first distillation stage is again distilled to produce another distillate free of cobalt and a cobalt concentrate as sump product. This cobalt concentrate is incorporated into pyridine, a non-orthosubstituted alkylpyridine or a mixture thereof to form a suspension. The suspension is then treated by a mixture of carbon monoxide and hydrogen at a temperature of 100.degree.Type: GrantFiled: June 5, 1981Date of Patent: December 20, 1983Assignee: Chemische Werke Huls AGInventors: Wolfgang H. E. Muller, Peter Hofmann
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Patent number: 4414409Abstract: Carbonylation of olefins is carried out in the presence of a hydroxylic compound, carbon monoxide and a catalyst system comprising an organic phosphine liganded palladium compound and a perfluorosulfonic acid.Type: GrantFiled: December 21, 1981Date of Patent: November 8, 1983Assignee: E. I. Du Pont de Nemours & CompanyInventor: Francis J. Waller
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Patent number: 4400300Abstract: A process for recovering and reactivating catalysts used in the reaction of olefins with carbon monoxide and alkanols. The catalysts consist of a cobalt compound and pyridine, a non-ortho-substituted alkylpyridine or a mixture thereof as the promoter. The reacted mixture contains fatty acid ester, unconverted alkanol, uncoverted olefin, catalyst and promoter and this reacted mixture is treated with oxygen or an oxygenated gas at a temperature of about 20.degree.-150.degree. C. to oxidize the cobalt compound. The oxidized mixture is then separated by distillation to remove unconverted alkanol and olefin, the promoter, the reaction products and the distillation residue obtained thereby is mixed with pyridine, a non-ortho-substituted alkylpyridine or a mixture thereof. The suspension so obtained is treated with a mixture of carbon monoxide and hydrogen at a temperature of 100.degree. to 250.degree. C. and at a pressure of at least 50 bars.Type: GrantFiled: April 22, 1981Date of Patent: August 23, 1983Assignee: Chemische Werke Huls AGInventors: Wolfgang H. E. Muller, Peter Hofmann
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Patent number: 4354978Abstract: Alkanoic acids containing largely the alpha-methyl isomers thereof, and/or the corresponding esters, are prepared by reacting an alpha-olefin, carbon monoxide and water and/or a monoalkanol in the presence of a catalytically effective amount of a catalyst composition comprising (i) a zero-valent Group VIII metal or metal alloy in which the Group VIII metal is the major component by weight thereof, (ii) an aryl ligand selected from the group consisting of arylarsine, arylstibine and arylbismuthine and (iii) a Lewis acid and/or hydrochloric acid.Type: GrantFiled: August 4, 1980Date of Patent: October 19, 1982Assignee: National Distillers & Chemical Corp.Inventors: Orville D. Frampton, William D. Baugh