Abstract: Catalysts suitable for the dimerization of a diolefin, e.g. butadiene to 4-vinylcyclohexene, are prepared by reacting (1) iron chloride and sodium nitrite or alternatively (2) iron nitrosyl chloride with (3) carbon monoxide in an organic solvent in the presence of a readily oxidizable metal, e.g. tin. The catalyst solution is filtered prior to use to remove particulate matter such as unreacted tin.While the reaction employing iron chloride and sodium nitrite is preferred, the catalyst produced by either method contains a minimum of reducing agent and by-products. It can be isolated and stored in the absence of the butadiene monomer while retaining its stability and activity.

Abstract: In a transition metal catalyst system, the improvement comprising including in the catalyst system an autoacceleration inhibitor, which (i) at about the temperature at which the catalyst system autoaccelerates, decomposes into a poison for the catalyst system; (ii) is present in the catalyst system in an amount sufficient to provide the quantity of poison required to inhibit the autoacceleration of the catalyst system at the autoacceleration temperature; and (iii) is either essentially inert at the normal operating temperature of the catalyst system or will cause substantially less inhibition of the catalyst system at the normal operating temperature than at the autoacceleration temperature.

Abstract: The present invention relates to a process for the hydroconversion of heavy crude oil and an improved regenerable catalyst for use therein. The process broadly comprises (a) introducing into a hydroconversion reaction zone a feedstock of crude oil, hydrogen, from about 10 to about 1000 wppm of an active phase source selected from the group consisting of Group VB metals, Group VIB metals, Group VIIB metals, Group VIIIB metals, Group IA metals, Group IIA metals, and mixtures thereof, and from about 0.1 to about 20.0 wt. % of a refractory carrier material having a surface area in the range of from about 10 to about 700 m.sup.2 /g, a total pore volume of from about 0.1 to about 2.0 cm.sup.3 /g, an average pore diameter in the range of from about 20 to about 4,000 .ANG., a particle size diameter in the range of from about 1 to about 1000 .mu.m and pore size distribution according to the following:______________________________________ Pores of radius r (.ANG.

Abstract: There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

Abstract: Ruthenium cobalt- or cobalt-containing catalysts which have been promoted with phosphonites or phosphinites effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of these phosphonite- or phosphinite-promoted cobalt or ruthenium- cobalt catalysts to form the monomethyl ether of ethylene glycol. In a like manner acetaldehyde may be converted to the corresponding propylene glycol monoether. The process may advantageously be carried out with high yields and selectivities in the presence of a polar or non-polar organic solvent in combination with the catalyst system of this invention.The invention is also directed to the phosphonite- or phosphinite-promoted cobalt and ruthenium-cobalt catalyst systems per se.

Abstract: The hydroformylation of olefins with rhodium complex catalysts is described. The catalysts employed comprises a rhodium complex with at least one phosphine having a specified structure, e.g., tris(benzyl)phosphine. Preferred phosphines have a pKa in the range of about 3.5 up to 5.3 and a cone angle in the range of about 160.degree. up to 195.degree.. Hydroformylation reactions at relatively low temperatures and pressure and yet with high rates of reaction and high selectivity to aldehyde product are obtained by the practice of the present invention.

Abstract: A method of inducing surface ensembles on a transition metal catalyst used in the conversion of a reactant gas or gas mixture, such as carbon monoxide and hydrogen into hydrocarbons (the Fischer-Tropsch reaction) is disclosed which comprises adding a Lewis base to the syngas (CO+H.sub.2) mixture before reaction takes place. The formation of surface ensembles in this manner restricts the number and types of reaction pathways which will be utilized, thus greatly narrowing the product distribution and maximizing the efficiency of the Fischer-Tropsch reaction. Similarly, amines may also be produced by the conversion of reactant gas or gases, such as nitrogen, hydrogen, or hydrocarbon constituents.

Abstract: A process for the preparation of a rhodium catalyst comprising dissolving a carboxylic acid salt of rhodium in a solvent taken from the class consisting of aliphatic, cycloaliphatic, aromatic hydrocarbons and mixtures thereof. The carboxylic acid has 2 to 18 carbon atoms. This salt is reacted with carbon monoxide and hydrogen to form a rhodium hydridrocarbonyl which is reacted with an aqueous solution of a triaryl phosphine. The aqueous solution may be present during the initial reaction of the rhodium salt or may be added thereafter. A catalyst which is the product of the foregoing process is also disclosed, as is a method of producing aldehydes using the catalyst.

Abstract: A colloidal hydrosilylation catalyst is provided by effecting reaction between a silicon hydride or a siloxane hydride and a Pt(O) or Pt(II) catalyst. The colloidal catalyst forms stable mixtures with olefinically unsaturated organopolysiloxanes.

Abstract: A catalyst for producing hydrogen gas from carbon monoxide and water, and a procedure for generating hydrogen gas from carbon monoxide and water in the presence of a catalyst. The catalyst is formed from a complex of a group VIII metal carbonyl and a heterocyclic base, and is of the formula M.sub.3-n M'.sub.n (CO).sub.12-x L.sub.x +yBwhereinM=RuM'=Fen is 0, 1 or 2x is 0, 1 or 2L is a triaryl or trialkyl phosphine or phospite,B is a chelating bidentate aromatic heterocyclic nitrogen-containing base, andy is a whole or fractional number from 1-6.

Abstract: Ruthenium-cobalt carbonyl catalysts which have been promoted with an organophosphite effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this phosphite-promoted ruthenium carbonyl cobalt catalyst to form the monomethyl ether of ethylene glycol. In a like manner acetaldehyde may be converted to the corresponding propylene glycol monoether. The process may advantageously be carried out with high yields and selectivities in the presence of a polar or non-polar organic solvent in combination with the catalyst system of this invention.The invention is also directed to certain of the organophosphite-promoted cobalt and ruthenium-cobalt carbonyl catalyst systems per se.

Abstract: A catalyst system having high activity and selectivity to carbonylation products comprises a rhodium-containing catalytically active component and a halogen-containing promoter component, the halogen being selected from the group consisting of bromine, iodine, bromide compounds, and iodide compounds.

Abstract: Supported initiators for the radiation-activated polymerization of cationically-polymerizable compounds, particularly epoxide group-containing compounds, are described. The supported initiators comprise a particulate carrier and a photocatalytic ionic salt. The supported initiators are especially useful for the polymerization of cationically-polymerizable compounds in which the ionic salt alone is not soluble.

Abstract: Transition metal-poly-phosphite complex catalyzed carbonylation processes, especially hydroformylation, as well as transition metal-poly-phosphite ligand complex compositions.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.The novel catalyst combination of R.sup.5 CCo.sub.3 (CO).sub.9 and Ru.sub.3 (CO).sub.12 is likewise claimed herein.

Abstract: A carboxylic acid, such as acetic acid, is prepared by carbonylation of a hydrocarbyl alcohol, such as methanol, by the use of a molybdenum-nickel or tungsten-nickel co-catalyst in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent and in the presence of an iodide.

Abstract: Carrier-supported catalyst for making monocarboxylic anhydrides by subjecting a suitable ester or ether to carbonylation. The carrier supported catalyst has an organosilicon compound containing an alkoxy or halogen group and also an organonitrogen, organophosphorus, organoarsenic, organosulfur, mercapto or thioether group as a polyfunctional adhesion promoter additively combined with the carrier material on the one hand, and with the noble metal compound of the 8th subgroup of the Periodic System of the elements, on the other hand.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.

Abstract: A catalyst and process useful at low temperatures (below about 160.degree. C.) and preferably in the range 80.degree.-120.degree. C. used in the production of methanol from carbon monoxide and hydrogen is disclosed. The catalyst is used in slurry form and comprises a complex reducing agent derived from the component structure NaH--RONa--M(OAc).sub.2 where M is selected from the group consisting of Ni, Pd, and Co and R is a lower alkyl group containing 1-6 carbon atoms. This catalyst is preferably used alone but is also effective in combination with a metal carbonyl of a group VI (Mo, Cr, W) metal. The preferred catalyst precursor is Nic (where M=Ni and R=tertiary amyl). Mo(CO).sub.6 is the preferred metal carbonyl if such component is used. The catalyst is subjected to a conditioning or activating step under temperature and pressure, similar to the parameters given above, to afford the active catalyst.

Abstract: Ruthenium carbonyl-cobalt carbonyl catalyst mixtures effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals, wherein said acetal may be prepared separately or in situ from an aldehyde and an alcohol. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this ruthenium carbonyl-cobalt carbonyl catalyst to form the monomethyl ether of ethylene glycol.The invention also is directed to the ruthenium carbonyl-promoted cobalt carbonyl catalysts per se, including novel precipitated forms of these ruthenium-cobalt carbonyl catalyst mixtures.

Abstract: A hydroformylation catalyst system consisting essentially of a complex combination (1) of rhodium, carbon monoxide and triarylphosphine or triarylphosphite ligand, a compound (2) of cobalt and a triarylphosphine or triarylphosphite compound (3), wherein said system contains a source of at least one conjugated diene (4).

Abstract: A rhodium catalyzed hydroformylation process carried out in the presence of free triarylphosphine ligand and free organic tertiary bisphosphine monoxide ligand, and catalytic precursor solutions for said process.

Abstract: A hydroformylation catalyst of the formulaL.sub.a CuCo(CO).sub.b L'cwherein L is a monodentate phosphine, a bidentate phosphine or a bidentate amine, a is 1-3, b is 3 or 4, c is 0 or 1; provided that, where b=4, c=0 and L' is CO, phosphine or phosphite. Where the catalysts have the formulaL.sub.a CuCo(CO).sub.4the compounds are novel.

Abstract: Regioselective and stereoselective synthesis of trans-internal olefins is effected with transition metal catalyst complexes having pairs of associated active sites. Photolytic conditions are generally employed.

Abstract: A process for producing linear aldehydes or alcohols from olefins using a mixed transition metal hydroformylation catalyst wherein the catalyst comprises a mixture of transition metal compounds wherein the first component is an anionic transition metal catalyst having a charge of at least -2. The formula of the anionic compound is generally defined as M.sup.+n [H.sub.y A.sub.x L.sub.z ].sup.-n wherein A represents Fe, Ru, Os, W, Cr, Co, Rh, Ir or Mo, M is a cationic species, n is an integer greater than or equal to 2, x is an integer greater than or equal to 1, y is an integer greater than or equal to 0 and z is an integer generally corresponding to the number of available coordination bonding sites of A. The second component is a Group VIII compound, preferably a halide or carbonyl of the Group VIII compound. These compounds exhibit high selectivity toward linear products.

Abstract: A liquid-phase catalyst is represented by the formula X:T:Z:Q, wherein X is molybdenum, tungsten or chromium, T is nickel, X and T being in zero valent form or in the form of a halide, an oxide, a carboxylate of 1 to 20 carbon atoms, a carbonyl or an hydride; Z is a halide source which is hydrogen halide, halogen, or an alkyl halide wherein the alkyl group contains 1 to 20 carbon atoms, and Q is the alkali metal component and is in the form of an iodide, a bromide, a chloride or a carboxylate as defined for X and T, the molar ratio of X to T being 0.1-10:1, the molar ratio of X+T to Q being 0.1-10:1, and the molar ratio of Z to X+T being 0.01-0.1:1.

Abstract: Novel ligand materials and transition metal complexes thereof are disclosed which are useful as solvents and/or catalysts for various processes, including catalytic conversion processes for the conversion of hydrocarbons or carbon monoxide, such as the hydrocarbonylation of olefins, hydrogenation using H.sub.2 or CO and H.sub.2 O, dehydrogenation, hydrocarbon synthesis, alcohol synthesis, and water-gas disproportionation catalysis. Among the novel ligand materials disclosed are compositions containing phosphine and arsine coordinating groups along with, e.g., groups comprising fluorines, ethynyl or ethenyl groups, quaternary ammonium, arsonium and/or phosphonium groups. Ligands containing M-O-L linkages and complexes thereof are also disclosed wherein M is selected from, for example, Si or Ti and L is selected from P or As. Also, various ion-exchanged ligand compositions, photoreactive compositions and the uses of such compositions are also described.

Abstract: A hydroformylation process for producing aldehydes using a bisphosphine monooxide ligand and catalytic precursor solutions for said process.

Abstract: This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

Abstract: A novel transition metal catalyst which has a phosphido-type linkage is much less subject to metal loss during operations because of its greater bond strength. This catalyst will hydrogenate unsaturated hydrocarbons under milder conditions than most prior art catalysts.

Abstract: Methyl acetate is prepared in good yield by reacting methanol with carbon monoxide in the presence of a homogeneous catalyst composition comprising a ruthenium-containing compound, a cobalt-containing compound and a quaternary onium salt or base, and heating the resulting mixture at an elevated temperature and pressure for sufficient time to produce the desired methyl acetate, and then recovering the same from the reaction mixture.

Abstract: A novel ethylene oligomerization catalyst is provided consisting essentially of a nickel compound, a phosphine compound, and an acid. In addition, an improved ethylene oligomerization process is provided which comprises contacting ethylene with the novel catalyst composition present, in an effective solvent, at a temperature from about 0.degree. C. to about 200.degree. C. As a result of the inventive process, high catalyst productivity and good selectivity to desired oligomeric products are obtained.

Abstract: Ethanol is selectively produced from the reaction of methanol with carbon monoxide and hydrogen in the presence of a transition metal carbonyl catalyst. Methanol serves as a solvent and may be accompanied by a less volatile co-solvent. The solution includes the transition metal carbonyl catalysts and a basic metal salt such as an alkali metal or alkaline earth metal formate, carbonate or bicarbonate. A gas containing a high carbon monoxide to hydrogen ratio, as is present in a typical gasifer product, is contacted with the solution for the preferential production of ethanol with minimal water as a byproduct. Fractionation of the reaction solution provides substantially pure ethanol product and allows return of the catalysts for reuse.

Abstract: The present invention relates to a process for producing ethanol and n-propanol by reacting methanol with carbon monoxide and hydrogen at elevated pressure and temperature. A system consisting of a cobalt compound, a ruthenium compound, an iodide, and an organic phosphine serves as the catalyst. The organic phosphine contains a group having a --SO.sub.3 M, --COOM or --OSO.sub.3 M radical.

Abstract: C.sub.4 compounds including n-butanol and n-butanal are produced by reacting methanol, hydrogen, and carbon monoxide, in the presence of a cobalt catalyst selected from the group consisting of (a) a cobalt carbonyl, (b) a hydrido cobalt carbonyl and (c) a cobalt-containing material convertible to a cobalt carbonyl or a hydrido cobalt carbonyl, an iodine promotor and a thiol defined by the formula:RSHwherein R is selected from the group consisting of saturated or unsaturated, straight or branched chain alkyl radicals having from one to 24 carbon atoms, cycloalkyl radicals having from three to 40 carbon atoms, aryl radicals having from six to 20 carbon atoms, aralkyl and alkaryl radicals having from six to 40 carbon atoms and halogen substituted derivatives thereof. A high degree of selectivity towards the formation of butanol and butanal is provided by using the cobalt entity and the thiol in a molar ratio in the range of about 2:1 to about 10:1, based on elemental cobalt and sulfur.

Abstract: Disclosed is a process for catalytic hydrogenolysis of p-substituted benzaldehyde-dialkyl-acetals of the general formula ##STR1## in which R is an alkyl group, an unsubstituted or substituted aryl group or an unsubstituted or substituted aralkyl group, by means of a catalyst system composed of cobalt carbonyl and at least one nitrogen-containing heterocyclic compound, such as pyridine, pyrrole, pyrrolidone or piperidine and a hydrogen/carbon monoxide mixture to give the corresponding p-substituted benzyl alkyl ether derivatives.

Abstract: 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 or tungsten-nickel co-catalyst in the presence of a promoter comprising an organo-phosphorus compound or an organo-nitrogen compound wherein the phosphorus and nitrogen are trivalent and in the presence of a halide.

Abstract: A silica-containing composition suitable for supporting chromium to produce a catalyst capable of giving high melt flow olefin polymers for such applications as injection molding and the like requiring a narrow molecular weight distribution, is produced by treating a silica-containing material at an elevated temperature with either (1), CO, (2) a bromine or iodine component, or (3) an oxygen-containing sulfur component, more specifically a carbon, oxygen and sulfur-containing component. Thereafter, anhydrous chromium can be added, for instance, by means of a hydrocarbon solution of a soluble chromium compound, and the resulting composition activated in air to produce a catalyst. The bromine or iodine treated silica contains bound bromine of iodine if the treating agent is HBr, HI, an organic halide of Br or I or elemental Br or I used in conjunction with a reducing agent.