Abstract: A solvent is at least partially separated from a catalyst. The catalyst comprises nickel and a bidentate phosphorus-containing ligand. The method for separation involves distilling a catalyst solution. The ratio of 2-pentenenitrile to 3-pentenenitrile in distillation column bottoms is controlled to reduce the amount of 3-pentenenitrile which is isomerized to form 2-methyl-3-butenenitrile. Isomerization of 3-pentenenitrile to 2-methyl-3-butenenitrile and subsequent isomerization of 2-methyl-3-butenenitrile to 2-methyl-2-butenenitrile, and/or hydrocyanation of 2-methyl-3-butenenitrile to methylglutaronitrile represents a loss in adiponitrile yield in a process for making adiponitrile.

Abstract: A process of hydrolyzing a monodentate, bidentate or tridentate phosphorus-based phosphite ester ligand or ligand blend for a transition metal catalyst comprising contacting the ligand or ligand blend with a hydrolysis catalyst of the formula (R11X11)nP(OH)3-n where n is 0, 1 or 2 wherein the ligand or ligand blend comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12)(R13—X13)P—X14—Y—X24—P(X22—R22)(X23—R23), (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12)(R13—X13)P—X14—Y—X32—P(X34—R34)—(X33—Y2—K24—P(X23—R23)—(X22—R22) or (iii) a monodentate phosphite ligand of formula (IV) P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene, followed by separation of the ligand hydrolysis products.

Abstract: The invention provides methods useful in the industrial scale process for hydrocyanation of butadiene to adiponitrile for recycle of unwanted byproduct 2-methyl-3-butenenitrile (2M3BN) by conversion to process intermediate pentenenitrile. The invention provides a process for generating catalysts useful for carrying out the hydrocyanation of butadiene to adiponitrile, the process comprising contacting the 2M3BN and a solution of a nickel-ligand catalyst in cis-2-pentenenitrile (cis-2PN), trans-2-pentenenitrile (trans-2PN), or a mixture thereof. The improved methods of the invention can provide improved catalyst solubility for bidentate ligands without a requirement for a Lewis acid catalyst promoter such as zinc chloride to be present.

Abstract: A process of stabilizing a bidentate or tridentate phosphorus-based phosphite ester ligand or mixture thereof in a hydrocyanation reaction milieu comprising water, wherein the ligand or ligand mixture comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12) (R13—X13) P—X14—Y—X24—P(X22—R22) (X23—R23) or (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12) (R13—X13) P—X14—Y—X32—P(X34—R34)—(X33—Y2—R24—P(X23—R23)—(X22—R22) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene group, comprising admixing the bidentate and/or tridentate with a stabilizing amount of one or more monodentate phosphite ligand of formula P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond, wherein the monodentate ligand has a rate of hydrolysis greater than the rate of hydrolysis of the bidentate or tridentate ligand in the presence of water in a hydrocyanation reaction milieu, and thereby preserve concentrations and proportions of the bidentate and/or trid

Abstract: In the hydrocyanation reaction of butadiene proceeding through pentenenitriles to adiponitrile, catalysis by complexes of zerovalent nickel with bidentate phosphorus-based ligands of the NiL2A type wherein L2 is a bidentate ligand and A is an unsaturated compound, can be rate-limited by the solubility of the catalytic complex. The present invention concerns solvent compositions for the nickel-ligand complex comprising mixtures of unsaturated nitriles that provide for increased metal solubility, particularly in the absence of a Lewis acid promoter, resulting in higher hydrocyanation reaction rates in an industrial-scale process for production of important nylon manufacturing intermediates. The mixed nitrile solvent compositions can include mixtures of pentenenitriles and/or methylbutenenitriles. The mixtures of mixed unsaturated nitriles can be, at least in part, from recycle streams from the hydrocyanation reaction for which the nickel-bidentate ligand complexes are used as catalysts.

Abstract: Disclosed herein are methods for recovering diphosphonite-containing compounds from mixtures comprising organic mononitriles and organic dinitriles, using multistage countercurrent liquid-liquid extraction. Recovery is enhanced with one or more method steps. In a first step, a portion of the heavy phase from the settling section of the first stage is recycled to the settling section of the first stage. In a second step, a portion of the light phase from the settling section of the first stage is recycled to the mixing section of the first stage. In a third step, the first stage takes place in a mixer-settler, a Lewis base is introduced into the settling section of the first stage, and a complex of Lewis acid and Lewis base is formed in this settling section. In a fourth step, a polyamine is added to the first stage.

Abstract: Pentenenitrile oligomers formed in a process for isomerizing cis-2-pentenenitrile to 3-pentenenitrile are minimized in the presence of an aluminum oxide catalyst. The process comprises providing an aluminum oxide catalyst having an alkali metal and/or alkaline earth metal and/or iron content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide and/or iron oxide, respectively of less than 5000 ppm by weight.

Abstract: Disclosed is a process for isomerizing cis-2-pentenenitrile to 3-pentenenitrile in the presence of a non-aluminum metal oxide catalyst, wherein: (a) the metal in the catalyst has an oxidation state in the range from +1 to +4; (b) the metal has a cation radius in the range from 0.35 to 1.0 ?; (c) the metal of the catalyst has a polarizing power, C/r, is in the range from 2 to >8, wherein C is the charge of the metal and r is the ionic radius in ?; (d) the bond network of the catalyst has a % ionicity of >20; (e) the metal oxide has an acidity strength in the range from strong to very weak; and (f) the metal oxide has a basicity (nucleophilicity) strength of weak to strong.

Abstract: Disclosed herein are methods for recovering diphosphite-containing compounds from mixtures comprising organic mononitriles and organic dinitriles, using liquid-liquid extraction. Also disclosed are treatments to enhance extractability of the diphosphite-containing compounds.

Abstract: A solvent is at least partially separated from a catalyst. The catalyst comprises nickel and a bidentate phosphorus-containing ligand. The method for separation involves distilling a catalyst solution. The ratio of 2-pentenenitrile to 3-pentenenitrile in distillation column bottoms is controlled to reduce the amount of 3-pentenenitrile which is isomerized to form 2-methyl-3-butenenitrile. Isomerization of 3-pentenenitrile to 2-methyl-3-butenenitrile and subsequent isomerization of 2-methyl-3-butenenitrile to 2-methyl-2-butenenitrile, and/or hydrocyanation of 2-methyl-3-butenenitrile to methylglutaronitrile represents a loss in adiponitrile yield in a process for making adiponitrile.

Abstract: Disclosed herein are methods for recovering diphosphonite-containing compounds from mixtures comprising organic mononitriles and organic dinitriles, using liquid-liquid extraction. Also disclosed are treatments to enhance extractability of the diphosphonite-containing compounds.

Abstract: Claimed is a process for producing a phosphorus-containing ligand, preferably a diphosphite ligand structure (DLS) such as structure I. The method includes contacting a phosphorochloridite (structure II) with a compound having the structure X—OH (which can be a bisaryl compound), and a tertiary organic amine to provide structure I? and as preferred embodiment structure I.

Abstract: Pentenenitrile oligomers formed in a process for isomerizing cis-2-pentenenitrile to 3-pentenenitrile are minimized in the presence of an aluminium oxide catalyst. The process comprises providing an aluminium oxide catalyst having an alkali metal and/or alkaline earth metal and/or iron content, measured in the form of alkali metal oxide and/or alkaline earth metal oxide and/or iron oxide, respectively of less than 5000 ppm by weight.

Abstract: In the hydrocyanation reaction of butadiene proceeding through pentenenitriles to adiponitrile, catalysis by complexes of zerovalent nickel with bidentate phosphorus-based ligands of the NiL2A type wherein L2 is a bidentate ligand and A is an unsaturated compound, can be rate-limited by the solubility of the catalytic complex. The present invention concerns solvent compositions for the nickel-ligand complex comprising mixtures of unsaturated nitriles that provide for increased metal solubility, particularly in the absence of a Lewis acid promoter, resulting in higher hydrocyanation reaction rates in an industrial-scale process for production of important nylon manufacturing intermediates. The mixed nitrile solvent compositions can include mixtures of pentenenitriles and/or methylbutenenitriles. The mixtures of mixed unsaturated nitriles can be, at least in part, from recycle streams from the hydrocyanation reaction for which the nickel-bidentate ligand complexes are used as catalysts.

Abstract: The invention provides methods useful in the industrial scale process for hydrocyanation of butadiene to adiponitrile for recycle of unwanted byproduct 2-methyl-3-butenenitrile (2M3BN) by conversion to process intermediate pentenenitrile. The invention provides a process for generating catalysts useful for carrying out the hydrocyanation of butadiene to adiponitrile, the process comprising contacting the 2M3BN and a solution of a nickel-ligand catalyst in cis-2-pentenenitrile (cis-2PN), trans-2-pentenenitrile (trans-2PN), or a mixture thereof. The improved methods of the invention can provide improved catalyst solubility for bidentate ligands without a requirement for a Lewis acid catalyst promoter such as zinc chloride to be present.

Abstract: Disclosed is a process for isomerizing cis-2-pentenenitrile to 3-pentenenitrile in the presence of a non-aluminium metal oxide catalyst, wherein: (a) the metal in the catalyst has an oxidation state in the range from +1 to +4; (b) the metal has a cation radius in the range from 0.35 to 1.0 ?; (c) the metal of the catalyst has a polarising power, C/r, is in the range from 2 to >8, wherein C is the charge of the metal and r is the ionic radius in ?; (d) the bond network of the catalyst has a % ionicity of >20; (e) the metal oxide has an acidity strength in the range from strong to very weak; and (f) the metal oxide has a basicity (nucleophilicity) strength of weak to strong.

Abstract: A method of stabilizing a phosphorus-based ligand or a ligand blend comprising a plurality of phosphorus-based ligands, wherein the ligand or ligand blend comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12) (R13—X13)P—X14—Y—X24—P (X22—R22) (X23—R23) (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12) (R13—X13)P—X14—Y—X32—P(X34—R34)—(X33—Y2—R24—P(X23—R23)—(X22—R22) or (iii) a monodentate phosphite ligand of formula (IV) P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond and each Y is optionally substituted C6-C20 arylene; the process comprising forming a mixture of the ligand or the ligand blend with a liquid which partially or fully solubilizes the ligand or ligand blend, the liquid consisting essentially of one or more of: (a) a solvent system that does not contain peroxidizable species; or, (b) a solvent system that is substantially free of a dissolved metal.

Abstract: A process of stabilizing a bidentate or tridentate phosphorus-based phosphite ester ligand or mixture thereof in a hydrocyanation reaction milieu comprising water, wherein the ligand or ligand mixture comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12) (R13—X13) P—X14—Y—X24—P(X22—R22) (X23—R23) or (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12) (R13—X13) P—X14—Y—X32—P(X34—R34)—(X33—Y2—R24—P(X23—R23)—(X22—R22) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene group, comprising admixing the bidentate and/or tridentate with a stabilizing amount of one or more monodentate phosphite ligand of formula P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond, wherein the monodentate ligand has a rate of hydrolysis greater than the rate of hydrolysis of the bidentate or tridentate ligand in the presence of water in a hydrocyanation reaction milieu, and thereby preserve concentrations and proportions of the bidentate and/or trid

Abstract: A process of hydrolyzing a monodentate, bidentate or tridentate phosphorus-based phosphite ester ligand or ligand blend for a transition metal catalyst comprising contacting the ligand or ligand blend with a hydrolysis catalyst of the formula (R11X11)nP(OH)3-n where n is 0, 1 or 2 wherein the ligand or ligand blend comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12)(R13—X13)P—X14—Y—X24—P(X22—R22)(X23—R23), (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12)(R13—X13)P—X14—Y—X32—P(X34—R34)—(X33—Y2—K24—P(X23—R23)—(X22—R22) or (iii) a monodentate phosphite ligand of formula (IV) P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene, followed by separation of the ligand hydrolysis products.

Abstract: The present invention relates to a process for hydrocyanating 3-pentenenitrile. The process can include feeding 3-pentenenitrile and HCN to a hydrocyanation reaction zone that includes a Lewis acid promoter, nickel, and a phosphorus-containing ligand. In various embodiments, the process can also include controlling water concentration within the hydrocyanation reaction zone sufficient to maintain a high activity of the ligand catalyst complex while recycling at least a portion of the ligand catalyst complex.