92 results about "Hydrocyanation" patented technology

A process for preparing a hydrocyanation catalyst comprising contacting a bidentate phosphorous-containing ligand with a molar excess of nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electropositive than nickel. Preferably, the nickel chloride is dried before use.

Hydrocyanation reactions employing multidentate phosphite ligands and multidentate phosphite ligands are disclosed. The ligands have phenyl containing substituents attached to the ortho position of the terminal phenol group and/or attached to the ortho position of the bridging group. Catalyst compositions havng such ligands achieve 97% or greater distribution in hydrocyanation.

Supported bis(phosphorus) ligands are disclosed for use in a variety of catalytic processes, including the isomerization, hydrogenation, hydroformylation, and hydrocyanation of unsaturated organic compounds. Catalysts are formed when the ligands are combined with a catalytically active metal, such as nickel.

Multidentate phosphite ligands are disclosed for use in reactions such as hydrocyanation and isomerization. The catalyst compositions made therefrom and the various catalytic processes which employ such multidentate phosphite ligands are also disclosed. In particular, the ligands have heteroatom-containing substituents on the carbon attached to the ortho position of the terminal phenol group.

The invention provides a hydrocyanation process for the production of adiponitrile and other dinitriles having six carbon atoms, the process comprising:

• • a) forming a reaction mixture in the presence of at least one Lewis acid, said reaction mixture comprising ethylenically unsaturated nitrites having five carbon atoms, hydrogen cyanide, and a catalyst precursor composition, by continuously feeding ethylenically unsaturated nitrites, hydrogen cyanide, and a catalyst precursor composition;
  • b) controlling X and Z, wherein X is the overall feed molar ratio of 2-pentenenitriles to all unsaturated nitriles and Z is the overall feed molar ratio of hydrogen cyanide to all unsaturated nitrites, by selecting a value for X in the range from about 0.001 to about 0.5, and a value for Z in the range from about 0.5/1 to about 0.99/1, such that the value of quotient Q, wherein

is in the range from about 0.2 to about 10, wherein 3PN is 3-pentenenitriles and 4PN is 4-pentenenitrile; and

• • c) withdrawing a reaction product mixture comprising adiponitrile;
  • wherein the ratio of the concentration of 2-pentenenitriles to the concentration of 3-pentenenitriles in the reaction mixture is from about 0.2/1 to about 10/1;
  • wherein the catalyst precursor composition comprises a zero-valent nickel and at least one bidentate phosphite ligand; and

wherein the bidentate phosphite ligand is selected from a member of the group represented by Formulas I and 11 as described herein.

The present invention relates to a process of hydrocyanation of ethylenically unsaturated organic compounds to compounds having at least one nitrile function, particularly the hydrocyanation of diolefins such as butadiene, or of substituted olefins such as alkene nitrites such as pentenenitriles; the subject hydrocyanation is carried out in the presence of a catalytic system comprising a metallic element and mono- and pluri-dentate organophosphorus ligands.

The invention provides a hydrocyanation process for the production of adiponitrile and other dinitriles having six carbon atoms, the process comprising:

• • a) forming a reaction mixture in the presence of at least one Lewis acid, said reaction mixture comprising ethylenically unsaturated nitriles having five carbon atoms, hydrogen cyanide, and a catalyst precursor composition, by continuously feeding ethylenically unsaturated nitriles, hydrogen cyanide, and a catalyst precursor composition;
  • b) controlling X and Z, wherein X is the overall feed molar ratio of 2-pentenenitriles to all unsaturated nitriles and Z is the overall feed molar ratio of hydrogen cyanide to all unsaturated nitriles, by selecting a value for X in the range from about 0.001 to about 0.5, and a value for Z in the range from about 0.5/1 to about 0.99/1, such that the value of quotient Q, wherein

is in the range from about 0.2 to about 10, wherein 3PN is 3-pentenenitriles and 4PN is 4-pentenenitrile; and

• • c) withdrawing a reaction product mixture comprising adiponitrile;
  • wherein the ratio of the concentration of 2-pentenenitriles to the concentration of 3-pentenenitriles in the reaction mixture is from about 0.2/1 to about 10/1;
  • wherein the catalyst precursor composition comprises a zero-valent nickel and at least one multidentate phosphorus-containing ligand;
  • wherein the multidentate phosphorus-containing ligand is selected from the group consisting of a phosphite, a phosphonite, a phosphinite, a phosphine, and a mixed phosphorus-containing ligand or a combination of such members; and
  • wherein the multidentate phosphorus-containing ligand gives acceptable results according to at least one protocol of the 2-Pentenenitrile Hydrocyanation Test Method.

A polymeric composition, a process for producing the composition, and a process for using the composition in, for example, hydrocyanation or isomerization are disclosed. The composition comprises repeat units derived from (1) a carbonyl compound, a monomer, and phosphorochloridite; (2) phosphorus trichloride, a polyhydric alcohol, and an aromatic diol; or (3) combinations of (1) and (2) in which the monomer can be a polyhydric alcohol, an amine, combinations thereof. The composition can further comprise a Group VIII metal and optionally a Lewis acid. The composition can be produced by (1) contacting a carbonyl compound with the monomer to produce an intermediate and contacting the intermediate with phosphorochloridite; (2) contacting phosphorus trichloride with a second polyhydric alcohol under a condition sufficient to produce a phosphorus-containing polymer and contacting the phosphorus-containing polymer with an aromatic diol; or (3) contacting an N,N-dialkyl dichlorophosphoramidite with a second polyhydric alcohol to produce a polymer phosphoramidite, contacting the polymer phosphoramidite with an acid such as HCl to produce the phospphorus-containing polymer, which is then contacted with an aromatic diol. The composition can be used as catalyst, for example, for converting an unsaturated organic compound to a nitrile and isomerizing a nitrile.

These disclosures relate to preparing nickel metal (Ni(0)) suited for use in catalyst systems, such as nickel complexes with phosphorus-containing ligands, useful to catalyze the hydrocyanation of ethylenically unsaturated compounds. The methods described herein can include use of steam during reduction of nickel.

The invention relates to a method for the extractive separation of nickel(0) complexes and phosphorus-containing ligands and/or free phosphorus-containin g ligands from a reaction discharge of a hydrocyanation of unsaturated mononitries to dinitriles, by means of a hydrocarbon, the hydrocarbon and the reaction discharge being separated into two phases at a temperature T (DEG C). The invention is characterised in that the content of nickel(0) complexes and phosphorus-containing ligands and/or free phosphorus-containing ligands in the reaction discharge of the hydrocyanation is at least y wt%, depending on the temperature T, and a maximum of 60 wt% independently of the temperature T. The numerical value of the minimum content y is indicated by the equation y = 0.5 T + 20, T being a dimensionless numerical value.

A novel nickel particulate form is provided that efficiently forms a zero-valent nickel complex with a phosphorus-containing ligands in an organic liquid to form a hydrocyanation catalyst. Particles in the nickel particulate form comprise nickel crystallites. For example, the nickel particulate form can have a BET Specific Surface Area of at least about 1 m²/gm; an average crystallite size less than about 20-25 nm, the nickel particulate form can have at least 10% of the crystallites in the nickel form can have can have a diameter (C10) of less than about 10 nm, and/or there are on average at least about 10¹⁵ surface crystallites per gram nickel. A ratio of BET SSA to C50 for the nickel particulate form can be at least about 0.1×10⁹ m/gm and preferably at least about 0.4×10⁹ m/gm. Methods of preparation and use are also provided.

The invention concerns a hydrocyanation method for ethylenically unsaturated organic compounds in particular to obtain nitriles, and more particularly hydrocyanation of substituted diolefins or of olefins for producing dinitriles, and/or the isomerization of nitriles obtained by hydrocyanation. The invention more particularly concerns hydrocyanation catalysed by a nickel-based compound. Thus the catalyst used in said production method is treated in output with hydrogen cyanide to recover and re-dissolve the nickel precipitated in the form of nickel hydroxide. The method enables to regenerate and prolong the life span of a catalyst charge. Moreover, it enables to reduce pollution in the installations using said method.

A process for preparing a hydrocyanation catalyst comprising contacting a bidentate phosphorous-containing ligand with nickel chloride in the presence of a nitrile solvent and a reducing metal which is more electropositive than nickel the nickel chloride being introduced as an aqueous solution and the water being removed concurrently with the reduction reaction by azeotropic distillation.

The invention discloses a novel tridentate phosphine ligand and application of the same to linear hydroformylation and similar reactions. The tridentate phosphine ligand is applied to efficient high-selectivity hydroformylation for the first time at present and applicable to efficient high-selectivity isomerized hydroformylation, hydrocarboxylation, hydrocyanation, isomerized formylation, hydroaminomethylation and the similar reactions. During the linear hydroformylation, selectivity of the tridentate phosphine ligand is obviously higher than that of a corresponding bidentate phosphine ligand. Besides, compared with a corresponding quadridentate phosphine ligand, the tridentate phosphine ligand is approximate in selectivity, easier to synthesize and higher in yield and displays higher TON (turnover number). The novel tridentate phosphine ligand selectively converts 1-hexylene and 1-octylene into n-heptaldehyde (used for synthesis of orange essence and rose essence) and n-nonaldehyde (flavoring matter) and is of great significance to hydroformylation-based industrial production.

A hydrocyanation reaction is used to react 1,3-butadiene with hydrogen cyanide in the presence of a catalyst to produce pentenenitriles, as well as reaction byproducts, such as methylglutaronitrile (MGN). The effluent from the hydrocyanation reaction is distilled in a particular manner to produce a pentenenitrile-enriched stream, a catalyst-enriched stream and a stream enriched in methylglutaronitrile (MGN). At least a portion of the catalyst enriched stream may be recycled to the hydrocyanation reaction. 3-pentenenitrile may be recovered and, optionally, further reacted with HCN to make adiponitrile (ADN).

The invention provides a preparation method of 3-pentenenitrile and a preparation method of adiponitrile. The preparation method of 3-pentenenitrile comprises the following steps: 1, performing the hydrocyanation reaction on raw material mixed solution of butadiene and hydrocyanic acid under the action of a catalyst so as to obtain a first mixture containing the 3-pentenenitrile; and 2, carrying out separation on the first mixture to obtain the 3-pentenenitrile, wherein the catalyst is a coordination complex consisting of monodentate phosphine, bidentate phosphine and zero-valent nickel. By adopting the method, the 3-pentenenitrile can be effectively, efficiently and economically prepared by using the butadiene and the hydrocyanic acid as the raw materials; the integral process is safe and reliable; the flow is simple; and moreover, production cost and equipment investment can be obviously reduced.

The present invention is directed to compositions of specific carboxylic acid, fatty acid or oil derivatives containing nitrile groups and methods of their preparation. The preparation involves a hydrocyanation reaction. A method of hydrgenating the nitrile containing carboxylic acid acids obtained by above hydrocyanation to produce amine containing carbixylic acids is also disclosed in this invention.

An process for preparing 3-pentenenitrile by hydrocyanating 1,3-butadiene, in which the process yield with regard to recycled 1,3-butadiene is maximized.

The invention provides a method and a device for preparing adiponitrile. The preparation method comprises the steps of a first hydrocyanation reaction, an isomerization reaction and a second hydrocyanation reaction. According to the method, the contents of specific components in a system is detected by adopting an online Raman spectrum, and reaction conditions are regulated and controlled based ona detection result, so accurate control on materials in each step in the reaction system is realized. The method provided by the invention can reduce the consumption of butadiene, and lower subsequent butadiene recovery energy consumption and equipment investment in the reaction; the content of hydrocyanic acid is monitored in real time, so hydrocyanic acid residues are reduced to a relatively low level, and the operation safety and the stability of a catalyst in the reaction process are improved; and the loss of the catalyst is reduced.