CN106975519B

CN106975519B - Method for preparing a catalyst system for hydrocyanation and isomerization

Info

Publication number: CN106975519B
Application number: CN201610842855.8A
Authority: CN
Inventors: 倪呈宝; 约翰·J·奥斯特麦尔
Original assignee: Invista Textiles UK Ltd
Current assignee: Invista Textiles UK Ltd
Priority date: 2015-09-23
Filing date: 2016-09-22
Publication date: 2021-09-07
Anticipated expiration: 2036-09-22
Also published as: CN106975519A

Abstract

A process for preparing a catalyst system for hydrocyanation of butadiene or one or more monoolefinic mononitriles which comprises contacting metallic nickel, at least one bidentate organophosphorus ligand and at least one compound of formula P (X)_aR_a)(X_bR_b)(X_cR_c) Reacting the compound in the presence of a liquid diluent in a single step; wherein X_a、X_bAnd X_cEach independently is oxygen or a single bond; and wherein R_a、R_bAnd R_cEach independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

Description

Method for preparing a catalyst system for hydrocyanation and isomerization

Technical Field

The invention relates to a method for producing a catalyst system for the hydrocyanation of butadiene or pentenenitriles. More precisely, the invention also relates to a process for the hydrocyanation of butadiene or pentenenitriles using the catalyst system prepared in a single-stage reaction and for the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile.

Background

Hydrocyanation catalyst systems that are particularly useful for the hydrocyanation of butadiene or pentenenitriles are known in the art. In particular, systems suitable for the hydrocyanation of 1, 3-butadiene to form pentenenitriles and the subsequent hydrocyanation of pentenenitriles to form adiponitrile are known in the commercially important field of nylon synthesis.

Such hydrocyanation reactions are carried out in the presence of zero-valent nickel catalyst complexes having monodentate or bidentate organophosphorus ligands, such as phosphites. There are various known methods for preparing zero-valent nickel complexes with monodentate organophosphorus ligands, including those described in US 3,903,120 and US 4,416,825. In U.S. Pat. No. 3,903,120, Ni [ P (OAr)₃]₄The complex of type is prepared by reacting elemental nickel with monodentate ligand P (OAr)₃At a temperature in the range of 0 ℃ to 150 ℃ in the presence of a halogen containing derivative of a monodentate ligand as a catalyst. US 4,416,825 describes a continuous process for preparing hydrocyanation catalysts comprising zero-valent nickel complexes with monodentate organophosphorus ligands by controlling the reaction temperature relative to the amount of monodentate ligand and conducting the reaction in the presence of chloride ions and an organic nitrile, such as adiponitrile.

There are several organophosphorus ligands available for making compositions having monodentate and bidentate (specificallyPhosphite) to produce a nickel catalyst complex. One method is nickel bis (1, 5-cyclooctadiene) [ Ni (COD) ]₂]Reaction with an organophosphite ligand. However, this method is based on Ni (COD)₂Are inefficient and uneconomical and therefore cannot be produced on a commercial scale. Another method is the use of anhydrous nickel chloride and zinc metal in the presence of organic phosphite ligands in situ reduction. This procedure was effective for both monodentate and bidentate organophosphite ligands, but resulted in the formation of one mole of zinc chloride per mole of nickel complex formed. The process is also difficult to perform in a commercial process because it requires precise metering of the two solids into the reactor and anhydrous nickel chloride is not readily available on a commercial scale.

Another way to prepare the organic phosphite ligand nickel catalyst complexes is to use catalytic amount of Ar₂PCl reacts finely divided nickel powder directly with an organophosphite ligand, where Ar is an aryloxy group, such as cresol, as disclosed in US 3,847,959. This method is effective for monodentate organophosphite ligands using commercially available nickel powders, but it cannot be used to prepare bidentate zero-valent nickel organophosphite complexes due to lack of reactivity.

US 8,815,186 discloses the direct preparation of bidentate zero valent nickel organophosphite catalyst complexes from nickel metal powders. However, nickel metal powders must be prepared by the specific methods disclosed therein. One disadvantage of this method is that it uses highly reactive pyrophoric nickel powders that must be handled in the absence of oxygen. In addition, it is necessary to use, for example, ZnCl₂If the catalyst is subsequently used for the hydrocyanation of butadiene or for the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile, traces of said acid are harmful.

Another method for preparing a bidentate zero-valent nickel organophosphite catalyst complex is the subject of EP 1414567, which describes a two-step process for preparing mixed bidentate and monodentate zero-valent nickel organophosphite catalyst complexes. The method comprises at least two steps. First, zero-valent nickel and P (OR)₃(wherein "R" is an organic group) to form a first system. Followed byIn the second step, the first system and two tooth organic phosphite ligand reaction to produce including single tooth material (i.e. containing and separate P (OR))₃Complexed nickel catalysts) and bidentate species (i.e., containing only bidentate organophosphite ligand or P (OR)₃And a mixture of bidentate organophosphite ligands) of nickel. This two-step process has the disadvantage of not being commercially viable, since it is not possible to recover the catalyst complex in a single standard extraction procedure for further use. Recovery is critical for reuse of the catalyst in a continuous process and economically necessary for reuse in a commercial process. Furthermore, it would be desirable to isolate the monodentate species (i.e., comprising P (OR) alone) prior to repeating the catalyst synthesis step₃Complexed nickel catalysts) and bidentate species (i.e., containing only bidentate organophosphite ligand or P (OR)₃And a mixture of bidentate organophosphite ligands) to repeat the two-step process, which would be extremely difficult, if not impossible. EP 1414567 also discloses a process in which Ni (COD)₂The m/p-tolyl phosphite and the bisdentate organophosphite ligand were reacted in a single step. Single step procedure by Ni (COD)₂The disadvantages described above, which are too expensive for commercial scale production, are plagued.

It is an object of the present invention to address one or more of these problems.

As used herein, the term "monodentate" as used in reference to organophosphorus ligands means a ligand having one phosphorus atom that can associate with a single nickel atom to form a nickel complex.

As used herein, the term "bidentate" used in reference to organophosphorus ligands means a ligand having two phosphorus atoms associated with a single nickel atom to form a nickel complex.

As used herein, the term "phosphite" means an organophosphorus compound containing a trivalent phosphorus atom bonded to three oxygen atoms.

As used herein, the term "phosphonite diester" means an organophosphorus compound comprising a trivalent phosphorus atom bonded to two oxygen atoms and one carbon atom.

As used herein, the term "phosphonite diester" means an organophosphorus compound comprising a trivalent phosphorus atom bonded to one oxygen atom and two carbon atoms.

As used herein, the term "phosphine" means an organophosphorus compound containing a trivalent phosphorus atom bonded to three carbon atoms.

As used herein, the term "tolyl" means a phenyl group substituted with a methyl group at the ortho, meta, or para positions.

As used herein, the term "comprising" encompasses "includes" as well as "consisting of and" consisting essentially of, e.g., a composition "comprising" X may consist of X alone or may include additional components, e.g., X + Y.

Disclosure of Invention

According to the present invention, there is provided a process for preparing a catalyst system for hydrocyanating butadiene or one or more monoolefinic mononitriles, the process comprising contacting metallic nickel, at least one bidentate organophosphorus ligand and at least one compound of formula P (X)_aR_a)(X_bR_b)(X_cR_c) Reacting the compound in the presence of a liquid diluent in a single step; wherein

X_a、X_bAnd X_cEach independently is oxygen or a single bond; and is

Wherein R is_a、R_bAnd R_cEach independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

According to another aspect of the present invention, there is provided a process for hydrocyanating butadiene, comprising:

i) by reacting metallic nickel, at least one bidentate organophosphorus ligand and at least one compound of the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is reacted in the presence of a liquid diluent in a single step to prepare a catalyst system, wherein X_a、X_bAnd X_cEach independently is oxygen or a single bond, and wherein R_a、R_bAnd R_cEach independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms; and is

ii) reacting butadiene with HCN in the presence of the catalyst system prepared in step i) to form a mixture comprising 3-pentenenitrile and 2-methyl-3-butenenitrile.

According to another aspect of the invention, there is provided a process for hydrocyanating one or more monoolefinic mononitriles, the process comprising:

ii) reacting one or more monoolefinic mononitriles with HCN in the presence of the catalyst system prepared in step i) to form a mixture comprising one or more dinitriles.

According to another aspect of the present invention, there is provided a process for isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile, the process comprising:

ii) isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile using the catalyst system prepared in step i).

Advantageously, a single step reaction can be carried out using commercially available nickel powders without the selectivity reduction and rearrangement shown in hydrocyanation reactions known in the art. For example, as shown in the examples, selectivities of 90% and higher are achieved in the hydrocyanation of pentenenitriles. The combination of high selectivity and the ability to use low cost readily available commercial nickel sources provides significant benefits and advantages for commercial operations. A particular advantage of the process is that it can be readily adapted to commercial operations since the nickel catalyst complex material can be recovered by standard extraction operations and simply reused. Thus, the advantages of low cost starting materials and high selectivity can be readily achieved on a commercial scale.

Advantageously, the method of preparing the catalyst system does not require the use of Lewis acids (Lewis acids), such as zinc chloride. The presence of lewis acids in the hydrocyanation of butadiene or the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile promotes the deleterious formation of Methylglutaronitrile (MGN). The catalyst system prepared by the process according to the invention can therefore be used directly in the hydrocyanation of butadiene or in the isomerization of 2-methyl-3-butenenitrile to 3-pentenenitrile. The disclosed catalyst systems and methods may also be used to make aldehydes from olefins by adding formyl groups (CHO) and hydrogen to carbon-carbon double bonds (hydroformylation).

Drawings

FIG. 1 illustrates a continuous process for hydrocyanating cis-and trans-3-pentenenitrile and 4-pentenenitrile to produce adiponitrile.

Detailed Description

The process of the invention for preparing the catalyst system entails reacting metallic nickel, a bidentate organophosphorus ligand and a compound of the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compounds are reacted in a single step in the presence of a liquid diluent. In this context, "single step" means metallic nickel, bidentate organophosphorus ligand and the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compounds are reacted simultaneously in the presence of a liquid diluent in a single vessel. In other words, there is no distinct step of adding reactants and no individualized stage in the progress of the reaction forming the catalyst system.

The monoolefinic mononitriles are preferably selected from pentenenitriles. Preferred pentenenitriles are selected from cis-and trans-3-pentenenitrile and 4-pentenenitrile. Prior to further use of the catalyst system (e.g. in step (ii) of the process of the present invention for hydrocyanating butadiene, for hydrocyanating monoolefinic mononitrile, and for isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile), the catalyst system is preferably filtered to remove metallic nickel, and nickel is not in the form of a complex. Next, the amount of reagent relative to nickel is calculated based on the amount of nickel remaining in the filtered catalyst system.

The process of the invention uses metallic nickel, preferably in the form of a powder. The metallic nickel is preferably commercially available metallic nickel, such as INCO 123 manufactured by Vale Canada Limited. The ability to use commercially available metallic nickel means that the process of the invention has the advantage of being relatively inexpensive and simple to perform. Metallic nickel may also be a highly reactive nickel powder prepared starting from alkaline nickel carbonate. The preparation of highly reactive nickel powders is described in US 2011/0196168 a1, US 8,815,186B 2, US 8,969,606B 1, and US 9,0240, 49B 2, which are incorporated herein by reference in their entirety.

For example, highly reactive nickel powder may be prepared from TIB Chemicals a.g. alkaline nickel carbonate containing about 0.5% sulfur. The nickel carbonate was calcined in flowing nitrogen followed by reduction in flowing hydrogen. The resulting nickel powder is pyrophoric and must not be allowed to contact an oxygen-containing gas (e.g., air). Alternatively, a nickel source (e.g., nickel sulfate) is mixed with an aqueous precipitant solution of sodium carbonate to produce a nickel carbonate containing about 0.5% or less sulfur, which is then calcined in flowing nitrogen gas, followed by reduction in flowing hydrogen gas. Alternatively, sulfur may be added to the calcined nickel oxide or nickel carbonate to produce a highly reactive nickel powder containing about 0.5% or less of sulfur.

The process of the invention for preparing the catalyst system is carried out in the presence of a liquid diluent. The liquid diluent may be an olefinically unsaturated nitrile, preferably a pentenenitrile, such as cis-2-pentenenitrile, trans-2-pentenenitrile, cis-3-pentenenitrile, trans-3-pentenenitrile, 4-pentenenitrile, 2-methyl-3-butenenitrile, trans-2-methyl-2-butenenitrile, cis-2-methyl-2-butenenitrile. The liquid diluent may also be a dinitrile, such as adiponitrile or methylglutaronitrile. The liquid diluent may also contain a non-polar solvent, for example an aliphatic hydrocarbon such as cyclohexane or an aromatic hydrocarbon such as benzene, toluene, o-xylene, m-xylene, p-xylene. The liquid diluent may comprise a mixture of any of the above mentioned compounds.

In the process for preparing the catalyst system, preferably at least about 4 molar equivalents, preferably at least about 5 molar equivalents, preferably not more than about 30 molar equivalents, preferably not more than about 15 molar equivalents, preferably not more than about 10 molar equivalents of P (X) relative to metallic nickel are used_aR_a)(X_bR_b)(X_cR_c)。

Preferably, at least about 1 molar equivalent, preferably at least about 2 molar equivalents, preferably at least about 3 molar equivalents, preferably not more than about 13 molar equivalents, preferably not more than about 8 molar equivalents, preferably not more than about 6 molar equivalents of the bidentate organophosphorus ligand is used relative to the metallic nickel.

Suitably, the process for preparing the catalyst system is carried out at a temperature of at least about 50 ℃, preferably at least about 70 ℃. Suitably, the temperature does not exceed about 130 ℃, preferably does not exceed about 110 ℃.

Preferably, in the process of the present invention for hydrocyanation of butadiene, the reaction of butadiene with HCN is carried out at a temperature of at least about 50 ℃, preferably at least about 70 ℃. Suitably, the temperature does not exceed about 180 ℃, preferably does not exceed about 160 ℃. Suitably, at least about 500 molar equivalents, preferably at least about 750 molar equivalents, and preferably not more than about 7000 molar equivalents, preferably not more than about 3500 molar equivalents of butadiene Ni (0) are used. Preferably, HCN is used in an amount of at least about 0.5 molar equivalents, preferably at least about 0.85 molar equivalents, preferably no more than about 0.95 molar equivalents, relative to butadiene. Preferably, about 0.90 molar equivalents of HCN relative to butadiene are used.

The hydrocyanation and isomerization processes as described herein are suitably carried out in a liquid diluent conventional in the art.

In the process of the present invention for hydrocyanating monoolefinic mononitriles, the monoolefinic mononitriles used in the step of reacting the monoolefinic mononitrile with HCN in the presence of the catalyst system prepared by the process of the present invention may suitably be 3-butenenitrile for the preparation of glutaronitrile, and/or pentenenitriles for the preparation of adiponitrile, such as cis-and trans-3-pentenenitrile and 4-pentenenitrile. The liquid diluent may advantageously be the same monoolefinic mononitrile that is reacted with HCN. Suitably, the reaction of the monoolefinic mononitrile with HCN is carried out at a temperature of at least about 20 deg.C, preferably at least about 40 deg.C. Suitably, the temperature does not exceed about 100 ℃, preferably does not exceed about 80 ℃. Suitably, at least about 500 molar equivalents, preferably at least about 750 molar equivalents, preferably not more than about 7000 molar equivalents, preferably not more than about 3500 molar equivalents of monoolefinic mononitrile relative to Ni (0) are used in the reaction of the monoolefinic mononitrile with HCN. HCN is preferably used in an amount of at least about 0.5 molar equivalents, preferably at least about 0.85 molar equivalents, preferably not more than about 0.95 molar equivalents, relative to the monoolefinic mononitrile. Preferably, about 0.90 molar equivalents of HCN relative to the monoolefinic mononitrile is used.

In the process of the present invention for hydrocyanating monoolefinic mononitriles, the step of reacting the monoolefinic mononitrile with HCN in the presence of the catalyst system of the present invention is advantageously carried out in the presence of at least one Lewis acid. Examples of suitable lewis acids are inorganic or organometallic compounds in which the cation is selected from the group comprising: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, lanthanum, europium, ytterbium, tantalum, samarium, and tin. Preferably, the at least one lewis acid is selected from the group consisting of: zinc chloride, ferrous chloride or a combination of zinc chloride and ferrous chloride. The at least one lewis acid is preferably anhydrous. The molar ratio of Lewis acid to Ni (0) used in the process is preferably at least about 0.9: 1, preferably no more than 1.1: 1.

The process of the present invention for isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile in the presence of the catalyst system of the present invention is suitably carried out at a temperature of at least about 80 deg.C, preferably at least about 100 deg.C. Preferably, the temperature is no more than about 160 ℃, preferably no more than about 140 ℃. Preferably, at least about 500 molar equivalents, preferably at least about 750 molar equivalents, preferably not more than about 7000 molar equivalents, preferably not more than about 3500 molar equivalents of 2-methyl-3-butenenitrile are used relative to Ni (0).

The process of the invention may be carried out batchwise, but preferably it is carried out in a semicontinuous or continuous manner. In the case of a continuous or semi-continuous process, the inventive process for hydrocyanation and isomerization operates under a continuous circulating catalyst loop in which the nickel catalyst material, along with ligand material, is extracted from the hydrocyanation or isomerization reaction and recycled to the step of preparing the catalyst system.

The extraction is carried out using procedures known in the art. One such procedure is disclosed in US 3,773,809, which is incorporated herein by reference in its entirety. Suitable solvents include aliphatic hydrocarbons having a boiling point in the range of about 30 ℃ to about 135 ℃. Typical straight chain aliphatic hydrocarbon solvents include n-pentane, n-hexane, n-heptane and n-octane and the corresponding branched chain hydrocarbons having boiling points in the range of about 30 ℃ to about 135 ℃. Typical cyclic hydrocarbon solvents include cyclopentane, cyclohexane, and cycloheptane, as well as the corresponding alkyl-substituted cyclic hydrocarbons having boiling points in the range of about 30 ℃ to about 135 ℃. Mixtures of linear and/or cyclic hydrocarbon solvents may be used. Preferred solvents include cyclohexane and methylcyclohexane or mixtures thereof. The extraction is suitably carried out at a temperature of at least about 10 c, preferably at least about 20 c. Suitably no more than about 100 c, preferably no more than about 70 c, preferably no more than about 60 c. Preferably, the composition of the product stream in the extraction is controlled such that the ratio of dinitriles to mononitriles is less than about 0.35, preferably about 0.3. Preferred ratios can be achieved by controlling the degree of conversion of mononitrile to dinitrile, if such reaction occurs in a particular process, or by manually introducing an amount of dinitrile until the desired ratio of dinitrile to mononitrile is achieved.

The bidentate organic phosphorus used in the process of the present invention may be a bidentate phosphite, a bidentate phosphonite diester or a bidentate phosphine.

When the bidentate organophosphorous ligand is a bidentate phosphite, the bidentate phosphite may be one or more selected from the group consisting of formula Ia, formula Ib, formula Ic, formula VII, formula VIII, formula IX or formula X:

wherein in formulae Ia, Ib and Ic:

O-Z-O and O-Z¹-O is each independently selected from the group consisting of structural formulae II, III, IV, V, and VI:

wherein in formulas II and III:

R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸and R⁹Independently selected from H, C₁To C₁₂Alkyl and C₁To C₁₂Alkoxy groups; x is O, S or CH (R)¹⁰)；

R¹⁰Is H or C₁To C₁₂An alkyl group;

wherein in formulas IV and V:

R²⁰and R³⁰Independently selected from H, C₁To C₁₂Alkyl and C₁To C₁₂Alkoxy and CO₂R¹³A group of compounds;

R¹³is C₁To C₁₂Alkyl or C₆To C₁₀Aryl, unsubstituted or substituted by C₁To C₄Alkyl substitution;

w is O, S or CH (R)¹⁴)；

R¹⁴Is H or C₁To C₁₂An alkyl group;

wherein in formula VI:

R¹⁵selected from the group consisting of H, C₁To C₁₂Alkyl and C₁To C₁₂Alkoxy and CO₂R¹⁶A group of compounds; r¹⁶Is C₁To C₁₂Alkyl or C₆To C₁₀Aryl, unsubstituted or substituted by C₁To C₄Alkyl substitution;

wherein in formulae Ia, Ib and Ic:

R¹is unsubstituted or substituted by one or more C₁To C₁₂Alkyl radical, C₁To C₁₂Phenyl substituted by alkoxy or by radicals of the formulae A and B, or- (CH)₂)_nOY²Wherein n is 1 to 4 and Y²Independently selected from cycloalkyl, aryl or C₁To C₁₈A group of alkyl groups;

or R¹Is unsubstituted or substituted by one or more C₁To C₁₂Alkyl or C₁To C₁₂Alkoxy-substituted naphthyl, or- (CH)₂)_nOY²Wherein n is 1 to 4 and Y²Independently selected from cycloalkyl, aryl or C₁To C₁₈A group of alkyl groups; or 5, 6, 7, 8-tetrahydro-1-naphthyl; or a group of the formulae A and B

Wherein in the formulae A and B,

Y¹independently selected from H, cycloalkyl or aryl or C₁To C₁₈A group of alkyl groups;

Y³independently selected from O or CH₂The group of (a) is selected,

bidentate phosphites of the formulae VII and VIII:

wherein the content of the first and second substances,

R⁴¹and R⁴⁵Independently selected from C₁To C₅A group consisting of hydrocarbon radicals, and R⁴²、R⁴³、R⁴⁴、R⁴⁶、R⁴⁷、R⁴⁸And R⁴⁹Each of which is independently selected from the group consisting of H and C₁To C₄A group consisting of hydrocarbyl groups;

or therein

R⁴¹Is methyl, ethyl, isopropyl or cyclopentyl;

R⁴²is H or methyl;

R⁴³is H or C₁To C₄A hydrocarbyl group;

R⁴⁴is H or methyl;

R⁴⁵is methyl, ethyl or isopropyl; and is

R⁴⁶、R⁴⁷、R⁴⁸And R⁴⁹Independently selected from the group consisting of H and C₁To C₄A group consisting of hydrocarbyl groups;

or therein

R⁴¹、R⁴⁴And R⁴⁵Is methyl;

R⁴²、R⁴⁶、R⁴⁷、R⁴⁸and R⁴⁹Is H; and is

R⁴³Is C₁To C₄A hydrocarbyl group;

or therein

R⁴¹Is isopropyl;

R⁴²is H;

R⁴³is C₁To C₄A hydrocarbyl group;

R⁴⁴is H or methyl;

R⁴⁵is methyl or ethyl;

R⁴⁶、R⁴⁸and R⁴⁹Is H or methyl; and is

R⁴⁷Is H, methyl or tert-butyl;

or therein

R⁴¹Is isopropyl or cyclopentyl;

R⁴⁵is methyl or isopropyl; and is

R⁴⁶、R⁴⁷、R⁴⁸And R⁴⁹Is H;

or wherein R is⁴¹Is different fromPropyl; r⁴²、R⁴⁶、R⁴⁸And R⁴⁹Is H; and R is⁴³、R⁴⁴、R⁴⁵And R⁴⁷Is methyl.

Bidentate phosphites of formula IX and X are:

wherein R is¹⁷Is isopropyl, R¹⁸Is hydrogen, and R¹⁹Is methyl;

wherein R is⁵⁰Is methyl, R⁵¹Is methyl, and R⁵²Is hydrogen.

Specific bidentate phosphite ligands that may be used in the process of the invention are:

the formula P (X) used in the process of the invention_aR_a)(X_bR_b)(X_cR_c) In the compound, X_a、X_bAnd X_cEach independently is oxygen or a single bond and R_a、R_bAnd R_cEach independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms. Different formula P (X)_aR_a)(X_bR_b)(X_cR_c) Mixtures of compounds or a single formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compounds may be used in the methods of the invention.

For example, formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound may be of the formula P (R)_a)(Rb)(R_c) The phosphine of (1); formula P (OR)_a)(Rb)(R_c)、P(R_a)(OR_b)(R_c) Or P (R)_a)(Rb)(OR_c) A diester of phosphonous acid of (a); formula P (R)_a)(OR_b)(OR_c)、P(OR_a)(Rb)(OR_c) OR P (OR)_a)(OR_b)(R_c) A diester of phosphonous acid of (a); OR formula P (OR)_a)(OR_b)(OR_c) Phosphite esters of (a). Preferably, formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is of the formula P (OR)_a)(OR_b)(OR_c) Phosphite esters of (a).

Is suitable for R_a、R_bAnd R_cThe alkyl groups of (a) are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Is suitable for R_a、R_bAnd R_cThe aryl group of (a) is a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 1-naphthyl group, a 2-naphthyl group, a1, 1 '-biphenol, a1, 1' -bis-2-naphthol.

Preferably, each R_a、R_bAnd R_cSelected from the group consisting of phenyl, o-tolyl, m-tolyl, and p-tolyl. More preferably, each R_a、R_bAnd R_cSelected from the group consisting of phenyl, m-tolyl, and p-tolyl. In a preferred process, P (X)_aR_a)(X_bR_b)(X_cR_c) Is of the formula P (OR)_a)(OR_b)(OR_c) And each R is_a、R_bAnd R_cSelected from the group consisting of phenyl, m-tolyl, and p-tolyl. Thus, P (X) is preferred_aR_a)(X_bR_b)(X_cR_c) Is a compound of the formula:

p (O-O-tolyl)_w(O-m-tolyl)_x(O-p-tolyl)_y(O-phenyl)_z

Wherein w, x, y and z are 0 or an integer of 1 to 3,and w + x + y + z is 3. Preferably, w is 0. One of x, y or z alone may preferably be 3, and the remaining two of x, y or z are 0. Thus, especially preferred is formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

Suitably, the formula P (X) used in the process of the invention_aR_a)(X_bR_b)(X_cR_c) The compound may be one or more selected from the group consisting of: p (O-O-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-O-tolyl) (O-m-tolyl) (O-phenyl), P (O-O-tolyl) (O-P-tolyl) (O-phenyl), P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-O-tolyl)₂(O-m-tolyl), P (O-O-tolyl)₂(O-P-tolyl), P (O-O-tolyl)₂(O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-O-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-O-tolyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃P (O-O-tolyl)₃. Preferably, formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound may be one or more selected from the group consisting of: p (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

For example, two of the formula P (X) can be used in a ratio of at least about 1: 4, preferably at least about 1: 2_aR_a)(X_bR_b)(X_cR_c) A compound is provided. Preferably no more than about 4: 1, preferably no more than about 2: 1. Suitably, P (O-m-tolyl) is used₃And P (O-P-tolyl)₃A mixture of (a). Preferably, the mixture is used at this rate of at least about 1: 4, preferably at least about 1: 2. Preferably no more than about 4: 1, preferably no more than about 2: 1.

The process of the present invention for preparing the catalyst system is preferably carried out in the presence of a catalytic amount of a compound selected from the group consisting of: p (X)_aR_a)₂Cl、P(X_aR_a)Cl₂Or mixtures thereof, wherein X_aAnd R_aAs defined above. Formula P (X)_aR_a)₂Cl and P (X)_aR_a)Cl₂The compound (b) serves as a carrier for P (X)_aR_a)(X_bR_b)(X_cR_c) A catalyst for the reaction with metallic nickel. Suitably, at least about 50ppm, preferably at least about 200ppm (measured as ppm chlorine by weight of the entire catalyst system) of P (X) is used_aR_a)₂Cl、P(X_aR_a)Cl₂Or mixtures thereof. Suitably, no more than about 500ppm, preferably no more than about 300ppm, is used.

The catalyst system prepared by the process of the present invention comprises an active nickel catalyst material comprising Ni (bidentate organophosphorus ligand)₂And mixed ligand complex Ni (P (X)_aR_a)(X_bR_b)(X_cR_c))_x(bidentate organophosphorous ligand), wherein x ═ 1 or 2. These active nickel species are soluble in the liquid diluent used in the process of the present invention and thus their presence can be determined by measuring the amount of dissolved Ni (0) in the system after filtering unreacted metallic nickel powder from the catalyst system.

FIG. 1 illustrates a continuous process for hydrocyanating cis-and trans-3-pentenenitrile and 4-pentenenitrile to produce adiponitrile. The catalyst system was prepared in a single step as follows: by adding nickel metal powder (1) of the INCO 123 type produced by Vale Canada Limited to the reactor A at 90 deg.CWith ligand 1, m-tricresyl phosphite having 2.0: a mixture of m-and p-tricresyl phosphite in p-tricresyl phosphite molar ratio and a catalytic amount of (TPP) comprising di-m-tolyl, di-p-tolyl and (m-tolyl) (p-tolyl) chlorophosphite₂A mixture of PCl.

The catalyst system is then passed through filter B, where the unreacted nickel metal powder is filtered out of the catalyst system and returned to reactor a via stream (2) in a continuous catalyst system preparation step along with fresh nickel metal powder (1).

After passing through the filter B, the catalyst system is transferred via stream 3 to a reactor C, in which hydrocyanation of cis-and trans-3-pentenenitrile and 4-pentenenitrile takes place. The mixture containing cis-and trans-3-pentenenitrile and 4-pentenenitrile is added via stream (4) and HCN via stream (5). The reactor contents were stirred at a temperature of 100 ℃ under atmospheric pressure.

The product stream (6) was transferred to extraction column D containing methylcyclohexane. The nickel catalyst and free ligand species are extracted into the methylcyclohexane phase, which is transferred via stream (9) to distillation column E. In distillation column E, methylcyclohexane is removed from the top of the column and transferred back to extraction column D via stream (8). Nickel catalyst and free ligand species are removed from the bottom of column E and transferred via stream (10) into reactor a for catalyst system regeneration.

Stream (7) contains the adiponitrile product.

The hydrocyanation of butadiene and the isomerization of 2-methyl-3-butenenitrile proceeds in an almost identical manner. Butadiene or 2-methyl-3-butenenitrile is added via stream (4) to the reactor (C), without adding HCN in the case of isomerization of 2-methyl-3-butenenitrile, but cis-and trans-3-pentenenitrile and 4-pentenenitrile.

The invention is further illustrated by the following non-limiting illustrative examples. The scope of the invention is defined by the appended claims.

Sources of Nickel catalyst used in the experiments

Two sources of nickel metal powder were used to prepare the nickel (0) catalyst complex described in the examples below.

The first nickel was INCO 123 nickel powder produced by Vale Canada Limited. This is a commercial grade nickel powder produced by Vale Canada Limited. This nickel will be referred to as nickel 1 in the examples below.

The second nickel is special nickel powder prepared by taking alkaline nickel carbonate as a starting material. The preparation of nickel powder and its use as a reactant to prepare nickel (0) phosphite catalysts is described in US 2011/0196168 a1, US 8,815,186B 2, US 8,969,606B 1 and US 9,0240, 49B 2, which are incorporated herein by reference in their entirety. The nickel metal powder has been shown to have a much higher reaction rate with the bidentate phosphite ligand for the INCO 123 nickel. The nickel used to prepare the specialty nickel powders used in the examples of the present invention was TIB Chemicals a.g. basic nickel carbonate, which contains about 0.5% sulfur. The nickel carbonate was calcined at a temperature of 350 ℃ for 1 hour in flowing nitrogen, followed by reduction at a temperature of 325 ℃ for two hours in flowing hydrogen. The resulting nickel powder is pyrophoric and must not be allowed to contact an oxygen-containing gas (e.g., air). This nickel will be referred to as nickel 2 in the examples below.

Phosphite ligands for use in experiments

The monodentate phosphite of the examples (i.e., formula P (X)_aR_a)(X_bR_b)(X_cR_c) Compound) is tricresyl phosphite (TPP). A specific TPP reagent used in the following examples is a mixture of m-and p-tricresyl phosphites having a molar ratio of m-to p-tricresyl phosphite of 2.0. The reagent also contains a small amount of (TPP) comprising di (m-tolyl) chlorophosphite, di (p-tolyl) chlorophosphite₂A mixture of PCl which acts as a catalyst for the reaction of m-and p-tricresyl phosphite with nickel metal powder.

Two bidentate phosphite ligands were used in the examples. The first bidentate ligand is designated ligand 1:

the second bidentate ligand is designated ligand 2:

abbreviations used in the examples:

T2M2BN trans-2-methyl-2-butenenitrile

2M3BN 2-methyl-3-butenenitrile

3PN 3-pentenenitrile

C2PN cis-2-pentenenitrile

C2M2BN cis-2-methyl-2-butenenitrile

T2PN trans-2-pentenenitrile

T3PN trans-3-pentenenitrile

4PN 4-pentenenitrile

C3PN cis-3-pentenenitrile

MGN methylglutaronitrile

ADN adiponitrile

Analytical method

Scope and application

The method is suitable for determining Dinitriles (DN) and Pentenenitriles (PN).

Principle of

The components were separated by capillary gas chromatography. Two internal standards were used: cyclohexanone for PN and octanedionitrile for DN to achieve better overall process accuracy and precision. Flame Ionization Detection (FID) is used to detect the separated components. Integration was performed using the EZChrom Elite data system.

Sensitivity, precision and accuracy

Sensitivity:

the limit of detection (LOD) or limit of quantification (LOQ) for all components has not been determined at this time. The applicable ranges for calibration are listed in the calibration section.

The accuracy is as follows:

accuracy was determined by multiple injections of QC (QC is a quality control sample in which the concentration of a known component is known) and ADN check samples.

	C2PN	VN^＊	T3PN	MGN	ADN
						QC-1	10.60	3.67	17.14	5.04	31.54
QC-2	10.58	3.67	17.14	5.048	31.53
						QC-3	10.60	3.67	17.15	5.048	31.54
Mean value of	10.59	3.67	17.14	5.04	31.54
						Theoretical value	10.61	3.68	16.57	4.94	30.90
Error%	-0.16	-0.21	3.44	2.00	2.06

VN ═ valeronitrile

	ADN accounting
		ADN accounting sample #1	100.44
ADN accounting sample #2	100.51
		ADN accounting sample #3	100.32
Mean value of	100.42
		Theoretical value	99.99
Error%	0.44

Precision:

precision was determined by multiple injections of QC and ADN check samples.

	C2PN	VN	T3PN	MGN	ADN
						QC-1	10.60	3.67	17.14	5.04	31.54
QC-2	10.58	3.67	17.14	5.04	31.53
						QC-3	10.60	3.67	17.15	5.04	31.54
Mean value of	10.59	3.67	17.14	5.04	31.54
						％RSD	0.07	0.06	0.02	0.03	0.02

Device

Gas chromatography: HP7890 II series (or equivalent) equipped with flame ionization detector, capillary flow-splitting/non-splitting inlet and auto liquid sampler.

Capillary column: j & W Scientific DB-23(30m 0.25mm I.D.. times.0.25 μm), Agilent P/N122-.

2.0mL autosampler screw cap vial Agilent P/N5182-

0.2 μm polypropylene syringe filter.

Metrohm 756KF Coulometric Titrator (Coulometric titror) or equivalent — direct injection, without a membrane electrode.

AQUASTAR AQC34 KF coulometric titrator equivalent — direct injection, burn-through electrodes, for aldehydes and ketones.

Operating conditions HP7890

The EZChrom Elite data system method comprises the following steps:

NIR0004_PNDN_front_2012-10-07.met

temperature of

Inlet temperature: 250 deg.C

Detector temperature: 300 deg.C

The oven temperature was 50 deg.C

Oven procedure:

temperature program	Rate (. degree. C./Min)	Temperature (. degree.C.)	Maintenance time (min.)	Total time (min.)
					1		50	3	3
2	5	80	0	9
					3	40	210	6	18.25
4	50	240	9.15	28

Brief description of the examples

Example 1 (comparative) shows the use of nickel 2 to make Ni [ TTP ]]₄Procedure for the catalyst.

Example 2 shows the procedure for making the catalyst of the invention using nickel 2.

Example 3 (comparative) shows the procedure for the isomerization of 2M3BN to T3PN using the catalyst from example 1, and the results obtained.

Example 4 shows the procedure for the isomerization of 2M3BN to T3PN using the inventive catalyst from example 2, and the results obtained.

Comparison of examples 3 and 4 shows that the catalyst of the invention made using nickel 2 gives much higher conversion of 2M3BN to T3 PN.

Example 5 (comparative) shows the procedure for hydrocyanation of T3PN to ADN using the catalyst from example 1, and the results obtained.

Example 6 shows the procedure for hydrocyanation of T3PN to ADN using the catalyst of the invention from example 2, and the results obtained.

A comparison of examples 5 and 6 shows that the inventive catalyst made using nickel 2 gives much higher selectivity to ADN (92.5% versus 75.3%).

Example 7 (comparative) shows the use of Nickel 1 to make Ni [ TTP ]]₄Procedure for the catalyst.

Example 8 shows the procedure for making the catalyst of the invention using nickel 1.

Example 9 (this comparison) shows the procedure for the isomerization of 2M3BN to T3PN using the catalyst from example 7, and the results obtained.

Example 10 shows the procedure for the isomerization of 2M3BN to T3PN using the inventive catalyst from example 8, and the results obtained.

A comparison of examples 9 and 10 shows that the catalyst of the invention using nickel 1 gives a much higher conversion of 2M3BN to T3 PN.

Example 11 (comparative) shows the procedure for hydrocyanation of T3PN to ADN using the catalyst from example 7, and the results obtained.

Example 12 shows the procedure for hydrocyanation of T3PN to ADN using the catalyst of the invention from example 8, and the results obtained.

A comparison of examples 11 and 12 shows that the catalyst of the invention using nickel 1 gives a much higher selectivity to ADN (92.1% versus 72.1%).

Example 13 shows a procedure for making a bidentate ligand catalyst using ligand 1 in the absence of TTP using nickel 2.

Example 14 shows a procedure for making a bidentate ligand catalyst using ligand 1 in the absence of TTP using nickel 1.

Examples 13 and 14 show much lower concentrations of Ni (0) than examples 1 and 2, which were conducted in the presence of TTP.

Example 15 shows the procedure for making the catalyst of the invention using ligand 2 and nickel 2.

Example 16 shows the procedure for making the catalyst of the invention using ligand 2 and nickel 1.

Example 17 shows the procedure for the isomerization of 2M3BN to T3PN using the catalyst from example 15, and the results obtained.

Example 18 shows the procedure for the isomerization of 2M3BN to T3PN using the catalyst of the invention from example 16, and the results obtained.

Examples 17 and 18 show that the catalysts of the invention made using ligand 2 give high conversion of 2M3BN to T3 PN.

Example 19 shows the procedure for hydrocyanation of T3PN to ADN using the catalyst from example 15, and the results obtained.

Example 20 shows the procedure for hydrocyanation of T3PN to ADN using the catalyst of the invention from example 16, and the results obtained.

Examples 19 and 20 both show high selectivity for ADN using ligand 2.

Example 21 shows a procedure for making a bidentate phosphite ligand catalyst using ligand 2 in the absence of TTP using nickel 2.

Example 22 shows a procedure for making a bidentate phosphite ligand catalyst using nickel 1 with ligand 2 in the absence of TTP.

Examples 21 and 22 show much lower concentrations of Ni (0) than examples 15 and 16, which were conducted in the presence of TTP.

Procedure and results

EXAMPLE 1 preparation of Nickel (0) Complex Using Nickel 2 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 4.0g TTP, 1.0g 3PN and 0.12g nickel 2. TTP mixtures containing small amounts of [ TTP]₂PCl to catalyze the reaction. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 78.6% TTP, 19.6% 3PN, and 1.94% soluble nickel (0), and had a TTP: Ni (0) molar ratio of 6.7.

Example 2: preparation of Nickel (0) complexes Using Nickel 2, ligand 1 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 0.94g TTP, 0.5g 3PN, 1.06g of the ligand 1 mixture (which contains 61.8% of ligand 1) and 0.027g nickel 2. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 79.5% mixed phosphite ligand, 19.9% 3PN, and 0.64% soluble nickel (0), and had a molar ratio of 10.2TTP/3.2 ligand 1/1.0Ni (0).

Example 3: isomerization of 2M3BN to 3PN Using the catalyst of example 1

The catalyst from example 1 was used to isomerize 2M3BN to 3 PN. Molar equivalents of nickel catalyst (0.036mmol Ni (0)) were mixed with 852 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.47	61.64	14.96	1.25	0.13	15.08	0.13	0.33	0.25
60min	6.55	59.88	14.99	1.28	0.14	16.68	0.15	0.34	0.28
										150min	6.59	57.76	14.99	1.31	0.17	18.68	0.15	0.36	0.33

these results show a minimal increase in 3PN concentration after 150min reaction (15.08% to 18.68%).

Example 4: isomerization of 2M3BN to 3PN Using the catalyst of example 2

The catalyst from example 2 was used to isomerize 2M3BN to 3 PN. One molar equivalent of nickel catalyst (0.037mmol Ni (0)) was mixed with 822 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.39	60.91	14.79	1.24	0.13	15.97	0.13	0.40	0.27
60min	6.43	43.41	14.82	1.27	0.14	33.32	0.16	0.46	0.78
										150min	6.46	26.16	14.81	1.31	0.15	50.43	0.17	0.53	1.95

these results show a much greater increase in 3PN concentration after 150min reaction compared to example 1 (15.97% to 50.43%), indicating much higher catalyst activity.

Example 5: hydrocyanation of 3PN to ADN Using the catalyst of example 1

The catalyst from example 1 was used to hydrocyanate 3PN to ADN. -Molar equivalents of nickel catalyst (0.0182mmol Ni (0)) to 1291 molar equivalents contained 1.05 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃, followed by the addition of 64 molar equivalents of HCN/hour of Ni in valeronitrile solvent. After 20.4 hours, the reaction mixture was analyzed, and the following results were obtained

MGN	ADN	ADN selectivity
			5.9％	17.9％	75.3％

MGN is an undesirable by-product of 3PN hydrocyanation.

Example 6: hydrocyanation of 3PN to ADN Using the catalyst of example 2

The catalyst from example 2 was used to hydrocyanate 3PN to ADN. Molar equivalents of nickel catalyst (0.0219mmol Ni (0)) to 1342 molar equivalents contain 0.99 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃, followed by the addition of 52 molar equivalents of HCN/hour Ni in valeronitrile solvent. After 25.9 hours, the reaction mixture was analyzed, and the following results were obtained

MGN	ADN	ADN selectivity
			3.3％	40.6％	92.5％

These results show a much higher selectivity to ADN (92.5%) than that obtained in example 5 (75.3%).

Example 7: preparation of Nickel (0) complexes Using Nickel 1 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 1.97g TTP, 0.5g 3PN and 0.088g nickel 1. TTP contains a small amount of [ TTP ]]₂PCl to catalyze the reaction. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 78.23% TTP, 19.86% 3PN, and 1.91% soluble nickel (0), and had a TTP to Ni (0) molar ratio of 6.8.

Example 8: preparation of Nickel (0) complexes Using Nickel 1, ligand 1 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 1.02g TTP, 0.51g 3PN, 1.00g ligand 1 mixture (which contains 61.8% ligand 1) and 0.058g nickel 1. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 79.24% mixed phosphite ligand, 20.01% 3PN, and 0.75% soluble nickel (0), and had a molar ratio of 8.9TTP/2.6 ligand 1/1.0Ni (0).

Example 9: isomerization of 2M3BN to 3PN Using the catalyst of example 7

The catalyst from example 7 was used to isomerize 2M3BN to 3 PN. Molar equivalents of nickel catalyst (0.032mmol Ni (0)) were mixed with 905 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.47	61.53	14.97	1.27	0.14	15.15	0.15	0.33	0.25
60min	6.53	59.81	15.00	1.36	0.14	16.68	0.14	0.33	0.28
										150min	6.60	57.75	15.00	1.39	0.15	18.61	0.14	0.35	0.33

these results show a minimal increase in 3PN concentration after 150min reaction (15.15% to 18.61%). It should be noted that the results of this experiment were almost identical to example 3. The only difference is that example 3 used a catalyst prepared from nickel 2, whereas example 9 used a catalyst prepared from nickel 1.

Example 10: isomerization of 2M3BN to 3PN Using the catalyst of example 8

The catalyst from example 8 was used to isomerize 2M3BN to 3 PN. One molar equivalent of nickel catalyst (0.031mmol Ni (0)) was mixed with 884 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.43	61.13	14.84	1.26	0.14	15.97	0.15	0.39	0.26
60min	6.44	45.54	14.86	1.29	0.14	31.15	0.15	0.43	0.69
										150min	6.46	27.87	14.86	1.32	0.15	48.69	0.16	0.50	1.77

these results show a much greater increase in 3PN concentration after 150min reaction compared to example 9 (15.97% to 48.69%), indicating much higher catalyst activity. The results shown here are very similar to those of example 4. The only difference is that example 4 used a catalyst prepared from nickel 2, whereas example 10 used a catalyst prepared from nickel 1.

Example 11: hydrocyanation of 3PN to ADN Using the catalyst of example 7

The catalyst from example 7 was used to hydrocyanate 3PN to ADN. Molar equivalents of nickel catalyst (0.0252mmol Ni (0)) to 1347 molar equivalents contain 1.03 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃ and then 79.2 molar equivalents HCN/hr Ni in valeronitrile solvent were added. After 17 hours, the reaction mixture was analyzed, and the following results were obtained

MGN	ADN	ADN selectivity
			1.86％	4.80％	72.1％

Example 12: hydrocyanation of 3PN to ADN Using the catalyst of example 8

The catalyst from example 8 was used to hydrocyanate 3PN to ADN. Molar equivalents of nickel catalyst (0.0210mmol Ni (0)) to 1399 molar equivalents contain 0.97 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃ and then 82.3 molar equivalents HCN/hr Ni in valeronitrile solvent were added. After 17 hours, the reaction mixture was analyzed, and the following results were obtained

MGN	ADN	ADN selectivity
			2.88％	33.5％	92.1％

These results show much higher selectivity to ADN (92.1%) than that obtained in example 11 (72.1%). The results shown here are very similar to those of example 6. The only difference was that example 6 used a catalyst prepared from nickel 2, while example 12 used a catalyst prepared from nickel 1.

Example 13: preparation of Nickel (0) complexes Using Nickel 2 and ligand 1 alone

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 0.95g of ligand 1 mixture (which contains 61.8% of ligand 1), 0.95g of 3PN and 0.024g of nickel 2. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 50.0% mixed phosphite ligand, 50.0% 3PN, and 0.016% soluble nickel. Compared to the amount of soluble nickel formed in example 2 (0.64%), very little soluble nickel (0) complex was formed in example 14 in the absence of TTP (0.016%).

Example 14: preparation of Nickel (0) complexes Using Nickel 1 and ligand 1 alone

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 0.95g of ligand 1 mixture (which contains 61.8% of ligand 1), 0.95g of 3PN and 0.024g of nickel 1. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 50.0% mixed phosphite ligand, 50.0% 3PN, and 0.0047% soluble nickel. The amount of soluble nickel formed in example 8 (0.75%) corresponded to, and very little soluble nickel (0) complex formed in example 14 (0.0047%) in the absence of TTP.

Example 15: preparation of Nickel (0) complexes Using Nickel 2, ligand 2 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 1.01g TTP, 0.52g 3PN, 1.07g ligand 2 mixture and 0.026g nickel 2. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 79.6% mixed phosphite ligand, 19.9% 3PN, and 0.50% soluble nickel, and had a molar ratio of 12.8TTP/5.5 ligand 2/1.0Ni (0).

Example 16: preparation of Nickel (0) complexes Using Nickel 1, ligand 2 and TTP

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 1.03g TTP, 0.50g 3PN, 1.06g ligand 2 mixture and 0.049g nickel 1. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 79.9% mixed phosphite ligand, 19.1% 3PN, and 0.93% soluble nickel, and had a 7.0TTP/2.9 ligand 2/1.0Ni (0) molar ratio.

Example 17: isomerization of 2M3BN to 3PN Using the catalyst of example 15

The catalyst from example 15 was used to isomerize 2M3BN to 3 PN. One molar equivalent of nickel catalyst (0.010mmol Ni (0)) was mixed with 788 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.38	60.64	14.73	1.26	0.15	15.92	0.29	0.63	0.28
60min	6.45	35.43	14.72	1.41	0.16	40.71	0.32	0.80	1.18
										150min	6.51	16.86	14.68	1.53	0.19	58.86	0.34	1.03	3.57

these results show that using ligand 2 gives similar results to ligand 1 (example 4).

Example 18: isomerization of 2M3BN to 3PN Using the catalyst of example 16

The catalyst from example 16 was used to isomerize 2M3BN to 3 PN. Molar equivalents of nickel catalyst (0.018mmol Ni (0)) were mixed with 808 molar equivalents of 2M3BN and the mixture was heated to 115 ℃. Samples (0.2g) were taken from the reactor at 0min, 60min and 150min and analyzed. The results are shown directly below:

	T2M2BN	2M3BN	C2PN	C2M2BN	T2PN	T3PN	4PN	C3PN	3PN/2M3BN
										0min	6.44	61.19	14.86	1.27	0.15	15.41	0.22	0.47	0.26
60min	6.48	35.72	14.69	1.44	0.15	40.66	0.22	0.64	1.16
										150min	6.50	16.05	14.85	1.47	0.16	59.89	0.24	0.81	3.80

these results show that using ligand 2 gives similar results to ligand 1 (example 10).

Example 19: hydrocyanation of 3PN to ADN Using the catalyst of example 15

The catalyst from example 15 was used to hydrocyanate 3PN to ADN. Molar equivalents of nickel catalyst (0.0261mmol Ni (0)) to 1309 molar equivalents contained 0.99 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃, followed by 77.0 molar equivalents of HCN/hr Ni in valeronitrile solvent. After 17 hours, the reaction mixture was analyzed and the following results were obtained:

MGN	ADN	ADN selectivity
			4.49％	49.77％	91.7％

The results obtained in example 19 are very similar to those obtained in example 6 using ligand 1.

Example 20: hydrocyanation of 3PN to ADN Using the catalyst of example 16

The catalyst from example 16 was used to hydrocyanate 3PN to ADN. Molar equivalents of nickel catalyst (0.0322mmol Ni (0)) to 1365 molar equivalents contain 1.01 molar equivalents of ZnCl₂3PN mixture of (1). The mixture was heated to 55 ℃ and then 80.3 molar equivalents of HCN/hr valeronitrile solvent were addedNi in (1). After 17 hours, the reaction mixture was analyzed, and the following results were obtained

MGN	ADN	ADN selectivity
			4.51％	63.95％	93.41％

The results obtained in example 20 are very similar to those obtained in example 12 using ligand 1.

Example 21: preparation of Nickel (0) complexes Using Nickel 2 and ligand 2 alone

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 2.0g of ligand 2, 1.0g of 3PN and 0.140g of nickel 2. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 66.7% mixed phosphite ligand, 33.3% 3PN, and 0.0211% soluble nickel (0). Compared to the amount of soluble nickel formed in example 15 (0.50%), very little soluble nickel (0) complex was formed in example 21 in the absence of TTP (0.0211%).

Example 22: preparation of Nickel (0) complexes Using Nickel 1 and ligand 2 alone

The following reactants were loaded into a 10mL flask equipped with a magnetic stir bar: 2.0g of ligand 2, 1.0g of 3PN and 0.142g of nickel 1. The mixture was heated to 90 ℃ and kept at said temperature for 24 hours with continuous stirring. The sample was then filtered under nitrogen atmosphere to remove unreacted nickel powder. The resulting solution of the catalyst complex contained 66.7% mixed phosphite ligand, 33.3% 3PN, and 0.000% soluble nickel. Compared to the amount of soluble nickel formed in example 16 (0.90%), a soluble nickel (0) complex was not formed in example 22 (0.000%) in the absence of TTP.

Claims

1. A method of preparing a catalyst system for hydrocyanating butadiene or one or more monoolefinic mononitriles, the method comprising contacting metallic nickel, at least one bidentate organophosphorus ligand, and at least one compound of formula P (X)_aR_a)(X_bR_b)(X_cR_c) Reacting the compound in the presence of a liquid diluent in a single step; wherein

X_a、X_bAnd X_cEach independently is oxygen or a single bond; and is

Wherein R is_a、R_bAnd R_cEach independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms; and is

The bidentate organophosphorus ligand is selected from the group consisting of:

2. the process of claim 1, wherein the monoolefinic mononitrile is or comprises one or more pentenenitriles.

3. The process according to claim 2, wherein the one or more pentenenitriles are selected from the group consisting of cis-3-pentenenitrile, trans-3-pentenenitrile and 4-pentenenitrile.

4. The method of claim 1, wherein is selected from the group consisting of P (X)_aR_a)₂Cl、P(X_aR_a)Cl₂And mixtures thereof for nickel complex formationA step of adding to the preparation of the catalyst system, wherein X_aIs oxygen or a single bond; and R is_aIs an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

5. The process of claim 4, wherein the catalyst for nickel complex formation is added in an amount of at least 50ppm and no more than 500ppm, measured as ppm chlorine by weight of the entire catalyst system.

6. The process of claim 1, wherein the liquid diluent comprises 3-pentenenitrile.

7. The method of claim 1, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more than one type of P (O-O-tolyl)_w(O-m-tolyl)_x(O-p-tolyl)_y(O-phenyl)_zA compound wherein w, x, y and z are independently 0 or an integer from 1 to 3, and w + x + y + z is 3.

8. The method of claim 7, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more compounds selected from the group consisting of: p (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

9. The process of claim 1, wherein the process is a continuous process.

10. A process for hydrocyanating butadiene comprising:

ii) reacting butadiene with HCN in the presence of the catalyst system prepared in step i) to form a mixture comprising 3-pentenenitrile and 2-methyl-3-butenenitrile; and is

The bidentate organophosphorus ligand is selected from the group consisting of:

11. the method of claim 10, wherein is selected from the group consisting of P (X)_aR_a)₂Cl、P(X_aR_a)Cl₂And mixtures thereof, wherein X is added to the step of preparing the catalyst system_aIs oxygen or a single bond; and R is_aIs an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

12. The process of claim 11, wherein the catalyst for nickel complex formation is added in an amount of at least 50ppm and no more than 500ppm, measured as ppm chlorine by weight of the entire catalyst system.

13. The process of claim 10, wherein the liquid diluent comprises 3-pentenenitrile.

14. According to claim 10The process of (1), wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more than one type of P (O-O-tolyl)_w(O-m-tolyl)_x(O-p-tolyl)_y(O-phenyl)_zA compound wherein w, x, y and z are independently 0 or an integer from 1 to 3, and w + x + y + z is 3.

15. The method of claim 14, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more compounds selected from the group consisting of: p (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

16. The process of claim 10, wherein the process is a continuous process.

17. A process for hydrocyanating one or more monoolefinic mononitriles, the process comprising:

ii) reacting the one or more monoolefinic mononitriles with HCN in the presence of the catalyst system prepared in step i) to form a mixture comprising one or more dinitriles;

wherein the bidentate organophosphorus ligand is selected from the group consisting of:

18. the process of claim 17, wherein the one or more monoolefinic mononitriles is or comprises one or more pentenenitriles.

19. The process of claim 18, wherein the one or more pentenenitriles are selected from cis-3-pentenenitrile, trans-3-pentenenitrile, and 4-pentenenitrile and the one or more dinitriles are or comprise adiponitrile.

20. The method of claim 17, wherein is selected from the group consisting of P (X)_aR_a)₂Cl、P(X_aR_a)Cl₂And mixtures thereof, wherein X is added to the step of preparing the catalyst system_aIs oxygen or a single bond; and R is_aIs an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

21. The process of claim 20, wherein the catalyst for nickel complex formation is added in an amount of at least 50ppm and no more than 500ppm, measured as ppm chlorine by weight of the entire catalyst system.

22. The process of claim 17, wherein the liquid diluent comprises 3-pentenenitrile.

23. The method of claim 17, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more than one type of P (O-O-tolyl)_w(O-m-position)Tolyl radical)_x(O-p-tolyl)_y(O-phenyl)_zA compound wherein w, x, y and z are independently 0 or an integer from 1 to 3, and w + x + y + z is 3.

24. The method of claim 23, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more compounds selected from the group consisting of: p (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

25. The process of claim 17, wherein the process is a continuous process.

26. A process for isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile, comprising:

ii) isomerizing 2-methyl-3-butenenitrile to 3-pentenenitrile using the catalyst system prepared in step i);

27. the method of claim 26, wherein is selected from the group consisting of P (X)_aR_a)₂Cl、P(X_aR_a)Cl₂And mixtures thereof, wherein X is added to the step of preparing the catalyst system_aIs oxygen or a single bond; and R is_aIs an alkyl group having 1 to 10 carbon atoms or an aryl group having 1 to 20 carbon atoms.

28. The process of claim 27, wherein the catalyst for nickel complex formation is added in an amount of at least 50ppm and no more than 500ppm, measured as ppm chlorine by weight of the entire catalyst system.

29. The process of claim 26, wherein the liquid diluent comprises 3-pentenenitrile.

30. The method of claim 26, wherein the formula P (X)_aR_a)(X_bR_b)(X_cR_c) The compound is one or more than one type of P (O-O-tolyl)_w(O-m-tolyl)_x(O-p-tolyl)_y(O-phenyl)_zA compound wherein w, x, y and z are independently 0 or an integer from 1 to 3, and w + x + y + z is 3.

31. The method of claim 30, wherein the formula P (X)_aR_a)(X_bR_b)(x_cR_c) The compound is one or more compounds selected from the group consisting of: p (O-m-tolyl) (O-phenyl)₂P (O-P-tolyl) (O-phenyl)₂P (O-m-tolyl) (O-P-tolyl) (O-phenyl), P (O-P-tolyl)₂(O-m-tolyl), P (O-P-tolyl)₂(O-phenyl), P (O-m-tolyl)₂(O-P-tolyl), P (O-m-tolyl)₂(O-phenyl), P (O-m-tolyl)₃P (O-P-tolyl)₃And P (O-phenyl)₃。

32. The process of claim 26, wherein the process is a continuous process.