Sulfur-containing phosphite ligand catalyst and adiponitrile preparation method

Abstract

The invention discloses a sulfur-containing phosphite ligand catalyst and an adiponitrile preparation method adopting the catalyst. The catalyst can effectively inhibit generation of nickel cyanogroup in the adiponitrile preparation process. The catalyst is prepared from zero-valent nickel and a monodentate or bidentate sulfur-containing phosphite ligand A, the molar ratio of the zero-valent nickel to the monodentate sulfur-containing phosphite ligand A is 1: 4, the molar ratio of the zero-valent nickel to the bidentate sulfur-containing phosphite ligand A is 1: 2, and the feeding molar ratio of the zero-valent nickel to the sulfur-containing phosphite ligand A is (0.2-50): 1. The coordination effect of hydrocyanic acid on zero-valent nickel atoms in the center of the catalyst is reduced through sulfur-containing groups in the ligand, and generation of cyano nickel in the reaction is effectively inhibited while high selectivity of the product is guaranteed. Meanwhile, due to the action of thiol or thiophenol atoms, the isomerization rate can be increased.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical production of adiponitrile. Specifically, it relates to a catalyst containing a sulfur-containing phosphite ligand, and a method for preparing adiponitrile using this catalyst. Using this catalyst can effectively inhibit the formation of nickel cyanide during the preparation of adiponitrile. Background Art

[0002] The domestic demand for adiponitrile will reach 1.2 million tons per year in 2025. The total planned domestic and foreign adiponitrile production capacity under construction reaches 1.43 million tons per year. In 2019, domestic adiponitrile plants were successively started and began to be put into production one after another after 2022. After the projects are successfully put into production, China will achieve the localization of adiponitrile, thus partially alleviating the current situation of "stuck neck" in adiponitrile supply.

[0003] There are many methods for synthesizing adiponitrile. Currently, the main process routes for producing adiponitrile are mainly two types: acrylonitrile electrolytic dimerization method and butadiene method. The synthesis of adiponitrile by the butadiene method mainly includes three steps: primary hydrocyanation, isomerization, and secondary hydrocyanation. The reaction equations for these three steps are as follows:

[0004]

[0005] Among them, in the three-step reaction of synthesizing adiponitrile by the butadiene method with a zero-valent nickel catalyst and a phosphorus-containing ligand as a homogeneous system, the problem is that the catalyst is easily coordinated with hydrocyanic acid to produce nickel cyanide precipitation, resulting in attenuation of catalytic efficiency, blockage of the reaction system, and increased production costs. Therefore, how to effectively reduce the loss of the catalyst and improve the utilization efficiency of the catalyst is an important research direction at present. Summary of the Invention

[0006] Aiming at the above problems existing in the prior art, the purpose of the present invention is to provide a zero-valent nickel catalyst containing a sulfur-containing phosphite ligand, and a catalyst composition containing this zero-valent nickel catalyst containing a sulfur-containing phosphite ligand. This catalyst composition is used for the preparation of adiponitrile and can effectively inhibit the formation of nickel cyanide during the preparation of adiponitrile. The zero-valent nickel catalyst containing a sulfur-containing phosphite ligand reduces the coordination effect of hydrocyanic acid on the central zero-valent nickel atom in the ligand, and while ensuring high product selectivity, effectively inhibits the formation of nickel cyanide in the reaction. To achieve the above purpose, the present invention provides the following technical solutions:

[0007] According to one aspect of the present invention, an object of the present invention is to provide a sulfur-containing phosphite ligand zero-valent nickel catalyst for preparing adiponitrile. The catalyst is prepared from zero-valent nickel and a monodentate or bidentate sulfur-containing phosphite ligand A. In its chemical structural formula, the molar ratio of zero-valent nickel to the monodentate sulfur-containing phosphite ligand A is 1:4, the molar ratio of zero-valent nickel to the bidentate sulfur-containing phosphite ligand A is 1:2, and the molar ratio of zero-valent nickel to the sulfur-containing phosphite ligand in the feed is 0.2 to 50:1, and the preferred range is 3 to 40:1.

[0008] Preferably, the sulfur-containing phosphite ligand A is a monodentate ligand represented by the following general formula I or a bidentate ligand represented by the following general formula II:

[0009]

[0010] Wherein, X and Y each independently selected from S and O atoms, rings A1, A2, A3 and A4 are the same or different from each other, and each independently selected from phenyl, naphthyl, furyl, pyranyl. The rings A1, A2, A3 and A4 may or may not contain 1 to 3 substituents, and the substituents are selected from C1-C4 alkyl, C1-C4 oxyalkyl, fluorine-substituted C1-C4 alkyl, fluorine-substituted C1-C4 oxyalkyl;

[0011] The six-membered ring represented by the dotted line in general formula II may or may not have the six-membered cyclohexyl structure.

[0012] Preferably, the sulfur-containing phosphite ligand is selected from the following structures:

[0013]

[0014]

[0015] Preferably, the sulfur-containing phosphite ligand zero-valent nickel catalyst is selected from the following compounds:

[0016] Nickel(0) tris(furfurylthiol) phosphite, Nickel(0) triphenylthiophenol phosphite, Nickel(0) phenyl(p - tolylthiophenol)(m - tolylthiophenol) phosphite, Nickel(0) di - p - tolyl(phenylthiophenol) phosphite, Nickel(0) o - tolyl(phenylthiol)(m - tolylthiol) phosphite, Nickel(0) ((4 - tert - butyl - phenolyl)-(4 - tert - butyl - phenylthiolyl)-(3 - isopropyl - phenolyl) phosphite), Nickel(0) ((ethylthio)-(o - methyl - phenolyl)-(3 - methyl - phenylthiolyl) phosphite), Nickel(0) ((1 - furfurylthio)-(o - methyl - phenolyl)-(m - methyl - phenylthiolyl) phosphite), Nickel(0) bis(furfurylthio)(p - cresolyl) phosphite, Nickel(0) bis(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1 - furfuryl - thio)-bisphosphite), Nickel(0) bis(([1,1'-biphenyl]-2,2'-bicyclohexyl) S,S,S',S'-tetrakis(1 - furfuryl - thio)-bisphosphite), Nickel(0) bis(1,1`-biphenolyl-[2-[2 - bis(4 - vinyl - phenylthiolyl) phosphite])), Nickel(0) bis(O,O'-([1,1'-biphenolyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphthylthiolato)bis(phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis(tris(phenylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris(tris(phenylthiolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis(phenolato(p-tolylthiolato)(m-tolylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris(phenolato(p-tolylthiolato)(m-tolylthiolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis(bis(p-tolyl)(phenylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris(bis(p-tolyl)(phenylthiolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis(o-tolyl(phenylthiolato)(m-tolylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris(o-tolyl(phenylthiolato)(m-tolylthiolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-phenylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris((ethylthio)-(o-methyl-phenolato)-(3-methyl-phenylthiolato)phosphite)nickel(0), bis(tris(furfurylthiolato)phosphite)-bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-phenylthiolato)phosphite)nickel(0), (tris(furfurylthiolato)phosphite)-tris((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-phenylthiolato)phosphite)nickel(0), bis(tris(phenylthiolato)phosphite)-bis(phenolato(p-tolylthiolato)(m-tolylthiolato)phosphite)nickel(0), (tris(phenylthiolato)phosphite)-tris(phenolato(p-tolylthiolato)(m-tolylthiolato)phosphite)nickel(0), bis(tris(phenylthiolato)phosphite)-bis(bis(p-tolyl)(phenylthiolato)phosphite)nickel(0), (tris(phenylthiolato)phosphite)-tris(bis(p-tolyl)(phenylthiolato)phosphite)nickel(0), bis(tris(phenylthiolato)phosphite)-bis(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), (tris(phenylthiolato)phosphite)-tris(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), bis(tris(phenylthiolato)phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl)S,S,S',S'-tetrakis(1-furfuryl-thio)-bis(phosphite)nickel(0), bis(tris(phenylthiolato)phosphite)-(([1,1'-biphenyl]-2,2'-Biphenylcyclohexane)S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)nickel(0), bis(triphenylthiol phosphite)-(1,1'-biphenolyl-[2-[2-bis(4-vinylphenylthiol)phosphite])nickel(0), bis(triphenylthiol phosphite)-(O,O'-([1,1'-biphenolyl]-2,2'-biphenyl)S,S,S',S'-tetrakis(1-naphthylthiolato)bis(phosphite)nickel(0), bis(phenylene(4-methylthiophenol)(3-methylthiophenol)phosphite)-bis(di-p-tolyl(phenylthiolato)phosphite)nickel(0), (phenylene(4-methylthiophenol)(3-methylthiophenol)phosphite)-tris(di-p-tolyl(phenylthiolato)phosphite)nickel(0), bis(phenylene(4-methylthiophenol)(3-methylthiophenol)phosphite)-bis(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)nickel(0), (phenylene(4-methylthiophenol)(3-methylthiophenol)phosphite)-tris(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)nickel(0), bis(di-p-tolyl(phenylthiolato)phosphite)-bis(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)nickel(0), (di-p-tolyl(phenylthiolato)phosphite)-tris(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)nickel(0), bis(di-p-tolyl(phenylthiolato)phosphite)-bis((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), (di-p-tolyl(phenylthiolato)phosphite)-tris((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), bis(di-p-tolyl(phenylthiolato)phosphite)-bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-phenylthiolato)phosphite)nickel(0), (di-p-tolyl(phenylthiolato)phosphite)-tris((ethylthio)-(o-methyl-phenolato)-(3-methyl-phenylthiolato)phosphite)nickel(0), bis(di-p-tolyl(phenylthiolato)phosphite)-bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-phenylthiolato)phosphite)nickel(0), (di-p-tolyl(phenylthiolato)phosphite)-tris((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-phenylthiolato)phosphite)nickel(0), bis(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)-bis((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), (o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)-tris((4-tert-butyl-phenolato)-(4-tert-butyl-phenylthiolato)-(3-isopropyl-phenolato)phosphite)nickel(0), bis(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)-bis(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), (o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)-tris(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), bis(o-tolyl(phenylthiolato)(3-methylthiophenolato)phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl)S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)nickel(0), bis((4-tert-butyl-phenolato)-(4-tert-butyl-benzenethiolato)-(3-isopropyl-phenolato)phosphite)-bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)nickel(0), ((4-tert-butyl-phenolato)-(4-tert-butyl-benzenethiolato)-(3-isopropyl-phenolato)phosphite)-tris((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)nickel(0), bis((4-tert-butyl-phenolato)-(4-tert-butyl-benzenethiolato)-(3-isopropyl-phenolato)phosphite)-bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)nickel(0), ((4-tert-butyl-phenolato)-(4-tert-butyl-benzenethiolato)-(3-isopropyl-phenolato)phosphite)-tris((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)nickel(0), bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)-bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)nickel(0), ((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)-tris((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)nickel(0), bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)-bis(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), ((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)-tris(bis(furfurylthio)-(p-cresolato)phosphite)nickel(0), bis((ethylthio)-(o-methyl-phenolato)-(3-methyl-benzenethiolato)phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)nickel(0), bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)nickel(0), bis((1-furfurylthio)-(o-methyl-phenolato)-(m-methyl-benzenethiolato)phosphite)-(([1,1'-biphenyl]-2,2'-bicyclohexane) S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)nickel(0), bis(bis(furfurylthio)-(p-cresolato)phosphite)-(1,1`-biphenolato-[2-[2-bis(4-vinyl-benzenethiolato)phosphite])nickel(0), (([1,1'-Biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfurylthio)-bis(phosphite)-(O,O'-([1,1'-biphenylene]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphthylthiol) bis(phosphite) nickel(0).

[0017] According to one aspect of the present invention, an object of the present invention is to provide a method for preparing the sulfur-containing phosphite ligand zero-valent nickel catalyst, and the method is carried out as follows: Under nitrogen protection at room temperature, elemental nickel powder is mixed with the sulfur-containing phosphite ligand A, and the temperature is raised to 100 °C and stirred at normal pressure for 4 hours to obtain it.

[0018] Preferably, the particle size of the elemental nickel powder is 2 - 50 nm, preferably 3 - 30 nm.

[0019] According to the second aspect of the present invention, a second object of the present invention is to provide a catalyst composition comprising the sulfur-containing phosphite ligand zero-valent nickel catalyst. The catalyst composition includes a Lewis acid, the sulfur-containing phosphite ligand zero-valent nickel catalyst, and a sulfur-containing phosphite ligand B, wherein the content ratios of the Lewis acid, zero-valent nickel catalyst, and sulfur-containing phosphite ligand B are: the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0 - 50:1, and the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0 - 100:1, where the value 0 in the molar ratio value indicates that this component may not be contained.

[0020] Preferably, the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0 - 12:1, and the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is: 0 - 30:1.

[0021] Preferably, the Lewis acid is selected from zinc acetate anhydrous, cerium acetate anhydrous, zirconium acetate anhydrous, zirconium acetylacetonate, aluminum trichloride, triisobutylaluminum, zinc sulfate, ferrous chloride, tin tetrachloride, ZnBr 2 、ZnI 2 、ZnCl 2 、ZnSO 4 、CuCl 2 、CuCl、Cu(O 3 SCF 3 ) 2 、CoCl 2 、CoI 2 、FeI 2 、FeCl 3 、FeCl 2 (tetrahydrofuran) 2 、TiCl 4 (tetrahydrofuran) 2 、TiCl 4 、TiCl 3, ClTi(OiPr) 3 , MnCl 2 , ScCl 3 , AlCl 3 , (C 8 H 17 )AlCl 2 ,

[0022] (C 8 H 17 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, (C 6 H 5 ) 2 AlCl, (C 6 H 5 ) 3 AlCl 2 , ReCl 5 , ZrCl 4 , NbCl 5 , VCl 3 , CrCl 2 , MoCl 5 , YCl 3 , CdCl 2 , LaCl 3 , Er(O 3 SCF 3 ) 3 , Yb(O 2 CCF 3 ) 3 , SmCl 3 , TaCl 5 , B(C 6 H 5 ) 3 , (C 6 H 5 ) 3 Sn CF 3 SO 3 , (C 6 H 5 ) 3 SnCH 3 C 6 H 5 SO 3 and (C 6 H 5 ) 3 Sn(C 6 H 5 ) 3One or more of BCN; preferably zinc acetate anhydrous, cerium acetate anhydrous, zirconium acetylacetonate, ferrous chloride, triphenylboron, and Cu(O 3 SCF 3 ) 2 One or more of.

[0023] Preferably, the sulfur-containing phosphite ligand B is the same as or different from the sulfur-containing phosphite ligand A. The sulfur-containing phosphite ligand B is a monodentate ligand represented by the following general formula III or a bidentate ligand represented by the following general formula IV::

[0024]

[0025] Wherein, X and Y are each independently selected from S and O atoms, and the rings A1, A2, A3, and A4 are the same as or different from each other, and are each independently selected from phenyl, naphthyl, furyl, and pyranyl. The rings A1, A2, A3, and A4 may or may not contain 1 to 3 substituents, and the substituents are selected from C1-C4 alkyl, C1-C4 oxyalkyl, fluorine-substituted C1-C4 alkyl, and fluorine-substituted C1-C4 oxyalkyl.

[0026] The six-membered ring represented by the dotted line in the general formula IV may or may not have the six-membered cyclohexyl structure. Preferably, the sulfur-containing phosphite ligand B is selected from the following structures:

[0027]

[0028]

[0029] According to the third aspect of the present invention, another object of the present invention is to provide a method for preparing adiponitrile, the method comprising the following steps:

[0030] 1) Mix 2-methyl-3-butenenitrile with the catalyst composition, and carry out an isomerization reaction in a reactor to generate 3-pentenenitrile, and the 3-pentenenitrile is subjected to conventional impurity removal and purification treatment;

[0031] 2) Mix 3-pentenenitrile with hydrocyanic acid and the catalyst composition, and carry out a hydrocyanation reaction to generate adiponitrile.

[0032] Preferably, in step 1), the molar ratio of 2-methyl-3-butenenitrile to the zero-valent nickel catalyst is 1 to 150:1, the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-30:1, and the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-12:1.

[0033] Preferably, in step 1), the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-25:1, and the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-8:1.

[0034] Preferably, the reaction pressure of the isomerization reaction in step 1) is 0.05 - 0.4 Mpa, the reaction temperature is 70 - 170 °C, and the heat preservation reaction is carried out for 1 - 24 hours. More preferably, the reaction temperature is 80 - 150 °C, and the heat preservation reaction is carried out for 1 - 10 hours.

[0035] Preferably, the reactor used in step 1) can be selected from an atmospheric pressure glass reactor, a thick-walled pressure-resistant glass reactor, and a stirred tank reactor.

[0036] Preferably, the molar ratio of 3-pentenenitrile to the zero-valent nickel catalyst in step 2) is 4 - 600:1, more preferably 5 - 70:1. The molar ratio of hydrocyanic acid to the zero-valent nickel catalyst is 0.001 - 400:1, more preferably 0.001 - 60:1. The molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0.2 - 100:1, more preferably 0.3 - 40:1. The molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0.2 - 12:1, more preferably 0.25 - 8:1.

[0037] Preferably, the reaction pressure of the hydrocyanation reaction in step 2) is 0.1 - 0.5 Mpa, the reaction temperature is 50 - 120 °C, more preferably 65 - 90 °C. The heat preservation reaction is carried out for 0.1 - 15 hours, more preferably 0.5 - 10 hours.

[0038] Beneficial effects

[0039] In the present invention, the coordination effect of hydrocyanic acid on the zero-valent nickel atom at the catalyst center is reduced by the sulfur-containing group in the ligand, effectively inhibiting the formation of nickel cyanide in the reaction while ensuring high selectivity of the product. At the same time, due to the action of thiol or thiophenol atoms, the isomerization rate can be accelerated. Specific embodiments

[0040] Hereinafter, the present invention will be described in detail. Before the description, it should be understood that the terms used in this specification and the appended claims should not be construed as limited to the general meaning and dictionary meaning, but should be interpreted according to the meaning and concept corresponding to the technical aspects of the present invention on the basis of the principle that allows the inventor to appropriately define the terms for the best interpretation. Therefore, the description presented here is only a preferred example for illustrative purposes and is not intended to limit the scope of the present invention. Thus, it should be understood that other equivalent methods or improved methods can be obtained without departing from the spirit and scope of the present invention.

[0041] In this text, terms such as "comprising", "including", "having", "containing" or any other similar terms are open - ended connectives and are intended to cover non - exclusive inclusions. For example, a composition or article containing plural elements is not limited to only those elements listed herein, but may also include other elements not explicitly listed but commonly inherent in the composition or article. In addition, unless otherwise clearly stated, the term "or" means an inclusive "or", rather than an exclusive "or". For example, any of the following situations satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists), A and B are both true (or exist). Further, in this text, the interpretations of the terms "comprising", "including", "having", "containing" should be regarded as having specifically disclosed and simultaneously covered closed or semi - closed connectives such as "consisting of" and "consisting essentially of".

[0042] In this text, all features or conditions defined in the form of numerical ranges or percentage ranges are only for the sake of brevity and convenience. Accordingly, the description of a numerical range or percentage range should be regarded as having covered and specifically disclosed all possible sub - ranges and individual values within the range, especially integer values. For example, the description of the range "1 to 8" should be regarded as having specifically disclosed all sub - ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., especially the sub - ranges defined by all integer values, and should be regarded as having specifically disclosed individual values such as 1, 2, 3, 4, 5, 6, 7, 8 within the range. Unless otherwise specified, the above - mentioned method of interpretation applies to all contents of the present invention, regardless of the breadth of the range.

[0043] If a quantity or other numerical or parametric value is expressed in the form of a range, a preferred range or a series of upper and lower limits, it should be understood that all ranges formed by any pair of the upper limit or preferred value of the range and the lower limit or preferred value of the range have been specifically disclosed herein, whether or not these ranges are separately disclosed. In addition, when a numerical range is mentioned in this text, unless otherwise stated, the range should include its endpoints and all integers and fractions within the range.

[0044] In this text, on the premise that the purpose of the invention can be achieved, a numerical value should be understood to have the precision of the significant digits of that numerical value. For example, the number 40.0 should be understood to cover the range from 39.50 to 40.49.

[0045] The following examples are only listed as examples of the embodiments of the present invention and do not constitute any limitation to the present invention. Those skilled in the art can understand that modifications within the scope not deviating from the essence and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, the reagents and instruments used in the following examples are all commercially available products.

[0046] Example 1

[0047] 2-Methyl-3-butenenitrile, tris(furfurylthiol) phosphite, nickel(0) tetrakis(tris(furfurylthiol) phosphite), and cerium acetate anhydrous were added to the isomerization reactor in a molar ratio of 80:4.5:1:1.5. The reaction pressure was controlled at 0.05 Mpa, the reaction temperature was 115 °C, and the reaction was carried out with heat preservation for 6 hours. After the reaction ended, the conversion rate was 90.1%, and the selectivity of the product 3-pentenenitrile was 97.9%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 0.8%.

[0048] Example 2

[0049] 2-Methyl-3-butenenitrile, triphenylthiol phosphite, nickel(0) tetrakis(triphenylthiol phosphite), and cerium acetate anhydrous were added to the isomerization reactor in a molar ratio of 80:4.5:1:1.5. The reaction pressure was controlled at 0.1 Mpa, the reaction temperature was 115 °C, and the reaction was carried out with heat preservation for 6 hours. After the reaction ended, the conversion rate was 89.9%, and the selectivity of the product 3-pentenenitrile was 95.1%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 1.0%.

[0050] Example 3

[0051] 2-Methyl-3-butenenitrile, tris(furfurylthiol) phosphite, nickel(0) tetrakis(triphenylthiol phosphite), and cerium acetate anhydrous were added to the isomerization reactor in a molar ratio of 80:4.5:1:1.5. The reaction pressure was controlled at 0.13 Mpa, the reaction temperature was 115 °C, and the reaction was carried out with heat preservation for 6 hours. After the reaction ended, the conversion rate was 89.5%, and the selectivity of the product 3-pentenenitrile was 97.1%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 0.9%.

[0052] Example 4

[0053] 2-Methyl-3-butenenitrile, tris(p-tolylthiol) phosphite, nickel(0) tetrakis(bis(p-tolyl)(phenylthiol) phosphite), and zinc acetate anhydrous were added to the isomerization reactor in a molar ratio of 80:4.5:1:1.5. The reaction pressure was controlled at 0.13 Mpa, the reaction temperature was 115 °C, and the reaction was carried out with heat preservation for 6 hours. After the reaction ended, the conversion rate was 88.5%, and the selectivity of the product 3-pentenenitrile was 97.0%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 1.0%.

[0054] Example 5

[0055] 2-Methyl-3-butenenitrile, tris(furfurylthiol) phosphite, (([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfurylthio)-bisphosphite)-(O,O'-([1,1'-biphenolyl5]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphthylthiol) bisphosphite) nickel(0), and cerium acetate anhydrous were added to an isomerization reactor in a molar ratio of 80:4.5:0.4:1.5. The reaction pressure was controlled at 0.13 Mpa and the reaction temperature was 115 °C, and the reaction was carried out with heat preservation for 6 hours. After the reaction was completed, the conversion rate was 88.1%, and the selectivity of the product 3-pentenenitrile was 97.2%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 0.7%.

[0056] Example 6

[0057] 3-Pentenenitrile, hydrocyanic acid, tris(furfurylthiol) phosphite, nickel(0) tetra((4-tert-butyl-phenolyl)-(4-tert-butyl-phenylthiolyl)-(3-isopropyl-phenolyl) phosphite), and ferrous chloride anhydrous were added to a hydrocyanation reactor in a molar ratio of 60:25:5:1:2. The reaction pressure was controlled at 0.4 Mpa and the reaction temperature was 75 °C, and the reaction was carried out with heat preservation for 5 hours. After the reaction was completed, the adiponitrile product was obtained through purification. The conversion rate was 55.1%, and the selectivity of the product adiponitrile was 75.0%. The formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 2.0%.

[0058] Example 7

[0059] 3-Pentenenitrile, hydrocyanic acid, (ethylthio)-(o-methyl-phenolyl)-(3-methyl-phenylthiolyl) phosphite, ((ethylthio)-(o-methyl-phenolyl)-(3-methyl-phenylthiolyl) phosphite)-tris(bis(furfurylthio)-(p-tolyl) phosphite) nickel(0), and ferrous chloride anhydrous were added to a hydrocyanation reactor in a molar ratio of 60:25:5:1:2. The reaction pressure was controlled at 0.3 Mpa and the reaction temperature was 75 °C, and the reaction was carried out with heat preservation for 5 hours. After the reaction was completed, the adiponitrile product was obtained through purification. The conversion rate was 55.0%, the selectivity of adiponitrile was 73.6%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 2.0%.

[0060] Example 8

[0061] 3-Pentenenitrile, hydrocyanic acid, (1-furfurylthio)-(o-methyl-phenol)-(m-methyl-benzenethiol) phosphite, bis(([1,1'-biphenyl]-2,2'-bicyclohexyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bis-phosphite) nickel(0), and anhydrous ferrous chloride were added to a hydrocyanation reactor in a molar ratio of 60:25:5:0.2:2. The reaction pressure was controlled at 0.4 Mpa, the reaction temperature was 75 °C, and the reaction was maintained for 5 hours. After the reaction, the adiponitrile product was obtained through purification. The conversion rate was 56.9%, the selectivity for adiponitrile was 74.5%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 1.7%.

[0062] Example 9

[0063] 3-Pentenenitrile, hydrocyanic acid, bis(furfurylthio)-(p-cresol) phosphite, tetrakis(bis(furfurylthio)-(p-cresol) phosphite) nickel(0), and anhydrous ferrous chloride were added to a hydrocyanation reactor in a molar ratio of 60:25:5:1:2. The reaction pressure was controlled at 0.3 Mpa, the reaction temperature was 75 °C, and the reaction was maintained for 5 hours. After the reaction, the adiponitrile product was obtained through purification. The conversion rate was 57.2%, the selectivity for adiponitrile was 75%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 2.1%.

[0064] Comparative Example 1

[0065] 2-Methyl-3-butenenitrile, tris(p-cresyl) phosphite (sulfur-free ligand), tetrakis(tris(phenylthiol) phosphite) nickel(0), and anhydrous cerium acetate were added to an isomerization reactor in a molar ratio of 80:4.5:1:1.5. The reaction pressure was controlled at 0.13 Mpa, the reaction temperature was 115 °C, and the reaction was maintained for 6 hours. After the reaction, the conversion rate was 88.5%, the selectivity for 3-pentenenitrile was 97.1%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 1.7%.

[0066] Comparative Example 2

[0067] 3-Pentenenitrile, hydrocyanic acid, tris(p-cresyl) phosphite, bis([2-(2-diphenoxyphosphino)phenol]biphenol phosphite) nickel(0), and anhydrous ferrous chloride were added to a hydrocyanation reactor in a molar ratio of 60:25:5:0.2:2. The reaction pressure was controlled at 0.4 Mpa, the reaction temperature was 75 °C, and the reaction was maintained for 5 hours. After the reaction, the adiponitrile product was obtained through purification. The conversion rate was 51.4%, the selectivity for adiponitrile was 69.3%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 3.9%.

[0068] Comparative Example 3

[0069] 3-Pentenenitrile, hydrocyanic acid, tris(p-tolyl) phosphite, nickel(0) bis([2-(2-diphenoxyphosphino)phenoxy]biphenyl phosphite), and copper trifluoromethanesulfonate were added to a hydrocyanation reactor in a molar ratio of 60:25:5:0.2:2. The reaction pressure was controlled at 0.4 Mpa, and the reaction temperature was 75 °C. The reaction was carried out for 5 hours with heat preservation. After the reaction, the adiponitrile product was obtained through purification. The conversion rate was 57.8%, the selectivity was 68.7%, and the formation rate of nickel cyanide in the system measured by ultraviolet absorption at 320 nm was 4.1%.

[0070] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of changes or substitutions, which should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A sulfur-containing phosphite ligand zero-valent nickel catalyst for preparing adiponitrile, wherein the catalyst is prepared from zero-valent nickel and a monodentate or bidentate sulfur-containing phosphite ligand A, wherein the molar ratio of zero-valent nickel to the monodentate sulfur-containing phosphite ligand A is 1:4, the molar ratio of zero-valent nickel to the bidentate sulfur-containing phosphite ligand A is 1:2, and the molar ratio of zero-valent nickel to the sulfur-containing phosphite ligand is 0.2 to 50:1, preferably 3 to 40:1; The sulfur-containing phosphite ligand A is a monodentate ligand represented by the following general formula I or a bidentate ligand represented by the following general formula II: in, X and Y are each independently selected from S and O atoms; rings A1, A2, A3 and A4 are the same or different and are each independently selected from phenyl, naphthyl, furyl, pyranyl; and the rings A1, A2, A3 and A4 may or may not contain 1 to 3 substituents selected from C1-C4 alkyl, C1-C4 oxyalkyl, fluorine-substituted C1-C4 alkyl, fluorine-substituted C1-C4 oxyalkyl; The six-membered ring represented by the dotted line in the general formula II means that the six-membered cyclohexyl structure may or may not exist.

2. The sulfur-containing phosphite ligand zero-valent nickel catalyst according to claim 1, characterized in that: The sulfur-containing phosphite ligand is selected from the following structures:

3. The sulfur-containing phosphite ligand zero-valent nickel catalyst according to claim 1, characterized in that: The sulfur-containing phosphite ligand zero-valent nickel catalyst is selected from the following compounds: Tetrakis(tris(furfurylthiol)phosphite)nickel(0),tetrakis(tristhiophenolphosphite)nickel(0),tetrakis(phenol(p-tolylthiophenol)(m-tolylthiophenol)phosphite)nickel(0),tetrakis(di-p-tolyl(thiophenol)phosphite)nickel(0),tetrakis(o-tolyl(thiophenol)(m-tolylthiophenol)phosphite)nickel(0),tetrakis((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol)phosphite)nickel(0),tetrakis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol)phosphite)nickel(0),tetrakis((1-furfurylthio)-(o-methyl-phenol)-(m-methyl -benzenethiophenol) phosphite) nickel (0), tetrakis(bis(furfurylthio)-(p-cresol) phosphite) nickel (0), bis(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis(([1,1'-biphenyl]-2,2'-biphenylcyclohexane) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis(1,1`-biphenol-[2-[2-bis(4-vinyl-benzenethiophenol) phosphite]) nickel (0), bis(O,O'-([1,1'-biphenol]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphtholthio)bisphosphite)nickel(0),bis(tris(furfuryl mercaptan) phosphite)-bis(tris(benzenethiophenol) phosphite)nickel(0),(tris(furfuryl mercaptan) phosphite)-tris(tris(benzenethiophenol) phosphite)nickel(0),bis(tris(furfuryl mercaptan) phosphite)-bis(phenolic(p-tolylthiophenol)(m-tolylthiophenol) phosphite)nickel(0),(tris(furfuryl mercaptan) phosphite)-tris(phenolic(p-tolylthiophenol)(m-tolylthiophenol) phosphite)nickel(0),bis(tris(furfuryl mercaptan) phosphite)-bis(di-p-tolyl(benzenethiophenol) phosphite)nickel(0),(tris(furfuryl mercaptan) phosphite)-tris(di-p-tolyl(benzenethiophenol) phosphite)nickel(0),bis(phosphite Tris(furfuryl mercaptan) ester)-bis(o-tolyl(thiophenol) (m-tolylthiophenol) phosphite) nickel (0), (tris(furfuryl mercaptan) ester)-tris(o-tolyl(thiophenol) (m-tolylthiophenol) phosphite) nickel (0), bis(tris(furfuryl mercaptan) ester)-bis((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite) nickel (0), (tris(furfuryl mercaptan) ester)-tris((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite) nickel (0), bis(tris(furfuryl mercaptan) ester)-bis((ethylthio)-(o-methyl-phenol)-(3-methyl- (Tris(furfurylthiol) phosphite) nickel (0), (tris(ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite) nickel (0), bis(tris(furfurylthiol) phosphite)-bis((1-furfurylthiol)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), (tris(furfurylthiol) phosphite)-tris((1-furfurylthiol)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), bis(thiophenol phosphite)-bis(phenol (p-toluenethiophenol) (m-toluenethiophenol) ester) nickel (0), (tris(thiophenol phosphite)-tris(phenol (p-toluenethiophenol)) (m-cresol thiophenol) ester) nickel (0), bis(triphenylthiophenol phosphite)-bis(di-p-tolyl(thiophenol) phosphite) nickel (0), (triphenylthiophenol phosphite)-tris(di-p-tolyl(thiophenol) phosphite) nickel (0), bis(triphenylthiophenol phosphite)-bis(bis(furfurylthio)-(p-cresol) phosphite) nickel (0), (triphenylthiophenol phosphite)-tris(bis(furfurylthio)-(p-cresol) phosphite) nickel (0), bis(triphenylthiophenol phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis(triphenylthiophenol phosphite)-(([1,1'-biphenyl]-2,2'-biphenylcyclohexane) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel(0), bis(triphenylthiophenol phosphite)-(1,1`-biphenyl-[2-[2-bis(4-vinyl-thiophenol)phosphite]) nickel(0), bis(triphenylthiophenol phosphite)-(O,O'-([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphthylthiophenol)bisphosphite)nickel(0),bis(phenol(p-tolylthiophenol)(m-tolylthiophenol) ester)-bis(p-tolyl(thiophenol) phosphite)nickel(0),(phenol(p-tolylthiophenol)(m-tolylthiophenol) ester)-tris(p-tolyl(thiophenol) phosphite)nickel(0),bis(phenol(p-tolylthiophenol)(m-tolylthiophenol) ester)-bis(o-tolyl(thiophenol)(m-tolylthiophenol) phosphite)nickel(0),(phenol(p-tolylthiophenol)(m-tolylthiophenol) ester)-tris(o-tolyl(thiophenol)(m-tolylthiophenol) phosphite)nickel(0),bis(p-tolyl(thiophenol) phosphite)-bis(phosphite) o-Tolyl(thiophenol)(m-tolylthiophenol) ester)nickel(0), (di-p-tolyl(thiophenol) phosphite)-tris(o-tolyl(thiophenol)(m-tolylthiophenol) phosphite)nickel(0), bis(di-p-tolyl(thiophenol) phosphite)-bis((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)nickel(0), (di-p-tolyl(thiophenol) phosphite)-tris((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)nickel(0), bis(di-p-tolyl(thiophenol) phosphite)-bis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phenol) phosphite) nickel (0), (di-p-tolyl (thiophenol) phosphite)-tris ((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite) nickel (0), bis (di-p-tolyl (thiophenol) phosphite)-bis ​​((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), (di-p-tolyl (thiophenol) phosphite)-tris ((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), bis (o-tolyl (thiophenol) phosphite) (m-tolylthiophenol) phosphite)-bis ​​((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isobutyl-thiophenol) Propyl-phenol) phosphite) nickel (0), (o-tolyl (thiophenol) (m-tolyl thiophenol) phosphite)-tris ((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite) nickel (0), bis (o-tolyl (thiophenol) (m-tolyl thiophenol) phosphite)-bis ​​(bis (furfurylthio)-(p-tolyl) phosphite) nickel (0), (o-tolyl (thiophenol) (m-tolyl thiophenol) phosphite)-tris (bis (furfurylthio)-(p-tolyl) phosphite) nickel (0), bis (o-tolyl (thiophenol) (m-tolyl thiophenol) phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite)nickel(0), bis((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)-bis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)nickel(0), ((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)-tris((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)nickel(0), bis((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)-bis((1-furfurylthio)-( o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), ((4-tert-butyl-phenol)-(4-tert-butyl-thiophenol)-(3-isopropyl-phenol) phosphite)-tris((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), bis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)-bis((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite) nickel (0), ((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)-tris((1-furfurylthio)-(o-methyl- phenol)-(m-methyl-thiophenol) phosphite) nickel (0), bis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)-bis(bis(furfurylthio)-(p-cresol) phosphite) nickel (0), ((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)-tris(bis(furfurylthio)-(p-cresol) phosphite) nickel (0), bis((ethylthio)-(o-methyl-phenol)-(3-methyl-thiophenol) phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis((1-furfurylthio) bis((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis((1-furfurylthio)-(o-methyl-phenol)-(m-methyl-thiophenol) phosphite)-(([1,1'-biphenyl]-2,2'-biphenyl and cyclohexane) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite) nickel (0), bis(bis(furfurylthio)-(p-cresol) phosphite)-(1,1`-biphenyl-[2-[2-bis(4-vinyl-thiophenol) phosphite]) nickel (0), (([1,1'-Biphenyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-furfuryl-thio)-bisphosphite)-(O,O'-([1,1'-biphenolyl]-2,2'-biphenyl) S,S,S',S'-tetrakis(1-naphtholthio)bisphosphite) nickel (0). , 4. The method for preparing a sulfur-containing phosphite ligand zero-valent nickel catalyst according to claim 1, wherein the method is carried out as follows: under nitrogen protection at room temperature, elemental nickel powder is mixed with sulfur-containing phosphite ligand A, the temperature is raised to 100° C., and the mixture is stirred at normal pressure for 4 hours to obtain the catalyst.

5. The preparation method according to claim 4, characterized in that: The particle size of the elemental nickel powder is 2-50 nm, preferably 3-30 nm.

6. A catalyst composition comprising the sulfur-containing phosphite ligand zero-valent nickel catalyst according to claim 1, wherein the catalyst composition comprises a Lewis acid, the sulfur-containing phosphite ligand zero-valent nickel catalyst and a sulfur-containing phosphite ligand B, wherein the content ratio of the Lewis acid, the zero-valent nickel catalyst and the sulfur-containing phosphite ligand B is: the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-50:1, and the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-100:1, wherein the value 0 in the molar ratio indicates that the component may not be present.

7. The catalyst composition according to claim 6, characterized in that Preferably, the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-12:1, and the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-30:1; Preferably, the Lewis acid is selected from anhydrous zinc acetate, anhydrous cerium acetate, anhydrous zirconium acetate, zirconium acetylacetonate, aluminum trichloride, triisobutylaluminum, zinc sulfate, ferrous chloride, tin tetrachloride, ZnBr2, ZnI2, ZnCl2, ZnSO4, CuCl2, CuCl, Cu(O3SCF3)2, CoCl2, CoI2, FeI2, FeCl3, FeCl2(tetrahydrofuran)2, TiCl4(tetrahydrofuran)2, TiCl4, TiCl3, ClTi(OiPr)3, MnCl2, ScCl3, AlCl3, (C8H 17 )AlCl2, (C8H 17 )2AlCl, (iso-C4H9)2AlCl, (C6H5)2AlCl, (C6H5)3AlCl2, ReCl5, ZrCl4, NbCl5, VCl3, CrCl2, MoCl5, YCl3, CdCl2, LaCl3, Er(O3SCF3)3, Yb(O2CCF3)3, SmCl3, TaCl5, B(C6H5)3, (C6H5)3SnCF3SO3, (C6H5)3SnCH3C6H5SO3 and (C6H5)3Sn(C6H5)3BCN; preferably one or more of anhydrous zinc acetate, anhydrous cerium acetate, zirconium acetylacetonate, ferrous chloride, triphenylboron and Cu(O3SCF3)2; Preferably, the sulfur-containing phosphite ligand B is the same as or different from the sulfur-containing phosphite ligand A, and the sulfur-containing phosphite ligand B is a monodentate ligand represented by the following general formula III or a bidentate ligand represented by the following general formula IV: wherein X and Y are each independently selected from S and O atoms; rings A1, A2, A3 and A4 are the same or different and are each independently selected from phenyl, naphthyl, furyl, pyranyl; and the rings A1, A2, A3 and A4 may or may not contain 1 to 3 substituents selected from C1-C4 alkyl, C1-C4 oxyalkyl, fluorine-substituted C1-C4 alkyl, fluorine-substituted C1-C4 oxyalkyl; The six-membered ring represented by the dotted line in the general formula IV may or may not contain the six-membered cyclohexyl structure; Preferably, the sulfur-containing phosphite ligand B is selected from the following structures:

8. A method for preparing adiponitrile, comprising the steps of: 1) 2-methyl-3-butenenitrile and The catalyst composition according to claim 6 is mixed and subjected to an isomerization reaction in a reactor to produce 3-pentenenitrile, wherein the 3-pentenenitrile is subjected to conventional impurity removal and purification treatment; 2) 3-pentenenitrile is mixed with hydrocyanic acid and the catalyst composition to undergo a hydrocyanation reaction to generate hexamethylenedinitrile.

9. The preparation method according to claim 8, characterized in that: Preferably, in step 1), the molar ratio of 2-methyl-3-butenenitrile to the zero-valent nickel catalyst is 1-150:1, the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-30:1, and the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-12:1; Preferably, in step 1), the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0-25:1, and the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0-8:1; Preferably, the reaction pressure of the isomerization reaction in step 1) is 0.05-0.4Mpa, the reaction temperature is 70-170°C, and the heat preservation reaction is carried out for 1-24 hours; more preferably, the reaction temperature is 80-150°C, and the heat preservation reaction is carried out for 1-10 hours; Preferably, the reactor used in step 1) is selected from a normal pressure glass reactor, a thick-walled pressure-resistant glass reactor, and a stirred tank reactor; Preferably, in step 2), the molar ratio of 3-pentenenitrile to the zero-valent nickel catalyst is 4-600:1, more preferably 5-70:1; the molar ratio of hydrocyanic acid to the zero-valent nickel catalyst is 0.001-400:1, more preferably 0.001-60:1; the molar ratio of the sulfur-containing phosphite ligand B to the zero-valent nickel catalyst is 0.2-100:1, more preferably 0.3-40:1; the molar ratio of the Lewis acid to the zero-valent nickel catalyst is 0.2-12:1, more preferably 0.25-8:1; Preferably, the reaction pressure of the hydrocyanation reaction in step 2) is 0.1-0.5 MPa, the reaction temperature is 50-120° C., more preferably 65-90° C.; the heat preservation reaction is 0.1-15 hours, more preferably 0.5-10 hours.

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