Hydrocyanation method

Abstract

Provided in the present invention is a hydrocyanation method. The hydrocyanation method is carried out in a reaction system containing an aromatic amine under the action of a nickel-monodentate phosphite ligand catalyst. The structure of the aromatic amine is as shown in formula I, wherein X1-X3 groups and Y1-Y3 groups separately comprise any one of hydrogen, an alkyl group, an alkoxy group, an alkylamino group, a hydroxyl group and an amino group. The hydrocyanation method of the present invention comprises the nickel-monodentate phosphite ligand catalyst and the aromatic amine having a specific structure; therefore, the time of the hydrocyanation method can be catalytically shortened, the accumulation of a ligand hydrolysate can be substantially reduced or eliminated, and the loss of the catalyst during the reaction can also be reduced. In the hydrocyanation method of the present invention, the reaction efficiency is high, the performance of the catalyst is stable, and the conversion rate of the raw materials and the selectivity of the product are higher; therefore, the hydrocyanation method can be used in a preparation process for large-scale preparation of adiponitrile from butadiene by means of a direct hydrocyanation method.

Description

Hydrocyanation process TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical synthesis, in particular to a hydrocyanation reaction method. BACKGROUND

[0002] Adiponitrile (ADN) is an important raw material intermediate for the production of nylon 66 and is an important link in the nylon and special polyurethane industry chain. Among the various production methods of adiponitrile, the direct hydrocyanation of butadiene method is the mainstream process and has the highest production capacity share in the world.

[0003] The process route for the production of adiponitrile by the direct hydrocyanation of butadiene is as follows:

[0004] The specific reaction steps include: one-step hydrocyanation, butadiene is added to hydrocyanic acid (HCN) under the action of a nickel catalyst to generate 2-methyl-3-butenenitrile (2M3BN) and 3-pentenenitrile (3PN); 2M3BN isomerization, 2M3BN is converted into 3PN by isomerization under the action of a nickel catalyst; two-step hydrocyanation, 3PN is isomerized into 4-pentenenitrile (4PN), which is then added to HCN to generate ADN and by-product 2-methylglutaronitrile (MGN), which requires a nickel catalyst and a Lewis acid additive and has a high requirement for catalyst activity, and is the key step in the entire reaction.

[0005] The direct hydrocyanation of butadiene involves a two-step hydrocyanation process. Taking the one-step hydrocyanation reaction as an example, the specific hydrocyanation reaction process is as follows:

[0006] Among them, the zero-valent nickel-phosphorus catalyst [NiL4] (L is a ligand) removes one molecule of ligand to form [NiL3], which then combines with HCN to generate [HNiL3CN]; it continues to lose one molecule of ligand to generate [HNiL2CN], which then combines with butadiene to generate an intermediate [C4H6-HNiL2CN]. The intermediate can react along two paths to generate 3PN and 2M3BN, respectively, and regenerate [NiL3] to continue to participate in the catalytic cycle reaction.

[0007] However, in actual production, the hydrocyanation reaction faces many difficulties: first, the presence of water in the reaction system may cause the hydrolysis of the phosphite ligand of the nickel catalyst, producing acidic hydrolysis products, further accelerating the hydrolysis of the ligand, and gradually causing the deactivation of the nickel-monodentate phosphite ligand catalyst; second, when the HCN concentration in the reaction system is high, it will attack the active nickel ([NiL3] and [NiL2]) of the hydrocyanation reaction to generate nickel cyanide (Ni(CN)2) precipitate, causing catalyst deactivation; third, the hydrocyanation reaction (especially the two-step hydrocyanation reaction) has a slow rate and a long residence time, resulting in a high amount of catalyst deactivation. Therefore, it is a technical problem to be solved to develop a hydrocyanation reaction process with high reaction efficiency, high stability, and effective avoidance of catalyst deactivation. SUMMARY

[0008] In view of the deficiencies in the prior art, the present application discloses a hydrocyanation reaction method which can not only shorten the reaction time, but also significantly reduce or eliminate the accumulation of ligand hydrolysis products, and reduce the amount of nickel cyanide precipitate and stabilize the catalyst.

[0009] To achieve the above technical purposes, on the one hand, the present application proposes a hydrocyanation reaction method which is carried out in a reaction system containing aromatic amines under the action of a nickel-monodentate phosphite ligand catalyst, and the structure of the aromatic amines is:

[0010] wherein, X 1 -X 3 group and Y 1 -Y 3 group respectively includes any one of hydrogen, alkyl, alkoxy, alkylamine, hydroxyl, amino.

[0011] As mentioned earlier, in the process of the hydrocyanation reaction method, the active nickel intermediate (such as [NiL3] and [NiL2]) is in a naked state due to the partial loss of the ligand, and is easily attacked by hydrocyanic acid, water and other polar molecules to generate nickel cyanide and hydrolysis products, causing catalyst loss. In the above technical solution, the aromatic amines containing the specific structure are a kind of compounds that have a strong complexation with nickel, which can coordinate with the active nickel intermediate in time in the hydrogenation reaction, thereby protecting the active nickel intermediate and reducing catalyst loss; at the same time, the aromatic amine compounds can form a hydrophobic environment around the active nickel intermediate, further reducing the possibility of catalyst hydrolysis and inhibiting the generation of hydrolysis products; and the improvement of the stability of the active nickel intermediate also effectively improves the overall hydrogenation reaction rate.

[0012] The effect of the hydrocyanation reaction method including the nickel-monodentate phosphite ligand catalyst and the aromatic amines is shown in the embodiments of the present application.

[0013] In further examples of the present application, the structure of X 1 -X 3 group and Y 1 -Y 3 group is optimized. Optionally, the structure of the alkyl group is -R, the structure of the alkoxy group is the structure of the alkylamine group is wherein the R group comprises any one of methyl, ethyl, isopropyl, tert-butyl.

[0014] In some optional examples of the present application, the aromatic amine can be selected from any one of Table 1.

[0015] Table 1

[0016] In further examples of the present application, the structure of the ligand comprised by the nickel-monodentate phosphite ligand catalyst is optimized. Optionally, the structure of the monodentate phosphite ligand is:

[0017] wherein R 1 , R 2 and R 3 group respectively comprises any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy.

[0018] In further examples of the present application, the ratio of the nickel-monodentate phosphite ligand catalyst to the aromatic amine in the hydrocyanation reaction method is explored and optimized. Optionally, the mass ratio of the nickel-monodentate phosphite ligand catalyst to the aromatic amine is 1:(0.05-0.8), further optionally 1:(0.1-0.6), which is conducive to effective coordination of the aromatic amine with the active nickel intermediate during the hydrocyanation reaction method, and improves the stability of the catalyst.

[0019] In further examples of the present application, the hydrocyanation reaction method is a hydrocyanation reaction method for preparing adiponitrile.

[0020] Further, the hydrocyanation reaction method comprises a one-step hydrocyanation reaction method for preparing pentenenitrile using butadiene as a raw material.

[0021] Still further, the reaction temperature of the one-step hydrocyanation reaction method is 40-110℃, preferably 50-95℃, which is a relatively mild temperature range, easy to control, and has strong process operability.

[0022] It should be noted that the pressure of the one-step hydrocyanation reaction method in the present application is not limited, and can be optionally 1-5 bar.

[0023] Further, the reaction time of the one-step hydrocyanation reaction method is 1-5h, and through analysis of the examples and comparative examples, it can be seen that the technical scheme of the present application can significantly improve the reaction rate, shorten the reaction time, and improve the overall process production efficiency.

[0024] Further, when the hydrocyanation reaction method is a one-step hydrocyanation reaction method, X 1 , X 3 , Y 1 , Y 3 in the structure of the aromatic amine are respectively selected from hydrogen or alkyl, X 2 , Y 2 are respectively selected from alkyl or alkoxy.

[0025] Further, the mass ratio of the nickel-monodentate phosphite ligand catalyst to butadiene in the one-step hydrocyanation reaction method is (0.5-3):1000, preferably (0.75-2.5):1000, and the present application can significantly improve the stability of the catalyst in the one-step hydrocyanation reaction method process by adding a small amount of a specific aromatic amine substance, and improve the reaction rate; after the reaction is completed, the aromatic amine can be separated and high-purity pentenenitrile product can be obtained through a separation and purification process such as extraction, rectification or extraction rectification.

[0026] Further, the hydrocyanation reaction method further comprises a two-step hydrocyanation reaction method for preparing adiponitrile from pentenenitrile as a raw material.

[0027] Further, the reaction temperature of the two-step hydrocyanation reaction method is 35-90℃, preferably 40-80℃, which is a relatively mild temperature range, easy to control, and the overall process has strong operability.

[0028] It should be noted that the pressure of the two-step hydrocyanation reaction method in the present application is not limited, and can be selected as 1-5bar.

[0029] Further, the reaction time of the one-step hydrocyanation reaction method is 1-10h, and through analysis of the examples and comparative examples, it can be seen that the technical scheme of the present application can significantly improve the reaction rate, shorten the reaction time, and improve the overall process production efficiency.

[0030] Further, in the two-step hydrocyanation reaction method, X 1 , X 3 , Y 1 , Y 3 in the structure of the aromatic amine are respectively selected from any one of hydrogen, alkyl or alkoxy, X 2 , Y 2 are respectively selected from alkoxy or alkylamine.

[0031] Further, the mass ratio of the nickel-monodentate phosphite ligand catalyst to the pentenenitrile in the two-step hydrocyanation reaction method is (0.5-3):1000, preferably (0.75-2.5):1000, and the stability of the catalyst in the one-step hydrocyanation reaction method can be significantly improved and the reaction rate can be increased by adding a trace amount of the specific aromatic amine substance; the aromatic amine can be separated and the high-purity adiponitrile product can be obtained through a separation and purification process such as extraction, rectification or extraction rectification after the reaction is completed.

[0032] Further, the two-step hydrocyanation reaction method is carried out in the presence of a cocatalyst, and the addition of the cocatalyst is beneficial to the synergistic improvement of the stability of the catalyst and the reaction rate; the cocatalyst includes one of zinc chloride, aluminum chloride, iron chloride, titanium tetrachloride and triphenylboron.

[0033] Further, the mass ratio of the nickel-monodentate phosphite ligand catalyst to the cocatalyst is (0.2-0.8):1, preferably (0.3-0.7):1, and the reaction rate can be synergistically optimized by optimizing the amount of the catalyst and the cocatalyst and the aromatic amine, the occurrence of side reactions can be reduced, and the reaction efficiency can be improved.

[0034] Compared with the prior art, the hydrocyanation reaction method of the present application includes a nickel-monodentate phosphite ligand catalyst and a specific structure of aromatic amine, which can not only catalyze the shortening of the time of the hydrocyanation reaction method, but also significantly reduce or eliminate the accumulation of ligand hydrolysis products and reduce the catalyst loss in the reaction. The hydrocyanation reaction method of the present application has high reaction efficiency, stable catalyst performance, high raw material conversion rate and high product selectivity, and can be used for the preparation process of adiponitrile prepared by directly hydrocyanating a large amount of butadiene. DETAILED DESCRIPTION

[0035] In order to facilitate the understanding of the present application, the present application will be described more fully below, and the preferred embodiments of the present application are given. It should be understood that these embodiments are only used for more detailed description, and should not be understood as limiting the present application in any form, i.e. not intended to limit the protection scope of the present application.

[0036] Unless otherwise defined, the technical terms used in the following examples have the same meaning as generally understood by those skilled in the art to which the present application belongs. The test reagents used in the following examples, unless otherwise specified, are conventional biochemical reagents; the experimental methods, unless otherwise specified, are conventional methods.

[0037] It should be noted that in the nickel-monodentate phosphite ligand catalyst, the coordination number of nickel is 4 or 6, generally 4; the present application aims to solve the technical problem of instability of the catalyst in the hydrocyanation reaction method in the prior art, so the number ratio relationship between each nickel and monodentate phosphite ligand in the example part of the present application will not be described again.

[0038] In the embodiment of the present application, the conversion rate of the hydrocyanation reaction method is calculated using the peak area percentage of gas chromatography, for example: the conversion rate of one-step hydrocyanation reaction method = (2M3BN + 3PN) / (2M3BN + 3PN + butadiene) x 100%, 3PN selectivity = 3PN / (2M3BN + 3PN) x 100%; the conversion rate of two-step hydrocyanation reaction method = (ADN + MGN) / (ADN + MGN + 3PN) x 100%, ADN selectivity = ADN / (ADN + MGN) x 100%; regarding the content of the catalyst in the reaction system, the Ni content in the supernatant can be used to characterize.

[0039] Example 1

[0040] A one-step hydrocyanation reaction method, which uses butadiene as raw material to prepare pentenenitrile in a reaction system containing aromatic amine under the action of a nickel-monodentate phosphite ligand catalyst, specifically:

[0041] (1) Material preparation: the catalyst used in this embodiment is a nickel-tris(2-ethylphenyl) phosphite catalyst, and its preparation method can be selected to include the following steps: ① synthesis of tris(2-ethylphenyl) phosphite ligand: under a nitrogen atmosphere, 2-ethylphenol (73.2 g, 0.6 mol) is added to a 250 mL round-bottom flask, and phosphorus trichloride (27.4 g, 0.2 mol) is added dropwise at room temperature. During the reaction, a large amount of HCl by-product is generated, which is absorbed by alkali solution; after the dropwise addition is completed, the reaction is stirred at room temperature for 1 h, and then slowly heated to 150°C until no HCl is generated; then the reaction product is purified by high vacuum distillation to obtain a product with a purity of more than 99%, with a yield of 98%; the product is characterized by 31P NMR and mass spectrometry, which confirms that the target structure is tris(2-ethylphenyl) phosphite; ② synthesis of nickel-tris(2-ethylphenyl) phosphite catalyst: tris(2-ethylphenyl) phosphite, nickel powder and 3-pentenenitrile are added to a round-bottom flask equipped with mechanical stirring, and the reaction is carried out under a nitrogen atmosphere at about 110°C for about 24 h under continuous stirring; after the reaction is completed, the unreacted nickel powder in the reaction product is removed by filtration under a nitrogen atmosphere to obtain the nickel-tris(2-ethylphenyl) phosphite catalyst containing 79% tris(2-ethylphenyl) phosphite, 19% pentenenitrile and 2% nickel.

[0042] It should be noted that the nickel powder mentioned in the embodiments of the present application is commercially available. In addition, the preparation process of the ligand and the preparation process of the nickel-monodentate phosphite ligand catalyst in the embodiments of the present application are only relatively optimal demonstrations, and those skilled in the art can select other ways to prepare the ligand or the nickel-monodentate phosphite ligand catalyst through non-creative labor, and in some working conditions, the ligand or the nickel-monodentate phosphite ligand catalyst of a suitable type can be directly purchased based on the technical solutions of the present application, which does not limit the protection scope of the present application.

[0043] (2) One-step hydrocyanation method: the nickel-tris(2-ethylphenyl) phosphite catalyst (1.5 mmol), aromatic amine A1 (0.9 mmol) and butadiene (2.0 mol) were placed in a stainless steel reactor, and after being replaced with nitrogen, the reaction system was heated to 50°C; then the hydrocyanic acid (1.9 mol) was slowly added into the reactor by pump, and the feeding time lasted for 2 h; after the feeding was completed, the reaction was continued at 50°C; as the reaction proceeded, samples were taken from the reactor at different times and analyzed, and the results are shown in Table 2.

[0044] Table 2

[0045] Example 2

[0046] A one-step hydrocyanation method, which uses butadiene as a raw material to prepare pentenenitrile in a reaction system containing an aromatic amine under the action of a nickel-monodentate phosphite ligand catalyst, specifically:

[0047] (1) Material preparation: the catalyst used in this embodiment is a nickel-tris(2-isopropyl-4-methoxyphenyl) phosphite catalyst, which is prepared by coordinating and complexing commercially available tris(2-isopropyl-4-methoxyphenyl) phosphite with nickel powder: tris(2-isopropyl-4-methoxyphenyl) phosphite, nickel powder and 3-pentenenitrile are added to a round-bottom flask equipped with mechanical stirring, and continuously stirred at about 120°C for about 24 h under a nitrogen atmosphere; after the reaction is completed, the unreacted nickel powder in the reaction material is removed by filtration under a nitrogen atmosphere, and the nickel-tris(2-isopropyl-4-methoxyphenyl) phosphite catalyst containing 81% tris(2-isopropyl-4-methoxyphenyl) phosphite, 17% pentenenitrile and 2% nickel is obtained.

[0048] (2) One-step hydrocyanation reaction method: nickel-tris(2-isopropyl-4- methoxyphenyl) phosphite catalyst (2.5 mmol), aromatic amine A3 (0.25 mmol) and butadiene (1.0 mol) were placed in a stainless steel reactor, after nitrogen replacement, the reaction system was heated to 95°C; then the hydrocyanic acid (0.95 mol) was slowly added into the reactor by pump, the feeding time lasted for 2h; after the feeding was completed, the reaction was continued at 95°C; as the reaction proceeded, samples were taken from the reactor at different times and analyzed, and the results are shown in Table 3.

[0049] Table 3

[0050] Example 3

[0051] Based on the one-step hydrocyanation reaction method shown in Example 1, the catalyst, raw materials and control parameters used in this example are the same as those in Example 1, the difference is that the aromatic amine added in the one-step hydrocyanation reaction method in this example is aromatic amine A9; by sampling the reaction system at different times for analysis, the reaction results are shown in Table 4.

[0052] Table 4

[0053] Combining Table 2 and Table 4, the effect of one-step hydrocyanation reaction method containing A1 aromatic amine is relatively better than that of hydrocyanation reaction method using A9 aromatic amine, in the actual reaction process, suitable aromatic amine can be selected according to the specific working conditions for catalyzing one-step hydrocyanation reaction method.

[0054] Example 4

[0055] A two-step hydrocyanation reaction method, which uses pentenenitrile as raw material, and under the action of nickel-monodentate phosphite ligand catalyst in a reaction system containing aromatic amine to prepare adiponitrile, specifically:

[0056] In this example, the nickel-tris(2-ethylphenyl) phosphite catalyst shown in Example 1 is used, the catalyst (5 mmol), anhydrous zinc chloride (16 mmol), aromatic amine A9 (0.5 mmol) and 3PN (2.0 mol) are placed in a stainless steel reactor, after nitrogen replacement, the reaction system is heated to 40°C; then the hydrocyanic acid (1.9 mol) is slowly added into the reactor by pump, the feeding time lasts for 2h; after the feeding is completed, the reaction is continued at 40°C; as the reaction proceeds, samples are taken from the reactor at different times and analyzed, and the results are shown in Table 5.

[0057] Table 5

[0058] Example 5

[0059] A two-step hydrocyanation reaction method, which is to prepare adiponitrile by using pentenenitrile as raw material, in the presence of aromatic amine in the reaction system, under the action of nickel-monodentate phosphite ligand catalyst, specifically:

[0060] In this example, the nickel-tris(2-isopropyl-4-methoxyphenyl) phosphite catalyst shown in Example 2 was used. The catalyst (0.6 mmol), anhydrous titanium tetrachloride (0.9 mmol), aromatic amine A11 (0.36 mmol) and 3PN (0.8 mol) were placed in a stainless steel reactor, and after being replaced with nitrogen, the reaction system was heated to 80°C. Then, hydrocyanic acid (0.76 mol) was slowly added to the reactor by pump, and the feeding time lasted for 2 h. After the feeding was completed, the reaction was continued at 80°C. As the reaction proceeded, samples were taken from the reactor at different times and analyzed, and the results are shown in Table 6.

[0061] Table 6

[0062] Example 6

[0063] Based on the two-step hydrocyanation reaction method shown in Example 4, the catalyst, raw materials and control parameters used in this example are the same as those in Example 4, except that the aromatic amine added in the two-step hydrocyanation reaction method in this example is aromatic amine A1. By sampling the reaction system at different times for analysis, the reaction results are shown in Table 7.

[0064] Table 7

[0065] Combining Tables 5 and 7, the effect of the two-step hydrocyanation reaction method containing A9 aromatic amine is relatively better than that of the hydrocyanation reaction method containing A1 aromatic amine. In actual reaction process, appropriate aromatic amine can be selected according to specific working conditions for catalyzing two-step hydrocyanation reaction method.

[0066] Comparative Example 1

[0067] Based on the one-step hydrocyanation reaction method shown in Example 1, the catalyst, raw materials and control parameters used in this comparative example are the same as those in Example 1, except that no aromatic amine is added in the one-step hydrocyanation reaction method in this comparative example. By sampling the reaction system at different times for analysis, the reaction results are shown in Table 8.

[0068] Table 8

[0069] Based on Table 2 and Table 8, it can be verified that the raw material conversion rate of the reaction system of Example 1 in which the aromatic amine A1 is added in the one-step hydrocyanation reaction method system is higher, and the Ni content in the clear solution is also higher. When the reaction time reaches 5h, the Ni content in the clear solution of the comparative example 1 reaction system without using the aromatic amine is reduced to 68% of the original, and the butadiene conversion rate is 62.75%, while the Ni content in the clear solution of the reaction system of Example 1 remains 97% of the original, and the butadiene conversion rate reaches 85.55%, which verifies that the nickel-monodentate phosphite ligand catalyst and the specific structure aromatic amine contained in the present application can significantly improve the reaction rate of the one-step hydrocyanation reaction method, and reduce the loss of the catalyst.

[0070] Comparative Example 2

[0071] Based on the two-step hydrocyanation reaction method shown in Example 4, the catalyst, raw material and control parameters used in the present comparative example are the same as those in Example 4, the difference is that no aromatic amine is added in the two-step hydrocyanation reaction method process of the present comparative example; by sampling the reaction system at different times for analysis, the reaction results are shown in Table 9.

[0072] Table 9

[0073] It can be verified by comparing Table 5 and Table 9 that after the same reaction time, the 3PN conversion rate of the reaction system of Example 3 in which the aromatic amine A9 is added in the two-step hydrocyanation reaction method system is higher, and the Ni content in the clear solution is also higher. When the reaction time reaches 10h, the Ni content in the clear solution of the comparative example 3 reaction system without using the aromatic amine is reduced to 66% of the original, and the butadiene conversion rate is 62.25%, while the Ni content in the clear solution of the reaction system of Example 3 remains 95% of the original, and the butadiene conversion rate reaches 73.35%, which verifies that the nickel-monodentate phosphite ligand catalyst and the specific structure aromatic amine contained in the present application can significantly improve the reaction rate of the two-step hydrocyanation reaction method, while reducing the loss of the catalyst.

[0074] Comparative Example 3

[0075] A two-step hydrocyanation reaction method, which prepares hexanedinitrile from pentenenitrile as raw material, in which the nickel-tris(2-ethylphenyl) phosphite catalyst shown in Example 1 is used, and in the specific preparation process, the catalyst (5mmol), anhydrous zinc chloride (16mmol) and 3PN (2.0mol) are placed in a stainless steel reaction kettle, and the following aromatic amine containing 1 aromatic ring is added:

[0076] The related parameters and control conditions of the present comparative example are the same as those of Example 4; the reaction system is sampled at different times for analysis, and the results are shown in Table 10.

[0077] Table 10

[0078] Comparative Example 4

[0079] A two-step hydrocyanation reaction method was used to prepare adiponitrile from pentenenitrile. In this comparative example, the nickel-tris(2-ethylphenyl)phosphite catalyst shown in Example 1 was used. During the preparation process, the catalyst (5 mmol), anhydrous zinc chloride (16 mmol), and 3PN (2.0 mol) were placed in a stainless steel reactor, and the following aromatic amine containing three aromatic rings was added:

[0080] The relevant parameters and control conditions of this comparative example were the same as those of Example 4. The reaction system was sampled and analyzed at different times, and the results are shown in Table 11.

[0081] Table 11

[0082] As can be verified from Tables 5, 10, and 11, the conversion rate and the stability of the catalyst of the hydrocyanation reaction method of the present application containing a specific structure aromatic amine with two aromatic rings are superior to those of the hydrocyanation reaction method catalyzed by aromatic amine containing one aromatic ring or three aromatic rings. It is speculated that the specific structure aromatic amine containing two aromatic rings in the present application can provide suitable steric hindrance, which promotes the improvement of the catalytic activity of the catalyst; at the same time, the electron-donating group in the aromatic amine contained in the hydrocyanation reaction method of the present application has more obvious electronic effect, which can enhance the complexation of N atom and active nickel intermediate, and enhance the protection effect on the catalyst; through the synergistic optimization of steric hindrance effect and electronic effect, the conversion rate, product selectivity, and stability of the catalyst of the hydrocyanation reaction method of the present application are improved.

[0083] It should be noted that the above content is a further detailed description of the present application in combination with specific embodiments, and the specific implementation of the present application should not be limited to these descriptions; the size data of the present embodiment does not limit the technical solution, but only shows one specific working condition. For ordinary skilled persons in the technical field to which the present application belongs, some simple improvements and refinements can be made without departing from the concept of the present application, and all of them should be regarded as falling within the scope of protection of the present application.

Claims

1. A hydrocyanation process characterized by, The hydrocyanation process is carried out in a reaction system comprising an aromatic amine having the structure: wherein X 1 -X 3 group and Y 1 -Y 3 include any one of hydrogen, alkyl, alkoxy, alkylamine, hydroxyl, and amino.

2. The hydrocyanation process of claim 1 wherein, the alkyl group has the formula -R, the alkoxy group has the formula the alkylamino group has the formula wherein the R group includes any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group.

3. The hydrocyanation process of claim 1 wherein, The structure of the monodentate phosphite ligand is: wherein R 1 , R 2 , and R 3 groups each include any one of hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy.

4. The hydrocyanation process of claim 1 wherein, The mass ratio of the nickel-monodentate phosphite ligand catalyst to the aromatic amine is 1:(0.05-0.8), preferably 1:(0.1-0.6).

5. The hydrocyanation process according to any one of claims 1 to 4 wherein, The hydrocyanation reaction method is a hydrocyanation reaction method for preparing adiponitrile.

6. The hydrocyanation process of claim 5 wherein, The hydrocyanation reaction method includes a one-step hydrocyanation reaction method for preparing pentenenitrile by taking butadiene as a raw material. Preferably, the reaction temperature of the one-step hydrocyanation reaction method is 40-110°C, preferably 50-95°C.

7. The hydrocyanation process of claim 6 wherein, In the one-step hydrocyanation process, the X 1 , X 3 , Y 1 , Y 3 groups in the structure of the aromatic amine are selected from hydrogen or alkyl, respectively, and the X 2 , Y 2 groups are selected from alkyl or alkoxy, respectively. And / or, the mass ratio of the nickel-monodentate phosphite ligand catalyst to butadiene in the one-step hydrocyanation reaction method is (0.5-3):1000, preferably (0.75-2.5):1000.

8. The hydrocyanation process of claim 5 wherein, The hydrocyanation reaction method further includes a two-step hydrocyanation reaction method for preparing adiponitrile by taking pentenenitrile as a raw material. Preferably, the reaction temperature of the two-step hydrocyanation reaction method is 35-90°C, preferably 40-80°C.

9. The hydrocyanation process of claim 8 wherein, In the two-step hydrocyanation process, the X 1 , X 3 , Y 1 , Y 3 groups in the structure of the aromatic amine are each selected from any one of hydrogen, alkyl or alkoxy, the X 2 , Y 2 groups are each selected from alkoxy or alkylamine groups; And / or, the mass ratio of the nickel-monodentate phosphite ligand catalyst to pentenenitrile in the two-step hydrocyanation reaction method is (0.5-3):1000, preferably (0.75-2.5):1000.

10. The hydrocyanation process of claim 8 wherein, The two-step hydrocyanation reaction method is carried out in the presence of a co-catalyst, and the co-catalyst includes at least one of zinc chloride, aluminum chloride, iron chloride, titanium tetrachloride, and triphenylboron. Preferably, the mass ratio of the nickel-monodentate phosphite ligand catalyst to the co-catalyst is (0.2-0.8):1, preferably (0.3-0.7):1.

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