Hydrocyanation catalysts, preparation methods and applications

Abstract

The hydrocyanation catalyst, its preparation method, and its application comprise the following components by weight: 5-30 parts nickel-phosphorus ligand, 0-10 parts auxiliary agent, 35-93.5 parts support, 1-15 parts binder, and 0.5-10 parts Lewis acid. The phosphorus ligand is a phosphite; the auxiliary agent is selected from one or more combinations of molybdenum, copper, and cobalt; the Lewis acid is selected from one or more combinations of zinc chloride, aluminum trichloride, and titanium tetrachloride; the support is selected from one or more combinations of zirconium oxide, silicon oxide, and titanium oxide; and the binder is alumina. The hydrocyanation catalyst of this application is a solid-phase catalyst for the cyanidation of butadiene to pentenoic acrylonitrile, possessing both cyanidation and isomerization activities, and exhibits good stability and easy recovery.

Description

Technical Field

[0001] This invention belongs to the technical field of butadiene hydrocyanation, and specifically refers to a hydrocyanation catalyst, its preparation method, and its application. Background Technology

[0002] Pentenonitriles, especially 3-pentenonitriles (3PN), are very important intermediates in the process of producing adiponitrile (ADN) by butadiene hydrocyanation, which in turn is a key intermediate in the production of nylon 66.

[0003] In recent years, with the rapid development of my country's economy, the nylon engineering plastics industry has experienced rapid growth, and the demand for nylon fibers has continued to expand. This is especially driven by the rapidly developing automotive industry and other consumer markets, leading to a year-on-year increase in domestic demand for nylon 66. my country has become the world's largest producer and consumer of nylon 66, and consequently, the demand for adiponitrile is also constantly rising.

[0004] Currently, there are four main production technologies for adiponitrile: adipic acid catalytic amination, acrylonitrile dimerization, butadiene hydrocyanation, and caprolactam. Among these, the direct hydrocyanation of butadiene to produce adiponitrile is the most popular technology.

[0005] The direct hydrocyanation of butadiene to synthesize adiponitrile mainly involves three steps: first, butadiene is hydrocyanated once to obtain pentenonitrile; then, 2-methyl-3-butenonitrile is isomerized to 3-pentenonitrile; and finally, 3-pentenonitrile is hydrocyanated a second time to obtain adiponitrile.

[0006] Existing butadiene hydrocyanation processes generally use homogeneous catalysts containing zero-valent nickel, Lewis acids, and phosphorus ligands. After the reaction, the catalyst needs to be recovered from the reaction products by methods such as distillation and extraction. This process is complex, energy-intensive, and the catalyst is prone to deactivation at high temperatures.

[0007] For example, patent CN200580003699.6 discloses a method for preparing 3-pentenonitrile by hydrocyanation of 1,3-butadiene using a homogeneously dissolved nickel(0) complex catalyst, and the catalyst is recovered through multiple distillation separations. However, some catalyst is lost due to high-temperature deactivation, long-term residence decomposition, or incomplete recovery during the reaction and distillation separation stages. Therefore, fresh catalyst needs to be continuously added during the implementation of this process, which will greatly increase the production cost. Summary of the Invention

[0008] To address the problem of difficult recovery of nickel (0)-complex catalysts in the process of butadiene hydrocyanation to pentenoic acrylonitrile synthesis in the prior art, the present invention aims to provide a hydrocyanation catalyst, a preparation method, and its application. This catalyst is a solid-phase catalyst for butadiene cyanation to pentenoic acrylonitrile synthesis that simultaneously possesses cyanidation and isomerization activities, and features good stability and easy recovery.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] The hydrocyanation catalyst comprises the following components in parts by weight:

[0011]

[0012] The phosphorus ligand is a phosphite;

[0013] The additive is selected from one or a combination of molybdenum, copper, and cobalt;

[0014] The Lewis acid is selected from one or a combination of zinc chloride, aluminum trichloride, and titanium tetrachloride.

[0015] In some technical solutions, the hydrocyanation catalyst includes the following components in parts by weight:

[0016]

[0017] The phosphite is selected from one or more of triphenyl phosphite, tributyl phosphite and tripropyl phosphite, and the molar ratio of the phosphite to metallic nickel is 0.1 to 0.5:1.

[0018] In some technical solutions, the support is selected from one or more combinations of zirconium oxide, silicon oxide and titanium oxide, and the particle size distribution of the support is 10-50 micrometers;

[0019] And / or, the adhesive is selected as alumina.

[0020] According to another aspect of the present invention, a method for preparing a hydrocyanation catalyst is further provided, comprising the following steps:

[0021] a) A nickel-aluminum alloy powder containing at least one metal from copper, cobalt, and molybdenum, a binder, a carrier, and an appropriate amount of pore-forming agent are kneaded, extruded, dried, and calcined to form catalyst precursor 1;

[0022] b) Place the above-mentioned catalyst precursor 1 into the catalyst preparation device, add 2 to 5 times the volume of catalyst precursor 1 in deionized water, and use a pump to circulate the impregnation solution therein.

[0023] c) Slowly add sodium hydroxide aqueous solution into the catalyst preparation device, control the pH value to 12-13, add phosphorus ligand to the outlet of the circulating impregnation liquid pump to mix it with the impregnation liquid and then enter the catalyst preparation device. Impregnation is completed after 3-10 hours, and catalyst precursor 2 and catalyst impregnation residue are obtained.

[0024] d) Slowly replace the remaining impregnation liquid in the catalyst preparation device with deionized water until the pH is less than 7.5, and then evaporate the water under an inert gas atmosphere to obtain catalyst precursor 3;

[0025] e) Prepare an anhydrous ethanol solution of Lewis acid and impregnate the catalyst precursor 3 with an excess of the solution. After sufficient aging, dry it under an inert atmosphere to obtain the hydrocyanation catalyst.

[0026] In some technical solutions, in step a:

[0027] The nickel-aluminum alloy powder has a particle size of 10–50 micrometers; and / or,

[0028] The pore-forming agent is selected from at least one of guar gum powder, methylcellulose and urea.

[0029] In some technical solutions, step c:

[0030] The phosphorus ligand is prepared as a 5-20% phosphite ethanol solution; and / or,

[0031] The concentration of the sodium hydroxide aqueous solution is 8-20%.

[0032] In some technical solutions, the Lewis acid in step d is prepared as a 0.3-5% zinc chloride, aluminum trichloride and / or titanium tetrachloride ethanol solution.

[0033] In some technical solutions, the drying temperature in step a is 80–150°C, the drying time is 4–20 hours, the calcination temperature is 400–550°C, and the calcination time is 3–7 hours; and / or,

[0034] The aging temperature in step e is 40-60℃, and the aging time is 3-24 hours.

[0035] According to another aspect of the present invention, the application of a hydrocyanation catalyst in the hydrocyanation of olefins to synthesize adiponitrile is further provided.

[0036] The hydrocyanation catalyst is the hydrocyanation catalyst described above or the hydrocyanation catalyst prepared by the above preparation method.

[0037] In some technical solutions, the hydrocyanation catalyst is applied to the primary cyanation reaction of butadiene to synthesize pentene nitrile. The raw materials, hydrogen cyanide and 1,3-butadiene, are mixed, vaporized, and then contacted with the hydrocyanation catalyst to carry out the hydrocyanation reaction. The reaction temperature is 60–150°C, the pressure is 0.1–0.5 MPa, and the weight hourly space velocity (WHSV) of hydrogen cyanide is 0.05–0.5 h⁻¹. -1 The molar ratio of hydrogen cyanide to 1,3-butadiene is 0.4 to 0.9:1.

[0038] The present invention, by employing the above technical solution, has at least the following beneficial effects:

[0039] 1. The hydrocyanation catalyst proposed in this invention, through the addition of components such as a support and binder, enables the cyanide and isomer active components to be uniformly dispersed and fixed on the surface and pores of the support, thereby producing a solid-phase catalyst with high catalytic activity, good stability and easy recovery.

[0040] 2. The method for preparing the hydrocyanation catalyst proposed in this invention involves kneading, extruding, drying, and calcining the raw material components to form catalyst precursor 1, followed by sequentially impregnating phosphorus ligands with alkali and Lewis acid with acid to obtain the hydrocyanation catalyst. In the preparation process, the strength and distribution of the two active centers, namely cyanidation and isomerization, are precisely controlled, thereby improving the linear selectivity of the product and the economic efficiency of the technology.

[0041] 3. The application of the hydrocyanation catalyst proposed in this invention in the synthesis of pentene nitrile from butadiene cyanation: Using the inexpensive nickel-aluminum alloy of this application as the nickel source, a solid-phase catalyst with both cyanation and isomerization activities for the synthesis of pentene nitrile from butadiene cyanation is prepared, realizing a heterogeneous reaction synthesis process for the synthesis of pentene nitrile from butadiene cyanation. The implementation of this technology can greatly simplify the catalyst recovery process in the production of adiponitrile, which is conducive to large-scale industrial production.

[0042] 4. The hydrocyanation catalyst, preparation method and application proposed in this invention can achieve a butadiene conversion rate of up to 86% in the primary cyanation reaction of butadiene, and the total selectivity of linear pentenonitrile (including 3-pentenonitrile, 4-pentenonitrile and 2-pentenonitrile) in the product is up to 85%, which has achieved good technical results. Detailed Implementation

[0043] The present invention is illustrated by the following non-limiting exemplary embodiments. Unless otherwise specified, all parts, proportions and percentages are by weight, and all reagents involved are commercially available products.

[0044] Example 1

[0045] Take 20g of nickel-aluminum alloy powder containing 0.5% copper with a particle size distribution of 15-50 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% triphenyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 15 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A1 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0046] Example 2

[0047] Take 10g of nickel-aluminum alloy powder containing 0.5% copper with a particle size distribution of 15-50 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% triphenyl phosphite ethanol solution was pumped into the circulating impregnation solution at a rate of 8 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A2 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0048] Example 3

[0049] Take 25g of nickel-aluminum alloy powder containing 2.5% copper with a particle size distribution of 15-50 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% triphenyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 20 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of a 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A3 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0050] Example 4

[0051] Take 20g of nickel-aluminum alloy powder containing 0.5% molybdenum with a particle size distribution of 15-50 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to self-circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% triphenyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 15 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A4 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0052] Example 5

[0053] Take 20g of nickel-aluminum alloy powder containing 0.5% cobalt with a particle size distribution of 15-50 micrometers, 200g of zirconium oxide with a particle size of 10-30 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% triphenyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 15 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen protective atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A5 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0054] Example 6

[0055] Take 20g of nickel-aluminum alloy powder containing 0.5% copper with a particle size distribution of 15-50 micrometers, 200g of titanium oxide with a particle size of 10-40 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% tributyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 22 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 4% aluminum trichloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A6 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0056] Example 7

[0057] Take 17g of nickel-aluminum alloy powder containing 0.5% copper with a particle size distribution of 10-20 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 40g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% tripropyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 4.4 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 240 g of a 1% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A7 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0058] Example 8

[0059] Take 20g of nickel-aluminum alloy powder containing 1% copper with a particle size distribution of 15-50 micrometers, 200g of silicon oxide with a particle size of 10-50 micrometers, 5g of guar gum powder, 15g of 40% aluminum sol and an appropriate amount of water, knead for 40 minutes, then extrude it into strips using an extruder, dry it at 120℃, and calcine it at 480℃ for 5 hours to obtain catalyst precursor 1; place the above catalyst precursor 1 into a catalyst preparation device, add it to 2L of deionized water, and use a pump to circulate the impregnation solution. After establishing the circulation, a 15% sodium hydroxide aqueous solution was slowly added dropwise into the catalyst preparation vessel, controlling the pH of the liquid in the reactor to be 12-13. Simultaneously, a 10% tripropyl phosphite ethanol solution was pumped into the circulating impregnation solution outlet at a rate of 15 g / h to mix with the impregnation solution before entering the catalyst preparation vessel. After 10 hours, impregnation was completed, yielding catalyst precursor 2 and catalyst impregnation residue. The impregnation residue in the catalyst preparation reactor was slowly replaced with deionized water until the pH was less than 7.5, and then the water was evaporated to dryness under a nitrogen protective atmosphere to obtain catalyst precursor 3 for the synthesis of pentenoic acid from butadiene hydrocyanation. 250 g of 2% zinc chloride ethanol solution was prepared, and this solution was used to impregnate catalyst precursor 3 in excess. After aging at 50°C for 10 hours, it was dried at 100°C under a nitrogen atmosphere to obtain catalyst A8 for the synthesis of pentenoic acid from butadiene hydrocyanation.

[0060] Example 9

[0061] The catalysts obtained in Examples 1 to 8 were evaluated respectively. Hydrogen cyanide and 1,3-butadiene were mixed at a molar ratio of 0.9:1, vaporized, and then introduced into the reactor to contact the catalyst. The reaction was carried out at a temperature of 100°C, a pressure of 0.3 MPa, and a hydrogen cyanide weight hourly space velocity of 0.2 h⁻¹. -1 The hydrocyanation reaction was carried out under certain conditions. After the reaction stabilized, the product was sampled and analyzed. The results are shown in Table 1.

[0062] Table 1

[0063] Catalyst number Butadiene conversion rate, % Total selectivity of linear pentenonitrile, % <![CDATA[A1]]> 85.67 82.33 <![CDATA[A2]]> 83.24 83.11 <![CDATA[A3]]> 84.78 83.77 <![CDATA[A4]]> 82.59 84.69 <![CDATA[A5]]> 85.29 81.47 <![CDATA[A6]]> 84.67 81.55 <![CDATA[A7]]> 86.33 85.71 <![CDATA[A8]]> 85.37 83.11

[0064] Analysis of the experimental data in Table 1 shows that:

[0065] The butadiene conversion rate is significantly affected by the content of nickel-phosphorus ligands. Catalyst A2 has a low content of active components, which is insufficient to affect the catalyst's activity, resulting in a lower butadiene conversion rate. Secondly, appropriate amounts of multivalent molybdenum, copper, and cobalt additives can regulate the electronic effect of the catalyst, thus affecting its activity. Catalyst A4 has a lower butadiene conversion rate due to its lower additive content. Furthermore, the particle size of the nickel-aluminum alloy powder during preparation has a certain impact on the catalyst activity. The nickel-aluminum alloy powder used in catalyst A7 has a particle size distribution of 10–20 micrometers. Smaller particle sizes increase the number of effective active centers, which is beneficial for improving catalyst activity and increasing butadiene conversion rate.

[0066] The selectivity of linear products is significantly affected by the matching between the nickel-phosphorus ligand and Lewis acid content. Too low a content results in slow isomerization rates of some non-linear products in the cyanide product, leading to low selectivity for linear products. Conversely, too high a content can increase other side reactions, affecting selectivity. Therefore, catalysts A5 and A6 exhibit low selectivity.

[0067] Example 10

[0068] The catalyst obtained in Example 7 was used for reaction evaluation. The process conditions were changed and the results are shown in Table 2.

[0069] Table 2

[0070]

[0071] As shown in Table 2, with other reaction conditions remaining constant, the conversion rate of butadiene increases as the molar ratio of hydrogen cyanide to 1,3-butadiene increases within the range of 0.4–0.9:1. When the molar ratio of hydrogen cyanide to 1,3-butadiene reaches its maximum value of 0.9:1, the conversion rate of butadiene further increases with increasing reaction temperature, and the overall selectivity of linear pentene nitrile also slightly improves. In addition, when the hydrocyanation reaction pressure increases and the hydrogen cyanide weight hourly space velocity decreases, the conversion rate of butadiene slightly improves, while the overall selectivity of linear pentene nitrile slightly decreases, and vice versa.

[0072] Example 11

[0073] The stability of the catalyst obtained in Example 1 was investigated. Hydrogen cyanide and 1,3-butadiene were mixed at a molar ratio of 0.9:1, vaporized, and then introduced into the reactor to contact the catalyst. The reaction was carried out at a temperature of 100°C, a pressure of 0.3 MPa, and a hydrogen cyanide weight hourly space velocity of 0.2 h⁻¹. -1 The hydrocyanation reaction was carried out under the specified conditions. After the reaction stabilized, the product was sampled and analyzed at regular intervals. The results are shown in Table 3.

[0074] Table 3 Catalyst stability test

[0075] Reaction time, h Butadiene conversion rate, % Total selectivity of linear pentenonitrile, % 15 85.67 82.33 200 85.88 82.74 600 84.96 82.36 800 85.37 82.67 1000 85.21 81.96 1200 85.46 81.79 1400 85.69 82.35 1600 84.89 82.67 1800 85.21 82.31 2000 85.76 82.56

[0076] As shown in Table 3, the hydrocyanation catalyst using the improved process and formulation of this application exhibits good stability under gas-solid two-phase reaction conditions.

[0077] The specific embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A hydrocyanation catalyst characterized in that, Components comprising the following parts by weight: Nickel-phosphorus ligand 10~25 parts Auxiliary agent 0.1~5 parts Carrier 60~85 parts Binder 5~10 parts Lewis acid 1~3 parts Wherein, the phosphorus ligand is a phosphite, the phosphite is selected from one or several combinations of triphenyl phosphite, tributyl phosphite and tripropyl phosphite, and the molar ratio of the phosphite to metal nickel is 0.1~0.5:1; The auxiliary agent is selected from one or several combinations of molybdenum, copper and cobalt; The Lewis acid is selected from one or several combinations of zinc chloride, aluminum chloride and titanium tetrachloride; The hydrocyanation catalyst is prepared by the following steps: a) knead, extrude, dry and calcine nickel-aluminum alloy powder containing at least one metal of copper, cobalt and molybdenum with particle size of 10~50 microns, binder, carrier and appropriate amount of pore forming agent into catalyst precursor 1; b) place the above catalyst precursor 1 into a catalyst preparation device, add deionized water to 2~5 times the volume of the catalyst precursor 1, and use a pump to make the impregnation liquid self-circulate; c) slowly add sodium hydroxide aqueous solution into the catalyst preparation device, control the pH value to be 12~13, add phosphorus ligand at the outlet of the circulating impregnation liquid pump to mix with the impregnation liquid, and then enter the catalyst preparation device, after 3~10 hours, the impregnation is completed, catalyst precursor 2 and catalyst impregnation residual liquid are obtained; d) slowly replace the impregnation residual liquid in the catalyst preparation device with deionized water until the pH is less than 7.5, then evaporate the water under an inert gas atmosphere to obtain catalyst precursor 3; e) prepare a Lewis acid anhydrous ethanol solution, and make the solution excessively impregnate in catalyst precursor 3, and then dry under an inert atmosphere after aging sufficiently to obtain a hydrocyanation catalyst.

2. The hydrocyanation catalyst according to claim 1, characterized in that: The carrier is selected from one or several combinations of zirconium oxide, silicon oxide and titanium oxide, and the particle size distribution of the carrier is 10-50 microns; And / or, the binder is selected from aluminum oxide.

3. Process for the preparation of a hydrocyanation catalyst as claimed in claim 1 or 2, characterized in that Comprising the following steps: a) knead, extrude, dry and calcine nickel-aluminum alloy powder containing at least one metal of copper, cobalt and molybdenum, binder, carrier and appropriate amount of pore forming agent into catalyst precursor 1; b) place the above catalyst precursor 1 into a catalyst preparation device, add deionized water to 2~5 times the volume of the catalyst precursor 1, and use a pump to make the impregnation liquid self-circulate; c) slowly add sodium hydroxide aqueous solution into the catalyst preparation device, control the pH value to be 12~13, add phosphorus ligand at the outlet of the circulating impregnation liquid pump to mix with the impregnation liquid, and then enter the catalyst preparation device, after 3~10 hours, the impregnation is completed, catalyst precursor 2 and catalyst impregnation residual liquid are obtained; d) slowly replace the impregnation residual liquid in the catalyst preparation device with deionized water until the pH is less than 7.5, then evaporate the water under an inert gas atmosphere to obtain catalyst precursor 3; e) prepare a Lewis acid anhydrous ethanol solution, and make the solution excessively impregnate in catalyst precursor 3, and then dry under an inert atmosphere after aging sufficiently to obtain a hydrocyanation catalyst.

4. The production method according to claim 3, characterized by, In step a: The particle size of the nickel-aluminum alloy powder is 10~50 microns; and / or, The pore-forming agent is selected from at least one of sesbania powder, methyl cellulose and urea.

5. The preparation method according to claim 3, characterized in that, In step c: The phosphorus ligand is formulated into a 5-20% phosphite ethanol solution; and / or, The concentration of the aqueous sodium hydroxide solution is 8-20%.

6. The preparation method according to claim 3, wherein, The Lewis acid in step e is formulated into a 0.3-5% zinc chloride, aluminum chloride and / or titanium chloride ethanol solution.

7. The preparation method according to claim 3, wherein, The drying temperature in step a is 80-150°C, the drying time is 4-20 hours, the calcination temperature is 400-550°C and the calcination time is 3-7 hours; and / or, The aging temperature in step e is 40-60°C and the aging time is 3-24 hours.

8. Use of a hydrocyanation catalyst in the synthesis of adiponitrile by hydrocyanation of an olefin, wherein, The hydrocyanation catalyst is the hydrocyanation catalyst according to claim 1 or 2 or the hydrocyanation catalyst prepared according to any one of claims 3-7.

9. The use according to claim 8, wherein, The hydrocyanation catalyst is applied to a first cyanation reaction of butadiene cyanide synthesis of pentenenitrile, raw material hydrogen cyanide and 1,3-butadiene are mixed and gasified, and then are contacted with the hydrocyanation catalyst to perform hydrocyanation reaction, the reaction temperature is 60-150 DEG C, the pressure is 0.1-0.5 MPa, the weight space velocity of hydrogen cyanide is 0.05-0.5 h-1, and the molar ratio of hydrogen cyanide to 1,3-butadiene is 0.4-0.9:

1. -1 , hydrogen cyanide and 1,3-butadiene are mixed and gasified, and then are contacted with the hydrocyanation catalyst to perform hydrocyanation reaction, the reaction temperature is 60-150 DEG C, the pressure is 0.1-0.5 MPa, the weight space velocity of hydrogen cyanide is 0.05-0.5 h-1, and the molar ratio of hydrogen cyanide to 1,3-butadiene is 0.4-0.9:1.

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