CN110511162B - Preparation method of adiponitrile - Google Patents
Preparation method of adiponitrile Download PDFInfo
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- CN110511162B CN110511162B CN201910501004.0A CN201910501004A CN110511162B CN 110511162 B CN110511162 B CN 110511162B CN 201910501004 A CN201910501004 A CN 201910501004A CN 110511162 B CN110511162 B CN 110511162B
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Abstract
The invention relates to a novel method for preparing adiponitrile. The method adopts adipic acid diester and ammonia gas as raw materials, and directly prepares adiponitrile through catalytic ammonolysis-dehydration reaction, and only by-products are generated to produce water and corresponding alcohol. The preparation method of adiponitrile avoids using virulent hydrocyanic acid as a raw material, and has the advantages of simple reaction process, cheap and easily-obtained catalyst, high raw material conversion rate, high product selectivity and easy separation.
Description
Technical Field
The invention belongs to the field of chemical industry, relates to a preparation method of adiponitrile, and particularly relates to a method for preparing adiponitrile by using adipate.
Background
Adiponitrile (ADN) is a very important organic chemical product. The hydrogenation reduction product of hexamethylene diamine is a monomer for preparing nylon materials such as nylon-66, nylon-610 and the like. Meanwhile, the 1, 6-Hexamethylene Diisocyanate (HDI) can be prepared from hexamethylene diamine and further used for producing adhesives and curing agents of high-end polyurethane coatings. With the wide application of nylon materials and polyurethane materials, the market demand of adiponitrile is gradually increased, and the global productivity exceeds 200 million tons.
Industrial methods for the synthesis of adiponitrile include adipic acid ammoniation dehydration, acrylonitrile dimerization, and butadiene hydrocyanation.
The adipic acid ammoniation dehydration method is a process for neutralizing adipic acid and ammonia gas to generate diammonium adipate, then preparing crude adiponitrile through catalytic dehydration reaction, and rectifying to obtain a finished product. The processes are divided into liquid phase process (US2273633A, US4599202A, CN103896805) and gas phase process (US3242204, US3481969A, US3454619A, US3674708A, US3574700A) according to the state of adipic acid in the reaction. The liquid phase method adopts phosphoric acid, phosphate or phosphate as a catalyst, the reaction temperature is 200-300 ℃, the melted adipic acid is aminated and dehydrated, and the product is subjected to the processes of heavy component removal, chemical treatment, vacuum distillation and the like to obtain the adiponitrile product, wherein the product yield is 84-93%, and the product quality is poor. The gas phase method has the reaction temperature of 350-420 ℃, adopts boron phosphate as a catalyst, adopts an instantaneous gasification and fluidized bed reactor, has the product selectivity of 92-96 percent, and improves the product quality and yield compared with the liquid phase method. Because adipic acid is easily decomposed and coked at high temperature, pipeline blockage and catalyst deactivation are easily caused, and the unit consumption of reaction is increased. The above process problems and high costs have led to the gradual obsolescence of this process in the last 90 th century.
The acrylonitrile electrolytic dimerization process uses propylene as a starting material. The catalytic oxidation of propylene with ammonia produces acrylonitrile, which is used to produce adiponitrile by electrolytic dimerization (EP0270390, US 4596638). The industrial synthesis process was first developed in the 60's of the 20 th century by Monsanto, USA, and underwent a new generation from diaphragm-type electrolysis to diaphragm-free electrolysis. The high acrylonitrile raw material cost and the electric power cost prevent the process route from being popularized in a large range.
Butadiene hydrocyanation produces adiponitrile by a three-step reaction of butadiene with hydrocyanic acid using as catalyst a complex of metallic Ni with phosphine ligands (US 3278575A; EP1344770a 1; US 4714773A; US 3853948A; j.chem. soc. dalton trans.1998, 2981; angelw.chem. int.ed.2014,53,9030). Firstly, carrying out a cyanation reaction on butadiene and hydrocyanic acid under the action of a catalyst to generate 3-pentenenitrile and 2-methyl-3-butenenitrile; further isomerizing the 2-methyl-3-butenenitrile to convert into 3-pentenenitrile, and further isomerizing the 3-pentenenitrile into 4-pentenenitrile under the catalytic action; 4-pentenenitrile is reacted with hydrocyanic acid to produce adiponitrile. The process route has low energy consumption and low cost, and is the most important preparation method of adiponitrile in the current market. However, the route is high in technical content and is in a high foreign monopoly state. In addition, hydrocyanic acid is a high-toxicity chemical, has high safety risk and heavy pollution, and has limited raw material supply.
Currently, adiponitrile production technology is monopolized by large multinational companies, such as Invitrogen in the United states, Rodia in France, Asahi chemical in Japan, and Pasteur in Germany. No enterprise can produce adiponitrile at home, and the Liaoyang branch of China try to promote the industrial construction of an adipic acid catalytic ammoniation method and an acrylonitrile electrolytic dimerization method successively, so that the industrial construction is not successful.
Adipic diesters can be obtained by the carbonyl esterification of butadiene with carbon monoxide, an alcohol, using Pd complexes as catalysts (EP 728733; U.S. Pat. No. 4,4350668; U.S. Pat. No. 4550195; Angew. chem. int. Ed.2014,53,9030; J.mol. Catal. A1995,104, 17). The reaction can effectively utilize abundant coal resources in China as a C1 source. Adipic diesters can also be prepared by conventional esterification reactions using adipic acid and an alcohol as starting materials and a solid or liquid acid as a catalyst (Green chem.,2016,18, 2193; chem.commun.,2015,51, 5020). The direct esterification reaction is simple and easy to operate and high in yield, and simultaneously can fully utilize the surplus capacity of the adipic acid.
Disclosure of Invention
The invention aims to provide a novel method for preparing adiponitrile, which adopts adipic acid diester and ammonia gas as raw materials, directly prepares the adiponitrile through ammonolysis-dehydration reaction under the action of a catalyst, and produces water and corresponding alcohol as byproducts. The method has the characteristics of safe raw materials, simple process, safe and clean reaction process, easy purification of products, high product purity, low cost, environmental protection and the like.
Specifically, the present application provides a method for preparing adiponitrile, comprising the steps of:
in the present invention, the adipic acid diester as a raw material includes, but is not limited to, any one of the following compounds: dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate and diphenyl adipate. Preferably, dimethyl adipate is used as starting material.
In the invention, the adipic acid diester can be preheated and vaporized before being mixed with ammonia gas, wherein the preheating temperature is 220-350 ℃, and can be 220 ℃, 221 ℃, 222 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 299 ℃ or 300 ℃ for example.
In the present invention, the molar ratio of the adipic acid diester to the ammonia gas is 1:2 to 1:20, preferably 1:3 to 1: 8.
In the present invention, the catalyst used includes various solid acids, metal oxides, metal-doped modified metal oxides and acidification-modified metal oxides.
Preferably, the solid acid catalyst includes, but is not limited to, any of the following compounds: heteropolyacids, phosphorylated SiO2Sulfated SiO2Phosphorylated activated carbon, sulfated activated carbon.
Preferably, the metal oxide catalyst includes, but is not limited to, any of the following compounds: ZrO (ZrO)2，Al2O3，TiO2， Fe2O3，Fe3O4，ZnO，CuO，Nb2O5，V2O5，B2O3，WO3。
Preferably, the metal doping modified metal oxide includes, but is not limited to, any one of the following compounds: ZrO doped with metal element2，Al2O3，TiO2，Fe2O3，Fe3O4，ZnO，CuO，Nb2O5，V2O5，B2O3，WO3(wherein the doping element can be Fe, Al, Zn, Ti, Nb, W, V)
Preferably, the acid-modified metal oxide includes, but is not limited to, any one of the following compounds: phosphorylated metal oxides (e.g. phosphorylated ZrO)2、Al2O3、TiO2、Fe2O3、Fe3O4、ZnO、CuO、Nb2O5、V2O5、B2O3、WO3) Metal oxides of sulphated type (e.g. sulphated ZrO)2、Al2O3、TiO2、Fe2O3、Fe3O4、ZnO、CuO、Nb2O5、V2O5、 B2O3、WO3) Borated metal oxides (e.g. borated ZrO)2、Al2O3、TiO2、Fe2O3、Fe3O4、ZnO、CuO、 Nb2O5、V2O5、B2O3、WO3)。
In the invention, the reaction temperature is 230-480 ℃, and preferably 300-350 ℃.
In the present invention, the reaction pressure used is 0.1 to 2MPa, preferably 0.1 to 0.5 MPa.
In the present invention, the adipic diester may be prepared by a variety of methods, including, but not limited to, the following: butadiene carbonyl esterification and adipate esterification processes. The butadiene carbonylation method is obtained by the carbonyl esterification reaction of butadiene, carbon monoxide and alcohol, and adopts Co or Pd complex as a catalyst; the adipate esterification method can be prepared by using adipic acid and alcohol as raw materials and solid acid or liquid acid as a catalyst through conventional esterification reaction.
Compared with the prior art, the invention has the following beneficial effects:
the method avoids using hydrocyanic acid raw materials related to a mainstream method internationally, is green and environment-friendly, and has low operation and management risks; the adipic acid diester used as the raw material has wide sources, can be obtained by adopting butadiene through a carbonylation method, and can also be obtained by adopting adipic acid through an esterification method; the catalyst used in the method is cheap and easy to obtain, the conversion rate of the raw material is high, and the product selectivity is high; the method has the advantages of simple and easy operation of reaction process, high product purity, easy separation and convenient large-scale production.
Drawings
FIG. 1 is a chemical reaction formula of the present invention
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Dimethyl adipate is used as a raw material, sulfated active carbon is used as a catalyst, and a fixed bed is used as a catalyst evaluation device. Tabletting sulfated activated carbon, sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 36% conversion of dimethyl adipate and 70% selectivity to adiponitrile.
Example 2
Adopts dimethyl adipate as a raw material and phosphorylates SiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating SiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 35% conversion of dimethyl adipate and 52% selectivity to adiponitrile.
Example 3
Adopts dimethyl adipate as a raw material and 100nm rutile type TiO2Is a catalyst, and the fixed bed is a catalyst evaluation device. Mixing nanometer TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. Adipic acid as raw materialThe feed rate of dimethyl ester was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 75% conversion of dimethyl adipate and 48% selectivity to adiponitrile.
Example 4
Adopts dimethyl adipate as a raw material and 50nm of Fe2O3Is a catalyst, and the fixed bed is a catalyst evaluation device. Mixing nano Fe2O3Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 32% conversion of dimethyl adipate and 39% selectivity to adiponitrile.
Example 5
Adopts dimethyl adipate as a raw material, 100nm Nb2O5As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Mixing the nano Nb2O5Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 51% conversion of dimethyl adipate and 76% selectivity to adiponitrile.
Example 6
Adopts dimethyl adipate as a raw material and 50nm monoclinic ZrO2Is a catalyst, and the fixed bed is a catalyst evaluation device. Nano ZrO is mixed with2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 70% conversion of dimethyl adipate and 38% selectivity to adiponitrile.
Example 7
ZrO modified by metal Cu and adopting dimethyl adipate as raw material2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. ZrO modified with metallic Cu2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 55% conversion of dimethyl adipate and 65% selectivity of adiponitrile.
Example 8
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 300 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). Raw materialsThe gas is gasified by a preheater and then mixed with ammonia gas to enter a reactor to carry out gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 61% conversion of dimethyl adipate and 75% selectivity to adiponitrile.
Example 9
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 330 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 71% conversion of dimethyl adipate and 78% selectivity to adiponitrile.
Example 10
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 95% conversion of dimethyl adipate and 90% selectivity to adiponitrile.
Example 11
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As catalyst, the fixed bed is catalystAnd an evaluation device. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 380 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 97% conversion of dimethyl adipate and 88% selectivity to adiponitrile.
Example 12
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials are directly mixed with ammonia gas without preheating and enter a reactor for reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and exhausted by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 89% conversion of dimethyl adipate and 80% selectivity to adiponitrile.
Example 13
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 160-200 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. Cold collected by gas chromatographyThe condensate has a conversion rate of adipic acid dimethyl ester of 88 percent and a selectivity of adiponitrile of 89 percent.
Example 14
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 160-200 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting dimethyl adipate was 0.2mL/min (1.22mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 76% conversion of dimethyl adipate and 83% selectivity to adiponitrile.
Example 15
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 160-200 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting dimethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 79.5mL/min (3.65 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 80% conversion of dimethyl adipate and 85% selectivity to adiponitrile.
Example 16
Adopts dimethyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 160-200 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. Raw material of hexanediThe feed rate of dimethyl ester was 0.15mL/min (0.92mmol/min) and the flow rate of ammonia gas was 163.5mL/min (7.28 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed a dimethyl adipate conversion of 79% and an adiponitrile selectivity of 87%.
Example 17
Adopts diethyl adipate as a raw material to phosphorylate TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the starting diethyl adipate was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 93% conversion of diethyl adipate and 90% selectivity of adiponitrile.
Example 18
Adopts dibutyl adipate as a raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the dibutyl adipate starting material was 0.1mL/min (0.61mmol/min) and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 88% conversion of dibutyl adipate and 90% selectivity to adiponitrile.
Example 19
Adopts diphenyl adipate as raw material and phosphorylates TiO2As the catalyst, a fixed bed was used as a catalyst evaluation apparatus. Phosphorylating TiO2Tabletting and sieving to obtain a catalyst (5mL) with the particle size of 40-60 meshes, filling the catalyst into a fixed bed reactor, raising the temperature of a preheater to 260 ℃, and raising the temperature of the reactor to 360 ℃. The feed rate of the raw material diphenyl adipate was 0.1mL/min (0.61mmol/min), and the flow rate of ammonia gas was 109mL/min (4.87 mmol/min). The raw materials flow through a preheater for gasification, then are mixed with ammonia gas and enter a reactor for gas-solid reaction, the obtained product is condensed and then subjected to gas-liquid separation, a liquid product is collected, and tail gas is absorbed and discharged by dilute sulfuric acid. The condensate collected by gas chromatography analysis showed 81% conversion of diphenyl adipate and 88% selectivity of adiponitrile.
The Applicant states that the present invention is illustrated by the above examples of the preparation of adiponitrile according to the invention, but the invention is not limited to the above process steps, i.e. it is not meant that the invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (14)
1. The preparation method of adiponitrile is characterized in that adipic acid diester and ammonia gas are used as raw materials to prepare the adiponitrile, and the preparation method comprises the following steps: adipic diester and ammonia gas are introduced into a reactor filled with a catalyst, and are subjected to ammonolysis-dehydration reaction under the action of the catalyst to directly prepare adiponitrile, and water and corresponding alcohol are simultaneously by-produced, wherein the reaction is as follows:
the adipic acid diester as the raw material is any one or the combination of at least two of the following compounds: dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate and diphenyl adipate;
the catalyst is supported solid acid, metal-doped modified metal oxide or acidized modified metal oxide;
the supported solid acid agent is phosphorylated SiO2Sulfated SiO2Phosphorylated or sulfated activated carbon;
the acidification modified metal oxide is a phosphorylated metal oxide or a sulfated metal oxide;
the phosphorylated metal oxide is phosphorylated ZrO2Phosphorylated Al2O3Phosphorylated TiO2Phosphorylated Fe2O3Phosphorylated Fe3O4Phosphorylated Nb2O5Phosphorylation of V2O5Or phosphorylating WO3；
The sulfated metal oxide is sulfated ZrO2Sulfated Al2O3Sulfated TiO2Sulfated Fe2O3Sulfated Fe3O4Sulfated Nb2O5Sulfated V2O5Or sulfated WO3；
The metal-doped modified metal oxide is any one of the following compounds: ZrO doped with metal element2、Al2O3、TiO2、Nb2O5、V2O5、WO3Or Cu-modified ZrO2
The doped metal element is Ti, Nb, W or V.
2. The method of claim 1, wherein the adipic acid diester starting material is dimethyl adipate or diethyl adipate.
3. The method according to claim 1, wherein the molar ratio of the adipic diester to the ammonia gas is 1:2 to 1: 20.
4. The method according to claim 1, wherein the adipic diester and the ammonia gas are fed into the reactor together or separately after being mixed.
5. The method of claim 4, wherein the adipic diester is mixed with ammonia gas and then co-fed into the reactor.
6. The method of claim 4, wherein the mixing of the adipic diester with ammonia comprises: directly feeding after gas-liquid mixing or feeding after gas-gas mixing after adipic acid diester is preheated and gasified.
7. The method as claimed in claim 6, wherein the adipic diester and ammonia gas are mixed by preheating raw materials, gasifying the raw materials and then feeding the raw materials into the reactor.
8. The method of claim 7, wherein the pre-heating temperature of the adipic diester is 220 ℃ to 350 ℃.
9. The method of claim 8, wherein the pre-heating temperature of the adipic diester is 270 ℃ to 330 ℃.
10. The process according to claim 1, wherein the reaction temperature employed is from 230 ℃ to 480 ℃.
11. The process according to claim 10, wherein the reaction temperature used is 300 to 350 ℃.
12. The method according to claim 1, wherein the reaction pressure used is 0.1 to 2 MPa.
13. The method according to claim 12, wherein the reaction pressure used is 0.1 to 0.5 MPa.
14. The method of claim 1, wherein the adipic diester is produced by a butadiene carbonyl esterification method or an adipic esterification method.
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