WO2020248403A1 - 一种己二腈的制备方法 - Google Patents

一种己二腈的制备方法 Download PDF

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WO2020248403A1
WO2020248403A1 PCT/CN2019/104398 CN2019104398W WO2020248403A1 WO 2020248403 A1 WO2020248403 A1 WO 2020248403A1 CN 2019104398 W CN2019104398 W CN 2019104398W WO 2020248403 A1 WO2020248403 A1 WO 2020248403A1
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adipate
gas
metal oxide
adiponitrile
catalyst
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PCT/CN2019/104398
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English (en)
French (fr)
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张锁江
徐宝华
王耀锋
徐晓峰
丁光荣
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中国科学院过程工程研究所
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Publication of WO2020248403A1 publication Critical patent/WO2020248403A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides

Definitions

  • This application belongs to the field of chemical industry and relates to a method for preparing adiponitrile.
  • this application relates to a method for preparing adiponitrile using adipate.
  • Adiponitrile is a very important organic chemical product.
  • the hydrogenated reduction product hexamethylene diamine is a monomer for preparing nylon materials such as nylon-66 and nylon-610.
  • 1,6-hexamethylene diisocyanate (HDI) can be prepared from hexamethylene diamine and further used in the production of adhesives and curing agents for high-end polyurethane coatings.
  • Industrial methods for synthesizing adiponitrile include adipic acid amination dehydration method, acrylonitrile dimerization method and butadiene hydrocyanation method.
  • the adipic acid ammoniation dehydration method is a process in which adipic acid and ammonia gas are neutralized to generate diammonium adipate, and then the crude adiponitrile is prepared by catalytic dehydration reaction, and the finished product is obtained after rectification. According to the different state of adipic acid in the reaction, it is divided into liquid phase method (US2273633A, US4599202A, CN103896805) and gas phase method (US3242204, US3481969A, US3454619A, US3674708A, US3574700A).
  • the liquid phase method uses phosphoric acid, phosphate ester or phosphate as the catalyst, the reaction temperature is 200°C ⁇ 300°C, the molten adipic acid is ammoniated and dehydrated, and the product is subjected to processes such as heavy component removal, chemical treatment and vacuum distillation to obtain adiponitrile
  • the product has a product yield of 84% to 93%, and the product quality is poor.
  • the reaction temperature of gas phase method is 350°C ⁇ 420°C, boron phosphate is used as catalyst, instant gasification and fluidized bed reactor are adopted, product selectivity can reach 92%-96%, and the product quality and yield are better than that of liquid phase method. improve.
  • the electrolytic dimerization of acrylonitrile uses propylene as the starting material.
  • Acrylonitrile is prepared by catalytic oxidation of propylene and ammonia
  • adiponitrile is prepared by electrolytic dimerization of acrylonitrile (EP0270390, US4596638).
  • the industrial synthesis method was first developed by Monsanto in the United States in the 1960s, and has undergone a replacement from diaphragm electrolysis to non-diaphragm electrolysis.
  • the high raw material cost of acrylonitrile and the cost of electricity hinder the wide-scale promotion of this process route.
  • the butadiene hydrocyanation method uses butadiene and hydrocyanic acid to prepare adiponitrile through a three-step reaction, using a complex formed by metal Ni and phosphine ligand as a catalyst (US3278575A; EP1344770A1; US4714773A; US3853948A; J.Chem .Soc.Dalton Trans.1998,2981.;Angew.Chem.Int.Ed.2014,53,9030).
  • butadiene and hydrocyanic acid undergo a cyanation reaction under the action of a catalyst to produce 3-pentenenitrile and 2-methyl-3-butenenitrile; 2-methyl-3-butenenitrile is further isomerized and transformed
  • 3-pentenenitrile is further isomerized to 4-pentenenitrile under catalysis; 4-pentenenitrile reacts with hydrocyanic acid to form adiponitrile.
  • the process route has low energy consumption and low cost, and is currently the most important method for preparing adiponitrile on the market. However, this route has high technical content and is in a high degree of foreign monopoly.
  • hydrocyanic acid is a highly toxic chemical with high safety risks, heavy pollution, and limited supply of raw materials.
  • Adipic acid diester can be obtained by carbonyl esterification reaction of butadiene with carbon monoxide and alcohol, using Pd complex as a catalyst (EP728733; US4350668; US4550195; Angew.Chem.Int.Ed.2014,53,9030; J. Mol. Catal. A 1995, 104, 17). This reaction can effectively use China's abundant coal resources as a source of C1.
  • adipic acid diesters can also be prepared by conventional esterification reactions, using adipic acid and alcohol as raw materials, and solid or liquid acids as catalysts (Green Chem., 2016, 18, 2193; Chem. Commun. ,2015,51,5020).
  • the direct esterification reaction is not only simple and easy to operate, high yield, but also can make full use of the excess capacity of adipic acid.
  • the purpose of this application is to provide a new method for preparing adiponitrile, which uses adipate diester and ammonia as raw materials, and directly prepares adiponitrile through the ammonolysis-dehydration reaction under the action of a catalyst, and is a by-product Water and the corresponding alcohol.
  • the method has the characteristics of safe raw materials, simple process, safe and clean reaction process, easy purification of the product, high product purity, low cost, and environmental protection.
  • this application provides a method for preparing adiponitrile, which includes the following steps:
  • the raw material adipic acid diester includes but is not limited to any of the following compounds: dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate And diphenyl adipate.
  • dimethyl adipate is used as a raw material.
  • the adipic acid diester can be preheated and gasified before being mixed with ammonia.
  • the preheating temperature is 220°C to 350°C, for example, 220°C, 221°C, 222°C, 230°C, 240°C , 250°C, 260°C, 270°C, 280°C, 290°C, 299°C or 300°C.
  • the molar ratio of adipic acid diester to ammonia gas is 1:2 to 1:20, and may be 1:3 to 1:8.
  • the catalysts used include various solid acids, metal oxides, metal doped modified metal oxides, and acidified modified metal oxides.
  • the solid acid catalyst includes but is not limited to any one of the following compounds: heteropoly acid, phosphorylated SiO 2 , sulfated SiO 2 , phosphorylated activated carbon, and sulfated activated carbon.
  • the metal oxide catalyst includes but is not limited to any one of the following compounds: ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , Fe 3 O 4 , ZnO, CuO, Nb 2 O 5 , V 2 O 5 , B 2 O 3 , WO 3 .
  • the metal-doped modified metal oxide includes, but is not limited to, any of the following compounds: ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , Fe 3 O doped with metal elements 4. ZnO, CuO, Nb 2 O 5 , V 2 O 5 , B 2 O 3 , WO 3 (the doping elements can be Fe, Al, Zn, Ti, Nb, W, V)
  • the acidified modified metal oxide includes, but is not limited to, any one of the following compounds: phosphorylated metal oxide (such as phosphorylated ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , Fe 3 O 4 , ZnO, CuO, Nb 2 O 5 , V 2 O 5 , B 2 O 3 , WO 3 ), sulfated metal oxides (such as sulfated ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3.
  • phosphorylated metal oxide such as phosphorylated ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , Fe 3 O 4 , ZnO, CuO, Nb 2 O 5 , V 2 O 5 , B 2 O 3 , WO 3
  • sulfated metal oxides such as sulfated ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3.
  • borated metal oxides such as borated ZrO 2 , Al 2 O 3 , TiO 2 , Fe 2 O 3 , Fe 3 O 4 , ZnO, CuO, Nb 2 O 5 , V 2 O 5 , B 2 O 3 , WO 3 ).
  • reaction temperature used is 230°C to 480°C, optionally 300 to 350°C.
  • reaction pressure used is 0.1-2 MPa, optionally 0.1-0.5 MPa.
  • the adipate diester can be prepared by a variety of methods, including but not limited to the following methods: butadiene carbonyl esterification method and adipic acid esterification method.
  • the butadiene carbonylation method is obtained by the carbonyl esterification reaction of butadiene with carbon monoxide and alcohol, using Co or Pd complex as the catalyst;
  • the adipic acid and alcohol can be used as the raw materials for the adipic acid and alcohol, and solid Acids or liquid acids are used as catalysts and are prepared by conventional esterification reactions.
  • the method of this application avoids the use of hydrocyanic acid raw materials involved in related mainstream methods, is environmentally friendly, and has low operation and management risks; the raw materials involved in this application have a wide range of sources of adipic acid diester, which can be obtained by using butadiene through carbonylation, or It can be obtained by esterification using adipic acid; the catalyst used in the method of this application is cheap and easy to obtain, the conversion rate of raw materials is high, and the product selectivity is high; the reaction process in the method of this application is simple and easy to operate, and the product has high purity and easy separation, which is convenient for large-scale produce.
  • Fig. 1 is a chemical formula showing the reaction steps of the method for preparing adiponitrile provided by the present invention.
  • sulfated activated carbon as the catalyst, and the fixed bed as the catalyst evaluation device.
  • the sulfated activated carbon was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 300°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw material flows through the preheater first, then is mixed with ammonia gas and enters the reactor, where gas-solid reaction occurs, the obtained product is condensed and gas-liquid is separated, the liquid product is collected, and the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 36%, and the selectivity of adiponitrile was 70%.
  • phosphorylated SiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 300°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 35%, and the selectivity of adiponitrile was 52%.
  • the catalyst Using dimethyl adipate as the raw material, 100nm rutile TiO 2 as the catalyst, and the fixed bed as the catalyst evaluation device. After sieving the nano-TiO 2 tablets, the catalyst (5 mL) with a particle size of 40-60 mesh is obtained and filled into a fixed bed reactor. The temperature of the preheater is increased to 260°C, and the temperature of the reactor is increased to 300°C. The feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 75%, and the selectivity of adiponitrile was 48%.
  • dimethyl adipate as raw material, 50nm Fe 2 O 3 as catalyst, and fixed bed as catalyst evaluation device.
  • the nano-Fe 2 O 3 is compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh. Fill it into the fixed-bed reactor.
  • the temperature of the preheater is increased to 260°C, and the temperature of the reactor is increased to 300°C .
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 32%, and the selectivity of adiponitrile was 39%.
  • dimethyl adipate as the raw material, 100 nm Nb 2 O 5 as the catalyst, and the fixed bed as the catalyst evaluation device.
  • the nano-Nb 2 O 5 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh. Fill it into a fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 300°C. .
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, the conversion rate of dimethyl adipate was 51%, and the selectivity of adiponitrile was 76%.
  • dimethyl adipate as the raw material, 50nm monoclinic ZrO 2 as the catalyst, and the fixed bed as the catalyst evaluation device.
  • the nano ZrO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh, and packed into a fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 300°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 70%, and the selectivity of adiponitrile was 38%.
  • Dimethyl adipate was used as the raw material, ZrO 2 modified with metal Cu was used as the catalyst, and the fixed bed was used as the catalyst evaluation device.
  • the metal Cu-modified ZrO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was raised to 260°C, and the temperature of the reactor was raised to 300°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, the conversion rate of dimethyl adipate was 55%, and the selectivity of adiponitrile was 65%.
  • phosphorylated TiO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes, and packed into a fixed bed reactor.
  • the temperature of the preheater was raised to 260°C, and the temperature of the reactor was raised to 300°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 61%, and the selectivity of adiponitrile was 75%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh, and packed into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 330°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 71%, and the selectivity of adiponitrile was 78%.
  • phosphorylated TiO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, the conversion rate of dimethyl adipate was 95%, and the selectivity of adiponitrile was 90%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh, and packed into a fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 380°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 97%, and the selectivity of adiponitrile was 88%.
  • dimethyl adipate phosphorylated TiO 2 as the catalyst
  • the fixed bed as the catalyst evaluation device.
  • the phosphorylated TiO 2 was pressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 40-60 mesh, and packed into the fixed-bed reactor, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials are directly mixed with ammonia gas and enter the reactor for reaction without preheating.
  • the obtained product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 89%, and the selectivity of adiponitrile was 80%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 160-200 mesh and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 88%, and the selectivity of adiponitrile was 89%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 160-200 mesh and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate is 0.2 mL/min (1.22 mmol/min), and the flow rate of ammonia gas is 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 76%, and the selectivity of adiponitrile was 83%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 160-200 mesh and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 79.5 mL/min (3.65 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dimethyl adipate was 80%, and the selectivity of adiponitrile was 85%.
  • phosphorylated TiO 2 was compressed into tablets and then sieved to obtain a catalyst (5 mL) with a particle size of 160-200 mesh and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dimethyl adipate was 0.15 mL/min (0.92 mmol/min), and the flow rate of ammonia gas was 163.5 mL/min (7.28 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid. Using gas chromatography to analyze the collected condensate, the conversion rate of dimethyl adipate was 79%, and the selectivity of adiponitrile was 87%.
  • phosphorylated TiO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material diethyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of diethyl adipate was 93%, and the selectivity of adiponitrile was 90%.
  • dibutyl adipate as the raw material, phosphorylated TiO 2 as the catalyst, and the fixed bed as the catalyst evaluation device.
  • the phosphorylated TiO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material dibutyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, and the conversion rate of dibutyl adipate was 88%, and the selectivity of adiponitrile was 90%.
  • diphenyl adipate phosphorylated TiO 2 as the catalyst
  • the fixed bed as the catalyst evaluation device.
  • the phosphorylated TiO 2 was compressed into tablets and sieved to obtain a catalyst (5 mL) with a particle size of 40 to 60 meshes and filled into the fixed bed reactor.
  • the temperature of the preheater was increased to 260°C, and the temperature of the reactor was increased to 360°C.
  • the feed rate of the raw material diphenyl adipate was 0.1 mL/min (0.61 mmol/min), and the flow rate of ammonia gas was 109 mL/min (4.87 mmol/min).
  • the raw materials flow through the preheater to gasify, and then are mixed with ammonia gas to enter the reactor, where a gas-solid reaction occurs.
  • the resulting product is condensed and separated into gas and liquid, and the liquid product is collected.
  • the tail gas is absorbed and vented by dilute sulfuric acid.
  • the collected condensate was analyzed by gas chromatography, the conversion rate of diphenyl adipate was 81%, and the selectivity of adiponitrile was 88%.

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Abstract

本文公开一种新的己二腈制备方法。该方法采用己二酸二酯与氨气作为原料，通过催化氨解-脱水反应直接制备己二腈，并且仅副产生成水和相应的醇。该己二腈制备方法避免使用剧毒的氢氰酸作为原料，反应过程简单、催化剂廉价易得、原料转化率高、产品选择性高且易分离。

Description

一种己二腈的制备方法 技术领域
本申请属于化工领域，涉及一种己二腈的制备方法，例如，本申请涉及一种使用己二酸酯来制备己二腈的方法。
背景技术
己二腈(ADN)是一种非常重要的有机化工产品。其加氢还原产物己二胺是制备尼龙-66、尼龙-610等尼龙材料的单体。同时1,6-己二异氰酸酯(HDI)可由己二胺制备，并进一步用于生产高端聚氨酯涂料的胶黏剂与固化剂。随着尼龙材料以及聚氨酯材料的广泛应用，己二腈的市场需求也逐渐增长，全球产能超过200万吨。
工业上合成己二腈的方法包括己二酸氨化脱水法、丙烯腈二聚法和丁二烯氢氰化法。
己二酸氨化脱水法是以己二酸与氨气中和生成己二酸二铵盐，进而催化脱水反应制备粗己二腈，精馏后得到成品的工艺。根据反应中己二酸状态的不同又分为液相法(US2273633A，US4599202A，CN103896805)和气相法(US3242204，US3481969A，US3454619A，US3674708A，US3574700A)。液相法采用磷酸、磷酸酯或磷酸盐作为催化剂，反应温度为200℃～300℃，熔融己二酸氨化脱水，产物经脱除重组分、化学处理和真空蒸馏等流程，得到己二腈产品，产品收率84％～93％，产品质量较差。气相法分反应温度350℃～420℃，采用磷酸硼作催化剂，采用瞬时气化和流化床反应器，产品选择性可达92％～96％，产品质量和收率较液相法有所提高。由于己二酸在高温下原料容易分解、结焦，容易造成管路堵塞以及催化剂失活，反应单耗也因此增加。以上工艺问题以及高昂的成本导致该方法在上世纪90年代逐渐被淘汰。
丙烯腈电解二聚法是采用丙烯作为初始原料。丙烯与氨气催化氧化制备丙烯腈，丙烯腈通过电解二聚制备己二腈(EP0270390，US4596638)。工业化合成方法于20世纪60年代由美国孟山都公司首先开发，并经历了隔膜式电解法到无隔膜式电解法的更新换代。高昂的丙烯腈原料成本以及电力成本阻碍了该工艺路线大范围的推广。
丁二烯氢氰化法以丁二烯与氢氰酸通过三步反应制备己二腈，采用金属Ni与膦配体形成的络合物作为催化剂(US3278575A；EP1344770A1；US4714773A；US3853948A；J.Chem.Soc.Dalton Trans.1998,2981.；Angew.Chem.Int.Ed.2014,53,9030)。首先丁二烯与氢氰酸在催化剂作用下进行氰化反应，生成3-戊烯腈和2-甲基-3-丁烯腈；2-甲基-3-丁烯腈进一步异构 化转化成3-戊烯腈，3-戊烯腈在催化作用下进一步异构化为4-戊烯腈；4-戊烯腈与氢氰酸反应生成己二腈。该工艺路线能耗低、成本低，是目前市场上最主要的己二腈制备方法。然而该路线技术含量高，处于高度国外垄断状态。此外氢氰酸为高毒化学品，安全风险大、污染重，原料供应受限。
目前，己二腈的生产工艺技术被一些大型跨国公司垄断，如美国的英威达、法国的罗地亚、日本的旭化成和德国的巴斯夫等。国内至今没有一家企业能够生产己二腈，中石油辽阳分公司和中石油辽阳分公司先后尝试推进己二酸催化氨化法以及丙烯腈电解二聚法的工业化建设，均未能获得成功。
己二酸二酯可以通过丁二烯与一氧化碳、醇通过羰基酯化反应获得，采用Pd配合物作为催化剂(EP728733；US4350668；US4550195；Angew.Chem.Int.Ed.2014,53,9030；J.Mol.Catal.A 1995,104,17)。该反应可以有效利用中国丰富的煤炭资源作为C1来源。此外，己二酸二酯还可以通过常规的酯化反应制得，采用己二酸与醇作为原料，以固体酸或液体酸作为催化剂(Green Chem.,2016,18,2193；Chem.Commun.,2015,51,5020)。直接酯化反应不仅简单易操作、产率高，同时能够充分利用己二酸的过剩产能。
发明内容
以下是对本文详细描述的主题概述。本概述并非是为了限制权利要求的保护范围。
本申请的目的在于提供一种新的己二腈制备方法，该方法采用己二酸二酯与氨气作为原料，在催化剂的作用下通过氨解-脱水反应直接制备己二腈，并且副产水和相应的醇。该方法原料安全、工艺简单、反应过程安全清洁、产品易纯化，具有产品纯度高、成本低、绿色环保等特点。
具体而言，本申请提供一种己二腈的制备方法，该方法包含以下步骤：
Figure PCTCN2019104398-appb-000001
本申请中，原料己二酸二酯包括但不限于下述化合物中的任意一种：己二酸二甲酯、己二酸二乙酯、己二酸二丙酯、己二酸二丁酯以及己二酸二苯酯。可选地，采用己二酸二甲酯作为原料。
本申请中，己二酸二酯在与氨气混合前可先进行预热气化，预热温度为220℃～350℃，例如可以是220℃，221℃，222℃，230℃，240℃，250℃，260℃，270℃，280℃，290℃，299℃ 或300℃。
本申请中，己二酸二酯与氨气的摩尔比为1:2～1:20，可选为1:3～1:8。
本申请中，所采用的催化剂包括各种固体酸，金属氧化物，金属掺杂改性的金属氧化物以及酸化改性的金属氧化物。
可选地，固体酸催化剂包括但不限于下述化合物中的任意一种：杂多酸，磷酸化SiO 2，硫酸化SiO 2，磷酸化活性炭，硫酸化活性炭。
可选地，金属氧化物催化剂包括但不限于下述化合物中的任意一种：ZrO 2，Al 2O 3，TiO 2，Fe 2O 3，Fe 3O 4，ZnO，CuO，Nb 2O 5，V 2O 5，B 2O 3，WO 3。
可选地，金属掺杂改性的金属氧化物包括但不限于下述化合物中的任意一种：金属元素掺杂的ZrO 2，Al 2O 3，TiO 2，Fe 2O 3，Fe 3O 4，ZnO，CuO，Nb 2O 5，V 2O 5，B 2O 3，WO 3(其中掺杂元素可以为Fe、Al、Zn、Ti、Nb、W、V)
可选地，酸化改性的金属氧化物包括但不限于下述化合物中的任意一种：磷酸化金属氧化物(如磷酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3)，硫酸化金属氧化物(如硫酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3)，硼酸化金属氧化物(如硼酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3)。
本申请中，所采用的反应温度为230℃～480℃，可选为300～350℃。
本申请中，所采用的反应压力为0.1～2MPa，可选为0.1～0.5MPa。
本申请中，己二酸二酯可由多种方法制得，包括但不限于以下方法：丁二烯羰基酯化法和己二酸酯化法。其中丁二烯羰基化法通过丁二烯与一氧化碳、醇通过羰基酯化反应获得，采用Co或Pd配合物作为催化剂；己二酸酯化法可己采用己二酸与醇作为原料，以固体酸或液体酸作为催化剂，通过常规的酯化反应制得。
相对于相关技术，本申请具有以下有益效果：
本申请方法避免使用相关主流方法涉及的氢氰酸原料，绿色环保、操作与管理风险低；本申请涉及的原料己二酸二酯来源广泛，既可以采用丁二烯通过羰基化法获得，也可以采用己二酸通过酯化法获得；本申请方法中所用催化剂廉价易得，原料转化率高，产品选择性高；本申请方法中反应过程简便易操作，产物纯度高易分离，便于大规模生产。
在阅读并理解了详细描述和附图后，可以明白其他方面。
附图说明
图1是示出本发明提供的己二腈的制备方法的反应步骤的化学式。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
采用己二酸二甲酯为原料，硫酸化活性炭为催化剂，固定床为催化剂评价装置。将硫酸化活性炭压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为36％，己二腈选择性为70％。
实施例2
采用己二酸二甲酯为原料，磷酸化SiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化SiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为35％，己二腈选择性为52％。
实施例3
采用己二酸二甲酯为原料，100nm金红石型的TiO 2为催化剂，固定床为催化剂评价装置。将纳米TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为75％，己二腈选择性为48％。
实施例4
采用己二酸二甲酯为原料，50nm的Fe 2O 3为催化剂，固定床为催化剂评价装置。将纳米Fe 2O 3压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热 器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为32％，己二腈选择性为39％。
实施例5
采用己二酸二甲酯为原料，100nm的Nb 2O 5作为催化剂，固定床为催化剂评价装置。将纳米Nb 2O 5压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为51％，己二腈选择性为76％。
实施例6
采用己二酸二甲酯为原料，50nm单斜晶型的ZrO 2为催化剂，固定床为催化剂评价装置。将纳米ZrO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为70％，己二腈选择性为38％。
实施例7
采用己二酸二甲酯为原料，金属Cu改性的ZrO 2作为催化剂，固定床为催化剂评价装置。将金属Cu改性的ZrO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为55％，己二腈选择性为65％。
实施例8
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至300℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为61％，己二腈选择性为75％。
实施例9
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至330℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为71％，己二腈选择性为78％。
实施例10
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为95％，己二腈选择性为90％。
实施例11
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至380℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为97％，己二腈选 择性为88％。
实施例12
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料不经预热直接与氨气混合进入反应器进行反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为89％，己二腈选择性为80％。
实施例13
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得160～200目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为88％，己二腈选择性为89％。
实施例14
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得160～200目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.2mL/min(1.22mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为76％，己二腈选择性为83％。
实施例15
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得160～200目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为79.5mL/min(3.65mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾 气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为80％，己二腈选择性为85％。
实施例16
采用己二酸二甲酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得160～200目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二甲酯的进料速率为0.15mL/min(0.92mmol/min)，氨气的流速为163.5mL/min(7.28mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二甲酯转化率为79％，己二腈选择性为87％。
实施例17
采用己二酸二乙酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二乙酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二乙酯转化率为93％，己二腈选择性为90％。
实施例18
采用己二酸二丁酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二丁酯的进料速率为0.1mL/min(0.61mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二丁酯转化率为88％，己二腈选择性为90％。
实施例19
采用己二酸二苯酯为原料，磷酸化TiO 2作为催化剂，固定床为催化剂评价装置。将磷酸化TiO 2压片后过筛，获得40～60目粒径的催化剂(5mL)装填入固定床反应器中，将预热器温度升至260℃，反应器温度升至360℃。原料己二酸二苯酯的进料速率为0.1mL/min(0.61 mmol/min)，氨气的流速为109mL/min(4.87mmol/min)。原料先流经预热器气化，然后与氨气混合进入反应器，发生气固反应，所得产物冷凝后气液分离，收集液体产物，尾气采用稀硫酸吸收放空。采用气相色谱分析收集的冷凝液，己二酸二苯酯转化率为81％，己二腈选择性为88％。
申请人声明，本申请通过上述实施例来说明本申请的己二腈的制备方法，但本申请并不局限于上述工艺步骤，即不意味着本申请必须依赖上述工艺步骤才能实施。

Claims (10)

  1. 一种己二腈的制备方法，其中，所述制备方法采用己二酸二酯与氨气作为原料制备己二腈，所述制备方法包括如下步骤：己二酸二酯与氨气通入装有催化剂的反应器中，在催化剂的作用下经氨解-脱水反应直接制备己二腈，同时副产水和相应的醇；反应如下所示：
    Figure PCTCN2019104398-appb-100001
  2. 根据权利要求1所述的己二腈的制备方法，其中，所述的己二酸二酯与氨气的摩尔比为1:2～1:20。
  3. 根据权利要求1所述的己二腈的制备方法，其中，所述的己二酸二酯与氨气的进料方式可以是混合后一起进入反应器，所述的己二酸二酯与氨气的混合方式包括但不限于以下方式：直接气-液混合后进料或己二酸二酯预热气化后气-气混合后进料；可选地，采用原料预热、气化后进入反应器；
  4. 根据权利要求3所述的己二腈的制备方法，其中，所述的己二酸二酯的预热温度为220℃～350℃，可选为220℃，221℃，222℃，230℃，240℃，250℃，260℃，270℃，280℃，290℃，299℃或300℃；可选地，预热温度为270℃～330℃。
  5. 根据权利要求1所述的己二腈的制备方法，其中，所述的原料己二酸二酯包括但不限于下述化合物中的任意一种或至少两种的组合：己二酸二甲酯、己二酸二乙酯、己二酸二丙酯、己二酸二丁酯以及己二酸二苯酯；可选地，所述的己二酸二酯原料为己二酸二甲酯或己二酸二乙酯。
  6. 根据权利要求1所述的己二腈的制备方法，其中，所述的催化剂包括固体酸，金属氧化物，金属掺杂改性的金属氧化物以及酸化改性的金属氧化物中的任意一种或者至少两种的组合；
    可选地，所述固体酸包括但不限于下述化合物中的任意一种：杂多酸，磷酸化SiO 2，硫酸化SiO 2，磷酸化活性炭，硫酸化活性炭；
    可选地，所述金属氧化物包括但不限于下述化合物中的任意一种：ZrO 2，Al 2O 3，TiO 2，Fe 2O 3，Fe 3O 4，ZnO，CuO，Nb 2O 5，V 2O 5，B 2O 3，WO 3；
    可选地，所述金属掺杂改性的金属氧化物包括但不限于下述化合物中的任意一种：金属元素掺杂的ZrO 2，Al 2O 3，TiO 2，Fe 2O 3，Fe 3O 4，ZnO，CuO，Nb 2O 5，V 2O 5，B 2O 3，WO 3，其中掺杂元素可以为Fe、Al、Zn、Ti、Nb、W、V中的任意一种或者至少两种的组合；
    可选地，所述酸化改性的金属氧化物包括但不限于下述化合物中的任意一种：磷酸化金 属氧化物，硫酸化金属氧化物，硼酸化金属氧化物；所述磷酸化金属氧化物包括磷酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3中的任意一种或者至少两种的组合，所述硫酸化金属氧化物包括硫酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3中的任意一种或者至少两种的组合，所述硼酸化金属氧化物包括硼酸化ZrO 2、Al 2O 3、TiO 2、Fe 2O 3、Fe 3O 4、ZnO、CuO、Nb 2O 5、V 2O 5、B 2O 3、WO 3中的任意一种或者至少两种的组合。
  7. 根据权利要求1所述的己二腈的制备方法，其中，所述的己二酸二酯与氨气的进料方式是分别进入反应器。
  8. 根据权利要求1所述的己二腈的制备方法，其中，所采用的反应温度为230℃～480℃，可选为300～350℃。
  9. 根据权利要求1所述的己二腈的制备方法，其中，所采用的反应压力为0.1～2MPa，可选为0.1～0.5MPa。
  10. 根据权利要求1所述的己二腈的制备方法，其中，本申请中己二酸二酯可由多种方法制得，包括但不限于以下方法：丁二烯羰基酯化法和己二酸酯化法。
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