CN111056972B - Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid - Google Patents
Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
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Abstract
The invention provides an application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid, wherein the alkyl quaternary phosphonium salt ionic liquid is prepared from corresponding imidazole and phosphate ester by one-step method through alkylation reaction of alkyl quaternary phosphonium salt, an ionic liquid catalyst, adipic acid and adiponitrile are added into a reaction kettle at a certain temperature, excessive ammonia gas is introduced, and the reaction lasts for a certain time to obtain the product adiponitrile. The method for synthesizing the ionic liquid is simple and convenient in operation process. The prepared ionic liquid is not easy to volatilize, difficult to oxidize and easy to recover; the ionic liquid has higher polarity and strong complexing ability; the anions and the cations can be freely combined, and the structure is easy to control; is not flammable and explosive, and has high thermal stability.
Description
Technical Field
The invention belongs to the technical field of adiponitrile synthesis, and particularly relates to application of a plasma modified alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid and ammonia gas.
Background
Adiponitrile as an important chemical raw material can react with hydrogen to generate hexamethylene diamine, and the hexamethylene diamine and adipic acid react to generate nylon 66 salt under a strict material proportion. Adiponitrile, therefore, is the most prominent and valuable industrial use of adiponitrile as an important intermediate in the synthesis of nylon 66.
The prior methods for synthesizing adiponitrile mainly comprise AN Acrylonitrile (AN) electrolytic dimerization method, a Butadiene (BD) method and AN adipic acid (ADA) catalytic ammoniation method. Among them, the adipic acid amination method is the method for synthesizing adiponitrile which has been most industrially used, and the method is currently classified into a liquid phase method and a gas phase method. Compared with a gas phase method, the liquid phase method can reduce the generation of byproducts and tar, and has simple process flow and less impurities. Therefore, the liquid phase method is mainly used industrially.
The reaction process for synthesizing adiponitrile by a liquid phase method can be roughly divided into two steps of neutralization and dehydration. In the dehydration process, liquid catalysts such as phosphoric acid or phosphoric acid esters are commonly used in industry. However, such catalysts face a series of problems: firstly, a large amount of phosphoric acid and phosphate can generate certain corrosion effect on a reactor, and normal production is influenced; secondly, the liquid catalyst is easy to dissolve in a reaction system, so that the loss of the catalyst is caused, and the production cost is increased; finally, phosphoric acid and the like may form polymers during the reaction, affecting heat transfer.
Ionic liquids have good properties: the catalyst is not easy to volatilize, difficult to oxidize, easy to recover, pollution-free and strong in dissolving capacity; high polarity and low complexing power; the anions and the cations can be freely combined, and the structure is easy to control; is not flammable and explosive, and has high thermal stability. Ionic liquids can be classified into four classes according to the different organic cation precursors, namely alkyl imidazoles, alkyl pyridines, alkyl quaternary ammonium salts and alkyl quaternary phosphonium salts. The literature reports that the ethyl methyl imidazole dihydrogen phosphate ionic liquid is applied to preparation of adiponitrile by cyanation of adipic acid, and an author conducts discontinuous reaction through a reaction kettle, and simultaneously introduces ammonia gas in batches, so that the operation steps are complex, the amplification production is not facilitated, and the industrialization is difficult to realize (CN 201710540292.1).
Disclosure of Invention
Based on the background technology, the invention aims to provide a synthesis method of alkyl quaternary phosphonium salt ionic liquid and application of the alkyl quaternary phosphonium salt ionic liquid in the reaction of synthesizing adiponitrile from adipic acid.
The general procedure for adiponitrile synthesis is: adding the ionic liquid catalyst, adipic acid and adiponitrile into a reaction kettle at a certain temperature, introducing excessive ammonia gas, reacting for a certain time, and analyzing the reaction product.
The invention also provides a method for producing adiponitrile by using the adipic acid liquid phase method, wherein the alkyl quaternary phosphonium salt ionic liquid obtained by the preparation method is used as a catalyst, adipic acid and a diluent are put into a reaction kettle, heated and stirred, ammonia gas is introduced, and the adiponitrile is generated after a period of reaction; the step of introducing ammonia gas is to introduce ammonia gas after the reaction temperature is reached or to introduce ammonia gas in stages.
Based on the above technical scheme, preferably, the diluent is at least one of adiponitrile, glutaronitrile and pimelonitrile.
Based on the technical scheme, the mass ratio of the adipic acid to the diluent is preferably 1: 1-1: 5, and preferably 1: 2.
Based on the technical scheme, the mass of the catalyst is preferably 1-20%, preferably 5% of the total mass of the adipic acid and the diluent.
Based on the technical scheme, the stirring speed in the reaction is preferably 100-2000r/min, and preferably 1000 r/min.
Based on the technical scheme, the reaction temperature is preferably 250-300 ℃, and preferably 270 ℃; the reaction time is 0.5h to 2h, preferably 1 h.
Based on the technical scheme, the flow rate of the introduced ammonia gas during the reaction is preferably 100L/h-600L/h, and is preferably 400L/h. Based on the technical scheme, the preferable preparation method of the alkyl quaternary phosphonium salt ionic liquid comprises the following steps:
(1) mixing an imidazole precursor with phosphate ester in a nitrogen atmosphere, and carrying out microwave heating reflux reaction, wherein the heating power is 0.5-5 kW.h, and the reaction time is 0.5-5 h; the molar ratio of the imidazole precursor to the phosphate is 0.8: 3-3: 0.8;
(2) washing with diethyl ether, and distilling under reduced pressure to remove the residual diethyl ether on the surface to obtain the alkyl quaternary phosphonium salt ionic liquid.
Based on the technical scheme, the imidazole precursor is preferably N-methylimidazole, N-ethylimidazole, N-butylimidazole, N-methylmorpholine and morpholine; the phosphate ester is as follows: trimethyl phosphate, triethyl phosphate or tributyl phosphate.
Based on the technical scheme, preferably, the heating power of the microwave heating reflux reaction is 2 kW.h, and the reaction time is 1 h; the molar ratio of the imidazole precursor to the phosphate ester is 1: 1.
Advantageous effects
(1) The method for synthesizing the ionic liquid is simple and convenient in operation process. The prepared ionic liquid is not easy to volatilize, difficult to oxidize and easy to recover; the ionic liquid has higher polarity and strong complexing ability; the anions and the cations can be freely combined, and the structure is easy to control; is not flammable and explosive, and has high thermal stability.
(2) In the synthesis of adiponitrile, the polarity and complexing ability of the ionic liquid promote the interaction between adiponitrile and adipic acid, improve the chemical reaction environment of adiponitrile synthesis, improve the conversion rate and selectivity of the reaction and reduce the generation of carbon on the surface of a reactor.
(3) During the reaction, the ionic liquid catalyst can slowly release phosphate ions, so that the concentration of the phosphate ions in the system can be controlled, and the corrosion to the reactor is reduced. Meanwhile, the ionic liquid catalyst is not easy to generate polyphosphoric acid, and the influence on heat transfer is reduced.
Detailed Description
Example l
Synthesizing ionic liquid 1, 3-dimethyl imidazole methyl phosphate: mixing N-methylimidazole with trimethyl phosphate according to a ratio of 1:12 under the protection of high-purity nitrogen, heating and refluxing for 1h by using microwaves (the heating power is 2 kW.h), washing for 3 times by using diethyl ether by using microwaves, distilling out residual diethyl ether under reduced pressure, and drying to obtain the product.
Example 2
Synthesizing an ionic liquid morpholine methyl phosphate: mixing morpholine and trimethyl phosphate according to a ratio of 1:12 under the protection of high-purity nitrogen, heating and refluxing for 1h by microwave (the heating power is 2 kW.h), washing with diethyl ether for 3 times, distilling out residual diethyl ether under reduced pressure, and drying to obtain the product.
Example 3
Synthesizing an ionic liquid N-methylmorpholine methyl phosphate: mixing N-methylmorpholine and trimethyl phosphate according to a ratio of 1:12 under the protection of high-purity nitrogen, heating and refluxing for 1h by microwave (the heating power is 2 kW.h), washing with diethyl ether for 3 times, distilling out residual diethyl ether under reduced pressure, and drying to obtain the product.
Example 4
Synthesizing ionic liquid 1-methylimidazole tributyl phosphate: mixing 1-methylimidazole and tributyl phosphate according to a ratio of 1:12 under the protection of high-purity nitrogen, heating and refluxing for 1h by using microwave (the heating power is 2 kW.h), washing for 3 times by using diethyl ether, distilling out residual diethyl ether under reduced pressure, and drying to obtain the product.
Example 5
7.3g of the catalyst prepared in example 1, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 150L/h, the stirring speed was 1500r/min, and the reaction temperature was 270 ℃. After the reaction is carried out for 60min, the yield of adiponitrile is 38.2%, the dehydration rate of adipic acid reaches 43.6%, and the carbon content on the surface of the reactor is 0.38%.
Example 6
7.3g of the catalyst prepared in example 1, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 270 ℃. After the reaction is carried out for 60min, the yield of adiponitrile is 46.1%, the dehydration rate of adipic acid reaches 49.2%, and the carbon content on the surface of the reactor is 0.29%.
Example 7
7.3g of the catalyst prepared in example 1, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 250 ℃. After the reaction is carried out for 60min, the yield of adiponitrile is 33.9%, the dehydration rate of adipic acid reaches 35.4%, and the carbon content on the surface of the reactor is 0.26%.
Example 8
7.3g of the catalyst prepared in example 1, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After the reaction is carried out for 60min, the yield of adiponitrile is 48.6%, the dehydration rate of adipic acid reaches 50.7%, and the carbon content on the surface of the reactor is 0.21%.
Example 9
7.3g of the catalyst prepared in example 1, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After 120min of reaction, the yield of adiponitrile is 54.5%, the dehydration rate of adipic acid reaches 55.7%, and the carbon content on the surface of the reactor is 0.18%.
Example 10
7.3g of the catalyst prepared in example 2, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After 120min of reaction, the yield of adiponitrile is 35.8%, the dehydration rate of adipic acid reaches 38.9%, and the carbon deposition on the surface of the reactor is 0.45%.
Example 11
7.3g of the catalyst prepared in example 3, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After 120min of reaction, the yield of adiponitrile is 35.1%, the dehydration rate of adipic acid reaches 39.8%, and the carbon deposition on the surface of the reactor is 0.46%.
Example 12
7.3g of the catalyst prepared in example 4, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After 120min of reaction, the yield of adiponitrile is 33.7%, the dehydration rate of adipic acid reaches 36.9%, and the carbon deposition on the surface of the reactor is 0.48%.
Example 13
7.3g of the catalyst prepared in example 4, 73g of adipic acid and 146g of adiponitrile were added into a reaction kettle, the flow of ammonia gas was 450L/h, the stirring speed was 1500r/min, and the reaction temperature was 300 ℃. After 120min of reaction, the yield of adiponitrile is 33.7%, the dehydration rate of adipic acid reaches 36.9%, and the carbon deposition on the surface of the reactor is 0.48%.
Example 14
7.3g of the catalyst of example 1, 73g of adipic acid and 146g of adiponitrile were added to a reaction kettle, the stirring speed was 1500r/min, the mixture was heated to 180 ℃ and ammonia was introduced stepwise to change adipic acid into ammonium adipate, the mixture was kept for thirty minutes, and then the temperature was raised to 300 ℃. After 120min of reaction, the yield of adiponitrile is 36.3%, the dehydration rate of adipic acid reaches 40.5%, and the carbon deposition on the surface of the reactor is 0.39%.
Comparative example 1
Taking phosphoric acid as a catalyst, weighing 1.825g of concentrated phosphoric acid with the mass fraction of 85%, 73g of adipic acid and 146g of adiponitrile, adding the weighed materials into a reaction kettle, wherein the flow rate of ammonia gas is 450L/h, the stirring speed is 1500r/min, and the reaction temperature is 300 ℃. After 120min of reaction, the yield of adiponitrile is 49.3%, the dehydration rate of adipic acid reaches 52.9%, and the carbon deposition on the surface of the reactor is 2.63%.
Claims (11)
1. A method for producing adiponitrile by using an adipic acid liquid phase method is characterized in that an ionic liquid is used as a catalyst, adipic acid and a diluent are added, heating and stirring are carried out, ammonia gas is introduced, and the adiponitrile is generated after reaction;
the preparation method of the ionic liquid comprises the following steps:
(1) mixing an imidazole precursor with phosphate ester in a nitrogen atmosphere, and carrying out microwave heating reflux reaction, wherein the heating power is 0.5-5 kW.h, and the reaction time is 0.5-5 h; the molar ratio of the imidazole precursor to the phosphate is 0.8: 3-3: 0.8;
(2) washing with diethyl ether, and distilling under reduced pressure to remove residual diethyl ether on the surface to obtain the ionic liquid;
the diluent is at least one of adiponitrile, glutaronitrile and pimelonitrile;
the imidazole precursor is N-methylimidazole, N-ethylimidazole or N-butylimidazole; the phosphate ester is as follows: trimethyl phosphate, triethyl phosphate, or tributyl phosphate;
the mass ratio of the adipic acid to the diluent is 1: 1-1: 5.
2. The method for producing adiponitrile according to claim 1, wherein the mass ratio of adipic acid to diluent is 1: 2.
3. The method for producing adiponitrile according to claim 1, wherein the mass of the catalyst is 1% to 20% of the total mass of adipic acid and the diluent.
4. The method for producing adiponitrile according to claim 3, wherein the mass of the catalyst is 5% of the total mass of adipic acid and the diluent.
5. The method for producing adiponitrile according to claim 1, wherein the stirring speed is 100-2000 r/min.
6. The method for producing adiponitrile according to claim 5, wherein the stirring speed is 1000r/min during the reaction.
7. The method for producing adiponitrile according to claim 1, wherein the reaction temperature is 250 ℃ to 300 ℃; the reaction time is 0.5-2 h.
8. The adipic acid liquid phase process for producing adiponitrile according to claim 7, wherein the reaction temperature is 270 ℃; the reaction time is 1 h.
9. The method for producing adiponitrile according to claim 1, wherein the flow rate of ammonia gas introduced during the reaction is 100L/h to 600L/h.
10. The method for producing adiponitrile according to claim 9, wherein the flow rate of ammonia gas introduced during the reaction is 400L/h.
11. The method for producing adiponitrile according to claim 1, wherein the heating power of the microwave heating reflux reaction is 2 kW-h, and the reaction time is 1 h; the molar ratio of the imidazole precursor to the phosphate ester is 1: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454619A (en) * | 1966-10-19 | 1969-07-08 | El Paso Products Co | Production of adiponitrile |
| US3607906A (en) * | 1967-11-22 | 1971-09-21 | Vickers Zimmer Ag | Method of mking nitriles from carboxylic acids |
| JPS4828420B1 (en) * | 1970-08-10 | 1973-09-01 | ||
| GB1397729A (en) * | 1971-10-11 | 1975-06-18 | Ici Ltd | Phosphate catalysts used in adiponitrile manufacture |
| DE2737210C2 (en) * | 1977-08-18 | 1983-06-23 | Bayer Ag, 5090 Leverkusen | Process for the production of nitriles |
| DE3424701A1 (en) * | 1984-07-05 | 1986-02-06 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING ADIPODINITRILE |
| DE3510876A1 (en) * | 1985-03-26 | 1986-10-02 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING ALIPHATIC DINITRILE |
| JP2004346150A (en) * | 2003-05-21 | 2004-12-09 | Asahi Kasei Chemicals Corp | Low hue polyester resin composition and its manufacturing method |
| EP2364214A1 (en) * | 2008-11-24 | 2011-09-14 | Technical University of Denmark | Method for preparation of amides from alcohols and amines by extrusion of hydrogen |
| CN103896805B (en) * | 2012-12-27 | 2015-04-15 | 鞍山市国锐化工有限公司 | Method and equipment for production of adiponitrile from adipic acid |
| CN203002344U (en) * | 2012-12-27 | 2013-06-19 | 鞍山市国锐化工有限公司 | Reactor |
| CN108546224B (en) * | 2014-04-16 | 2022-05-27 | 中国石化扬子石油化工有限公司 | Process for the manufacture of nitriles and their corresponding amines |
| CN204147839U (en) * | 2014-08-25 | 2015-02-11 | 中国石油天然气集团公司 | Adiponitrile cyanation device |
| CN204265662U (en) * | 2014-08-25 | 2015-04-15 | 中国石油天然气集团公司 | Adiponitrile production system |
| CN106146345B (en) * | 2015-04-17 | 2018-05-04 | 中国石油天然气股份有限公司 | Method for producing adiponitrile by adipic acid liquid phase method |
| CN109206343A (en) * | 2017-07-04 | 2019-01-15 | 中国石化扬子石油化工有限公司 | A kind of preparation method of adiponitrile |
| CN108821997B (en) * | 2018-06-01 | 2021-03-16 | 重庆华峰聚酰胺有限公司 | Preparation method of adiponitrile and product thereof |
| CN208944112U (en) * | 2018-08-24 | 2019-06-07 | 中国化学赛鼎宁波工程有限公司 | A kind of adiponitrile cyanation device |
| CN109678756B (en) * | 2018-12-25 | 2021-09-17 | 上海交通大学 | Reaction device and method for producing adiponitrile |
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