CN114933548A - Method for producing dodecanedinitrile by pyrolyzing and ammoniating 1, 1' -dicyclohexylamine peroxide - Google Patents

Method for producing dodecanedinitrile by pyrolyzing and ammoniating 1, 1' -dicyclohexylamine peroxide Download PDF

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CN114933548A
CN114933548A CN202210605286.0A CN202210605286A CN114933548A CN 114933548 A CN114933548 A CN 114933548A CN 202210605286 A CN202210605286 A CN 202210605286A CN 114933548 A CN114933548 A CN 114933548A
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peroxide
dicyclohexylamine
ammonia
catalyst
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CN114933548B (en
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黄杰军
邓生财
徐林
丁克鸿
张政
吕丽
马庆炎
李明
薛维海
张寅�
张子鑫
蒋旭
史晓波
秦娜娣
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Jiangsu Yangnong Chemical Group Co Ltd
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention provides a method for producing dodecanedinitrile through thermal decomposition and ammoniation of 1, 1' -dicyclo hexylamine peroxide, which comprises the following steps: mixing the 1, 1' -dicyclo hexylamine peroxide solution with the preheated ammonia water solution, and performing thermal deammonification reaction under the action of a catalyst to obtain a mixed product containing dodecane dinitrile and 6-aminocapronitrile. According to the method, 1' -dicyclohexanamine peroxide is used as a raw material, and dodecane dinitrile is directly produced through pyrolysis and ammoniation, so that the generation of unstable 11-cyano undecanoic acid is reduced, the problem of coking and blockage caused by a large amount of tar generated by high-temperature pyrolysis of 11-cyano undecanoic acid is avoided, the selectivity of a target product dodecane dinitrile is improved, and a high-added-value 6-aminocapronitrile product can be co-produced; the method is simple to operate, low in cost and good in industrialization prospect.

Description

Method for producing dodecanedinitrile by pyrolyzing and ammoniating 1, 1' -dicyclohexylamine peroxide
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for producing dodecane dinitrile by pyrolyzing and ammoniating 1, 1' -dicyclohexylamine peroxide.
Background
The long carbon chain nylon is a special nylon, generally refers to a nylon material with more than 10 methylene groups in the molecular chain, and has higher flexibility because of more methylene groups, and the hydrophilicity of the nylon material is reduced because of the reduction of the density of amide groups on the chain. The special nylon mainly comprises PA12, PA1212 and the like, wherein PA12 has the highest proportion, can be used as engineering plastics, has the characteristics of low water absorption, low temperature resistance, stable dimension, strong toughness and the like, can be widely used in the fields of automobiles, communication and the like, and can also be used as a conveying pipeline, so that the demand is high, and the synthesis process is one of the current research focuses.
The dodecanedinitrile is used as an important intermediate for synthesizing nylon materials such as PA12, PA1212 and the like, the synthesis process is also important, the dodecanedinitrile is mainly prepared by dehydrating dodecanedioic acid and dodecanediamide at present, but the raw materials also need to be synthesized, so that the preparation steps are more. The production process of PA12 by a cyclohexanone method is another production line, and comprises the steps of preparing 1,1 '-dicyclohexanamine Peroxide (PXA) from cyclohexanone, preparing cyanoundecanoic acid from PXA through pyrolysis, preparing aminododecanoic acid after hydrogenation, and preparing PA12 through further polymerization, wherein in the production line, the byproduct impurities are more in the process of preparing 11-cyanoundecanoic acid from 1, 1' -dicyclohexanamine peroxide, and the subsequent product separation process is complex and difficult to purify.
CN 109678754A discloses a preparation method of 11-cyano undecanoic acid, which comprises the following steps: 1, 1' -dicyclo hexylamine peroxide is subjected to self-decomposition reaction under the action of a rare earth metal compound and a free radical initiator to generate a target product 11-cyano undecanoic acid, but the method can also generate byproducts such as cyclohexanone, caprolactam and the like, the pyrolysis product is complex, the product yield is low, and the post-treatment separation is complex; although this process is capable of producing 11-cyanoundecanoic acid, PA12 is produced via aminododecanoic acid, rather than directly dodecanedinitrile.
CN 107445850A discloses a preparation method of 12-aminododecanoic acid, which takes 10-undecylenic acid as a raw material, carries out substitution reaction with hydrogen bromide to generate 11-bromo-undecanoic acid, then carries out cyanidation reaction with a catalyst, a cyaniding reagent and an alkaline substance to generate 11-cyano-undecanoic acid, and finally generates a product, namely 12-aminododecanoic acid through reduction reaction; the method is also used for synthesizing long carbon chain nylon by using a 12-aminododecanoic acid intermediate, and does not relate to the preparation of a dodecanedinitrile intermediate.
In conclusion, for the synthesis of dodecanedinitrile, a new process route is required to be found, so that dodecanedinitrile can be directly produced from 1, 1' -dicyclohexanamine peroxide, a large amount of tar generated by the production of an 11-cyanoundecanoic acid intermediate product is avoided, the selectivity of a target product is improved, other high-value products are obtained by co-production, and the application prospect is expanded.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for producing dodecane dinitrile by pyrolyzing and ammoniating 1,1 '-dicyclohexylamine peroxide, which takes 1, 1' -dicyclohexylamine peroxide as a raw material and directly produces dodecane dinitrile by pyrolyzing and ammoniating, so that the generation of unstable 11-cyanoundecanoic acid is reduced, the problem of coking and blockage caused by a large amount of tar generated by high-temperature pyrolysis of 11-cyanoundecanoic acid is avoided, the stability of the obtained target product is good, the selectivity of the target product is effectively improved, and meanwhile, a high-added-value 6-aminocapronitrile product is co-produced, so that the method has a good industrial prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for producing dodecanedinitrile by thermal pyrolysis ammoniation of 1, 1' -dicyclohexylamine peroxide, which comprises the following steps:
mixing the 1, 1' -dicyclo hexylamine peroxide solution with the preheated ammonia water solution, and performing thermal deammonification reaction under the action of a catalyst to obtain a mixed product containing dodecane dinitrile and 6-aminocapronitrile.
In the invention, in the current process flow for preparing nylon such as PA12 and the like by taking 1,1 ' -dicyclohexanamine peroxide as a raw material, 11-cyano undecanoic acid is generated after pyrolysis of the 1,1 ' -dicyclohexanamine peroxide, but no method for directly preparing dodecanedinitrile from the 11-cyano undecanoic acid exists, but the dodecanedinitrile is prepared from the 1,1 ' -dicyclohexanamine peroxide by adopting a pyrolysis ammoniation mode, the dodecanedinitrile has good stability, the generation of unstable 11-cyano undecanoic acid can be effectively reduced, the problem of coking blockage caused by a large amount of tar generated by high-temperature pyrolysis of the 11-cyano undecanoic acid is avoided, the selectivity of a target product dodecanedinitrile is improved, and simultaneously a high-added-value 6-aminocapronitrile product can be co-produced; the method is simple to operate, low in cost and good in industrialization prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
In a preferred embodiment of the present invention, the solvent of the 1, 1' -dicyclohexylamine peroxide solution is an alcohol.
Preferably, the alcoholic solvent comprises any one of methanol, ethanol, propanol, n-butanol or isopropanol, or a combination of at least two of these, typical but non-limiting examples being: a combination of methanol and ethanol, a combination of propanol and isopropanol, a combination of ethanol, propanol and n-butanol, a combination of methanol, ethanol, propanol and isopropanol, and the like.
Preferably, the mass fraction of the 1, 1' -dicyclohexylamine peroxide solution is 1 to 50 wt%, such as 1 wt%, 5 wt%, 10 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt%, or 50 wt%, but not limited to the recited values, and other non-recited values within the range of the values are also applicable.
In the invention, the 1, 1' -dicyclo hexylamine peroxide raw material solution takes organic alcohol as a solvent, and the advantages are mainly that: the raw materials and the target product have high solubility in organic alcohol; the boiling point of the organic alcohol is low, and the energy consumption for separation is low; and moreover, the toxicity is low, and the environment is protected.
In a preferred embodiment of the present invention, the mass fraction of the aqueous ammonia solution is 10 to 50 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the preheating temperature of the aqueous ammonia solution is 300 to 600 ℃, for example 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the aqueous ammonia solution is preheated to form a gas phase mixture of ammonia and water vapor.
According to the invention, the ammonia water solution is preheated in advance to form a gas phase mixture, which is beneficial to mixing and heating with the 1, 1' -dicyclohexylamine peroxide raw material, so that the uniformity of the raw material mixing is ensured, the intermediate product can be aminated in time, and the yield of dodecane dinitrile is improved.
In a preferred embodiment of the present invention, the mixing of the 1, 1' -dicyclohexylamine peroxide solution and the aqueous ammonia solution is carried out in a venturi mixer.
Preferably, the venturi mixer comprises an atomizing chamber, a mixing chamber and an expansion chamber in sequence along the material flow direction, and a nozzle is arranged in the atomizing chamber.
Preferably, the 1, 1' -dicyclohexanamine peroxide solution is sprayed in an atomized form through a nozzle, the ammonia water solution is sprayed from the other inlet of the atomizing chamber, and the ammonia water solution and the fixed bed reactor jointly pass through the mixing chamber and the expanding chamber and enter the fixed bed reactor.
According to the invention, the structural design and division of the venturi mixer are mainly used for uniformly mixing two raw materials, the 1,1 '-dicyclohexylamine peroxide solution and the ammonia water solution are added from different inlets, and the problem that the two solutions are mixed in liquid phase in advance, otherwise the internal temperature of the reactor is difficult to control within a pyrolysis target temperature range is avoided, and the 1, 1' -dicyclohexylamine peroxide solution can quickly reach the pyrolysis temperature after being pretreated and then mixed in an aerosol phase.
As a preferred technical scheme of the invention, the pyrolysis ammoniation reaction is carried out in a fixed bed reactor.
Preferably, the fixed bed reactor is packed with a catalyst.
Preferably, the catalyst comprises any one of alumina, aluminophosphate, borophosphate, MCM-41, MCM-22, HY zeolite or zeolite Beta or a combination of at least two of these, typical but non-limiting examples being: combinations of aluminum oxide and aluminum phosphate, aluminum phosphate and boron phosphate, MCM-41 and MCM-22, aluminum oxide, boron phosphate and HY zeolite, boron phosphate, MCM-41 and Beta zeolite, and the like.
In a preferred embodiment of the present invention, the solute molar ratio of the 1, 1' -dicyclohexanamine peroxide solution to the ammonia water solution is 1 (3-8), for example, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the invention, the molar ratio of 1,1 '-dicyclohexanamine peroxide to ammonia is an important factor influencing the conversion rate of raw materials and the selectivity of dodecane dinitrile, and if the molar ratio of the 1, 1' -dicyclohexanamine peroxide to ammonia is too large, namely the adding amount of ammonia is too small, the selectivity of dodecane dinitrile and 6-aminocapronitrile is reduced, and the yield of target products is influenced; if the molar ratio of the two is too small, the pH value of the system will be increased, and partial products will be hydrolyzed to generate impurities.
Preferably, the mass space velocity of the dosage of the catalyst compared with that of the 1, 1' -dicyclo hexylamine peroxide solution is 0.2-5 h -1 E.g. 0.2h -1 、0.5h -1 、1h -1 、1.5h -1 、2h -1 、3h -1 、4h -1 Or 5h -1 And the like, but are not limited to the recited values, and other values not recited within the numerical range are also applicable.
In a preferred embodiment of the present invention, the temperature of the thermal decomposition/amination reaction is 300 to 500 ℃, for example, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃, but the temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the time of the thermal decomposition and amination reaction is 0.6 to 3s, for example, 0.6s, 1s, 1.5s, 2s, 2.5s, or 3s, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
In the present invention, the mass space velocity of the feed of the 1,1 ' -dicyclohexylamine peroxide solution is compared with the time of the pyrolysis ammoniation reaction, the former is the mass of the mixed 1,1 ' -dicyclohexylamine peroxide solution flowing through the catalyst per unit mass of the catalyst per unit time, and the latter is the time required for the 1,1 ' -dicyclohexylamine peroxide to pass through the catalyst.
As the preferable technical scheme of the invention, after the pyrolysis ammoniation reaction, the reaction system is cooled and condensed, and ammonia and alcohol solvent are separated.
Preferably, the separation mode of the mixed product comprises any one or a combination of at least two of rectification, extraction or recrystallization, and the combination is typically but not limited to: a combination of rectification and extraction, a combination of extraction and recrystallization, a combination of rectification, extraction and recrystallization, and the like.
As a preferred technical scheme of the invention, the mixed product also comprises cyclohexanone.
Preferably, the purity of dodecanedinitrile after separation of the mixture is 99.5% or more, for example 99.5%, 99.6%, 99.7%, 99.8%, or 99.9%, etc., but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
mixing 1-50 wt% of 1,1 '-dicyclohexylamine peroxide alcoholic solution and 10-50 wt% of preheated ammonia water solution in a Venturi mixer, wherein the preheating temperature of the ammonia water solution is 300-600 ℃, a gas-phase mixture of ammonia and water vapor is formed after preheating, the alcohol comprises any one or combination of at least two of methanol, ethanol, propanol, n-butanol or isopropanol, the molar ratio of the 1, 1' -dicyclohexylamine peroxide solution to the ammonia water solution is 1 (3-8), a thermal deammonification reaction is carried out under the action of a catalyst, the thermal deammonification reaction is carried out in a fixed bed reactor, the catalyst comprises any one or combination of at least two of aluminum oxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, the mass space velocity of the catalyst is 0.2-5 h compared with the mass space velocity of the 1, 1' -dicyclo hexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 300-500 ℃, the time is 0.6-3 s, a mixed product containing dodecane dinitrile and 6-aminocapronitrile is obtained, the mixed product further comprises cyclohexanone, and the separation mode of the mixed product comprises any one or combination of at least two of rectification, extraction and recrystallization.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, 1' -dicyclohexanamine peroxide is used as a raw material, and dodecane dinitrile is directly produced through pyrolysis and ammoniation, so that the generation of unstable 11-cyano undecanoic acid is reduced, the problem of coking blockage caused by a large amount of tar generated by high-temperature pyrolysis of 11-cyano undecanoic acid is avoided, the selectivity of a target product dodecane dinitrile is improved, and a high-value-added 6-aminocapronitrile product can be co-produced;
(2) the method is simple to operate, low in cost and good in industrialization prospect.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
In part, embodiments of the present invention provide a process for the production of dodecanedinitrile from the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, the process comprising the steps of:
mixing the 1, 1' -dicyclo hexylamine peroxide solution with the preheated ammonia water solution, and performing thermal deammonification reaction under the action of a catalyst to obtain a mixed product containing dodecane dinitrile and 6-aminocapronitrile.
The following are typical but non-limiting examples of the invention:
example 1:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
mixing an ethanol solution of 1,1 ' -dicyclohexylamine peroxide with the mass fraction of 10 wt% with a preheated ammonia water solution with the mass fraction of 10 wt% in a Venturi mixer, wherein the preheating temperature of the ammonia water solution is 500 ℃, a gas-phase mixture of ammonia and water vapor is formed after preheating, the solute molar ratio of the 1,1 ' -dicyclohexylamine peroxide solution to the ammonia water solution is 1:3, the 1,1 ' -dicyclohexylamine peroxide solution is sprayed in an atomization mode through a nozzle, the gas-phase mixture of the ammonia water is sprayed from the other inlet of an atomization chamber, and the two pass through a mixing chamber and an expansion chamber together and enter a fixed bed reactor to generatePerforming pyrolysis ammoniation reaction, filling a spherical active aluminum oxide catalyst in the fixed bed reactor, wherein the mass space velocity of the dosage of the catalyst compared with that of 1, 1' -dicyclohexylamine peroxide solution is 0.2h -1 And the temperature of the pyrolysis ammoniation reaction is 500 ℃, the time is 1.5s, a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification.
In the embodiment, the dodecanedinitrile product can be directly prepared by the method, the 1, 1' -dicyclohexanide raw material is basically and completely converted, the yield of the dodecanedinitrile can reach 58.5%, the yield of the co-produced 6-aminocapronitrile reaches 20.6%, and the yield of the cyclohexanone is 10.9%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Example 2:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
mixing a methanol solution of 1, 1' -dicyclo hexylamine peroxide with the mass fraction of 5 wt% and a preheated ammonia water solution with the mass fraction of 15 wt% in a Venturi mixer, the preheating temperature of the ammonia water solution is 550 ℃, a gas phase mixture of ammonia and water vapor is formed after preheating, the solute molar ratio of the 1, 1' -dicyclo hexylamine peroxide solution to the ammonia water solution is 1:5, the 1, 1' -dicyclohexylamine peroxide solution is sprayed in an atomizing form through a nozzle, the gaseous mixture of the ammonia water is sprayed from the other inlet of the atomizing chamber, the two pass through the mixing chamber and the expanding chamber together and enter the fixed bed reactor to carry out pyrolysis and ammoniation reaction, the method is characterized in that a spherical active aluminum phosphate catalyst is filled in the fixed bed reactor, and the mass space velocity of the catalyst is 2h compared with that of a1, 1' -dicyclohexylamine peroxide solution. -1 And the temperature of the pyrolysis ammoniation reaction is 320 ℃, the time is 3s, a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is extraction.
In this embodiment, the dodecanedinitrile product can be directly prepared by the above method, and the 1, 1' -peroxydicyclohexylamine raw material is basically and completely converted, wherein the yield of the dodecanedinitrile can reach 46.2%, the yield of the co-produced 6-aminocapronitrile reaches 19.3%, and the yield of the cyclohexanone reaches 24.5%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Example 3:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
mixing a propanol solution of 1, 1' -dicyclo hexylamine peroxide with the mass fraction of 20 wt% with a preheated ammonia water solution with the mass fraction of 20 wt% in a Venturi mixer, the preheating temperature of the ammonia water solution is 400 ℃, a gas phase mixture of ammonia and water vapor is formed after preheating, the solute molar ratio of the 1, 1' -dicyclo hexylamine peroxide solution to the ammonia water solution is 1:4, the 1, 1' -dicyclohexylamine peroxide solution is sprayed in an atomizing form through a nozzle, the gaseous mixture of the ammonia water is sprayed from the other inlet of the atomizing chamber, the two pass through the mixing chamber and the expanding chamber together and enter the fixed bed reactor to carry out pyrolysis and ammoniation reaction, the method is characterized in that a spherical active boron phosphate catalyst is filled in the fixed bed reactor, and the mass space velocity of the catalyst is 1h compared with that of a1, 1' -dicyclohexylamine peroxide solution. -1 And the temperature of the pyrolysis ammoniation reaction is 350 ℃, the time is 2.5s, a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is recrystallization.
In the embodiment, the dodecanedinitrile product can be directly prepared by the method, the 1, 1' -dicyclohexanide raw material is basically and completely converted, the yield of the dodecanedinitrile can reach 42.3%, the yield of the co-produced 6-aminocapronitrile reaches 18.8%, and the yield of the cyclohexanone reaches 28.9%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Example 4:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
1, 1' -dicyclohexanyl peroxide in 30 wt%Mixing an amine n-butanol solution and a preheated ammonia water solution with the mass fraction of 30 wt% in a Venturi mixer, wherein the preheating temperature of the ammonia water solution is 450 ℃, a gas-phase mixture of ammonia and water vapor is formed after preheating, the solute molar ratio of the 1,1 ' -dicyclohexylamine peroxide solution to the ammonia water solution is 1:6, the 1,1 ' -dicyclohexylamine peroxide solution is sprayed in an atomization mode through a nozzle, the gas-phase mixture of the ammonia water is sprayed from the other inlet of the atomization chamber, the two pass through a mixing chamber and an expansion chamber together, enter a fixed bed reactor to perform a pyrolysis ammoniation reaction, the fixed bed reactor is filled with an MCM-41 molecular sieve catalyst, and the mass space velocity of the catalyst compared with that of the 1,1 ' -dicyclohexylamine peroxide solution is 3h -1 And the temperature of the pyrolysis ammoniation reaction is 400 ℃, the time is 2s, a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is extraction.
In the embodiment, the dodecanedinitrile product can be directly prepared by the method, the 1, 1' -dicyclohexanide raw material is basically and completely converted, the yield of the dodecanedinitrile can reach 40.1%, the yield of the co-produced 6-aminocapronitrile reaches 19.8%, and the yield of the cyclohexanone is 30.1%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Example 5:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
mixing an ethanol solution of 40 wt% of 1,1 '-dicyclohexylamine peroxide and a preheated ammonia water solution with the mass fraction of 50 wt% in a Venturi mixer, wherein the preheating temperature of the ammonia water solution is 600 ℃, a gas-phase mixture of ammonia and water vapor is formed after preheating, the molar ratio of solutes in the 1, 1' -dicyclohexylamine peroxide solution and the ammonia water solution is 1:8, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomization mode through a nozzle, the gas-phase mixture of the ammonia water is sprayed from the other inlet of an atomization chamber, the two pass through a mixing chamber and an expansion chamber together and enter a fixed bed reactor to carry out a pyrolysis ammoniation reaction, and the pyrolysis ammoniation reaction is carried out, wherein the ammonia water solution is obtained by mixing the ethanol solution of 1, 1' -dicyclohexylamine peroxide with the mass fraction of 50 wt%, and the gas-phase mixture of the ammonia water is sprayed from the other inlet of the atomization chamberA spherical active aluminum oxide catalyst is filled in the fixed bed reactor, and the mass space velocity of the dosage of the catalyst compared with the mass space velocity of the 1, 1' -dicyclo hexylamine peroxide solution is 0.2h -1 And the temperature of the pyrolysis ammoniation reaction is 500 ℃ and the time is 0.8s, so that a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification and extraction.
In this embodiment, the dodecanedinitrile product can be directly prepared by the above method, and the 1, 1' -peroxydicyclohexylamine raw material is basically and completely converted, wherein the yield of the dodecanedinitrile can reach 50.2%, the yield of the co-produced 6-aminocapronitrile reaches 17.5%, and the yield of the cyclohexanone is 22.3%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Example 6:
this example provides a process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, comprising the steps of:
mixing 25 wt% of isopropanol solution of 1, 1' -dicyclo hexylamine peroxide and 30 wt% of preheated ammonia water solution in a Venturi mixer, the preheating temperature of the ammonia water solution is 350 ℃, a gas phase mixture of ammonia and water vapor is formed after preheating, the solute molar ratio of the 1, 1' -dicyclo hexylamine peroxide solution to the ammonia water solution is 1:3, the 1, 1' -dicyclo hexylamine peroxide solution is sprayed in an atomizing form through a nozzle, the ammonia gas phase mixture is sprayed from the other inlet of the atomizing chamber, the ammonia gas phase mixture and the ammonia gas phase mixture enter the fixed bed reactor through the mixing chamber and the expanding chamber together to carry out pyrolysis and ammoniation reaction, HY zeolite catalyst is filled in the fixed bed reactor, and the mass space velocity of the catalyst in comparison with that of 1, 1' -dicyclohexylamine peroxide solution is 5 h. -1 And the temperature of the pyrolysis ammoniation reaction is 450 ℃, the time is 1s, a mixed product containing dodecane dinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification.
In this embodiment, the dodecanedinitrile product can be directly prepared by the above method, and the 1, 1' -peroxydicyclohexylamine raw material is basically and completely converted, wherein the yield of the dodecanedinitrile can reach 35.6%, the yield of the co-produced 6-aminocapronitrile reaches 38.1%, and the yield of the cyclohexanone reaches 21.3%; the method is simple to operate, the system is not easy to coke, and the economical efficiency is high.
Comparative example 1:
this comparative example provides a process for the pyrolytic production of 11-cyanoundecanoic acid from 1, 1' -dicyclohexylamine peroxide, which is referred to the process of example 1, with the following differences: the ammonia water solution is replaced by water vapor, and the catalyst is replaced by stainless steel balls.
In the comparative example, 1' -dicyclohexylamine peroxide is directly pyrolyzed without undergoing an ammoniation reaction, so that 11-cyanoundecanoic acid is generated, and polymerization easily occurs at high temperature to generate a large amount of tar, so that a fixed bed pipeline is blocked, and long-time continuous operation is not easy to occur; other reaction products comprise cyclohexanone and caprolactam, and the total yield of the products is only about 70 percent.
It can be seen from the above examples and comparative examples that 1, 1' -dicyclohexylamine peroxide is used as a raw material in the method of the present invention, and dodecane dinitrile is directly produced through pyrolysis and ammoniation, such that generation of unstable 11-cyano undecanoic acid is reduced, a problem of coking and blockage caused by a large amount of tar generated by high temperature pyrolysis of 11-cyano undecanoic acid is avoided, selectivity of target dodecane dinitrile is improved, and a high value-added 6-aminocapronitrile product can be co-produced; the method has the advantages of simple operation, low cost and good industrialization prospect.
The present invention is illustrated by the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed methods and apparatuses, which means that the present invention must not be implemented by the above-mentioned detailed methods and apparatuses. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the method of the present invention and additions of ancillary steps, selection of specific means, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A process for the production of dodecanedinitrile by the pyrolytic ammoniation of 1, 1' -peroxydicyclohexylamine, characterized in that it comprises the following steps:
mixing the 1, 1' -dicyclo hexylamine peroxide solution with the preheated ammonia water solution, and performing thermal deammonification reaction under the action of a catalyst to obtain a mixed product containing dodecane dinitrile and 6-aminocapronitrile.
2. The method of claim 1, wherein the solvent of the 1, 1' -dicyclohexylamine peroxide solution is an alcohol;
preferably, the alcohol solvent comprises any one of methanol, ethanol, propanol, n-butanol or isopropanol or a combination of at least two of the same;
preferably, the mass fraction of the 1, 1' -dicyclo hexylamine peroxide solution is 1-50 wt%.
3. The method according to claim 1 or 2, wherein the mass fraction of the aqueous ammonia solution is 10 to 50 wt%;
preferably, the preheating temperature of the ammonia water solution is 300-600 ℃;
preferably, the aqueous ammonia solution is preheated to form a gas phase mixture of ammonia and water vapor.
4. The process according to any one of claims 1 to 3, characterized in that the mixing of the 1, 1' -dicyclohexylamine peroxide solution and the aqueous ammonia solution is carried out in a Venturi mixer;
preferably, the venturi mixer comprises an atomizing chamber, a mixing chamber and an expansion chamber in sequence, and a nozzle is arranged in the atomizing chamber;
preferably, the 1, 1' -dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the ammonia water solution is sprayed from the other inlet of the atomization chamber, and the ammonia water solution and the fixed bed reactor jointly pass through the mixing chamber and the expansion chamber and enter the fixed bed reactor.
5. The process according to any one of claims 1 to 4, wherein the pyrolysis amination reaction is carried out in a fixed bed reactor;
preferably, the fixed bed reactor is filled with a catalyst;
preferably, the catalyst comprises any one of alumina, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite or a combination of at least two of the above.
6. The method according to any one of claims 1 to 5, wherein the molar ratio of the solute in the 1, 1' -dicyclohexylamine peroxide solution to the solute in the aqueous ammonia solution is 1 (3-8);
preferably, the mass space velocity of the dosage of the catalyst compared with that of the 1, 1' -dicyclo hexylamine peroxide solution is 0.2-5 h -1 。
7. The method according to any one of claims 1 to 6, wherein the temperature of the thermal decomposition and amination reaction is 300 to 500 ℃;
preferably, the time of the pyrolysis ammoniation reaction is 0.6-3 s.
8. The method as claimed in any one of claims 1 to 7, wherein after the thermal decomposition ammoniation reaction, the reaction system is cooled and condensed to separate ammonia and alcohol solvent;
preferably, the separation mode of the mixed product comprises any one or a combination of at least two of rectification, extraction and recrystallization.
9. The process of any one of claims 1-8, wherein the mixed product further comprises cyclohexanone;
preferably, the purity of dodecanedinitrile after separation of the mixed product reaches more than 99.5%.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
mixing 1-50 wt% of 1, 1' -dicyclo hexylamine peroxide alcoholic solution and 10-50 wt% of preheated ammonia water solution in a Venturi mixer, wherein the preheating temperature of the ammonia water solution is 300 to EPreheating at 600 ℃ to form a gas phase mixture of ammonia and water vapor, wherein the alcohol comprises any one or combination of at least two of methanol, ethanol, propanol, n-butanol or isopropanol, the molar ratio of solutes in the 1,1 '-dicyclohexylamine peroxide solution and the ammonia water solution is 1 (3-8), the thermal deammonification reaction is carried out under the action of a catalyst, the thermal deammonification reaction is carried out in a fixed bed reactor, the catalyst comprises any one or combination of at least two of aluminum oxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, and the mass space velocity of the catalyst compared with the 1, 1' -dicyclohexylamine peroxide solution is 0.2-5 h -1 The temperature of the pyrolysis ammoniation reaction is 300-500 ℃, the time is 0.6-3 s, a mixed product containing dodecane dinitrile and 6-aminocapronitrile is obtained, the mixed product further comprises cyclohexanone, and the separation mode of the mixed product comprises any one or combination of at least two of rectification, extraction and recrystallization.
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