CN114933548B - Method for producing dodecanedinitrile by pyrolysis and ammonification of 1,1' -dicyclohexylamine peroxide - Google Patents

Method for producing dodecanedinitrile by pyrolysis and ammonification of 1,1' -dicyclohexylamine peroxide Download PDF

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CN114933548B
CN114933548B CN202210605286.0A CN202210605286A CN114933548B CN 114933548 B CN114933548 B CN 114933548B CN 202210605286 A CN202210605286 A CN 202210605286A CN 114933548 B CN114933548 B CN 114933548B
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dicyclohexylamine
solution
peroxide
dodecanedinitrile
pyrolysis
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CN114933548A (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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    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C2601/00—Systems containing only non-condensed rings
    • 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 by pyrolysis and ammonification of 1,1' -dicyclohexylamine peroxide, which comprises the following steps: mixing the 1,1' -dicyclohexylamine peroxide solution with the preheated ammonia water solution, and carrying out pyrolysis ammonification reaction under the action of a catalyst to obtain a mixed product containing dodecanedinitrile and 6-aminocapronitrile. According to the method, 1' -dicyclohexylamine peroxide is used as a raw material, and dodecanedinitrile is directly produced through pyrolysis and ammonification, so that the generation of unstable 11-cyano undecanoic acid is reduced, the problem of coking and blocking caused by the fact that 11-cyano undecanoic acid generates a large amount of tar due to high-temperature pyrolysis is avoided, the selectivity of a target product dodecanedinitrile is improved, and meanwhile, a 6-aminocapronitrile product with high added value can be co-produced; the method is simple to operate, low in cost and good in industrialization prospect.

Description

Method for producing dodecanedinitrile by pyrolysis and ammonification of 1,1' -dicyclohexylamine peroxide
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for producing dodecanedinitrile by pyrolysis and ammonification of 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 a molecular chain, and has higher flexibility due to more methylene groups, and reduced hydrophilicity due to reduced density of amide groups on the chain. The special nylon mainly comprises PA12, PA1212 and the like, wherein the PA12 has the highest proportion, can be used as engineering plastics, has the characteristics of low water absorption, low temperature resistance, stable size, stronger toughness and the like, can be widely used in the fields of automobiles, communication and the like, and also can be used as a conveying pipeline, so that the demand of the special nylon is larger, and the synthesis process is one of the important points of the current research.
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, and the dodecanedinitrile is mainly prepared by dehydration of dodecanedioic acid and dodecanediamide at present, but the raw materials also need to be synthesized, so that more preparation steps are caused. The production of PA12 by the cyclohexanone method is another production line, the production process comprises the steps of preparing 1,1 '-dicyclohexylamine Peroxide (PXA) from cyclohexanone, preparing cyano undecanoic acid by PXA pyrolysis, preparing amino dodecanoic acid after hydrogenation, and preparing PA12 by further polymerization, but the process for preparing 11-cyano undecanoic acid from 1,1' -dicyclohexylamine peroxide in the above route has more byproduct impurities, the subsequent product separation process is complex, and the purification is difficult.
CN 109678754a discloses a process for the preparation of 11-cyanoundecanoic acid, which comprises: under the action of rare earth metal compound and free radical initiator, 1' -dicyclohexylamine peroxide generates self-decomposition reaction to generate target product 11-cyano undecanoic acid, but the method also generates byproducts such as cyclohexanone, caprolactam and the like, and 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 producing dodecanedinitrile.
CN 107445850a discloses a process for preparing 12-aminododecanoic acid, which comprises, using 10-undecylenic acid as raw material, carrying out substitution reaction with hydrogen bromide to generate 11-bromoundecanoic acid, carrying out cyanidation reaction with catalyst, cyanidation reagent and alkaline substance to generate 11-cyanoundecanoic acid, carrying out reduction reaction, finally generating the product 12-aminododecanoic acid; the method is also used for synthesizing long carbon chain nylon from a 12-aminododecanoic acid intermediate, and does not relate to the preparation of a dodecanedinitrile intermediate.
In summary, for the synthesis of dodecanedinitrile, a new process route is also required to be sought, so that the dodecanedinitrile can be directly produced from 1,1' -dicyclohexylamine peroxide, thereby avoiding the generation of a large amount of tar due to the generation of 11-cyano undecanoic acid intermediate product, improving the selectivity of target products, simultaneously co-producing other high-value products, and expanding the application prospect.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for producing dodecanedinitrile by pyrolysis and ammonification of 1,1 '-dicyclohexylamine peroxide, which takes 1,1' -dicyclohexylamine peroxide as a raw material, and is used for producing dodecanedinitrile directly by pyrolysis and ammonification, so that the generation of unstable 11-cyano undecanoic acid is reduced, the problem of coking and blocking caused by a large amount of tar generated by high-temperature pyrolysis of 11-cyano undecanoic acid is avoided, the stability of an obtained target product is good, the selectivity of the target product is effectively improved, and meanwhile, the 6-aminocapronitrile product with high added value is coproduced, so that the method has a good industrialized prospect.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for producing dodecanedinitrile by pyrolysis and ammonification of 1,1' -dicyclohexylamine peroxide, which comprises the following steps:
mixing the 1,1' -dicyclohexylamine peroxide solution with the preheated ammonia water solution, and carrying out pyrolysis ammonification reaction under the action of a catalyst to obtain a mixed product containing dodecanedinitrile and 6-aminocapronitrile.
In the present invention, in the technical process of preparing nylon such as PA12 by using 1,1' -dicyclohexylamine peroxide as a raw material, 11-cyano undecanoic acid is generated after pyrolysis of the 1,1' -dicyclohexylamine peroxide, but a method for directly preparing dodecanedinitrile from 11-cyano undecanoic acid is not available, but the invention adopts a pyrolysis ammoniation mode to prepare dodecanedinitrile from 1,1' -dicyclohexylamine peroxide, the dodecanedinitrile has good stability, can effectively reduce the generation of unstable 11-cyano undecanoic acid, avoid the problem of coking and blocking caused by a large amount of tar generated by high-temperature pyrolysis of the 11-cyano undecanoic acid, improve the selectivity of the target product, and simultaneously can co-produce the 6-aminocapronitrile product with high added value; the method is simple to operate, low in cost and good in industrialization prospect.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the solvent of the 1,1' -dicyclohexylamine peroxide solution is alcohol.
Preferably, the alcohol solvent comprises any one or a combination of at least two of methanol, ethanol, propanol, n-butanol or isopropanol, typical but non-limiting examples of which are: 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 50wt%, such as 1wt%, 5wt%, 10wt%, 20wt%, 25wt%, 30wt%, 40wt% or 50wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the raw material solution of 1,1' -peroxide dicyclohexylamine takes organic alcohol as a solvent, and has the following main advantages: the solubility of the raw materials and the target products in organic alcohol is high; the boiling point of the organic alcohol is low, and the separation energy consumption is low; and 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 50wt%, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, etc., but the aqueous ammonia solution is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
The preheating temperature of the aqueous ammonia solution is preferably 300 to 600 ℃, for example 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the aqueous ammonia solution is preheated to form a vapor phase mixture of ammonia and water vapor.
In the invention, the ammonia water solution is preheated in advance to form a gas phase mixture, which is helpful for mixing and heating the raw material of the 1,1' -peroxide dicyclohexylamine, ensures the uniformity of raw material mixing, ensures that intermediate products can be ammoniated in time, and improves the yield of dodecanedinitrile.
As a preferred embodiment of the present invention, the mixing of the 1,1' -dicyclohexylamine peroxide solution and the aqueous ammonia solution is performed in a venturi mixer.
Preferably, the venturi mixer sequentially comprises an atomization chamber, a mixing chamber and an expansion chamber along the material flow direction, and a nozzle is arranged in the atomization chamber.
Preferably, the 1,1' -dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, and the ammonia water solution is sprayed from the other inlet of the atomizing chamber, and the ammonia water solution pass through the mixing chamber and the expansion chamber together and enter the fixed bed reactor.
In the invention, the structural design and division of the Venturi mixer are mainly used for enabling two raw materials to be uniformly mixed, and adding the 1,1 '-dicyclohexylamine peroxide solution and the ammonia water solution from different inlets is also used for avoiding the problem that the two raw materials are mixed in advance in liquid phase, otherwise, the internal temperature of a reactor is difficult to control in a pyrolysis target temperature range, and aerosol mixing is carried out after pretreatment, so that the 1,1' -dicyclohexylamine peroxide solution can reach the pyrolysis temperature rapidly.
As a preferred embodiment of the present invention, the thermal decomposition ammonification reaction is performed in a fixed bed reactor.
Preferably, the fixed bed reactor is filled with a catalyst.
Preferably, the catalyst comprises any one or a combination of at least two of aluminum oxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, typical but non-limiting examples of which are: a combination of aluminum oxide and aluminum phosphate, a combination of aluminum phosphate and boron phosphate, a combination of MCM-41 and MCM-22, a combination of aluminum oxide, boron phosphate and HY zeolite, a combination of boron phosphate, MCM-41 and Beta zeolite, and the like.
In a preferred embodiment of the present invention, the molar ratio of the solute in the 1,1' -dicyclohexylamine peroxide solution to the aqueous ammonia solution is 1 (3-8), for example, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8, etc., but the present invention is not limited to the recited values, and other values not recited in the range of the recited values are equally applicable.
In the invention, the molar ratio of 1,1' -dicyclohexylamine peroxide to ammonia is an important factor influencing the raw material conversion rate and the selectivity of dodecanedinitrile, and if the molar ratio of the two is too large, namely the addition amount of ammonia is too small, the selectivity of dodecanedinitrile and 6-aminocapronitrile is reduced, and the yield of a target product is influenced; if the molar ratio of the two is too small, the pH value of the system becomes high, so that partial products are hydrolyzed to generate impurities.
Preferably, the catalyst is used in an amount of 0.2 to 5 hours compared with the mass space velocity of the 1,1' -dicyclohexylamine peroxide solution -1 For example 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 non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature of the thermal decomposition ammonification reaction is 300 to 500 ℃, for example 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
Preferably, the pyrolysis and ammonification reaction is performed for 0.6 to 3 seconds, for example, 0.6 seconds, 1 seconds, 1.5 seconds, 2 seconds, 2.5 seconds, or 3 seconds, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
In the present invention, the mass space velocity of the 1,1' -dicyclohexylamine peroxide solution feed is compared with the time of the pyrolytic ammonification reaction, the former refers to the mass of the mixed 1,1' -dicyclohexylamine peroxide solution flowing over the catalyst per unit mass per unit time, and the latter refers to the time required for the 1,1' -dicyclohexylamine peroxide to pass through the catalyst.
As a preferable technical scheme of the invention, after the pyrolysis and ammonification reaction, the reaction system is cooled and condensed, and ammonia and an alcohol solvent are separated.
Preferably, the separation means of the mixed product comprises any one or a combination of at least two of rectification, extraction or recrystallization, typical but non-limiting examples of which are: 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 embodiment of the present invention, the mixed product further comprises cyclohexanone.
Preferably, after separation of the mixed product, the purity of dodecanedinitrile is greater than 99.5%, for example 99.5%, 99.6%, 99.7%, 99.8% or 99.9%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferred technical solution of the present invention, the method comprises the steps of:
mixing an alcohol solution of 1,1' -dicyclohexylamine peroxide with the mass fraction of 1-50 wt% with an ammonia solution with the mass fraction of 10-50 wt% after preheating in a venturi mixer, wherein the preheating temperature of the ammonia solution is 300-600 ℃, the ammonia solution and the water vapor form a gas phase mixture after preheating, the alcohol comprises any one or a combination of at least two of methanol, ethanol, propanol, n-butyl alcohol and isopropanol, the solute molar ratio of the 1,1' -dicyclohexylamine peroxide solution and the ammonia solution is 1 (3-8), the pyrolysis and ammonification reaction occurs under the action of a catalyst, the pyrolysis and ammonification reaction is carried out in a fixed bed reactor, the catalyst comprises any one or a combination of at least two of aluminum trioxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, and the using amount of the catalyst is 0.2-5 h compared with the mass airspeed of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 300-500 ℃ and the time is 0.6-3 s, so that a mixed product containing dodecanedinitrile and 6-aminocapronitrile is obtained, the mixed product also comprises cyclohexanone, and the separation mode of the mixed product comprises any one or a 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' -dicyclohexylamine peroxide is used as a raw material, and dodecanedinitrile is directly produced through pyrolysis and ammonification, so that the generation of unstable 11-cyano undecanoic acid is reduced, the problem of coking and blocking caused by the fact that 11-cyano undecanoic acid generates a large amount of tar due to high-temperature pyrolysis is avoided, the selectivity of a target product dodecanedinitrile is improved, and meanwhile, a 6-aminocapronitrile product with high added value can be co-produced;
(2) The method is simple to operate, low in cost and good in industrialization prospect.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The present invention provides in part a process for the production of dodecanedinitrile from the pyrolytic amination of 1,1' -dicyclohexylamine peroxide, the process comprising the steps of:
mixing the 1,1' -dicyclohexylamine peroxide solution with the preheated ammonia water solution, and carrying out pyrolysis ammonification reaction under the action of a catalyst to obtain a mixed product containing dodecanedinitrile and 6-aminocapronitrile.
The following are exemplary but non-limiting examples of the invention:
example 1:
this example provides a process for the production of dodecanedinitrile from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing an ethanol solution of 1,1 '-dicyclohexylamine peroxide with the mass fraction of 10wt% with an ammonia solution with the mass fraction of 10wt% after preheating in a venturi mixer, wherein the preheating temperature of the ammonia solution is 500 ℃, a gas phase mixture of ammonia gas and water vapor is formed after preheating, the mole ratio of solute in the 1,1' -dicyclohexylamine peroxide solution to solute in the ammonia solution is 1:3, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the gas phase mixture of ammonia water is sprayed from the other inlet of an atomization chamber, the two mixture together pass through a mixing chamber and an expansion chamber and enter a fixed bed reactor to carry out pyrolysis and ammonification reaction, the fixed bed reactor is filled with a spherical active aluminum oxide catalyst, and the mass airspeed of the catalyst is 0.2h compared with that of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 500 ℃ and the time is 1.5s, and a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine raw material is basically and completely converted, wherein 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 from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing a methanol solution of 1,1 '-dicyclohexylamine peroxide with a mass fraction of 5wt% with a preheated ammonia solution with a mass fraction of 15wt% in a venturi mixer, wherein the preheating temperature of the ammonia solution is 550 ℃, a gas phase mixture of ammonia gas and water vapor is formed after preheating, the mole ratio of solute in the 1,1' -dicyclohexylamine peroxide solution to solute in the ammonia solution is 1:5, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the gas phase mixture of ammonia water is sprayed from the other inlet of an atomization chamber, the two mixture together pass through a mixing chamber and an expansion chamber and enter a fixed bed reactor to carry out pyrolysis and ammonification reaction, the fixed bed reactor is filled with a spherical active aluminum phosphate catalyst, and the mass airspeed of the catalyst is 2h compared with that of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammonification reaction is 320 ℃ and the time is 3s, and a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is extraction.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine 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 is 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 from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing a propanol solution of 1,1 '-dicyclohexylamine peroxide with the mass fraction of 20wt% with a preheated ammonia solution with the mass fraction of 20wt% in a venturi mixer, wherein the preheating temperature of the ammonia solution is 400 ℃, a gas phase mixture of ammonia gas and water vapor is formed after preheating, the mole ratio of solute in the 1,1' -dicyclohexylamine peroxide solution to solute in the ammonia solution is 1:4, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the gas phase mixture of ammonia water is sprayed from the other inlet of an atomization chamber, the two mixture together pass through a mixing chamber and an expansion chamber and enter a fixed bed reactor to carry out pyrolysis and ammonification reaction, the fixed bed reactor is filled with a spherical active boron phosphate catalyst, and the mass airspeed of the catalyst is 1h compared with that of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 350 ℃ and the time is 2.5s, so that a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is recrystallization.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine raw material is basically and completely converted, wherein 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 is 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 from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing an n-butanol solution of 1,1' -dicyclohexylamine peroxide with a mass fraction of 30wt% with a preheated aqueous ammonia solution with a mass fraction of 30wt% in a venturi mixer, wherein the preheating temperature of the aqueous ammonia solution is 450 ℃, a gas phase mixture of ammonia gas and water vapor is formed after preheating, the mole ratio of solute in the 1,1' -dicyclohexylamine peroxide solution to solute in the aqueous ammonia solution is 1:6, the 1,1' -dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, and the gas of the aqueous ammonia is sprayed inSpraying the phase mixture from the other inlet of the atomizing chamber, passing through the mixing chamber and the expansion chamber, and entering a fixed bed reactor for pyrolysis and ammonification, wherein the fixed bed reactor is filled with MCM-41 molecular sieve catalyst, and the dosage of the catalyst is 3h compared with the mass airspeed of 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammonification reaction is 400 ℃ and the time is 2s, and a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is extraction.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine raw material is basically and completely converted, wherein 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 from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing an ethanol solution of which the mass fraction is 40wt% of 1,1 '-dicyclohexylamine peroxide with an ammonia solution of which the mass fraction is 50wt% after being preheated in a venturi mixer, wherein the preheating temperature of the ammonia solution is 600 ℃, a gas-phase mixture of ammonia gas and water vapor is formed after being preheated, the mole ratio of solute in the 1,1' -dicyclohexylamine peroxide solution to solute in the ammonia solution is 1:8, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the gas-phase mixture of the ammonia water is sprayed from the other inlet of an atomization chamber, the two are jointly passed through a mixing chamber and an expansion chamber and enter a fixed bed reactor to carry out pyrolysis ammoniation reaction, the fixed bed reactor is filled with a spherical active aluminum oxide catalyst, and the mass airspeed of the catalyst is 0.2h compared with the mass airspeed of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 500 ℃ and the time is 0.8s, and a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification and extraction.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine 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 from the thermal oxidative amination of 1,1' -dicyclohexylamine peroxide, comprising the steps of:
mixing an isopropanol solution of which the mass fraction is 25wt% of 1,1 '-dicyclohexylamine peroxide with an ammonia solution of which the mass fraction is 30wt% after preheating in a venturi mixer, wherein the preheating temperature of the ammonia solution is 350 ℃, a gas-phase mixture of ammonia gas and water vapor is formed after preheating, the solute molar ratio of the 1,1' -dicyclohexylamine peroxide solution to the ammonia solution is 1:3, the 1,1 '-dicyclohexylamine peroxide solution is sprayed in an atomized form through a nozzle, the gas-phase mixture of the ammonia water is sprayed from the other inlet of an atomization chamber, the two are jointly passed through a mixing chamber and an expansion chamber and enter a fixed bed reactor to carry out pyrolysis ammoniation reaction, the fixed bed reactor is filled with an HY zeolite catalyst, and the mass airspeed of the catalyst is 5h compared with that of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammonification reaction is 450 ℃ and the time is 1s, and a mixed product containing dodecanedinitrile, cyclohexanone and 6-aminocapronitrile is obtained, and the separation mode of the mixed product is rectification.
In the embodiment, the method can be used for directly preparing a dodecanedinitrile product, and the 1,1' -peroxide dicyclohexylamine 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 is 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 production of 11-cyanoundecanoic acid by pyrolysis of 1,1' -dicyclohexylamine peroxide, with reference to the process in example 1, with the difference that: the ammonia solution is replaced by water vapor, and the catalyst is replaced by stainless steel balls.
In the comparative example, since 1,1' -dicyclohexylamine peroxide is directly pyrolyzed but not ammoniated, 11-cyano undecanoic acid is produced, and polymerization is easily carried out under high temperature conditions to produce a large amount of tar, thereby blocking fixed bed pipelines and being not easy to continuously run for a long time; other reaction products include 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 the method of the invention uses 1,1' -dicyclohexylamine peroxide as raw material, and produces dodecanedinitrile directly through pyrolysis and ammoniation, thereby reducing the generation of unstable 11-cyano undecanoic acid, avoiding the problem of coking and blocking caused by the generation of a large amount of tar oil due to high-temperature pyrolysis of 11-cyano undecanoic acid, improving the selectivity of the target product dodecanedinitrile, and simultaneously being capable of co-producing 6-aminocapronitrile product with high added value; the method is simple to operate, low in cost and good in industrialization prospect.
The present invention is described in detail by the above embodiments, but the present invention is not limited to the above detailed methods and apparatuses, i.e. it does not mean that the present invention must be implemented by the above detailed methods and apparatuses. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.

Claims (18)

1. A process for the production of dodecanedinitrile by the pyrolytic amination of 1,1' -dicyclohexylamine peroxide, characterized in that it comprises the following steps:
mixing a1, 1 '-dicyclohexylamine peroxide solution with a preheated ammonia water solution, wherein a solvent of the 1,1' -dicyclohexylamine peroxide solution is alcohol, and carrying out pyrolysis ammoniation reaction under the action of a catalyst, wherein the catalyst is selected from any one or a combination of at least two of aluminum oxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, the temperature of the pyrolysis ammoniation reaction is 300-500 ℃, and the time is 0.6-3 s, so that a mixed product containing dodecanedinitrile and 6-aminocapronitrile is obtained.
2. The method of claim 1, wherein the alcohol comprises any one or a combination of at least two of methanol, ethanol, propanol, n-butanol, or isopropanol.
3. The method according to claim 1, wherein the mass fraction of the 1,1' -dicyclohexylamine peroxide solution is 1-50 wt%.
4. The method according to claim 1, wherein the mass fraction of the aqueous ammonia solution is 10-50wt%.
5. The method according to claim 1, wherein the preheating temperature of the aqueous ammonia solution is 300-600 ℃.
6. The method of claim 5, wherein the aqueous ammonia solution is preheated to form a vapor phase mixture of ammonia and water vapor.
7. Process according to claim 1, characterized in that the mixing of the 1,1' -dicyclohexylamine peroxide solution and the aqueous ammonia solution is carried out in a venturi mixer.
8. The method of claim 7, wherein the venturi mixer comprises, in order, an atomizing chamber, a mixing chamber, and a diverging chamber, the atomizing chamber having a nozzle disposed therein.
9. Process according to claim 8, wherein the 1,1' -dicyclohexylamine peroxide solution is injected in atomized form through a nozzle and the aqueous ammonia solution is injected from the other inlet of the atomizing chamber, both together passing through the mixing chamber, the expansion chamber and into the fixed bed reactor.
10. The method of claim 1, wherein the pyrolytic ammonification reaction is conducted in a fixed bed reactor.
11. The method of claim 10 wherein the fixed bed reactor contains a catalyst.
12. The method according to claim 1, wherein the solute molar ratio of the 1,1' -dicyclohexylamine peroxide solution to the aqueous ammonia solution is 1 (3-8).
13. The method according to claim 1, wherein the catalyst is used in an amount of 0.2 to 5 hours compared to the mass space velocity of the 1,1' -dicyclohexylamine peroxide solution -1 。
14. The method according to claim 1, wherein after the pyrolysis and ammonification reaction, the reaction system is cooled and condensed, and ammonia and alcohol solvent are separated.
15. The method of claim 14, wherein the separation of the mixed product comprises any one or a combination of at least two of rectification, extraction or recrystallization.
16. The method of claim 1, wherein the mixed product further comprises cyclohexanone.
17. The method of claim 14, wherein the purity of dodecanedinitrile after separation of the mixed product is greater than 99.5%.
18. The method according to claim 1, characterized in that it comprises the steps of:
mixing an alcohol solution of 1,1' -dicyclohexylamine peroxide with the mass fraction of 1-50wt% with ammonia with the mass fraction of 10-50wt% after preheatingMixing aqueous solution in a Venturi mixer, wherein the preheating temperature of the aqueous ammonia solution is 300-600 ℃, the aqueous ammonia solution is preheated to form a gas phase mixture of ammonia gas and water vapor, the alcohol is selected from any one or a combination of at least two of methanol, ethanol, propanol, n-butyl alcohol and isopropanol, the solute molar ratio of the 1,1 '-dicyclohexylamine peroxide solution to the aqueous ammonia solution is 1 (3-8), the pyrolysis and ammonification reaction is carried out in a fixed bed reactor under the action of a catalyst, the pyrolysis and ammonification reaction is carried out in the fixed bed reactor, the catalyst is selected from any one or a combination of at least two of aluminum trioxide, aluminum phosphate, boron phosphate, MCM-41, MCM-22, HY zeolite or Beta zeolite, and the mass airspeed of the catalyst is 0.2-5 h compared with the mass airspeed of the 1,1' -dicyclohexylamine peroxide solution -1 The temperature of the pyrolysis ammoniation reaction is 300-500 ℃ and the time is 0.6-3 s, so that a mixed product containing dodecanedinitrile and 6-aminocapronitrile is obtained, the mixed product also comprises cyclohexanone, and the separation mode of the mixed product comprises any one or a combination of at least two of rectification, extraction and recrystallization.
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