CN107286051A - Oximes technique reacts method of controlling security under the conditions of mixed catalyst - Google Patents

Oximes technique reacts method of controlling security under the conditions of mixed catalyst Download PDF

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Publication number
CN107286051A
CN107286051A CN201610191799.6A CN201610191799A CN107286051A CN 107286051 A CN107286051 A CN 107286051A CN 201610191799 A CN201610191799 A CN 201610191799A CN 107286051 A CN107286051 A CN 107286051A
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CN
China
Prior art keywords
catalyst
cyclohexanone
conditions
reaction
fresh
Prior art date
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Pending
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CN201610191799.6A
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Chinese (zh)
Inventor
徐伟
张帆
姜杰
黄飞
李永祥
费轶
石宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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Application filed by China Petroleum and Chemical Corp, Sinopec Qingdao Safety Engineering Institute filed Critical China Petroleum and Chemical Corp
Priority to CN201610191799.6A priority Critical patent/CN107286051A/en
Publication of CN107286051A publication Critical patent/CN107286051A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Method of controlling security is reacted under the conditions of mixed catalyst the present invention relates to a kind of oximes technique, the problem of security is poor in the prior art is mainly solved.The present invention reacts method of controlling security by using a kind of oximes technique under the conditions of mixed catalyst, in the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, under the conditions of using mixed catalyst during generation catalyst inactivation, safe and reliable Ammoximation reaction conversion ratio and selective safety control measures are provided, to ensure the security of Ammoximation reaction, prevent the technical scheme that gas phase fires and preferably solve above mentioned problem, available in cyclohexanone oxamidinating technique.

Description

Oximes technique reacts method of controlling security under the conditions of mixed catalyst
Technical field
Method of controlling security is reacted under the conditions of mixed catalyst the present invention relates to a kind of oximes technique.
Background technology
Caprolactam is the monomer of synthetic fibers and engineering plastics, is always market important industrial chemicals in short supply in China.Mesh Before, most of production of caprolactam changes into cyclohexanone oxime using cyclohexanone, then is rearranged into the process route of caprolactam. It is a kind of environmental protection that the direct ammoxidation of cyclohexanone that conversion from cyclohexanone to cyclohexanone oxime is used, which prepares cyclohexanone oxime technique, The technique of low energy consumption.Cyclohexanone oxamidinating synthesizing cyclohexane 1 ketoxime new technology is in lower pressure using cyclohexanone, ammonia and hydrogen peroxide Under, the tert-butyl alcohol is solvent, using titanium-silicon molecular sieve catalyst, the one-step synthesis cyclohexanone oxime in continuous slurry bed reactor, Its reaction equation is (1)：
NH3+H2O2+C6H10O=C6H11ON+2H2O
This method directly prepares cyclohexanone oxime, instead of traditional azanol preparation technology, substantially reduces technological process, saves Investment, not producing ammonium sulfate byproduct, it is to avoid the production of nitrogen oxides and oxysulfide, great to environment protection significance, application prospect is wide It is general, receive extensive attention.
Under normal operation, Ammoximation reaction is carried out under high conversion, high selectivity, but when raw material proportioning it is improper and/or During catalyst activity reduction, main reaction speed declines, main to occur following side reaction：
4H2O2+2NH3=N2O+7H2O
3H2O2+2NH3=N2+6H2O
2H2O2=2H2O+O2
As main reaction conversion ratio and selectivity decline, decomposing hydrogen dioxide solution produces oxygen and hydrogen peroxide and ammonia reaction generation laughing gas Amount gradually increase, may cause to form explosive mixed gas in reactor, such as running into burning things which may cause a fire disaster, high temperature or electrostatic spark will Produce blast.
The titanium-silicon molecular sieve catalyst that Ammoximation reaction is used can be regeneration after fresh catalyst, fresh catalyst inactivation Catalyst or fresh catalyst mixed regeneration catalyst.This technology method passes through the hexamethylene under the conditions of mixed catalyst Conversion ratio and selective changing rule, determine the security control bar of reaction conversion ratio and selectivity in ketone oxamidinating course of reaction Part, it is to avoid blast accident occurs for gas phase, it is ensured that the safety and steady operation of device.
The content of the invention
The technical problems to be solved by the invention are that there is provided a kind of new amidoxime chemical industry for the problem of security is poor in the prior art Skill reacts method of controlling security under the conditions of mixed catalyst.This method has the preferable advantage of security.
To solve the above problems, the technical solution adopted by the present invention is as follows：A kind of oximes technique is under the conditions of mixed catalyst Method of controlling security is reacted, in the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, mixed catalyst bar is being used Occur to arrange there is provided the security control of safe and reliable Ammoximation reaction conversion ratio and selectivity during catalyst inactivation under part Apply, to ensure the security of Ammoximation reaction, prevent gas phase and fire；Wherein, mixed catalyst be fresh catalyst with The mixture of regenerated catalyst or the catalyst mixture formed by catalyst addition fresh catalyst into positive use, wherein Fresh catalyst mass fraction is 1%-99%；During Ammoximation reaction cyclohexanone conversion value is gradually reduced, using corresponding Treatment measures：(1) by way of adding fresh catalyst, addition is the 10%-50% of existing catalyst in reaction system, To improve the conversion ratio of cyclohexanone；(2) cyclohexanone conversion ratio is not lower than 90%, is stopped when less than 90%, cuts off dioxygen Water and fed cyclohexanone, more terminating reaction, catalyst changeout；During Ammoximation reaction cyclohexanone oxime is selectively gradually reduced, Using corresponding treatment measures：(1) by way of adding fresh catalyst, addition is existing catalysis in reaction system The 10%-50% of agent, to improve the conversion ratio of cyclohexanone；(2) cyclohexanone oxime selectively not lower than 95%, when less than 95% When stop, cut-out hydrogen peroxide and fed cyclohexanone, more terminating reaction, catalyst changeout.
In above-mentioned technical proposal, it is preferable that fresh catalyst addition is the 20%-30% of existing catalyst in reaction system.
In above-mentioned technical proposal, it is preferable that regenerated catalyst is fresh catalyst inactivation later by washing, boiling, tertiary fourth Reusable catalyst after alcohol cleaning, dry or roasting, its catalytic activity is generally fresh catalyst 50%-99%.
Method of controlling security is reacted under the conditions of mixed catalyst the present invention relates to a kind of oximes technique.Main purpose of the present invention It is more preferable control reaction conversion ratio and selectivity under the conditions of using mixed catalyst to be, is prevented due in reactor tail gas Oxygen and laughing gas too high levels and cause reactor to explode, it is ensured that the operation of the safety and steady of device, achieve preferable technology effect Really.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
In the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, using titanium-silicon molecular sieve catalyst, mixed catalyst For fresh catalyst and the mixture of regenerated catalyst, wherein fresh catalyst and regenerated catalyst mass ratio are 8：2；Regeneration Catalyst is repeatable after washing, boiling, tert-butyl alcohol cleaning, dry or roasting after fresh catalyst is inactivated makes Catalyst, its catalytic activity is generally the 80% of fresh catalyst.Catalyst occurs under the conditions of using mixed catalyst There is provided safe and reliable Ammoximation reaction conversion ratio and the safety control measures of selectivity in inactivation, to ensure amidoxime Change the security of reaction, prevent gas phase and fire.When Ammoximation reaction cyclohexanone conversion ratio is 91%, fresh urge is added Agent, addition is 30% of catalytic amount in reaction system, and the conversion ratio of cyclohexanone can be made to come back to 99%.
【Embodiment 2】
In the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, using titanium-silicon molecular sieve catalyst, mixed catalyst For fresh catalyst and the mixture of regenerated catalyst, wherein fresh catalyst and regenerated catalyst mass ratio are 9：1；Regeneration Catalyst is repeatable after washing, boiling, tert-butyl alcohol cleaning, dry or roasting after fresh catalyst is inactivated makes Catalyst, its catalytic activity is generally the 90% of fresh catalyst.Catalyst occurs under the conditions of using mixed catalyst There is provided safe and reliable Ammoximation reaction conversion ratio and the safety control measures of selectivity in inactivation, to ensure amidoxime Change the security of reaction, prevent gas phase and fire.When Ammoximation reaction cyclohexanone conversion ratio is 95%, fresh urge is added Agent, addition is 20% of catalytic amount in reaction system, and the conversion ratio of cyclohexanone can be made to come back to more than 99%.
【Embodiment 3】
In the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, using titanium-silicon molecular sieve catalyst, mixed catalyst For fresh catalyst, wherein fresh catalyst and regenerated catalyst mass ratio are 5：5；Regenerated catalyst is lost for fresh catalyst The reusable catalyst after washing, boiling, tert-butyl alcohol cleaning, dry or roasting later living, it is catalyzed work Property is generally the 70% of fresh catalyst.There is provided safety during generation catalyst inactivation under the conditions of using mixed catalyst The safety control measures of reliable Ammoximation reaction conversion ratio and selectivity, to ensure the security of Ammoximation reaction, are prevented Generation gas phase is fired.When Ammoximation reaction cyclohexanone conversion ratio is 89%, stop in emergency, cut-out hydrogen peroxide and cyclohexanone enter Material, more terminating reaction, catalyst changeout.
【Embodiment 4】
In the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, using titanium-silicon molecular sieve catalyst, mixed catalyst For fresh catalyst and the mixture of regenerated catalyst, wherein fresh catalyst and regenerated catalyst mass ratio are 7：3；Regeneration Catalyst is repeatable after washing, boiling, tert-butyl alcohol cleaning, dry or roasting after fresh catalyst is inactivated makes Catalyst, its catalytic activity is generally the 90% of fresh catalyst.Catalyst occurs under the conditions of using mixed catalyst There is provided safe and reliable Ammoximation reaction conversion ratio and the safety control measures of selectivity in inactivation, to ensure amidoxime Change the security of reaction, prevent gas phase and fire.When Ammoximation reaction cyclohexanone oxime is selectively 98%, add fresh Catalyst, addition is 10% of catalytic amount in reaction system, and the conversion ratio of cyclohexanone can be made to come back to more than 99%.
【Embodiment 5】
In the process unit of hydrogen peroxide oxidation Cyclohexanone Production cyclohexanone, using titanium-silicon molecular sieve catalyst, mixed catalyst For fresh catalyst, wherein fresh catalyst ratio is 3 for wherein fresh catalyst and regenerated catalyst mass ratio：7；Regeneration Catalyst is repeatable after washing, boiling, tert-butyl alcohol cleaning, dry or roasting after fresh catalyst is inactivated makes Catalyst, its catalytic activity is generally the 50% of fresh catalyst.Catalyst occurs under the conditions of using mixed catalyst There is provided safe and reliable Ammoximation reaction conversion ratio and the safety control measures of selectivity in inactivation, to ensure amidoxime Change the security of reaction, prevent gas phase and fire.When Ammoximation reaction cyclohexanone oxime is selectively 94%, should promptly it stop Car, cut-out hydrogen peroxide and fed cyclohexanone, more terminating reaction, catalyst changeout.
Obviously, using corresponding conversion ratio of the present invention and the method for controlling security of selectivity, it is effectively ensured oximes anti- Security is answered, prevents blast accident, it is to avoid unplanned parking, it is ensured that the safety and steady operation of device, is achieved preferably Technique effect.

Claims (3)

1. a kind of oximes technique reacts method of controlling security under the conditions of mixed catalyst, in hydrogen peroxide oxidation Cyclohexanone Production ring In the process unit of hexanone, there is provided safe and reliable ammonia during generation catalyst inactivation under the conditions of using mixed catalyst The safety control measures of oximation reaction conversion ratio and selectivity, to ensure the security of Ammoximation reaction, prevent gas phase Fire；Wherein, mixed catalyst is the mixture of fresh catalyst and regenerated catalyst or catalyst is added into positive use Catalyst mixture formed by fresh catalyst, wherein fresh catalyst mass fraction are 1%-99%；Ammoximation reaction hexamethylene During ketone conversion value is gradually reduced, using corresponding treatment measures：(1) by way of adding fresh catalyst, Addition is the 10%-50% of existing catalyst in reaction system, to improve the conversion ratio of cyclohexanone；(2) cyclohexanone conversion ratio Not lower than 90%, stopped when less than 90%, cut-out hydrogen peroxide and fed cyclohexanone, more terminating reaction, catalyst changeout； During Ammoximation reaction cyclohexanone oxime is selectively gradually reduced, using corresponding treatment measures：(1) it is fresh by adding The mode of catalyst, addition is the 10%-50% of existing catalyst in reaction system, to improve the conversion ratio of cyclohexanone；(2) Cyclohexanone oxime selectively not lower than 95%, stops when less than 95%, cut-out hydrogen peroxide and fed cyclohexanone, terminating reaction, More catalyst changeout.
2. oximes technique reacts method of controlling security under the conditions of mixed catalyst according to claim 1, it is characterised in that Fresh catalyst addition is the 20%-30% of existing catalyst in reaction system.
3. oximes technique reacts method of controlling security under the conditions of mixed catalyst according to claim 1, it is characterised in that Regenerated catalyst is that fresh catalyst inactivation can be weighed after washing, boiling, tert-butyl alcohol cleaning, dry or roasting later The catalyst used again, its catalytic activity is generally the 50%-99% of fresh catalyst.
CN201610191799.6A 2016-03-30 2016-03-30 Oximes technique reacts method of controlling security under the conditions of mixed catalyst Pending CN107286051A (en)

Priority Applications (1)

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Application Number Priority Date Filing Date Title
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949191A (en) * 2014-05-13 2014-07-30 湖北三宁化工股份有限公司 Device and method for continuously adding catalysts in cyclohexanone oximation reaction

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103949191A (en) * 2014-05-13 2014-07-30 湖北三宁化工股份有限公司 Device and method for continuously adding catalysts in cyclohexanone oximation reaction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘卫东: "氨肟化法制备环己酮肟的工艺条件的优化", 《广州化工》 *
李红梅: "氨肟化反应中双氧水分解的影响因素探讨", 《合成纤维工业》 *

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Effective date of registration: 20190711

Address after: 100728 Chaoyangmen North Street, Chaoyang District, Chaoyang District, Beijing

Applicant after: Sinopec Corp.

Applicant after: Qingdao Safety Engineering Research Institute of Sinopec Co., Ltd.

Applicant after: SINOPEC Research Institute of Petroleum Processin

Address before: 266071 218 Yanan three road, Shinan District, Qingdao, Shandong

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Application publication date: 20171024