CN102161008B - Method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene - Google Patents
Method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene Download PDFInfo
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- CN102161008B CN102161008B CN2011100472028A CN201110047202A CN102161008B CN 102161008 B CN102161008 B CN 102161008B CN 2011100472028 A CN2011100472028 A CN 2011100472028A CN 201110047202 A CN201110047202 A CN 201110047202A CN 102161008 B CN102161008 B CN 102161008B
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- 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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- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene, comprising the following steps of: a) conveying reaction products obtained in a partial hydrogenation system of benzene into a precipitator for splitting phase so as to separate an oil phase and a water phase; b) leading the oil phase obtained by separation in the step a to enter a filter so as to separate out solids such as a catalyst and the like; c) carrying out flash vaporization on an oil-phase filtrate obtained by filtering in the step b so as to separate out a remaining gas phase; and d) carrying out washing on the oil phase flash-vaporized in the step c, extracting water-soluble substances to obtain an extracting phase, and leading the extracting phase oil phase to enter a following rectification procedure. In the catalyst recovery method, the catalyst can return to the reaction system for circular use, so that the unit consumption of the catalyst is obviously reduced, and the energy consumption can be reduced.
Description
Technical field
The present invention relates to a kind of catalyst recovery method, particularly relate to the catalyst recovery method that a kind of benzene partial hydrogenation prepares cyclohexene.
Background technology
Cyclohexene has active two keys, and is of many uses as Organic Chemicals.But cyclohexene direct hydration cyclohexanol processed particularly, this not only can shorten the production process route of caprolactam and adipic acid, and has high economic benefit.The preparation method of cyclohexene has at present: dehydration of cyclohexanol method, cyclohexane halide are taken off halocarbon method, reducing process etc., but these preparation method's cost height, technology is very complicated, can not satisfy the needs of large-scale industrial production.Doing a large amount of research and experiment aspect the exploration cyclohexene new preparation process abroad.Du pont company added water additives such as solube metallic inorganic salts or metal carbonyl in aqueous phase system in 1972, carry out the producing cyclohexene with benzene selective hydrogenation reaction with ruthenium catalyst, the cyclohexene yield reaches more than 32%, improved the cyclohexene productive rate greatly, be an economy, industrial feasible cyclohexene produces route.For seeking desirable catalyst and reaction process condition so that the partial hydrogenation of benzene can to obtain higher benzene conversion ratio and cyclohexene selective, a large amount of research work and continuous acquisition of technology progress have been carried out for many years, up to the eighties in last century, company of Japanese Asahi Chemical Industry just realizes for the first time suitability for industrialized production.
The mononuclear aromatics partial hydrogenation that CN1079727A proposes prepares the method for cyclohexene, product must be through gas-liquid separator and the oil-water separator of an outside after leaving reactor, telling hydrogeneous gas phase and contain the water of catalyst, thereby obtain containing the oil-phase product of cyclohexene.
CN1696087A proposes a kind of equipment for producing cyclohexenol through benzene plus hydrogen, establish in comprising multistage stirring vane and spiral heat exchange coil autoclave and on the baffle plate of band raster, the baffle plate on carry potential overflow weir and the reducing center sedimentation pipe of deflection plate are arranged, sedimentation core, the isostructural phase-splitter of sedimentation piece are arranged down.The oil phase crude product that reactor adopts the overflow mode to tell is transported to phase-splitter, and a little gas of deviating to carry secretly in phase-splitter, sedimentation go out to contain the outstanding slurry of water of catalyst, obtains containing the oil-phase product of cyclohexene.
Above-mentioned measure purpose is that catalyst, co-catalyst and dispersant etc. are separated from reactant liquor and Returning reacting system as much as possible.Although equipment such as phase-splitter are improved, but because the unstability of operation and the dissolubility of catalyst, still there are expensive catalysts, co-catalyst and dispersant that quantity can not be ignored not separate and cause loss from separator, improved the operating cost of device.In addition, owing to directly go later separation also to cause the problems such as fouling of equipment easily.
Summary of the invention
The technical problem to be solved in the present invention provides the catalyst recovery method that a kind of benzene partial hydrogenation prepares cyclohexene, and the catalyst Returning reacting system is recycled, and significantly reduces the unit consumption of catalyst, cuts down the consumption of energy.
For solving the problems of the technologies described above, the invention provides the catalyst recovery method that a kind of benzene partial hydrogenation prepares cyclohexene, comprise the steps:
A) product that benzene partial hydrogenation reaction system is obtained is sent into settler and is carried out phase-splitting, so that oil phase and aqueous phase separation contain cyclohexene, cyclohexane, benzene etc. in the oil phase, water is the outstanding slurry that contains catalyst;
B) oil phase that separation obtains among the step a enters filter and isolates solids such as catalyst;
C) step b filtration is obtained oil phase filtrate and carry out flash distillation, isolate remaining gas phase, remove residual gas such as unreacted hydrogen;
D) step c is washed through the oil phase after the flash distillation, extract that water-soluble substances obtains extraction phase in the catalyst, the raffinate phase oil phase enters follow-up rectification working process.
Above-mentioned catalyst recovery method, wherein, the water that obtains among the described step a returns benzene partial hydrogenation reaction system; Described step b filters the filter cake that obtains and returns benzene partial hydrogenation reaction system; The extraction phase that described steps d obtains returns benzene partial hydrogenation reaction system.
Above-mentioned catalyst recovery method, wherein, the pressure of flash distillation is 0.4-0.6MPa among the described step c.
Above-mentioned catalyst recovery method, wherein, institute's water consumption and oil phase substance weight ratio are 1 in the described steps d: 1-1: 20, be preferably 1: 5-1: 10.
Benzene partial hydrogenation of the present invention prepares and adopts traditional ruthenium catalyst in the reaction system of cyclohexene, co-catalyst can adopt zinc sulfate, dispersant can adopt zirconia, adopts method of the present invention can with solid matter such as catalyst, co-catalyst and dispersant and water-soluble substances is basic all to reclaim.Settler and filter used in the catalyst recovery method of the present invention are conventional equipment, can buy in market.
Benzene partial hydrogenation of the present invention prepares the catalyst recovery method of cyclohexene, catalyst in the reaction system, co-catalyst and dispersant effectively can be reclaimed, Returning reacting system is recycling, significantly reduced the consumption of materials such as catalyst, co-catalyst, can cut down the consumption of energy, and can prevent the equipment scaling of subsequent handling.
The specific embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
The reacted reaction mixture of benzene partial hydrogenation reaction system is joined in the settler, after settler separates, the water that contains catalyst turns back in the reaction system and recycles, contain cyclohexene, cyclohexane, the oil phase of materials such as benzene enters into filter, oil phase filters through filter, the filter cake that contains catalyst that obtains turns back in the reaction system and recycles, oil phase filtrate enters into flash tank and carries out flash distillation, flashing pressure is 0.5MPa, isolate unreacted hydrogen and other residual gas, enter water washing device through the oil phase after the flash distillation, the weight ratio of institute's water consumption and oil phase substance is 1: 5, through washing, water-soluble substances in the catalyst is extracted from oil phase, obtain extraction phase, extraction phase is turned back to reaction system recycle, the raffinate phase that obtains enters follow-up rectification working process.
Adopt the catalyst recovery method of present embodiment, the rate of recovery of catalyst can reach 99.9%, effectively reduces the loss of catalyst.
Embodiment 2
The reaction mixture of benzene partial hydrogenation reaction system is joined in the settler, after settler separates, the water that contains catalyst turns back in the reaction system and recycles, contain cyclohexene, cyclohexane, the oil phase of materials such as benzene enters into filter, oil phase filters through filter, the filter cake that contains catalyst that obtains turns back in the reaction system and recycles, oil phase filtrate enters into flash tank and carries out flash distillation, flashing pressure is 0.4MPa, isolate unreacted hydrogen and other residual gas, enter water washing device through the oil phase after the flash distillation, the weight ratio of institute's water consumption and oil phase substance is 1: 1, through washing, water-soluble substances in the catalyst is extracted from oil phase, obtain extraction phase, extraction phase is turned back to reaction system recycle, the raffinate phase that obtains enters follow-up rectification working process.
Adopt the catalyst recovery method of present embodiment, the rate of recovery of catalyst can reach 99.7%, effectively reduces the loss of catalyst.
Embodiment 3
The reaction mixture of benzene partial hydrogenation reaction system is joined in the settler, after settler separates, the water that contains catalyst turns back in the reaction system and recycles, contain cyclohexene, cyclohexane, the oil phase of materials such as benzene enters into filter, oil phase filters through filter, the filter cake that contains catalyst that obtains turns back in the reaction system and recycles, oil phase filtrate enters into flash tank and carries out flash distillation, flashing pressure is 0.5MPa, isolate unreacted hydrogen and other residual gas, enter water washing device through the oil phase after the flash distillation, the weight ratio of institute's water consumption and oil phase substance is 1: 10, through washing, water-soluble substances in the catalyst is extracted from oil phase, obtain extraction phase, extraction phase is turned back to reaction system recycle, the raffinate phase that obtains enters follow-up rectification working process.
Adopt the catalyst recovery method of present embodiment, the rate of recovery of catalyst can reach 99.8%, effectively reduces the loss of catalyst.
Embodiment 4
The reaction mixture of benzene partial hydrogenation reaction system is joined in the settler, after settler separates, the water that contains catalyst turns back in the reaction system and recycles, contain cyclohexene, cyclohexane, the oil phase of materials such as benzene enters into filter, oil phase filters through filter, the filter cake that contains catalyst that obtains turns back in the reaction system and recycles, oil phase filtrate enters into flash tank and carries out flash distillation, flashing pressure is 0.6MPa, isolate unreacted hydrogen and other residual gas, enter water washing device through the oil phase after the flash distillation, the weight ratio of institute's water consumption and oil phase substance is 1: 20, through washing, water-soluble substances in the catalyst is extracted from oil phase, obtain extraction phase, extraction phase is turned back to reaction system recycle, the raffinate phase that obtains enters follow-up rectification working process.
Adopt the catalyst recovery method of present embodiment, the rate of recovery of catalyst can reach 99.7%, effectively reduces the loss of catalyst.
Claims (4)
1. a benzene partial hydrogenation prepares the catalyst recovery method of cyclohexene, comprises the steps:
A) product that benzene partial hydrogenation reaction system is obtained is sent into settler and is carried out phase-splitting, so that oil phase and aqueous phase separation, the water that obtains returns benzene partial hydrogenation reaction system;
B) oil phase that separation obtains among the step a enters filter and isolates solids, and the filter cake that obtains returns benzene partial hydrogenation reaction system;
C) step b filtration is obtained oil phase filtrate and carry out flash distillation, isolate remaining gas phase;
D) step c is washed through the oil phase after the flash distillation, extract water-soluble substances and obtain extraction phase, extraction phase returns benzene partial hydrogenation reaction system, and the raffinate phase oil phase enters follow-up rectification working process.
2. catalyst recovery method as claimed in claim 1, wherein, the pressure of flash distillation is 0.4-0.6MPa among the described step c.
3. catalyst recovery method as claimed in claim 1, wherein, institute's water consumption and oil phase substance weight ratio are 1 in the described steps d: 1-1: 20.
4. catalyst recovery method as claimed in claim 3, wherein, institute's water consumption and oil phase substance weight ratio are 1 in the described steps d: 5-1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100472028A CN102161008B (en) | 2011-02-28 | 2011-02-28 | Method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100472028A CN102161008B (en) | 2011-02-28 | 2011-02-28 | Method for recovering catalyst in preparation of cyclohexene by partial hydrogenation of benzene |
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| CN102161008A CN102161008A (en) | 2011-08-24 |
| CN102161008B true CN102161008B (en) | 2013-08-21 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659502B (en) * | 2012-04-24 | 2014-06-18 | 中国天辰工程有限公司 | Partial hydrogenation of benzene process method capable of recycling catalysts |
| CN109158113A (en) * | 2018-07-18 | 2019-01-08 | 北京华和拓科技开发有限责任公司 | A kind of partial hydrogenation of benzene catalyst recovery system and its implementation |
| CN109438167B (en) * | 2018-12-27 | 2024-04-12 | 成都科特瑞兴科技有限公司 | Cyclohexene energy-saving production system and production method |
| CN111056903B (en) * | 2019-11-29 | 2022-05-13 | 河北美邦膜科技有限公司 | Process and device for recovering benzene partial hydrogenation catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079727A (en) * | 1992-01-24 | 1993-12-22 | 旭化成工业株式会社 | The method of mononuclear aromatics partial hydrogenation |
| CN1696087A (en) * | 2005-05-17 | 2005-11-16 | 中国神马集团有限责任公司 | Equipment for producing cyclohexenol through benzene plus hydrogen |
| CN1696086A (en) * | 2005-05-17 | 2005-11-16 | 郑州大学 | Technique for producing cyclohexenol through benzene plus hydrogen, catalyst applied and preparation method |
| CN101850225A (en) * | 2010-06-28 | 2010-10-06 | 中国天辰工程有限公司 | Benzene selective hydrogenation device |
-
2011
- 2011-02-28 CN CN2011100472028A patent/CN102161008B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079727A (en) * | 1992-01-24 | 1993-12-22 | 旭化成工业株式会社 | The method of mononuclear aromatics partial hydrogenation |
| CN1696087A (en) * | 2005-05-17 | 2005-11-16 | 中国神马集团有限责任公司 | Equipment for producing cyclohexenol through benzene plus hydrogen |
| CN1696086A (en) * | 2005-05-17 | 2005-11-16 | 郑州大学 | Technique for producing cyclohexenol through benzene plus hydrogen, catalyst applied and preparation method |
| CN101850225A (en) * | 2010-06-28 | 2010-10-06 | 中国天辰工程有限公司 | Benzene selective hydrogenation device |
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