CN113717130B - Continuous production method of epoxycyclohexane - Google Patents
Continuous production method of epoxycyclohexane Download PDFInfo
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- CN113717130B CN113717130B CN202111171406.2A CN202111171406A CN113717130B CN 113717130 B CN113717130 B CN 113717130B CN 202111171406 A CN202111171406 A CN 202111171406A CN 113717130 B CN113717130 B CN 113717130B
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- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000010924 continuous production Methods 0.000 title claims abstract description 37
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 311
- 239000003054 catalyst Substances 0.000 claims abstract description 241
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 146
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims abstract description 97
- 238000000926 separation method Methods 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000000605 extraction Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 26
- 238000007670 refining Methods 0.000 claims abstract description 25
- 239000008346 aqueous phase Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000012071 phase Substances 0.000 claims description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000011964 heteropoly acid Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 31
- 239000002351 wastewater Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- -1 small-molecule olefins Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention provides a continuous production method of cyclohexene oxide, which comprises the following steps: s1, mixing a catalyst, a hydrogen peroxide solution and cyclohexene raw materials, and performing at least two-stage epoxidation reaction; s2, conveying the cyclohexene material obtained in the step S1 to a cyclohexene refining tower for separation; s3, conveying the material containing the catalyst and the cyclohexene oxide obtained in the step S2 to at least one stage of epoxidation reaction to serve as a raw material; s4, conveying an aqueous phase obtained by oil-water separation of a product of the final stage epoxidation reaction in the step S1 to a catalyst extraction tower, and injecting cyclohexene materials extracted from the top of a cyclohexene separation tower into the lower part of the catalyst extraction tower to recover cyclohexene oxide; s5, feeding a part of materials containing the catalyst and the cyclohexene oxide extracted from the tower bottom of the product tower in the step S2 into a catalyst regeneration device for catalyst regeneration, and feeding the regenerated catalyst into at least one stage of epoxidation reaction for use. The invention realizes the recovery of the catalyst and the stable continuous production of the cyclohexene oxide, and has high yield of the cyclohexene oxide and lower material consumption and energy consumption.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a continuous production method of epoxy cyclohexane.
Background
The epoxy cyclohexane is a fine chemical raw material with active chemical properties, can be used as an intermediate for synthesizing various chemical products, is an organic solvent with strong dissolving capacity, has very wide application, and can be used in the fields of medicines, pesticides, solvents, plasticizers, curing agents, flame retardants, diluents, adhesives, surfactants, biodegradable material monomers and the like. The most promising application among them is the copolymerization of cyclohexene oxide and carbon dioxide to produce polycyclohexenyl carbonate (PCHC), which is considered as a promising alternative to conventional Polystyrene (PS) plastics.
The scholars at home and abroad have conducted a great deal of research on the production of the cyclohexene oxide, and the industrial progress is that the process is carried out by the hydrogen peroxide and cyclohexene epoxidation technology, and the process is pollution-free to the environment, and is a green and environment-friendly process for preparing the cyclohexene oxide.
The existing olefin epoxidation catalysts are mainly divided into two main types, namely titanium-silicon molecular sieve catalysts and heteropolyacid quaternary ammonium salt system catalysts, wherein the titanium molecular sieve catalysts such as TS-1 and the like are determined by virtue of pore structure characteristics and are mainly applied to the epoxidation reaction of small-molecule olefins such as propylene and the like, solvents such as methanol and the like are required to be used in the reaction process, and the deactivation of the molecular sieve catalysts is generally caused by loss of active species titanium, active site agglomeration and the like, so that the catalyst regeneration is difficult and has high cost, and the catalyst needs to be directly replaced after the industrialization is generally deactivated. The heteropolyacid system catalyst is widely applied to olefin epoxidation reaction, but the activity of the heteropolyacid salt catalyst is obviously reduced when the application time is increased in the reaction process, and the recycling performance of the heteropolyacid catalyst and the recovery rate of the catalyst are main problems for restricting the industrial application of the heteropolyacid catalyst.
Patent CN1401640a Xi Zuwei et al developed a reaction control phase transfer catalyst, in which the catalyst was dissolved in the reaction system to undergo epoxidation reaction, and after the reaction was completed, the catalyst was precipitated from the reaction system to be changed into a heterogeneous catalyst, and the process adopted intermittent reaction, and a large amount of solvents such as methylene dichloride were used in the process, and the catalyst was recycled, so that the catalyst had the problems of long catalyst precipitation and separation time, large loss, and high catalyst use cost. Patent CN101343261B proposes that during the oxidation reaction, the hydrogen peroxide conversion rate is increased, so that the catalyst can be completely separated out, thereby improving the recovery rate of the oil phase catalyst, but the catalyst loss is unavoidable in the water phase, and the expensive olefin must be excessive compared with the cheap hydrogen peroxide, so that the cyclohexene loss is greater due to cyclohexene polymerization. Patent CN101992125B proposes a method for regenerating heteropolyacid quaternary ammonium salt catalyst, firstly, washing the deactivated catalyst with solvent, then dissolving the catalyst with mixed solvent of halogenated hydrocarbon containing hydrogen peroxide, and supplementing phosphorus source and quaternary ammonium salt to regenerate the catalyst. However, the method has long process route, low treatment efficiency and high cost, and cannot meet the industrial requirements. Patent CN108073143a recognizes that by regulating the catalyst particle size, the particle size of the precipitated catalyst can be increased, the recovery rate of the catalyst is improved, but still there is a catalyst loss of more than 2kg/t, and the residual product of the rectifying still is lost. Patent CN110156726a proposes a method for recovering an inactivated heteropolyacid catalyst from a pot raffinate and regenerating it, but no patent reports on recovery of an aqueous phase catalyst due to a catalyst loss of more than 15% in the aqueous phase. The subject group proposes a reaction rectification method in patent CN112142689a, in which the catalyst stays in the reactor all the time, the catalyst is not lost, and only the deactivated catalyst is discharged and fresh catalyst is supplemented, but the problems of catalyst deactivation and catalyst recycling still exist.
Therefore, in order to apply the method of applying the heteropolyacid quaternary ammonium salt catalyst to the epoxidation reaction of olefin and hydrogen peroxide to industrially prepare olefin oxide or olefin epoxide, development of a technology which has high reactant conversion rate and high reaction yield and can improve the utilization rate of the catalyst and realize complete recovery of the catalyst and low material consumption and low energy consumption for producing olefin epoxide is urgently needed.
Disclosure of Invention
The technical problem solved by the invention is to provide a continuous production method of cyclohexene oxide, wherein the water phase is separated from the refined cyclohexene after each stage of reaction as the next stage of reaction raw material through multistage epoxidation reaction, the temperature is gradually raised for each stage of reaction to ensure complete hydrogen peroxide conversion, the concentration of the cyclohexene oxide in the system is low, and the reaction yield is high; the cyclohexene and the cyclohexene oxide are adopted to extract and recycle the lost catalyst in the water phase, and simultaneously, the cyclohexene is injected into the bottom of the extraction tower, so that the cyclohexene oxide in the water phase is further recycled, and the utilization rate of the catalyst and the raw materials is improved; the catalyst is dissolved in organic phase of cyclohexene oxide, cyclohexene and the like, circulated along with high boiling point substances of the cyclohexene oxide and the like, and regenerated after being deactivated, so that the activity of the catalyst is ensured to be stable.
In order to solve the above problems, an aspect of the present invention provides a continuous production apparatus for epoxycyclohexane, comprising:
the device comprises a cyclohexene separation tower, a cyclohexene refining tower, a product tower and at least two stages of reaction crude separation devices, wherein each stage of reaction crude separation device comprises an epoxidation reactor and an oil-water separator;
in each stage of the reaction coarse separation device, a discharge port of the epoxidation reactor is connected with a feed port of the oil-water separator, and an oil phase outlet of the oil-water separator is connected with a feed port of the cyclohexene separation tower; the water phase outlet of the oil-water separator of the reaction coarse separation device at the previous stage is connected with the feed inlet of the epoxidation reactor of the reaction coarse separation device at the next stage, the top discharge outlet of the cyclohexene separation tower is connected with the feed inlet of the cyclohexene refining tower, the bottom discharge outlet of the cyclohexene refining tower is connected with the feed inlet of the epoxidation reactor of the reaction coarse separation device at least one stage, the bottom discharge outlet of the cyclohexene separation tower is connected with the feed inlet of the product tower, and the bottom discharge outlet of the product tower is connected with the feed inlet of the epoxidation reactor of the reaction coarse separation device at least one stage.
The continuous production device of the cyclohexene oxide adopts multistage epoxidation reaction, and fresh catalyst, hydrogen peroxide solution and cyclohexene enter a first-stage reaction coarse separation device to carry out epoxidation reaction; oil-water separation of products after each stage of epoxidation reaction; the water phase is used as a raw material of the next stage epoxidation reaction, the oil phase enters a cyclohexene separation tower to separate cyclohexene materials and materials rich in cyclohexene oxide and catalyst, the cyclohexene materials are sent to a cyclohexene refining tower to separate refined cyclohexene, the refined cyclohexene is used as a raw material of at least one stage of epoxidation reaction, the materials rich in cyclohexene oxide and catalyst are sent to a product tower to separate a cyclohexene oxide product and materials rich in catalyst and a small amount of cyclohexene oxide, and the materials rich in catalyst and a small amount of cyclohexene oxide are used as raw materials of at least one stage of epoxidation reaction. According to the continuous production device of the cyclohexene oxide, at least two stages of reactors are connected in series step by step, oil-water separation is carried out after each stage of reaction, products are separated in time, the side reaction loss of the high-temperature and high-concentration hydrolysis and the like of the cyclohexene oxide caused by high reaction temperature and long residence time in the next stage is prevented, the concentration of the cyclohexene oxide in a system is low, and the reaction yield is high; the temperature can be gradually increased in each stage of epoxidation reaction, the complete conversion of hydrogen peroxide is ensured, the content of peroxide in the final wastewater is reduced, and the wastewater treatment is facilitated.
Preferably, the method further comprises:
a catalyst extraction column;
the water phase outlet of the oil-water separator of the reaction coarse separation device at the last stage is connected with the feed inlet of the catalyst extraction tower, the oil phase outlet of the catalyst extraction tower is connected with the feed inlet of the cyclohexene separation tower, the middle and upper discharge port of the cyclohexene separation tower is connected with the extractant feed inlet of the catalyst extraction tower, and the top discharge port of the cyclohexene separation tower is connected with the bottom extractant feed inlet of the catalyst extraction tower.
The invention relates to a continuous production device of cyclohexene oxide, which adopts a solvent-free system for reaction, the loss rate of a conventional heteropolyacid catalyst in a water phase is about 15 percent, and the invention adopts cyclohexene materials containing 5 to 30 percent of cyclohexene oxide at a discharge hole at the upper middle part of a cyclohexene separation tower for extraction and recovery of the catalyst in the water phase, the materials containing cyclohexene from the top of the cyclohexene separation tower are injected at the lower part of the catalyst extraction tower for countercurrent contact, the catalyst is further recovered, almost all the catalyst in the catalyst is transferred into an oil phase, meanwhile, the dissolved cyclohexene oxide product in the water phase is extracted and recovered, and the product is returned to the cyclohexene separation tower, and waste water almost containing no catalyst is discharged outside the catalyst extraction tower, so that the loss of the catalyst is greatly reduced, and the yield of the cyclohexene oxide is improved.
Preferably, the method further comprises:
a catalyst regeneration device;
the tower kettle discharge port of the product tower is also connected with the feed inlet of the catalyst regeneration device, and the discharge port of the catalyst regeneration device is connected with the feed inlet of the epoxidation reactor of the reaction coarse separation device of at least one stage.
The continuous production device of the cyclohexene oxide is a solvent-free system epoxidation reaction, the catalyst is dissolved in an oil phase, the catalyst is circularly reacted in a system along with a small amount of the cyclohexene oxide product and the like, and the catalyst is regenerated through a catalyst regeneration device after the activity is reduced, so that the stability of the activity of the epoxidation catalyst is ensured.
Preferably, a tower bottom discharge port of the cyclohexene refining tower is connected with a feed port of the epoxidation reactor of each stage of the reaction crude separation device; and a tower bottom discharge hole of the product tower is connected with a feed inlet of the epoxidation reactor of each stage of the reaction coarse separation device.
Further, the device comprises a two-stage reaction coarse separation device, and an oil phase outlet of an oil-water separator of the first-stage reaction coarse separation device is connected with a feed inlet at the middle lower part of the cyclohexene separation tower; the oil phase outlet of the oil-water separator of the second-stage reaction coarse separation device is connected with the middle-upper feed inlet of the cyclohexene separation tower.
In another aspect, the present invention provides a continuous production method of cyclohexene oxide, comprising the steps of:
s1, mixing a catalyst, a hydrogen peroxide solution and cyclohexene raw materials, and performing at least two-stage epoxidation reaction; oil-water separation is carried out on the products of each stage of epoxidation reaction, the water phase obtained by separation is sent to the next stage of epoxidation reaction to be used as raw material, and the oil phase obtained by separation is sent to a cyclohexene separation tower to separate cyclohexene from cyclohexene oxide; cyclohexene materials are extracted from the top of the cyclohexene separation tower, and materials containing cyclohexene oxide and catalyst are extracted from the tower bottom;
s2, conveying the cyclohexene material obtained in the step S1 to a cyclohexene refining tower for separation, and conveying refined cyclohexene obtained by separation to at least one stage of epoxidation reaction as a raw material; the material containing the epoxycyclohexane and the catalyst in the step S1 is sent to a product tower for separation, and epoxycyclohexane products and materials containing the catalyst and the epoxycyclohexane are obtained;
and S3, conveying the material containing the catalyst and the cyclohexene oxide obtained in the step S2 to at least one stage of epoxidation reaction to serve as a raw material.
The continuous production method of the cyclohexene oxide adopts multistage epoxidation reaction, and fresh catalyst, hydrogen peroxide solution and cyclohexene are subjected to first-stage epoxidation reaction; oil-water separation of products after each stage of epoxidation reaction; the water phase is used as a raw material of the next stage epoxidation reaction, the oil phase enters a cyclohexene separation tower to separate cyclohexene materials and materials rich in cyclohexene oxide and catalyst, the cyclohexene materials are sent to a cyclohexene refining tower to separate refined cyclohexene, the refined cyclohexene is used as a raw material of at least one stage of epoxidation reaction, the materials rich in cyclohexene oxide and catalyst are sent to a product tower to separate a cyclohexene oxide product and materials rich in catalyst and a small amount of cyclohexene oxide, and the materials rich in catalyst and a small amount of cyclohexene oxide are used as raw materials of at least one stage of epoxidation reaction. According to the continuous production method of the cyclohexene oxide, at least two stages of epoxidation reactions are serially connected step by step, oil-water separation is carried out after each stage of reaction, products are separated in time, and the high reaction temperature and long residence time of the next stage of reaction are prevented from causing the loss of side reactions such as hydrolysis and the like of the cyclohexene oxide at high temperature and high concentration, and the concentration of the cyclohexene oxide in a system is low, and the reaction yield is high.
Preferably, the method further comprises:
and S4, sending the water phase separated from the oil and water of the product of the final stage epoxidation reaction in the step S1 to a catalyst extraction tower, taking the material containing 5% -30% of cyclohexene oxide extracted from the cyclohexene separation tower as an extracting agent, and injecting the cyclohexene oxide extracted from the top of the cyclohexene separation tower into the lower part of the catalyst extraction tower to recover the cyclohexene oxide.
In the continuous production method of cyclohexene oxide, the water phase separated from the oil and water of the product of the final stage of epoxidation reaction is sent to a catalyst extraction tower because of containing partial catalyst, in the catalyst extraction tower, cyclohexene materials containing 5% -30% of cyclohexene oxide from a cyclohexene separation tower are contacted with waste water containing the catalyst, the catalyst in the cyclohexene materials is extracted to an oil phase, the cyclohexene materials are injected into the lower part of the catalyst extraction tower for countercurrent contact, the catalyst is further recovered, the dissolved cyclohexene oxide in the water phase is recovered, the catalyst in the water phase is almost completely transferred to the oil phase, and the waste water almost containing the catalyst is returned to the cyclohexene separation tower, and the waste water almost containing the catalyst is discharged outside the tower kettle of the catalyst extraction tower. Thereby greatly reducing the loss of the catalyst and improving the yield of the cyclohexene oxide.
Preferably, the method further comprises:
s5, feeding a part of materials containing the catalyst and the epoxycyclohexane extracted from the tower bottom of the product tower in the step S2 into a catalyst regeneration device for catalyst regeneration, and feeding the regenerated catalyst into at least one stage of epoxidation reaction for use.
The continuous production method of the cyclohexene oxide is a solvent-free system epoxidation reaction, the catalyst is dissolved in an oil phase, the catalyst is circularly reacted in a system along with a small amount of the cyclohexene oxide product and the like, and the catalyst is regenerated through a catalyst regeneration device after the activity is reduced, so that the stability of the activity of the epoxidation catalyst is ensured.
Preferably, in step S5, the catalyst regeneration includes sequentially performing: extracting, filtering, washing, activating hydrogen peroxide and drying; in the continuous production method of the cyclohexene oxide, the catalyst regeneration process is simple, only a small amount of hydrogen peroxide is consumed, and the catalyst consumption cost is greatly reduced.
Wherein the extracting agent is one or more of ethanol, ethyl acetate, petroleum ether, dichloromethane and chloroform; preferably, the extracting agent is one or a mixture of more of ethanol and ethyl acetate;
the washing is to wash with organic solvent and deionized water; the organic solvent is one or more of ethanol, diethyl ether, ethyl acetate, petroleum ether, dichloromethane and chloroform;
the hydrogen peroxide activation is carried out in a water phase, the concentration of the hydrogen peroxide is 1% -50%, and the mass ratio of the hydrogen peroxide to the catalyst is (0.5-10): 1, a step of; preferably, the concentration of the hydrogen peroxide is 5% -30%;
the drying temperature is 25-100 ℃, preferably 30-80 ℃.
Preferably, in step S1:
the catalyst is a heteropolyacid quaternary ammonium salt catalyst; further preferably, the catalyst is a phosphotungstic heteropolyacid quaternary ammonium salt catalyst or a phosphomolybdic heteropolyacid quaternary ammonium salt catalyst; further preferably, the catalyst is a phosphotungstic heteropolyacid quaternary ammonium salt catalyst.
The mol ratio of cyclohexene to hydrogen peroxide is (1-10): 1, a step of; further preferably, the molar ratio of cyclohexene to hydrogen peroxide solution is (1-6): 1, a step of; further preferably, the molar ratio of cyclohexene to hydrogen peroxide is (1.5-5): 1.
the addition amount of the catalyst is 0.02% -5% of the total mass of cyclohexene, hydrogen peroxide solution and the catalyst; preferably, the addition amount of the catalyst is 0.05% -3% of the total mass of cyclohexene, hydrogen peroxide and the catalyst; further preferably, the addition amount of the catalyst is 0.5% -2% of the total mass of cyclohexene, hydrogen peroxide and the catalyst.
The temperature of the epoxidation reaction of the next stage is higher than that of the epoxidation reaction of the previous stage;
the reaction temperature of the first stage epoxidation reaction is 30-100 ℃; preferably, the reaction temperature of the first stage epoxidation reaction is from 30 to 80 ℃; further preferably, the reaction temperature of the first stage epoxidation reaction is from 35 to 60 ℃;
the residence time of the first stage epoxidation reaction is 0.5 to 6 hours; preferably, the residence time of the first stage epoxidation reaction is from 1 to 5 hours; further preferably, the residence time of the first stage epoxidation reaction is from 2 to 4 hours;
the reaction temperature of the second stage epoxidation reaction is 35-100 ℃; preferably, the reaction temperature of the second stage epoxidation reaction is from 35 to 80 ℃; further preferably, the reaction temperature of the second stage epoxidation reaction is 40 to 70 ℃;
the residence time of the second stage epoxidation reaction is 0.5-8h; preferably, the residence time of the second stage epoxidation reaction is from 1 to 6 hours; it is further preferred that the residence time of the second stage epoxidation reaction is from 2 to 5 hours.
According to the continuous production method of the cyclohexene oxide, the temperature is gradually increased in each stage of epoxidation reaction, the complete conversion of hydrogen peroxide is ensured, the content of peroxide in the final wastewater is reduced, and the wastewater treatment is facilitated.
Preferably, the number of theoretical plates of the cyclohexene separation column, the cyclohexene refining column, the product column and the catalyst extraction column is 3-30; preferably, the number of theoretical plates of the cyclohexene separating column is 5-20; the theoretical plate number of the cyclohexene refining tower is 5-20; the theoretical plate number of the product tower is 10-30; the theoretical plate number of the catalyst extraction tower is 3-10;
the reflux ratio of the cyclohexene separation tower, the cyclohexene refining tower and the product tower is 1-10, and the pressure is 10-101.325kPa (absolute pressure); preferably, the reflux ratio of the product column is from 2 to 8; the pressure of the cyclohexene separating column and the cyclohexene refining column is 30-101.325kPa (absolute pressure); the pressure of the product tower is 10-50kPa (absolute pressure);
in the catalyst extraction tower, the mass ratio of the cyclohexene material to the material containing 5% -30% of cyclohexene oxide is (0.1-10): 1, preferably (1-6): 1, a step of; the mass ratio of the cyclohexene material to the material containing 5% -30% of cyclohexene oxide to the water phase of the catalyst extraction tower is (0.5-20): 1, preferably (1-10): 1, a step of; the extraction temperature is 30-60 ℃, preferably 40-60 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the continuous production method of the cyclohexene oxide adopts multistage epoxidation reaction, and fresh catalyst, hydrogen peroxide solution and cyclohexene are subjected to first-stage epoxidation reaction; oil-water separation of products after each stage of epoxidation reaction; the water phase is used as a raw material of the next stage epoxidation reaction, the oil phase enters a cyclohexene separation tower to separate cyclohexene materials and materials rich in cyclohexene oxide and catalyst, the cyclohexene materials are sent to a cyclohexene refining tower to separate refined cyclohexene, the refined cyclohexene is used as a raw material of at least one stage of epoxidation reaction, the materials rich in cyclohexene oxide and catalyst are sent to a product tower to separate a cyclohexene oxide product and materials rich in catalyst and a small amount of cyclohexene oxide, and the materials rich in catalyst and a small amount of cyclohexene oxide are used as raw materials of at least one stage of epoxidation reaction. According to the continuous production method of the cyclohexene oxide, at least two stages of epoxidation reactions are serially connected step by step, oil-water separation is carried out after each stage of reaction, products are separated in time, the side reaction loss of the high-temperature high-concentration hydrolysis and the like of the cyclohexene oxide caused by high reaction temperature and long residence time in the next stage is prevented, the concentration of the cyclohexene oxide in a system is low, and the reaction yield is high; the temperature is gradually increased in each stage of epoxidation reaction, so that the complete conversion of hydrogen peroxide is ensured, the content of peroxide in the final wastewater is reduced, and the wastewater treatment is facilitated;
2. according to the continuous production method of the cyclohexene oxide, the water phase separated from oil and water of the product of the final stage epoxidation reaction is sent to the catalyst extraction tower because of containing partial catalyst, in the catalyst extraction tower, cyclohexene materials containing 5% -30% of cyclohexene oxide from the cyclohexene separation tower are contacted with waste water containing the catalyst, the catalyst in the cyclohexene materials is extracted to an oil phase, the materials containing cyclohexene are injected into the lower part of the catalyst extraction tower for countercurrent contact, the catalyst is further recovered, the dissolved cyclohexene oxide in the water phase is recovered, the catalyst in the water phase is almost completely transferred to the oil phase, and the waste water almost containing the catalyst is returned to the cyclohexene separation tower, and the waste water almost containing the catalyst is discharged outside the tower kettle of the catalyst extraction tower. The method adopts a solvent-free system for reaction, and the loss rate of the conventional heteropolyacid catalyst in the water phase is about 15 percent, and the method adopts a mode of extracting and recycling the catalyst in the water phase by an oil phase to recycle the lost catalyst in the water phase, and simultaneously extracts and recycles the epoxy cyclohexane product dissolved in the water phase, thereby greatly reducing the loss of the catalyst and improving the yield of the epoxy cyclohexane;
3. the continuous production method of the cyclohexene oxide is a solvent-free system epoxidation reaction, the catalyst is dissolved in an oil phase, and the catalyst is circularly reacted in a system along with a small amount of the cyclohexene oxide product and the like, and the catalyst is regenerated through a catalyst regeneration device after the activity is reduced, so that the stability of the activity of the epoxidation catalyst is ensured;
4. in the continuous production method of the cyclohexene oxide, the catalyst regeneration process is simple, only a small amount of hydrogen peroxide is consumed, and the catalyst consumption cost is greatly reduced.
Drawings
FIG. 1 is a schematic structural view of a continuous production apparatus for cyclohexene oxide according to example 1 of the present invention.
Wherein: a 1-cyclohexene separation column; a 2-cyclohexene refining column; 3-a product column; 4-a first epoxidation reactor; 5-a first oil-water separator; a 6-second epoxidation reactor; 7-a second oil-water separator; 8-a catalyst extraction column; 9-a catalyst regeneration device.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, a continuous production apparatus for cyclohexene oxide of the present embodiment comprises:
a cyclohexene separating column 1, a cyclohexene refining column 2, a product column 3, a primary reaction crude separation device and a secondary reaction crude separation device, wherein the primary reaction crude separation device comprises a first epoxidation reactor 4 and a first oil-water separator 5, and the secondary reaction crude separation device comprises a second epoxidation reactor 6 and a second oil-water separator 7;
the first epoxidation reactor 4 is provided with a feed inlet for fresh catalyst, hydrogen peroxide solution and cyclohexene; the discharge port of the first epoxidation reactor 4 is connected with the feed port of the first oil-water separator 5; the discharge port of the second epoxidation reactor 6 is connected with the feed port of the second oil-water separator 7; the oil phase outlet of the first oil-water separator 5 is connected with the middle-lower feed inlet of the cyclohexene separating tower 1, the oil phase outlet of the second oil-water separator 7 is connected with the middle-upper feed inlet of the cyclohexene separating tower 1, and the water phase outlet of the first oil-water separator 5 is connected with the feed inlet of the second epoxidation reactor 6; the top discharge port of the cyclohexene separating column 1 is connected with the feed port of the cyclohexene refining column 2; a tower kettle discharge port of the cyclohexene separation tower 1 is connected with a feed port of the product tower 3; the tower kettle discharge port of the cyclohexene refining tower 2 is respectively connected with the feed inlets of the first epoxidation reactor 4 and the second epoxidation reactor 6, and the tower kettle discharge port of the product tower 3 is connected with the feed inlets of the first epoxidation reactor 4 and the second epoxidation reactor 6.
Fresh catalyst materials, hydrogen peroxide solution and cyclohexene materials are injected into a first epoxidation reactor, epoxidation reaction is carried out under certain temperature, pressure and stirring and mixing conditions, and products after the reaction are sent into a first oil-water separator for oil-water separation; the oil phase material separated in the first oil-water separator is sent to a feeding hole at the middle lower part of a cyclohexene separating tower, the separated water phase material containing part of unreacted hydrogen peroxide is sent to a second epoxidation reactor together with the circulating catalyst material from the tower bottom of the product tower and the refined cyclohexene material from the cyclohexene refining tower, the epoxidation reaction is carried out under the conditions of certain temperature, pressure and stirring and mixing, the hydrogen peroxide is completely converted, and the reaction liquid enters the second oil-water separator for oil-water separation; the oil phase separated by the second oil-water separator is sent to the middle upper part of a cyclohexene separating tower; the cyclohexene separation tower is used for separating cyclohexene from cyclohexene oxide and the like, cyclohexene materials extracted from the tower top are sent to a cyclohexene refining tower, and materials rich in the cyclohexene oxide and the catalyst at the tower bottom are sent to a product tower; and separating out the epoxycyclohexane product from the tower top of the product tower, and recycling materials rich in catalyst, a small amount of epoxycyclohexane and the like in the tower bottom back to the first epoxidation reactor and the second epoxidation reactor for continuous reaction.
Further, the method further comprises the following steps: a catalyst extraction column 8;
the water phase outlet of the second oil-water separator 7 is connected with the feed inlet of the catalyst extraction tower 8, the oil phase outlet of the catalyst extraction tower 8 is connected with the feed inlet of the cyclohexene separation tower 1, the middle-upper discharge port of the cyclohexene separation tower 1 is connected with the extractant feed inlet of the catalyst extraction tower 8, and the top discharge port of the cyclohexene separation tower 1 is connected with the bottom extractant feed inlet of the catalyst extraction tower 8.
The aqueous phase material separated by the second oil-water separator is sent to a catalyst extraction tower because of containing partial catalyst, in the catalyst extraction tower, the catalyst in the catalyst extraction tower is extracted to an oil phase through contacting cyclohexene material containing 5-30% cyclohexene oxide from the middle upper part of the cyclohexene separation tower with waste water containing the catalyst, the cyclohexene material from the top of the cyclohexene separation tower is injected into the lower part of the catalyst extraction tower for countercurrent contact, the catalyst is further recovered, the cyclohexene oxide of the solvent in the aqueous phase is recovered, almost all the catalyst in the catalyst is transferred to the oil phase, and the waste water almost containing the catalyst is returned to the cyclohexene separation tower, and the waste water almost containing the catalyst is discharged outside the catalyst extraction tower.
Further, the method further comprises the following steps: a catalyst regeneration device 9;
the tower kettle discharge port of the product tower 3 is also connected with the feed inlet of the catalyst regeneration device 9, and the discharge port of the catalyst regeneration device 9 is respectively connected with the feed inlets of the first epoxidation reactor 4 and the second epoxidation reactor 6.
And (3) feeding a part of materials rich in catalyst in the tower bottoms of the product towers extracted in the reaction process into a catalyst regeneration device to complete the regeneration of the catalyst, and supplementing regenerated or fresh catalyst materials in the first epoxidation reactor and the second epoxidation reactor.
Example 2
The continuous production method of the cyclohexene oxide comprises the following steps:
s1, mixing 0.2kg/h of a phosphotungstic acid quaternary ammonium salt catalyst, 3kg/h of a 30% hydrogen peroxide solution and 12kg/h of fresh cyclohexene, performing two-stage epoxidation reaction in series, putting fresh materials into a first-stage epoxidation reaction, and putting a water phase separated from the first-stage epoxidation reaction into a second-stage epoxidation reaction; specifically, the reaction temperature of the primary epoxidation reaction is 40 ℃, the retention time is 4 hours, the reaction temperature of the secondary epoxidation reaction is 60 ℃, the retention time is 4 hours, and the volume ratio of the reactor of the primary epoxidation reaction to the reactor of the secondary epoxidation reaction is 2:1; oil-water separation is carried out on products of the primary epoxidation reaction and the secondary epoxidation reaction, and water phase obtained by the separation of the primary epoxidation reaction is sent to the secondary epoxidation reaction as raw material; the oil phase obtained by the first-stage epoxidation reaction is sent to the middle lower part of a cyclohexene separating tower, and the oil phase obtained by the second-stage epoxidation reaction is sent to the middle upper part of the cyclohexene separating tower for separating cyclohexene from cyclohexene oxide; cyclohexene materials are extracted from the top of the cyclohexene separating tower, and materials containing cyclohexene oxide and catalyst are extracted from the tower bottom; wherein the theoretical plate number of the cyclohexene separating column is 15, the reflux ratio is 2, and the pressure is 50kPa absolute pressure;
s2, delivering the cyclohexene material obtained in the step S1 to a cyclohexene refining tower for separation, extracting refined cyclohexene from the bottom of the cyclohexene refining tower, and delivering the refined cyclohexene material to a primary epoxidation reaction and a secondary epoxidation reaction as raw materials; the materials containing the epoxy cyclohexane and the catalyst in the step S1 are sent to a product tower for separation, the epoxy cyclohexane product is extracted from the top of the product tower, and the materials containing the catalyst and the epoxy cyclohexane are extracted from the tower bottom; wherein the theoretical plate number of the cyclohexene refining column is 15, the reflux ratio is 2, and the pressure is 50kPa absolute pressure; the theoretical plate number of the product tower is 20, the reflux ratio is 5, and the pressure is 20kPa absolute pressure;
s3, delivering the materials containing the catalyst and the cyclohexene oxide extracted from the tower bottom of the product tower in the step S2 to a primary epoxidation reaction and a secondary epoxidation reaction as raw materials;
s4, sending the water phase separated from oil and water of the product of the secondary epoxidation reaction in the step S1 to a catalyst extraction tower, taking a material containing 5% -30% of cyclohexene oxide extracted from the upper part of a cyclohexene separation tower as an extracting agent, and injecting the cyclohexene material extracted from the top of the cyclohexene separation tower into the lower part of the catalyst extraction tower to recover the cyclohexene oxide; wherein the theoretical plate number of the catalyst extraction tower is 8; in the catalyst extraction tower, the mass ratio of cyclohexene material to material containing 5% -30% of cyclohexene oxide is 5; the mass ratio of cyclohexene material to material containing 5% -30% of cyclohexene oxide to the water phase of the catalyst extraction tower is 10; the extraction temperature is 40 ℃;
and S5, feeding a part of materials containing the catalyst and the epoxy cyclohexane extracted from the tower bottom of the product tower in the step S2 into a catalyst regeneration device for catalyst regeneration, and feeding the regenerated catalyst into a primary epoxidation reaction and a secondary epoxidation reaction as raw materials. Wherein, the catalyst regeneration comprises the following steps of sequentially carrying out the following steps of: extracting, filtering, washing, activating with hydrogen peroxide and drying. The extractant adopted in the extraction is ethyl acetate; the washing is to adopt organic solvents of ethyl acetate and ethanol to wash for 1-2 times respectively, and then deionized water is adopted for washing; the hydrogen peroxide is activated in the water phase, the concentration of the hydrogen peroxide is 5% -15%, and the mass ratio of the hydrogen peroxide to the catalyst is 4; the temperature of drying was 40 ℃.
Example 3
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation reaction in an amount of 0.075kg/h at a primary epoxidation reaction temperature of 35℃and the secondary epoxidation reaction temperature of 45 ℃.
Example 4
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation reaction in an amount of 0.075kg/h at a primary epoxidation reaction temperature of 35℃and the secondary epoxidation reaction temperature of 50 ℃.
Example 5
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation reaction in an amount of 0.1kg/h at a primary epoxidation reaction temperature of 45℃and in a secondary epoxidation reaction at a secondary epoxidation reaction temperature of 50 ℃.
Example 6
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation at 0.2kg/h, the primary epoxidation temperature was 45℃and the secondary epoxidation temperature was 60 ℃.
Example 7
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation at 0.5kg/h, the primary epoxidation temperature was 45℃and the secondary epoxidation temperature was 60 ℃.
Example 8
The procedure of the continuous production method of epoxycyclohexane in this example was the same as in example 2 except that the fresh catalyst was added in the primary epoxidation at 0.5kg/h, the primary epoxidation temperature was 45℃and the secondary epoxidation temperature was 70 ℃.
Table 1 shows the hydrogen peroxide conversion, cyclohexene conversion and cyclohexene selectivity after various reaction times in the continuous process for the production of cyclohexene oxide in example 2.
TABLE 1
Table 2 shows the hydrogen peroxide conversion, cyclohexene conversion and cyclohexene selectivity after 4 hours of reaction in the continuous production method of cyclohexene oxide in each of the above examples. As can be seen from the data in Table 2, the catalyst addition amount of the invention is within 0.5% -3% of the total feed, and the two-stage reaction can obtain better reaction effect, and the reaction is continuous and stable.
TABLE 2
Table 3 shows the catalyst content and the epoxycyclohexane content in the wastewater in each example, and the data in the following table show that the content of the catalyst in the water phase is less than 500mg/L, and the loss rate of the converted catalyst is less than 1%; and the content of the epoxycyclohexane in the wastewater is lower than 100ppm, so that the loss of the catalyst is small, and the loss of the epoxycyclohexane in the water phase is low.
TABLE 3 Table 3
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (3)
1. A continuous production method of cyclohexene oxide, which is characterized by comprising the following steps:
s1, mixing a catalyst, a hydrogen peroxide solution and cyclohexene raw materials, and performing at least two-stage epoxidation reaction; oil-water separation is carried out on the products of each stage of epoxidation reaction, the water phase obtained by separation is sent to the next stage of epoxidation reaction to be used as raw material, and the oil phase obtained by separation is sent to a cyclohexene separation tower to separate cyclohexene from cyclohexene oxide; cyclohexene materials are extracted from the top of the cyclohexene separation tower, materials containing cyclohexene oxide and a catalyst are extracted from the tower bottom, the catalyst is a heteropolyacid quaternary ammonium salt catalyst, and the molar ratio of cyclohexene to hydrogen peroxide is (1-10): 1, the addition amount of the catalyst is 0.02% -5% of the total mass of cyclohexene, hydrogen peroxide solution and the catalyst, the temperature of the subsequent stage epoxidation reaction is higher than that of the previous stage epoxidation reaction, the reaction temperature of the first stage epoxidation reaction is 30-100 ℃, the retention time of the first stage epoxidation reaction is 0.5-6h, the reaction temperature of the second stage epoxidation reaction is 35-100 ℃, and the retention time of the second stage epoxidation reaction is 0.5-8h;
s2, conveying the cyclohexene material obtained in the step S1 to a cyclohexene refining tower for separation, and conveying refined cyclohexene obtained by separation to at least one stage of epoxidation reaction as a raw material; the material containing the epoxycyclohexane and the catalyst in the step S1 is sent to a product tower for separation, and epoxycyclohexane products and materials containing the catalyst and the epoxycyclohexane are obtained;
s3, conveying the material containing the catalyst and the cyclohexene oxide obtained in the step S2 to at least one stage of epoxidation reaction to serve as a raw material;
s4, sending an aqueous phase obtained by oil-water separation of a product of the final stage epoxidation reaction in the step S1 to a catalyst extraction tower, taking a material containing 5% -30% of cyclohexene oxide extracted from the cyclohexene separation tower as an extracting agent, and injecting the cyclohexene material extracted from the top of the cyclohexene separation tower into the lower part of the catalyst extraction tower to recover the cyclohexene oxide, wherein the theoretical plate number of the catalyst extraction tower is 3-30, and the mass ratio of the cyclohexene material to the material containing 5% -30% of cyclohexene oxide in the catalyst extraction tower is 1: (0.1-10), the mass ratio of the cyclohexene material and the material containing 5% -30% of cyclohexene oxide to the aqueous phase of the catalyst extraction column is (0.5-20): 1, the extraction temperature is 30-60 ℃;
s5, feeding a part of materials containing the catalyst and the epoxycyclohexane extracted from the tower bottom of the product tower in the step S2 into a catalyst regeneration device for catalyst regeneration, and feeding the regenerated catalyst into at least one stage of epoxidation reaction for use.
2. The continuous production method of cyclohexene oxide according to claim 1, wherein:
in step S5, the catalyst regeneration includes sequentially performing: extracting, filtering, washing, activating hydrogen peroxide and drying;
wherein the extracting agent is one or more of ethanol, ethyl acetate, petroleum ether, dichloromethane and chloroform;
the washing is to wash with organic solvent and deionized water; the organic solvent is one or more of ethanol, diethyl ether, ethyl acetate, petroleum ether, dichloromethane and chloroform;
the hydrogen peroxide activation is carried out in a water phase, the concentration of the hydrogen peroxide is 1% -50%, and the mass ratio of the hydrogen peroxide to the catalyst is (0.5-10): 1, a step of;
the drying temperature is 25-100 ℃.
3. The continuous production method of cyclohexene oxide according to claim 1, wherein:
the number of theoretical plates of the cyclohexene separating tower, the cyclohexene refining tower and the product tower is 3-30;
the reflux ratio of the cyclohexene separating tower, the cyclohexene refining tower and the product tower is 1-10, and the pressure is 10-101.325kPa.
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