CN116217339B - Method and device for preparing cyclohexanol by cyclohexene hydration - Google Patents

Method and device for preparing cyclohexanol by cyclohexene hydration Download PDF

Info

Publication number
CN116217339B
CN116217339B CN202310519100.4A CN202310519100A CN116217339B CN 116217339 B CN116217339 B CN 116217339B CN 202310519100 A CN202310519100 A CN 202310519100A CN 116217339 B CN116217339 B CN 116217339B
Authority
CN
China
Prior art keywords
catalyst
hydration
cyclohexene
cyclohexanol
inner cylinder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202310519100.4A
Other languages
Chinese (zh)
Other versions
CN116217339A (en
Inventor
郝子健
张春元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zibo Huafeng Aluminum Co ltd
Original Assignee
Zibo Huafeng Aluminum Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zibo Huafeng Aluminum Co ltd filed Critical Zibo Huafeng Aluminum Co ltd
Priority to CN202310519100.4A priority Critical patent/CN116217339B/en
Publication of CN116217339A publication Critical patent/CN116217339A/en
Application granted granted Critical
Publication of CN116217339B publication Critical patent/CN116217339B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
    • 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
    • B01D11/0492—Applications, solvents used
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/0035—Periodical feeding or evacuation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to the technical field of carbocyclic compounds, in particular to a method and a device for preparing cyclohexanol by cyclohexene hydration. Adding cyclohexene solution, water and a catalyst into a hydration reactor, wherein an inner cylinder and a stirrer positioned in the inner cylinder are arranged in the hydration reactor, and the stirrer is provided with a double-layer stirring paddle; under the action of the upper stirring paddle, cyclohexene reacts with water to obtain a reaction solution, the reaction solution moves in the inner cylinder from top to bottom under the action of the lower stirring paddle, the reaction solution moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, and an organic phase in the reaction solution is separated from a catalyst slurry in the upper space of the inner cylinder; the organic phase flows out from the upper part of the hydration reactor, the cyclohexanol is removed from the catalyst slurry through extraction, and the catalyst is regenerated in the presence of the ionic liquid containing imidazole functional groups and then returns to the hydration reactor for continuous cyclic utilization. The invention realizes the regeneration of the catalyst, and the cyclohexene conversion rate and the cyclohexanol yield are greatly improved.

Description

Method and device for preparing cyclohexanol by cyclohexene hydration
Technical Field
The invention relates to the technical field of carbocyclic compounds, in particular to a method and a device for preparing cyclohexanol by cyclohexene hydration.
Background
Cyclohexanol is an intermediate raw material for producing chemical products such as medicines, coatings, dyes and the like, and is industrially produced by cyclohexene hydration. In cyclohexene hydration reaction, the cyclohexene conversion rate is low and is only about 9-11% due to the limitation of incomplete catalyst regeneration and the catalyst itself.
Chinese patent CN102872910a discloses a method for regenerating cyclohexene hydration catalyst, which comprises steps of stripping the molecular sieve catalyst water solution with reduced activity in cyclohexane hydration reaction to remove entrained organic matters, oxidizing the catalyst solution to further remove oil, filtering the catalyst after oil removal to remove impurities, stabilizing, and the like. In the oxidation step, air or hydrogen peroxide is used for further oxidizing residual organic matters, the oxidation treatment pressure is 0-0.1MPa, and the temperature is 80-100 ℃. The main innovation point of the patent is that organic matters are oxidized by gas stripping oil, air or hydrogen peroxide, so that the activity of the catalyst is recovered.
Chinese patent CN109553507a discloses a method and system for increasing cyclohexene conversion, mainly comprising a hydration process and a continuous catalyst regeneration process, the continuous catalyst regeneration process mainly comprising (1) flash evaporation: water and catalyst (catalyst slurry) enter a catalyst flash tank, oil (cyclohexene as a main component) on the surface is subjected to pressure reduction flash evaporation and separation, cyclohexene is separated and recovered, and the loss of oil separation is supplemented by high-purity water with the same amount; (2) regeneration: after flash evaporation, the mixture enters a catalyst regeneration tank, and meanwhile, hydrogen peroxide is added into the catalyst regeneration tank from a hydrogen peroxide storage tank to further oxidize oil (cyclohexanol as a main component) in the catalyst slurry into organic acid (cyclohexanoic acid as a main component); (3) washing: the regenerated catalyst slurry is sent to a catalyst washing tank and is added with high-purity water for washing; after washing, the catalyst is sent to a regenerated catalyst filter, mother liquor in cyclohexanol catalyst slurry is filtered, and then the mother liquor enters the catalyst filter again, and the catalyst is recycled until the catalyst is qualified after washing, and the catalyst regeneration is completed; (4) returning: the regenerated catalyst is sent back to the cyclohexanol reactor, and the catalyst is flashed, regenerated, washed and returned. Through the measures, the cyclohexene conversion rate is improved from 7-9% to 11-12%, and the unit consumption and regeneration period of the catalyst required in operation are reduced.
In the above patent, the regeneration of the catalyst is performed by oxidizing the organic matters by the oxidizing agent, but the oxidizing agent oxidizes the organic matters to generate acid matters such as organic acid, so that the silicon aluminum on the catalyst is lost, the conversion rate of cyclohexene is reduced, and the activity and the service life of the catalyst are affected.
Disclosure of Invention
The invention aims to provide a method for preparing cyclohexanol by cyclohexene hydration, which realizes the regeneration of a catalyst and greatly improves the cyclohexene conversion rate and the cyclohexanol yield; the invention also provides a device for realizing the method for preparing cyclohexanol by cyclohexene hydration.
The method for preparing cyclohexanol by cyclohexene hydration comprises the following steps: adding cyclohexene solution, water and a catalyst into a hydration reactor, wherein an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, and the stirrer is provided with an upper stirring paddle and a lower stirring paddle; under the action of the upper stirring paddle, cyclohexene and water are subjected to hydration reaction to obtain reaction liquid, the reaction liquid moves in the inner cylinder from top to bottom under the action of the lower stirring paddle, the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder; the organic phase flows out from the upper part of the hydration reactor, the catalyst slurry flows out from the bottom of the hydration reactor and enters an extraction device for extraction and removal of cyclohexanol, the catalyst slurry after removal of cyclohexanol enters a catalyst activity restorer, the catalyst in the catalyst slurry after removal of cyclohexanol is regenerated in the presence of ionic liquid containing imidazole functional groups to obtain catalyst slurry containing regenerated catalyst, the catalyst slurry containing regenerated catalyst is filtered and washed to obtain regenerated catalyst, and the regenerated catalyst returns to the hydration reactor for continuous recycling.
Wherein:
the diameter ratio of the inner cylinder to the hydration reactor is 0.3-0.7:1.
The upper stirring paddle is a straight blade stirring paddle and is used for carrying out hydration reaction on cyclohexene and the catalyst; the lower stirring paddle is an inclined blade stirring paddle and is used for driving the reaction liquid downwards so as to enable the reaction liquid to circularly flow inside and outside the inner cylinder, in particular to enable the reaction liquid to move from top to bottom in the inner cylinder, and to enable the reaction liquid to move from bottom to top in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor.
The included angle between the inclined blade stirring paddle and the horizontal plane is 30-60 degrees, and the inclined blade stirring paddle is inclined downwards by taking the vertical central line of the stirrer as a reference.
The catalyst is ZSM-5 type silicon-aluminum molecular sieve, and the ZSM-5 type silicon-aluminum molecular sieve is 30-60wt.% of the water consumption.
The hydration reaction temperature is 120-130 ℃, the hydration reaction pressure is 0.4-0.6MPa, and the hydration reaction residence time is 0.8-1.5h.
The mol ratio of cyclohexene to water in the cyclohexene solution is 1:1.05-1.1.
One or more of benzene, cyclohexane, cyclohexene or methylcyclopentane are used as an extractant for extraction and removal of cyclohexanol. The extractant is capable of extracting cyclohexanol and other organics in the catalyst slurry into the oil phase.
The ionic liquid containing the imidazole functional group is 1-butyl-3-methylimidazole acetate.
The mass ratio of the catalyst slurry after cyclohexanol removal to the ionic liquid containing imidazole functional groups is 1:0.01-0.05.
The regeneration temperature is 20-100 ℃.
The catalyst slurry contains water, catalyst, residual cyclohexanol, other organic matters and the like.
The invention uses the ionic liquid containing imidazole functional groups to act on the catalyst, thereby regenerating the catalyst and having higher activity. In the process of preparing cyclohexanol by cyclohexene hydration reaction, organic matters, metals and other substances are easily attached to the outer surface of the catalyst, so that the catalyst is deactivated. The conventional treatment method is to oxidize residual organic matters on the catalyst by using an oxidant, but the method can simultaneously generate acid matters such as organic acid and the like, so that silicon aluminum of the catalyst is lost, and the catalytic activity is reduced. The invention adopts the 1-butyl-3-methylimidazole acetate to regenerate the catalyst, thereby avoiding the occurrence of the problems.
Because hydrogen bonds are formed between the 1-butyl-3-methylimidazole acetate and the residual organic matters, the residual organic matters are attracted by the 1-butyl-3-methylimidazole acetate, so that the residual organic matters are separated from the outer surface of the catalyst, and the regeneration of the catalyst is promoted. The imidazole group in the 1-butyl-3-methylimidazole acetate can generate free radicals, and the metal and the free radicals can form coordination bonds, so that the metal is attracted to be separated from the outer surface of the catalyst, and the regeneration of the catalyst is also promoted.
The catalyst in the catalyst slurry after cyclohexanol removal is regenerated in the presence of the ionic liquid containing imidazole functional groups to obtain catalyst slurry containing regenerated catalyst, the catalyst slurry containing regenerated catalyst is filtered and washed to obtain regenerated catalyst, and the regenerated catalyst is returned to the hydration reactor for continuous recycling. Filtering and washing the obtained washing liquid, and recycling the washing liquid into the process after sedimentation treatment.
The device for realizing the method for preparing cyclohexanol by hydration of cyclohexene comprises a hydration reactor, an extraction device, a catalyst activity restorer and a filter washing machine which are sequentially connected, wherein the filter washing machine is also connected with the hydration reactor, an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, an upper stirring paddle and a lower stirring paddle are arranged on the stirrer, the upper part of the hydration reactor is connected with an organic phase outflow pipeline, the middle part of the hydration reactor is connected with a cyclohexene solution inflow pipeline and a water pipe, the bottom of the hydration reactor is connected with a catalyst slurry outflow pipeline, and the catalyst slurry outflow pipeline is connected with the extraction device;
the extraction device is connected with an extractant inflow pipeline, an extraction oil phase outflow pipeline and an extraction water phase outflow pipeline, and the extraction water phase outflow pipeline is connected with the catalyst activity restorer;
the top of the catalyst activity restorer is connected with an ionic liquid adding pipeline containing imidazole functional groups, and the bottom of the catalyst activity restorer is connected with a filtering and washing machine.
The filtering and washing machine is connected with a desalted water inflow pipeline and a washing liquid outlet pipeline; the filter washer is also connected with the lower part of the hydration reactor through a pipeline.
The beneficial effects of the invention are as follows:
the method mainly comprises a step of preparing cyclohexanol by cyclohexene hydration and a step of regenerating catalyst activity, wherein the content of cyclohexanol in a reaction solution of the step of preparing cyclohexanol by cyclohexene hydration is 20.16-26.53 wt%; in the catalyst activity regeneration procedure, cyclohexanol and other organic matters are extracted and removed firstly, and then ionic liquid containing imidazole functional groups is added to restore the activity of the catalyst, so that the catalyst is prevented from being influenced by the organic matters, metals and oxidants.
Cyclohexene and a catalyst are added into a hydration reactor, an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, and the stirrer is provided with an upper stirring paddle and a lower stirring paddle; cyclohexene and water are subjected to hydration reaction under the action of an upper stirring paddle to obtain reaction liquid, the reaction liquid moves in the inner cylinder from top to bottom under the action of a lower stirring paddle, the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, full reaction is carried out, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder. The invention realizes the design of the reaction zone and the separation zone by arranging the inner barrel, and the effect of the upper stirring paddle and the lower stirring paddle in the reaction zone can be exerted to the maximum extent. The organic phase in the reaction liquid is spatially separated from the catalyst slurry at the upper part of the inner cylinder due to the difference in density, and the organic phase is small in density, whereas the catalyst slurry is approximately dense.
The catalyst slurry after cyclohexanol removal enters a catalyst activity restorer, and the catalyst in the catalyst slurry after cyclohexanol removal is regenerated in the presence of the ionic liquid containing imidazole functional groups to obtain catalyst slurry containing regenerated catalyst, so that the activity of the catalyst is restored. The invention avoids the use of an oxidant, furthest reduces the generation of organic acids such as formic acid, acetic acid and the like, reduces the influence of the organic acids on the catalyst, and greatly prolongs the service life of the catalyst.
The arrangement of the inner cylinder and the upper and lower layers of stirring paddles and the regeneration of the catalyst exert a synergistic effect, can improve the content of cyclohexanol in the reaction liquid from 9-12wt.% to 20.16-26.53wt.%, greatly reduces the energy consumption of a cyclohexanol preparation device, and reduces the cyclohexene circulation amount from 139t/h to 56.8t/h by about 60%. The cyclohexene conversion rate of the invention is 23.65-30.03%, and compared with the existing cyclohexene conversion rate of 7-12%, the cyclohexene conversion rate of the invention is greatly improved. The yield of cyclohexanol is 17.16-22.60%, and the yield is also greatly improved.
Drawings
FIG. 1 is a schematic diagram of the apparatus for preparing cyclohexanol by hydration of cyclohexene in accordance with the present invention;
wherein: 1. a hydration reactor; 2. an inner cylinder; 3. extracting an oil phase effluent line; 4. adding an ionic liquid containing imidazole functional groups into the pipeline; 5. a catalyst activity restorer; 6. a filter washer; 7. desalted water inflow line; 8. a wash effluent line; 9. an extraction aqueous phase outflow line; 10. an extraction device; 11. the extractant flows into the pipeline; 12. a catalyst slurry outflow line; 13. a lower stirring paddle; 14. cyclohexene solution flows into the line; 15. an organic phase effluent line; 16. an upper stirring paddle; 17. a water pipe.
Detailed Description
The present invention is specifically described and illustrated below with reference to examples.
Example 1
(1) Adding water and a catalyst ZSM-5 type silicon-aluminum molecular sieve into a hydration reactor, wherein the ZSM-5 type silicon-aluminum molecular sieve is 60wt.% of the water consumption; adding cyclohexene solution into a hydration reactor under the conditions of 61423kg/h, 115 ℃ and 0.6MPa, and carrying out hydration reaction for 1h under the conditions of 120 ℃ and 0.55 MPa; 96.15wt.% cyclohexene, 0.038wt.% cyclohexanol, 1.34wt.% cyclohexane, 0.25wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.072wt.% benzene, 0.082wt.% toluene, the remainder being impurities; the molar ratio of cyclohexene to water is 1:1.1;
an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, the diameter ratio of the inner cylinder to the hydration reactor is 0.5:1, and the stirrer is provided with an upper layer of stirring paddles and a lower layer of stirring paddles; the upper layer stirring paddle is a straight blade stirring paddle, and the lower layer stirring paddle is an inclined blade stirring paddle; under the action of the upper stirring paddle, cyclohexene and water are subjected to hydration reaction to obtain reaction liquid, the reaction liquid moves in the inner cylinder from top to bottom under the action of the lower stirring paddle, the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder; the organic phase flows out from the upper part of the hydration reactor. In the organic phase, 72.52wt.% cyclohexene, 20.71wt.% cyclohexanol, 1.33wt.% cyclohexane, 0.29wt.% methylcyclopentene, 0.68wt.% methylcyclohexane, 0.071wt.% benzene, 0.081wt.% toluene, the remainder being impurities; the conversion of cyclohexene was 24.58% and the yield of cyclohexanol was 17.63%.
(2) The catalyst slurry obtained by separation flows out from the bottom of the hydration reactor, the flow rate is 2550kg/h, the temperature is 125 ℃, the pressure is 0.55MPa, the catalyst slurry enters an extraction device after heat exchange and temperature reduction to 60 ℃, an extractant is added into the extraction device at the flow rate of 3550kg/h, wherein 0.11wt.% of methylcyclopentane and 99.89wt.% of cyclohexane are extracted and removed from the catalyst slurry, the extracted oil phase contains 0.11wt.% of methylcyclopentane, 2.82wt.% of cyclohexanol and 96.92wt.% of cyclohexane, the rest is impurities, and the extracted oil phase enters an extracted oil phase outflow pipeline.
(3) The catalyst slurry after cyclohexanol removal enters a catalyst activity restorer from an extraction water phase outflow pipeline, the flow rate is 2550kg/h, 1-butyl-3-methylimidazole acetate is added into the catalyst activity restorer at the flow rate of 127.5kg/h, the catalyst is regenerated for 0.8h at 60 ℃, the regenerated catalyst is obtained after filtering and desalted water washing, and the regenerated catalyst returns to a hydration reactor for continuous recycling.
(4) The regenerated catalyst is returned to the hydration reactor, the recycling process is the same as the step (1), 73.41wt.% cyclohexene, 20.16wt.% cyclohexanol, 1.34wt.% cyclohexane, 0.26wt.% methylcyclopentene, 0.67wt.% methylcyclohexane, 0.072wt.% benzene and 0.080wt.% toluene in the obtained organic phase, and the rest is impurities; the conversion of cyclohexene was 23.65%, and the yield of cyclohexanol was 17.16%.
Example 2
(1) Adding water and a catalyst ZSM-5 type silicon-aluminum molecular sieve into a hydration reactor, wherein the ZSM-5 type silicon-aluminum molecular sieve is 45wt.% of the water consumption; adding cyclohexene solution into a hydration reactor under the conditions of 59684kg/h, 115 ℃ and 0.6MPa, and carrying out hydration reaction for 0.8h under the conditions of 125 ℃ and 0.4 MPa; 96.15wt.% cyclohexene, 0.038wt.% cyclohexanol, 1.34wt.% cyclohexane, 0.25wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.072wt.% benzene, 0.082wt.% toluene, the remainder being impurities; the molar ratio of cyclohexene to water is 1:1.05;
an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, the diameter ratio of the inner cylinder to the hydration reactor is 0.3:1, and the stirrer is provided with an upper layer of stirring paddles and a lower layer of stirring paddles; the upper layer stirring paddle is a straight blade stirring paddle, and the lower layer stirring paddle is an inclined blade stirring paddle; under the action of the upper stirring paddle, cyclohexene and water are subjected to hydration reaction to obtain reaction liquid, the reaction liquid moves in the inner cylinder from top to bottom under the action of the lower stirring paddle, the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder; the organic phase flows out from the upper part of the hydration reactor. 70.31wt.% cyclohexene, 23.06wt.% cyclohexanol, 1.32wt.% cyclohexane, 0.30wt.% methylcyclopentene, 0.69wt.% methylcyclohexane, 0.073wt.% benzene, 0.083wt.% toluene, the remainder being impurities; the conversion of cyclohexene was 26.87% and the yield of cyclohexanol was 19.64%.
(2) The catalyst slurry obtained by separation flows out from the bottom of the hydration reactor, the flow rate is 2580kg/h, the temperature is 125 ℃, the pressure is 0.55MPa, the catalyst slurry enters an extraction device after heat exchange and temperature reduction are carried out to 60 ℃, an extractant is added into the extraction device, the flow rate is 3590kg/h, wherein 20wt.% of methylcyclopentane and 80wt.% of cyclohexene are added into the extraction device, and cyclohexanol in the catalyst slurry is removed by extraction; the extracted oil phase contains 18wt.% methylcyclopentane, 2.82wt.% cyclohexanol and 78.89wt.% cyclohexene, and the rest is impurities, and the extracted oil phase enters an extracted oil phase outflow pipeline.
(3) The catalyst slurry after cyclohexanol removal enters a catalyst activity restorer from an extraction water phase outflow pipeline, the flow rate is 2580kg/h, 1-butyl-3-methylimidazole acetate is added into the catalyst activity restorer at the flow rate of 77.4kg/h, the catalyst is regenerated for 0.5h at 100 ℃, the regenerated catalyst is obtained after filtering and desalted water washing, and the regenerated catalyst returns to a hydration reactor for continuous recycling.
(4) The regenerated catalyst is returned to the hydration reactor, and the recycling process is the same as the step (1), 71.27wt.% cyclohexene, 22.93wt.% cyclohexanol, 1.31wt.% cyclohexane, 0.28wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.072wt.% benzene and 0.082wt.% toluene in the obtained organic phase, and the balance impurities; the conversion of cyclohexene was 25.88%, and the yield of cyclohexanol was 19.53%.
Example 3
(1) Adding water and a catalyst ZSM-5 type silicon-aluminum molecular sieve into a hydration reactor, wherein the ZSM-5 type silicon-aluminum molecular sieve is 30wt.% of the water dosage; adding cyclohexene solution into a hydration reactor under the conditions of 51326kg/h, 115 ℃ and 0.6MPa, and carrying out hydration reaction for 1.5h under the conditions of 130 ℃ and 0.6 MPa; 96.15wt.% cyclohexene, 0.038wt.% cyclohexanol, 1.34wt.% cyclohexane, 0.25wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.072wt.% benzene, 0.082wt.% toluene, the remainder being impurities; the molar ratio of cyclohexene to water is 1:1.08;
an inner cylinder and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder, the diameter ratio of the inner cylinder to the hydration reactor is 0.7:1, and the stirrer is provided with an upper layer of stirring paddles and a lower layer of stirring paddles; the upper layer stirring paddle is a straight blade stirring paddle, and the lower layer stirring paddle is an inclined blade stirring paddle; under the action of the upper stirring paddle, cyclohexene and water are subjected to hydration reaction to obtain reaction liquid, the reaction liquid moves in the inner cylinder from top to bottom under the action of the lower stirring paddle, the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder and the inner wall of the hydration reactor from bottom to top, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder; the organic phase flows out from the upper part of the hydration reactor. In the organic phase, 66.58wt.% cyclohexene, 27.86wt.% cyclohexanol, 1.30wt.% cyclohexane, 0.27wt.% methylcyclopentene, 0.72wt.% methylcyclohexane, 0.070wt.% benzene, 0.080wt.% toluene, the remainder being impurities. The conversion of cyclohexene was 30.75%, and the yield of cyclohexanol was 23.73%.
(2) The catalyst slurry obtained by separation flows out from the bottom of the hydration reactor, the flow rate is 2510kg/h, the temperature is 125 ℃, the pressure is 0.55MPa, the catalyst slurry enters an extraction device after heat exchange and temperature reduction are carried out to 60 ℃, an extractant is added into the extraction device at the flow rate of 3530kg/h, wherein 0.57wt.% of benzene and 99.21wt.% of cyclohexane are added into the extraction device, and cyclohexanol in the catalyst slurry is removed by extraction; the extracted oil phase contains 0.43wt.% benzene, 2.82wt.% cyclohexanol and 95.83wt.% cyclohexane, and the rest is impurities, and the extracted oil phase enters an extracted oil phase outflow pipeline.
(3) The catalyst slurry after cyclohexanol removal enters a catalyst activity restorer from an extraction water phase outflow pipeline, the flow rate is 2510kg/h, 1-butyl-3-methylimidazole acetate is added into the catalyst activity restorer at the flow rate of 25.1kg/h, the catalyst is regenerated for 1h at 20 ℃, the regenerated catalyst is obtained after filtering and desalted water washing, and the regenerated catalyst returns to a hydration reactor for continuous recycling.
(4) The regenerated catalyst is returned to the hydration reactor, and the recycling process is the same as the step (1), 67.28wt.% cyclohexene, 26.53wt.% cyclohexanol, 1.32wt.% cyclohexane, 0.25wt.% methylcyclopentene, 0.72wt.% methylcyclohexane, 0.071wt.% benzene and 0.079wt.% toluene in the obtained organic phase, and the rest impurities; the conversion of cyclohexene was 30.03%, and the yield of cyclohexanol was 22.60%.
Comparative example 1
The catalyst slurry obtained in the example 1 after cyclohexanol removal is put into a catalyst activity restorer, 27.5wt.% hydrogen peroxide is introduced into the catalyst activity restorer, the mass ratio of hydrogen peroxide to catalyst slurry is 0.05:1, the reaction is carried out for 0.8h at 60 ℃, the regenerated catalyst is obtained after filtering and washing with desalted water, and the regenerated catalyst is returned into a hydration reactor for continuous recycling.
The regenerated catalyst was returned to the hydration reactor and recycled in the same manner as in step (1) of example 1, with 85.41wt.% cyclohexene, 8.86wt.% cyclohexanol, 1.33wt.% cyclohexane, 0.24wt.% methylcyclopentene, 0.69wt.% methylcyclohexane, 0.069wt.% benzene, 0.081wt.% toluene and the balance impurities in the obtained organic phase; the conversion of cyclohexene was 11.17% and the yield of cyclohexanol was 7.52%.
Comparative example 2
The catalyst slurry obtained in the example 1 after cyclohexanol removal is put into a catalyst activity restorer, air is introduced into the catalyst activity restorer, the mass ratio of the air consumption to the catalyst slurry is 0.05:1, the reaction is carried out for 0.8h at 60 ℃, the regenerated catalyst is obtained after filtering and washing with desalted water, and the regenerated catalyst is returned into a hydration reactor for continuous recycling.
The regenerated catalyst was returned to the hydration reactor and recycled in the same manner as in step (1) of example 1, with 85.92wt.% cyclohexene, 8.34wt.% cyclohexanol, 1.30wt.% cyclohexane, 0.22wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.068wt.% benzene, 0.083wt.% toluene and the balance impurities in the organic phase; the conversion of cyclohexene was 10.64%, and the yield of cyclohexanol was 7.08%.
Comparative example 3
The hydration reactor was not provided with an inner tube, only a stirrer was provided, and the rest of the procedure was the same as in example 1. 84.52wt.% cyclohexene, 9.43wt.% cyclohexanol, 1.32wt.% cyclohexane, 0.27wt.% methylcyclopentene, 0.71wt.% methylcyclohexane, 0.073wt.% benzene, 0.080wt.% toluene in the resulting organic phase, the remainder being impurities; the conversion of cyclohexene was 12.10%, and the yield of cyclohexanol was 8.01%.
Comparative example 4
The hydration reactor is internally provided with an inner cylinder and a stirrer, the stirrer is only provided with an upper stirring paddle, and the rest steps are the same as those of the embodiment 1. 85.21wt.% cyclohexene, 9.19wt.% cyclohexanol, 1.30wt.% cyclohexane, 0.28wt.% methylcyclopentene, 0.72wt.% methylcyclohexane, 0.072wt.% benzene, 0.082wt.% toluene and the balance impurities in the resulting organic phase; the conversion of cyclohexene was 11.38%, and the yield of cyclohexanol was 7.81%.
Comparative example 5
The hydration reactor is internally provided with an inner cylinder and a stirrer, the stirrer is only provided with a lower stirring paddle, and the rest steps are the same as those of the embodiment 1. 84.94wt.% cyclohexene, 9.03wt.% cyclohexanol, 1.32wt.% cyclohexane, 0.27wt.% methylcyclopentene, 0.7wt.% methylcyclohexane, 0.071wt.% benzene, 0.080wt.% toluene in the resulting organic phase, the remainder being impurities; the conversion of cyclohexene was 11.66% and the yield of cyclohexanol was 7.67%.
The device for realizing the method for preparing cyclohexanol by cyclohexene hydration is shown in fig. 1, and comprises a hydration reactor 1, an extraction device 10, a catalyst activity restorer 5 and a filter washer 6 which are sequentially connected, wherein the filter washer 6 is also connected with the hydration reactor 1, an inner cylinder 2 and a stirrer are arranged in the hydration reactor 1, the stirrer is positioned in the inner cylinder 2, an upper stirring paddle 16 and a lower stirring paddle 13 are arranged on the stirrer, the upper part of the hydration reactor 1 is connected with an organic phase flow pipeline 15, the middle part is connected with a cyclohexene solution inflow pipeline 14 and a water pipe 17, the bottom is connected with a catalyst slurry outflow pipeline 12, and the catalyst slurry outflow pipeline 12 is connected with the extraction device 10;
the extraction device 10 is connected with an extractant inflow pipeline 11, an extraction oil phase outflow pipeline 3 and an extraction water phase outflow pipeline 9, and the extraction water phase outflow pipeline 9 is connected with the catalyst activity restorer 5;
the top of the catalyst activity restorer 5 is connected with an ionic liquid adding pipeline 4 containing imidazole functional groups, and the bottom is connected with a filtering and washing machine 6.
The filter washer 6 is connected with a desalted water inflow line 7 and a washing liquid outlet line 8; the filter-scrubber 6 is also connected to the lower part of the hydration reactor 1 by a line.
The diameter ratio of the inner cylinder 2 to the hydration reactor 1 is 0.3-0.7:1.
The upper layer stirring paddle 16 is a straight blade stirring paddle, and the lower layer stirring paddle 13 is an inclined blade stirring paddle. The included angle between the inclined blade stirring paddle and the horizontal plane is 30-60 degrees. The inclined blade stirring paddles are inclined downwards by taking the vertical center line of the stirrer as a reference, and the included angle between the inclined blade stirring paddles and the horizontal plane in the examples and the comparative examples is preferably 60 degrees.

Claims (9)

1. A method for preparing cyclohexanol by cyclohexene hydration, which is characterized by comprising the following steps: adding cyclohexene solution, water and a catalyst into a hydration reactor (1), wherein an inner cylinder (2) and a stirrer are arranged in the hydration reactor, the stirrer is positioned in the inner cylinder (2), and the stirrer is provided with an upper stirring paddle (16) and a lower stirring paddle (13); under the action of an upper stirring paddle (16), cyclohexene and water are subjected to hydration reaction to obtain reaction liquid, the reaction liquid moves in the inner cylinder (2) from top to bottom under the action of a lower stirring paddle (13), the reaction liquid moves in an annular channel formed between the outer wall of the inner cylinder (2) and the inner wall of the hydration reactor (1) from bottom to top, and an organic phase and catalyst slurry in the reaction liquid are separated in the upper space of the inner cylinder (2); the organic phase flows out from the upper part of the hydration reactor (1), the catalyst slurry flows out from the bottom of the hydration reactor (1) and enters an extraction device (10) to extract and remove cyclohexanol, the catalyst slurry after the cyclohexanol is removed enters a catalyst activity restorer (5), the catalyst in the catalyst slurry after the cyclohexanol is removed is regenerated under the existence of ionic liquid containing imidazole functional groups to obtain catalyst slurry containing regenerated catalyst, the catalyst slurry containing regenerated catalyst is filtered and washed to obtain regenerated catalyst, and the regenerated catalyst returns to the hydration reactor (1) to be continuously recycled;
the upper layer stirring paddle (16) is a straight blade stirring paddle, and the lower layer stirring paddle (13) is an oblique blade stirring paddle; the ionic liquid containing imidazole functional groups is 1-butyl-3-methylimidazole acetate;
the catalyst is ZSM-5 type silicon-aluminum molecular sieve.
2. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: the diameter ratio of the inner cylinder (2) to the hydration reactor (1) is 0.3-0.7:1.
3. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: the ZSM-5 type silicon aluminum molecular sieve is 30-60wt.% of the water.
4. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: the hydration reaction temperature is 120-130 ℃, the hydration reaction pressure is 0.4-0.6MPa, and the hydration reaction residence time is 0.8-1.5h.
5. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: one or more of benzene, cyclohexane, cyclohexene or methylcyclopentane are used as an extractant for extraction and removal of cyclohexanol.
6. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: the mass ratio of the catalyst slurry after cyclohexanol removal to the ionic liquid containing imidazole functional groups is 1:0.01-0.05.
7. The method for preparing cyclohexanol by hydration of cyclohexene according to claim 1, wherein: the regeneration temperature is 20-100 ℃.
8. An apparatus for realizing the method for preparing cyclohexanol by cyclohexene hydration according to any one of claims 1-7, comprising a hydration reactor (1), an extraction device (10), a catalyst activity restorer (5) and a filter washer (6) which are connected in sequence, wherein the filter washer (6) is further connected with the hydration reactor (1), characterized in that: an inner cylinder (2) and a stirrer are arranged in the hydration reactor (1), the stirrer is arranged in the inner cylinder (2), an upper stirring paddle (16) and a lower stirring paddle (13) are arranged on the stirrer, an organic phase outflow pipeline (15) is connected to the upper part of the hydration reactor (1), a cyclohexene solution inflow pipeline (14) and a water pipe (17) are connected to the middle part of the hydration reactor, a catalyst slurry outflow pipeline (12) is connected to the bottom of the hydration reactor, and the catalyst slurry outflow pipeline (12) is connected to the extraction device (10);
the extraction device (10) is connected with an extractant inflow pipeline (11), an extraction oil phase outflow pipeline (3) and an extraction water phase outflow pipeline (9), and the extraction water phase outflow pipeline (9) is connected with the catalyst activity restorer (5);
the top of the catalyst activity restorer (5) is connected with an ionic liquid adding pipeline (4) containing imidazole functional groups, and the bottom of the catalyst activity restorer is connected with a filtering and washing machine (6).
9. The apparatus according to claim 8, wherein: the filtering and washing machine (6) is connected with a desalted water inflow pipeline (7) and a washing liquid outlet pipeline (8); the filter washer (6) is also connected with the lower part of the hydration reactor (1) through a pipeline.
CN202310519100.4A 2023-05-10 2023-05-10 Method and device for preparing cyclohexanol by cyclohexene hydration Active CN116217339B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310519100.4A CN116217339B (en) 2023-05-10 2023-05-10 Method and device for preparing cyclohexanol by cyclohexene hydration

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310519100.4A CN116217339B (en) 2023-05-10 2023-05-10 Method and device for preparing cyclohexanol by cyclohexene hydration

Publications (2)

Publication Number Publication Date
CN116217339A CN116217339A (en) 2023-06-06
CN116217339B true CN116217339B (en) 2023-07-18

Family

ID=86591498

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310519100.4A Active CN116217339B (en) 2023-05-10 2023-05-10 Method and device for preparing cyclohexanol by cyclohexene hydration

Country Status (1)

Country Link
CN (1) CN116217339B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6756516B2 (en) * 2001-07-02 2004-06-29 Exxonmobil Chemical Patents Inc. Treatment of acid catalysts
WO2015079957A1 (en) * 2013-11-28 2015-06-04 株式会社ダイセル Method for producing cyclic olefin compound
CN217568658U (en) * 2022-06-06 2022-10-14 河北美邦工程科技股份有限公司 Entrained catalyst treatment system for cyclohexene hydration reaction

Also Published As

Publication number Publication date
CN116217339A (en) 2023-06-06

Similar Documents

Publication Publication Date Title
CN1847206A (en) Synthesis process of cyclohexanone and cyclohexanol
CN1868988A (en) Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol
CN107089924A (en) A kind of azanol, hydroxylamine salt, the combined producing process of cyclohexanone oxime
CN103012120A (en) Method for preparing terephthalic acid by oxidation refining process
CN107903183A (en) Method of comprehensive utilization and device containing sour DMF solution
CN106672911A (en) Oxidation-extraction technology for production of hydrogen peroxide by anthraquinone process
CN102249916B (en) Continuous production process for tributyl citrate
WO2011015000A1 (en) Process and device for preparing benzaldehyde and benzyl alcohol by multistage oxidation of toluene
CN111889059A (en) Reaction device and process for preparing DOTP
CN116217339B (en) Method and device for preparing cyclohexanol by cyclohexene hydration
CN115894400B (en) Process for preparing epoxy chloropropane by directly oxidizing chloropropene by using liquid-solid circulating fluidized bed reactor
CN112321435B (en) Method for continuously synthesizing 2-nitropropane by adopting slurry bed
CN212076906U (en) Side-line reaction type dioxolane production process device
CN214612314U (en) Five processing system of schizolysis carbon with washing process
CN104557810A (en) Method for producing furfuraldehyde from pentose solution by adopting impinging stream reactor
CN109553507B (en) Method and system for improving cyclohexene conversion rate
CN102898268B (en) Method for continuously producing cyclohexene
CN210683639U (en) Cyclohexane oxidation reaction device
CN107540523B (en) Method for reducing sodium salt content in crude alcohol ketone material containing alkali liquor
CN107400046B (en) Process method for preparing methyl isobutyl ketone by acetone liquid phase one-step method
CN110577461B (en) Cyclohexane oxidation reaction device and method
CN114772774A (en) Nitrochlorobenzene production wastewater treatment method
CN1631538A (en) Regenerating, cleaning and separating method of titanium silicon molecular sieve catalyst
CN210340725U (en) Production device for synthesizing methyl succinic acid by water-phase catalytic hydrogenation of itaconic acid
CN109082681B (en) Preparation device and method of template agent of ammoximation catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant