CN116726814A - Preparation method and device of cyclohexenyl cyclohexanone - Google Patents
Preparation method and device of cyclohexenyl cyclohexanone Download PDFInfo
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- CN116726814A CN116726814A CN202310769321.7A CN202310769321A CN116726814A CN 116726814 A CN116726814 A CN 116726814A CN 202310769321 A CN202310769321 A CN 202310769321A CN 116726814 A CN116726814 A CN 116726814A
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- cyclohexanone
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- cyclohexane
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- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 215
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000007670 refining Methods 0.000 claims abstract description 47
- 238000010992 reflux Methods 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 36
- 230000000630 rising effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 37
- 239000000539 dimer Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 15
- 239000002699 waste material Substances 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 29
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 abstract description 19
- 238000004817 gas chromatography Methods 0.000 abstract description 13
- 238000006482 condensation reaction Methods 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 10
- 238000010924 continuous production Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 38
- 239000000047 product Substances 0.000 description 37
- 235000010292 orthophenyl phenol Nutrition 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 239000013638 trimer Substances 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000032798 delamination Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- 125000005580 triphenylene group Chemical group 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 2
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 241000207199 Citrus Species 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and a preparation device of cyclohexanone, and relates to the technical field of chemical industry. The preparation method comprises the steps of adding cyclohexanone, cyclohexane and a catalyst Y-Al into a reaction kettle 2 O 3 Controlling the reaction temperature at 110-120 ℃; the rising steam is condensed by a reflux condenser and then flows back into the reaction kettle; the materials in the reaction kettle are subjected to light component removalAnd (3) treating to remove cyclohexane and water, and refining to remove cyclohexanone after light removal to obtain a finished product. The device mainly comprises a reaction kettle with a jacket and stirring, a light component removing tower and a refining tower. The continuous production process comprises condensation reaction, removal of water and cyclohexane by a light component removal tower, separation of cyclohexanone by a refining tower and obtaining the cyclohexenyl cyclohexanone product. The reaction kettle material is analyzed by gas chromatography to obtain the single pass conversion rate of the cyclohexanone condensation reaction of more than 29.11 percent, the selectivity of the cyclohexenyl cyclohexanone of more than 99.99 percent, and the product is analyzed to obtain the cyclohexenyl cyclohexanone with the purity of more than 99.99 percent.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to optimization of a production process flow of cyclohexenyl cyclohexanone as an intermediate of o-phenylphenol. In particular to a method for continuously preparing high-purity cyclohexenyl cyclohexanone under normal pressure.
Background
Cyclohexenyl cyclohexanone is mainly an organic intermediate prepared by dehydration condensation of cyclohexanone, and is mainly used as a raw material of o-phenylphenol (OPP) of a citrus sterilizing preservative. Is also a solvent for carbamate herbicides, and is also used in the aspects of wood preservatives, pesticides and the like. O-phenylphenol (OPP) is an organic chemical product with very wide application, and is widely applied to the fields of sterilization and corrosion prevention, printing and dyeing auxiliary agents, surfactants, stabilizers and flame retardants for synthesizing novel plastics, resins and high polymer materials, and the like. The high-purity cyclohexenyl cyclohexanone is very important for preparing o-phenylphenol by dehydrogenation, so the invention has great significance in the technological process for continuously preparing the high-purity cyclohexenyl cyclohexanone.
The cyclohexanone condensation dehydrogenation route is a more technological route adopted by OPP manufacturers at home and abroad in recent years. The cyclohexanone liquid phase is condensed into dimer (cyclohexenyl cyclohexanone), the dimer is catalyzed and dehydrogenated into OPP by gas phase, and then the pure OPP is obtained by distillation and recrystallization. The cyclohexanone raw material is easy to obtain, the cost is low, the whole process is simple and easy to implement, and the environmental safety of the process is particularly improved over the former process routes.
The main mode of synthesizing cyclohexenyl cyclohexanone is that cyclohexanone is heated under the action of catalyst to make self-condensation reaction to produce 2- (1-cyclohexenyl) cyclohexanone, small quantity of 2-cyclohexylidene cyclohexanone and water, and at high temperature can produce decahydrogenated triphenylene (trimer) and polymer. The main reaction formula is as follows:
the resulting 2- (1-cyclohexenyl) cyclohexanone and 2-cyclohexylidene cyclohexanone can be used in dehydrogenation to prepare OPP. Cyclohexenyl cyclohexanone is currently mainly produced and applied in China as an intermediate for preparing o-phenylphenol. The related patents and documents are also mostly related to o-phenylphenol.
There have been some studies and reports on the preparation of cyclohexenyl cyclohexanone by condensation of cyclohexanone.
USP4002693 uses sulfuric acid as catalyst, 500g cyclohexanone and 100g 50% sulfuric acid are mixed, and kept at 90-100 ℃ for 20min under N2 bubbling or stirring, and 170g cyclohexenyl cyclohexanone can be obtained through analysis.
In the research and synthesis of o-phenylphenol, the method adopts 98% concentrated sulfuric acid as cyclohexanone condensation catalyst, the reaction is carried out for 2 hours at 112-115 ℃, the reaction product is distilled under normal pressure, and fractions at 270-272 ℃ are collected, so that the total yield can reach 90%.
Chen Gongyan and the like research the application of the dealuminated ultrastable Y molecular sieve DUSY catalyst in cyclohexanone condensation reaction, and the single pass yield of the dimer can reach 49.5% when no water carrying agent is used and the reaction is carried out for 4 hours at 138 ℃ by using 5% of DUSY-2 (the silicon-aluminum ratio is 8.95).
Yue Lili and Jiang Wenwei respectively test the influence of acid and alkali catalysts on the reaction, naOH is used as a catalyst, the consumption of the NaOH is 0.5% (mol) of the raw material, the reaction temperature is 155 ℃, the water generated by the reaction is taken out of the system by cyclohexanone after the reaction for 1.5-2 hours, the cyclohexanone is circulated and continuously participates in the reaction to obtain a thick dark brown red crude product, the dimer is obtained through reduced pressure distillation, the conversion rate of the cyclohexanone can reach 71.5%, and the reaction selectivity of the dimer is 89.5%.
Chen Yao et al studied a solid acid catalyst for cyclohexanone condensation and compared with concentrated sulfuric acid as the catalyst, the better solid acid catalyst had a cyclohexanone conversion of 52%, a yield of 49% and a selectivity of 94% or more at an addition level of 3% for 40 minutes.
CN101003471 relates to a method for continuously producing cyclohexenyl cyclohexanone under the catalysis of solid superacid, which specifically comprises the processes of pre-mixing, pre-heating, reacting, water washing and alkali washing. The single pass conversion rate of cyclohexanone is lower than 50%, and the selectivity of cyclohexenyl cyclohexanone is lower than 97%.
The catalyst used in the method for preparing cyclohexenyl cyclohexanone is a strong acid and alkali or solid acid catalyst, the single-pass selectivity of the reaction is less than 97%, the selectivity is low, the product contains trimerization or polymer to make the purity of dimer lower, and the purity of cyclohexenyl cyclohexanone is at least more than 99.5% in the industrial dehydrogenation preparation of o-phenylphenol. The catalyst separated after the reaction is over is more required to be subjected to water washing or alkali washing treatment, so that a large amount of wastewater containing organic matters is generated, and the environment is polluted. The refining part is mostly high vacuum rectification, has high requirements on equipment, and has low purity and huge energy consumption even if adopting normal pressure rectification.
Disclosure of Invention
The invention aims to overcome the defects of low selectivity, high equipment requirement, large organic wastewater amount, high energy consumption, low purity and the like, and provides a process for continuously preparing high-purity cyclohexenyl cyclohexanone at normal pressure on the basis of energy conservation and environmental protection, in particular to a method for continuously preparing cyclohexenyl cyclohexanone by removing water and cyclohexane from cyclohexanone through a dehydration condensation and light component removal tower and removing cyclohexanone from a refining tower.
The cyclohexanone condensation reaction is a reversible reaction, and the generated water is discharged in time, so that the reaction rate and the conversion rate can be improved. Because the boiling point of the decahydro triphenylene (trimer) is higher, the problems of high energy consumption, low efficiency and the like of product separation caused by the fact that the product contains the trimer and the polymer are considered, and more impurities are generated during the subsequent gas phase dehydrogenation for preparing the o-phenylphenol to seriously influence the purity of the o-phenylphenol. Therefore, the improvement of the single-pass selectivity of cyclohexenyl cyclohexanone in the reaction section is particularly critical for the subsequent refining and dehydrogenation production of o-phenylphenol. Experiments show that the reduction of the single-pass conversion rate of the reaction is beneficial to improving the selectivity of the cyclohexenyl cyclohexanone. The invention mainly reduces the single-pass conversion rate of the reaction by the total reflux of the reaction kettle.
Too high a cyclohexanone condensation reaction temperature may lead to trimerization and polymerization, whereas the condensation reaction rate of cyclohexanone is low at 120 ℃. Cyclohexane is added to reduce the boiling point of components, accelerate the reaction rate at 120 ℃ and improve the single pass conversion rate of the reaction.
According to the characteristics, aiming at the problems existing in the prior study, the invention provides the following specific technical scheme:
the invention provides a process for continuously preparing high-purity cyclohexenyl cyclohexanone at normal pressure.
The continuous preparation device comprises a cyclohexanone raw material tank 1, a cyclohexane raw material tank 2, a reaction kettle 3 with a jacket and stirring, a reflux condenser 4, a filter 5, a crude dimer intermediate tank 6, a centrifugal pump 7, a light component removing tower 8, a reflux condenser 9, an oil-water separator 10, a cyclohexane intermediate tank 11, a centrifugal pump 12, a waste liquid tank 13, a reboiler 14, a centrifugal pump 15, a refining tower 16, a reflux condenser 17, a cyclohexanone intermediate tank 18, a centrifugal pump 19, a reboiler 20 and a dimer finished product tank 21.
The device comprises a reaction kettle, a light component removing tower and a refining tower, wherein the reaction kettle is connected with the light component removing tower through a crude dimer intermediate tank, the light component removing tower is connected with the refining tower, and the reaction kettle is connected with a cyclohexanone raw material tank and a cyclohexane raw material tank; the top of the light component removal tower is connected with an oil-water separator, and the oil-water separator is connected with a cyclohexane intermediate tank and a waste liquid tank; the bottom of the light component removing tower is connected with the refining tower through a reboiler;
the top of the refining tower is connected with a cyclohexanone intermediate tank, and the cyclohexanone intermediate tank is connected with a cyclohexanone raw material tank;
the bottom of the refining tower is connected with a dimer finished product tank.
Preferably, the top of the light component removing tower is connected with a reflux condenser, and the top of the refining tower is connected with the reflux condenser. The reaction kettle is also connected with a reflux condenser, and the cyclohexane intermediate tank is communicated with a cyclohexane raw material tank.
The continuous production process of the invention comprises condensation reaction, removal of water and cyclohexane by a light component removal tower, separation of cyclohexanone by a refining tower and obtaining the cyclohexenyl cyclohexanone product. Cyclohexanone, cyclohexane and catalyst are put into a reaction kettle in proportion, materials in the reaction kettle are sent into a dimer intermediate tank after the catalyst is removed through a filter, materials in the dimer intermediate tank are introduced into the middle part of a light component removal tower, cyclohexane and water are extracted from the top of the tower, an oil phase enters the cyclohexane intermediate tank after layering through an oil-water separator, and a water phase enters a waste liquid tank. Introducing the material at the tower bottom of the light component removal tower into a refining tower, extracting cyclohexanone from the tower top of the refining tower, and filling finished products after cyclohexenyl cyclohexanone which is the product at the tower bottom enters a dimer finished product tank.
The process method comprises the following steps:
(1) Adding cyclohexanone, cyclohexane and catalyst Y-Al into a reaction kettle 2 O 3 Controlling the reaction temperature at 110-120 ℃;
(2) The rising steam is condensed by a reflux condenser and then flows back into the reaction kettle;
(3) And (3) carrying out light removal treatment on materials in the reaction kettle to remove cyclohexane and water, and refining to remove cyclohexanone after light removal to obtain a finished product.
The specific content of the step (3) is preferably as follows:
(1) Materials in the reaction kettle react for 2-3 hours, then the materials are filtered to remove the catalyst and then are pumped into the middle part of a light component removal tower, the overhead components of the light component removal tower are cyclohexane and water, and the materials in the reaction kettle are cyclohexanone and cyclohexenyl cyclohexanone;
(2) The upper layer of the cyclohexane and water enter a cyclohexane raw material tank for recycling after layering in a layering device, and the lower layer enters a waste liquid tank;
(3) And introducing tower kettle materials into the middle part of the refining tower, distilling cyclohexanone at the top of the refining tower, wherein the tower kettle materials are the product cyclohexenyl cyclohexanone.
Further preferably, the temperature of the reaction kettle is controlled to be 115-120 ℃ and the temperature of the tower kettle of the light component removal rectifying tower is 160-170 ℃.
Further preferably, the temperature of the bottom of the purification rectifying tower is 270-280 ℃.
Preferably Y-Al 2 O 3 The mass of the catalyst is 5-10% of the total mass of the cyclohexanone, and the mass of the cyclohexane is 8-12% of the total mass of the cyclohexanone。
Preferably Y-Al 2 O 3 The mass of the catalyst is 8% of the total mass of cyclohexanone and cyclohexane, and the mass of the cyclohexane is 10% of the total mass of cyclohexanone.
Preferably said Y-Al 2 O 3 The particle size of the catalyst is 100-140 meshes.
Preferably said gamma-Al 2 O 3 The catalyst particle size was 120 mesh.
Cyclohexanone, cyclohexane and gamma-Al 2 O 3 The catalyst is added into a reaction kettle from a raw material tank according to a certain proportion, stirred and heated to a certain temperature to react. The rising steam of the reaction kettle is condensed by a reflux condenser and then flows back into the kettle, and the materials in the reaction kettle stay for 2-3h and then enter a dimer intermediate tank from the bottom of the kettle by a filter.
The materials in the dimer intermediate tank are sent into the middle part of the light component removal tower, rising steam is condensed by a reflux condenser and then enters an oil-water separator, the water phase enters a waste liquid tank, and the oil phase is pumped into a cyclohexane intermediate tank by a material conveying pump for recycling. The material in the bottom of the light component removing tower is pumped into the middle of the refining tower by a material conveying pump.
Rising steam in the refining tower is condensed by a reflux condenser and then sent into a cyclohexanone raw material tank for recycling, and tower kettle materials are sent into a dimer finished product tank. The process flow is shown in figure 1.
The gas chromatographic analysis shows that the conversion rate of the condensation reaction in the reaction kettle is above 29.11%, the selectivity reaches 99.99% (see figure 2), and the purity of the dimer in the fine product tank is 99.99% (see figure 3).
The reaction kettle, the light component removing tower and the refining tower are all provided with condensers, which can be air coolers or water coolers; the cooling medium can be circulating water, low-temperature water, chilled water or other cooling medium such as low-temperature materials in the system. The reaction kettle is provided with a jacket, the light component removing tower and the refining tower are provided with reboilers, and heat sources used by the jacket and the reboilers can be fresh steam, heat conducting oil or material steam generated in the system.
The material components in the dimer intermediate tank are cyclohexenyl cyclohexanone, cyclohexane and water. The oil phase in the oil-water separator at the top of the light component removal tower is cyclohexane, the water phase is water, the material components at the tower bottom are cyclohexanone and cyclohexenyl cyclohexanone, the distillate component at the top of the refining tower is cyclohexanone, and the product cyclohexenyl cyclohexanone is at the tower bottom.
Cyclohexanone and Y-Al 2 O 3 The catalyst and a proper amount of cyclohexane are put into a reaction kettle with a jacket and stirring, fully mixed and heated.
The beneficial effects are that:
(1) The invention optimizes the existing production process of cyclohexenyl cyclohexanone, and the existing process is characterized in that the reaction kettle product contains trimer, generally comprises a one-kettle three-tower (reaction kettle, a dehydration tower, a refining tower and a dimer tower), and the invention adopts the production process flow of a one-kettle two-tower (reaction kettle, a light component removal tower and a refining tower) because the reaction kettle material basically does not contain trimerization and polymerization products, thereby greatly reducing the equipment cost. And the cyclohexenyl cyclohexanone is prepared under normal pressure, so that the operation is safer and more convenient, and the defects of high cost, high material requirement and the like of high-vacuum rectifying equipment used in the prior art are avoided. The whole process is carried out under continuous conditions, so that the damage to people and the application of equipment are reduced, the waste water amount is small, the organic matter content is low, no waste gas is generated basically due to the processes of total reflux of the reaction kettle, layering of the layering device and the like, the safety is realized, the environment is protected, and the feasibility is greatly improved.
(2) The selectivity of the cyclohexenyl cyclohexanone in the condensation reaction stage of the process method reaches 99.99 percent (see figure 2), so that the cyclohexenyl cyclohexanone is changed from a light component to a heavy component in the traditional refining process, the temperature required by rectification is greatly reduced, the rectification separation difficulty is greatly reduced, the energy consumption is greatly reduced, and the product purity is greatly improved while the energy is saved. The purity of the cyclohexenyl cyclohexanone product can reach 99.99 percent (see figure 3). Because the decahydro triphenylene and the poly condensate can not be used for preparing the o-phenylphenol, the high-purity cyclohexenyl cyclohexanone prepared by the method creates favorable conditions for preparing the o-phenylphenol by dehydrogenation, and has extremely important production and application values.
(3) In the process method, the raw materials cyclohexanone and cyclohexane can be pumped back to the raw material tank through the material conveying pump after being distilled off from the top of the tower for recycling, the process is continuous, the application is not needed, the operation is more convenient, the energy is saved, the consumption is reduced, the cost is reduced, and the application prospect is wide.
Drawings
FIG. 1 is a process flow diagram of the present invention
Cyclohexanone feed tank 1, cyclohexane feed tank 2, jacketed and stirred reaction kettle 3, reflux condenser 4, filter 5, crude dimer intermediate tank 6, centrifugal pump 7, light component removal column 8, reflux condenser 9, oil-water separator 10, cyclohexane intermediate tank 11, centrifugal pump 12, waste liquid tank 13, reboiler 14, centrifugal pump 15, refining column 16, reflux condenser 17, cyclohexanone intermediate tank 18, centrifugal pump 19, reboiler 20 and dimer finished product tank 21, A is cyclohexanone, B is cyclohexane, C is catalyst Y-Al 2 O 3 D is outlet material (water, cyclohexane, cyclohexanone and cyclohexenyl cyclohexanone) at the bottom of the reaction kettle after the catalyst is removed, E is oil phase (cyclohexane) of an oil-water separator of the light component removal tower, F is water phase (water) of the oil-water separator of the light component removal tower, G is feeding material of a refining tower (cyclohexanone and cyclohexenyl cyclohexanone), H is discharging material of the top of the refining tower (cyclohexanone), and I is discharging material of the bottom of the refining tower (cyclohexenyl cyclohexanone).
FIG. 2 is a chromatogram of the reaction vessel bottom material in example 1, wherein cyclohexane, cyclohexanone and cyclohexenyl cyclohexanone are sequentially arranged from left to right in order of peak.
Figure 3 is cyclohexenyl cyclohexanone with a product purity of 99.99% or higher.
FIG. 4 is a chromatogram of the reaction tank bottoms of comparative example 1, showing cyclohexane, cyclohexanone, cyclohexenyl cyclohexanone and trimer in the order of the peaks from left to right.
FIG. 5 is a chromatogram of the product of comparative example 1, showing cyclohexenylcyclohexanone and trimer in the order of the peaks from left to right.
FIG. 6 is a chromatogram of the reaction tank bottoms in example 2, showing cyclohexane, cyclohexanone and cyclohexenyl cyclohexanone in the order of the peaks from left to right.
FIG. 7 is a chromatogram of the reaction tank bottoms in example 3, showing cyclohexane, cyclohexanone and cyclohexenyl cyclohexanone in the order of the peaks from left to right.
FIG. 8 is a chromatogram of the reaction tank bottoms of comparative example 2, showing cyclohexane, cyclohexanone, cyclohexenyl cyclohexanone and trimer in the order of the peaks from left to right.
FIG. 9 is a chromatogram of the reaction tank bottoms of comparative example 3, showing cyclohexane, cyclohexanone, cyclohexenyl cyclohexanone and trimer in the order of the peaks from left to right.
FIG. 10 is a chromatogram of the product of comparative example 3, showing cyclohexenylcyclohexanone and trimer in the order of the peaks from left to right.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
Example 1
3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 120-mesh Y-Al are added into 5000L of reaction kettle 3 with a stirring and jacket 2 O 3 The catalyst is evenly mixed, then steam is introduced for preheating and continuously heating, the temperature of the reaction kettle 3 is controlled to be 120 ℃, water generated by the reaction is distilled out together with cyclohexane, the water is condensed by a reflux condenser 4 and then is totally refluxed, a tower kettle sample is taken after 2 hours of reaction, and the single pass conversion rate of cyclohexanone is 29.11%, and the reaction selectivity is 99.99% (see figure 2). Filtering the mixed solution from the lower part of the reaction kettle through a filter 5, sending the filtered mixed solution into a crude dimer intermediate tank 6, then sending the filtered mixed solution into a light component removing tower 8 through a centrifugal pump 7 at a flow rate of 1000L/h, raising the temperature of the tower kettle of the light component removing tower 8 to 165 ℃, evaporating water and cyclohexane together, condensing the water and cyclohexane through a reflux condenser 9, and sending the condensed water and cyclohexane into an oil-water separator 10 at a flow rate of about 340L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the tower bottom of the light component removal tower is a mixture of cyclohexanone and cyclohexenyl cyclohexanone, the mixture is sent into a refining tower 16 by a centrifugal pump 15 at a flow rate of 660L/h, the temperature of the tower bottom is continuously raised to 278 ℃, the cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone is pumped into a raw material tank by a centrifugal pump 19 to be recycled as raw material, wherein the flow rate is 440L/h.The bottoms product was fed into dimer finishing tank 21 at a flow rate of 220L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: cyclohexenyl cyclohexanone is 99.99% or more (see figure 3).
Gas chromatography apparatus and analysis conditions:
device name: a high performance gas chromatograph; instrument model: GC-6891N; the manufacturing factory: nanjing Kejie detection technology development Co.
Analysis conditions: column front pressure: 50kpa; the split ratio is 100:1; sample injection amount is 0.5 mu L; detector temperature: 290 ℃; injector temperature: 300 ℃. Column temperature: heating to 180deg.C, maintaining for 3min, heating to 260deg.C at 10deg.C/min, maintaining for 14min, and analyzing for 25min.
The treatment method comprises the following steps: area normalization method.
Comparative example 1
A continuous production of cyclohexenyl cyclohexanone was carried out in the same apparatus as in example 1, and 3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 120-mesh Y-Al were charged into 5000L of a reaction vessel 3 having a stirring and jacket 2 O 3 The catalyst is evenly mixed, then steam is introduced for preheating and continuously heating, the temperature of the reaction kettle 3 is controlled to be 140 ℃, water generated by the reaction is distilled out together with cyclohexane, the water is condensed by a reflux condenser 4 and then is totally refluxed, a tower kettle sample is taken after 2 hours of reaction, the single pass conversion rate of cyclohexanone is 59.33%, and the reaction selectivity is 95.47% (see figure 4). Filtering the mixed solution from the lower part of the reaction kettle through a filter 5, sending the filtered mixed solution into a crude dimer intermediate tank 6, then sending the filtered mixed solution into a light component removing tower 8 through a centrifugal pump 7 at a flow rate of 1000L/h, raising the temperature of the tower kettle of the light component removing tower 8 to 165 ℃, evaporating water and cyclohexane together, condensing the water and cyclohexane through a reflux condenser 9, and sending the condensed water and cyclohexane into an oil-water separator 10 at a flow rate of about 370L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the tower bottom of the light component removal tower is a mixture of cyclohexanone and cyclohexenyl cyclohexanone, the mixture is sent into a refining tower 16 by a centrifugal pump 15 at the flow rate of 630L/h, the temperature of the tower bottom is continuously increased to 278 ℃, the cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone intermediate tank is pumped into raw materials by a centrifugal pump 19The tank was recycled as a raw material at a flow rate of 250L/h. The bottoms product was fed into dimer finishing tank 21 at a flow rate of 380L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: cyclohexenyl cyclohexanone 95.47%, and the polyvidone 4.53% (see FIG. 5).
The gas chromatography apparatus and the analysis conditions were the same as in example 1.
Example 2
A continuous production of cyclohexenyl cyclohexanone was carried out in the same apparatus as in example 1, and 3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 120-mesh Y-Al were charged into 5000L of a reaction vessel 3 having a stirring and jacket 2 O 3 The catalyst is evenly mixed, then steam is introduced for preheating and continuously heating, the temperature of the reaction kettle 3 is controlled to be 110 ℃, water generated by the reaction is distilled out together with cyclohexane, the water is condensed by a reflux condenser 4 and then is totally refluxed, a tower kettle sample is taken after 2 hours of reaction, and the single pass conversion rate of cyclohexanone is 22.79%, and the reaction selectivity is 99.99% (see figure 6). Filtering the mixed solution from the lower part of the reaction kettle through a filter 5, sending the filtered mixed solution into a crude dimer intermediate tank 6, then sending the filtered mixed solution into a light component removing tower 8 through a centrifugal pump 7 at a flow rate of 1000L/h, raising the temperature of the tower kettle of the light component removing tower 8 to 165 ℃, evaporating water and cyclohexane together, condensing the water and cyclohexane through a reflux condenser 9, and sending the condensed water and cyclohexane into an oil-water separator 10 at a flow rate of about 300L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the tower bottom of the light component removal tower is a mixture of cyclohexanone and cyclohexenyl cyclohexanone, the mixture is sent into a refining tower 16 by a centrifugal pump 15 at the flow rate of 700L/h, the temperature of the tower bottom is continuously raised to 278 ℃, the cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone is pumped into a raw material tank by a centrifugal pump 19 to be recycled as raw material, wherein the flow rate is 520L/h. The bottoms product enters dimer product tank 21 at a flow rate of 180L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: cyclohexenyl cyclohexanone is 99.99% or more (see figure 3).
The gas chromatography apparatus and the analysis conditions were the same as in example 1.
Example 3
In the same apparatus as in example 1, cyclohexenyl cyclohexanone was continuously produced to 5000L reaction kettle 3 with stirring and jacket is added with 3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 200 mesh Y-Al 2 O 3 The catalyst is evenly mixed, then steam is introduced for preheating and continuously heating, the temperature of the reaction kettle 3 is controlled to be 120 ℃, water generated by the reaction and cyclohexane with water-carrying agent are distilled out, the water is condensed by a reflux condenser 4 and then is totally refluxed, a tower kettle sample is taken after 2 hours of reaction, the single pass conversion rate of cyclohexanone is 28.35%, and the reaction selectivity is 99.99% (see figure 7). Filtering the mixed solution from the lower part of the reaction kettle through a filter 5, sending the filtered mixed solution into a crude dimer intermediate tank 6, then sending the filtered mixed solution into a light component removing tower 8 through a centrifugal pump 7 at a flow rate of 1000L/h, raising the temperature of the tower kettle of the light component removing tower 8 to 165 ℃, evaporating water and cyclohexane together, condensing the water and cyclohexane through a reflux condenser 9, and sending the condensed water and cyclohexane into an oil-water separator 10 at a flow rate of about 330L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the tower bottom of the light component removal tower is a mixture of cyclohexanone and cyclohexenyl cyclohexanone, the mixture is sent into a refining tower 16 by a centrifugal pump 15 at a flow rate of 670L/h, the temperature of the tower bottom is continuously raised to 278 ℃, the cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone is pumped into a raw material tank by a centrifugal pump 19 to be recycled as raw material, wherein the flow rate is 460L/h. The bottoms product was fed into dimer finishing tank 21 at a flow rate of 210L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: cyclohexenyl cyclohexanone is 99.99% or more (see figure 3).
The gas chromatography apparatus and the analysis conditions were the same as in example 1.
Comparative example 2
A continuous production of cyclohexenyl cyclohexanone was carried out in the same apparatus as in example 1, and 3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 200 mesh Y-Al were charged into 5000L of a reaction vessel 3 having a stirring and jacket 2 O 3 The catalyst is evenly mixed, then steam is introduced for preheating and continuously heating, the temperature of the reaction kettle 3 is controlled to be 140 ℃, water generated by the reaction and cyclohexane with water-carrying agent are distilled out, the water is condensed by a reflux condenser 4 and then is totally refluxed, a tower kettle sample is taken after 2 hours of reaction, the single pass conversion rate of cyclohexanone is 58.69%, and the reaction selectivity is 95.47% (see figure 8). The mixed solution is passed through from the lower portion of reaction kettleFiltering by a filter 5, feeding into a crude dimer intermediate tank 6, feeding into a light component removing tower 8 by a centrifugal pump 7, and increasing the temperature of the tower bottom of the light component removing tower 8 to 165 ℃ at a flow rate of 1000L/h, evaporating water and cyclohexane together, condensing by a reflux condenser 9, and feeding into an oil-water separator 10 at a flow rate of about 360L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the tower bottom of the light component removal tower is a mixture of cyclohexanone and cyclohexenyl cyclohexanone, the mixture is sent into a refining tower 16 by a centrifugal pump 15 at a flow rate of 640L/h, the temperature of the tower bottom is continuously raised to 278 ℃, the cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone is pumped into a raw material tank by a centrifugal pump 19 to be recycled as raw material, wherein the flow rate is 270L/h. The bottoms product was fed into dimer finishing tank 21 at a flow rate of 370L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: cyclohexenyl cyclohexanone 95.47%, and the polyvidone 4.53% (see FIG. 5).
The gas chromatography apparatus and the analysis conditions were the same as in example 1.
Comparative example 3
3000kg of cyclohexanone, 300kg of cyclohexane and 264kg of 120-mesh Y-Al are added into 5000L of reaction kettle 3 with a stirring and jacket 2 O 3 The catalyst is evenly mixed and then is introduced into steam for preheating and continuously heating, the temperature of a reaction kettle 3 is controlled to be 120 ℃, water generated by the reaction and cyclohexane are distilled out, the water is condensed by a reflux condenser 4 and enters a layering device, an upper oil phase of the layering device returns to the kettle, a lower water phase of the layering device enters a waste liquid tank, a tower kettle sample is taken after the reaction for 2 hours, the single pass conversion rate of cyclohexanone is 66.87%, and the reaction selectivity is 97.23% (see figure 9). Filtering the mixed solution from the lower part of the reaction kettle through a filter 5, sending the filtered mixed solution into a crude dimer intermediate tank 6, then sending the filtered mixed solution into a light component removing tower 8 through a centrifugal pump 7 at a flow rate of 1000L/h, raising the temperature of the tower kettle of the light component removing tower 8 to 165 ℃, evaporating water and cyclohexane together, condensing the water and cyclohexane through a reflux condenser 9, and sending the condensed water and cyclohexane into an oil-water separator 10 at a flow rate of about 100L/h. After delamination, the upper cyclohexane is sent into a cyclohexane intermediate tank 11, and then is pumped into a cyclohexane raw material tank for recycling by a centrifugal pump 12, and the water phase is sent to a waste liquid tank 13. The discharge of the bottom of the light component removal tower is the mixture of cyclohexanone and cyclohexenyl cyclohexanoneThe product is sent into a refining tower 16 by a centrifugal pump 15 at a flow rate of 900L/h, the temperature of the tower kettle is continuously raised to 278 ℃, cyclohexanone at the tower top is condensed by a reflux condenser 17 and then enters a cyclohexanone intermediate tank 18, and the cyclohexanone intermediate tank is pumped into a raw material tank by a centrifugal pump 19 to be used as a raw material for recycling, wherein the flow rate is 600L/h. The bottoms product was fed into dimer finishing tank 21 at a flow rate of 300L/h. The tower bottom product is analyzed by gas chromatography and comprises the following components: the composition of the material is as follows: cyclohexenyl cyclohexanone 97.23%, a polytropic compound 2.77% (see fig. 10).
The gas chromatography apparatus and the analysis conditions were the same as in example 1.
Claims (10)
1. A preparation method of cyclohexenyl cyclohexanone is characterized in that:
(1) Adding cyclohexanone, cyclohexane and a catalyst gamma-Al into a reaction kettle 2 O 3 Controlling the reaction temperature at 110-120 ℃;
(2) The rising steam is condensed by a reflux condenser and then flows back into the reaction kettle;
(3) And (3) carrying out light removal treatment on materials in the reaction kettle to remove cyclohexane and water, and refining to remove cyclohexanone after light removal to obtain a finished product.
2. The method of manufacturing according to claim 1, characterized in that: the specific content of the step (3) is as follows:
(1) Materials in the reaction kettle react for 2-3 hours, then the materials are filtered to remove the catalyst and then are pumped into the middle part of a light component removal tower, the overhead components of the light component removal tower are cyclohexane and water, and the materials in the reaction kettle are cyclohexanone and cyclohexenyl cyclohexanone;
(2) The upper layer of the cyclohexane and water enter a cyclohexane raw material tank for recycling after layering in a layering device, and the lower layer enters a waste liquid tank;
(3) And introducing tower kettle materials into the middle part of the refining tower, distilling cyclohexanone at the top of the refining tower, wherein the tower kettle materials are the product cyclohexenyl cyclohexanone.
3. The preparation method according to claim 1 or 2, characterized in that: the temperature of the reaction kettle is 115-120 ℃, and the temperature of the tower kettle of the light component removal rectifying tower is 160-170 ℃.
4. The preparation method according to claim 1 or 2, characterized in that: the temperature of the tower bottom of the refining rectifying tower is 270-280 ℃.
5. The method of manufacturing according to claim 1, characterized in that: gamma-Al 2 O 3 The mass of the catalyst is 5-10% of the total mass of the cyclohexanone, and the mass of the cyclohexane is 8-12% of the total mass of the cyclohexanone.
6. The method of manufacturing according to claim 5, wherein: gamma-Al 2 O 3 The mass of the catalyst is 8% of the total mass of cyclohexanone and cyclohexane, and the mass of the cyclohexane is 10% of the total mass of cyclohexanone.
7. The method of manufacturing according to claim 1, characterized in that: said gamma-Al 2 O 3 The particle size of the catalyst is 100-140 meshes.
8. The method of manufacturing according to claim 7, wherein: said gamma-Al 2 O 3 The catalyst particle size was 120 mesh.
9. An apparatus for preparing a cyclohexenyl cyclohexanone according to any one of claims 1 to 8, characterized in that: the device comprises a reaction kettle (3), a light component removing tower (8) and a refining tower (16),
the reaction kettle (3) is connected with a light component removing tower (8) through a coarse dimer intermediate tank (6), the light component removing tower (8) is connected with a refining tower (16),
the reaction kettle (3) is connected with a cyclohexanone raw material tank (1) and a cyclohexane raw material tank (2), and the reaction kettle (3) is also connected with a reflux condenser (4);
the top of the light component removal tower (8) is connected with an oil-water separator (10), and the oil-water separator (10) is connected with a cyclohexane intermediate tank (11) and a waste liquid tank (13);
the bottom of the light component removing tower (8) is connected with a refining tower (16) through a reboiler (14);
the top of the refining tower (16) is connected with a cyclohexanone intermediate tank (18);
the bottom of the refining tower (16) is connected with a dimer finished product tank (21).
10. The apparatus according to claim 9, wherein: the top of the light component removing tower (8) is connected with a reflux condenser (9), and the top of the refining tower (16) is connected with a reflux condenser (17);
the cyclohexane intermediate tank (11) is communicated with the cyclohexane raw material tank (2), and the cyclohexanone intermediate tank (18) is connected with the cyclohexanone raw material tank (1).
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