CN104803951A - Method for preparing high-quality epoxy cyclohexane by adopting micro-flow field reaction technology - Google Patents
Method for preparing high-quality epoxy cyclohexane by adopting micro-flow field reaction technology Download PDFInfo
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- CN104803951A CN104803951A CN201510249275.3A CN201510249275A CN104803951A CN 104803951 A CN104803951 A CN 104803951A CN 201510249275 A CN201510249275 A CN 201510249275A CN 104803951 A CN104803951 A CN 104803951A
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- cyclohexene
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 123
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims abstract description 114
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 55
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical group FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- IAJKTOIWQHTZOS-UHFFFAOYSA-N 1,1,1-trifluoro-3-phenylpropan-2-one Chemical compound FC(F)(F)C(=O)CC1=CC=CC=C1 IAJKTOIWQHTZOS-UHFFFAOYSA-N 0.000 claims description 6
- MNOONJNILVDLSW-UHFFFAOYSA-N 2-chloro-2,2-difluoro-1-phenylethanone Chemical compound FC(F)(Cl)C(=O)C1=CC=CC=C1 MNOONJNILVDLSW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- SUNMBRGCANLOEG-UHFFFAOYSA-N 1,3-dichloroacetone Chemical compound ClCC(=O)CCl SUNMBRGCANLOEG-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- -1 titanium modified silica Chemical class 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DMWISQNDYKMXFB-UHFFFAOYSA-N 1-chlorocyclohexan-1-ol Chemical compound OC1(Cl)CCCCC1 DMWISQNDYKMXFB-UHFFFAOYSA-N 0.000 description 1
- CCHNWURRBFGQCD-UHFFFAOYSA-N 2-chlorocyclohexan-1-one Chemical compound ClC1CCCCC1=O CCHNWURRBFGQCD-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical group C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 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
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing high-quality cyclohexene oxide by adopting a micro-flow field reaction technology, which is a method for preparing high-quality cyclohexene oxide by using cyclohexene, a catalyst, aqueous hydrogen peroxide, a stabilizer EDTA-2Na, inorganic base and acetonitrile in a channel modular reaction device. Compared with the prior art, the method has the advantages of simplicity, easiness in control, easiness in obtaining and obtaining of raw materials, high efficiency and the like, and the epoxy cyclohexane prepared by the method is high in purity and beneficial to industrial production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for preparing high-quality cyclohexene oxide by adopting a micro-flow field reaction technology.
Background
Due to the existence of very active epoxy groups in the molecular structure, the epoxy cyclohexane can react with amine, phenol, alcohol, carboxylic acid and the like to generate a series of compounds with high added values, and can be synthesized by taking the epoxy cyclohexane as a raw material: the pesticide is propargite; unsaturated resin with high hardness, high temperature resistance and acid and alkali resistance; novel, highly efficient photosensitive coatings and photosensitive adhesives; a crown ether; a polycarbonate; important fine chemicals are adipaldehyde, etc. In addition, the epoxy resin reactive diluent is an organic solvent with strong dissolving capacity and can be used as an epoxy resin reactive diluent.
At present, the scale of the epoxy cyclohexane production device in Europe and America is not large, and most of the epoxy cyclohexane production devices are not produced. The Keppie of the biggest Kemante pesticide company in the United states is higher than that of Yueyang Changde in production cost of epoxy cyclohexane, and the Yueyang Changde is designated as the only supplier because the production cost of epoxy cyclohexane which is a raw material of the Kemante pesticide company is higher than that of the Yueyang Changde. In the production method of epoxy cyclohexane, the original main process for preparing epoxy cyclohexane by cyclohexane comprises the following steps: a. oxidizing cyclohexane into cyclohexanone, chlorinating into chlorocyclohexanone, hydrogenating into chlorocyclohexanol, and cyclizing into cyclohexene oxide in the presence of alkali; b. oxidizing cyclohexane into cyclohexanol, dehydrating the cyclohexanol into cyclohexene, and oxidizing the cyclohexene into cyclohexene oxide; c. dehydrogenation of cyclohexane into cyclohexene followed by epoxidation into cyclohexene oxide. These processes all have the problems of long route, more side reactions, low yield and the like, and the cyclohexane serving as a raw material is only an initial raw material and is finally attributed to the problem that the cyclohexene serving as a direct raw material. In the production method of cyclohexene oxide, the hypochlorite method generates a large amount of wastes such as salt-containing wastewater, namely about 20 tons of wastewater is generated for each ton of cyclohexene oxide, so that the energy consumption is high and the equipment corrosion is serious. The halcon method is severely restricted by the market capacity of byproducts due to byproducts of hydroxyl-containing compounds such as phenethyl alcohol or tert-butyl alcohol. The hydrogen peroxide method takes hydrogen peroxide as an oxygen source, is a relatively green process, and has the production capacity of over 99 percent of the world. However, this method generally uses a large amount of organic solvent, thereby increasing production costs.
CN101343261A discloses that cyclohexene oxide is prepared by catalytic oxidation of a catalyst prepared according to CN1204970C with hydrogen peroxide as an oxidant, and the method shortens the reaction time and improves the recovery efficiency of the catalyst. CN101020669A discloses a method for preparing cyclohexene oxide by reacting cyclohexene at 20-70 ℃ for 20h under the action of hydrogen peroxide and a composite catalyst, wherein the method does not use an organic solvent, has high yield, and can partially recover the composite catalyst. CN101691363A discloses a method for preparing cyclohexene oxide by using a silicon-titanium molecular sieve as a catalyst and adding a basic auxiliary agent, but the catalyst has a small particle size and is difficult to recover, which makes industrial application difficult. CN101348472A discloses a method for preparing cyclohexene oxide by using titanium modified silica as a catalyst and cyclohexene and organic peroxide as substrates, which can solve the problems of environmental pollution and equipment corrosion, but has complex catalyst preparation and expensive organic peroxide price, and cannot realize large-scale industrial production.
The manufacturers for domestic large-scale production include Shandong high-density silver eagle chemical fiber company Limited (called high-density silver eagle for short), Yueyang Changde chemical industry Limited (called Yueyang Changde for short), Yueyang petrochemical general factory Longxing industry corporation (called Longxing industry for short) and the like. However, the operation of the manufacturers is also a batch method, the yield is low, the automatic control level of the equipment is low, the continuous production cannot be realized, the preparation of the required catalyst is complex, the reutilization property is poor, and the production cost is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing high-quality cyclohexene oxide by adopting a micro-flow field reaction technology, so as to solve the problems of overhigh production cost, complex reaction process, low efficiency and the like in the prior art.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing high-quality cyclohexene oxide by adopting a micro-flow field reaction technology comprises the following steps:
(1) mixing cyclohexene and a catalyst, and dissolving the mixture in an organic solvent for later use;
(2) mixing aqueous hydrogen peroxide solution, a stabilizer EDTA-2Na, inorganic alkaline aqueous solution and acetonitrile for later use;
(3) respectively injecting the mixed systems obtained in the step (1) and the step (2) into a micro-structure mixer in a micro-channel modular reaction device, uniformly mixing, and injecting into the micro-structure reactor for reaction at 25-60 ℃ for 5-15 min;
(4) introducing the mixed system obtained in the step (3) into a product collector, sequentially washing the organic phase with a sodium carbonate aqueous solution and water until the pH value is 7.0, and drying to obtain cyclohexene oxide;
wherein,
the microchannel modular reaction device comprises a microstructure mixer, a microstructure reactor and a product collector which are sequentially connected through pipelines; wherein, the first raw material storage tank and the second raw material storage tank are respectively connected with the microstructure mixer.
Wherein the product collection device may be cooled with an ice-water mixture to terminate the reaction.
Wherein the reaction raw materials and products are fed in and out by precise and low-pulsation pumps, such as HPLC pumps or syringe pumps.
Wherein the microstructure mixer is slit plate mixer LH25(Hastelloy C); the microstructure reactor is a meaander bioreactor HC, sandwich bioreactor HC, fixed bed meaander bioreactor HC, preferably sandwich bioreactor HC.
In the step (1), the catalyst is trifluoroacetophenone, acetone, acetophenone, 1, 3-dichloroacetone, 2-chloro-2, 2-difluoroacetophenone, 1, 1, 1-trifluoro-3-phenylacetone, 2, 3, 3, 3-pentafluoro-1-phenylacetone, preferably trifluoroacetophenone, 2-chloro-2, 2-difluoroacetophenone, 1, 1, 1-trifluoro-3-phenylacetone or 2, 2, 3, 3, 3-pentafluoro-1-phenylacetone; wherein the mol ratio of the cyclohexene to the catalyst is 1:0.01 to 0.3.
In the step (1), the mol ratio of the cyclohexene to the catalyst is 1:0.01 to 0.3, preferably 1:0.01 to 0.1.
In the step (2), the concentration of solute hydrogen peroxide in the aqueous hydrogen peroxide solution is 30 wt%;
in the step (2), the inorganic base is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or cesium carbonate, preferably potassium carbonate, cesium carbonate or sodium carbonate; wherein, the concentration of the inorganic base in the inorganic base aqueous solution is 1 mol/L.
In the step (2), the molar ratio of acetonitrile to cyclohexene is 1: 1-6, preferably 1: 1-4; the molar ratio of solute hydrogen peroxide to acetonitrile in the aqueous hydrogen peroxide solution is 1: 1-6, preferably 1: 1-4; the mass percentage of the stabilizer EDTA-2Na and the cyclohexene is 1-5%, preferably 1-4%, and the volume ratio of the inorganic base to the acetonitrile is 2: 1.
in the step (4), the concentration of solute sodium carbonate in the sodium carbonate aqueous solution is 5 wt%.
Has the advantages that:
compared with the prior art, the method has the advantages of simplicity, easiness in control, easiness in obtaining and obtaining of raw materials, high efficiency and the like, and the epoxy cyclohexane prepared by the method is high in purity and beneficial to industrial production.
Drawings
FIG. 1 is a schematic diagram of the reaction scheme of the present invention.
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
(the embodiment section is modified after the technical solution is modified)
The reaction raw materials are input into a micro mixer and subsequent equipment by a precise and low-pulsation pump (such as an HPLC pump or an injection pump), so that the materials can continuously pass through the microchannel modular reaction device and the residence time of the materials is controlled. The second microstructure reactor and the product collection vial are connected by a length of polytetrafluoroethylene capillary which can be immersed in an ice-water bath to terminate the reaction.
The microstructure mixer is slit plate mixer LH25(Hastelloy C) or valve-assisted mixer (Hastelloy C); purchased from Ehrfeld Mikrotechnik BTS GmbH, model number 0109-4-0004-F respectively; 0111-2-0014-F.
The microstructure reactor is a meander reactivor HC, sandwich reactivor HC, fixed bed meander reactivor HC and Hastelloy capillary; preferably, the sandwich reactiver HC is purchased from Ehrfeld Mikrotechnik BTSGmbH, and the models are 0211-2-0314-F respectively; 0213-1-0004-F; 0222-2-2004-F.
Example 1:
cyclohexene and trifluoroacetophenone are dissolved in an organic solvent, wherein the molar ratio of cyclohexene to trifluoroacetophenone is 1:0.01 and is marked as solution A, hydrogen peroxide, a stabilizer EDTA-2Na, potassium carbonate and acetonitrile are mixed, the molar ratio of acetonitrile to cyclohexene is 1:1, the molar ratio of hydrogen peroxide to acetonitrile is 1:1, the addition amount of the stabilizer EDTA-2Na is 1% of the weight of cyclohexene, the addition volume amount of an inorganic base potassium carbonate solution is 2 times of the addition volume amount of acetonitrile, and is marked as solution B, the solutions A and B are injected into a microchannel modular reaction device, the discharge of a microstructure reactor is introduced into a separator, the organic phase is washed by 5 wt% of sodium carbonate solution and distilled water respectively until the pH value is 7.0, and drying is carried out to obtain the epoxycyclohexane, wherein the conversion rate of the cyclohexene raw material is 91.4%.
Example 2:
cyclohexene and trifluoroacetophenone are dissolved in an organic solvent, wherein the molar ratio of cyclohexene to trifluoroacetophenone is 1:0.1 and is marked as solution A, meanwhile, hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base potassium carbonate and acetonitrile are mixed, the molar ratio of acetonitrile to cyclohexene is 1:4, the molar ratio of hydrogen peroxide to acetonitrile is 1:4, the addition amount of the stabilizer EDTA-2Na is 4% of the weight of cyclohexene, the addition volume amount of the inorganic base potassium carbonate is 2 times of the addition volume amount of acetonitrile, and is marked as solution B, the solution A and the solution B are injected into a microchannel modular reaction device, the discharge of a microstructure reactor is introduced into a separator, the organic phase is washed by 5 wt% of sodium carbonate solution and distilled water respectively until the pH value is 7.0, and drying is carried out to obtain the cyclohexene oxide, and the conversion rate of the cyclohexene raw material is 94.9%.
Example 3:
dissolving cyclohexene and trifluoroacetophenone in an organic solvent, wherein the molar ratio of cyclohexene to trifluoroacetophenone is 1:0.05, marking as a solution A, simultaneously mixing hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base potassium carbonate and acetonitrile, wherein the molar ratio of acetonitrile to cyclohexene is 1:2, the molar ratio of hydrogen peroxide to acetonitrile is 1:2, the addition amount of the stabilizer EDTA-2Na is 2% of the weight of cyclohexene, the addition volume amount of the inorganic base potassium carbonate is 2 times of the addition volume amount of acetonitrile, marking as a solution B, injecting the solution A and the solution B into a microchannel modular reaction device, discharging from a microstructure reactor, introducing into a separator, washing an organic phase with 5 wt% of sodium carbonate solution and distilled water respectively until the pH value is 7.0, and drying to obtain cyclohexene oxide, wherein the conversion rate of the cyclohexene raw material is 98.5%.
Example 4:
cyclohexene and trifluoroacetophenone are dissolved in an organic solvent, wherein the molar ratio of cyclohexene to trifluoroacetophenone is 1:0.05 and is marked as solution A, meanwhile, hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic alkali sodium carbonate and acetonitrile are mixed, the molar ratio of acetonitrile to cyclohexene is 1:2, the molar ratio of hydrogen peroxide to acetonitrile is 1:2, the addition amount of the stabilizer EDTA-2Na is 2% of the weight of cyclohexene, the addition volume amount of the inorganic alkali sodium carbonate is 2 times of the addition volume amount of acetonitrile, and is marked as solution B, the solution A and the solution B are injected into a microchannel modular reaction device, the discharge of a microstructure reactor is introduced into a separator, the organic phase is washed by 5 wt% of sodium carbonate solution and distilled water respectively until the pH value is 7.0, and drying is carried out to obtain cyclohexene oxide, wherein the conversion rate of the cyclohexene raw material is 92.5%.
Example 5:
cyclohexene and trifluoroacetophenone are dissolved in an organic solvent, wherein the molar ratio of cyclohexene to trifluoroacetophenone is 1:0.05 and is marked as solution A, meanwhile, hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base cesium carbonate and acetonitrile are mixed, the molar ratio of acetonitrile to cyclohexene is 1:2, the molar ratio of hydrogen peroxide to acetonitrile is 1:2, the addition amount of the stabilizer EDTA-2Na is 2% of the weight of cyclohexene, the addition volume amount of the inorganic base cesium carbonate is 2 times of the addition volume amount of acetonitrile, and is marked as solution B, the solution A and the solution B are injected into a microchannel modular reaction device, the discharge of a microstructure reactor is introduced into a separator, the organic phase is washed by 5 wt% of sodium carbonate solution and distilled water respectively until the pH value is 7.0, and drying is carried out to obtain cyclohexene oxide, and the conversion rate of the cyclohexene raw material is 99.5%.
Example 6:
dissolving cyclohexene and 2-chloro-2, 2-difluoroacetophenone in an organic solvent, wherein the molar ratio of cyclohexene to 2-chloro-2, 2-difluoroacetophenone is 1:0.05, marking as solution A, simultaneously mixing hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base cesium carbonate and acetonitrile, wherein the molar ratio of acetonitrile to cyclohexene is 1:2, the molar ratio of hydrogen peroxide to acetonitrile is 1:2, the addition amount of the stabilizer EDTA-2Na is 2% of the weight of cyclohexene, the addition volume amount of the inorganic base cesium carbonate is 2 times of the addition volume amount of acetonitrile, marking as solution B, injecting the A and B solutions into a microchannel modular reaction device, discharging the microstructure reactor, introducing into a separator, washing an organic phase with 5 wt% sodium carbonate solution and distilled water respectively until the pH is epoxy at 7.0, drying to obtain the cyclohexane, the cyclohexene feed conversion was 98.4%.
Example 7:
dissolving cyclohexene and 1, 1, 1-trifluoro-3-phenyl acetone in an organic solvent, wherein the molar ratio of the cyclohexene to the 1, 1, 1-trifluoro-3-phenyl acetone is 1:0.05, marked as solution A, simultaneously mixing hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base cesium carbonate and acetonitrile, wherein the molar ratio of the acetonitrile to the cyclohexene is 1:2, the molar ratio of the hydrogen peroxide to the acetonitrile is 1:2, the adding amount of the stabilizer EDTA-2Na is 2% of the weight of the cyclohexene, the adding volume amount of the inorganic base cesium carbonate is 2 times of the adding volume amount of the acetonitrile, marked as solution B, injecting the A and B solutions into a microchannel modular reaction device, discharging the microstructure reactor into a separator, washing the organic phase with 5 wt% sodium carbonate solution and distilled water respectively until the pH value is 7.0, drying to obtain the cyclohexene oxide, wherein the conversion rate of the cyclohexene raw material is 98.8%.
Example 8:
dissolving cyclohexene and 2, 2, 3, 3, 3-pentafluoro-1-phenyl acetone in an organic solvent, wherein the molar ratio of the cyclohexene to the 2, 2, 3, 3, 3-pentafluoro-1-phenyl acetone is 1:0.05, marked as solution A, simultaneously mixing hydrogen peroxide, a stabilizer EDTA-2Na, an inorganic base cesium carbonate and acetonitrile, wherein the molar ratio of the acetonitrile to the cyclohexene is 1:2, the molar ratio of the hydrogen peroxide to the acetonitrile is 1:2, the adding amount of the stabilizer EDTA-2Na is 2% of the weight of the cyclohexene, the adding amount of the inorganic base cesium carbonate is 2 times of the adding amount of the acetonitrile, marked as solution B, injecting the solution A and the solution B into a microchannel modular reaction device, discharging the microstructure reactor, introducing the discharging material into a separator, washing the organic phase with 5 wt% sodium carbonate solution and distilled water respectively to pH 7.0, drying to obtain the cyclohexene oxide, wherein the conversion rate of the cyclohexene raw material is 98.8%.
Claims (10)
1. A method for preparing high-quality cyclohexene oxide by adopting a micro-flow field reaction technology is characterized by comprising the following steps:
(1) mixing cyclohexene and a catalyst, and dissolving the mixture in an organic solvent for later use;
(2) mixing aqueous hydrogen peroxide solution, a stabilizer EDTA-2Na, inorganic alkaline aqueous solution and acetonitrile for later use;
(3) respectively injecting the mixed systems obtained in the step (1) and the step (2) into a micro-channel modular reaction device, and reacting for 5-15 min at 25-60 ℃ in a micro-structure reactor of the micro-channel modular reaction device;
(4) and (4) introducing the mixed system obtained in the step (3) into a product collector, sequentially washing the organic phase with a sodium carbonate aqueous solution and water until the pH value is 7.0, and drying to obtain the cyclohexene oxide.
2. The method according to claim 1, wherein in step (1), the catalyst is trifluoroacetophenone, acetone, acetophenone, 1, 3-dichloroacetone, 2-chloro-2, 2-difluoroacetophenone, 1, 1, 1-trifluoro-3-phenylpropanone, 2, 3, 3, 3-pentafluoro-1-phenylpropanone, preferably trifluoroacetophenone, 2-chloro-2, 2-difluoroacetophenone, 1, 1, 1-trifluoro-3-phenylpropanone or 2, 2, 3, 3, 3-pentafluoro-1-phenylpropanone.
3. The process according to claim 1, wherein in the step (1), the molar ratio of cyclohexene to catalyst is 1:0.01 to 0.3.
4. The process according to claim 3, wherein in the step (1), the molar ratio of cyclohexene to catalyst is 1:0.01 to 0.1.
5. The production method according to claim 1, wherein in the step (2), the concentration of solute hydrogen peroxide in the aqueous hydrogen peroxide solution is 30 wt%.
6. The production method according to claim 1, wherein in the step (2), the inorganic base is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, or cesium carbonate; wherein, the concentration of the inorganic base in the inorganic base aqueous solution is 1 mol/L.
7. The method according to claim 6, wherein in the step (2), the inorganic base is potassium carbonate, cesium carbonate or sodium carbonate.
8. The process according to claim 1, wherein in the step (2), the molar ratio of acetonitrile to cyclohexene is 1: 1-6, wherein the molar ratio of hydrogen peroxide to acetonitrile is 1: 1-6, the mass percentage of EDTA-2Na and cyclohexene is 1-5%, and the volume ratio of the inorganic alkaline aqueous solution to acetonitrile is 2: 1.
9. the preparation method according to claim 1, wherein in the step (2), the microchannel modular reaction device comprises a microstructure mixer, a microstructure reactor and a product collector which are connected in sequence through pipelines; wherein, the first raw material storage tank and the second raw material storage tank are respectively connected with the microstructure mixer.
10. The method according to claim 1, wherein in the step (4), the solute sodium carbonate is present in an aqueous solution of sodium carbonate at a concentration of 5 wt%.
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