CN104803951A - Method for preparing high-quality cyclohexene oxide by adopting micro flow field reaction technology - Google Patents
Method for preparing high-quality cyclohexene oxide 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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- tetrahydrobenzene
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- acetonitrile
- hydrogen peroxide
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005516 engineering process Methods 0.000 title claims abstract description 9
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 title abstract 4
- 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 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 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 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 17
- 239000011707 mineral Substances 0.000 claims description 17
- 235000010755 mineral Nutrition 0.000 claims description 17
- 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
- 239000003513 alkali Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 12
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 10
- 235000015320 potassium carbonate Nutrition 0.000 claims description 9
- DORVUDHGAXTKRQ-UHFFFAOYSA-N 1-fluoro-3-phenylpropan-2-one Chemical compound FCC(=O)CC1=CC=CC=C1 DORVUDHGAXTKRQ-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
- 239000007864 aqueous solution Substances 0.000 claims description 5
- UXFMWGAEKWXBIP-UHFFFAOYSA-N 1-fluoro-1-phenylpropan-2-one Chemical compound CC(=O)C(F)C1=CC=CC=C1 UXFMWGAEKWXBIP-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- 238000003860 storage Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 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 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 34
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 230000008676 import Effects 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 4
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 yield is high Substances 0.000 description 3
- 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 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 241001292396 Cirrhitidae Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 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
- 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
- 239000000047 product Substances 0.000 description 2
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 2
- UENGBOCGGKLVJJ-UHFFFAOYSA-N 2-chloro-1-(2,4-difluorophenyl)ethanone Chemical compound FC1=CC=C(C(=O)CCl)C(F)=C1 UENGBOCGGKLVJJ-UHFFFAOYSA-N 0.000 description 1
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 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
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling 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
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000013070 direct material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 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
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 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
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 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
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000010457 zeolite 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. According to the method, cyclohexene, catalysts, an aqueous hydrogen peroxide solution, a sterilizing agnet EDTA-2Na, inorganic base and acetonitrile are used for preparation in a channel modularized reaction device to obtain the high-quality cyclohexene oxide. Compared with the prior art, the method provided by the invention has the advantages that simplicity is realized, the control is easy, the raw materials can be easily obtained and have low price, the efficiency is high, and the like. In addition, the cyclohexene oxide prepared by the method provided by the invention is very high, and the industrial production can be favorably realized.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of method adopting miniflow field reaction technology to prepare high-quality epoxy cyclohexane.
Background technology
Epoxy cyclohexane, owing to there is very active epoxy group(ing) in molecular structure, can react with amine, phenol, alcohol, carboxylic acid etc. the compound generating a series of high added value, as with it for raw material can synthesize: agricultural chemicals propargite; The unsaturated polyester of high rigidity, high temperature resistant, acid and alkali-resistance; Novel, efficient photoactive coating and photosensitive adhesive; Crown ether; Polycarbonate; Important fine chemicals hexanedial etc.In addition, the organic solvent that it or a kind of dissolving power are very strong, can be used as epoxide resin reactive diluent.
The epoxy cyclohexane production equipment scale of current European and American areas is also little, and most not production.The maximum propargite agricultural chemicals company Chemtura of the U.S. is because the production cost of its raw material-epoxy cyclohexane is higher than the prosperous moral in Yueyang, and stop it producing resolutely, the prosperous moral in appointment Yueyang is unique supplier.In the production method of epoxy cyclohexane, prepare original main technique of epoxy cyclohexane with hexanaphthene: a. for pimelinketone, is chlorination pimelinketone through chlorination by cyclohexane oxidation, and hydrogenation is chlorination hexalin, then cyclisation is epoxy cyclohexane in the presence of a base; B. be hexalin by cyclohexane oxidation, after being dehydrated into tetrahydrobenzene, reoxidize as epoxy cyclohexane; C. be tetrahydrobenzene by cyclohexane dehydrogenation, then epoxy turn to epoxy cyclohexane.These techniques all also exist that route is long, side reaction is many or the problem such as yield is low, and hexanaphthene be raw material is only initial feed, is finally still summed up as the problem that tetrahydrobenzene does direct material.In the production method of epoxy cyclohexane, hypochlorite method produces the refuses such as a large amount of brine wastes---and often produce one ton of epoxy cyclohexane and will produce about 20 tons of waste water, energy consumption is large, and equipment corrosion is serious.Halcon method (halcon), because of the compound of the hydroxyls such as by-product phenylethyl alcohol or the trimethyl carbinol, produces the restriction being seriously subject to by product market capacity.Peroxide passivation is oxygen source with hydrogen peroxide, and be a kind of relatively green technique, throughput accounts for more than 99% of the world.But the method uses a large amount of organic solvent under normal circumstances, thus adds production cost.
It is raw material that CN101343261A discloses with tetrahydrobenzene, and hydrogen peroxide is oxygenant, and prepare epoxy cyclohexane with the catalyst prepared according to CN1204970C oxidation, the method shortens the reaction times, improves the organic efficiency of catalyzer.CN101020669A discloses tetrahydrobenzene under hydrogen peroxide, composite catalyst effect, reacts 20h, prepare the method for epoxy cyclohexane at 20-70 DEG C, and not with an organic solvent, yield is high, and composite catalyst can be partially recycled for this method.CN101691363A discloses using Ti-Si zeolite as catalyzer, adds alkaline assistant, prepare the method for epoxy cyclohexane, but this type of catalyst grain size is less, reclaims difficulty and causes very difficult industrial applications.CN101348472A discloses a kind of using titanium improved silica as catalyzer, tetrahydrobenzene and organo-peroxide prepare the method for epoxy cyclohexane as substrate, this method can solve the problem of environmental pollution and the corrosion to equipment, but catalyst preparing is complicated, organo-peroxide is expensive, can not large-scale industrial production.
There are Shandong highly dense Yin Ying chemical fibre limited-liability company (being called for short highly dense silver-colored hawk), yueyang, hunan prosperous Dehua work Industrial Co., Ltd. (being called for short the prosperous moral in Yueyang) and Long Xing industrial corporation of Yueyang general petrochemicals factory (being called for short grand emerging industry) etc. in the producer of domestic large-scale production.But these producers adopt or interrupter method operation, output is less, and equipment automatic control level is low, can not continuous prodution, and required catalyst preparing is complicated, and reusing is poor, and production cost is higher.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method adopting miniflow field reaction technology to prepare high-quality epoxy cyclohexane, and too high with the production cost solving prior art existence, reaction process is complicated, the problems such as efficiency is not high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
Adopt miniflow field reaction technology to prepare a method for high-quality epoxy cyclohexane, it comprises the steps:
(1) by for subsequent use after being dissolved in organic solvent after tetrahydrobenzene and catalyst mix;
(2) by for subsequent use after the mixing of aqueous hydrogen peroxide solution, stablizer EDTA-2Na, inorganic base aqueous solution and acetonitrile;
(3) mixed system of gained in step (1) and step (2) is injected the microstucture mixer of microchannel module reaction unit respectively, at mixing rear injection micro-structured reactor 25 ~ 60 DEG C, react 5 ~ 15min;
(4), after the mixed system of gained in step (3) being imported product-collecting device, be 7.0 by aqueous sodium carbonate and water washing organic phase to pH successively, drying, obtains epoxy cyclohexane;
Wherein,
Described microchannel module reaction unit comprises the microstucture mixer, micro-structured reactor and the product-collecting device that are connected successively by pipeline; Wherein, the first raw material storage tank is connected with microstucture mixer respectively with the second raw material storage tank.
Wherein, product collecting device can carry out termination reaction with mixture of ice and water cooling.
Wherein, reaction raw materials and product are by accurately and the pump of low pulse (as HPLC pump or syringe pump) realizes input and output.
Wherein, microstucture mixer is slit plate mixer LH25 (Hastelloy C); Micro-structured reactor is meanderreactor HC, sandwich reactor HC, fixed bed meander reactor HC, preferred sandwich reactor HC.
In step (1), described catalyzer is trifluoroacetophenone, acetone, methyl phenyl ketone, 1,3-DCA, 2-chloro-2,2-difluoro acetophenone, 1,1,1-tri-fluoro-3-phenyl-acetone, 2,2,3,3, the fluoro-1-phenyl-acetone of 3-five, chloro-2, the 2-difluoro acetophenones of preferred trifluoroacetophenone, 2-, 1, the fluoro-3-phenyl-acetone of 1,1-tri-or 2,2, the fluoro-1-phenyl-acetone of 3,3,3-five; Wherein, the mol ratio of tetrahydrobenzene and catalyzer is 1:0.01 ~ 0.3.
In step (1), the mol ratio of tetrahydrobenzene and catalyzer is 1:0.01 ~ 0.3, preferred 1:0.01 ~ 0.1.
In step (2), in aqueous hydrogen peroxide solution, the concentration of solute hydrogen peroxide is 30wt%;
In step (2), mineral alkali is sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide, cesium carbonate, preferred salt of wormwood, cesium carbonate or sodium carbonate; Wherein, in inorganic base aqueous solution, inorganic paper mill wastewater is 1mol/L.
In step (2), the mol ratio of acetonitrile and tetrahydrobenzene is 1:1 ~ 6, preferred 1:1 ~ 4; In aqueous hydrogen peroxide solution, the mol ratio of solute hydrogen peroxide and acetonitrile is 1:1 ~ 6, preferred 1:1 ~ 4; The mass percent of stablizer EDTA-2Na and tetrahydrobenzene is 1 ~ 5%, preferably 1 ~ 4%, and the volume ratio of mineral alkali and acetonitrile is 2:1.
In step (4), in aqueous sodium carbonate, the concentration of solute sodium carbonate is 5wt%.
Beneficial effect:
Compared with prior art, the inventive method has simple and easy to control, and starting material are easy to get cheap, the more high advantage of efficiency, and the epoxy cyclohexane purity that the inventive method prepares is very high, is conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is reaction process schematic diagram of the present invention.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
(embodiment part is revised after technical scheme has been revised again)
Reaction raw materials by accurately and the pump of low pulse (as HPLC pump or syringe pump) realize in input micro mixer and equipment afterwards thereof, thus enable material realize continuing through microchannel module reaction unit to control its residence time simultaneously.Connected by the polytetrafluoro kapillary of a segment length between second micro-structured reactor and product-collecting bottle, it can be made to be immersed in ice-water bath with termination reaction.
Described microstucture mixer is slit plate mixer LH25 (Hastelloy C), valve-assistedmixer (Hastelloy C); Purchased from Ehrfeld Mikrotechnik BTS GmbH, model is respectively 0109-4-0004-F; 0111-2-0014-F.
Micro-structured reactor is meander reactor HC, sandwich reactor HC, fixed bed meander reactorHC, Hastelloy kapillary; Preferred sandwich reactor HC, purchased from Ehrfeld Mikrotechnik BTSGmbH, model is respectively 0211-2-0314-F; 0213-1-0004-F; 0222-2-2004-F.
Embodiment 1:
Tetrahydrobenzene and trifluoroacetophenone are dissolved in organic solvent, wherein the mol ratio of tetrahydrobenzene and trifluoroacetophenone is 1:0.01, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, salt of wormwood mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:1, the mol ratio of hydrogen peroxide and acetonitrile is 1:1, the add-on of stablizer EDTA-2Na is 1% of tetrahydrobenzene weight, the volume that adds of mineral alkali solution of potassium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 91.4%.
Embodiment 2:
Tetrahydrobenzene and trifluoroacetophenone are dissolved in organic solvent, wherein the mol ratio of tetrahydrobenzene and trifluoroacetophenone is 1:0.1, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali salt of wormwood mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:4, the mol ratio of hydrogen peroxide and acetonitrile is 1:4, the add-on of stablizer EDTA-2Na is 4% of tetrahydrobenzene weight, the volume that adds of mineral alkali salt of wormwood is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 94.9%.
Embodiment 3:
Tetrahydrobenzene and trifluoroacetophenone are dissolved in organic solvent, wherein the mol ratio of tetrahydrobenzene and trifluoroacetophenone is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali salt of wormwood mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of mineral alkali salt of wormwood is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 98.5%.
Embodiment 4:
Tetrahydrobenzene and trifluoroacetophenone are dissolved in organic solvent, wherein the mol ratio of tetrahydrobenzene and trifluoroacetophenone is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, inorganic bases sodium carbonate mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of inorganic bases sodium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 92.5%.
Embodiment 5:
Tetrahydrobenzene and trifluoroacetophenone are dissolved in organic solvent, wherein the mol ratio of tetrahydrobenzene and trifluoroacetophenone is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali cesium carbonate mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of mineral alkali cesium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 99.5%.
Embodiment 6:
By tetrahydrobenzene and 2-chloro-2, 2-difluoro acetophenone is dissolved in organic solvent, wherein tetrahydrobenzene and 2-chloro-2, the mol ratio of 2-difluoro acetophenone is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali cesium carbonate mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of mineral alkali cesium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 98.4%.
Embodiment 7:
By tetrahydrobenzene and 1, 1, the fluoro-3-phenyl-acetone of 1-tri-is dissolved in organic solvent, wherein tetrahydrobenzene and 1, 1, the mol ratio of the fluoro-3-phenyl-acetone of 1-tri-is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali cesium carbonate mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of mineral alkali cesium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 98.8%.
Embodiment 8:
By tetrahydrobenzene and 2, 2, 3, 3, the fluoro-1-phenyl-acetone of 3-five is dissolved in organic solvent, wherein tetrahydrobenzene and 2, 2, 3, 3, the mol ratio of the fluoro-1-phenyl-acetone of 3-five is 1:0.05, be labeled as solution A, simultaneously by hydrogen peroxide, stablizer EDTA-2Na, mineral alkali cesium carbonate mixes with acetonitrile, wherein the mol ratio of acetonitrile and tetrahydrobenzene is 1:2, the mol ratio of hydrogen peroxide and acetonitrile is 1:2, the add-on of stablizer EDTA-2Na is 2% of tetrahydrobenzene weight, the volume that adds of mineral alkali cesium carbonate is 2 times that acetonitrile adds volume, be labeled as solution B, above-mentioned A and B solution are injected in microchannel module reaction unit, micro-structured reactor discharging imports in separator, use 5wt% sodium carbonate solution respectively, distilled water wash organic phase is to pH=7.0, dry, obtain epoxy cyclohexane, tetrahydrobenzene feed stock conversion is 98.8%.
Claims (10)
1. adopt miniflow field reaction technology to prepare a method for high-quality epoxy cyclohexane, it is characterized in that, comprise the steps:
(1) by for subsequent use after being dissolved in organic solvent after tetrahydrobenzene and catalyst mix;
(2) by for subsequent use after the mixing of aqueous hydrogen peroxide solution, stablizer EDTA-2Na, inorganic base aqueous solution and acetonitrile;
(3) mixed system of step (1) and step (2) gained is injected microchannel module reaction unit respectively, in the micro-structured reactor of microchannel module reaction unit, react 5 ~ 15min at 25 ~ 60 DEG C;
(4), after the mixed system of gained in step (3) being imported product-collecting device, be 7.0 by aqueous sodium carbonate and water washing organic phase to pH successively, drying, obtains epoxy cyclohexane.
2. preparation method according to claim 1, is characterized in that, in step (1), described catalyzer is trifluoroacetophenone, acetone, methyl phenyl ketone, 1, chloro-2, the 2-difluoro acetophenones of 3-Dichloro acetone, 2-, 1,1,1-tri-fluoro-3-phenyl-acetone, 2,2,3,3, the fluoro-1-phenyl-acetone of 3-five, chloro-2, the 2-difluoro acetophenones of preferred trifluoroacetophenone, 2-, 1, the fluoro-3-phenyl-acetone of 1,1-tri-or 2,2, the fluoro-1-phenyl-acetone of 3,3,3-five.
3. preparation method according to claim 1, is characterized in that, in step (1), the mol ratio of tetrahydrobenzene and catalyzer is 1:0.01 ~ 0.3.
4. preparation method according to claim 3, is characterized in that, in step (1), the mol ratio of tetrahydrobenzene and catalyzer is 1:0.01 ~ 0.1.
5. preparation method according to claim 1, is characterized in that, in step (2), in aqueous hydrogen peroxide solution, the concentration of solute hydrogen peroxide is 30wt%.
6. preparation method according to claim 1, is characterized in that, in step (2), mineral alkali is sodium carbonate, salt of wormwood, sodium hydroxide, potassium hydroxide or cesium carbonate; Wherein, in inorganic base aqueous solution, inorganic paper mill wastewater is 1mol/L.
7. preparation method according to claim 6, is characterized in that, in step (2), mineral alkali is salt of wormwood, cesium carbonate or sodium carbonate.
8. preparation method according to claim 1, it is characterized in that, in step (2), the mol ratio of acetonitrile and tetrahydrobenzene is 1:1 ~ 6, the mol ratio of hydrogen peroxide and acetonitrile is 1:1 ~ 6, the mass percent of EDTA-2Na and tetrahydrobenzene is 1 ~ 5%, and the volume ratio of inorganic base aqueous solution and acetonitrile is 2:1.
9. preparation method according to claim 1, is characterized in that, in step (2), described microchannel module reaction unit comprises the microstucture mixer, micro-structured reactor and the product-collecting device that are connected successively by pipeline; Wherein, the first raw material storage tank is connected with microstucture mixer respectively with the second raw material storage tank.
10. preparation method according to claim 1, is characterized in that, in step (4), in aqueous sodium carbonate, the concentration of solute sodium carbonate is 5wt%.
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