CN104878052A - Method for preparing 1,2-epoxyhexane by using fixed-bed micro-channel reaction device - Google Patents
Method for preparing 1,2-epoxyhexane by using fixed-bed micro-channel reaction device Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 54
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 title abstract 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 232
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000012074 organic phase Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000011949 solid catalyst Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 57
- 239000007800 oxidant agent Substances 0.000 claims description 45
- 230000035484 reaction time Effects 0.000 claims description 18
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 14
- 108010093096 Immobilized Enzymes Proteins 0.000 claims description 14
- 108090001060 Lipase Proteins 0.000 claims description 14
- 239000004367 Lipase Substances 0.000 claims description 14
- 102000004882 Lipase Human genes 0.000 claims description 14
- 235000019421 lipase Nutrition 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 108010048733 Lipozyme Proteins 0.000 claims description 9
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 claims description 2
- 102000002322 Egg Proteins Human genes 0.000 claims description 2
- 108010000912 Egg Proteins Proteins 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000014103 egg white Nutrition 0.000 claims description 2
- 210000000969 egg white Anatomy 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract 3
- 230000003321 amplification Effects 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
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- 238000009776 industrial production Methods 0.000 abstract 1
- 238000009434 installation Methods 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 108090000790 Enzymes Proteins 0.000 description 14
- 102000004190 Enzymes Human genes 0.000 description 14
- 208000035126 Facies Diseases 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000005070 sampling Methods 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 230000009466 transformation Effects 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 2
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- 239000003929 acidic solution Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for preparing 1,2-epoxyhexane by using a fixed-bed micro-channel reaction device. The method comprises the following steps: dissolving 1-hexene into a solvent so as to obtain a 1-hexene solution; dissolving an oxidized reagent into a solvent so as to obtain an oxidized reagent solution; adding a solid catalyst into the fixed-bed micro-channel reaction device; and respectively pumping the 1-hexene solution and the oxidized reagent solution into the fixed-bed micro-channel reaction device, keeping the reaction residence time for 8-25 min, feeding an upper organic phase into a continuous centrifuge, and carrying out continuous washing on the obtained product. The preparation and post-treatment of 1,2-epoxyhexane provided by the invention are a continuous process, so that a preparation process has the advantages of easiness for control, high safety, mild reaction conditions, short reaction residence time, stable product quality, environment friendliness, and the like. The method has the characteristics of simple production device, easiness for installation and removal, and convenience for carrying and moving. Convenient adjustment can be performed by simply increasing and decreasing the number of the micro-channels, so that an amplification effect similar to that in industrial production does not exist.
Description
Technical field
The invention belongs to Field of Fine Chemicals, be specifically related to a kind of method adopting reaction unit immobilized fixed lipase catalyzed 1-hexene epoxy in fixed bed microchannel to prepare 1,2-oxepane.
Background technology
Enzyme catalyzed synthesis compound is compared with traditional chemical method, although be subject to the restriction of reaction type, it has reaction conditions gentleness, raw material dosage is few, product is easily separated, the advantage such as stereoselectivity and regioselectivity is high, environmental protection.Lipase is the enzyme that a class has multiple catalysis; energy catalysis Lipase absobed, transesterify, Ester hydrolysis, epoxy synthesis, polyisocyanate polyaddition, acid amides synthesis etc., be widely used in many industrial circles such as food, medical and health, chemical, environment protection and energy development.
1,2-oxepane is class purposes organic raw material and intermediate very widely.Olefin epoxidation process traditional at present mainly contained acid system, halogenohydrin method and indirect oxidation method, but all have that production cost is high, equipment corrosion, organic peroxide acid price comparison used be expensive, be difficult to separate from reactant, the problems such as manufacturing requirements is high.Thus, direct styrene catalyzed epoxidised research more and more comes into one's own in a mild condition.Immobilized lipase is paid attention to widely with the advantage of the catalytic performance of its excellence in conjunction with fixed-bed micro-reactor.
The method of current preparation 1,2-oxepane mainly uses catalyst 1-hexene epoxy, such as Horacio F.Oliva (Green Chem., 2006,8,923-936) etc. people Nov 435 makes catalyzer, urea peroxide is oxygenant, by vinylbenzene epoxy.This method reaction times 161h, yield 73%.And we utilize micro passage reaction transformation efficiency to reach as high as 92%, selectivity can reach 99%, the reaction times also shortens to 8-25 minute.Patent 201210226971.9 discloses a kind of method of immobilization bed solid-carried catalyst synthesis epoxy cyclohexane.Compare common immobilization bed, the pickup groove space of fixed bed micro passage reaction is less, and space-time yield, products collection efficiency, selectivity are higher.So cost of capital and raw materials cost can be reduced simultaneously.This is particularly compared with conventional tube reactor, and fixed bed micro passage reaction uses catalyst productivity during same catalyst to increase at a certain temperature, i.e. space-time gain in yield.Speciality Petrochemicals, 2014,31,28-31 have employed Fe_TS_1 catalysis 1-hexene epoxidation synthesis 1,2-oxepane.Wherein the transformation efficiency of 1-hexene is 34%, optimal reaction temperature 343K (70 DEG C).Total institute is known, and the boiling point of 1-hexene 65 DEG C, reaction needed is carried out or refluxed with chilled brine in autoclave.Severe reaction conditions, feed stock conversion are low, and catalyst preparation process is complicated.Guangdong chemical industry, 2014,41,34-35 have employed the method for N-TS-1 catalysis 1-hexene epoxidation synthesis 1,2-oxepane and condition and is similar to Fe_TS_1 catalysis 1-hexene epoxidation and synthesizes 1,2-oxepane.Just feed stock conversion slightly improves.Above-mentioned method is all mainly carry out catalyzed reaction by preparing special catalyzer, and condition that is narrower, reaction is harsh all to there is feed stock conversion low catalyst preparation complexity, catalysis scope, the reaction times longer (general 5-40h).In reaction process, need to use a large amount of acidic solution, thus increase the requirement of aftertreatment and environment protection, aftertreatment is relatively loaded down with trivial details, and environmental pollution is serious.
Summary of the invention
Problem to be solved by this invention be for 1-hexene epoxidation can not continuous seepage, level of automation is low, power consumption is serious, side reaction is serious, environmental pollution, security is not high, epoxidation speed is low, can not the defect such as continuous seepage and a kind of method preparing high-quality epoxy alkane proposed.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is dissolved in solvent prepares 1-hexene solution;
(2) oxidising agent is dissolved in solvent prepares oxidising agent solution;
(3) solid catalyst is joined in the reaction unit of fixed bed microchannel;
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, keep reaction time 8-25min, react at 15-65 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain 1,2-oxepane.
In step (1) and (2), described solvent is ethyl acetate, acetone, hexanaphthene, toluene or dimethyl formamide, ethyl acetate.
In step (1), in the 1-hexene solution of preparation, solute 1-hexene concentration is 0.3-1.5g/mL, preferred 0.6-1.5g/mL.
In step (2), described oxidising agent is the mixture of stablizer and urea peroxide, or stablizer and 30wt%H
2o
2the mixture of the aqueous solution; Wherein, described stablizer is EDTA or urea.
In step (2), the mass ratio of stablizer EDTA and 1-hexene is 0.006-0.021:1, preferred 0.01-0.015:1.
In step (2), the mass ratio of stablizer urea and 1-hexene is 0.01-0.028:1, preferred 0.018-0.025:1.
In step (2), the mol ratio of urea peroxide and 1-hexene is 2-6:1, preferred 4-6:1.
In step (2), H
2o
2be 4-12:1 with the mol ratio of 1-hexene, preferred 6-9:1.
In step (3), described fixed bed microchannel reaction unit comprises the micro mixer, the fixed bed micro-structured reactor that are linked in sequence successively by pipeline, and reaction raw materials is realized in input micro mixer and equipment afterwards thereof by pump.The preferred model of micro mixer is slit plate mixer LH25 (Hastelloy C); The preferred model of fixed bed micro-structured reactor is fixed bedmeander reactor HC (Beyer Co., Ltd).
In step (3), described solid catalyst is immobilized Candida sp.99-125 (enzyme 70,000 U/g alive, Beijing University of Chemical Technology provides), immobilized Nov 435 (enzyme 10000U/g alive, purchased from Novozymes Company), immobilized Lipozym TLIM (enzyme 250IUN/g alive, purchased from Nanjing Cheng Na Chemical Co., Ltd.), immobilized LipozymeRMIM (enzyme 275IUN/g alive, purchased from Nanjing Cheng Na Chemical Co., Ltd.), immobilized Lipase AY30G (enzyme 30,000 U/g alive, purchased from Amano Enzyme INC NAGOYA, Japan), immobilized Lipase F-AP (enzyme 30U/mg alive, purchased from Sigma company), immobilized Lipozyme TL100 (enzyme 100KLU/g alive, purchased from Chinese Medicine Foreign Trade Company), immobilized Lipozyme (enzyme 20,000 U/g alive, purchased from Habio Enzyme) and immobilized Lipozyme hen egg white (enzyme is lived 70,000 U/g, purchased from Amano company) in any one, preferred immobilized Nov 435, immobilized Candida sp.99-125, immobilized Lipase AY30G, immobilized Lipase F-AP, immobilized Lipozyme TL100, most preferably immobilized Nov 435 and immobilized Candida sp.99-125.These immobilized lipases above-mentioned are all business-like enzymes, and stable performance, reaction conditions are gentle, environmental protection.The mass ratio adding quality and 1-hexene of immobilized enzyme is 0.15-1.2:1, preferred 0.8-1.2:1.
In step (4), the residence time preferred 15-25min.
In step (4), the velocity ratio of 1-hexene solution and oxidising agent solution is 0.02-0.07mL/min:0.16-0.30mL/min.
In step (4), the preferred 28-35 DEG C of temperature of reaction.
Beneficial effect: present invention process level of automation high and low carbocyclic ring guarantor, energy-saving and emission-reduction, existing production Problems existing can be overcome, avoid using acid-reaction material and the safety, the environmental problem that cause, improve the transformation efficiency of 1-hexene, Reaction time shorten (lower than 25 minutes), reduce the content of by product, greatly improve 1, the security of 2-oxepane production process, improve the quality of product simultaneously, feed stock conversion is the highest by 91%, the selectivity of 1,2-oxepane reaches as high as 96%.
Accompanying drawing explanation
Fig. 1 is apparatus of the present invention schematic diagram.
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.
Following examples fixed bed microchannel reaction unit used comprises the micro mixer, the fixed bed micro-structured reactor that are linked in sequence successively by pipeline, and reaction raw materials is realized in input micro mixer and equipment afterwards thereof by pump.The preferred model of micro mixer is slit plate mixer LH25 (Hastelloy C); The preferred model of fixed bed micro-structured reactor is fixed bedmeander reactor HC (Beyer Co., Ltd).
Embodiment 1:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent toluene, be mixed with the 1-hexene solution of 1.5g/mL.
(2) EDTA and urea peroxide mixture are added in solvent toluene, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 4:1, and the mass ratio of stablizer EDTA and 1-hexene is 0.01:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Candida sp.99-125, the mass ratio adding quality and 1-hexene is 0.8:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.05mL/min:0.2mL/min, keep reaction time 20min, react at 30 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 80%, selectivity 95%.
1,2-oxepane
1H-NMR(δ,ppm,CHLOROFORM-D):0.87(t,J＝7.0,3H),1.28-1.43(m,4H),1.44-1.51(m,2H),2.41(dd,J＝5.2and 2.7Hz,1H),2.69(dd,J＝4.8and 4.4H
Z,1H),2.85(m,1H)；13C-NMR(δ,ppm,CHLOROFORM-D):12.96，21.54，27.12，31.21，46.05，51.34。
(detection method: detection feed stock conversion and selectivity of product gas phase are monitored: Agilent gas chromatograph 7890A; Fid detector; HP-5 capillary column (0.32mm*0.25um*30m); Injector temperature 280 DEG C, sample size 1uL, detects mouth temperature 280 DEG C, splitting ratio 10:1, septum purge 3mL/min.Column oven starting temperature 30 DEG C, stops 2min.5 DEG C/min is warmed up to 110 DEG C, and 50 DEG C/min is warmed up to 260 DEG C.)
Embodiment 2:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 1.2g/mL.
(2) EDTA and urea peroxide mixture are added in solvent ethyl acetate, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 6:1, and the mass ratio of stablizer EDTA and 1-hexene is 0.012:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Candida sp.99-125, the mass ratio adding quality and 1-hexene is 1:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.17mL/min, keep reaction time 25min, react at 35 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 82%, selectivity 96%.
Embodiment 3:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 1.0g/mL.
(2) EDTA and urea peroxide mixture are added in solvent ethyl acetate, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 5:1, and the mass ratio of stablizer EDTA and 1-hexene is 0.015:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Candida sp.99-125, the mass ratio adding quality and 1-hexene is 1.2:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at (0.06mL/min:0.28mL/min), keep reaction time 15min, react at 28 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 86%, selectivity 92%.
Embodiment 4:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent dimethylformamide, be mixed with the 1-hexene solution of 0.9g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent dimethylformamide, preparation oxidising agent solution; 30wt%H
2o
2be 6:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.018:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipozym TLIM, the mass ratio adding quality and 1-hexene is 1:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.17mL/min, keep reaction time 25min, react at 30 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 90%, selectivity 36%.
Embodiment 5:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 0.7g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent ethyl acetate, preparation oxidising agent solution; 30wt%H
2o
2be 9:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.025:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipozyme, the mass ratio adding quality and 1-hexene is 1.2:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.23mL/min, keep reaction time 20min, react at 28 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 90%, selectivity 48%.
Embodiment 6:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 1.4g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent ethyl acetate, preparation oxidising agent solution; 30wt%H
2o
2be 8:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.02:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipozym TL100, the mass ratio adding quality and 1-hexene is 0.8:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.21mL/min, keep reaction time 21min, react at 35 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 78%, selectivity 75%.
Embodiment 7:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 0.6g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent ethyl acetate, preparation oxidising agent solution; 30wt%H
2o
2be 7:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.021:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipase AY30G, the mass ratio adding quality and 1-hexene is 1.2:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.19mL/min, keep reaction time 23min, react at 35 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 72%, selectivity 84%.
Embodiment 8:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 0.4g/mL.
(2) urea peroxide is added in solvent ethyl acetate, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 5:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipase AY30G, the mass ratio adding quality and 1-hexene is 1.2:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.17mL/min, keep reaction time 24min, react at 34 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 70%, selectivity 82%.
Embodiment 9:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent acetone, be mixed with the 1-hexene solution of 1.0g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent acetone, preparation oxidising agent solution; 30wt%H
2o
2be 8:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.019:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Lipase F-AP, the mass ratio adding quality and 1-hexene is 0.8:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.21mL/min, keep reaction time 21min, react at 32 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 68%, selectivity 73%.
Embodiment 10:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 1.0g/mL.
(2) by urea and 30wt%H
2o
2mixture adds in solvent ethyl acetate, preparation oxidising agent solution; 30wt%H
2o
2be 9:1 with the mol ratio of 1-hexene, the mass ratio of stablizer urea and 1-hexene is 0.025:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Nov 435, the mass ratio adding quality and 1-hexene is 1.3:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.23mL/min, keep reaction time 20min, react at 29 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 81%, selectivity 90%.
Embodiment 11:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent ethyl acetate, be mixed with the 1-hexene solution of 1.2g/mL.
(2) EDTA and urea peroxide mixture are added in solvent ethyl acetate, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 6:1, and the mass ratio of stablizer EDTA and 1-hexene is 0.012:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Nov 435, the mass ratio adding quality and 1-hexene is 1:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.03mL/min:0.17mL/min, keep reaction time 25min, react at 35 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 83%, selectivity 95%.
Embodiment 12:
A kind of method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it comprises the steps:
(1) 1-hexene is joined in solvent hexanaphthene, be mixed with the 1-hexene solution of 1.0g/mL.
(2) EDTA and urea peroxide mixture are added in solvent hexanaphthene, preparation oxidising agent solution; The mol ratio of urea peroxide and 1-hexene is 5:1, and the mass ratio of stablizer EDTA and 1-hexene is 0.015:1.
(3) joined in the reaction unit of fixed bed microchannel by immobilized enzyme Nov 435, the mass ratio adding quality and 1-hexene is 1.2:1.
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, the velocity ratio of 1-hexene solution and oxidising agent solution controls at 0.06mL/min:0.28mL/min, keep reaction time 15min, react at 28 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain high-quality 1,2-oxepane, sampling air inlet facies analysis, feed stock conversion 80%, selectivity 91%.
Claims (10)
1. the method adopting fixed bed microchannel reaction unit to prepare 1,2-oxepane, it is characterized in that, it comprises the steps:
(1) 1-hexene is dissolved in solvent prepares 1-hexene solution;
(2) oxidising agent is dissolved in solvent prepares oxidising agent solution;
(3) solid catalyst is joined in the reaction unit of fixed bed microchannel;
(4) the oxidising agent solution that 1-hexene solution step (1) obtained and step (2) obtain pumps in the fixed bed microchannel reaction unit after step (3) process respectively, keep reaction time 8-25min, react at 15-65 DEG C, upper organic phase enters continuous centrifugal machine, after continuous washing, obtain 1,2-oxepane.
2. employing fixed bed microchannel according to claim 1 reaction unit prepares 1, the method of 2-oxepane, it is characterized in that, in step (1) and (2), described solvent is ethyl acetate, acetone, hexanaphthene, toluene or dimethyl formamide.
3. employing fixed bed microchannel according to claim 1 and 2 reaction unit prepares the method for 1,2-oxepane, it is characterized in that, in step (1), in the 1-hexene solution of preparation, solute 1-hexene concentration is 0.3-1.5g/mL.
4. employing fixed bed microchannel according to claim 1 and 2 reaction unit prepares 1, the method of 2-oxepane, is characterized in that, in step (2), described oxidising agent is the mixture of stablizer and urea peroxide, or stablizer and 30wt%H
2o
2the mixture of the aqueous solution; Wherein, described stablizer is EDTA or urea.
5. employing fixed bed microchannel according to claim 4 reaction unit prepares the method for 1,2-oxepane, it is characterized in that, in step (2), the mass ratio of stablizer EDTA and 1-hexene is 0.006-0.021:1.
6. employing fixed bed microchannel according to claim 4 reaction unit prepares the method for 1,2-oxepane, it is characterized in that, in step (2), the mass ratio of stablizer urea and 1-hexene is 0.01-0.028:1.
7. employing fixed bed microchannel according to claim 4 reaction unit prepares the method for 1,2-oxepane, it is characterized in that, in step (2), the mol ratio of urea peroxide and 1-hexene is 2-6:1.
8. employing fixed bed microchannel according to claim 4 reaction unit prepares the method for 1,2-oxepane, it is characterized in that, in step (2), and H
2o
2be 4-12:1 with the mol ratio of 1-hexene.
9. employing fixed bed microchannel according to claim 4 reaction unit prepares 1, the method of 2-oxepane, it is characterized in that, in step (3), described fixed bed microchannel reaction unit comprises the micro mixer, the fixed bed micro-structured reactor that are linked in sequence successively by pipeline, and reaction raw materials is realized in input micro mixer and equipment afterwards thereof by pump.
10. employing fixed bed microchannel according to claim 1 reaction unit prepares 1, the method of 2-oxepane, it is characterized in that, in step (3), described solid catalyst is any one in immobilized Candida sp.99-125, immobilized Nov 435, immobilized Lipozym TLIM, immobilized Lipozyme RMIM, immobilized Lipase AY30G, immobilized Lipase F-AP, immobilized Lipozyme TL100, immobilized Lipozyme and immobilized Lipozyme hen egg white; The mass ratio adding quality and 1-hexene of immobilized enzyme is 0.15-1.2:1.
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| CN112375801A (en) * | 2020-10-22 | 2021-02-19 | 复旦大学 | Micro-reaction system and method for continuously preparing (R) -3-hydroxy-5-hexenoic acid ester by using same |
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