CN113045515A - Method for preparing 2, 3-epoxy-1, 4-butanediol by using microchannel reactor - Google Patents
Method for preparing 2, 3-epoxy-1, 4-butanediol by using microchannel reactor Download PDFInfo
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- PENWRXZLRDTNBI-UHFFFAOYSA-N [3-(hydroxymethyl)oxiran-2-yl]methanol Chemical compound OCC1OC1CO PENWRXZLRDTNBI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 33
- 239000011964 heteropoly acid Substances 0.000 claims description 15
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 238000004880 explosion Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 102000016938 Catalase Human genes 0.000 description 10
- 108010053835 Catalase Proteins 0.000 description 10
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 3
- 239000000006 Nitroglycerin Substances 0.000 description 3
- 229960003711 glyceryl trinitrate Drugs 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 2
- 229910003893 H2WO4 Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- RDLIBIDNLZPAQD-UHFFFAOYSA-N 1,2,4-butanetriol trinitrate Chemical compound [O-][N+](=O)OCCC(O[N+]([O-])=O)CO[N+]([O-])=O RDLIBIDNLZPAQD-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004814 ceramic processing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 239000003721 gunpowder Substances 0.000 description 1
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- 238000005459 micromachining Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
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- 230000009965 odorless effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
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- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/14—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by free hydroxyl radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
A method for preparing 2, 3-epoxy-1, 4-butanediol by using a microchannel reactor comprises the steps of preparing 1, 4-butylene glycol and a catalyst into a mixed solution according to a certain proportion, then respectively inputting the mixed solution and a hydrogen peroxide solution into the microchannel reactor to be fully mixed, preheating the mixed material in a first temperature zone of the microchannel reactor, then inputting the mixed solution into a second temperature zone to perform epoxidation reaction, adding a hydrogen peroxide decomposer solution into a reaction liquid flowing out of the second temperature zone to remove redundant hydrogen peroxide, and continuously extracting and concentrating the obtained product liquid by using an ester organic solvent to obtain a product 2, 3-epoxy-1, 4-butanediol. The invention can obviously improve the reaction efficiency, greatly shorten the reaction time, avoid the explosion risks caused by product polymerization, hydrogen peroxide aggregation and the like which may occur in the kettle type reaction, facilitate the control of the production process, reduce the production cost and overcome the defects of high labor intensity, long production period, low product quality and the like in the traditional production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for preparing 2, 3-epoxy-1, 4-butanediol by using a microchannel reactor.
Background
1,2, 4-Butanetriol (BT) is a colorless, odorless, transparent, water-soluble, viscous syrup-like polyol, and commercially available 1,2, 4-butanetriol is generally a straw yellow to brown viscous liquid, has sweetness, and is non-toxic. BT is an important organic synthesis intermediate and is widely applied to the fields of military industry, medicines, tobacco, cosmetics, papermaking, agriculture, high polymer materials and the like. The nitro compound (BTTN) is a good energetic plasticizer, can replace nitroglycerin to be used as an NEPE propellant and a high-energy and high-new formula propellant, has lower impact sensitivity than nitroglycerin, good thermal stability, and lower toxicity, volatility and hygroscopicity than nitroglycerin, and can be mixed with other energetic plasticizers for use, so that the low-temperature mechanical property of gunpowder based on nitrocellulose can be obviously improved. BT can be used as a sustained release agent in medicine, controls the release speed of the medicine, and is a key intermediate for synthesizing various medicines such as antiviral compounds, platelet activity factors and the like; BT can be used as a cigarette additive, can eliminate the poison of nitro compounds to human bodies, and reduces the harm of tar components; BT, an important component of antimicrobial activity, is effective in preventing microbial growth; in the color developing solution, the color chroma and the adhesive force can be increased; BT is used as a cross-linking agent of a high polymer material in the field of the high polymer material; in addition, BT can also be used as an anti-drying agent of high-grade ink, a surface treatment agent of high-grade clothes, a ceramic processing aid, special-purpose packaging, storage and transportation and the like, and 2, 3-epoxy-1, 4-butylene glycol is a key intermediate for synthesizing high-purity 1,2, 4-butanetriol.
In the prior art, the main process for synthesizing 2, 3-epoxy-1, 4-butylene glycol comprises the following aspects:
(1) european patent EP297444 discloses a process for preparing a catalyst in the presence of an acid or an oxide of a metal of groups IV-VIII, in the presence of H2O2Epoxidizing 3-buten-1-ol in the solution to obtain 2, 3-epoxy-1, 4-butanediol;
(2) japanese patent JP59070632, H2WO4And 2-butene-1, 4-diol is epoxidized in the presence of N-methylmorpholine to produce 2, 3-epoxy-1, 4-butanediol;
(3) chinese patent ZL200510003777.4 describes the synthesis of 2, 3-epoxy-1, 4-butanediol by epoxidation of 2-butene-1, 4-diol under the action of a phosphotungstic heteropoly acid salt catalyst;
(4) the Chinese patent CN200610147610.X discloses a method for synthesizing 2, 3-epoxy-1, 4-butylene glycol, which comprises the following steps: adding the mixed solution of butylene glycol and N-methylmorpholine into H2O2And H2WO4Is reacted and then MnO is added2Reacting and filtering to obtain the 2, 3-epoxy-1, 4-butanediol.
The processes all adopt an intermittent reaction device for production, the productivity is limited, the hydrogen peroxide liquid holdup is large in the production process of the intermittent reaction device, and the explosion risk is high.
Disclosure of Invention
The invention aims to provide a method for preparing 2, 3-epoxy-1, 4-butanediol by using a microchannel reactor, which has the advantages of remarkably improving the reaction efficiency, greatly shortening the reaction time, avoiding the risk of explosion caused by product polymerization or hydrogen peroxide aggregation which may occur in a kettle type reaction, increasing the safety, reducing the production cost, facilitating the control of the production process, and overcoming the defects of high labor intensity, long production period, low product quality and the like in the traditional production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing 2, 3-epoxy-1, 4-butanediol by using a microchannel reactor, which comprises the following steps:
1) dissolving 1, 4-butylene glycol and a catalyst in water to prepare a mixed solution, wherein the molar ratio of the 1, 4-butylene glycol to the catalyst is 1:0.05 to 0.2;
2) respectively inputting the mixed solution prepared in the step 1) and the hydrogen peroxide solution into a first mixing module of a microchannel reactor, and fully mixing; wherein the mol ratio of the 1, 4-butylene glycol to the hydrogen peroxide is 1, 4-butylene glycol: hydrogen peroxide ═ 1: 1.0 to 1.5;
3) the materials are fully mixed and then enter a first temperature zone for preheating, wherein the preheating temperature is 20-50 ℃, and the heating time is 5-20 s; the preheated material enters a second temperature zone to carry out epoxidation reaction, the reaction temperature is 50-90 ℃, the reaction time is 10-60 s, and after the reaction is finished, the reaction liquid flows into a second mixing module;
4) in addition, a hydrogen peroxide decomposer solution with the concentration of 5-50% is input into the second mixing module and is fully mixed with the reaction liquid, then the mixture enters the reaction module to react, the reaction temperature is 20-50 ℃, the reaction time is 5-30 s, and a product liquid is obtained after the reaction is finished;
5) and continuously extracting the product liquid by using an ester organic solvent, and concentrating the obtained extract liquid to obtain the 2, 3-epoxy-1, 4-butanediol.
Preferably, the concentration of the 1, 4-butylene glycol in the mixed solution is 0.1-3.0 mol/L, and the mass concentration of the hydrogen peroxide solution is 3-30%.
Preferably, the catalyst is phosphotungstic heteropoly acid with a molecular formula of H3PW12O40nH20, wherein n is 0 to 12.
Preferably, the hydrogen peroxide decomposer is catalase.
Preferably, the ester organic solvent is one of ethyl formate, ethyl acetate, methyl acetate and isopropyl acetate.
Preferably, a plurality of mixing modules and a plurality of reaction modules are arranged in the microchannel reactor, a material mixing channel is arranged in each mixing module, and a reaction material channel is arranged in each reaction module.
Preferably, the inner diameter of the reaction material channel is 0.5-5 mm.
The method adopts a microchannel reactor, 1, 4-butylene glycol and a catalyst are dissolved in water to prepare a mixed solution, then the mixed solution and a hydrogen peroxide solution are respectively input into the microchannel reactor to be fully mixed, then the mixed solution and the hydrogen peroxide solution enter a first temperature zone to be preheated, and then enter a second temperature zone to be subjected to epoxidation reaction, and a dual-temperature zone mode is adopted for reaction, so that the defects of low raw material conversion rate, low reaction selectivity, uneven material mixing, epoxy compound polymerization caused by long reaction time and the like in the traditional reaction kettle caused by step-by-step operation are overcome, and the operability and safety of the reaction are improved; and after epoxidation, adding a hydrogen peroxide decomposer into the reaction liquid to remove unreacted hydrogen peroxide in the reaction liquid, and finally, continuously extracting and concentrating to obtain the 2, 3-epoxy-1, 4-butanediol.
The Microchannel reactor (Microreactor/Microchannel reactor) is a continuous flow pipeline reactor, and is a device which is manufactured by micromachining technology, has a characteristic dimension of 10-1000 micrometers, and controls chemical reaction in a tiny reaction space.
The narrow microchannel in the microreactor shortens the distance and time of mass transfer, and the increased specific surface area also provides a larger place for the mass transfer process, thereby realizing the rapid mixing of reaction materials and realizing the complete radial mixing in the millisecond range. The narrow microchannel of the microreactor also increases the temperature gradient, and the increased specific surface area greatly enhances the heat transfer capacity of the reactor. Therefore, the development of the microchannel reactor technology for synthesizing the 2, 3-epoxy-1, 4-butylene glycol has important practical significance.
The invention has the beneficial effects that:
1) the invention utilizes the microchannel reactor, and reaction materials are quickly and fully mixed, so that the mass transfer efficiency is improved, the reaction time is greatly shortened, and the reaction efficiency is obviously improved.
2) The reaction materials of the invention contain explosive chemicals such as hydrogen peroxide, the microchannel reactor avoids the risk of explosion caused by the accumulation of products and hydrogen peroxide which may appear in the kettle type reaction, increases the safety, is convenient to control the production process, and overcomes the defects of high labor intensity, high production cost, low product quality and the like in the traditional production.
3) The invention adopts the microchannel reactor for reaction, avoids the defects of low conversion rate of raw materials, low reaction selectivity and the like in the kettle type reaction, is favorable for improving the yield, simultaneously improves the product quality, and has the reaction selectivity of more than 98 percent, the conversion rate of the raw materials of more than 95 percent and the product yield of more than 90 percent.
4) The micro-channel reactor is small in occupied area, flexible production can be achieved, and the automation level of production is improved.
Drawings
FIG. 1 is a reaction scheme of an embodiment of the present invention.
Detailed Description
The invention is further illustrated with reference to the following specific examples and figures, but the invention is not limited thereto.
The microchannel reactor provided by the embodiment of the invention adopts a Corning G1 reactor which is a heart-shaped structure module microchannel reactor and is made of corrosion-resistant and pressure-resistant glass, the pressure tolerance of the reactor is at most 1.8MPa, materials are input into a microchannel reaction system by a metering pump, the feeding amount of the materials is controlled by changing the flow, the conveying range of the flow is from 0ml/min to 120ml/min, and a pressure gauge, a safety valve, a one-way valve, a back pressure valve and the like are arranged on a material conveying pipeline.
The microchannel reactor comprises a T1 area and a T2 area which are connected by a connecting channel: the T1 zone comprises a first mixing module, a first temperature zone and a second temperature zone, and the T2 zone comprises a second mixing module and a reaction module; a dual temperature zone is formed in zone T1: the method comprises the following steps that a first temperature zone preheating zone and a second temperature zone reaction zone are respectively provided with three modules, gradient heating is realized between the two temperature zones, the temperatures of the two temperature zones are controlled by two cooling and heating systems which operate independently, temperature balance can be achieved in a short time, reaction materials are mixed in a mixing module, then the mixture is input into a first temperature zone of a high-flux microchannel reactor for preheating, and the mixture reaches the reaction temperature in the second temperature zone, so that the 2, 3-epoxy-1, 4-butanediol is synthesized; then enters a T2 mixing module to be mixed with the hydrogen peroxide decomposer solution, and then enters a reaction module to react to remove the excessive hydrogen peroxide.
Example 1
Preparing 1, 4-butylene glycol and phosphotungstic heteropoly acid into a 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution, wherein the concentration of the 1, 4-butylene glycol in the mixed solution is 1.5mol/L, the molar ratio of the 1, 4-butylene glycol to the phosphotungstic heteropoly acid is 1:0.07, then pumping the 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution and a 30% hydrogen peroxide solution into a T1 area mixing module of a microchannel reactor at the flow rates of 20ml/min and 5ml/min respectively, mixing, then entering a first temperature area for preheating, setting the temperature to be 30 ℃, keeping the time to be 8s, entering a second temperature area for epoxidation reaction of the pre-heated mixed material, setting the reaction temperature to be 60 ℃, inputting the reaction liquid after the reaction to the T2 area mixing module, then pumping a catalase solution to the T2 area mixing module, the input amount of the catalase solution is 0.25 times of the molar amount of the hydrogen peroxide, the catalase solution enters a T2 zone reaction module, the reaction is carried out for 15s at the temperature of 30 ℃, the product liquid after the reaction is continuously extracted and concentrated by an organic solvent, the 2, 3-epoxy-1, 4-butanediol is obtained, the selectivity of the 1, 4-butenediol is 98.65 percent in the reaction process, the conversion rate is 97.3 percent, and the hydrogen peroxide residue in the product is 0.01 percent.
Example 2
Preparing 1, 4-butylene glycol and phosphotungstic heteropoly acid into a 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution, wherein the concentration of the 1, 4-butylene glycol in the mixed solution is 1.0mol/L, the molar ratio of the 1, 4-butylene glycol to the phosphotungstic heteropoly acid is 1:0.05, then pumping the 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution and a 25% hydrogen peroxide solution into a T1 area mixing module of a microchannel reactor at the flow rates of 24ml/min and 4ml/min respectively, mixing, then entering a first temperature area for preheating, setting the temperature at 35 ℃, keeping the time at 10s, entering a pre-heated mixed material into a second temperature area for epoxidation reaction, setting the reaction temperature at 75 ℃, setting the reaction time at 45s, inputting the reaction liquid after the reaction is completed into a T2 area mixing module, and then pumping a catalase solution into a T2 area mixing module, the input amount of the catalase solution is 0.2 times of the molar amount of the hydrogen peroxide, the catalase solution enters a T2 zone reaction module, the reaction is carried out for 15s at the temperature of 30 ℃, the product liquid after the reaction is continuously extracted and concentrated by an organic solvent, so as to obtain the 2, 3-epoxy-1, 4-butanediol, the selectivity of the 1, 4-butenediol is 98.37%, the conversion rate is 98.2%, and the hydrogen peroxide residue in the product is 0.07%.
Example 3
Preparing 1, 4-butylene glycol and phosphotungstic heteropoly acid into a 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution, wherein the concentration of the 1, 4-butylene glycol in the mixed solution is 2.0mol/L, the molar ratio of the 1, 4-butylene glycol to the phosphotungstic heteropoly acid is 1:0.2, then pumping the 1, 4-butylene glycol/phosphotungstic heteropoly acid mixed solution and a 25% hydrogen peroxide solution into a T1 area mixing module of a microchannel reactor at the flow rates of 30ml/min and 7.5ml/min respectively, mixing, then entering a first temperature area for preheating, setting the temperature at 25 ℃, keeping the time at 10s, entering a pre-heated mixed material into a second temperature area for epoxidation reaction, setting the reaction temperature at 85 ℃, setting the reaction time at 30s, inputting the reaction liquid after the reaction into the T2 area mixing module, then pumping a catalase solution into the T2 area mixing module, the input amount of the catalase solution is 0.2 times of the molar amount of the hydrogen peroxide, the catalase solution enters a T2 zone reaction module, the reaction is carried out for 15s at the temperature of 30 ℃, the product liquid after the reaction is continuously extracted and concentrated by an organic solvent, so as to obtain the 2, 3-epoxy-1, 4-butanediol, the selectivity of the 1, 4-butenediol is 99.41 percent in the reaction process, the conversion rate is 98.6 percent, and the hydrogen peroxide residue in the product is 0.01 percent.
Claims (6)
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| CN1803747A (en) * | 2005-01-11 | 2006-07-19 | 中国科学院大连化学物理研究所 | 1,2,4-butanetriol synthesis method |
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| US20180059545A1 (en) * | 2016-08-31 | 2018-03-01 | Rohm And Haas Electronic Materials Korea Ltd. | Monomers, polymers and photoresist compositions |
| CN109928943A (en) * | 2019-04-08 | 2019-06-25 | 江苏扬农化工集团有限公司 | A kind of method of micro passage reaction synthesizing epoxypropane |
| CN110156725A (en) * | 2019-05-10 | 2019-08-23 | 江苏扬农化工集团有限公司 | A kind of method that micro passage reaction prepares epoxychloropropane |
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| CN1803747A (en) * | 2005-01-11 | 2006-07-19 | 中国科学院大连化学物理研究所 | 1,2,4-butanetriol synthesis method |
| CN101696157A (en) * | 2009-10-29 | 2010-04-21 | 上海福尔福特种材料科技发展有限公司 | Method for preparing 1,2,4-butanetriol |
| US20180059545A1 (en) * | 2016-08-31 | 2018-03-01 | Rohm And Haas Electronic Materials Korea Ltd. | Monomers, polymers and photoresist compositions |
| CN109928943A (en) * | 2019-04-08 | 2019-06-25 | 江苏扬农化工集团有限公司 | A kind of method of micro passage reaction synthesizing epoxypropane |
| CN110156725A (en) * | 2019-05-10 | 2019-08-23 | 江苏扬农化工集团有限公司 | A kind of method that micro passage reaction prepares epoxychloropropane |
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