CN116947805A - Method and device for continuously synthesizing chloroethylene carbonate in micro-channel - Google Patents
Method and device for continuously synthesizing chloroethylene carbonate in micro-channel Download PDFInfo
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- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 182
- 239000003999 initiator Substances 0.000 claims abstract description 98
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 83
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 93
- 239000007788 liquid Substances 0.000 claims description 66
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 42
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 38
- 238000001802 infusion Methods 0.000 claims description 37
- 238000003860 storage Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004817 gas chromatography Methods 0.000 claims description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- -1 Polytetrafluoroethylene Polymers 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- 238000005260 corrosion Methods 0.000 claims description 6
- 229910000856 hastalloy Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000012320 chlorinating reagent Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 54
- 239000011259 mixed solution Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 239000000460 chlorine Substances 0.000 description 15
- 229910052801 chlorine Inorganic materials 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 230000001502 supplementing effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- PQLFROTZSIMBKR-UHFFFAOYSA-N ethenyl carbonochloridate Chemical compound ClC(=O)OC=C PQLFROTZSIMBKR-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- HIGQQEOWQNDHJD-UHFFFAOYSA-N 4,4-dichloro-1,3-dioxolan-2-one Chemical compound ClC1(Cl)COC(=O)O1 HIGQQEOWQNDHJD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro 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
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/02—Feed or outlet devices; Feed or outlet control devices for feeding measured, i.e. prescribed quantities of reagents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application provides a method and a device for continuously synthesizing chloroethylene carbonate in a microchannel, wherein sulfuryl chloride is selected as a chlorinating reagent, and reaction raw materials of ethylene carbonate solution, sulfuryl chloride and initiator solution are respectively heated by a preheating section of the microchannel, then enter a first microchannel mixer for mixing, and then enter a first microchannel for reaction; and adding an initiator solution after a period of reaction, mixing the initiator solution with the material reacted by the first micro-reaction channel in a second micro-channel mixer, and then entering a second micro-reaction channel for further reaction to obtain the product chloroethylene carbonate. The application is green, economical, safe, efficient and easy to operate, compared with the traditional chloroethylene carbonate batch reaction process, the application obviously shortens the reaction period and improves the reaction selectivity.
Description
Technical Field
The application belongs to the technical field of preparation of chloroethylene carbonate, and particularly relates to a method and a device for continuously synthesizing chloroethylene carbonate in a microchannel.
Background
Chloroethylene carbonate (CEC) is an important fine chemical raw material and is an intermediate for organic synthesis of pesticides and medicines. In addition, it can be used for preparing fluoroethylene carbonate (FEC) and Vinylene Carbonate (VC) which are additives of lithium battery electrolyte. The high-purity chloroethylene carbonate can also be directly used as a flame retardant additive of the lithium battery electrolyte, so that the cycle performance of the lithium battery electrolyte is improved, and the service life of the battery is prolonged. Therefore, the chloroethylene carbonate has wide application prospect.
At present, the synthesis of chloroethylene carbonate (CEC) is mainly prepared by taking Ethylene Carbonate (EC) as a raw material and carrying out chlorination reaction under the action of a chlorinating reagent such as chlorine or sulfuryl chloride. The reaction is a strong exothermic reaction, the flying temperature in the reaction is easy to cause complex side reactions, and the synthesis process using sulfuryl chloride as a chlorine source is mainly an intermittent process, so that the production efficiency is seriously influenced.
The American society of chemistry, 77 (14): 3789-3793 (1955) proposed for the first time the synthesis of chloroethylene carbonate under the action of ultraviolet light using chlorine as the chlorinating agent. Adding EC into a three-neck flask, heating to melt EC, starting magnetic stirring, heating to a certain temperature under irradiation of ultraviolet lamp, and introducing dry Cl 2 CEC was obtained after 24h of reaction with a final yield of 69%. The reaction lasts long and the reaction yield is low. CN115845769A reports a reaction system for continuously synthesizing chloroethylene carbonate by photocatalysis, EC is continuously added into a reactor at a flow rate of 20-50 g/min, and a chlorine flow is adopted to carry out chlorination reaction on raw materials under the photocatalysis effect, wherein the flow rate of the chlorine is 5-12.5L/min. The reaction temperature is 40-70 ℃, the reaction time is 7-10 min, and the product yield is 85%.
Compared with sulfuryl chloride, the chlorine has the advantages of poor reaction stability, uncontrollable process, high requirement on production equipment and low reaction selectivity. In contrast, sulfuryl chloride is relatively convenient to use as a chlorinating agent, and the reaction is relatively mild and stable.
CN115504955a discloses a synthesis method of chloroethylene carbonate, adding ethylene carbonate into a reaction kettle, melting and stirring at a rotation speed of 150-200r/min and a temperature of 85-95 ℃, dropwise adding methylene dichloride saturated solution of sulfuryl chloride and azodiisobutyronitrile, reacting for 2-3h, distilling the reaction solution at a pressure of minus 0.04-0.09MPa to remove the sulfuryl chloride, and rectifying and collecting at a pressure of 200Pa and a temperature of 90-91 ℃ to obtain chloroethylene carbonate.
In summary, in the existing synthesis process of chloroethylene carbonate, when chlorine is used as a chlorinating reagent, the reaction stability is poor, the toxicity of the chlorine is strong, serious pollution is easy to cause, and the method brings a difficult problem for the large-scale production of chloroethylene carbonate. Sulfuryl chloride can be a good alternative to the chlorinating agent of the process compared to chlorine. However, in the traditional intermittent synthesis process using sulfuryl chloride as a chlorinating agent, the reaction heat release amount is large, and the slow dropping process of the sulfuryl chloride is easy to cause longer residence time of chlorine radicals in the reaction process, so that more byproducts (dichloro ethylene carbonate) are generated, and the yield of the chloro ethylene carbonate is reduced; in addition, the batch synthesis process has low production efficiency and is difficult to be used for industrial scale production. Therefore, the novel synthesis process of chloroethylene carbonate is of great significance.
Disclosure of Invention
The application aims to overcome the defects in the prior art, and provides a method and a device for continuously synthesizing chloroethylene carbonate in a microchannel by using ethylene carbonate and sulfuryl chloride as raw materials.
In view of the shortcomings of the prior art, the application aims to provide a method for continuously synthesizing chloroethylene carbonate in a microchannel, which comprises the following steps:
(1) Respectively heating a reaction raw material ethylene carbonate solution and sulfuryl chloride and an initiator solution through respective micro-channel preheating sections, then mixing the materials in a first micro-channel mixer, and then allowing the materials to enter a first micro-reaction channel for reaction;
(2) When the reaction materials react in the first micro-reaction channel for a period of time, adding an initiator solution, mixing the initiator solution with the materials reacted by the first micro-reaction channel in a second micro-channel mixer, and then further reacting in the second micro-reaction channel to obtain the product chloroethylene carbonate by reaction synthesis.
The application is further arranged to control the molar ratio between the ethylene carbonate and the sulfuryl chloride within the range of 1:1-2, preferably 1:1.6, by adjusting the concentration and flow rate of the ethylene carbonate solution and the sulfuryl chloride. Further, the mass ratio of the initiator to the ethylene carbonate is controlled to be 1:50-300 by adjusting the concentration and the flow rate of the initiator solution; preferably 1:200.
The application further provides that the initiator is selected from azo initiator or peroxy initiator, wherein the azo initiator is Azodiisobutyronitrile (AIBN), azodiisoheptonitrile (ABVN) and the like, and the peroxy initiator is benzoyl peroxide. More preferably, the initiator is AIBN.
The concentration of the ethylene carbonate solution is 0.5-2 g/mL; the concentration of the initiator solution is 0.001-0.1g/mL; the mass fraction of the sulfuryl chloride is 98%. Wherein the solvent in the ethylene carbonate solution and the initiator solution is one or a mixture of acetonitrile, ethyl acetate, carbon tetrachloride, methylene dichloride and the like; acetonitrile is preferred.
The application is further arranged that the flow rate of the ethylene carbonate solution is 0.5-10 mL/min, and the flow rate of the sulfuryl chloride is 0.5-10 mL/min; the initiator is added step by step, namely initiator solution is continuously added through the first micro-channel mixer and the second micro-channel mixer respectively, and the flow rate of each initiator solution which is introduced into the first micro-channel mixer and the second micro-channel mixer is 1-10mL/min.
The application is further arranged that the reaction temperature of the reaction is 70-100 ℃, preferably 90 ℃; the reaction temperature of the reaction is controlled by a constant-temperature water bath; the reaction time through the micro-reaction channel is 30 to 60 minutes, preferably 40 minutes.
The application is further arranged that after the gas-liquid separation of the reacted product, the gas enters the tail gas treatment system. Preferably, the tail gas treatment method of the application is to introduce the gas containing sulfur dioxide and hydrogen chloride after the reaction into a gas washing bottle of 30% sodium hydroxide solution for treatment.
The application is further arranged that after gas-liquid separation of the reacted product, the liquid enters a liquid storage system. Furthermore, in order to analyze and detect the liquid product, the reacted liquid is cooled, added with organic amine to adjust the pH value, and analyzed by gas chromatography to obtain the content of chloroethylene carbonate in the reacted liquid. Preferably, the organic amine is one of aliphatic amines such as diethylamine, triethylamine, trimethylamine, isopropylamine, and the like, and more preferably triethylamine.
The application also provides a device for continuously synthesizing chloroethylene carbonate in the micro-channel, which comprises an infusion metering pump for three materials of raw material ethylene carbonate, sulfuryl chloride and an initiator, a micro-channel preheating section corresponding to each, a first micro-channel mixer, a first micro-reaction channel, a second micro-channel mixer, a second micro-reaction channel and a product collector, wherein:
the feeding end of the transfusion metering pump is respectively connected with the liquid storage bottles of all materials, the discharging end of the transfusion metering pump is connected with one end of a corresponding micro-channel preheating section, the other end of the micro-channel preheating section is connected to the inlet end of the first micro-channel mixer, the outlet end of the first micro-channel mixer is connected to the inlet end of the first micro-reaction channel, the outlet end of the first micro-reaction channel is connected with the inlet end of the second micro-reaction channel through the second micro-channel mixer, the inlet end of the second micro-channel mixer is also connected with the micro-channel preheating section corresponding to the initiator material, and the outlet end of the second micro-reaction channel is connected to the product collector.
The application is further provided that the infusion metering pump is a corrosion-resistant, pressure-stable, accurate-flow-rate, low-pulse high-pressure tetrafluoro infusion pump or hastelloy infusion pump; preferably, the infusion metering pump of the ethylene carbonate and the initiator is a hastelloy infusion pump, and the infusion metering pump of the sulfuryl chloride is a high-pressure tetrafluoro infusion pump. And the liquid storage bottle of the sulfuryl chloride is a shading liquid storage bottle.
The application further provides that the microchannel preheating section, the first microchannel mixer, the second microchannel are made of Polytetrafluoroethylene (PTFE), polytetrafluoroethylene Plastic (PFA), or an alloy coated with a corrosion resistant coating. The microchannel preheating section, the first microchannel and the second microchannel are microchannel coils with spiral structures; and the inner diameter of the micro-channel coil of the first micro-reaction channel and the second micro-reaction channel is 1-6 mm.
The application is further arranged that the first micro-channel mixer is a cross-shaped micro-mixer, and the second micro-channel mixer is a T-shaped micro-mixer; the ratio of the tube lengths of the first micro-reaction channel to the second micro-reaction channel is 2:8-8:2.
Compared with the prior art, the application has the beneficial effects that:
(1) Compared with the traditional photochlorination reaction, the method adopts sulfuryl chloride as a chlorinating reagent, has the advantages of relatively mild and stable reaction and higher selectivity, avoids using high-toxicity chlorine, and is suitable for the green high-efficiency large-scale preparation of chloroethylene carbonate.
(2) Compared with the traditional batch process, the synthesis of the chloroethylene carbonate is carried out in a microchannel reactor, the specific surface area of the microchannel is larger, the heat and mass transfer efficiency is higher, and the side reaction caused by the flying temperature can be effectively avoided; compared with the traditional intermittent synthesis method of chloroethylene carbonate, the method has the advantages that the reaction time is shortened to be within 90 minutes, and the selectivity of a target product is improved to 95%; according to the application, the initiator is added in a distributed manner, and the initiator is added in the reaction process, so that the service life of chlorine radicals is prolonged, the further reaction is promoted, and the conversion rate of the reaction is improved; the two-stage micro-channel mixer is used for mixing and feeding, so that the mixing effect of two materials of raw material ethylene carbonate and sulfuryl chloride is enhanced, the raw materials are more fully contacted, the concentration distribution of chlorine free radicals is more uniform, and the efficient synthesis of the chloroethylene carbonate is realized.
(3) The application selects the high-pressure tetrafluoropump and the hastelloy infusion pump, so that the proportion control of raw materials is more accurate, the generation and termination of the reaction are controlled by accurately controlling the residence time, and the deep chlorination side reaction caused by longer residence time of chlorine free radicals is avoided.
(4) The gas generated in the reaction process can be used for recycling, and can be absorbed by alkaline substances, so that the exhaust emission of waste gas is effectively reduced, and the environmental pollution is further reduced; in addition, the application selects organic amines such as triethylamine and the like to regulate and control the pH value of the liquid after the reaction, and reduces the influence of acidic reaction liquid on the chromatographic column.
Drawings
FIG. 1 is a schematic flow chart of the continuous synthesis of chloroethylene carbonate in a microchannel of the application.
Wherein, 1, a stock solution bottle of ethylene carbonate solution, 2, a transfusion metering pump of ethylene carbonate solution, 3, a micro-channel preheating section of ethylene carbonate solution, 4, a stock solution bottle of sulfuryl chloride, 5, a transfusion metering pump of sulfuryl chloride, 6, a micro-channel preheating section of sulfuryl chloride, 7, a stock solution bottle of initiator solution, 8, a transfusion metering pump of initiator solution, 9, a micro-channel preheating section of an initiator solution, 10, a first micro-channel mixer, 11, a first micro-reaction channel, 12, a control valve, 13, a second micro-channel mixer, 14, a second micro-reaction channel, 15, a product collector, 16, an exhaust valve, 17, a tail gas processor, 18, a liquid discharge valve, 19 and a liquid storage bottle.
Detailed Description
The technical scheme of the application is clearly and completely described in the following by specific embodiments. It is to be understood that the described embodiments are only some, but not all, of the embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art.
As shown in fig. 1, the micro-reaction system for continuously synthesizing chloroethylene carbonate by using ethylene carbonate and sulfuryl chloride as raw materials according to the application comprises three infusion metering pumps 2, 5 and 8 for raw materials of ethylene carbonate, sulfuryl chloride and an initiator, respectively corresponding micro-channel preheating sections 3, 6 and 9, a first micro-channel mixer 10, a first micro-channel 11, a second micro-channel mixer 13, a second micro-channel 14 and a product collector 15, wherein:
the feeding ends of the three-material infusion metering pumps 2, 5 and 8 are respectively connected with ethylene carbonate, sulfuryl chloride and initiator liquid storage bottles 1, 4 and 7, the discharging ends are connected with one ends of corresponding micro-channel preheating sections 3, 6 and 9, the other ends of the micro-channel preheating sections 3, 6 and 9 are connected to the inlet end of a first micro-channel mixer 10, the outlet end of the first micro-channel mixer 10 is connected to the inlet end of a first micro-reaction channel 11, the outlet end of the first micro-reaction channel 11 is connected with the inlet end of a second micro-reaction channel 14 through a second micro-channel mixer 13, the inlet end of the second micro-channel mixer 13 is also connected with the micro-channel preheating section 9 corresponding to the initiator material, and the outlet end of the second micro-reaction channel 14 is connected to a product collector 15.
Furthermore, the infusion metering pump is a high-pressure tetrafluoro infusion pump or a hastelloy infusion pump which is corrosion-resistant, stable in pressure, accurate in flow rate and low in pulse; preferably, the infusion metering pump 2 of ethylene carbonate and the infusion metering pump 7 of the initiator are hastelloy infusion pumps, and the infusion metering pump 4 of sulfuryl chloride is a high-pressure tetrafluoro infusion pump.
Further, the liquid storage bottle 4 of the sulfuryl chloride is a shading liquid storage bottle.
Further, the microchannel preheating sections 3, 6, 9, the first microchannel mixer 10, the first microchannel 11, the second microchannel mixer 13, and the second microchannel 14 in the described microreaction system are made of Polytetrafluoroethylene (PTFE), polytetrafluoroethylene Plastic (PFA), or an alloy coated with a corrosion-resistant coating. Wherein, the microchannel preheating sections 3, 6 and 9, the first microchannel 11 and the second microchannel 14 are preferably spiral microchannel coils made of corrosion-resistant polytetrafluoroethylene; the inner diameter of the microchannel coil of the first and second micro-reaction channels 11 and 14 is preferably 1 to 6mm.
Further, the first micro-channel mixer 10 is a cross-shaped micro-mixer, the second micro-channel mixer 13 is a T-shaped micro-mixer, and both the micro-mixers have an enhanced mixing effect, and the first micro-channel mixer 10 includes three inlet ends and one outlet end, wherein the three inlet ends are respectively used for feeding and mixing three materials; the second micro-channel mixer 13 comprises two inlet ends and one outlet end, wherein the two inlet ends are respectively used for mixing materials reacted through the first micro-reaction channel 11 and supplementary initiator feed; materials entering the micro mixer are efficiently mixed through the internal microstructure, and liquid after mixing flows out from the outlet end and enters a micro reaction channel connected with the liquid for reaction.
The micro-reaction channel is divided into a front section and a rear section, and is used for adding the initiator step by step in the reaction process so as to strengthen the further progress of the reaction and improve the reaction conversion rate. Specifically, a control valve 12 is arranged between the second microchannel mixer 13 and the microchannel preheating section 9 corresponding to the initiator material, and is used for controlling the flow of the initiator which is supplemented into the second microchannel mixer 13 and participates in the microreaction.
Further, the product collector 15 is arranged as a gas membrane separator to separate the gas and the liquid of the reaction materials collected after the reaction, the top end of the product collector 15 is connected with a tail gas treatment system, and the side end is connected with a liquid storage system. Preferably, the exhaust gas treatment system comprises an exhaust valve 16 connected with the top end of the product collector 15 and an exhaust gas treatment device 17 connected with the exhaust valve 16, and can be configured as a gas washing bottle; the liquid storage system comprises a liquid discharge valve 18 connected with the side end of the product collector 15 and a liquid storage bottle 19 connected with the liquid discharge valve 18.
The application discloses a method for continuously synthesizing chloroethylene carbonate by utilizing a micro-reaction system, which specifically comprises the following steps:
(1) The ethylene carbonate and the initiator are respectively dissolved in the solvent and placed in the liquid storage bottles 1 and 7, and the sulfuryl chloride is also placed in the shading liquid storage bottle 4.
(2) And opening three material infusion metering pumps 2, 5 and 8, heating the reaction raw materials of ethylene carbonate solution, sulfuryl chloride and initiator solution through corresponding micro-channel preheating sections 3, 6 and 9 respectively, mixing in a first micro-channel mixer 10, and entering a first micro-reaction channel 11 for reaction.
(3) When the reaction materials react in the first micro-reaction channel 11 for a period of time, that is, flow to the outlet end of the first micro-reaction channel 11, the initiator solution is added, and the initiator solution and the materials reacted through the first micro-reaction channel 11 enter the second micro-channel mixer 13 to be mixed, and enter the second micro-reaction channel 14 to be further reacted. The materials reacted by the second micro-reaction channel 14 enter a product collector 15 for collection.
Further, the reaction temperature of the reaction is controlled by a constant temperature water bath. Specifically, the preheating temperature of the microchannel preheating sections 3, 6 and 9 is controlled by a constant-temperature water bath.
Further, by adjusting the concentration and flow rate of the vinyl carbonate solution and the sulfuryl chloride, the molar ratio between the vinyl carbonate and the sulfuryl chloride is controlled within the range of 1:1-2, preferably 1:1.6.
Further, the initiator is selected from azo-type initiator or peroxy-type initiator, wherein the azo-type initiator is Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN) and the like, and the peroxy-type initiator is benzoyl peroxide. More preferably, the initiator is AIBN. Further, the mass ratio of the initiator to the ethylene carbonate is controlled to be 1:50-300 by adjusting the concentration and the flow rate of the initiator solution; preferably 1:200.
Further, the ethylene carbonate is dissolved in a solvent to form ethylene carbonate solution, and the concentration of the solution is 0.5-2 g/mL; the initiator is also dissolved in a solvent to form an initiator solution, and the concentration of the solution is 0.001-0.1g/mL; the mass fraction of the sulfuryl chloride is 98%. Wherein the solvent is one or a mixture of acetonitrile, ethyl acetate, carbon tetrachloride, methylene dichloride and the like; acetonitrile is preferred.
Further, the flow rate of the ethylene carbonate solution is 0.5-10 mL/min, and the flow rate of the sulfuryl chloride is 0.5-10 mL/min. The initiator is added in steps, and the initiator solution is continuously added through the first micro-channel mixer 10 and the second micro-channel mixer 13 respectively. The adding position of the initiator solution is the middle part of the total micro-reaction channel, the total micro-reaction channel is divided into the first micro-reaction channel 11 and the second micro-reaction channel 14, the ratio of the tube lengths of the first micro-reaction channel 11 to the second micro-reaction channel 14 is 2:8-8:2, and the flow rate of each initiator solution fed into the first micro-channel mixer 10 and the second micro-channel mixer 13 is 1-10mL/min.
Further, the reaction temperature of the reaction is 70-100 ℃, preferably 90 ℃; the reaction time through the micro-reaction channel is 30 to 60 minutes, preferably 40 minutes.
Further, after the gas-liquid separation of the material entering the product collector 15, the gas enters the tail gas treatment system. Preferably, the tail gas treatment method of the application is to introduce the gas containing sulfur dioxide and hydrogen chloride after the reaction into a gas washing bottle of 30% sodium hydroxide solution for treatment.
Further, after the gas-liquid separation of the material entering the product collector 15, the liquid enters a liquid storage system. Furthermore, in order to analyze and detect the liquid product, the reacted liquid is cooled to 2-10 ℃ and kept for 10-50 min, then organic amine is added to adjust the pH value, and the content of chloroethylene carbonate in the reacted liquid is analyzed by gas chromatography. Preferably, the organic amine is a fatty amine such as diethylamine, triethylamine, trimethylamine, isopropylamine, and the like, and more preferably triethylamine.
The following examples all employ the above-described continuous synthesis of vinyl chlorocarbonate to prepare vinyl chlorocarbonate.
Example 1
(1) 68g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred to a 100mL volumetric flask, after the volume is fixed, an acetonitrile solution of 0.68g/mL of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle A for use.
(2) 1.8g of AIBN is placed in a beaker, 10mL of acetonitrile is added for dissolution, after the AIBN is completely dissolved, the AIBN is transferred to a 100mL volumetric flask, after the AIBN is fixed in volume, 0.018g/mL of acetonitrile solution of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle B for use.
(3) 50mL of sulfuryl chloride was transferred to a light-shielding stock solution bottle C for use.
(4) The length of the preheating section of each micro-channel is set to be 6m, the length of the total micro-reaction channel is set to be 20m, wherein the first micro-reaction channel and the second micro-reaction channel are respectively 10m, and the residence time of the total micro-reaction channel is set to be 20.9min.
(5) After the constant-temperature circulating water bath is heated to 95 ℃, three infusion metering pumps are synchronously opened, and the flow is 3mL/min. And when the reaction is carried out for 10min, opening a control valve for supplementing the initiator, and further carrying out the reaction by supplementing the initiator, wherein the flow rate of an infusion metering pump of the initiator and the opening of the control valve are regulated at the moment, so that the flow rate of the initiator solution entering the two sections of micro-reaction channels is 3mL/min.
(6) And (3) cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 87.8%, and the selectivity of the chloroethylene carbonate is 94.5%.
Comparative example 1
In the comparative example, the initiator is not added step by step, but is mixed with the reaction raw materials at the beginning of the reaction, specifically:
(1) 68g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred into a 100mL volumetric flask, and after the volume is fixed, the acetonitrile solution of the ethylene carbonate of 0.68g/mL is prepared. To the mixed solution was added 0.9g of initiator AIBN and the mixed solution was transferred to reservoir A for use.
(2) To 50mL of sulfuryl chloride was added initiator AIBN 0.9g, and the mixed solution was transferred to a light-shielding liquid bottle B for use.
(3) The length of the preheating section of each micro-channel is 6m, the length of the total micro-reaction channel is 20m, the reaction section is not needed to be segmented, and the residence time of the total micro-reaction channel is 20.9min.
(4) After the constant-temperature circulating water bath is heated to 95 ℃, two infusion metering pumps are synchronously opened, and the flow is 3mL/min.
(5) And (3) cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 59.8%, and the selectivity of the chloroethylene carbonate is 95.5%.
Example 2
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred to a 100mL volumetric flask, after the volume is fixed, 1g/mL of acetonitrile solution of the ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle A for use.
(2) 1.5g of AIBN is placed in a beaker, 10mL of acetonitrile is added for dissolution, after the AIBN is completely dissolved, the AIBN is transferred to a 100mL volumetric flask, after the AIBN is fixed in volume, an acetonitrile solution of 0.015g/mL of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle B for use.
(3) 50mL of sulfuryl chloride was transferred to a light-shielding stock solution bottle C for use.
(4) The length of the preheating section of each micro-channel is set to be 6m, the length of the total micro-reaction channel is set to be 10m, wherein the first micro-reaction channel and the second micro-reaction channel are respectively 5m, and the residence time of the total micro-reaction channel is 15.7min.
(5) After the constant-temperature circulating water bath is heated to 95 ℃, three infusion metering pumps are synchronously opened, and the flow is 1mL/min. And when the reaction is carried out for 7min, opening a control valve for supplementing the initiator, and further carrying out the reaction by supplementing the initiator, wherein the flow rate of an infusion metering pump of the initiator and the opening of the control valve are regulated at the moment, so that the flow rate of the initiator solution entering the two sections of micro-reaction channels is 1mL/min.
(6) And cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 86.5%, and the selectivity of the chloroethylene carbonate is 94.4%.
Comparative example 2
In the comparative example, the initiator is not added step by step, but is mixed with the reaction raw materials at the beginning of the reaction, specifically:
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred into a 100mL volumetric flask, and after the volume is fixed, 1g/mL of acetonitrile solution of ethylene carbonate is prepared. To the mixed solution was added 0.8g of initiator AIBN and the mixed solution was transferred to reservoir A for use.
(2) To 50mL of sulfuryl chloride was added initiator AIBN 0.8g, and the mixed solution was transferred to a light-shielding liquid bottle B for use.
(3) The length of the preheating section of each micro-channel is 6m, the length of the total micro-reaction channel is 10m, the reaction section is not needed to be segmented, and the residence time of the total micro-reaction channel is 15.7min.
(4) After the constant-temperature circulating water bath is heated to 95 ℃, two infusion metering pumps are synchronously opened, and the flow is 1mL/min.
(5) And cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 34.3%, and the selectivity of the chloroethylene carbonate is 95.2%.
Example 3
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred to a 100mL volumetric flask, after the volume is fixed, 1g/mL of acetonitrile solution of the ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle A for use.
(2) 1.8g of AIBN is placed in a beaker, 10mL of acetonitrile is added for dissolution, after the AIBN is completely dissolved, the AIBN is transferred to a 100mL volumetric flask, after the AIBN is fixed in volume, 0.018g/mL of acetonitrile solution of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle B for use.
(3) 50mL of sulfuryl chloride was transferred to a light-shielding stock solution bottle C for use.
(4) The length of the preheating section of each micro-channel is set to be 6m, the length of the total micro-reaction channel is set to be 40m, wherein the first micro-reaction channel and the second micro-reaction channel are respectively 20m, and the residence time of the total micro-reaction channel is 62.8min.
(5) After the constant-temperature circulating water bath is heated to 95 ℃, three infusion metering pumps are synchronously opened, and the three flows are all 1mL/min. And when the reaction is carried out for 30min, opening a control valve for supplementing the initiator, and further carrying out the reaction by supplementing the initiator, wherein the flow rate of an infusion metering pump of the initiator and the opening of the control valve are regulated at the moment, so that the flow rate of the initiator solution entering the two sections of micro-reaction channels is 1mL/min.
(6) And cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 95.3%, and the selectivity of the chloroethylene carbonate is 91.7%.
Comparative example 3
In the comparative example, the initiator is not added step by step, but is mixed with the reaction raw materials at the beginning of the reaction, specifically:
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred into a 100mL volumetric flask, and after the volume is fixed, 1g/mL of acetonitrile solution of ethylene carbonate is prepared. To the mixed solution was added 0.9g of initiator AIBN and the mixed solution was transferred to reservoir A for use.
(2) To 50mL of sulfuryl chloride was added initiator AIBN 0.9g, and the mixed solution was transferred to a light-shielding liquid bottle B for use.
(3) The length of the tube of each micro-channel preheating section is 6m, the length of the tube of the overall micro-reaction channel is 40m, the reaction section does not need to be segmented, and the residence time of the overall micro-reaction channel is 62.8min.
(4) After the constant-temperature circulating water bath pump is heated to 95 ℃, the two infusion metering pumps are synchronously opened, and the flow is 1mL/min.
(5) And cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 69.2%, and the selectivity of the chloroethylene carbonate is 92.5%.
Example 4
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred to a 100mL volumetric flask, after the volume is fixed, 1g/mL of acetonitrile solution of the ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle A for use.
(2) 1.6g of AIBN is placed in a beaker, 10mL of acetonitrile is added for dissolution, after the AIBN is completely dissolved, the AIBN is transferred to a 100mL volumetric flask, after the AIBN is fixed in volume, an acetonitrile solution of 0.016g/mL of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle B for use.
(3) 50mL of sulfuryl chloride was transferred to a light-shielding stock solution bottle C for use.
(4) The length of the preheating section of each micro-channel is set to be 6m, the length of the total micro-reaction channel is set to be 30m, wherein the first micro-reaction channel and the second micro-reaction channel are respectively 15m, and the residence time of the total micro-reaction channel is 47.1min.
(5) After the constant-temperature circulating water bath pump is heated to 95 ℃, three infusion metering pumps are synchronously opened, and the flow is 1mL/min. And when the reaction is carried out for 25min, opening a control valve for supplementing the initiator, and further carrying out the reaction by supplementing the initiator, wherein the flow rate of an infusion metering pump of the initiator and the opening of the control valve are regulated at the moment, so that the flow rate of the initiator solution entering the two sections of micro-reaction channels is 1mL/min.
(6) And (3) cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by chromatography, wherein the conversion rate of the ethylene carbonate is 91.6%, and the selectivity of the chloroethylene carbonate is 92.8%.
Example 5
(1) 100g of ethylene carbonate is placed in a beaker, 30mL of acetonitrile is added for dissolution, after the ethylene carbonate is completely dissolved, the ethylene carbonate is transferred to a 100mL volumetric flask, after the volume is fixed, 1g/mL of acetonitrile solution of the ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle A for use.
(2) 1.7g of AIBN is placed in a beaker, 10mL of acetonitrile is added for dissolution, after the AIBN is completely dissolved, the AIBN is transferred to a 100mL volumetric flask, after the AIBN is fixed in volume, an acetonitrile solution of 0.017g/mL of ethylene carbonate is prepared, and the mixed solution is transferred to a liquid storage bottle B for use.
(3) 50mL of sulfuryl chloride was transferred to a light-shielding stock solution bottle C for use.
(4) The length of the preheating section of each micro-channel is set to be 6m, the length of the total micro-reaction channel is set to be 30m, wherein the first micro-reaction channel and the second micro-reaction channel are respectively 15m, and the residence time of the total micro-reaction channel is 16min.
(5) After the constant-temperature circulating water bath pump is heated to 95 ℃, three infusion metering pumps are synchronously opened, and the flow is 4mL/min. And when the reaction is carried out for 8min, opening a control valve for supplementing the initiator, and further carrying out the reaction by supplementing the initiator, wherein the flow rate of an infusion metering pump of the initiator and the opening of the control valve are regulated at the moment, so that the flow rate of the initiator solution entering the two sections of micro-reaction channels is 4mL/min.
(6) And cooling the liquid in the liquid storage bottle after the reaction at 2 ℃ for 30min, adding triethylamine to regulate the pH value, and detecting by gas chromatography, wherein the conversion rate of the ethylene carbonate is 90.3%, and the selectivity of the chloroethylene carbonate is 92.4%.
The present application has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present application and to implement the same, but not to limit the scope of the present application, and all equivalent changes or modifications made according to the spirit of the present application should be covered in the scope of the present application.
Claims (10)
1. A method for continuously synthesizing chloroethylene carbonate in a microchannel, which is characterized by comprising the following steps:
(1) The method comprises the steps of respectively heating a reaction raw material ethylene carbonate solution and sulfuryl chloride and an initiator solution through a micro-channel preheating section, mixing the materials in a first micro-channel mixer, and then allowing the materials to enter a first micro-reaction channel for reaction;
(2) And adding an initiator solution, mixing the initiator solution and the material reacted by the first micro-reaction channel in a second micro-channel mixer, and then entering a second micro-reaction channel for further reaction to obtain the product chloroethylene carbonate.
2. The method for continuously synthesizing chloroethylene carbonate according to claim 1, wherein the molar ratio between raw material ethylene carbonate and sulfuryl chloride is controlled to be 1:1-2, preferably 1:1.6 by adjusting the concentration and flow rate of ethylene carbonate solution and sulfuryl chloride; the mass ratio of the initiator to the ethylene carbonate is controlled to be 1:50-300 by adjusting the concentration and the flow rate of the initiator solution; preferably 1:200.
3. The method for continuously synthesizing chloroethylene carbonate according to claim 1, wherein the initiator is selected from azo-type initiator or peroxy-type initiator, the azo-type initiator is Azobisisobutyronitrile (AIBN) or Azobisisoheptonitrile (ABVN), and the peroxy-type initiator is benzoyl peroxide.
4. The method for continuously synthesizing chloroethylene carbonate according to claim 2, wherein the concentration of the ethylene carbonate solution is 0.5 to 2g/mL; the concentration of the initiator solution is 0.001-0.1g/mL; the mass fraction of the sulfuryl chloride is 98%; the solvent in the ethylene carbonate solution and the initiator solution is one or a mixture of a plurality of acetonitrile, ethyl acetate, carbon tetrachloride, methylene dichloride and the like.
5. The method for continuously synthesizing chloroethylene carbonate according to claim 2, wherein the flow rate of the ethylene carbonate solution is 0.5-10 mL/min, and the flow rate of sulfuryl chloride is 0.5-10 mL/min; the initiator is added step by step, and the flow rate of each initiator solution flowing into the first micro-channel mixer and the second micro-channel mixer is 1-10mL/min.
6. The method for continuously synthesizing chloroethylene carbonate according to claim 1, wherein the reaction temperature of the reaction is 70-100 ℃, and the reaction temperature is controlled by a constant-temperature water bath; the reaction time of the micro-reaction channel is 30-60 minutes.
7. The method for continuously synthesizing chloroethylene carbonate according to claim 1, wherein after gas-liquid separation of the reacted product, the gas enters a tail gas treatment system, preferably the gas containing sulfur dioxide and hydrogen chloride after reaction is introduced into a gas washing bottle of 30% sodium hydroxide solution for treatment; the liquid enters a liquid storage system, the reacted liquid is cooled and then added with organic amine to adjust the pH, and then the content of chloroethylene carbonate in the reacted liquid is analyzed by gas chromatography; the organic amine is one of diethylamine, triethylamine, trimethylamine and isopropylamine.
8. An apparatus for a method of continuously synthesizing chloroethylene carbonate according to any one of claims 1 to 7, comprising an infusion metering pump for three streams of raw ethylene carbonate and sulfuryl chloride and initiator, a respective microchannel preheating section, a first microchannel mixer, a first microchannel, a second microchannel mixer, a second microchannel, and a product collector, wherein:
the feeding end of the transfusion metering pump is respectively connected with the liquid storage bottles of all materials, the discharging end of the transfusion metering pump is connected with one end of a corresponding micro-channel preheating section, the other end of the micro-channel preheating section is connected to the inlet end of the first micro-channel mixer, the outlet end of the first micro-channel mixer is connected to the inlet end of the first micro-reaction channel, the outlet end of the first micro-reaction channel is connected with the inlet end of the second micro-reaction channel through the second micro-channel mixer, the inlet end of the second micro-channel mixer is also connected with the micro-channel preheating section corresponding to the initiator material, and the outlet end of the second micro-reaction channel is connected to the product collector.
9. The apparatus for continuously synthesizing chloroethylene carbonate according to claim 8, wherein the infusion metering pump is a high-pressure tetrafluoro infusion pump or hastelloy infusion pump; the microchannel preheating section, the first microchannel mixer, the first microchannel, the second microchannel mixer and the second microchannel are made of Polytetrafluoroethylene (PTFE), polytetrafluoroethylene Plastic (PFA) or an alloy coated with a corrosion-resistant coating.
10. The apparatus for continuously synthesizing chloroethylene carbonate according to claim 8, wherein the microchannel preheating section and the first and second micro-reaction channels are microchannel coils having a spiral structure; the inner diameters of the micro-channel coil pipes of the first micro-reaction channel and the second micro-reaction channel are 1-6 mm; the first micro-channel mixer is a cross-shaped micro-mixer, and the second micro-channel mixer is a T-shaped micro-mixer; the ratio of the tube lengths of the first micro-reaction channel to the second micro-reaction channel is 2:8-8:2.
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