CN115716815B - Method and system for continuously preparing vinylene carbonate - Google Patents
Method and system for continuously preparing vinylene carbonate Download PDFInfo
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- CN115716815B CN115716815B CN202211654128.0A CN202211654128A CN115716815B CN 115716815 B CN115716815 B CN 115716815B CN 202211654128 A CN202211654128 A CN 202211654128A CN 115716815 B CN115716815 B CN 115716815B
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000000945 filler Substances 0.000 claims abstract description 18
- 238000003379 elimination reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 238000001704 evaporation Methods 0.000 claims description 60
- 230000008020 evaporation Effects 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000012295 chemical reaction liquid Substances 0.000 claims description 40
- 238000003860 storage Methods 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000005086 pumping Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 18
- 239000010962 carbon steel Substances 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 18
- 229920003023 plastic Polymers 0.000 claims description 18
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000010907 mechanical stirring Methods 0.000 claims description 12
- 238000010606 normalization Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 claims description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229920000578 graft copolymer Polymers 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 7
- -1 polyhydroxymethylene Polymers 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical class C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 241000232299 Ralstonia Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Silicon Polymers (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a method and a system for continuously preparing vinylene carbonate, which belong to the technical field of organic synthesis, and specifically adopt chloroethylene carbonate as a raw material, generate vinylene carbonate through elimination reaction by a tower reactor with an alkaline filler with a special structure, the alkaline filler with the special structure is a silica modified graft polymer and has a repeating structural unit of-A-B-C, the filler after reaction can be recycled after alkaline washing and drying, compared with the existing triethylamine acid binding agent, the recycling step is less, the salt content of a reaction solution is greatly reduced, the subsequent purification step is simple and convenient, the reaction yield is remarkably improved, and the method is more suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method and a system for continuously preparing vinylene carbonate.
Background
Vinylene carbonate (Vinylene Carbonate, VC for short) is a colorless lithium battery electrolyte additive, has a density of 1.36g/cm at 20 ℃, is an important organic intermediate, and can effectively improve the charge and discharge efficiency and storage resistance of the battery. VC can be used as a chemical raw material to synthesize an intermediate aromatic compound, and can also be polymerized into polyvinyl carbonate by a monomer, so that polyhydroxymethylene with good biocompatibility and no toxicity can be further synthesized.
The prior art for synthesizing VC mainly comprises the following methods, liu Xiaobo and the like (Chinese patent ZL 104844556) which disclose a method for continuously preparing VC by using a tubular reactor, wherein sulfonyl chloride and ethylene carbonate are used for synthesizing chloroethylene carbonate, and chloroethylene carbonate reacts with triethylamine in the tubular reactor in an organic solvent to generate VC. Although the continuous production is realized through the tubular reactor in the aspects of synthesizing raw materials and preparing products, the triethylamine hydrochloride and the polymer are easy to be blocked because the tubular reactor is difficult to post-treat, and the real continuous production is difficult to realize.
Niu Huizhu et al (Chinese patent ZL 106905288) discloses a method for synthesizing VC by reacting chloroethylene carbonate with dehydrated pyridine in tertiary butyl ether organic solvent at a certain temperature, wherein the purity of VC is 99.5% after purification treatment; according to the method, pyridine is used as an acid binding agent, the recovery efficiency of the acid binding agent is improved, but the reaction time in the preparation process of the system is long, the VC yield is low, and industrial production cannot be really realized.
Li Chaodeng (Chinese patent ZL 201210440209) discloses a method for preparing vinylene carbonate by directly reacting chloroethylene carbonate with triethylamine, which reduces the use of an organic solvent and reduces the cost, but the method requires inert gas for protection, and the polymerization is obvious due to higher VC concentration, so that continuous production cannot be realized.
Disclosure of Invention
To solve the above problems, it is an object of the present invention to provide a method and system for continuously producing vinylene carbonate.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
a process for continuously preparing vinylene carbonate comprising the steps of:
1) Storing chloroethylene carbonate and a solvent in a carbon steel lining plastic tank to obtain a mixed solution, pumping the mixed solution into three-stage series-connected tower reactors through a high-pressure plunger pump, heating the three-stage tower reactors to 50-100 ℃, continuously passing the mixed solution through the three-stage tower reactors at the same flow rate to perform elimination reaction to obtain a vinylene carbonate reaction solution, pumping the vinylene carbonate reaction solution out through the three-stage tower reactors, and storing the vinylene carbonate reaction solution in a 304 storage tank;
the tower reactor is filled with a silica grafting modified polymer filler;
the solvent is any one or two of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl tertiary butyl ether, ethyl acetate, tetrahydrofuran or benzonitrile;
the mass volume ratio of the chloroethylene carbonate to the solvent is 0.2-0.4 kg:1L;
the feeding speed of the mixed liquid is 0.02-0.05L/min, and the pressure of the high-pressure plunger pump is 1.0-1.5 Mpa;
the structure of the silicon dioxide graft modified polymer contains a repeating structural unit of-A-B-C, wherein the structural formula of A, B, C is
Wherein m=0 to 5, n=0 to 5;
2) Carrying out flash evaporation and rectification treatment on the vinylene carbonate reaction liquid obtained in the step 1) to obtain vinylene carbonate;
the flash evaporation feeding speed is 0.01-0.05L/min, the flash evaporation vacuum degree is 20-30 mbar, and the flash evaporation temperature is 60-120 ℃;
the rectification feeding speed is 0.01-0.05L/min, the rectification vacuum degree is 10-20 mbar, the bottom temperature is 60-100 ℃, and the top temperature is 30-50 ℃.
Preferably, the solvent is dimethyl carbonate, diethyl carbonate or benzonitrile.
Preferably, the mass volume ratio of the chloroethylene carbonate to the solvent is 0.2-0.3 kg:1L.
Preferably, the feeding speed of the mixed solution is 0.02-0.03L/min, the heating temperature of the three-stage tower reactor is 50-80 ℃, and the feeding pressure of the high-pressure plunger pump is 1.0-1.2 Mpa.
Preferably, the silica graft modified polymer is prepared according to the following method: dispersing silicon dioxide with the particle size of 10-500 nm and a silane coupling agent KH-858 in toluene, adding polyethylene polyamine and alkyl aldehyde, heating and refluxing under the protection of nitrogen for reaction for 3-4 hours, spin-drying the obtained product, washing with an organic solvent and deionized water, and drying to obtain a silicon dioxide grafted modified polymer;
the structural formula of the alkyl aldehyde is
m=0~5；
The structural formula of the polyethyl polyamine is
n=0~5；
The dosage of the silane coupling agent KH-858 is 0.5% -1% of the dosage of silicon dioxide;
the mole ratio of the silicon dioxide, the polyethylene polyamine and the alkyl aldehyde is 1: 2-3: 2-3;
the mass ratio of toluene to silicon dioxide is 4-5: 1, a step of;
the organic solvent is acetone, ethanol or acetonitrile.
Preferably, the silica graft modified polymer contains repeating structural units of-A-B-C, wherein A, B, C has the formula
Wherein m=1 to 2, n=1 to 2.
Preferably, the flash evaporation feeding speed is 0.01-0.02L/min, the flash evaporation vacuum degree is 20-25 mbar, and the flash evaporation temperature is 60-80 ℃.
Preferably, the rectification feeding speed is 0.01-0.02L/min, the rectification vacuum degree is 10-15 mbar, the tower bottom temperature is 60-80 ℃, and the tower top temperature is 30-35 ℃.
The system for continuously preparing the vinylene carbonate comprises a carbon steel lining plastic tank, a ball valve, a high-pressure plunger pump, a tower reactor, a 304 storage tank, flash evaporation equipment and rectification equipment; the carbon steel lining plastic tank comprises a chloroethylene carbonate inlet and a solvent inlet, the feeding speed is controlled through a ball valve, and the carbon steel lining plastic tank is connected with the tower reactor through a high-pressure plunger pump; the tower reactor comprises three-stage serial tower reactors, wherein each tower reactor is filled with silica grafted modified polymer filler; the outlet of the first-stage tower reactor is communicated with the inlet of the second-stage tower reactor through a high-pressure plunger pump; the outlet of the second-stage tower reactor is communicated with the inlet of the third-stage tower reactor through a high-pressure plunger pump; the outlet of the three-stage tower reactor is communicated with a 304 storage tank through a ball valve; 304 the outlet of the storage tank is communicated with the inlet of the flash evaporation equipment through a ball valve; the outlet of the flash distillation device is communicated with the inlet of the rectification device.
Compared with the prior art, the invention has the following advantages:
according to the method for continuously preparing the vinylene carbonate, the reaction time is greatly shortened, the salt content of the reaction solution is greatly reduced, the yield of synthesizing the vinylene carbonate is remarkably improved, the subsequent purification steps are simple and convenient, and the production efficiency is greatly improved.
The method avoids the use of a centrifugal filtration operation section of the traditional process, the polyamine hydrochloride generated by the reaction is easier to remove than the existing method, the alkaline filler can be recycled and reused after alkali washing and drying, and the method has fewer steps than the existing triethylamine acid binding agent recovery, is simple and convenient in process, and is more suitable for industrial production.
The invention has the advantages of less occupied equipment in the purification stage, simple and convenient operation, high automation level and obviously improved production efficiency, and is suitable for large-scale preparation.
Drawings
FIG. 1 is a schematic diagram showing the connection of the equipment of a system for continuously producing vinylene carbonate according to the present invention;
in the figure, a 1-stage tower reactor; a 2-second stage tower reactor; 3-three-stage tower reactor; 4-a flash apparatus; 5-rectifying equipment; a 6-chloroethylene carbonate inlet; 7-solvent inlet; 8-10-ball valve; 11-13-high pressure plunger pump; 14-304 storage tanks; 15-carbon steel lining plastic tank.
Detailed Description
The foregoing is further elaborated by the following description of embodiments of the present invention, which are given by way of example only, and should not be construed as limiting the scope of the present invention. All techniques implemented based on the above description of the invention are within the scope of the invention.
The silicon dioxide used in the invention is purchased from Beijing An Bi biological science and technology Co., ltd; the silane coupling agent KH-858 is purchased from Zhejiang Ralstonia chemical Co.
The chloroethylene carbonate is added from a chloroethylene carbonate inlet 6, the solvent is added from a solvent inlet 7, the mixed solution of chloroethylene carbonate and the solvent is stored in a carbon steel lining plastic tank 15, the mixed solution controls the feeding speed through a ball valve 8 and is pumped into a primary tower reactor 1 through a high-pressure plunger pump 11 to carry out elimination reaction, the mixed solution continuously passes through a secondary tower reactor 2 and a tertiary tower reactor 3 at the same flow speed to carry out elimination reaction, the primary tower reactor 1 and the secondary tower reactor 2 are communicated through a high-pressure plunger pump 12, the secondary tower reactor 2 and the tertiary tower reactor 3 are communicated through a high-pressure plunger pump 13, the obtained vinylene carbonate reaction solution flows out of a tertiary tower reactor 3 and is stored in a 304 storage tank 14, the tertiary tower reactor 3 and the 304 storage tank 14 are communicated through a ball valve 9, the reaction solution stored in the 304 storage tank 14 is introduced into a flash evaporation device 4 to carry out purification treatment, and the 304 storage tank 14 is communicated with the flash evaporation device 4 through a ball valve 10; the flash evaporation device 4 is communicated with the rectification device 5.
Example 1
Synthesis of silica graft modified polymer (m=n=1): 1kg of silicon dioxide with the particle size of 50nm and 0.01kg of silane coupling agent KH-858 are added into 5kg of toluene, mechanical stirring is used for uniformly dispersing the system, 3.43kg of diethylenetriamine and 3.3kg of glutaraldehyde are added, heating reflux is carried out for 3 hours under the protection of nitrogen, the obtained product is spin-dried, then washing is carried out by using acetone and deionized water, and the silicon dioxide graft modified polymer is obtained after drying, wherein the yield is 95%.
Adding 0.24kg of chloroethylene carbonate and 1.2L of dimethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.0Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.02L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 50 ℃ to obtain a vinylene carbonate reaction solution, pumping the reaction solution out of the three-stage tower reactor, storing the reaction solution in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.01L/min, controlling the flash evaporation vacuum degree to be 20mbar and controlling the flash evaporation temperature to be 60 ℃; the rectification feeding speed is 0.01L/min, and the rectification vacuum degree is 10 mbar; the temperature of the bottom of the tower is 60 ℃, the temperature of the top of the tower is 30 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 85 percent.
Example 2
Synthesis of silica graft modified polymer (m=n=1): 1kg of silicon dioxide with the particle size of 30nm and 0.005kg of silane coupling agent KH-858 are added into 4kg of toluene, mechanical stirring is used for uniformly dispersing the system, 3.52kg of diethylenetriamine and 3.5kg of glutaraldehyde are added, heating reflux is carried out for 4 hours under the protection of nitrogen, the obtained product is spun dry, then ethanol and deionized water are used for washing, and the silicon dioxide graft modified polymer is obtained after drying, wherein the yield is 95%.
Adding 0.54kg of chloroethylene carbonate and 1.8L of diethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.2Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.03L/min to perform elimination reaction, filling a silica grafted modified polymer filler into the tower reactor, heating the tower reactor to 80 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.02L/min, controlling the flash evaporation vacuum degree to be 25mbar and controlling the flash evaporation temperature to be 80 ℃; the rectification feeding speed is 0.02L/min, and the rectification vacuum degree is 15 mbar; the temperature of the bottom of the tower is 80 ℃, the temperature of the top of the tower is 35 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 86 percent.
Example 3
Synthesis of silica graft modified polymer (m=n=2): 1kg of silicon dioxide with the particle size of 10nm and 0.007kg of silane coupling agent KH-858 are added into 4.5kg of toluene, mechanical stirring is used for uniformly dispersing the system, 7.3kg of triethylenetetramine and 5.7kg of glyoxal are added, heating reflux is carried out for 3 hours under the protection of nitrogen, the obtained product is dried in a spinning way, then acetone and deionized water are used for washing, and the silicon dioxide graft modified polymer is obtained after drying, wherein the yield is 96%.
Adding 1.2kg of chloroethylene carbonate and 3L of ethyl acetate into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.5Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.05L/min to perform elimination reaction, filling a silica grafted modified polymer filler into the tower reactor, heating the tower reactor to 100 ℃ to obtain a vinylene carbonate reaction solution, pumping the reaction solution out of the three-stage tower reactor, storing the reaction solution in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.05L/min, controlling the flash evaporation vacuum degree to be 30mbar and controlling the flash evaporation temperature to be 120 ℃; the rectification feeding speed is 0.05L/min, and the rectification vacuum degree is 20mbar; the temperature of the bottom of the tower is 100 ℃, the temperature of the top of the tower is 50 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 83 percent.
Example 4
Synthesis of silica graft modified polymer (m=1, n=2): 1kg of silicon dioxide with the particle size of 70nm and 0.01kg of silane coupling agent KH-858 are added into 5kg of toluene, mechanical stirring is used for uniformly dispersing the system, 5kg of triethylenetetramine and 3.5kg of glutaraldehyde are added, heating reflux is carried out for 4 hours under the protection of nitrogen, the obtained product is dried in a spinning way, then acetonitrile and deionized water are used for washing, and the silicon dioxide grafted modified polymer is obtained after drying, wherein the yield is 96%.
Adding 0.37kg of chloroethylene carbonate and 1.5L of methyl ethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.1Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.025L/min to perform elimination reaction, filling a silica grafted modified polymer filler into the tower reactor, heating the tower reactor to 60 ℃ to obtain vinylene carbonate reaction liquor, pumping the reaction liquor out of the three-stage tower reactor, storing the reaction liquor in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.02L/min, controlling the flash evaporation vacuum degree to be 22mbar and controlling the flash evaporation temperature to be 70 ℃; the rectification feeding speed is 0.02L/min, and the rectification vacuum degree is 12 mbar; the temperature of the bottom of the tower is 70 ℃, the temperature of the top of the tower is 33 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 88 percent.
Example 5
Synthesis of silica graft modified polymer (m=5, n=5): 1kg of silicon dioxide with the particle size of 100nm and 0.009kg of silane coupling agent KH-858 are added into 4.7kg of toluene, mechanical stirring is used for uniformly dispersing the system, 9.4kg of hexaethylene heptamine and 5.5kg of nonanal are added, heating reflux is carried out for 3.5 hours under the protection of nitrogen, the obtained product is dried by spinning, then acetone and deionized water are used for washing, and the silicon dioxide grafted modified polymer is obtained after drying, wherein the yield is 96%.
Adding 0.84kg of chloroethylene carbonate and 2.4L of benzonitrile into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.4Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.04L/min to perform elimination reaction, filling a silica grafted modified polymer filler into the tower reactor, heating the tower reactor to 90 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.04L/min, controlling the flash evaporation vacuum degree to be 28mbar and controlling the flash evaporation temperature to be 100 ℃; the rectification feeding speed is 0.04L/min, and the rectification vacuum degree is 17 mbar; the temperature of the bottom of the tower is 90 ℃, the temperature of the top of the tower is 40 ℃, and the VC with the purity of 99.95% is obtained, and the yield of the VC in the whole process is 86%.
Example 6
Synthesis of silica graft modified polymer (m=0, n=0): adding 1kg of silicon dioxide with the particle size of 500nm and 0.01kg of silane coupling agent KH-858 into 5kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 2kg of ethylenediamine and 3kg of succinaldehyde, heating and refluxing for 3 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetone and deionized water, and drying to obtain the silicon dioxide graft modified polymer with the yield of 95%.
Adding 0.74kg of chloroethylene carbonate and 2.1L of tetrahydrofuran into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pumping pressure of a high-pressure plunger pump to be 1.3Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.035/L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 80 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1 percent through gas phase normalization.
Purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.03L/min, controlling the flash evaporation vacuum degree to be 25mbar and controlling the flash evaporation temperature to be 90 ℃; the rectification feeding speed is 0.04L/min, and the rectification vacuum degree is 20mbar; the temperature of the bottom of the tower is 80 ℃, the temperature of the top of the tower is 35 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 84 percent.
While the foregoing describes the embodiments of the present invention, it is not intended to limit the scope of the present invention, and various modifications or variations may be made by those skilled in the art without the need for inventive effort on the basis of the technical solutions of the present invention.
Claims (6)
1. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 50nm and 0.01kg of silane coupling agent KH-858 into 5kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 3.43kg of diethylenetriamine and 3.3kg of glutaraldehyde, heating and refluxing for 3 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetone and deionized water, and drying to obtain a silicon dioxide graft modified polymer with the yield of 95%;
adding 0.24kg of chloroethylene carbonate and 1.2L of dimethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquor, controlling the pressure of a high-pressure plunger pump to be 1.0Mpa, continuously passing the mixed liquor through a three-stage tower reactor at the speed of 0.02L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 50 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.01L/min, controlling the flash evaporation vacuum degree to be 20mbar and controlling the flash evaporation temperature to be 60 ℃; the rectification feeding speed is 0.01L/min, and the rectification vacuum degree is 10 mbar; the temperature of the bottom of the tower is 60 ℃, the temperature of the top of the tower is 30 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 85 percent.
2. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 30nm and 0.005kg of silane coupling agent KH-858 into 4kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 3.52kg of diethylenetriamine and 3.5kg of glutaraldehyde, heating and refluxing for 4 hours under the protection of nitrogen, spin-drying the obtained product, washing with ethanol and deionized water, and drying to obtain a silicon dioxide graft modified polymer with the yield of 95%;
adding 0.54kg of chloroethylene carbonate and 1.8L of diethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquid, controlling the pumping pressure of a high-pressure plunger pump to be 1.2Mpa, continuously passing the mixed liquid through a three-stage tower reactor at the speed of 0.03L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 80 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.02L/min, controlling the flash evaporation vacuum degree to be 25mbar and controlling the flash evaporation temperature to be 80 ℃; the rectification feeding speed is 0.02L/min, and the rectification vacuum degree is 15 mbar; the temperature of the bottom of the tower is 80 ℃, the temperature of the top of the tower is 35 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 86 percent.
3. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 10nm and 0.007kg of silane coupling agent KH-858 into 4.5kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 7.3kg of triethylenetetramine and 5.7kg of glyoxal, heating and refluxing for 3 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetone and deionized water, and drying to obtain a silicon dioxide graft modified polymer with the yield of 96%;
adding 1.2kg of chloroethylene carbonate and 3L of ethyl acetate into a carbon steel lining plastic storage tank to obtain mixed liquid, controlling the pumping pressure of a high-pressure plunger pump to be 1.5Mpa, continuously passing the mixed liquid through a three-stage tower reactor at the speed of 0.05L/min for carrying out elimination reaction, filling a silica grafted modified polymer filler into the tower reactor, heating the tower reactor to 100 ℃ to obtain a vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.05L/min, controlling the flash evaporation vacuum degree to be 30mbar and controlling the flash evaporation temperature to be 120 ℃; the rectification feeding speed is 0.05L/min, and the rectification vacuum degree is 20mbar; the temperature of the bottom of the tower is 100 ℃, the temperature of the top of the tower is 50 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 83 percent.
4. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 70nm and 0.01kg of silane coupling agent KH-858 into 5kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 5kg of triethylenetetramine and 3.5kg of glutaraldehyde, heating and refluxing for 4 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetonitrile and deionized water, and drying to obtain a silicon dioxide grafted modified polymer with the yield of 96%;
adding 0.37kg of chloroethylene carbonate and 1.5L of methyl ethyl carbonate into a carbon steel lining plastic storage tank to obtain mixed liquid, controlling the pumping pressure of a high-pressure plunger pump to be 1.1Mpa, continuously passing the mixed liquid through a three-stage tower reactor at the speed of 0.025L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 60 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.02L/min, controlling the flash evaporation vacuum degree to be 22mbar and controlling the flash evaporation temperature to be 70 ℃; the rectification feeding speed is 0.02L/min, and the rectification vacuum degree is 12 mbar; the temperature of the bottom of the tower is 70 ℃, the temperature of the top of the tower is 33 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 88 percent.
5. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 100nm and 0.009kg of silane coupling agent KH-858 into 4.7kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 9.4kg of hexaethyleneheptamine and 5.5kg of nonanal dialdehyde, heating and refluxing for 3.5 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetone and deionized water, and drying to obtain a silicon dioxide grafted modified polymer with the yield of 96%;
adding 0.84kg of chloroethylene carbonate and 2.4L of benzonitrile into a carbon steel lining plastic storage tank to obtain mixed liquid, controlling the pumping pressure of a high-pressure plunger pump to be 1.4Mpa, continuously passing the mixed liquid through a three-stage tower reactor at the speed of 0.04L/min to perform elimination reaction, filling a silica graft modified polymer filler into the tower reactor, heating the tower reactor to 90 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.04L/min, controlling the flash evaporation vacuum degree to be 28mbar and controlling the flash evaporation temperature to be 100 ℃; the rectification feeding speed is 0.04L/min, and the rectification vacuum degree is 17 mbar; the temperature of the bottom of the tower is 90 ℃, the temperature of the top of the tower is 40 ℃, and the VC with the purity of 99.95% is obtained, and the yield of the VC in the whole process is 86%.
6. A process for the continuous preparation of vinylene carbonate, characterized in that: the method comprises the following steps: synthesis of silica graft modified polymer: adding 1kg of silicon dioxide with the particle size of 500nm and 0.01kg of silane coupling agent KH-858 into 5kg of toluene, uniformly dispersing the system by using mechanical stirring, adding 2kg of ethylenediamine and 3kg of succinaldehyde, heating and refluxing for 3 hours under the protection of nitrogen, spin-drying the obtained product, washing with acetone and deionized water, and drying to obtain a silicon dioxide graft modified polymer with the yield of 95%;
adding 0.74kg of chloroethylene carbonate and 2.1L of tetrahydrofuran into a carbon steel lining plastic storage tank to obtain mixed liquid, controlling the pumping pressure of a high-pressure plunger pump to be 1.3Mpa, continuously passing the mixed liquid through a three-stage tower reactor at the speed of 0.035/L/min to perform elimination reaction, filling a silicon dioxide grafted modified polymer filler into the tower reactor, heating the tower reactor to 80 ℃ to obtain vinylene carbonate reaction liquid, pumping the reaction liquid out of the three-stage tower reactor, storing the reaction liquid in a 304 storage tank, and detecting that the chloroethylene carbonate content is lower than 0.1% through gas phase normalization;
purifying the vinylene carbonate reaction liquid by a flash evaporation device and a rectifying device, controlling the flash evaporation feeding speed to be 0.03L/min, controlling the flash evaporation vacuum degree to be 25mbar and controlling the flash evaporation temperature to be 90 ℃; the rectification feeding speed is 0.04L/min, and the rectification vacuum degree is 20mbar; the temperature of the bottom of the tower is 80 ℃, the temperature of the top of the tower is 35 ℃, and the VC with the purity of 99.95 percent is obtained, and the yield of the VC in the whole process is 84 percent.
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| CN104744423A (en) * | 2015-03-17 | 2015-07-01 | 沈阳化工大学 | Method for continuously producing vinylene carbonate |
| CN104844556A (en) * | 2015-04-30 | 2015-08-19 | 荣成青木高新材料股份有限公司 | Method for continuously preparing vinylene carbonate by tubular reactor |
| CN113527252A (en) * | 2021-09-17 | 2021-10-22 | 山东海科新源材料科技股份有限公司 | Method for synthesizing vinylene carbonate for electrolyte |
| CN114011107A (en) * | 2021-11-18 | 2022-02-08 | 中建安装集团有限公司 | Novel device and method for continuously producing high-purity vinylene carbonate |
| CN115073414A (en) * | 2022-06-22 | 2022-09-20 | 浙江天硕氟硅新材料科技有限公司 | Synthesis method of high-purity vinylene carbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104744423A (en) * | 2015-03-17 | 2015-07-01 | 沈阳化工大学 | Method for continuously producing vinylene carbonate |
| CN104844556A (en) * | 2015-04-30 | 2015-08-19 | 荣成青木高新材料股份有限公司 | Method for continuously preparing vinylene carbonate by tubular reactor |
| CN113527252A (en) * | 2021-09-17 | 2021-10-22 | 山东海科新源材料科技股份有限公司 | Method for synthesizing vinylene carbonate for electrolyte |
| CN114011107A (en) * | 2021-11-18 | 2022-02-08 | 中建安装集团有限公司 | Novel device and method for continuously producing high-purity vinylene carbonate |
| CN115073414A (en) * | 2022-06-22 | 2022-09-20 | 浙江天硕氟硅新材料科技有限公司 | Synthesis method of high-purity vinylene carbonate |
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