CN114917855B - Reaction system and method for continuously preparing perfluoroalkyl vinyl ether - Google Patents
Reaction system and method for continuously preparing perfluoroalkyl vinyl ether Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 74
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title abstract description 21
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 103
- 238000011084 recovery Methods 0.000 claims abstract description 85
- 239000002994 raw material Substances 0.000 claims abstract description 77
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 52
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 230000000911 decarboxylating effect Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 27
- 238000007599 discharging Methods 0.000 claims description 24
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 150000004673 fluoride salts Chemical class 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 3
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims description 3
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 36
- DAVCAHWKKDIRLY-UHFFFAOYSA-N 1-ethenoxy-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC=C DAVCAHWKKDIRLY-UHFFFAOYSA-N 0.000 description 15
- 239000012043 crude product Substances 0.000 description 13
- KNTAWQGTEDFAID-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propane Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(F)(F)F KNTAWQGTEDFAID-UHFFFAOYSA-N 0.000 description 10
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 8
- 239000007790 solid phase Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- RJBJXVAPYONTFE-UHFFFAOYSA-N 1,1,1,2,3,3-hexafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F RJBJXVAPYONTFE-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920001774 Perfluoroether Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1812—Tubular reactors
- B01J19/1818—Tubular reactors in series
-
- 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
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a reaction system and a method for continuously preparing perfluoroalkyl vinyl ether, wherein the reaction system comprises a salifying screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salifying screw reactor, and a decarboxylation screw reactor for decarboxylating carboxylate in the carboxylate solution, wherein a raw material recovery feed inlet of the raw material recovery reactor is connected with a first discharge outlet through a pipeline, and the raw material recovery reactor is also connected with a recovery tank for condensing and collecting unreacted raw materials; the reaction system also comprises a condenser, a product collecting tank and a bottom liquid collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, gas-phase products are collected in the product collecting tank through condensation of the product condenser, and liquid-solid mixed phase decarboxylation bottom liquid flows into the bottom liquid collecting tank through the pipeline. The invention can realize continuous salification and decarboxylation, has simple reaction operation steps and is easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of fluoride engineering, and particularly relates to a technology for preparing perfluoroalkyl vinyl ether.
Background
The perfluoroalkyl vinyl ether is a fluorine-containing monomer with wide application, and has a general formula:
the perfluoroalkyl vinyl ether has larger bond energy of C-F bond, so pi bond in double bond is more relaxed and is easy to polymerize with other monomers, thus being often used as a comonomer to be copolymerized with fluorine-containing olefin such as tetrafluoroethylene monomer and the like to obtain a special functional polymer material. In addition, because the copolymerization of the perfluoroalkyl vinyl ether introduces a flexible branched chain into the original high polymer chain, the crystallinity of the polymer is reduced, and other properties of the polymer, such as low temperature resistance, solvent resistance, toughness, tear resistance, adhesion performance with a base material and the like, can be improved on the basis of not changing the original excellent properties of the fluoropolymer.
There are many methods for preparing perfluoroalkyl vinyl ethers, mainly by thermal cracking to remove CO after reacting acyl fluorides with metal salt compounds to form carboxylates 2 And metal fluorides. The methods for preparing perfluoroalkyl vinyl ethers by salt decarboxylation of acyl fluorides can be divided into two main categories:
the first is to use a one-step process in which the acyl fluoride is directly decarboxylated with a metal carbonate in a reactor above the decarboxylation temperature of the intermediate carboxylate to give the vinyl ether.
The U.S. patent No. 3321532 adopts acyl fluoride and sodium carbonate to directly form salt in a tubular reactor for decarboxylation, the decarboxylation temperature is 300 ℃, and the yield is up to 95%; U.S. patent No. 3291843 also uses a tubular reactor where acyl fluoride and silica are cleaved to ether at 390 ℃ with yields up to 85%; chinese patent CN101213168A of 3M Innovative Co., ltd. Adopts acyl fluoride and metal carbonate in a stirred bed reactor at Wen Tuosuo, decarboxylation temperature of 100-300 ℃ and yield of about 70%; chinese patent CN1196666C from the company glauber's salt adopts a high temperature decarboxylation of acyl fluoride with metal carbonate in a fluidized bed with a conversion of 100%, but only 55%; the giant group company patent CN102702035B describes a method for continuously preparing fluorinated vinyl ether by using a twin-screw extruder, the front section of the twin-screw is salted and the rear section of the twin-screw is decarboxylated, the decarboxylation section temperature is 180-320 ℃, and the conversion rate is 88.2% at the maximum. As can be seen from the above patent, the yield of the vinyl ether prepared by one-step decarboxylation is not high, and the main problem is that in the solid phase decarboxylation process, the vinyl ether product can react with residual raw material acyl fluoride to generate byproducts, so that the product yield is reduced; in addition, due to the high solid phase decarboxylation temperature and uneven heating, the decomposition and carbonization of the vinyl ether product are easy to cause, so that the problems of carbon deposition and wall adhesion are caused, the reactor is difficult to clean, and the heat transfer effect of the reactor wall is reduced.
The second category is to adopt a two-step method comprising a two-step method of solid phase decarboxylation and a two-step method of liquid phase decarboxylation: the former refers to reacting acyl fluoride under the mixture of organic solvent and carbonate or in aqueous solution of sodium hydroxide, potassium hydroxide or sodium carbonate to form salt, then removing the solvent to obtain dry salt, and then directly raising Wen Tuosuo the dry salt to obtain vinyl ether product; the latter refers to the use of acyl fluorides in a mixture of solvent and carbonate salt at low temperature followed by decarboxylation at high temperature to give the product.
The Chinese-Hao morning photoperiod institute patent CN101659602B adopts a method of firstly removing solvent and then solid-phase decarboxylation in a reaction kettle or a cracking furnace, the patent describes that this method can reduce the amount of by-product hydrogen-containing ether, and the product yield is less than 80%; chinese patent CN100338013C from asahi chemical corporation reports a similar method for preparing fluorovinyl ethers by salt formation, desolventizing and then solid phase decarboxylation; the patent CN102992969B of Shanghai Sanai Fu New Material Co., ltd. Discloses a process route for producing fluorine-containing vinyl ether by acyl fluoride and cylindrical decarboxylation equipment with a scraping plate, namely, the acyl fluoride is salified, a solvent is removed, and then the acyl fluoride is coated in a scraping plate cylinder for heating and decarboxylation, wherein the decarboxylation temperature is 120-250 ℃, and the product yield can reach 96 percent at most. The two-step solid phase decarboxylation has the common problems of solid phase decarboxylation, namely, the decarboxylation temperature is high, side reactions are easy to occur, residues such as fluoride salt and the like are difficult to clean, and in addition, the two-step solid phase decarboxylation has the defects of complex operation and difficult solvent removal.
The method for obtaining perfluoroalkyl vinyl ether by adding organic amine as a catalyst into polar solvent, salifying perfluoroalkoxypropionyl fluoride and carbonate at low temperature and decarboxylating at 120-160 ℃ is disclosed in Chinese-Hao Chen photo-chemical institute patent CN101215225B, and the yield is 92.3%. The patent CN103965023B of the group of the neutral blue sky is prepared by decarboxylating perfluoro alkoxy propionyl fluoride and a salifying agent at 20-80 ℃ under the action of a catalyst to prepare corresponding fluoro alkyl vinyl ether, and the yield can reach 93.8% at the highest under a small amount of laboratory conditions. The above schemes are two-step liquid phase decarboxylation, they all adopt one pot reaction of reaction kettle, the solvent layer is thick, the products after decarboxylation can not pass through the solvent layer rapidly, stay in the solvent for a long time, can react with vinyl ether products and residual acyl fluoride raw materials in the solvent further to produce the accessory substance, and when adopting this one pot liquid phase decarboxylation, intermittent operation is many, can not continuous production, in addition, the solvent and catalyst used for liquid phase decarboxylation can not be recycled, have great influence on environment.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a reaction system and a method for continuously preparing perfluoroalkyl vinyl ether, which can continuously form salt and decarboxylate, and enable the salt forming and decarboxylation reaction to be more thorough.
In one aspect, a reaction system for continuously preparing perfluoroalkyl vinyl ether is provided, comprising a salifying screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salifying screw reactor, and a decarboxylation screw reactor for decarboxylating carboxylate in the carboxylate solution,
the salt forming screw reactor comprises a first tubular shell axially and horizontally arranged and a first screw arranged in the first tubular shell, blades are axially distributed on the first screw, a first feed inlet is formed in the front part of the first tubular shell, a first discharge outlet, a first exhaust outlet and a first bottom exhaust outlet are formed in the rear part of the first tubular shell, and the first discharge outlet is formed in the side wall of the middle upper part of the first tubular shell;
the raw material recovery feed inlet of the raw material recovery reactor is connected with the first discharge outlet through a pipeline, and the raw material recovery reactor is also connected with a recovery tank for condensing and collecting unreacted raw materials;
the decarboxylation screw reactor comprises a second tubular shell axially and horizontally arranged and a second screw arranged in the second tubular shell, blades are axially distributed on the second screw, a second feeding port is formed in the front part of the second tubular shell, a second discharging port, a second exhaust port and a second bottom exhaust port are formed in the rear part of the second tubular shell, and the second discharging port is formed in the side wall of the middle lower part of the second tubular shell;
the raw material recovery discharging port of the raw material recovery reactor is connected with the second feeding port, so that the salt solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor in the reaction process,
the reaction system also comprises a condenser, a product collecting tank and a bottom liquid collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, gas-phase products are collected in the product collecting tank through condensation of the product condenser, and liquid-solid mixed phase decarboxylation bottom liquid flows into the bottom liquid collecting tank through the pipeline.
Preferably, the blade is a helical blade or a paddle.
Preferably, the distance between the outer edge of the blade and the inner wall of the tubular shell is 1-10mm.
Preferably, the salt solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor by a metering pump.
Preferably, the salt forming screw reactor is provided with a first discharging shoveling plate corresponding to the first discharging hole.
Preferably, the decarboxylation screw reactor is correspondingly provided with a second discharging shoveling plate at the second discharging hole.
In another aspect, a method for continuously preparing perfluoroalkyl vinyl ether is provided, wherein the reaction system for continuously preparing perfluoroalkyl vinyl ether is used for continuous production, and the method comprises the following steps:
1) Adding a solvent and a salifying agent into a salifying screw reactor, continuously introducing acyl fluoride under stirring to enable the acyl fluoride and the salifying agent to generate salifying reaction to generate corresponding carboxylate, continuously supplementing the solvent and the salifying agent after the reaction is completed, and continuously reacting to obtain carboxylate solution;
2) Continuously flowing the carboxylate solution in the salifying screw reactor into a raw material recovery reactor, and continuously recovering unreacted acyl fluoride into a recovery tank under heating and stirring;
3) Carboxylate solution in the raw material recovery reactor is continuously pumped into a decarboxylation screw reactor, decarboxylation reaction is carried out under heating and stirring, perfluoroalkyl vinyl ether is obtained and is condensed and collected in a product collecting tank, and fluoride salt solid generated by decarboxylation is sent into a base solution collecting tank along with a solvent.
Preferably, the solvent is one or more of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and N-methylpyrrolidone; and/or the salt forming agent is one or two of potassium carbonate and sodium carbonate.
Preferably, the mass ratio of acyl fluoride to solvent participating in the reaction in the salt forming screw reactor is 1:0.5 to 5; and/or the molar ratio of acyl fluoride to salifying agent is 1:1 to 2.
Preferably, the reaction temperature in the salifying screw reactor is 5-40 ℃; and/or the reaction temperature in the decarboxylation screw reactor is 120-180 ℃.
The invention adopts the technical scheme and has the following beneficial effects:
preparing carboxylate solution in a salifying screw reactor, recovering unreacted acyl fluoride in the salifying screw reactor by a raw material recovery reactor, continuously pumping the carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor, carrying out decarboxylation reaction under heating and stirring to obtain perfluoroalkyl vinyl ether, condensing and collecting the perfluoroalkyl vinyl ether in a product collecting tank, and sending a fluoride salt solid generated by decarboxylation into a base solution collecting tank along with a solvent. Therefore, the method can continuously form salt and decarboxylate, has simple reaction operation steps, and is easy for industrial production.
Different from the conventional screw reactor, the screw reactor used in the invention is provided with a discharge hole at a specific height of the side surface, and is provided with a corresponding discharge shoveling plate, and the distance from the outer edge of the blade to the wall is required to be within a specified range;
firstly, a first discharge hole is arranged at the middle upper part of a first tubular shell, a second discharge hole is arranged at the middle lower part of a second tubular shell, and by arranging a proper discharge hole position, the sufficient reaction residence time can be ensured, so that the salt formation and decarboxylation reactions are more thorough; the liquid level of the salt solution in the decarboxylation screw reactor can be kept low, the thin layer decarboxylation is realized, the residence time of the product in the solvent is reduced, the production of byproducts is reduced, and the purity of the product is improved.
Secondly, the salt forming and decarboxylation screw reactors are provided with stirring paddles or helical blades, so that the reaction can occur under stirring and mixing, the uniformity of heating (or heat dissipation) is ensured, and the reaction is sufficient; and the discharge shoveling plate is matched with the discharge shoveling plate, and the distance from the outer edge of the shorter blade to the wall can ensure that fluoride salt generated by reaction is discharged along with the solvent in time, so that the accumulation of wall is avoided, the carbonization of the fluoride salt in the reactor is prevented, and the problem of frequent disassembly and cleaning of the reactor is solved.
In addition, the decarboxylation screw reactor can enable carboxylate solution to undergo continuous decarboxylation reaction under low-temperature heating and stirring, so that continuous low-temperature liquid-phase decarboxylation reaction can be performed under higher carboxylate solution concentration, continuous product discharge is kept, decarboxylation base solution is continuously discharged, the purity and yield of the product are improved, salt accumulation is reduced, and meanwhile, the decarboxylation screw reactor has certain advantages in improving yield and is suitable for industrial production.
The specific technical scheme and the beneficial effects of the invention are described in detail in the following detailed description with reference to the accompanying drawings.
Drawings
The invention is further described with reference to the drawings and detailed description which follow:
FIG. 1 is a schematic structural diagram of a reaction system for continuously producing perfluoroalkyl vinyl ethers according to the invention;
FIG. 2 is a schematic structural view of a salt-forming screw reactor according to the present invention;
FIG. 3 is a schematic view of the structure of the first screw in the present invention;
FIG. 4 is a schematic diagram of the structure of a decarboxylation screw reactor in the present invention;
FIG. 5 is a schematic view of the structure of the second screw of the present invention;
in the figure, the reference numerals are a salt forming screw reactor 1, a first feeding pipe 10, a second feeding pipe 11, a third feeding pipe 12, a first pipeline 13, a second pipeline 14, a third pipeline 15, a fourth pipeline 16, a fifth pipeline 17 and a sixth pipeline 18; a raw material recovery reactor 2, a first condenser 3, a recovery tank 4, a metering pump 5, a decarboxylation screw reactor 6, a bottom liquid collection tank 7, a second condenser 8 and a product collection tank 9;
the first pipe type shell 100, a first discharge port 112, a first condensate water outlet 113, a first bottom purge port 114, a first steam outlet 115, a first exhaust port 116, a motor 120, a first screw 130, paddle blades 131 and a first discharge shoveling plate 132;
the second pipe type shell 200, a second feed inlet 210, a second discharge outlet 212, a second condensate outlet 213, a second bottom drain outlet 214, a second steam outlet 215, a second exhaust outlet 216, a second screw 230, a helical blade 231 and a second discharge shoveling plate 232.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. The following description of at least one exemplary embodiment is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1 to 5, a reaction system for continuously producing a perfluoroalkyl vinyl ether comprises a salifying screw reactor 1 for producing a carboxylate solution, a raw material recovery reactor 2 for recovering unreacted acyl fluoride in the salifying screw reactor 1, a decarboxylation screw reactor 6 for decarboxylating carboxylate in the carboxylate solution, a first condenser 3, a second condenser 8, a product collection tank 9, and a base liquid collection tank 7.
As shown in fig. 2 and 3, the salifying screw reactor 1 includes a first tubular housing 100 disposed horizontally in an axial direction, a first screw 130 disposed in the first tubular housing, wherein blades are axially distributed on the first screw 130, a first feed inlet and a first condensate outlet 113 are disposed at a front portion of the first tubular housing 100, a first discharge outlet 112, a first exhaust outlet 116, a first bottom purge outlet 114, and a first steam outlet 115 are disposed at a rear portion of the first tubular housing 100, and the first discharge outlet 112 is disposed on a middle upper side wall of the first tubular housing 100.
As one embodiment, the blades provided on the first screw 130 are paddle blades 131. The paddle-shaped blades 131 are formed by welding round steel and comprise radial sections and axial sections, the middle parts of the axial sections are connected with the outer ends of the radial sections, and the radial sections and the axial sections form a T shape. Four sets of paddle blades 131 are provided in total, and are distributed axially along the first screw 130, and the four sets of paddle blades 131 are distributed at intervals of 90 degrees in the circumferential direction of the first screw 130, wherein the axial positions of two sets of paddle blades 131 on the first screw correspond to each other and are distributed at intervals of 180 degrees in the circumferential direction, and the axial positions of the other two sets of paddle blades 131 on the first screw correspond to each other and are distributed at intervals of 180 degrees in the circumferential direction. The two sets of paddle blades 131 and the other two sets of paddle blades 131 are staggered in the axial direction of the first screw, and the projections in the radial direction can be partially overlapped in the axial section.
Further, the edge of the paddle 131 is spaced from the inner wall of the first tubular housing 100 by a distance of 1 to 10mm, preferably 5mm. The first screw 130 is provided with a first discharging shoveling plate 132 corresponding to the first discharging hole 112.
Wherein, first feed inlet department is equipped with inlet pipe one 10, inlet pipe two 11, inlet pipe three 12. A first feed pipe 10 introduces a solvent into the salt-forming screw reactor 1, a second feed pipe 11 introduces an alkali metal carbonate into the salt-forming screw reactor 1, and a third feed pipe 12 introduces an acyl fluoride into the salt-forming screw reactor 1. The raw material recovery feed inlet of the raw material recovery reactor 2 is connected with a first discharge outlet 112 through a first pipeline 13, and the raw material recovery reactor 2 is also connected with a recovery tank 4 for condensing and collecting unreacted raw materials. The first steam outlet 115 is connected to the second pipe 14, the second pipe 14 is connected to the first condenser 3, and the third pipe 15 is connected between the raw material recovery reactor 2 and the recovery tank 4. Acyl fluoride and alkali metal carbonate react in the salifying screw reactor 1 to obtain carboxylate solution, the carboxylate solution flows into the raw material recovery reactor 2 through a first discharging shoveling plate 132 under the action of a first discharging shoveling plate 13, unreacted acyl fluoride and carbon dioxide generated by the reaction are collected in a recovery tank 4 through a third pipeline 15, and carbon dioxide tail gas enters a tail gas absorption system for absorption treatment.
In addition, referring to the existing tubular reactor, other structures of the salifying screw reactor 1 are further provided with a motor 120, a speed reducer, a sealing assembly and a jacket outside the reactor, wherein the motor 120 is connected with the speed reducer, and an output shaft of the speed reducer is connected with the first screw 130.
As shown in fig. 4 and 5, similar to the structure of the salt forming screw reactor 1, the decarboxylation screw reactor 6 includes a second tubular housing 200 horizontally disposed in an axial direction, a second screw 230 disposed in the second tubular housing, the second screw being axially provided with blades, a second inlet 210 and a second condensate outlet 213 being disposed at a front portion of the second tubular housing, and a second outlet 212, a second exhaust port 216, a second bottom purge port 214, and a second steam outlet 215 being disposed at a rear portion of the second tubular housing, the second outlet 212 being disposed at a middle-lower side wall of the second tubular housing 200.
Wherein, the raw material recovery discharging port of the raw material recovery reactor 2 is connected with the second feeding port, so that the salt solution in the raw material recovery reactor 2 is continuously fed into the decarboxylation screw reactor 6 in the reaction process. The second steam outlet 215 is connected to a fifth pipe 17, and the fifth pipe 17 is connected to the second condenser 8. The second condenser 8 is connected with the product collection tank 9 through a pipeline six 18.
As an embodiment, the blades provided on the second screw 230 are helical blades 231, and extend helically in the axial direction of the second screw 230. The edge of the spiral vane 231 is spaced from the inner wall of the second tubular housing 200 by a distance of 1-10mm, preferably 5mm. A second discharging shoveling plate 232 is arranged at the position of the second screw 230 corresponding to the second discharging hole 212.
Further, a connecting pipeline and a metering pump 5 are arranged between the raw material recovery discharging port of the raw material recovery reactor 2 and the second feeding port 210 of the decarboxylation screw reactor 6, and the salt solution in the raw material recovery reactor 2 is continuously fed into the decarboxylation screw reactor 6 by the metering pump 5.
When the reaction system is used, raw materials are continuously put into the salt forming screw reactor 1, and after stirring reaction is carried out for a certain time, the raw materials are continuously discharged to the raw material recovery reactor 2. The stirring reaction time in the salifying screw reactor 1 is determined by the position of a discharge hole, and the reasonable position of the discharge hole is arranged, so that the salifying reaction can be ensured to be thorough. In this embodiment, the first discharge port 112 is disposed at a position in the middle of the height of the first tubular housing 100, and the distance between the first discharge port and the center line of the first tubular housing in the height direction is 1-10cm, preferably 5cm.
The carboxylate solution entering the raw material recovery reactor 2 is continuously pumped into the decarboxylation screw reactor 6 by a metering pump 5 while the raw material acyl fluoride is recovered under stirring and heating, and the decarboxylation reaction is carried out under the heating of a reactor jacket of the decarboxylation screw reactor 6, so that a gas-phase product is obtained. The reaction residence time is determined by the position of a discharge hole, and through setting a proper position of the discharge hole, the salt solution liquid level in the reactor is kept low while the decarboxylation reaction is complete, so that the thin-layer decarboxylation is realized, and the byproducts are reduced. In this embodiment, the second discharging hole 212 is disposed at the lower part of the height of the second tubular housing 200, and the distance between the second discharging hole and the bottom wall in the second tubular housing is 1-20cm, preferably 5cm.
In addition, the fluoride salt solution generated by decarboxylation is spirally pushed to a second discharge hole by a second screw rod, the second discharge hole is connected with a pipeline IV 16, and the fluoride salt solution flows into the bottom solution collecting tank 7 under the action of a second discharge shoveling plate to prevent accumulation of fluoride salt in the reactor and wall formation. Finally, the crude product generated by the reaction is condensed and collected in a product collection tank 9 through a second condenser 8.
The invention also relates to a method for preparing perfluoroalkyl vinyl ether by taking perfluoroalkoxy acyl fluoride as a raw material and continuously salifying and decarboxylating:
1) Adding a proper amount of solvent and salifying agent into a salifying screw reactor, introducing low temperature water into a jacket of the reactor, continuously introducing acyl fluoride represented by a general formula (I) under stirring to carry out salifying reaction with the salifying agent to generate corresponding carboxylate (represented by the general formula (I)), continuously adding the solvent and the salifying agent according to a certain proportion after the reaction is completed, continuously reacting to obtain carboxylate solution, and synchronously generating CO 2 The acyl fluoride is condensed and recovered and then enters a tail gas absorption system for absorption treatment;
2) Continuously flowing carboxylate solution in the salifying screw reactor into a raw material recovery reactor under the action of a discharge shoveling plate, continuously recovering unreacted acyl fluoride into a recovery tank under stirring and heating, and collecting a certain amount for recycling;
3) Continuously pumping carboxylate solution in a raw material recovery reactor into a decarboxylation screw reactor, carrying out decarboxylation reaction under heating and stirring to obtain perfluoroalkyl vinyl ether represented by a formula (III), condensing and collecting the perfluoroalkyl vinyl ether in a product collecting tank, feeding fluoride salt solid generated by decarboxylation into a base solution collecting tank along with a solvent by a discharge shoveling plate, and recycling after centrifugal desalting, wherein the related reaction formula is as follows:
wherein M is an alkali metal atom; n=0, 1,2.
The solvent is one or more of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and N-methyl pyrrolidone, preferably tetraethylene glycol dimethyl ether.
The salt forming agent is one or two of potassium carbonate and sodium carbonate, preferably potassium carbonate.
The mass ratio of acyl fluoride to solvent which are reacted in the salifying screw reactor is 1:0.5 to 5, preferably 1:0.5 to 2, the mol ratio of acyl fluoride to salifying agent is 1: 1-2, preferably 1:1.05 to 1.25; the salt forming reaction temperature is 5-40 ℃, preferably 15-30 ℃; the recovery temperature of the acyl fluoride is 60-100 ℃, preferably 80-90 ℃; the decarboxylation temperature is 120-180 ℃, preferably 120-140 ℃, and in addition, the liquid level of the carboxylate solution in the decarboxylation screw reactor can be kept at 1-20cm, preferably 5-15cm through the arrangement of the position of a discharge hole.
The invention is further illustrated below with reference to examples.
Example 1:
10kg of solvent diethylene glycol dimethyl ether and 3.5kg of anhydrous sodium carbonate are added into a salifying screw reactor, stirring is started, raw material perfluoro (2-methyl-3-oxahexyl) fluoride is continuously pumped into the salifying screw reactor at the speed of 10kg/h, and the two materials react in the salifying screw reactor to generate salt, wherein the reaction temperature is controlled to be 30 ℃, and the reaction time is controlled to be 1h. After the reaction, continuously feeding diethylene glycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous sodium carbonate at a rate of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 80 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the sodium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 130 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
A total of 5 hours of feeding was carried out, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was fed, 2.6kg of acyl fluoride was recovered, and 35.2kg of perfluoro-n-propyl vinyl ether crude product was collected, wherein the perfluoro-n-propyl vinyl ether content was 96.25%. The perfluoro-n-propyl vinyl ether product yield was 89.21%.
Example 2:
10kg of solvent diethylene glycol dimethyl ether and 3.5kg of anhydrous sodium carbonate are added into a salifying screw reactor, stirring is started, raw material perfluoro (2-methyl-3-oxahexyl) fluoride is continuously pumped into the salifying screw reactor at the speed of 10kg/h, and the two materials react in the salifying screw reactor to generate salt, and the reaction temperature is controlled to be 15 ℃ and the reaction time is controlled to be 1h. After the reaction, continuously feeding diethylene glycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous sodium carbonate at a rate of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 90 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the sodium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 130 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
A total of 5 hours of feeding was performed, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was fed, 3.1kg of acyl fluoride was recovered, and 35.6kg of perfluoro-n-propyl vinyl ether crude product was collected, wherein the perfluoro-n-propyl vinyl ether content was 95.72%. The perfluoro-n-propyl vinyl ether product yield was 90.69%.
Example 3:
adding 10kg of solvent tetraethylene glycol dimethyl ether and 3.5kg of anhydrous sodium carbonate into a salt-forming screw reactor, starting stirring, continuously pumping raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at a speed of 10kg/h, and controlling the reaction temperature to be 30 ℃ and the reaction time to be 1h. After the reaction, continuously feeding tetraethyleneglycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous sodium carbonate at a rate of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 90 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the sodium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 140 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
A total of 5 hours of feeding was carried out, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was fed, 2.4kg of acyl fluoride was recovered, and 36.2kg of perfluoro-n-propyl vinyl ether crude product was collected, wherein the perfluoro-n-propyl vinyl ether content was 95.11%. The perfluoro-n-propyl vinyl ether product yield was 90.28%.
Example 4:
adding 10kg of solvent tetraethylene glycol dimethyl ether and 4.5kg of anhydrous potassium carbonate into a salt-forming screw reactor, starting stirring, continuously pumping raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at a speed of 10kg/h, and controlling the reaction temperature to be 30 ℃ and the reaction time to be 1h. After the reaction, continuously feeding tetraethyleneglycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous potassium carbonate at a rate of 4.5 kg/h;
after the obtained potassium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 90 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the potassium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 140 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
A total of 5 hours of feeding was carried out, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was fed, 2.3kg of acyl fluoride was recovered, and 36.5kg of perfluoro-n-propyl vinyl ether crude product was collected, wherein the perfluoro-n-propyl vinyl ether content was 96.78%. The perfluoro-n-propyl vinyl ether product yield was 92.43%.
Example 5:
adding 10kg of solvent tetraethylene glycol dimethyl ether and 3.0kg of anhydrous potassium carbonate into a salifying screw reactor, starting stirring, continuously pumping raw materials 2, 5-bis (trifluoromethyl) -3, 6-dioxaundecanoyl fluoride into the salifying screw reactor at a speed of 10kg/h, and performing salifying reaction in the salifying screw reactor, wherein the reaction temperature is controlled to be 30 ℃, and the reaction time is controlled to be 1h. After the reaction, continuously feeding diethylene glycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous potassium carbonate at a rate of 3.0 kg/h;
after the obtained potassium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 80 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the potassium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 140 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
The total charge was 5h, 50kg of the starting material 2, 5-bis (trifluoromethyl) -3, 6-dioxaundecano fluorononanoyl fluoride was charged, 1.1kg of the acyl fluoride was recovered, and the yield of 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether was collected as a crude product of 39.7kg, wherein the 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether content was 93.81%. The yield of 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether was 87.80%.
Example 6:
adding 10kg of solvent tetraethylene glycol dimethyl ether and 4.5kg of anhydrous potassium carbonate into a salt-forming screw reactor, starting stirring, continuously pumping raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at a speed of 10kg/h, and controlling the reaction temperature to be 30 ℃ and the reaction time to be 1h. After the reaction, continuously feeding tetraethyleneglycol dimethyl ether at a rate of 10kg/h and continuously feeding anhydrous potassium carbonate at a rate of 4.5 kg/h;
after the obtained potassium carboxylate solution reaches the position of a discharge hole, continuously flowing into a raw material recovery reactor under the action of a discharge shoveling plate, starting the raw material recovery reactor to stir, controlling the temperature to be 90 ℃, and collecting unreacted acyl fluoride in a recovery tank through a recovery condenser;
the potassium carboxylate solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor at the speed of 20kg/h by a metering pump, decarboxylation reaction is carried out in the decarboxylation screw reactor, the reaction temperature is 140 ℃, and the crude product generated by the reaction is condensed by a condenser and is collected in a product collecting tank.
For 1 month, adding 2330.5kg of perfluoro (2-methyl-3-oxahexyl) fluoride, wherein 101.2kg of acyl fluoride is recovered (90 kg is recycled into the system, and the rest 11.2kg is collected in a recovery tank), and 1785.8kg of perfluoro-n-propyl vinyl ether crude product is collected, wherein the perfluoro-n-propyl vinyl ether content is 96.10%. The perfluoro-n-propyl vinyl ether product yield was 92.07%. The reactor is disassembled, and the phenomenon of salt accumulation and wall formation is basically avoided by removing a small amount of salt-containing solution in the reactor.
While the invention has been described in terms of specific embodiments, it will be appreciated by those skilled in the art that the invention is not limited to the specific embodiments described above. Any modifications which do not depart from the functional and structural principles of the present invention are intended to be included within the scope of the appended claims.
Claims (4)
1. A reaction system for continuously preparing perfluoroalkyl vinyl ether is characterized by comprising a salifying screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salifying screw reactor and a decarboxylation screw reactor for decarboxylating carboxylate in the carboxylate solution,
the salt forming screw reactor comprises a first tubular shell axially and horizontally arranged and a first screw arranged in the first tubular shell, blades are axially distributed on the first screw, a first feed inlet is formed in the front part of the first tubular shell, a first discharge outlet, a first exhaust outlet and a first bottom exhaust outlet are formed in the rear part of the first tubular shell, and the first discharge outlet is formed in the side wall of the middle upper part of the first tubular shell;
the raw material recovery feed inlet of the raw material recovery reactor is connected with the first discharge outlet through a pipeline, and the raw material recovery reactor is also connected with a recovery tank for condensing and collecting unreacted raw materials;
the decarboxylation screw reactor comprises a second tubular shell axially and horizontally arranged and a second screw arranged in the second tubular shell, blades are axially distributed on the second screw, a second feeding port is formed in the front part of the second tubular shell, a second discharging port, a second exhaust port and a second bottom exhaust port are formed in the rear part of the second tubular shell, and the second discharging port is formed in the side wall of the middle lower part of the second tubular shell;
the raw material recovery discharging port of the raw material recovery reactor is connected with the second feeding port, so that the salt solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor in the reaction process,
the reaction system also comprises a condenser, a product collecting tank and a bottom liquid collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, gas-phase products are condensed and collected in the product collecting tank through the product condenser, and liquid-solid mixed phase decarboxylation bottom liquid flows into the bottom liquid collecting tank through a pipeline;
the distance between the outer edges of the blades and the inner wall of the tubular shell is 1-10mm, a first discharging shoveling plate is arranged at a first discharging hole of the salt-forming screw reactor, and a second discharging shoveling plate is arranged at a second discharging hole of the decarboxylation screw reactor;
the continuous production is carried out by adopting the reaction system, which comprises the following steps:
1) Adding a solvent and a salifying agent into a salifying screw reactor, and continuously introducing acyl fluoride under stirring, wherein the mass ratio of the acyl fluoride to the solvent is 1: 0.5-5, wherein the mol ratio of acyl fluoride to salifying agent is 1: 1-2, controlling the reaction temperature to be 5-40 ℃, enabling acyl fluoride and a salifying agent to generate salifying reaction to generate corresponding carboxylate, continuously supplementing a solvent and the salifying agent after the reaction is completed, and continuously reacting to obtain carboxylate solution;
2) Continuously flowing the carboxylate solution in the salifying screw reactor into a raw material recovery reactor, and continuously recovering unreacted acyl fluoride into a recovery tank under heating and stirring;
3) And continuously pumping carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor, and carrying out decarboxylation reaction under heating and stirring, wherein the reaction temperature is 120-180 ℃, obtaining perfluoroalkyl vinyl ether, condensing and collecting the perfluoroalkyl vinyl ether in a product collecting tank, and conveying fluoride salt solid generated by decarboxylation into a base solution collecting tank along with a solvent.
2. A reaction system for continuously preparing perfluoroalkyl vinyl ethers according to claim 1, wherein: the blade is a helical blade or a paddle.
3. A reaction system for continuously preparing perfluoroalkyl vinyl ethers according to claim 1, wherein: the salt solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor by a metering pump.
4. A reaction system for continuously preparing perfluoroalkyl vinyl ethers according to claim 1, wherein: the solvent is one or more than two of diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and N-methyl pyrrolidone; and/or the salt forming agent is one or two of potassium carbonate and sodium carbonate.
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Denomination of invention: A reaction system and method for continuous preparation of perfluoroalkyl vinyl ether Granted publication date: 20240312 Pledgee: Bank of Jinhua Limited by Share Ltd. Pledgor: ZHEJIANG YONGHE FLUOROCHEMICAL CO.,LTD. Registration number: Y2024980041896 |