CN114917855A - 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 83
- -1 perfluoroalkyl vinyl ether Chemical compound 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 104
- 239000002994 raw material Substances 0.000 claims abstract description 79
- 238000011084 recovery Methods 0.000 claims abstract description 69
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 51
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 33
- 230000000911 decarboxylating effect Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 26
- 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 17
- 238000004064 recycling Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 11
- 230000001502 supplementing effect Effects 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 9
- 150000004673 fluoride salts Chemical class 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 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
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 42
- 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
- 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 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 10
- 229910052700 potassium Inorganic materials 0.000 description 9
- 239000011591 potassium Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000007790 solid phase Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007789 gas Substances 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
- 229920001774 Perfluoroether Polymers 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
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 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
- 238000004140 cleaning Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 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
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 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
- 239000011521 glass Substances 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 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
- 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
- 238000003466 welding Methods 0.000 description 1
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- 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
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- 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, which comprises a salt-forming screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salt-forming 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 further comprises a condenser, a product collecting tank and a base solution collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, a gas-phase product is condensed and collected in the product collecting tank through the product condenser, and a liquid-solid mixed phase decarboxylation base solution flows into the base solution collecting tank through a 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 fluorine chemical industry, and particularly relates to a technology for preparing perfluoroalkyl vinyl ether.
Background
Perfluoroalkyl vinyl ether is a widely used fluorine-containing monomer, and has a general formula:
the perfluoroalkyl vinyl ether has larger bond energy due to the C-F bond, so that the pi bond in the contained double bond is more relaxed and is easy to polymerize with other monomers, and the perfluoroalkyl vinyl ether is often used as a comonomer and copolymerized with fluorine-containing olefin such as tetrafluoroethylene monomer to obtain a special functional polymer material. In addition, due to the copolymerization of the perfluoroalkyl vinyl ether, a flexible branched chain is introduced into the original high molecular chain, and the crystallinity of the polymer is reduced, so that other properties of the polymer, such as low temperature resistance, solvent resistance, toughness, tearing resistance, bonding performance with a base material and the like, can be improved on the basis of not changing the original excellent properties of the fluoropolymer.
Perfluoroalkyl vinyl ethers are prepared by a number of processes, mainly by the thermal cracking of acyl fluorides after reaction with metal salt compounds to form carboxylic acid salts 2 And metal fluorides. The method for preparing perfluoroalkyl vinyl ether by salifying and decarboxylating acyl fluoride mainly comprises two types:
the first method is one-step process, in which acyl fluoride reacts with metal carbonate to decarboxylate in a reactor at the decarboxylation temperature higher than that of intermediate carboxylate to obtain vinyl ether.
In the US3321532, acyl fluoride and sodium carbonate are directly salified and decarboxylated in a tubular reactor, wherein the decarboxylation temperature is 300 ℃, and the highest yield is 95%; U.S. Pat. No. 3,3291843 also uses a tubular reactor, where acyl fluoride and silica are cracked into ethers at 390 deg.C, with a yield up to 85%; the Chinese patent CN101213168A of 3M Innovation limited company adopts acyl fluoride and metal carbonate to carry out high-temperature decarboxylation in a stirred bed reactor, wherein the decarboxylation temperature is 100-300 ℃, and the yield is about 70%; the Chinese patent CN1196666C of Asahi glass company adopts the method of decarboxylation of acyl fluoride and metal carbonate in a fluidized bed at high temperature, the conversion rate is 100%, but the yield is only 55%; the patent CN102702035B of Juhua group company describes a method for continuously preparing fluorinated vinyl ether by using a double-screw extruder, wherein the front section of the double screw extruder is salified and the rear section of the double screw extruder is decarboxylated, the temperature of the decarboxylation section is 180-320 ℃, and the highest conversion rate is 88.2%. As can be seen from the above patents, the yield of the olefin ether prepared by decarboxylation in one step is not high, and the main problem is that during the solid-phase decarboxylation process, the olefin ether product reacts with the residual raw material acyl fluoride to generate a byproduct, thereby reducing the product yield; in addition, the solid phase decarboxylation temperature is high, the heating is uneven, the decomposition and carbonization of the olefin ether product are easily caused, 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 type adopts a two-step method, comprising two-step solid phase decarboxylation and two-step liquid phase decarboxylation: the former method comprises the steps of reacting acyl fluoride in a mixture of an organic solvent and carbonate or an aqueous solution of sodium hydroxide, potassium hydroxide or sodium carbonate to form salt, removing the solvent to obtain dry salt, and performing high-temperature decarboxylation on the dry salt to obtain an olefin ether product; the latter refers to the use of acyl fluoride to form a salt at low temperature in a mixture of solvent and carbonate, followed by decarboxylation at high temperature to give the product.
The patent CN101659602B of Zhonghao Chen photochemical research institute adopts a method of firstly removing a solvent and then performing solid-phase decarboxylation in a reaction kettle or a cracking furnace, and describes that the method can reduce the amount of by-products, namely hydrogen-containing ether, and the product yield is less than 80 percent; the similar method of preparing fluorine-containing vinyl ether by salt desolvation and solid-phase decarboxylation is reported in the Chinese patent CN100338013C of Asahi chemical Co Ltd; a process for preparing fluorine-containing vinyl ether from acyl fluoride and a cylindrical decarboxylation apparatus with scraper are disclosed in Shanghai Sanai-Fuxin New Material Co., Ltd, patent CN102992969B, which comprises salifying acyl fluoride, removing solvent, coating in a scraper cylinder, heating for decarboxylation at 120-250 deg.C and the highest product yield can reach 96%. The schemes belong to two-step solid phase decarboxylation, and have the common problems of the solid phase decarboxylation, namely high decarboxylation temperature, easy occurrence of side reaction, difficult cleaning of generated fluoride salt and other residues, and in addition, the two-step solid phase decarboxylation also has the defects of complex operation and difficult solvent removal.
The patent CN101215225B of Zhonghao Chen optical chemical research institute discloses a method for obtaining perfluoroalkyl vinyl ether by adding organic amine as a catalyst into a polar solvent, forming salt of perfluoroalkoxy propionyl fluoride and carbonate at low temperature, and decarboxylating at 120-160 ℃, wherein the yield of the perfluoroalkyl vinyl ether reaches 92.3%. Under the action of a catalyst, perfluoro alkoxy propionyl fluoride and a salt forming agent are salified at 20-80 ℃, and decarboxylation is performed at 110-150 ℃ to prepare the corresponding fluoroalkyl vinyl ether, so that the highest yield can reach 93.8% under the preparation of a small amount of laboratory conditions. The technical scheme is two-step liquid phase decarboxylation, the two steps of liquid phase decarboxylation adopt a reaction kettle one-pot method for reaction, the solvent layer is thick, a product after decarboxylation cannot rapidly penetrate through the solvent layer, the product stays in a solvent for a long time, and can further react with an alkene ether product in the solvent and a residual acyl fluoride raw material to generate a byproduct, and when the one-pot method is adopted for liquid phase decarboxylation, the intermittent operation is more, continuous production cannot be realized, in addition, the solvent and the catalyst used for the liquid phase decarboxylation cannot be recycled, and the environmental influence is large.
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 decarboxylation, and enable the salt forming and decarboxylation reactions to be more thorough.
On the one hand, the reaction system for continuously preparing the perfluoroalkyl vinyl ether is provided, which comprises a salt-forming screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salt-forming screw reactor and a decarboxylation screw reactor for decarboxylating carboxylate in the carboxylate solution, wherein,
the salifying screw reactor comprises a first tubular shell and a first screw, wherein the first tubular shell is axially and horizontally arranged, the first screw is arranged in the first tubular shell, blades are axially distributed on the first screw, a first feed port is formed in the front part of the first tubular shell, a first discharge port, a first exhaust port and a first bottom exhaust port are formed in the rear part of the first tubular shell, and the first discharge port 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 and a second screw, wherein the second tubular shell is axially and horizontally arranged, the second screw is arranged in the second tubular shell, blades are axially distributed on the second screw, a second feed port is formed in the front part of the second tubular shell, a second discharge port, a second exhaust port and a second bottom drain port are formed in the rear part of the second tubular shell, and the second discharge port is formed in the side wall of the middle lower part of the second tubular shell;
the raw material recycling discharge hole of the raw material recycling reactor is connected with the second feed hole, so that the salt solution in the raw material recycling reactor is continuously fed into the decarboxylation screw reactor in the reaction process,
the reaction system further comprises a condenser, a product collecting tank and a base solution collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, a gas-phase product is condensed and collected in the product collecting tank through the product condenser, and a liquid-solid mixed phase decarboxylation base solution flows into the base solution collecting tank through a pipeline.
Preferably, the blade is a helical blade or a paddle blade.
Preferably, the distance between the outer edge of the blade and the inner wall of the tubular shell is 1-10 mm.
Preferably, the salt solution in the feed recovery reactor is continuously fed to 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 port.
Preferably, the decarboxylation screw reactor is provided with a second discharge shoveling plate corresponding to the second discharge port.
In another aspect, a method for continuously preparing perfluoroalkyl vinyl ether is provided, which uses the reaction system for continuously preparing perfluoroalkyl vinyl ether to perform continuous production, and comprises the following steps:
1) adding a solvent and a salt forming agent into a salt forming screw reactor, continuously introducing acyl fluoride under stirring to perform salt forming reaction on the acyl fluoride and the salt forming agent to generate corresponding carboxylate, continuously supplementing the solvent and the salt forming agent after the reaction is completed, and continuously reacting to obtain a carboxylate solution;
2) continuously flowing carboxylate solution in the salifying screw reactor into a raw material recovery reactor, and continuously recovering unreacted acyl fluoride into a recovery tank under the conditions of heating and stirring;
3) and continuously pumping a carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor, heating and stirring to perform decarboxylation reaction to obtain perfluoroalkyl vinyl ether, condensing and collecting the perfluoroalkyl vinyl ether in a product collecting tank, and conveying a fluoride salt solid generated by decarboxylation into a base solution collecting tank along with a solvent.
Preferably, the solvent is one or a combination of 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 the combination of potassium carbonate and sodium carbonate.
Preferably, the mass ratio of the acyl fluoride and the 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 salt forming agent is 1: 1 to 2.
Preferably, the reaction temperature in the salt-forming screw reactor is 5-40 ℃; and/or the reaction temperature in the decarboxylation screw reactor is 120-180 ℃.
By adopting the technical scheme, the invention has the following beneficial effects:
preparing carboxylate solution in a salt-forming screw reactor, recovering unreacted acyl fluoride in the salt-forming 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 a decarboxylation reaction under heating and stirring to obtain 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. Therefore, the method can continuously salify 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 port at a specific height on the side surface and a corresponding discharge shoveling plate at the same time, and the distance between the outer edge of the blade and the wall is required to be within a specified range;
firstly, a first discharge port is arranged at the middle upper part of a first tubular shell, a second discharge port is arranged at the middle lower part of a second tubular shell, and a proper discharge port position is arranged, so that enough reaction residence time can be ensured, and salt forming and decarboxylation reactions are more thorough; and the liquid level of the salt solution in the decarboxylation screw reactor can be kept low, thin-layer decarboxylation is realized, the retention time of the product in the solvent is reduced, the generation of byproducts is reduced, and the product purity is improved.
Secondly, the salifying and decarboxylating screw reactors are provided with stirring paddles or helical blades, so that the reaction can be carried out under stirring and mixing, the uniform heating (or heat dissipation) is ensured, and the reaction is sufficient; and the discharging shoveling plates are matched with the reactor, and the distance between the outer edge of the blade and the wall is shorter, so that fluoride salt generated by the reaction can be discharged along with a solvent in time, the wall is not accumulated, the fluoride salt is prevented from being carbonized in the reactor, and the problem of frequent disassembly and cleaning of the reactor is solved.
In addition, adopt this decarboxylation screw reactor, can make carboxylate solution take place continuous decarboxylation under the low temperature heating stirring, realize under higher carboxylate solution concentration, also can carry out continuous low temperature liquid phase decarboxylation, keep the product to discharge in succession, and the continuous row of decarboxylation base solution expects, promote product purity and yield, when reducing the long-pending salt, also have certain advantage to promoting output, suitable industrial production uses.
The following detailed description of the present invention will be provided in conjunction with the accompanying drawings.
Drawings
The invention is further described with reference to the accompanying drawings and the detailed description below:
FIG. 1 is a schematic diagram of a reaction system for continuously preparing a perfluoroalkylvinyl ether according to the present invention;
FIG. 2 is a schematic view of the structure of a salt-forming screw reactor according to the present invention;
FIG. 3 is a schematic view of the first screw of the present invention;
FIG. 4 is a schematic diagram of the decarboxylation screw reactor of the present invention;
FIG. 5 is a schematic view of the second screw of the present invention;
the reference numbers in the figure are that a salifying 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; the system comprises a raw material recovery reactor 2, a first condenser 3, a recovery tank 4, a metering pump 5, a decarboxylation screw reactor 6, a base solution collection tank 7, a second condenser 8 and a product collection tank 9;
a first tubular shell 100, a first discharge port 112, a first condensed water outlet 113, a first bottom drain port 114, a first steam outlet 115, a first exhaust port 116, a motor 120, a first screw 130, a paddle blade 131, and a first discharge shovelling plate 132;
a second tubular shell 200, a second feed inlet 210, a second discharge outlet 212, a second condensed water 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 shovelling plate 232.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1 to 5, a reaction system for continuously preparing perfluoroalkyl vinyl ether comprises a salt-forming screw reactor 1 for preparing carboxylate solution, a raw material recovery reactor 2 for recovering unreacted acyl fluoride in the salt-forming 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 collecting tank 9, and a base solution collecting tank 7.
As shown in fig. 2 and fig. 3, the salt-forming screw reactor 1 includes a first tubular casing 100 disposed horizontally in the axial direction, and a first screw 130 disposed in the first tubular casing, where the first screw 130 has blades distributed along the axial direction, a first feed port and a first condensed water outlet 113 are disposed at the front portion of the first tubular casing 100, a first discharge port 112, a first exhaust port 116, a first bottom drain port 114, and a first steam outlet 115 are disposed at the rear portion of the first tubular casing 100, and the first discharge port 112 is disposed at the middle upper side wall of the first tubular casing 100.
In one embodiment, the blades of the first screw 130 are paddle-shaped blades 131. Paddle blade 131 comprises round steel welding, including radial section and axial segment, and the middle part of axial segment is connected with the outer end of radial section, and radial section and axial segment constitution T font. A total of four sets of paddle blades 131 are provided, 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 two sets of paddle blades 131 correspond to axial positions on the first screw and are distributed at intervals of 180 degrees in the circumferential direction, and the other two sets of paddle blades 131 correspond to axial positions on the first screw and are distributed at intervals of 180 degrees in the circumferential direction. The two groups of paddle blades 131 and the other two groups of paddle blades 131 are staggered in the axial direction on the first screw, but the projections in the radial direction may partially overlap in the axial section.
Further, the edge of the paddle blade 131 is spaced from the inner wall of the first tubular housing 100 by a distance of 1 to 10mm, preferably 5 mm. A first discharging shovelling plate 132 is arranged at the position of the first screw 130 corresponding to the first discharging port 112.
Wherein, the first feed inlet is provided with a first feed pipe 10, a second feed pipe 11 and a third feed pipe 12. Feed line one 10 introduces solvent into the salt-forming screw reactor 1, feed line two 11 introduces alkali metal carbonate into the salt-forming screw reactor 1, and feed line three 12 introduces acyl fluoride into the salt-forming screw reactor 1. The raw material recycling feed inlet of the raw material recycling reactor 2 is connected with the first discharge outlet 112 through a first pipeline 13, and the raw material recycling reactor 2 is further connected with a recycling tank 4 for condensing and collecting unreacted raw materials. The first steam outlet 115 is connected with a second pipeline 14, the second pipeline 14 is connected with the first condenser 3, and a third pipeline 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 a carboxylate solution, the carboxylate solution flows into the raw material recovery reactor 2 through a pipeline I13 under the action of a first discharging shoveling plate 132, unreacted acyl fluoride flows through a pipeline III 15 along with carbon dioxide generated by the reaction, condensate is collected in a recovery tank 4, and carbon dioxide tail gas enters a tail gas absorption system for absorption treatment.
In addition, the other structures of the salt-forming screw reactor 1 refer to the existing tubular reactor, and 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 the axial direction, and a second screw 230 disposed in the second tubular housing, wherein blades are axially distributed on the second screw, a second feed inlet 210 and a second condensed water outlet 213 are disposed at the front portion of the second tubular housing, a second discharge outlet 212, a second exhaust port 216, a second bottom drain outlet 214, and a second steam outlet 215 are disposed at the rear portion of the second tubular housing, and the second discharge outlet 212 is disposed at a sidewall of a lower middle portion of the height of the second tubular housing 200.
Wherein, the raw material recycling discharge hole of the raw material recycling reactor 2 is connected with the second feed inlet, so that the salt solution in the raw material recycling reactor 2 is continuously fed into the decarboxylation screw reactor 6 in the reaction process. The second steam outlet 215 is connected to the pipe five 17, and the pipe five 17 is connected to the second condenser 8. The second condenser 8 is connected with the product collecting tank 9 through a pipeline six 18.
In one embodiment, the blades of 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 to 10mm, preferably 5 mm. A second discharging shovelling plate 232 is arranged at the position of the second screw 230 corresponding to the second discharging port 212.
Furthermore, a connecting pipeline and a metering pump 5 are arranged between the raw material recycling discharge port of the raw material recycling reactor 2 and the second feed port 210 of the decarboxylation screw reactor 6, and the salt solution in the raw material recycling reactor 2 is continuously fed into the decarboxylation screw reactor 6 through the metering pump 5.
When the reaction system is used, raw materials are continuously fed into the salt-forming screw reactor 1, stirred and reacted for a certain time, and then continuously discharged to the raw material recovery reactor 2. The stirring reaction time in the salification screw reactor 1 is determined by the position of the discharge port, and the reasonable position of the discharge port is set, so that the salification reaction can be ensured to be thorough. In this embodiment, the first discharge port 112 is disposed at the middle position of the first tubular housing 100, and the distance between the first discharge port and the centerline of the first tubular housing in the height direction is 1-10cm, preferably 5 cm.
And (3) the carboxylate solution entering the raw material recovery reactor 2 is stirred and heated, while the raw material acyl fluoride is recovered, continuously fed into a decarboxylation screw reactor 6 by a metering pump 5, and subjected to decarboxylation reaction under the heating of a reactor jacket of the decarboxylation screw reactor 6 to obtain a gas-phase product. The reaction residence time is determined by the position of the discharge port, and by setting the proper position of the discharge port, the decarboxylation reaction can be ensured to be thorough, the liquid level of the salt solution in the reactor is kept low, the thin-layer decarboxylation is realized, and the byproducts are reduced. In this embodiment, the second discharge port 212 is disposed at the lower part of the height of the second tubular housing 200, and the distance between the second discharge port and the inner bottom wall of the second tubular housing is 1-20cm, preferably 5 cm.
In addition, the fluoride salt solution that decarboxylation produced is spiral propelling movement to the second discharge gate by the second screw rod, and second discharge gate connecting tube four 16 flows into base solution collecting tank 7 under the effect of second ejection of compact flight, prevents that fluoride salt from gathering, the knot wall in reactor inside. Finally, the crude product generated by the reaction is condensed and collected in a product collecting tank 9 by a second condenser 8.
The invention also relates to a method for preparing perfluoroalkyl vinyl ether by continuously salifying and decarboxylating by taking the perfluoroalkoxy acyl fluoride as the raw material, which comprises the following steps:
1) adding a proper amount of solvent and salt forming agent into a salt-forming 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 perform salt-forming reaction with the salt forming agent to generate corresponding carboxylate (represented by the general formula (I)), continuously supplementing the solvent and the salt forming agent according to a certain proportion after the reaction is completed, continuously reacting to obtain a carboxylate solution, and synchronously generating CO 2 Condensing and recovering acyl fluoride, and then performing absorption treatment on the tail gas in a tail gas absorption system;
2) continuously flowing carboxylate solution in the salifying screw reactor into a raw material recovery reactor under the action of a discharging shoveling plate, continuously recovering unreacted acyl fluoride into a recovery tank under stirring and heating, and collecting a certain amount of acyl fluoride for recycling;
3) the continuous pumping of carboxylate solution in the raw materials recovery reactor is to the decarboxylation screw reactor in, takes place decarboxylation reaction under the heating stirring, obtains the perfluoroalkyl vinyl ether that formula (III) shows, and the condensation is collected in the product collecting tank, and the fluoride salt solid that the decarboxylation produced is along with the solvent, sends into the base solution collecting tank by ejection of compact flight, recycles after the centrifugation desalination, and relevant reaction formula is as follows:
wherein M is an alkali metal atom; n is 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 participating in the reaction in the salt-forming screw reactor is 1: 0.5 to 5, preferably 1: 0.5-2, wherein the molar ratio of the acyl fluoride to the salt forming agent is 1: 1-2, preferably 1: 1.05 to 1.25; the temperature of the salt forming reaction is 5-40 ℃, preferably 15-30 ℃; the recovery temperature of the acyl fluoride is 60-100 ℃, preferably 80-90 ℃; the heating 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 between 1 and 20cm, preferably between 5 and 15cm through the position arrangement of a discharge port.
The invention is further illustrated by the following examples.
Example 1:
adding 10kg of diethylene glycol dimethyl ether and 3.5kg of anhydrous sodium carbonate into a salt-forming screw reactor, starting stirring, continuously pumping a raw material of perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the perfluoro (2-methyl-3-oxahexyl) fluoride in the salt-forming screw reactor, controlling the reaction temperature to be 30 ℃, and reacting for 1 h. After the reaction is finished, diethylene glycol dimethyl ether is continuously supplemented at the speed of 10kg/h, and anhydrous sodium carbonate is continuously supplemented at the speed of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the discharge hole, the sodium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 80 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
and feeding the sodium carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor at a speed of 20kg/h continuously by a metering pump, carrying out a decarboxylation reaction in the decarboxylation screw reactor at a reaction temperature of 130 ℃, condensing a crude product generated by the reaction by a condenser, and collecting the crude product in a product collecting tank.
In total, the amount of the raw material was 5 hours, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was charged, 2.6kg of the acyl fluoride was recovered, and 35.2kg of a crude perfluoro-n-propyl vinyl ether product having a perfluoro-n-propyl vinyl ether content of 96.25% was collected. The yield of perfluoro-n-propyl vinyl ether product is 89.21%.
Example 2:
adding 10kg of diethylene glycol dimethyl ether and 3.5kg of anhydrous sodium carbonate serving as solvents into a salt-forming screw reactor, starting stirring, continuously pumping the raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the diethyl glycol dimethyl ether and the anhydrous sodium carbonate in the salt-forming screw reactor, and controlling the reaction temperature to be 15 ℃ and the reaction time to be 1 h. After the reaction is finished, continuously supplementing diethylene glycol dimethyl ether at the speed of 10kg/h, and continuously supplementing anhydrous sodium carbonate at the speed of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the discharge hole, the sodium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 90 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
sodium carboxylate solution in the raw material recovery reactor is continuously fed into a 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 crude products generated by the reaction are condensed by a condenser and collected in a product collecting tank.
For a total of 5 hours, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride was charged, wherein 3.1kg of acyl fluoride was recovered, and 35.6kg of a crude perfluoro-n-propyl vinyl ether product having a perfluoro-n-propyl vinyl ether content of 95.72% was collected. The yield of the perfluoro-n-propyl vinyl ether product is 90.69 percent.
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 a raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the perfluoro (2-methyl-3-oxahexyl) fluoride and the raw material in the salt-forming screw reactor, controlling the reaction temperature to be 30 ℃, and reacting for 1 h. After the reaction is finished, continuously supplementing tetraethyleneglycol dimethyl ether at the speed of 10kg/h, and continuously supplementing anhydrous sodium carbonate at the speed of 3.5 kg/h;
after the obtained sodium carboxylate solution reaches the discharge port, the sodium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 90 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
and feeding the sodium carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor at a speed of 20kg/h continuously by a metering pump, carrying out a decarboxylation reaction in the decarboxylation screw reactor at a reaction temperature of 140 ℃, condensing a crude product generated by the reaction by a condenser, and collecting the crude product in a product collecting tank.
In total, 5 hours, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride, 2.4kg of which is recovered, was charged, and 36.2kg of a crude perfluoro-n-propyl vinyl ether product having a perfluoro-n-propyl vinyl ether content of 95.11% was collected. The yield of perfluoro-n-propyl vinyl ether product is 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 the raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the perfluoro (2-methyl-3-oxahexyl) fluoride and the salt-forming screw reactor, controlling the reaction temperature to be 30 ℃ and the reaction time to be 1 h. After the reaction is finished, continuously supplementing tetraethylene glycol dimethyl ether at the speed of 10kg/h, and continuously supplementing anhydrous potassium carbonate at the speed of 4.5 kg/h;
after the obtained potassium carboxylate solution reaches the discharge port, the potassium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 90 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
and (3) continuously feeding the potassium carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor at the speed of 20kg/h by a metering pump, carrying out decarboxylation reaction in the decarboxylation screw reactor at the reaction temperature of 140 ℃, condensing and collecting a crude product generated by the reaction in a product collecting tank by a condenser.
In total, 5 hours, 50kg of perfluoro (2-methyl-3-oxahexyl) fluoride, 2.3kg of acyl fluoride was charged, and 36.5kg of a crude perfluoro-n-propyl vinyl ether product having a perfluoro-n-propyl vinyl ether content of 96.78% was collected. The yield of perfluoro-n-propyl vinyl ether product is 92.43%.
Example 5:
adding 10kg of solvent tetraethylene glycol dimethyl ether and 3.0kg of anhydrous potassium carbonate into a salt-forming screw reactor, starting stirring, continuously pumping the raw material 2, 5-bis (trifluoromethyl) -3, 6-dioxaundecafluoroanyl fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the raw material and the raw material in the salt-forming screw reactor, controlling the reaction temperature to be 30 ℃, and reacting for 1 h. After the reaction is finished, diethylene glycol dimethyl ether is continuously supplemented at the speed of 10kg/h, and anhydrous potassium carbonate is continuously supplemented at the speed of 3.0 kg/h;
after the obtained potassium carboxylate solution reaches the discharge port, the potassium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 80 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
and (3) continuously feeding the potassium carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor at the speed of 20kg/h by a metering pump, carrying out decarboxylation reaction in the decarboxylation screw reactor at the reaction temperature of 140 ℃, condensing and collecting a crude product generated by the reaction in a product collecting tank by a condenser.
For a total of 5 hours, 50kg of the starting material 2, 5-bis (trifluoromethyl) -3, 6-dioxaundecafluoroaroyl fluoride was charged, 1.1kg of the acyl fluoride was recovered, and the yield of 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether was collected as 39.7kg of a crude product having a 2- (heptafluoropropoxy) hexafluoropropyl trifluorovinyl ether content of 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 a raw material perfluoro (2-methyl-3-oxahexyl) fluoride into the salt-forming screw reactor at the speed of 10kg/h, carrying out salt-forming reaction on the perfluoro (2-methyl-3-oxahexyl) fluoride in the salt-forming screw reactor, controlling the reaction temperature to be 30 ℃, and reacting for 1 h. After the reaction is finished, continuously supplementing tetraethyleneglycol dimethyl ether at the speed of 10kg/h, and continuously supplementing anhydrous potassium carbonate at the speed of 4.5 kg/h;
after the obtained potassium carboxylate solution reaches the discharge port, the potassium carboxylate solution continuously flows into a raw material recovery reactor under the action of a discharge shoveling plate, the raw material recovery reactor is started to stir, the temperature is controlled to be 90 ℃, and unreacted acyl fluoride is collected in a recovery tank through a recovery condenser;
and (3) continuously feeding the potassium carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor at the speed of 20kg/h by a metering pump, carrying out decarboxylation reaction in the decarboxylation screw reactor at the reaction temperature of 140 ℃, condensing and collecting a crude product generated by the reaction in a product collecting tank by a condenser.
The work-in-white was continuously fed for 1 month, 2330.5kg of perfluoro (2-methyl-3-oxahexyl) fluoride was added in total, 101.2kg of the acyl fluoride was recovered (90kg had been recycled to the system, the remaining 11.2kg was collected in a recovery tank), 1785.8kg of a crude perfluoro-n-propyl vinyl ether product was collected, the perfluoro-n-propyl vinyl ether content was 96.10%. The yield of the perfluoro-n-propyl vinyl ether product is 92.07 percent. The reactor is disassembled, and the phenomenon of salt accumulation and wall deposition is basically avoided except a small amount of salt-containing solution in the reactor.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that the invention is not limited thereto but is intended to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims. Any modification which does not depart from the functional and structural principles of the present invention is intended to be included within the scope of the claims.
Claims (10)
1. A reaction system for continuously preparing perfluoroalkyl vinyl ether is characterized by comprising a salt-forming screw reactor for preparing carboxylate solution, a raw material recovery reactor for recovering unreacted acyl fluoride in the salt-forming screw reactor, and a decarboxylation screw reactor for decarboxylating carboxylate in the carboxylate solution, wherein,
the salifying screw reactor comprises a first tubular shell and a first screw, wherein the first tubular shell is axially and horizontally arranged, the first screw is arranged in the first tubular shell, blades are axially distributed on the first screw, a first feed port is formed in the front part of the first tubular shell, a first discharge port, a first exhaust port and a first bottom exhaust port are formed in the rear part of the first tubular shell, and the first discharge port is formed in the side wall of the middle upper part of the first tubular shell;
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 decarboxylation screw reactor comprises a second tubular shell and a second screw, wherein the second tubular shell is axially and horizontally arranged, the second screw is arranged in the second tubular shell, blades are axially distributed on the second screw, a second feed port is formed in the front part of the second tubular shell, a second discharge port, a second exhaust port and a second bottom drain port are formed in the rear part of the second tubular shell, and the second discharge port is formed in the side wall of the middle lower part of the second tubular shell;
the raw material recycling discharge hole of the raw material recycling reactor is connected with the second feed hole, so that the salt solution in the raw material recycling reactor is continuously fed into the decarboxylation screw reactor in the reaction process,
the reaction system further comprises a condenser, a product collecting tank and a base solution collecting tank, wherein decarboxylation reaction occurs in the decarboxylation screw reactor, a gas-phase product is condensed and collected in the product collecting tank through the product condenser, and a liquid-solid mixed phase decarboxylation base solution flows into the base solution collecting tank through a pipeline.
2. The reaction system for continuously preparing perfluoroalkyl vinyl ether according to claim 1, characterized in that: the blades are helical blades or paddles.
3. The reaction system for continuously preparing perfluoroalkyl vinyl ether according to claim 1, characterized in that: the distance between the outer edge of the blade and the inner wall of the tubular shell is 1-10 mm.
4. The reaction system for continuously preparing perfluoroalkyl vinyl ether according to claim 1, characterized in that: and the salt solution in the raw material recovery reactor is continuously fed into the decarboxylation screw reactor by a metering pump.
5. The reaction system for continuously preparing perfluoroalkyl vinyl ether according to claim 1, characterized in that: the salification screw reactor is provided with a first discharging shoveling plate corresponding to the first discharging hole.
6. The reaction system for continuously preparing perfluoroalkyl vinyl ether according to claim 1, characterized in that: and the decarboxylation screw reactor is provided with a second discharge shoveling plate corresponding to the second discharge hole.
7. A process for continuously producing a perfluoroalkyl vinyl ether, characterized in that a reaction system for continuously producing a perfluoroalkyl vinyl ether according to any one of claims 1 to 6 is used for continuous production, comprising the steps of:
1) adding a solvent and a salt forming agent into a salt forming screw reactor, continuously introducing acyl fluoride under stirring to enable the acyl fluoride and the salt forming agent to generate salt forming reaction to generate corresponding carboxylate, continuously supplementing the solvent and the salt forming agent after the reaction is completed, and continuously reacting to obtain a carboxylate solution;
2) continuously flowing carboxylate solution in the salifying screw reactor into a raw material recovery reactor, and continuously recovering unreacted acyl fluoride into a recovery tank under the conditions of heating and stirring;
3) and continuously pumping a carboxylate solution in the raw material recovery reactor into a decarboxylation screw reactor, heating and stirring to perform decarboxylation reaction to obtain perfluoroalkyl vinyl ether, condensing and collecting the perfluoroalkyl vinyl ether in a product collecting tank, and conveying a fluoride salt solid generated by decarboxylation into a base solution collecting tank along with a solvent.
8. The process according to claim 7, wherein: the solvent is one or the combination of 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 the combination of potassium carbonate and sodium carbonate.
9. The process according to claim 7, wherein: 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 salt forming agent is 1: 1 to 2.
10. The process according to claim 7, wherein: the reaction temperature in the salifying screw reactor is 5-40 ℃; and/or the reaction temperature in the decarboxylation screw reactor is 120-180 ℃.
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