CN115246766A - Method for treating fluorinated tail gas in perfluoropolyether synthesis process - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000010702 perfluoropolyether Substances 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title abstract description 14
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 26
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 8
- UPVJEODAZWTJKZ-UPHRSURJSA-N (z)-1,2-dichloro-1,2-difluoroethene Chemical group F\C(Cl)=C(/F)Cl UPVJEODAZWTJKZ-UPHRSURJSA-N 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 238000003672 processing method Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003682 fluorination reaction Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- OYAUGTZMGLUNPS-UHFFFAOYSA-N 1,1,1,2,3,3,3-heptafluoro-2-(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)propane Chemical compound FC(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)F OYAUGTZMGLUNPS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 8
- 229920001973 fluoroelastomer Polymers 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 44
- 239000000047 product Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 238000006298 dechlorination reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 3
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000856 hastalloy Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- LMFJKKGDLAICPF-UHFFFAOYSA-N phenanthrene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC3=CC=CC=C3C2=C1 LMFJKKGDLAICPF-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003633 blood substitute Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
-
- 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
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- 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
- C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C71/00—Esters of oxyacids of halogens
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a method for treating fluorinated tail gas in a perfluoropolyether synthesis process. The processing method mainly comprises the following steps: reacting the fluorinated tail gas with fluorine gas to obtain an intermediate B, reacting the intermediate B with 1,2-difluoro-1,2-dichloroethylene to obtain an intermediate C, and reacting the intermediate C with zinc to obtain a product. The product obtained by the invention can be used as a raw material for researching and producing special fluorine-containing polymers such as low temperature-resistant fluororubber, high temperature-resistant fluororubber and medium-resistant fluororubber as a fluorine-containing alkyl vinyl ether monomer. Therefore, the invention provides a more green and economic fluorinated tail gas treatment method, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for treating fluorinated tail gas in a perfluoropolyether synthesis process.
Background
Perfluoropolyether, which was originally studied by Sianesi in the 60 th century of 20 th century, is a relatively special perfluoropolymer compound, the average molecular weight of which is varied from 500 to 15000, and the molecule contains only C, F, O. Perfluoropolyethers with different molecular weights have wide application in the aspects of lubricating oil, heat conduction oil, insulating materials, vacuum pump oil, blood substitutes, plastic additives and the like. The high molecular weight perfluoropolyether has low volatility, wide liquid temperature range and excellent viscosity-temperature characteristics after being subjected to stabilization treatment, and is used as an excellent lubricant in the fields of aerospace industry, electronic industry, electrical industry, nuclear industry and the like.
At present, there are two main methods for synthesizing perfluoropolyether, one is photocatalytic polymerization, such as photo-oxidative polymerization technology of tetrafluoroethylene or hexafluoropropylene; another is anionic polymerization, such as the anionic polymerization of perfluoroepoxide (hexafluoropropylene or tetrafluorooxetane). Both the end groups of perfluoropolyethers prepared by photo-oxidative polymerization and anionic polymerization contain active acid fluorides, and in order to improve the stability of the perfluoropolyethers, the end groups need to be stabilized. The method of stabilization is to fluorinate the end groups. The end group fluorinated perfluoropolyether has the best stability and is an important technology for industrially preparing the perfluoropolyether.
The main components of the tail gas after the fluorination of the perfluoropolyether end group are as follows: fluorophosphoric acid, trifluoroacetyl fluoride, pentafluoropropionyl fluoride and the like, which are important intermediates for preparing fluoroalkyl vinyl ethers. At present, the method for treating fluorinated tail gas in the perfluoropolyether synthesis process comprises the following steps: and (3) washing the fluorinated tail gas with water, then washing with alkali, and finally emptying. The disadvantages of this treatment are: firstly, substances contained in the tail gas are not effectively utilized; secondly, a large amount of fluorine-containing waste liquid is produced to form secondary pollution, and the subsequent treatment of the waste liquid causes pressure on environmental protection.
The recovery and comprehensive utilization of compounds such as fluorophosphoric acid, trifluoroacetyl fluoride and pentafluoropropionyl fluoride are still lack of corresponding research at present, so that a better idea for green treatment of fluorinated tail gas is also lacked at present, which is a problem to be solved in the field urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating fluorinated tail gas in a perfluoropolyether synthesis process, and aims to realize a safe and environment-friendly treatment method with high added value aiming at the fluorinated tail gas in the perfluoropolyether synthesis process.
A preparation method of fluorine-containing alkyl vinyl ether comprises the following steps:
step 1, reacting a raw material A with fluorine gas to obtain an intermediate B,
step 2, reacting the intermediate B with 1,2-difluoro-1,2-dichloroethylene to obtain an intermediate C,
step 3, reacting the intermediate C with zinc to obtain a product D,
wherein R is selected from F or C 1 -C 10 A perfluoroalkyl group.
Preferably, R is selected from F, trifluoromethyl or pentafluoroethyl.
Preferably, step 1 is carried out under the action of a catalyst, wherein the catalyst is selected from one or a compound of two or more of KF, naF, csF and LiF.
Preferably, the reaction conditions in the step 1 are that the reaction temperature is 100-400 ℃ and the reaction pressure is 0-0.1 MPa.
Preferably, in step 1, the introduction flow rate of the fluorine gas is 10 to 500L/h.
Preferably, the reaction conditions of the step 2 are that the reaction temperature is-25 ℃ to-10 ℃, and the reaction pressure is 0-0.1 Mpa;
and/or introducing the reaction tail gas after the reaction in the step 2 into the reactor in the step 1 for recycling.
Preferably, step 3 is carried out under the action of an initiator selected from zinc chloride;
and/or, the step 3 is carried out under the action of an organic solvent, wherein the organic solvent is one or a mixture of two or more of dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide and poly perfluoroisopropyl ether oil.
The invention also provides a method for treating the tail gas from the fluorination of the end groups of the perfluoropolyether, which takes the tail gas from the fluorination process of the end groups of the perfluoropolyether as the raw material A and prepares the product D according to the preparation method.
Preferably, the main component of the tail gas of the perfluoropolyether end group fluorination process comprises COF 2 、CF 3 COF and CF 3 CF 2 COF。
Preferably, the product D obtained is CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 The product D is separated by rectification.
The invention provides a brand-new, high-added-value, safe and environment-friendly treatment method, which can be used for treating fluorinated tail gas in a perfluoropolyether synthesis process in an industrial scale and greatly reduce the influence of three wastes on the environment. According to the method provided by the invention, the fluorinated tail gas in the synthesis process of the perfluoropolyether can be turned into treasure, and the prepared fluorine-containing alkyl vinyl ether monomer is used as a raw material for researching and producing special fluorine-containing polymers such as low temperature resistant fluororubber, high temperature resistant fluororubber and medium resistant fluororubber, so that the method has high economic benefit.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
Example 1
This example was carried out by reacting the fluorinated tail gas (containing COF) from the perfluoropolyether synthesis process 2 、CF 3 COF and CF 3 CF 2 COF) as a raw material to prepare CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 。
Wherein R is F, trifluoromethyl or pentafluoroethyl.
The process flow is shown in figure 1.
In the first reaction step:
the catalyst is alkali metal fluoride, including but not limited to KF, naF, csF, liF and their compound. NaF is preferred in this embodiment.
The reaction temperature is controlled at 400 ℃ and the reaction pressure is controlled at 0.1MPa.
The raw material fluorine gas to be used may be diluted with an inert gas and used, or may be used as it is. The fluorine gas introduction flow rate is 10 to 500L/h. Including but not limited to nitrogen, helium, argon, and the like. In this embodiment, it is preferable that the fluorine gas obtained by electrolysis is diluted to 40% (V/V) with nitrogen gas and fed into the reactor A, and that the off gas is fed into the reactor A at 200L/h.
The reactor of the first step reaction is made of corrosion-resistant materials such as hastelloy, nickel-chromium stainless steel, molybdenum-chromium stainless steel or carbon steel passivated by fluorine gas. Is provided with a metering device, a heating device and a gas distribution device.
In the second reaction step:
the reaction temperature is controlled at-10 ℃, and the reaction pressure of the reactor is controlled at 0.1MPa.
The 1,2-difluoro-1,2-dichloroethylene is added into the reactor in liquid phase, and the adding amount is 80% of the volume of the reactor.
The reactor for reaction is made of corrosion-resistant and low-temperature-resistant materials such as Hastelloy, nickel-chromium stainless steel, molybdenum-chromium stainless steel, tetrafluoro resin lining or tetrafluoro resin materials and the like. The pressure-resistant reactor is equipped with a cooling device, a stirring device, and a conduit and a distribution device for introducing a gas into the liquid phase. The reactor is filled with stuffing to increase the exchange strength of matter in the reaction.
Since the fluorine gas, which is a highly corrosive gas, is introduced into the reactor, its accessories, and packing are made of a material resistant to corrosion by fluorine gas. Including but not limited to hastelloy, nickel-chromium stainless steel, molybdenum-chromium stainless steel, tetrafluoro resin or tetrafluoro resin lined, carbon steel material passivated by fluorine gas, etc.
In the third reaction step:
1) An organic solvent with a tank volume of 30 to 70% (preferably 50% in this example) was added to a dechlorination reactor (GSH type magnetic stirring reactor), and then zinc powder and zinc chloride with a zinc powder weight of 5% were added as an initiator. Then, the stirring is started, the stirring speed is 80 to 300r/min (300 r/min is preferred in the embodiment), and the temperature is raised to 60 to 100 ℃ (70 ℃ is preferred in the embodiment).
2) The intermediate C is continuously added into a dechlorination reaction kettle, and the reaction is carried out at the temperature of 60-100 ℃ (preferably 70 ℃ in the embodiment). The molar ratio of the intermediate C to the zinc powder to the organic solvent is 1:3 to 4:8 to 10 (in the present embodiment, 1. The intermediate product is slowly added, and the addition rate is controlled according to the proportion that the organic solvent volume is 5L, and the intermediate product is added into the reactor at 300-600 g (400 g is preferred in the embodiment) per hour.
3) And (3) allowing a gas-phase product obtained by the reaction in the dechlorination reaction kettle to pass through a reflux condenser and then completely collect the gas-phase product into a mixed monomer collecting bottle, and placing the crude monomer collecting bottle into a-45 ℃ cold trap. The collected mixed monomers are purified. The purification is carried out in a rectifying device, the rectifying device comprises a rectifying tower, a condenser and a tower kettle, and the operating pressure of the rectifying tower is controlled below 0.1MPa.
In the dechlorination reaction, the organic solvent is dimethyl sulfoxide.
The gauge pressure of the dechlorination reaction kettle is controlled to be 0.1MPa.
And sampling a gas outlet of the reactor B, and performing gas chromatography. The analysis results show that: main component COF of fluorinated tail gas in perfluoropolyether-free synthesis process 2 、CF 3 COF、CF 3 CF 2 COF。
The product D is a mixed monomer, and various modified special monomers with the content of more than or equal to 99.95 percent are respectively obtained after the product D is purified by a rectifying tower. In this example, the three special modified monomers obtained were CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 Three compounds.
Example 2
This example treats the fluorinated off-gas from the perfluoropolyether synthesis process in the same manner as in example 1, except that the process conditions are modified as follows:
catalyst KF is added into a reactor, then fluorine gas prepared by electrolysis is diluted to 60% (V/V) by nitrogen and then is introduced into a reactor A, tail gas is introduced into the reactor A according to 200L/h, the reaction temperature is controlled at 100 ℃, and the reaction pressure is controlled at 0.1MPa.
The reacted gas enters a reactor B to react with 1,2-difluoro-1,2-dichloroethylene. The reaction temperature is controlled at-25 ℃ and the reaction pressure is controlled at 0.1MPa.
In this example, product D is CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 Three compounds.
Example 3
This example treats the fluorinated off-gas from the perfluoropolyether synthesis process in the same manner as in example 1, except that the process conditions are modified as follows:
adding a catalyst CsF into a reactor, diluting fluorine gas prepared by electrolysis to 85% (V/V) by using nitrogen, introducing the diluted fluorine gas into the reactor A, introducing tail gas into the reactor A at a rate of 200L/h, controlling the reaction temperature at 400 ℃ and the reaction pressure at 0.1MPa.
The reacted gas enters a reactor B to react with 1,2-difluoro-1,2-dichloroethylene. The reaction temperature is controlled at-10 ℃ and the reaction pressure is controlled at 0.1MPa.
In this example, product D is CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 Three compounds.
As can be seen from the above examples, the invention can treat the fluorinated tail gas in the perfluoropolyether synthesis process and convert the fluorinated tail gas into a recyclable product. The invention overcomes the defects that the fluorinated tail gas treatment process is not environment-friendly enough and the fluorine-containing compound can not be recycled in the prior art, provides a more green and economic fluorinated tail gas treatment method, and has good application prospect.
Claims (10)
1. The preparation method of the fluorine-containing alkyl vinyl ether is characterized by comprising the following steps:
step 1, reacting a raw material A with fluorine gas to obtain an intermediate B,
step 2, reacting the intermediate B with 1,2-difluoro-1,2-dichloroethylene to obtain an intermediate C,
step 3, reacting the intermediate C with zinc to obtain a product D,
wherein R is selected from F or C 1 -C 10 A perfluoroalkyl group.
2. The method of claim 1, wherein: r is selected from F, trifluoromethyl or pentafluoroethyl.
3. The method of claim 1, wherein: the step 1 is carried out under the action of a catalyst, wherein the catalyst is one or a compound of two or more of KF, naF, csF and LiF.
4. The method of claim 1, wherein: the reaction conditions of the step 1 are that the reaction temperature is 100-400 ℃ and the reaction pressure is 0-0.1 MPa;
and/or in step 1, the introduction flow rate of the fluorine gas is 10 to 500L/h.
5. The method of claim 1, wherein: the reaction conditions of the step 2 are that the reaction temperature is-25 ℃ to-10 ℃ and the reaction pressure is 0-0.1 Mpa;
and/or introducing the reaction tail gas after the reaction in the step 2 into the reactor in the step 1 for recycling.
6. The method of claim 1, wherein: step 3 is carried out under the action of an initiator, wherein the initiator is selected from zinc chloride;
and/or, the step 3 is carried out under the action of an organic solvent, wherein the organic solvent is one or a mixture of two or more of dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide and poly perfluoroisopropyl ether oil.
7. A method for treating perfluoropolyether end group fluorinated tail gas is characterized by comprising the following steps: the method takes tail gas of a perfluoropolyether end group fluorination process as a raw material A, and prepares a product D according to the preparation method of any one of claims 1-6.
8. The process of claim 7, wherein: the main component of the tail gas of the perfluoropolyether end group fluorination process comprises COF 2 、CF 3 COF and CF 3 CF 2 COF。
9. The processing method according to claim 7, characterized in that: the product D obtained is CF 3 OCF＝CF 2 、CF 3 CF 2 OCF＝CF 2 And CF 3 CF 2 CF 2 OCF＝CF 2 The product D is separated by rectification.
10. Product D obtained by the process according to any one of claims 1 to 9.
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