CN115651184A - Fluorine-containing polyether carboxylic acid type surfactant and preparation method thereof - Google Patents
Fluorine-containing polyether carboxylic acid type surfactant and preparation method thereof Download PDFInfo
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- 239000004094 surface-active agent Substances 0.000 title claims abstract description 44
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 13
- 229910052731 fluorine Inorganic materials 0.000 title description 13
- 239000011737 fluorine Substances 0.000 title description 13
- 239000004721 Polyphenylene oxide Substances 0.000 title description 5
- 229920000570 polyether Polymers 0.000 title description 5
- 238000004821 distillation Methods 0.000 claims abstract description 53
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000007539 photo-oxidation reaction Methods 0.000 claims abstract description 26
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000004341 Octafluorocyclobutane Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims abstract description 4
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000005336 cracking Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 5
- 230000000171 quenching effect Effects 0.000 claims description 5
- RZSJYVBYLBNFGQ-UHFFFAOYSA-N difluoromethane hydrochloride Chemical compound FCF.Cl RZSJYVBYLBNFGQ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000006392 deoxygenation reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims 1
- 230000007017 scission Effects 0.000 claims 1
- 238000000199 molecular distillation Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 39
- 239000002904 solvent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ORNGPPZBMMHKPM-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethane Chemical compound FC(F)(F)C(F)(F)OC(F)(F)C(F)(F)F ORNGPPZBMMHKPM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 150000001265 acyl fluorides Chemical class 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WZEOZJQLTRFNCU-UHFFFAOYSA-N trifluoro(trifluoromethoxy)methane Chemical compound FC(F)(F)OC(F)(F)F WZEOZJQLTRFNCU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of surfactant preparation, and discloses a fluoropolyether carboxylic acid type surfactant and a preparation method thereof, wherein the preparation method comprises the following steps: preparing perfluoroethylene; taking part of the prepared perfluoroethylene and octafluorocyclobutane to react in a reaction kettle to prepare perfluoropropylene; introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization reaction to obtain a primary product; carrying out primary heating distillation on a primary product obtained by photo-oxidative polymerization; deoxidizing the primary heating distillation product to obtain an oxygen-free product; and heating and distilling the obtained oxygen-free product to obtain the fluoropolyether carboxylic acid type surfactant. The intelligent heating distillation control device not only improves the current situation that the automation degree of the original molecular distillation equipment is low, but also realizes the rapid and accurate control of the distillation temperature through an intelligent fuzzy control algorithm, improves the distillation efficiency and improves the quality of the prepared surfactant.
Description
Technical Field
The invention belongs to the technical field of surfactant preparation, and particularly relates to a fluoropolyether carboxylic acid type surfactant and a preparation method thereof.
Background
At present, dispersion processes for the polymerization of fluorinated monomers (fluoromonomers) in aqueous media are well known. Such processes employ a surfactant, i.e., a dispersant, to provide stability and enable the polymerization to proceed to commercially acceptable solids concentrations. The main chain of the molecule of the fluorine-containing polyether carboxylic acid type surfactant contains ether bonds, and oxygen atoms on the ether bonds are beneficial to biodegradation of the fluorine-containing polyether carboxylic acid type surfactant, so that residues of the fluorine-containing polyether carboxylic acid type surfactant in organisms and natural environments can be eliminated, and enrichment can not be caused. Meanwhile, it has a surface activity not weaker than that of fluorine-containing carboxylic acid or fluorine-containing alkylsulfonic acid, and thus has attracted increasing attention in recent years.
However, the fluorine-containing solvents used in the past include perfluoromethyl ether and perfluoroethyl ether; expensive and difficult to obtain in the market; the small molecular by-products generated in the photo-oxidation process can be recovered together with the fluorine-containing olefin, and are not easy to be separated and removed, which can result in the yield of the photo-oxidation reaction being reduced.
Because the oxygen removal treatment is carried out at a high temperature of 100-300 ℃, the treatment time is dozens of hours, and the carboxylic acid after hydrolysis necessarily contains hydrofluoric acid, the oxygen removal treatment has serious corrosion to equipment, is easy to cause equipment accidents and is not beneficial to industrial production.
At the same time
Through the above analysis, the problems and defects of the prior art are as follows:
(1) The existing fluorine-containing solvents comprise perfluoromethyl ether and perfluoroethyl ether; expensive to market and difficult to obtain; the micromolecular by-products generated in the photo-oxidation process can be recovered together with the fluorine-containing olefin and are not easy to be separated and removed, so that the yield of the photo-oxidation reaction is reduced.
(2) The oxygen removal treatment causes serious corrosion to equipment, is easy to cause equipment accidents and is not beneficial to industrial production.
(3) The automation degree of the existing preparation process of the surfactant is not high, and the temperature cannot be accurately controlled in the distillation treatment stage, so that the prepared surfactant has low qualification rate.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a fluoropolyether carboxylic acid type surfactant and a preparation method thereof.
The present invention is achieved by a method for producing a fluoropolyether carboxylic acid type surfactant, comprising:
diluting chlorodifluoromethane by using water vapor, and preparing perfluoroethylene by combining the pyrolysis of the chlorodifluoromethane catalyzed and diluted by a metal fluoride catalyst;
secondly, taking part of the prepared perfluoroethylene and octafluorocyclobutane to react in a reaction kettle to prepare perfluoropropylene; introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization reaction to obtain a primary product;
performing primary heating distillation on a primary product obtained by the photo-oxidative polymerization reaction by using a heating distillation intelligent control device; deoxidizing the primary heating distillation product to obtain an oxygen-free product;
and step four, carrying out heating distillation on the obtained oxygen-free product by using a heating distillation intelligent control device again to obtain the fluoropolyether carboxylic acid type surfactant.
Further, the preparation of perfluoroethylene by diluting the monochlorodifluoromethane with water vapor and combining the pyrolysis of the diluted monochlorodifluoromethane catalyzed by a metal fluoride catalyst comprises the following steps:
firstly, respectively preheating difluorochloromethane and water vapor by using a preheating device to obtain preheated difluorochloromethane and water vapor; heating the metal fluoride catalyst to 500 ℃ in a nitrogen atmosphere;
secondly, introducing preheated chlorodifluoromethane, steam and the metal fluoride catalyst into a high-nickel alloy cracking reactor to crack the chlorodifluoromethane at 790 ℃ and 0.16 MPa;
then, quenching the gas obtained by cracking, and treating the gas after quenching by using a hydrogen chloride absorber;
and finally, sequentially carrying out water washing, alkali washing, freeze dehydration and drying by a drying device, freezing and compressing and multi-tower rectification on the cracked gas to obtain the perfluoroethylene.
Further, the volume ratio of perfluoroethylene to perfluoropropylene is 3:2.
Further, the prepared perfluoroethylene and perfluoropropylene are introduced into a photo-oxidation reaction tank for photo-oxidation polymerization reaction, and the photo-oxidation polymerization reaction comprises the following steps:
firstly, vacuumizing a reactor of a photo-oxidation reaction tank, flushing the reactor with helium, vacuumizing again, and repeating for 2-3 times; filling the prepared perfluoroethylene and perfluoropropylene into a reactor in a vacuum state;
secondly, after the pressure of the reactor is adjusted by helium, starting a high-pressure mercury lamp and an evaporation device, detecting whether the temperature in the reactor reaches a preset temperature value or not by using a temperature detector, and if the temperature does not reach the preset temperature value, adjusting the temperature until the temperature reaches the preset temperature value;
finally, carrying out photo-oxidative polymerization reaction on the perfluoroethylene and the perfluoropropylene at a constant temperature of a preset temperature value to obtain a primary product.
Further, the performing temperature adjustment includes: the temperature adjustment was performed at a rate of 1 ℃ per minute.
Further, the deoxidation treatment of the primary heating distillation product is carried out to obtain an oxygen-free product, and the oxygen-free product comprises:
firstly, uniformly stirring an obtained oxygen-free product for a period of time by using a stirring device, and standing to obtain a primary deoxidation product;
secondly, introducing oxygen-free gas into the obtained preliminary deoxygenation product, and reacting at 100 ℃ for a period of time to obtain the oxygen-free product.
Further, the heating distillation intelligent control device comprises:
the pressure data acquisition module is connected with the central control module and is used for acquiring pressure data of the steam module by using the pressure sensor;
the temperature acquisition module is connected with the central control module and is used for acquiring temperature data of the steam module by using the temperature sensor;
the central control module is connected with the pressure data acquisition module, the temperature acquisition module, the distillation parameter acquisition module, the pressure regulation module, the temperature regulation module, the steam module, the condensation module and the collection module and is used for controlling each module to normally work by utilizing a single chip microcomputer or a controller;
the distillation parameter acquisition module is connected with the central control module and is used for acquiring current heating distillation parameters of the substance to be subjected to heating distillation;
the pressure adjusting module is connected with the central control module and is used for adjusting the pressure of the steam module based on preset heating distillation parameters and the current pressure value of the steam module;
the temperature adjusting module is connected with the central control module and is used for adjusting the temperature of the steam module based on preset heating distillation parameters and the current temperature value of the steam module;
the steam module is connected with the central control module and is used for generating steam by utilizing the heating device and the flow-winding device;
the condensation module is connected with the central control module and is used for carrying out condensation treatment by using a condensation device;
and the collecting module is connected with the central control module and is used for collecting the condensed product by using the liquid storage barrel.
Further, the heating distillation of the obtained oxygen-free product by using the heating distillation intelligent control device is carried out, and then:
and hydrolyzing and salinizing the refined product obtained by heating and distilling to obtain the fluoropolyether carboxylic acid type surfactant.
Further, the step of hydrolyzing and salinizing the refined product obtained by heating and distilling to obtain the fluoropolyether carboxylic acid type surfactant comprises the following steps:
and naturally cooling the refined product to room temperature, and hydrolyzing and salinizing the refined product in a sodium hydroxide solution to obtain the fluoropolyether carboxylic acid type surfactant.
The invention also aims to provide the fluoropolyether carboxylic acid type surfactant prepared by the preparation method of the fluoropolyether carboxylic acid type surfactant.
In combination with the technical solutions and the technical problems to be solved, please analyze the advantages and positive effects of the technical solutions to be protected in the present invention from the following aspects:
first, aiming at the technical problems existing in the prior art and the difficulty in solving the problems, the technical problems to be solved by the technical scheme of the present invention are closely combined with the technical scheme to be protected and the results and data in the research and development process, and some creative technical effects brought after the problems are solved are analyzed in detail and deeply. The specific description is as follows:
the intelligent heating distillation control device not only improves the current situation of low automation degree of the original molecular distillation equipment, but also realizes the quick and accurate control of the distillation temperature through an intelligent fuzzy control algorithm, improves the distillation efficiency and improves the quality of the distillation product and the prepared surfactant.
Secondly, considering the technical scheme as a whole or from the perspective of products, the technical effect and advantages of the technical scheme to be protected by the invention are specifically described as follows:
the fluoropolyether carboxylic acid type surfactant and the preparation method thereof provided by the invention use fluoropolyether acyl fluoride with relatively small molecular weight in the intermediate product of the photooxidation reaction as the solvent, thereby directly saving the purchase cost of the solvent, avoiding the recovery and refining processes when other fluorine-containing solvents are used, and greatly saving the production cost; meanwhile, micromolecular byproducts generated in the photooxidation process and fluorine-containing olefin are recovered together to influence the yield, and the preparation method has the advantages of high yield, few byproducts, low production cost and low risk; the boiling point of the acyl fluoride is lower than that of the corresponding carboxylic acid, so the rectification process is better controlled, and the quality is easier to control.
Drawings
FIG. 1 is a flow chart of a method for preparing a fluoropolyether carboxylic acid type surfactant according to an embodiment of the present invention;
FIG. 2 is a flow chart of a process for preparing perfluoroethylene by diluting methyl difluorochloride with water vapor and catalytically cracking the diluted methyl difluorochloride with a metal fluoride catalyst according to an embodiment of the present invention;
FIG. 3 is a flow chart of a method for introducing the perfluoroethylene and the perfluoropropylene prepared by the method provided by the embodiment of the invention into a photo-oxidation reaction tank for photo-oxidation polymerization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, a method for preparing a fluoropolyether carboxylic acid type surfactant provided by the embodiment of the present invention includes:
s101, diluting chlorodifluoromethane by using water vapor, and preparing perfluoroethylene by combining the cracking of the chlorodifluoromethane catalyzed and diluted by a metal fluoride catalyst;
s102, taking part of the prepared perfluoroethylene and octafluorocyclobutane to react in a reaction kettle to prepare perfluoropropylene; introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization reaction to obtain a primary product;
s103, performing primary heating distillation on a primary product obtained by the photo-oxidative polymerization reaction by using a heating distillation intelligent control device; deoxidizing the primary heating distillation product to obtain an oxygen-free product;
s104, carrying out heating distillation on the obtained oxygen-free product by using the heating distillation intelligent control device again to obtain a refined product; and hydrolyzing and salinizing the refined product to obtain the fluoropolyether carboxylic acid type surfactant.
As shown in fig. 2, the preparation of perfluoroethylene by diluting difluoromethane chloride with water vapor and combining the diluted difluoromethane chloride with cracking of metal fluoride catalyst includes:
s201, respectively carrying out preheating treatment on difluorochloromethane and water vapor by using a preheating device to obtain preheated difluorochloromethane and water vapor; heating the metal fluoride catalyst to 500 ℃ in a nitrogen atmosphere;
s202, introducing preheated chlorodifluoromethane, steam and the metal fluoride catalyst into a high-nickel alloy cracking reactor to crack the chlorodifluoromethane at 790 ℃ and 0.16 MPa;
s203, quenching the gas obtained by cracking, and treating the quenched gas by using a hydrogen chloride absorber;
and S204, sequentially carrying out water washing, alkali washing, freeze dehydration and drying by a drying device, freeze compression and multi-tower rectification on the cracked gas to obtain the perfluoroethylene.
The volume ratio of perfluoroethylene to perfluoropropylene provided by the embodiment of the present invention is 3:2.
The method for introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization comprises the following steps:
s301, vacuumizing a reactor of the photo-oxidation reaction tank, flushing the reactor with helium, vacuumizing again, and repeating for 2-3 times; filling the prepared perfluoroethylene and perfluoropropylene into a reactor in a vacuum state;
s302, after the pressure of the reactor is adjusted by helium, starting a high-pressure mercury lamp and an evaporation device, detecting whether the temperature in the reactor reaches a preset temperature value or not by using a temperature detector, and if the temperature does not reach the preset temperature value, adjusting the temperature until the temperature reaches the preset temperature value;
s303, carrying out a photo-oxidative polymerization reaction on the perfluoroethylene and the perfluoropropylene at a constant temperature of a preset temperature value to obtain a primary product.
The preparation method provided by the embodiment of the invention carries out deoxidation treatment on the primary heating distillation product to obtain an oxygen-free product, and comprises the following steps:
firstly, uniformly stirring an obtained oxygen-free product for a period of time by using a stirring device, and standing to obtain a primary deoxidation product;
secondly, introducing oxygen-free gas into the obtained preliminary deoxygenation product, and reacting at 100 ℃ for a period of time to obtain the oxygen-free product.
The heating distillation intelligent control device provided by the embodiment of the invention comprises:
the pressure data acquisition module is connected with the central control module and is used for acquiring pressure data of the steam module by using the pressure sensor;
the temperature acquisition module is connected with the central control module and is used for acquiring temperature data of the steam module by using the temperature sensor;
the central control module is connected with the pressure data acquisition module, the temperature acquisition module, the distillation parameter acquisition module, the pressure regulation module, the temperature regulation module, the steam module, the condensation module and the collection module and is used for controlling each module to normally work by utilizing a single chip microcomputer or a controller;
the distillation parameter acquisition module is connected with the central control module and is used for acquiring current heating distillation parameters of the substance to be subjected to heating distillation;
the pressure adjusting module is connected with the central control module and is used for adjusting the pressure of the steam module based on preset heating distillation parameters and the current pressure value of the steam module;
the temperature adjusting module is connected with the central control module and is used for adjusting the temperature of the steam module based on preset heating distillation parameters and the current temperature value of the steam module;
the steam module is connected with the central control module and is used for generating steam by utilizing the heating device and the flow-winding device;
the condensation module is connected with the central control module and is used for carrying out condensation treatment by using a condensation device;
and the collecting module is connected with the central control module and used for collecting the condensed product by utilizing the liquid storage barrel.
The preparation method provided by the embodiment of the invention comprises the following steps of hydrolyzing and salinizing a refined product obtained by heating and distilling to obtain the fluoropolyether carboxylic acid type surfactant:
and naturally cooling the refined product to room temperature, and hydrolyzing and salinizing the refined product in a sodium hydroxide solution to obtain the fluoropolyether carboxylic acid type surfactant.
It should be noted that the embodiments of the present invention can be realized by hardware, software, or a combination of software and hardware. The hardware portion may be implemented using dedicated logic; the software portions may be stored in a memory and executed by a suitable instruction execution system, such as a microprocessor or specially designed hardware. Those skilled in the art will appreciate that the apparatus and methods described above may be implemented using computer executable instructions and/or embodied in processor control code, such code being provided on a carrier medium such as a disk, CD-or DVD-ROM, programmable memory such as read only memory (firmware), or a data carrier such as an optical or electronic signal carrier, for example. The apparatus and its modules of the present invention may be implemented by hardware circuits such as very large scale integrated circuits or gate arrays, semiconductors such as logic chips, transistors, or programmable hardware devices such as field programmable gate arrays, programmable logic devices, etc., or by software executed by various types of processors, or by a combination of hardware circuits and software, e.g., firmware.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A method for producing a fluoropolyether carboxylic acid type surfactant, characterized by comprising:
step one, diluting chlorodifluoromethane by using water vapor, and preparing perfluoroethylene by combining the pyrolysis of the chlorodifluoromethane catalyzed and diluted by a metal fluoride catalyst;
step two, taking part of the prepared perfluoroethylene and octafluorocyclobutane to react in a reaction kettle to prepare perfluoropropylene; introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization reaction to obtain a primary product;
performing primary heating distillation on a primary product obtained by the photo-oxidative polymerization reaction by using a heating distillation intelligent control device; deoxidizing the primary heating distillation product to obtain an oxygen-free product;
and step four, carrying out heating distillation on the obtained oxygen-free product by using a heating distillation intelligent control device again to obtain the fluoropolyether carboxylic acid type surfactant.
2. The method for producing the fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the diluting of difluoromethane chloride with steam and the production of perfluoroethylene by the cleavage of difluoromethane chloride diluted with a metal fluoride catalyst comprise:
firstly, respectively preheating difluorochloromethane and water vapor by using a preheating device to obtain preheated difluorochloromethane and water vapor; heating a metal fluoride catalyst to 500 ℃ in a nitrogen atmosphere;
secondly, introducing preheated chlorodifluoromethane, steam and the metal fluoride catalyst into a high-nickel alloy cracking reactor for cracking the chlorodifluoromethane at 790 ℃ and 0.16 MPa;
then, quenching the gas obtained by cracking, and treating the gas after quenching by using a hydrogen chloride absorber;
and finally, sequentially carrying out water washing, alkali washing, freeze dehydration and drying by a drying device, freezing and compressing and multi-tower rectification on the cracked gas to obtain the perfluoroethylene.
3. The method for producing the fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the volume ratio of perfluoroethylene to perfluoropropylene is 3:2.
4. The method for preparing the fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the step of introducing the prepared perfluoroethylene and perfluoropropylene into a photo-oxidation reaction tank for photo-oxidation polymerization comprises the following steps:
firstly, vacuumizing a reactor of a photo-oxidation reaction tank, flushing the reactor with helium, vacuumizing again, and repeating for 2-3 times; filling the prepared perfluoroethylene and perfluoropropylene into a reactor in a vacuum state;
secondly, after the pressure of the reactor is adjusted by helium, starting a high-pressure mercury lamp and an evaporation device, detecting whether the temperature in the reactor reaches a preset temperature value or not by using a temperature detector, and if the temperature does not reach the preset temperature value, adjusting the temperature until the temperature reaches the preset temperature value;
finally, carrying out photo-oxidative polymerization reaction on the perfluoroethylene and the perfluoropropylene at a constant temperature of a preset temperature value to obtain a primary product.
5. The method for producing a fluoropolyether carboxylic acid type surfactant according to claim 4, wherein the temperature adjustment comprises:
the temperature adjustment was performed at a rate of 1 ℃ per minute.
6. The process for producing a fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the subjecting the primary heated distillation product to a deoxidation treatment to obtain an oxygen-free product comprises:
firstly, uniformly stirring an obtained oxygen-free product for a period of time by using a stirring device, and standing to obtain a primary deoxidation product;
secondly, introducing oxygen-free gas into the obtained preliminary deoxygenation product, and reacting at 100 ℃ for a period of time to obtain the oxygen-free product.
7. The method for producing a fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the intelligent control device for heating distillation comprises:
the pressure data acquisition module is connected with the central control module and is used for acquiring pressure data of the steam module by using the pressure sensor;
the temperature acquisition module is connected with the central control module and is used for acquiring temperature data of the steam module by using the temperature sensor;
the central control module is connected with the pressure data acquisition module, the temperature acquisition module, the distillation parameter acquisition module, the pressure regulation module, the temperature regulation module, the steam module, the condensation module and the collection module and is used for controlling each module to normally work by utilizing a single chip microcomputer or a controller;
the distillation parameter acquisition module is connected with the central control module and is used for acquiring current heating distillation parameters of the substance to be heated and distilled;
the pressure adjusting module is connected with the central control module and is used for adjusting the pressure of the steam module based on preset heating distillation parameters and the current pressure value of the steam module;
the temperature adjusting module is connected with the central control module and is used for adjusting the temperature of the steam module based on preset heating distillation parameters and the current temperature value of the steam module;
the steam module is connected with the central control module and is used for generating steam by utilizing the heating device and the flow-winding device;
the condensation module is connected with the central control module and is used for carrying out condensation treatment by using a condensation device;
and the collecting module is connected with the central control module and is used for collecting the condensed product by using the liquid storage barrel.
8. The method for preparing fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the step of subjecting the obtained oxygen-free product to heating distillation again by using the heating distillation intelligent control device is further performed by:
and hydrolyzing and salinizing the refined product obtained by heating and distilling to obtain the fluoropolyether carboxylic acid type surfactant.
9. The process for producing a fluoropolyether carboxylic acid type surfactant according to claim 1, wherein the step of hydrolyzing and salifying the refined product obtained by the distillation under heating to obtain a fluoropolyether carboxylic acid type surfactant comprises the steps of:
and naturally cooling the refined product to room temperature, and hydrolyzing and salinizing the refined product in a sodium hydroxide solution to obtain the fluoropolyether carboxylic acid type surfactant.
10. A fluoropolyether carboxylic acid type surfactant prepared by the method for preparing a fluoropolyether carboxylic acid type surfactant according to any one of claims 1 to 9.
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