CN1830929A - Method for separating and recovery difluorochloromethane azeotropic hexafluoropropene - Google Patents
Method for separating and recovery difluorochloromethane azeotropic hexafluoropropene Download PDFInfo
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Abstract
A process for separating and recovering bifluoro-chloromethane-hexafluoropropene azeotrope includes such steps as passing said gas-state mixed azeotrope through gas separating membrane to obtain penetrated bifluoro-chloromethane gas and residual hexafluoropropene gas, condensing the residual gas, rectifying to obtain pure hexafluoropropene, recovering the mixed azeotrope from tower top, returning it along with said penetrated gas back to rectifying system in tetrafluoro ethene production apparatus, and rectifying separation to recover bifluoro-chloromethane.
Description
Technical field
The present invention relates to the separation and the recovery method of a kind of difluorochloromethane-R 1216 azeotrope novelty, be by special efficient gas separation membrane initial gross separation difluorochloromethane-R 1216 azeotrope more specifically, destroy its azeotropic ratio, reclaim the method for difluorochloromethane (HCFC-22 or F-22) and R 1216 (HFP) then with rectifying respectively.
Background technology
Fluorine is first element of VII main group, the electronegativity maximum, and atomic radius is little, and van der Waals radius is 0.135nm, and is only big slightly than hydrogen atom van der Waals radius 0.12nm.Hydrogen atom in the organic compound can be replaced by the fluorine atom that volume is more or less the same mostly, forms the organofluorine compound of One's name is legion.Because the electronegativity that fluorine is big, polarizability and weak Intermolecular Forces that little atomic radius, fluorine carbon bond is low, often change after introducing fluorine in the organic compound with remarkable physicochemical property, have various special propertys, therefore, organofluorine compound now has been widely used in the national economy every field. and the organic fluorine product of scale operation at present has small molecules fluorochemicals and polymer fluorochemicals and fluoro-containing pesticide and medicine intermediates such as fluoroplastics, fluoroelastomer such as cooling agent, aerosol, whipping agent, fire-fighting medium.
The fluoropolymer thing is the product that production technique is the most complicated, technology content is the highest in the organic fluorine industry, existing hundreds of kinds on the market, and the whole world year industrial scale surpasses 100,000 tons, and its purposes spreads all trades and professions.Fluorochemical monomer develops so far as the raw material of fluoropolymer, has synthesized hundreds of compound, and wherein most important have tetrafluoroethylene (TFE), R 1216 (HFP), trifluorochloroethylene, vinylidene, vinyl fluoride etc. ten to plant fluorine-containing monoolefines.
Tetrafluoroethylene is present turnout maximum, most important fluorochemical monomer, and it is the raw material of tetrafluoroethylene, is the comonomer of many fluorinated copolymers, also is the intermediate of multiple fluorochemicals.The tetrafluoroethylene production level has been represented the level of a national organic fluorine industrial development.
Among the product that tetrafluoroethylene sees Ruff in 1933 etc. the earliest when tetrafluoro-methane is carried out thermolysis in carbon arc. but realize that really industrial production is after finding tetrafluoroethylene, equal to propose difluorochloromethane in 1945 by J.D.Park and prepare by pyrolysis.The production of tetrafluoroethylene large-scale development starts from nineteen forty-six, and first industrialized unit of Parker's Regensburg of w.va. was gone into operation in nineteen fifty.Because this path of preparing tetrafluoroethylene route raw material is easy to get, method is simple, technology reaches its maturity, is convenient to industrial production, so this method is widely adopted.
The technology that the present difluorochloromethane that still uses in industrialization is in the world made tetrafluoroethylene has two kinds: blank pipe pyrolysis and superheated vapour dilution pyrolysis.
The pyrolysis of difluorochloromethane blank pipe is that du pont company is developed the earliest and carried out industrialized production method.Difluorochloromethane in tube furnace in 800 ℃～900 ℃, at normal pressure with do not have to carry out pyrolysis under the situation of thinner.Except that E.I.Du Pont Company, the Mitsui fluorine chemistry company of early stage Britain ICI company, Japan and Atofina of France adopt difluorochloromethane blank pipe pyrolytic technique.USSR (Union of Soviet Socialist Republics) is also the same with China early stage pilot plant to be to adopt the blank pipe pyrolysis method to produce tetrafluoroethylene.
Water vapor dilution pyrolysis is the novel process that grows up the end of the fifties to the beginning of the sixties.Superheated vapour dilution method for pyrolysis be with the superheated vapour that is higher than pyrolysis temperature as thermal barrier, mix in advance and pyrolysis with the difluorochloromethane raw material that is preheating near temperature of reaction.Superheated vapour provides pyrolysis required heat on the one hand, has reduced the difluorochloromethane dividing potential drop on the other hand, has obtained effect preferably. because this method transformation efficiency height, by product is few, and the productive rate height, it has become one of industrial important method of producing tetrafluoroethylene.In the world except that E.I.Du Pont Company, most of company all adopts water vapor dilution pyrolytic technique to produce tetrafluoroethylene at present, and maximum single covering device ability reaches 20000 tons/year.
The chemical process of difluorochloromethane pyrolytic reaction is very complicated, and pyrolysis product has more than 30 component.Principal product is a tetrafluoroethylene, and by product also has R 1216, Perfluorocyclobutane, Vcon, trifluorochloroethylene, methyl chlorofluoride and contains HF hydrocarbon except that hydrogenchloride, also has carbon monoxide, hydrogen fluoride etc. in addition.
No matter produce tetrafluoroethylene with the difluorochloromethane pyrolysis, be blank pipe pyrolysis or superheated vapour dilution pyrolysis, and above-mentioned these by products all exist.
The superheated vapour heat of dilution under a kind of special reaction condition is vented one's spleen, and mainly composition (after removing hydrogenchloride) is as follows:
| The component title | Quality/% |
| Difluorochloromethane | 41.4 |
| Tetrafluoroethylene | 55.5 |
| Trifluoromethane | 0.173 |
| Trifluoro-ethylene | 0.027 |
| Methylene fluoride | 0.013 |
| The component title | Quality/% |
| R 1216 | 0.345 |
| Methyl chlorofluoride | 0.185 |
| H(CF 2CF 2) 2Cl | 0.149 |
| H(CF 2CF 2) 3Cl | 0.106 |
| Carbon monoxide | 1.68 |
The separation of pyrolysis gas is an important component part during tetrafluoroethylene is produced.Its main task is: (1). tetrafluoroethylene monomer is purified; (2). the recovery of difluorochloromethane; (3). the separation and the recovery of useful component in the by product (as R 1216); (4). the processing of raffinate spent acid.
In the process of venting one's spleen with traditional rectificating method heat of dissociation, can form the azeotrope that difluorochloromethane and R 1216 are formed, azeotrope is impossible in addition isolating by conventional distillation or rectifying means.But in the tetrafluoroethylene production process, difluorochloromethane must be separated with R 1216.Otherwise, if circulating, the azeotrope that difluorochloromethane is formed with R 1216 carries out pyrolytic reaction, R 1216 forms the macromole product easily when pyrolysis, stop up reactive system and after-treatment system, cause frequent unplanned parking, cause production capacity to descend, production cost improves, the aggrandizement apparatus unsafe factor.If the azeotrope of difluorochloromethane and R 1216 composition directly is discharged into atmosphere, can cause the tetrafluoroethylene yield to descend, the unit cost of production raises, and causes environmental pollution.
Separating the method that difluorochloromethane-the R 1216 azeotrope generally adopts at present is extraction fractional distillation, promptly in mixture, add a kind of solvent (extraction agent), difluorochloromethane-R 1216 relative volatility is changed, thereby destroyed azeotropic system, normal rectifying carried out.
The extraction agent that extracting rectifying is selected for use has two big classes: polarity extracting agent (as DMF, methyl alcohol, acetone, glycol dimethyl ether etc.) selective dissolution difluorochloromethane; Hexafluoropropene dimers selective dissolution R 1216.
The step that typical extracting rectifying flow process (see figure 3) comprises is:
(1). azeotropic mixture enters extractive distillation column 17 by pipeline 1 with liquid state, fresh extraction agent is added by pipeline 27, the round-robin extraction agent is by pipeline 25, enter from extractive distillation column 17 top sprays by following pump 26 with the fresh extraction agent of adding, in extractive distillation column 17, the mixed extracting rectifying that carries out of azeotropic mixture and extraction agent.
(2). obtain volatile components from extractive distillation column 17 cats head, volatile components enters water wash column 19 by pipeline 18, and fresh water enters water wash column 19 by pipeline 21, washes the sewage of volatile components and discharges from pipeline 22.Through volatile components process moisture eliminator 20 drying and dehydratings of washing, obtained removing the volatile components A of extraction agent impurity and moisture.
(3). the extraction agent of extractive distillation column 17 tower stills and not volatile components enter extraction agent recovery tower 23, the extraction agent of recovery returns extractive distillation column 17 via recycle pump 26 by pipeline 25.Obtain not volatile components from extraction agent recovery tower 23 cats head, enter water wash column 28 by pipeline 24, fresh water enters water wash column 28 by pipeline 30, washes the sewage of volatile components and discharges from pipeline 31.Through not volatile components process moisture eliminator 29 drying and dehydratings of washing, obtained removing the not volatile components B of extraction agent impurity and moisture.
Though the extraction rectification technique that extensively adopts separates difluorochloromethane-R 1216 azeotrope now, there is following shortcoming in this method:
1. technical process complexity, equipment is many, troublesome poeration.
2. it is poor to reclaim product purity, need wash with water or activated carbon absorbs and removes extraction agent, produces new environmental pollution.
3. extraction agent is lossy in the operational process, adopts low price extraction agent processing power little, adopts efficient extraction agent to cost an arm and a leg, and increases running cost.
4. extracting rectifying process and extraction agent removal process all need with chilled brine and steam, and the extraction agent circulation needs pump delivery, energy consumption height.
5. the extracting rectifying process is for band press operation process, and inflammable as the extraction agent that uses, leakage causes security incident easily.
Summary of the invention
The object of the present invention is to provide a kind of difluorochloromethane-R 1216 azeotrope to separate and recovery method. this method technical process is simple, and equipment is few, and is easy to operate; The difluorochloromethane and the R 1216 purity height that reclaim need not introduced extraction agent in the Separation and Recovery process, do not produce new pollution; The Separation and Recovery process need not consume extraction agent, and running cost is low; Do not need extraction agent to reclaim and working cycle, energy consumption is low; Do not need to use inflammable extraction agent, safer.
The present invention seeks to reach like this, a kind of difluorochloromethane-R 1216 azeotrope separates and recovery method, characteristics are: in envrionment temperature, under self pressure, difluorochloromethane-R 1216 azeotropic mixture is passed through the gas delivery membrane module with gaseous state, obtain the infiltration gas that is mainly difluorochloromethane and the residual air of oozing that is mainly R 1216 of two strands of destroyed azeotropic ratios by the gas delivery membrane module, to ooze the condenser liquefaction of residual air process and collect condensate storage, enter rectifying tower then, obtain pure R 1216 from the tower still after the rectifying, from a small amount of azeotropic mixture of recovered overhead; After reclaiming pure R 1216, the a small amount of azeotropic mixture that reclaims in the rectifying is returned original low pressure gas holder in the tetrafluoroethylene production equipment together together with infiltration gas, and enter original distillation system in the tetrafluoroethylene production equipment, carry out normal rectifying separation and reclaim the difluorochloromethane process.
Difluorochloromethane of the present invention-R 1216 azeotrope separates and recovery method, in envrionment temperature, under the autogenous pressure, difluorochloromethane-R 1216 azeotropic mixture is passed through the gas delivery membrane module with gaseous state, obtain the infiltration gas that is mainly difluorochloromethane and the residual air of oozing that is mainly R 1216 of two strands of destroyed azeotropic ratios by the gas delivery membrane module, to permeate gas respectively and ooze residual air and liquefy separately, advance rectifying tower then respectively and reclaim pure difluorochloromethane and R 1216, a small amount of azeotropic mixture that reclaims returns the gas delivery membrane module again in the rectifying, and circulation is reclaimed.
Difluorochloromethane of the present invention-R 1216 azeotropic mixture is meant the azeotropic mixture that forms under tetrafluoroethylene ordinary production temperature and pressure condition, it consists of difluorochloromethane 80%-90%, R 1216 10%-20%.
Difluorochloromethane of the present invention-R 1216 azeotropic mixture consist of difluorochloromethane 87%, R 1216 13%.
Gas delivery membrane module of the present invention is the industrial equipments of carried out gas delivery that must the component combination by gas separation membrane and other.
Dissolving-parsing film that gas separation membrane of the present invention is made for the speciality polymer material.
Dissolving of the present invention-parsing film is the rubbery state polymeric membrane of azeotropic mixture that can be by dissolving-resolving speed difference separation difluorochloromethane and R 1216 or in the vitreous state polymeric membrane any one.
The invention has the advantages that this technical process is simple, equipment is few, thereby easy to operate; Need not introduce extraction agent in the Separation and Recovery process, thereby the difluorochloromethane and the R 1216 purity height that reclaim; The Separation and Recovery process need not consume extraction agent, thereby does not produce new environmental pollution, and it is low to reduce running cost; Do not need extraction agent to reclaim and working cycle, thereby energy consumption is low; Do not need to use inflammable extraction agent, thus safer.
Description of drawings
Fig. 1 is difluorochloromethane of the present invention-R 1216 azeotrope separation and recovery method one
The embodiment schema.
Fig. 2 is another embodiment schema of difluorochloromethane of the present invention-R 1216 azeotrope separation and recovery method.
Fig. 3 is the difluorochloromethane-R 1216 extracting rectifying schema in the prior art.
Among the figure: A is a volatile components; B is volatile components not; 1,9,15 be the pipeline of azeotropic mixture; 2 is the gas delivery membrane module; 3 is based on the gas-pervious pipeline of oozing of difluorochloromethane; 4 is original low pressure gas holder in the tetrafluoroethylene production equipment; 5 are the pipeline that oozes residual air based on R 1216; 6,12 is condenser; 7,13 is condensate storage; 8,14 is rectifying tower; 10 for reclaiming the pipeline of R 1216; 11 is gas compressor; 16 for reclaiming the pipeline of difluorochloromethane; 17 is extractive distillation column; 18 is the pipeline of volatile components; 19,28 is water wash column; 20,29 is moisture eliminator; 21,30 for introducing the pipeline of fresh water; 22,31 is the pipeline of sewage effluent; 23 is the extraction agent recovery tower; 24 is the pipeline of volatile components not; 25 is the pipeline of cycling extraction agent; 26 is the extraction agent recycle pump; 27 for adding the pipeline of fresh extraction agent.
Embodiment
Following embodiment will help the understanding of the present invention more, but not constitute the restriction to content of the present invention.
The gas of above-mentioned two strands of destroyed azeotropic ratios is meant the infiltration gas that is mainly difluorochloromethane and is mainly the residual air of oozing of R 1216, because oozing residual air is not azeotropic mixture, therefore can separate by general, well-known rectifying. make and ooze residual air earlier through condensing air liquefaction, collect receiving tank, enter rectifying tower then.
Difluorochloromethane-R 1216 azeotropic mixture be the azeotropic mixture that under the specified temp of tetrafluoroethylene ordinary production and specified pressure condition, forms, it is formed because of service temperature and pressure different nuance, compositing range is difluorochloromethane 80%-90%, R 1216 10%-20%.
The composition of difluorochloromethane-R 1216 azeotropic mixture is difluorochloromethane 87% under the typical production situation, R 1216 13%.
To be that the many institutes of gas film separation industries are all know the also pattern of widespread use to the process pattern of the azeotrope by dissolving-resolving speed difference initial gross separation difluorochloromethane and R 1216. pressure difference as the motivating force situation under, difluorochloromethane and R 1216 are penetrated into low-tension side by dissolving-resolving from the high-tension side of film, because seepage velocity difference, the fast gas of seepage velocity easily by and the slow gas of seepage velocity is retained down, thereby reach the purpose of initial gross separation.
The residual air liquefaction process that oozes of indication of the present invention is the condensation collection process.
The rectifying of indication of the present invention is that the band that generally adopts in the fluorine chemical is pressed rectifying.
Rectifying tower of the present invention be generally adopt in the fluorine chemical can be by the rectifying tower of design pressure operation.
Gas delivery membrane module 2 is a YZ-III type membrane separation unit by the product grade that Yangzhong City, Chinese Jiangsu Sai Rui Engineering Co., Ltd produces and sells; Condenser 6,12 condensation areas are 15m
2, condensate storage 7,13 volumes are 0.8m
3, the tower still volume of rectifying tower 8,14, extraction agent recovery tower 23 is 0.6m
3, the equal carrying vapour chuck of tower still, the high 10m of body of the tower, body of the tower internal diameter are 0.2m, overhead condensation area 15m
2, the high 10m of water wash column 19,28 bodies of the tower, the body of the tower internal diameter is 0.2m, these equipment materials are carbon steel, design pressure 2.5MPa; 180 ℃ of process steam temperature, chilled brine temperature-35 ℃.
Embodiment 1
Please in conjunction with Fig. 1,20 ℃ of envrionment temperatures, under pressure 0.5MPa (absolute pressure) condition, (amount of substance consists of difluorochloromethane 87% to difluorochloromethane-R 1216 azeotropic mixture, R 1216 13%) passes through gas delivery membrane module 2 by pipeline 1 with gaseous state, obtain the gas of two strands of destroyed azeotropic ratios from gas delivery membrane module 2: promptly one is that (amount of substance consists of difluorochloromethane 97.67% to main infiltration gas for difluorochloromethane (HCFC-22), R 1216 2.33%), introducing TFE production equipment low pressure gas holder 4 by pipeline 3 reclaims; Another strand is for oozing residual air (amount of substance consists of difluorochloromethane 14.2%, R 1216 85.8%) based on R 1216 (HFP).
Ooze residual air by pipeline 5-35 ℃ of condenser 6 condensations of process earlier, collect condensate storage 7, enter rectifying tower 8 rectifying then, rectifying tower 8 control conditions are pressure 0.5MPa (absolute pressure), and tower still temperature is 15 ℃, and tower top temperature is 2 ℃.Obtaining purity from the tower still after the rectifying is 99.6% R 1216 (HFP), and the R 1216 collecting amount that reclaims from pipeline 10 is 10kg/h, and a small amount of azeotropic mixture that produces from cat head enters 4 recovery of TFE production equipment low pressure gas holder by pipeline 9.So a small amount of azeotropic mixture that produces in the rectifying is returned original low pressure gas holder in the tetrafluoroethylene production system together together with infiltration gas, and enter original distillation system in the tetrafluoroethylene production system, carry out normal rectifying separation and reclaim the difluorochloromethane process, the purity that reclaims is that 99.5% difluorochloromethane returns the tetrafluoroethylene cracking system that feeds intake, and production can normally move.
Embodiment 2
Please in conjunction with Fig. 2, under 20 ℃ of envrionment temperatures, pressure 0.5MPa (absolute pressure) condition, (amount of substance consists of difluorochloromethane 87% to difluorochloromethane-R 1216 azeotropic mixture, R 1216 13%) passes through gas delivery membrane module 2 by pipeline 1 with gaseous state, obtain the gas of two strands of destroyed azeotropic ratios from gas delivery membrane module 2: promptly one is main infiltration gas (amount of substance consists of difluorochloromethane 97.67%, R 1216 2.33%) for difluorochloromethane (HCFC-22); Another strand is for oozing residual air (amount of substance consists of difluorochloromethane 14.2%, R 1216 85.8%) based on R 1216 (HFP).
Ooze residual air by pipeline 5-35 ℃ of condenser 6 condensations of process earlier, collect condensate storage 7, enter rectifying tower 8 rectifying then, rectifying tower control condition is pressure 0.5MPa (absolute pressure), and tower still temperature is 15 ℃, and tower top temperature is 2 ℃.Obtaining purity from the tower still after the rectifying is 99.6% R 1216 (HFP), and the R 1216 collecting amount that reclaims from pipeline 10 is 10kg/h, gets back to the 2 continuation circulation separation of gas delivery membrane module from a small amount of azeotropic mixture that cat head produces by pipeline 9.
Infiltration gas arrives gas compressor 11 by pipeline 3, the gas of compression is earlier through-35 ℃ of condenser 12 condensations, phlegma is collected condensate storage 13, enter rectifying tower 14 rectifying then, rectifying tower 14 control conditions are pressure 1.5MPa (absolute pressure), tower still temperature is 40 ℃, and tower top temperature is 33 ℃.Obtaining purity from the tower still after the rectifying is 99.5% difluorochloromethane (F-22), and the difluorochloromethane collecting amount that reclaims from pipeline 16 is 42kg/h.Get back to the 2 continuation circulation separation of gas delivery membrane module from a small amount of azeotropic mixture that cat head produces by pipeline 15.
Claims (7)
1, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene separates and recovery method, it is characterized in that under envrionment temperature, self pressure, difluorochloromethane-R 1216 azeotropic mixture is passed through the gas delivery membrane module with gaseous state, obtain the infiltration gas that is mainly difluorochloromethane and the residual air of oozing that is mainly R 1216 of two strands of destroyed azeotropic ratios by the gas delivery membrane module, to ooze the condenser liquefaction of residual air process and collect condensate storage, enter rectifying tower then, obtain pure R 1216 from the tower still after the rectifying, from a small amount of azeotropic mixture of recovered overhead; After reclaiming pure R 1216, the a small amount of azeotropic mixture that reclaims in the rectifying is returned original low pressure gas holder in the tetrafluoroethylene production equipment together together with infiltration gas, and enter original distillation system in the tetrafluoroethylene production equipment, carry out normal rectifying separation and reclaim the difluorochloromethane process.
2, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 1 separates and recovery method, it is characterized in that in envrionment temperature, under the autogenous pressure, difluorochloromethane-R 1216 azeotropic mixture is passed through the gas delivery membrane module with gaseous state, obtain the infiltration gas that is mainly difluorochloromethane and the residual air of oozing that is mainly R 1216 of two strands of destroyed azeotropic ratios by the gas delivery membrane module, to permeate gas respectively and ooze residual air and liquefy separately, advance rectifying tower then respectively and reclaim pure difluorochloromethane and R 1216, a small amount of azeotropic mixture that reclaims returns the gas delivery membrane module again in the rectifying, and circulation is reclaimed.
3, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 1 and 2 separates and recovery method, it is characterized in that described difluorochloromethane-R 1216 azeotropic mixture is meant the azeotropic mixture that forms under tetrafluoroethylene ordinary production temperature and pressure condition, it consists of difluorochloromethane 80%-90%, R 1216 10%-20%.
4, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 3 separates and recovery method, and what it is characterized in that described difluorochloromethane-R 1216 azeotropic mixture consists of difluorochloromethane 87%, R 1216 13%.
5, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 1 and 2 separates and recovery method, it is characterized in that the industrial equipments of described gas delivery membrane module for carried out gas delivery that must the component combination by gas separation membrane and other.
6, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 5 separates and recovery method, it is characterized in that dissolving-parsing film that described gas separation membrane is made for the speciality polymer material.
7, a kind of difluorochloromethanazeotropic azeotropic hexafluoropropene according to claim 6 separates and recovery method, it is characterized in that described dissolving-parsings film is the rubbery state polymeric membrane of the azeotropic mixture that can pass through dissolving-resolving speed difference separation difluorochloromethane and R 1216 or in the vitreous state polymeric membrane any one.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100376523C (en) * | 2006-12-25 | 2008-03-26 | 山东东岳高分子材料有限公司 | Method and equipment for recovering F22 and hexafluoro propylene in tetrafluoroethylene production |
| CN101973843A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for preparing tetrafluoroethylene through dilution and pyrolysis of difluorochloromethane and water vapor |
| CN101973842A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for producing tetrafluoroethylene through pyrolysis of difluorochloromethane |
| CN102267851A (en) * | 2011-06-07 | 2011-12-07 | 上海三爱富新材料股份有限公司 | Separation method of hexafluoropropylene and monochlorodifluoromethane (F22) mixture |
| CN110078586A (en) * | 2019-05-06 | 2019-08-02 | 聊城氟尔新材料科技有限公司 | The device and technique of a kind of tetrafluoroethene coproduction hexafluoropropene and application |
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- 2006-02-22 CN CNB2006100384420A patent/CN100513369C/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100376523C (en) * | 2006-12-25 | 2008-03-26 | 山东东岳高分子材料有限公司 | Method and equipment for recovering F22 and hexafluoro propylene in tetrafluoroethylene production |
| CN101973843A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for preparing tetrafluoroethylene through dilution and pyrolysis of difluorochloromethane and water vapor |
| CN101973842A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for producing tetrafluoroethylene through pyrolysis of difluorochloromethane |
| CN102267851A (en) * | 2011-06-07 | 2011-12-07 | 上海三爱富新材料股份有限公司 | Separation method of hexafluoropropylene and monochlorodifluoromethane (F22) mixture |
| CN102267851B (en) * | 2011-06-07 | 2013-12-25 | 上海三爱富新材料股份有限公司 | Separation method of hexafluoropropylene and monochlorodifluoromethane (F22) mixture |
| CN110078586A (en) * | 2019-05-06 | 2019-08-02 | 聊城氟尔新材料科技有限公司 | The device and technique of a kind of tetrafluoroethene coproduction hexafluoropropene and application |
| CN110078586B (en) * | 2019-05-06 | 2022-05-27 | 聊城氟尔新材料科技有限公司 | Device and process for co-production of hexafluoropropylene from tetrafluoroethylene and application of device |
| CN114395127A (en) * | 2021-12-29 | 2022-04-26 | 山东华夏神舟新材料有限公司 | Polyimide resin for fluorine-containing gas separation and preparation method thereof |
| CN114395127B (en) * | 2021-12-29 | 2023-08-22 | 山东华夏神舟新材料有限公司 | Polyimide resin for separating fluorine-containing gas and preparation method thereof |
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