CN102675038B - Preparation method of 2, 3, 3, 3-tetrafluoropropene - Google Patents
Preparation method of 2, 3, 3, 3-tetrafluoropropene Download PDFInfo
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Abstract
The invention provides a preparation method of 2, 3, 3, 3-tetrafluoropropene, which comprises the following steps: taking monochlorodifluoromethane (R22) and methane chloride (methyl chloride) as raw materials and carrying out thermal cracking reaction at a high temperature of 600-1000 DEG C under the condition that N2 exits to prepare the 2, 3, 3, 3-tetrafluoropropene, wherein the volume ratio of the monochlorodifluoromethane to the methane chloride is 1-3:1, and the retention time of a reactant is 0.01-0.2 seconds. The reaction raw material used in the preparation method is easy to obtain, the defect of high cost of the used raw material in the prior art is overcome, the production cost is greatly reduced, and the reaction process is simple. The prepared 2, 3, 3, 3-tetrafluoropropene has the advantages of zero ODP and low GWP and can be used as a substitute of an automotive air-conditioning refrigerant.
Description
Technical field
The present invention relates to the preparation method of fluorinated olefin, it is a kind of refrigeration agent of novel, excellent performance, be specially 2,3,3, the preparation method of 3-tetrafluoeopropene (HFO-1234yf), it has the latent value (low GWP) of lower Greenhouse effect, zero depletion of the ozone layer is dived value (zero odp) and caused people's extensive concern, the invention belongs to technical field of chemistry.
Background technology
In recent years, global warming problem was day by day serious, and the discharge that reduces greenhouse gases has become one of focus of global environmental protection." Montreal Agreement book " determined the superseded timetable of HCFCs, and the substitute of HCFCs is mainly HFCs and their mixed thing at present, comprises R-32, R-134a, R-152a etc.Although the consumption ozone latent energy value (ODP) of HFCs is 0, it has the higher Greenhouse effect value (GWP) of diving, and is listed in the annex of greenhouse gases by Kyoto Protocol.Along with Greenhouse effect are more and more serious, people also pay attention to more to environmental problem, and from environmental requirement, HFCs is far from the ideal substitute of HCFCs.For meeting environmental requirement, it is 0 that the refrigeration agent substitute of a new generation requires not chloride element and ODP value, on this basis to low GWP value future development, it is found that in recent years 2,3,3,3-tetrafluoeopropene (HFO-1234yf) is as refrigeration agent substitute of new generation, its ODP is not only 0, but also has low GWP value, has good market outlook.And about 2,3,3, the preparation technology of 3-tetrafluoeopropene (HFO-1234yf) becomes the focus of research at present.
The technology of preparing of external HFO-1234yf starts from the 1950's, has the patent of Du Pont and Dow Chemical Company to see report.The Marquis david M of Du Pont delivered Preparation of 2,3,3 in 1964,3-tetrafluopropene[p] CA690037.1964-07-07, it is that raw material prepares 2,3 that described method is mainly by monochloro methane and tetrafluoroethylene, 3,3-tetrafluoeopropene, this process do not adopt catalyzer, temperature up to the condition of 950 ℃ under reaction preparation 2,3,3,3-tetrafluoeopropene, result shows that transformation efficiency also only has 13%, so be not suitable for realizing industrialization.Since entering 21 century, Du Pont and Honeywell affiliated company have delivered again a series of with HFC-245eb, HFC-215cb, HFC-225cb, HFC-235cb, HFC-245cb etc. prepare Patents and the document of HFC-1234yf for raw material, WO2008030440 (A2) discloses with 1, 2, 3, 3, 3-five fluorine propylene (HFC-1225ye) are that raw material first prepares 1 through hydro-reduction under associated catalysts exists, 1, 1, 1, 2, 3-five fluorine propylene (HFC-245eb) then HFC-245eb at non-water, thereby under existing, Non-alchoholic solvents existence and phase-transfer catalyst obtain target product HFC-1234yf by react de-HF with alkaline aqueous solution.This reaction reaction raw materials used is more expensive, and is difficult to obtain, thereby has increased cost, and because de-HF will use such as the organic solvent such as ether, aryl nitrile, environmental pollution is more serious in addition, so hindered the development of industrialization.The eighties in 20th century, large King Company also started the preparation research to HFO-1234yf, and HFO-1234yf is mainly as polymerization single polymerization monomer and comonomer at that time, and great Jin publication number is US73038947, and the basic skills of introduction is for take fluoro ethanol as raw material, (general formula is R
fcF
2cH
2zOH) with the thionyl chloride effect that is catalyzer at aminocompound under, in DMF solution, reaction prepares R
fcF
2cH
2cl, then products therefrom R
fcF
2cH
2thereby Cl reacts and obtains target product with metallic zinc, owing to will using poisonous organic solvent thionyl chloride in reaction process, so be difficult to after reaction process the organic solvent using, in this patent, second step reaction yield is very low in addition, considers this method and is difficult to realize industrialization.21 century is particularly after 2004, HFO-1234yf is as the potential environmental protection refrigerant of one, its preparation method enters flourish period, the multiple synthetic route of having prepared aspect developing at HFO-1234yf such as Du Pont, Honeywell, great Jin, wherein just there are several operational paths with industrialization potentiality, if Du Pont is with CX
3the syntheti c route that CCl=CClY (X, Y select to F or Cl) is raw material and Honeywell are with CCl
2=CClCH
2cl great Jin is with CHF
2cF
2cH
2oH is the syntheti c route of starting raw material.In research syntheti c route, their separation to HFO-1234yf and method of purification have also been done large quantity research, if the publication number of du pont company's application is CN101351428A, the patent Introduction of the WO2008130919 of the patent of US2008308763 and Honeywell application from HFC-245cb, HF, in HFO-1234yf, separate the method that obtains pure HFO-1234yf, its basic ideas are for to introduce distillation tower by tertiary mixture, HFC-245cb first reclaims from tower reactor bottom, HF and HFO-1234yf form binary azeotrope or nearly azeotrope is drawn and entered another distillation tower from tower top, at the bottom of fractionation by distillation tower, form HF enrichment phase, pump around circuit is to last distillation tower, tower top forms HFO-1234yf enrichment phase, introduce again another distillation tower, transformation distillation had both obtained HFO-1234yf.HFO-1234yf is just walking realizing the road of suitability for industrialized production.The research of the domestic preparation to HFO-1234yf is less, almost has no the report of HFO-1234yf industrialization technology aspect.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, in order to realize production domesticization and the industrialization of HFO-1234yf, the invention provides a kind of 2,3,3 of suitability for industrialized production that is suitable for, the preparation method of 3-tetrafluoeopropene (HFO-1234yf).
Technical scheme of the present invention is as follows:
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, with difluorochloromethane (R
22) and monochloro methane (methyl chloride) be raw material, at N
2gas exist under, under 600～1000 ℃ of hot conditionss, heat scission reaction makes 2,3,3,3-tetrafluoeopropene; Wherein, described difluorochloromethane and monochloro methane volume ratio are 1～3: 1, reactant residence time 0.01～0.2s.
According to the present invention, preferred, described difluorochloromethane and monochloro methane volume ratio are 1.5～2.5: 1, and further preferably difluorochloromethane and monochloro methane volume ratio are 1.8～2.2: 1.
According to the present invention, preferred, a kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the steps:
(1) raw material mixture
By proportioning, to passing into difluorochloromethane and monochloro methane in mixing vessel as hybrid reaction gas, then pass into nitrogen, the volume ratio that passes into nitrogen is 5%～30% of hybrid reaction gas volume, reacts front premix;
(2) cracking
Replace 3-5min to passing into nitrogen in reactor, more pre-step (1) mixed gas is passed in reactor, control 600～1000 ℃ of temperature of reaction, pressure 0～1MPa, the residence time of reactant in reactor is 0.01～0.2s;
(3) import and fill the quenching apparatus of water or alkali lye from reactor product mixed flow out, chilling obtains the mixture flow that contains 2,3,3,3-tetrafluoeopropene (HFO-1234yf); Then carry out drying treatment;
(4) mixture of step (3) gained is obtained by fractionation by distillation pure 2,3,3,3-tetrafluoeopropene (HFO-1234yf) product.
According to the present invention, preferred, the volume ratio that step (1) passes into nitrogen is 10%～15% of hybrid reaction gas volume.
According to the present invention, preferred, in step (2), temperature of reaction is 750～950 ℃, and the residence time of reactant in reactor is 0.05～0.1s.
According to the present invention, preferred, the reactor in step (2) heats up and adopts Resistant heating mode.
According to the present invention, preferred, described in step (2), reaction pressure is 0.1～0.5MPa.Further preferred reaction pressure is 0.2～0.4MPa.
According to the present invention, preferred, the quenching apparatus adopting in step (3) is the air collector that fills alkali lye.Not only can be by reacted mixture chilling, but also reach the object of deacidification.In step (3), mixture is dry by prior art, carries out drying treatment by vitriol oil drying installation.
In above-mentioned steps of the present invention (3), mixture liquid is dry, and sampling adopts gc analysis compositions of mixtures, and wherein 2,3,3, the massfraction of 3-tetrafluoeopropene (HFO-1234yf) is 13～20%.
The present invention's reaction raw materials used is commercial.In step of the present invention (1), mixing vessel used can be steel cylinder.
The reactor used material of the present invention be not with difluorochloromethane (R
22) material that reacts with monochloro methane (methyl chloride) makes, and is selected from palladium metal, silver or high carbon steel material, considers reaction cost problem, the preferred SUS316 stainless steel of the present invention tubular reactor processed.
Described SUS316 stainless steel tubular reactor processed is placed in vitrified pipe, and vitrified pipe outside looping resistance wire is with the insulation of pure aluminium silicate insulating cotton, temperature required by the Resistant heating with temperature controller and thermopair control reaction.
Technical characterstic of the present invention:
1, first, the present invention is with the lower difluorochloromethane (R of price
22) with monochloro methane (methyl chloride) be reaction raw materials, mechanism is CHClF
2hot conditions is cracked into difluorocarbene, and two molecule difluorocarbenes are combined into a part tetrafluoroethylene, thereby tetrafluoroethylene continues to react and obtain target product with monochloro methane.A key factor is the volume ratio of two kinds of reactants, and the present invention finds described difluorochloromethane (R
22) with monochloro methane (methyl chloride) volume ratio 1～3: the 1st, suitable, most preferably be 1.8～2.2: 1.In the time that the two reaction volume ratio exceedes 2.2: 1, difluorochloromethane (R
22) can be superfluous, cause the waste of raw material.
2, the present invention is raw materials used is mixture before reaction, and the two all exists with gas phase form in mixing vessel, has guaranteed that the volume ratio of charging is accurately controlled.
3, the present invention surprisingly finds to be filled with 5%～30% nitrogen, and preferred volume ratio is 10%～15%, also has the effect of heat-transfer medium except can be used as diluent gas; The excessive reactant contact probability that causes of nitrogen volume ratio reduces, thereby causes productive rate to reduce, and nitrogen volume ratio is too small makes reaction obtain polymkeric substance or the mixed polymers that molecular weight is larger, and can not get target product 2,3,3,3-tetrafluoeopropene (HFO-1234yf).
4, reaction of the present invention is thermal cracking processes, 600～1000 ℃ of temperature of reaction, further preferably 750～950 ℃, the too low reaction institute energy requirement that do not reach of temperature of reaction, cannot obtain target product, the too high meeting of temperature of reaction causes carbonization, thereby stops up reaction unit.Reaction unit type of heating can be used electrically heated comparatively easily, reaction unit can be put in an electric heater unit or High Temperature Furnaces Heating Apparatus, and this reaction adopts Resistant heating mode that heat is provided.
5, reaction of the present invention, the residence time of reactant in reaction unit is preferably 0.05～0.1s of reaction times, too short reactant contact of the residence time not exclusively, cause products collection efficiency lower, easily there is autohemagglutination or the mixed poly-product that produces high molecular in overstand, and can not get target product 2,3,3,3-tetrafluoeopropene (HFO-1234yf).The length that the determinative of the residence time of reactant in reaction unit is reaction unit and the product of cross-sectional area, be the volume of reaction unit and the uninterrupted of participating in reactant gases, the residence time is the ratio of reaction unit volume and gas flow size.After reaction unit is determined, the residence time can be controlled by the uninterrupted of controlling reactant gases.
6, reaction pressure of the present invention is at normal pressure or be slightly larger than under condition of normal pressure and carry out, preferably 0.1～0.5MPa, and the excessive generation that impels autohemagglutination or mixed poly-reaction of reaction pressure, thus can not get target product.
7, reaction of the present invention, by from reaction unit, the mixture of reaction products out imports in the quenching apparatus that fills water or alkali lye at once, thereby avoid the generation of secondary reaction, the quenching apparatus that the present invention preferably adopts is the air collector that fills alkali lye, not only can be by reacted mixture chilling, but also reach the object of deacidification, and deacidification effect will be got well compared with cold water, mixture after deacidification is through super-dry, then sampling, gas-chromatography is carried out analysis of mixtures composition, 2, 3, 3, the separation method of 3-tetrafluoeopropene (HFO-1234yf) from mixture can adopt distillation, thereby by 2, 3, 3, 3-tetrafluoeopropene (HFO-1234yf) is isolated from mixture, obtain purity higher 2, 3, 3, 3-tetrafluoeopropene (HFO-1234yf) product.
Compared with prior art excellent results of the present invention:
Preparation method provided by the invention without catalyzer, has overcome the easy coking and deactivation of catalyzer, continuous defect with short production cycle in reaction process.The present invention's reaction raw materials used be easy to get and commercially available price lower, thereby the cost that also makes this route prepare target product reduces greatly.The present invention has optimized the proportioning of raw material, in reaction raw materials, is filled with nitrogen, has overcome the easy carbonization of pyroreaction, avoids finishing the phenomenon that carbon easily causes device to stop up, thereby has reduced the maintenance of installing, and has improved device service efficiency.The present invention is prepared 2,3,3, and 3-tetrafluoeopropene has advantages of zero odp, low GWP, can be used as the ideal substitute of car air conditioner refrigerant.
Embodiment
Below in conjunction with embodiment, the present invention is described further, it should be noted that, following embodiment is only for explanation, and not for limiting the present invention.The various variations that those skilled in the art's derivation according to the present invention is made all should be within the desired protection domain of the application's claim.In embodiment, reaction unit used is this area conventional equipment, and reaction raw materials used is commercial product.
Embodiment 1:
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, with difluorochloromethane (R
22) and monochloro methane (methyl chloride) be raw material, under hot conditions, there is scission reaction and obtain 2,3,3,3-tetrafluoeopropene.Chemical equation is as follows:
2CHClF
2+CH
3Cl→CF
3CF＝CH
2+3HCl
In the steel cylinder that is 8L to volume, be filled with 27.3g monochloro methane, 93.5g difluorochloromethane, be then filled with nitrogen 5g, premix.
Be that 6mm, the long SUS316 stainless steel tubulation formula reactor assembly for 40cm are placed in vitrified pipe by internal diameter, vitrified pipe outside looping resistance wire, with the insulation of pure aluminium silicate insulating cotton, temperature required by the Resistant heating with temperature controller and thermopair control reaction.
Adjust temperature controller registration, first reaction unit is preheated, until temperature-stable after 750 ℃, replace to passing into nitrogen in reaction unit, reaction unit is replaced after 3-5min, again the reaction mixture that premix prepares is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 6.78L/min, Controlling System pressure is 0.4MPa, import and fill the quenching apparatus of alkali lye from reaction unit product mixed flow out, chilling obtains containing 2,3, the mixture flow of 3,3-tetrafluoeopropene (HFO-1234yf); In sampling gas chromatographic analysis mix products 2,3,3,3-tetrafluoeopropene massfraction is 14.8%.After super-dry, mixture flow finally obtains 2,3,3,3-tetrafluoeopropene product through rectifying separation again.
Embodiment 2:
As described in Example 1, difference is: adjust temperature controller registration, first reaction unit is preheated, until temperature-stable after 850 ℃, replace to passing into nitrogen in reaction unit, reaction unit is replaced after 3-5min, again the reaction mixture that mixture is good is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 6.78L/min, Controlling System pressure is 0.4MPa, import and fill the quenching apparatus of alkali lye from reaction unit product mixed flow out, chilling obtains containing 2, 3, 3, the mixture flow of 3-tetrafluoeopropene (HFO-1234yf), sampling gas chromatographic analysis analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 14.1%.After super-dry, mixture flow finally obtains 2,3,3,3-tetrafluoeopropene product through separating again.
Embodiment 3:
As described in Example 1, difference is: adjust temperature controller registration, first reaction unit is preheated, until temperature-stable after 950 ℃, replace to passing into nitrogen in reaction unit, reaction unit is replaced after 3-5min, then the reaction mixture that mixture is good is passed in reaction unit; Other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 13.2%.
Embodiment 4:
As described in Example 1, difference is: adjust temperature controller registration, first reaction unit is preheated,, after 750 ℃, replace to passing into nitrogen in reaction unit until temperature-stable, reaction unit is replaced after 3-5min, again the reaction mixture that mixture is good is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 8.48L/min, and Controlling System pressure is 0.4MPa, and other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 16.5%.
Embodiment 5:
As described in Example 1, difference is: the flow that enters reaction unit by under meter control mixed gas is 11.3L/min, and Controlling System pressure is 0.4MPa; Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 19.2%.
Embodiment 6:
As described in Example 1, difference is: adjust temperature controller registration, reaction unit preheats,, after 850 ℃, replace to passing into nitrogen in reaction unit until temperature-stable, reaction unit is replaced after 3-5min, again the reaction mixture that mixture is good is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 8.48L/min, and Controlling System pressure is 0.4MPa, and other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 13.6%.
Embodiment 7:
As described in Example 1, difference is: adjust temperature controller registration, reaction unit preheats,, after 950 ℃, replace to passing into nitrogen in reaction unit until temperature-stable, reaction unit is replaced after 3-5min, again the reaction mixture that mixture is good is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 11.3L/min, and Controlling System pressure is 0.4MPa, and other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 13.2%.
The increase constant, reactant gases flow velocity of Comprehensive Correlation embodiment 1,4,5 temperature of reaction is under the condition shortening in the reaction times, obtain 2,3,3, the productive rate of 3-tetrafluoeopropene increases, and experimental result shows difluorochloromethane (R
22) and the transformation efficiency of monochloro methane (methyl chloride) reduce.
The increase of Comprehensive Correlation embodiment 1,6,7 risings along with temperature of reaction, reactant gases flow velocity is the shortening in reaction times, obtain 2,3,3, the productive rate of 3-tetrafluoeopropene approaches, and experimental result shows difluorochloromethane (R
22) and the transformation efficiency ratio of monochloro methane (methyl chloride) approach quantitatively.
Embodiment 8:
As described in Example 1, difference is:, after 950 ℃, replace to passing into nitrogen in reaction unit until temperature-stable, reaction unit is replaced after 3-5min, Controlling System pressure is 0.3MPa, and other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 15.2%.
Embodiment 9:
As described in Example 1, difference is:, after 950 ℃, replace to passing into nitrogen in reaction unit until temperature-stable, reaction unit is replaced after 3-5min, Controlling System pressure is 0.2MPa, and other step is with embodiment 1.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 15.9%.
Embodiment 10:
As described in Example 1, difference is: in the steel cylinder that is 8L to volume, be filled with 27.3g monochloro methane, and be filled with 70.2g difluorochloromethane, be then filled with nitrogen 5g.Adjust temperature controller registration, first reaction unit is preheated, until temperature-stable after 750 ℃, replace to passing into nitrogen in reaction unit, reaction unit is replaced after 3-5min, again the reaction mixture that mixture is good is passed in reaction unit, the flow that enters reaction unit by under meter control mixed gas is 6.78L/min, Controlling System pressure is 0.4MPa, from reaction unit product mixed flow out through over-quenching alkali cleaning, dry after, more finally obtain 2,3 through rectifying separation, 3,3-tetrafluoeopropene product.Mixture flow sampling gas chromatographic analysis, in mix products 2,3,3,3-tetrafluoeopropene massfraction is 14.9%.
Embodiment 11:
As described in Example 1, difference is: in the steel cylinder that is 8L to volume, be filled with 27.3g monochloro methane, and be filled with 116.9g difluorochloromethane, be then filled with nitrogen 5g.Other step is with embodiment 1.In mixture flow sampling gas chromatographic analysis mix products 2,3,3,3-tetrafluoeopropene massfraction is 14.6%.
Comprehensive Correlation embodiment 1,8,9, under temperature of reaction the same terms, only changes system response pressure, along with reducing of reaction pressure, and target product 2,3,3,3-tetrafluoeopropene presents the trend of continuous increase.I.e. this reaction is the reaction that molecule sum increases, and pressure reduces balance and is moved, thereby has occurred that certain limit internal pressure reduces, and products collection efficiency raises.
Comprehensive Correlation embodiment 1,10,11 under temperature of reaction, system pressure the same terms, changes the mixed ratio of two kinds of reaction raw materials in the selected scope of the present invention, little on the yield impact of target product.
Claims (4)
1. one kind 2,3,3, the preparation method of 3-tetrafluoeopropene, step is as follows:
(1) raw material mixture
By proportioning, to passing into difluorochloromethane and monochloro methane in mixing vessel as hybrid reaction gas, then pass into nitrogen, the volume ratio that passes into nitrogen is 5%～30% of hybrid reaction gas volume, reacts front premix;
Described difluorochloromethane and monochloro methane volume ratio are 1～3:1;
(2) cracking
Replace 3-5min to passing into nitrogen in reactor, more pre-step (1) mixed gas is passed in reactor, control 750～950 ℃ of temperature of reaction, pressure 0.1～0.5MPa, the residence time of reactant in reactor is 0.05～0.1s;
Reactor used is the tubular reactor of the stainless steel of SUS316; Described SUS316 stainless steel tubular reactor processed is placed in vitrified pipe, and vitrified pipe outside looping resistance wire is with the insulation of pure aluminium silicate insulating cotton, temperature required by the Resistant heating with temperature controller and thermopair control reaction;
(3) the product mixed flow reflecting imports and fills in the quenching apparatus of water or alkali lye, and chilling obtains the mixture flow that contains 2,3,3,3-tetrafluoeopropene;
(4) mixture of step (3) is obtained by fractionation by distillation pure 2,3,3,3-tetrafluoeopropene product.
2. as claimed in claim 12,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that, described difluorochloromethane and monochloro methane volume ratio are 1.5～2.5:1.
3. as claimed in claim 12,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that, described difluorochloromethane and monochloro methane volume ratio are 1.8～2.2:1.
4. as claimed in claim 12,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that, the volume ratio that step (1) passes into nitrogen is 10%～15% of hybrid reaction gas volume.
5, as claimed in claim 12,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that, described in step (2), reaction pressure is 0.2～0.4MPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3402771A4 (en) * | 2016-01-14 | 2019-07-31 | Srf Limited | Process for the preparation of olefin containing fluorine |
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| JP5201284B1 (en) * | 2012-03-14 | 2013-06-05 | 旭硝子株式会社 | Method for producing 2,3,3,3-tetrafluoropropene |
| CN103833511B (en) * | 2012-11-26 | 2016-01-20 | 山东东岳高分子材料有限公司 | The preparation method of 2,3,3,3-tetrafluoeopropene |
| CN105111041B (en) * | 2015-08-18 | 2017-11-21 | 巨化集团技术中心 | A kind of method that tetrafluoropropene HFO1234yf is synthesized with tetrafluoroethene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2931840A (en) * | 1958-11-25 | 1960-04-05 | Du Pont | Process for preparing 2, 3, 3, 3-tetrafluoropropene |
| CN101913989A (en) * | 2010-09-07 | 2010-12-15 | 西安近代化学研究所 | Production method of 2,3,3,3-tetrafluoropropene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2931840A (en) * | 1958-11-25 | 1960-04-05 | Du Pont | Process for preparing 2, 3, 3, 3-tetrafluoropropene |
| CN101913989A (en) * | 2010-09-07 | 2010-12-15 | 西安近代化学研究所 | Production method of 2,3,3,3-tetrafluoropropene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3402771A4 (en) * | 2016-01-14 | 2019-07-31 | Srf Limited | Process for the preparation of olefin containing fluorine |
| JP7014709B2 (en) | 2016-01-14 | 2022-02-01 | エスアールエフ リミテッド | Method for producing fluorine-containing olefin |
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