CN1634902A - Clean preparation process for hexafluropropylene oxide - Google Patents
Clean preparation process for hexafluropropylene oxide Download PDFInfo
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- CN1634902A CN1634902A CNA2004100553839A CN200410055383A CN1634902A CN 1634902 A CN1634902 A CN 1634902A CN A2004100553839 A CNA2004100553839 A CN A2004100553839A CN 200410055383 A CN200410055383 A CN 200410055383A CN 1634902 A CN1634902 A CN 1634902A
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- propylene oxide
- oxide hexafluoride
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- environment
- supercutical fluid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses an environmental protection method for preparing hexafluropropylene oxide from hexafluoropropylene by dioxygen liquid phase oxidation method. The method employs at least one supercritical fluid as solvent for replacing the CFCs with destructive effect to atmospheric ozone layer. The supercritical fluid as solvent is used in the invention which can reduce induction period of reaction and prevent the temperature raise in short time at the beginning of reaction.
Description
Technical field
The present invention relates to a kind of green technology of preparing of Propylene oxide hexafluoride, promptly is solvent with the supercutical fluid, and the R 1216 liquid-phase oxidation prepares Propylene oxide hexafluoride.
Technical background
Propylene oxide hexafluoride is an important fluoro-containing intermediate, is the important source material of producing Perfluoroacetone, perfluor Virahol, PFPE and perfluoroalkyl vinyl ether etc.
The preparation method of Propylene oxide hexafluoride has many, as photochemical oxidation method and radiological chemistry oxidation style, patent GB1034492 and patent UK931578 have introduced R 1216 can oxidation generate Propylene oxide hexafluoride under the initiation of light and different ionized radiation sources, but this method exists the equipment complexity, reacts unfavorable factor such as relatively danger.Patent US3775438 and patent JP52053804 have reported that also the R 1216 catalytic gas phase oxidation prepares the method for Propylene oxide hexafluoride in addition, and this arts demand carries out in high temperature under the effect of catalyzer, and the transformation efficiency of reaction and selectivity are all undesirable.There is Propylene oxide hexafluoride to prepare again by the electrochemical oxidation process of R 1216.But above three kinds of methods still do not possess the value of commercial exploitation.
There is the Propylene oxide hexafluoride preparation method of industrial significance that R 1216 nucleophilic oxidation style and liquid-phase oxidation of molecular oxygen method are arranged at present.
Patent JP83131976 and patent EP64293 propose to make oxygenant with hydrogen peroxide or chlorine bleach liquor, and the R 1216 oxidation prepares the method for Propylene oxide hexafluoride.By selecting suitable solvent and phase-transfer catalyst then can improve the result of reaction.In this synthetic method, reaction must be controlled at low temperature liquid phase to be carried out, owing to there is the hydrogen fluoride by product to generate in the reaction, the corrosion of conversion unit also is a bigger problem simultaneously, has a large amount of waste water to produce in addition in the reaction process, must handle.
The problem that adopts the liquid-phase oxidation of molecular oxygen rule can avoid the nucleophilic oxidation style to bring.The liquid-phase oxidation of molecular oxygen method is in the presence of certain temperature, pressure and solvent, and the hexafluoro-propylene direct oxidation generates Propylene oxide hexafluoride.Identical with the nucleophilic oxidation style, in this technology, choice of Solvent is a The key factor.It is generally acknowledged that hexafluoro-propylene is difficult to dissolving in general solvent, only have solvability preferably in the solvent of Chlorofluorocarbons (CFCs) and perfluoroalkanes.Proposed to prepare the method for Propylene oxide hexafluoride as solvent as patent CN1320598, and patent US3536733 has proposed different solvent selection schemes, comprising tetracol phenixin, CFC-113, CFC-11 etc. with Chlorofluorocarbons (CFCs).In the industrial production of reality, because the perfluoroalkanes solvent is difficult to obtain and costs an arm and a leg, generally all select for use Chlorofluorocarbons (CFCs) (CFCs) as CFC-113, CFC-11 and CFC-12 make solvent, and wherein CFC-113 is the most commonly used.But because CFCs has destruction to atmospheric ozone layer, classified as Ozone Depleting Substances by Montreal Protocol on Substances that Deplete the Ozone Layer, each national capital must be eliminated at the appointed time.For this reason, patent JP2003040879 proposes to adopt CF
2ClCF
2CHFCl and CF
3(CF
2)
5H makes solvent CFC alternative-113, but the solvent that this patent proposed is difficult to obtain while CF first
2ClCF
2CHFCl also still belongs to the material that damages the ozone layer.Therefore selecting a kind of while not only functional, cheap and easy to get but also environment amenable solvent, is the key factor that realizes the green production of Propylene oxide hexafluoride.
Summary of the invention
The present invention will solve is existing Propylene oxide hexafluoride preparation method has the problem of destruction to atmospheric ozone layer, and a kind of preparation method of Propylene oxide hexafluoride of environment-friendly type is provided.
The present invention also to provide a kind of inductive phase short, speed of response is fast and the preparation method of the Propylene oxide hexafluoride of reacting balance.
The present invention also will provide the preparation method of the high Propylene oxide hexafluoride of a kind of reaction preference.
To achieve the above object of the invention, the present invention adopts following technical scheme: the environment-friendly preparation method thereof of Propylene oxide hexafluoride, R 1216 is generated Propylene oxide hexafluoride with the liquid-phase oxidation of molecular oxygen method, it is characterized in that this method adopts at least a supercutical fluid as solvent.
Characteristics of the present invention are to adopt supercutical fluid to make the CFCs that solvent substitutes normality, and in supercutical fluid, R 1216 is subjected to the oxidation of molecular oxygen to generate Propylene oxide hexafluoride like this.
The present invention adopts supercutical fluid to make solvent, substitutes the CFCs that atmospheric ozone layer is had destruction, thereby realizes the green production of Propylene oxide hexafluoride.
In the present invention, all in principle supercutical fluids can be selected as the solvent that reacts.Preferentially these supercutical fluids are zero hydrogen fluorohydrocarbon (HFCs) for consuming the ozone latent energy value; More preferably, the critical temperature of selected hydrogen fluorohydrocarbon approaches to react needed temperature, is 0.8～1.2 to be advisable with reduced temperature generally.Supercutical fluid can be made solvent separately and use, and also can two or more mix use.
Supercutical fluid had both had the same good solubility energy of liquid, and it is little to have viscosity as gas again simultaneously, the characteristic that spread coefficient is big, so supercutical fluid is particularly suitable for the reaction that some are subjected to diffusion control.When liquid-phase oxidation of molecular oxygen prepared Propylene oxide hexafluoride, if use the CFC-113 solvent, oxidizing reaction had usually and occurs an inductive phase.And use supercutical fluid to make solvent in the present invention, and shorten the inductive phase of reaction even disappearance, thereby the carrying out of having accelerated reaction also can prevent to produce the phenomenon that heats up suddenly in initial reaction stage simultaneously, make to react to become more steady.This is another characteristics of the present invention.
Another characteristics of the present invention are to select suitable supercutical fluid for use, not only help improving speed of response, can also improve the reaction preference of Propylene oxide hexafluoride simultaneously, thereby improve the yield of Propylene oxide hexafluoride.
The raw material that the present invention prepares Propylene oxide hexafluoride is a R 1216, and the autoclave discontinuous that is reflected at a band stirring is carried out.Before the reaction beginning, at first add R 1216 and supercutical fluid, slowly heat up then.When treating that temperature reaches the temperature of reaction of setting, aerating oxygen is controlled the feeding amount of each oxygen in case reaction heats up too high off and on.
The ingredient proportion of supercutical fluid of the present invention and R 1216 does not have strict requirement.In general, the ingredient proportion that improves supercutical fluid helps improving the selectivity of Propylene oxide hexafluoride, but high ingredient proportion will influence the throughput of reactor.The suitable supercutical fluid and the ingredient proportion of R 1216 are 1～20 among the present invention, are preferably 2～15, more preferably are 3～10.
In the present invention, temperature of reaction has bigger influence to reaction result, and general temperature of reaction should be controlled at 60～180 ℃, is preferably 80～160 ℃, more preferably is 90～140 ℃.Temperature is too low, and reaction becomes very slow, and reaction simultaneously has and occurs very long inductive phase.And temperature is too high, can cause the decomposition of Propylene oxide hexafluoride, influences the yield of product.
Embodiment
Be described in detail embodiments of the present invention below
Embodiment 1
Add the overcritical HFC-227ea of 500g and the R 1216 of 100g respectively in the stainless steel cauldron that 1 liter of band stirs, be warming up to 120 ℃ gradually, equilibrium temperature is after half an hour, and slowly aerating oxygen is treated to stop aerating oxygen after oxygen partial pressure reaches 0.2MPa.Because exothermic heat of reaction, temperature of reaction and pressure rise, therefore should by the time temperature of reaction and pressure recovery and stable after aerating oxygen again, and the dividing potential drop of control oxygen is 0.2MPa.Aerating oxygen is used the gas chromatographic analysis reaction product after 12 hours so repeatedly, and the transformation efficiency that calculates R 1216 is 99.4%, and the selectivity of Propylene oxide hexafluoride is 43.5%, does not observe the inductive phase of reaction.
Embodiment 2
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid is used HFC-143a instead, and the transformation efficiency that obtains R 1216 is 89.1%, and the selectivity of Propylene oxide hexafluoride is 34.4%, and observing reaction has 3 hours inductive phase.
Embodiment 3
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid is used HFC-134a instead, and the reaction times is 10 hours.The transformation efficiency that obtains R 1216 is 96.8%, and the selectivity of Propylene oxide hexafluoride is 44.3%, and observing reaction has 2 hours inductive phase.
Embodiment 4
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid is used HFC-125 instead, and temperature of reaction is 110 ℃, and the reaction times is 4 hours, and the dividing potential drop of each aerating oxygen is 0.5MPa.The transformation efficiency that obtains R 1216 is 89.6%, and the selectivity of Propylene oxide hexafluoride is 61.3%, does not observe the inductive phase of reaction.
Embodiment 5
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid changes HFC-236fa into, and the transformation efficiency that obtains R 1216 is 97.1%, and the selectivity of Propylene oxide hexafluoride is 64.0%, does not observe the inductive phase of reaction.
Embodiment 6
Reaction unit is identical with embodiment 5 with operational condition, but temperature of reaction is 130 ℃, and in 9 hours reaction times, the transformation efficiency that obtains R 1216 is 91.0%, and the selectivity of Propylene oxide hexafluoride is 66.9%, does not observe the inductive phase of reaction.
Embodiment 7
Reaction unit is identical with embodiment 5 with operational condition, but the ingredient proportion of HFC-236fa and R 1216 is 7.5 (weight ratios), the transformation efficiency that obtains R 1216 is 76.1%, and the selectivity of Propylene oxide hexafluoride is 69.7%, does not observe the inductive phase of reaction.
Embodiment 8
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid changes carbonic acid gas into, and the transformation efficiency that obtains R 1216 is 80.9%, and the selectivity of Propylene oxide hexafluoride is 20.5%.
Embodiment 9
Reaction unit is identical with embodiment 1 with operational condition, but supercutical fluid changes propane into, and the transformation efficiency that obtains R 1216 is 55.6%, and the selectivity of Propylene oxide hexafluoride is 35.8%.
Comparative example
Reaction unit is identical with embodiment 1 with operational condition, but reaction solvent is CFC-113, reacts after 12 hours, and the transformation efficiency that obtains R 1216 is 96.1%, and the selectivity of Propylene oxide hexafluoride is 55.8%, and observing reaction has 4 hours inductive phase.
Claims (8)
1, the environment-friendly preparation method thereof of Propylene oxide hexafluoride generates Propylene oxide hexafluoride with R 1216 with the liquid-phase oxidation of molecular oxygen method, it is characterized in that this method adopts at least a supercutical fluid as solvent.
2, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 1, the consumption ozone latent energy value that it is characterized in that described supercutical fluid are zero.
3, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 2 is characterized in that described supercutical fluid is hydrogen fluorohydrocarbon (HFCs).
4, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 3 is characterized in that described supercutical fluid is HFC-227ea, HFC-143a, HFC-134a, HFC-125, HFC-236fa any one or two kinds and above combination wherein.
5, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 3 is characterized in that the critical temperature of described hydrogen fluorohydrocarbon (HFCs) approaches to react needed temperature.
6, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 5, the critical temperature that it is characterized in that described hydrogen fluorohydrocarbon (HFCs) is for reacting temperature required 0.8～1.2 times.
7, as the environment-friendly preparation method thereof of any one described Propylene oxide hexafluoride of claim 1～6, the ingredient proportion that it is characterized in that described supercutical fluid and R 1216 is 1～20.
8, the environment-friendly preparation method thereof of Propylene oxide hexafluoride as claimed in claim 7 is characterized in that temperature of reaction should be controlled at 60～180 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100553839A CN1285583C (en) | 2004-09-01 | 2004-09-01 | Clean preparation process for hexafluropropylene oxide |
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|---|---|---|---|
| CNB2004100553839A CN1285583C (en) | 2004-09-01 | 2004-09-01 | Clean preparation process for hexafluropropylene oxide |
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| CN1634902A true CN1634902A (en) | 2005-07-06 |
| CN1285583C CN1285583C (en) | 2006-11-22 |
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| CNB2004100553839A Active CN1285583C (en) | 2004-09-01 | 2004-09-01 | Clean preparation process for hexafluropropylene oxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966498B (en) * | 2006-11-14 | 2010-05-12 | 上海三爱富新材料股份有限公司 | Hexafluoroepoxypropane preparation process |
| CN101456849B (en) * | 2008-12-30 | 2011-05-11 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
| CN102822155A (en) * | 2010-03-29 | 2012-12-12 | 大金工业株式会社 | Method for producing carbonyl fluoride and hexafluoropropylene oxide |
| CN104557797A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Method for shortening induction period of epoxidation reaction of hexafluoropropylene |
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
| CN104672177A (en) * | 2013-12-03 | 2015-06-03 | 浙江化工院科技有限公司 | Hexafluropropylene oxide continuous production technique |
-
2004
- 2004-09-01 CN CNB2004100553839A patent/CN1285583C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966498B (en) * | 2006-11-14 | 2010-05-12 | 上海三爱富新材料股份有限公司 | Hexafluoroepoxypropane preparation process |
| CN101456849B (en) * | 2008-12-30 | 2011-05-11 | 清华大学 | Method and apparatus for preparing epoxypropane by catalyzing propone epoxidation at supercritical condition |
| CN102822155A (en) * | 2010-03-29 | 2012-12-12 | 大金工业株式会社 | Method for producing carbonyl fluoride and hexafluoropropylene oxide |
| CN102822155B (en) * | 2010-03-29 | 2015-07-08 | 大金工业株式会社 | Method for producing carbonyl fluoride and hexafluoropropylene oxide |
| CN104557797A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Method for shortening induction period of epoxidation reaction of hexafluoropropylene |
| CN104557788A (en) * | 2013-10-28 | 2015-04-29 | 浙江蓝天环保高科技股份有限公司 | Preparation method of hexafluoropropylene oxide |
| CN104557797B (en) * | 2013-10-28 | 2017-09-19 | 浙江蓝天环保高科技股份有限公司 | A kind of method for shortening hexafluoropropene epoxidation reaction induction period |
| CN104672177A (en) * | 2013-12-03 | 2015-06-03 | 浙江化工院科技有限公司 | Hexafluropropylene oxide continuous production technique |
| CN104672177B (en) * | 2013-12-03 | 2018-05-15 | 浙江化工院科技有限公司 | A kind of hexafluoropropylene oxide continuous production processes |
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| Publication number | Publication date |
|---|---|
| CN1285583C (en) | 2006-11-22 |
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Owner name: SINOCHEM LANTIAN CO., LTD. Free format text: FORMER OWNER: ZHEJIANG LANTIAN ENVIRONMENT PROTECTING SCI-TECH CO., LTD. Effective date: 20130221 Owner name: ZHEJIANG LANTIAN ENVIRONMENT PROTECTING SCI-TECH C Effective date: 20130221 |
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Free format text: CORRECT: ADDRESS; FROM: 310012 HANGZHOU, ZHEJIANG PROVINCE TO: 310051 HANGZHOU, ZHEJIANG PROVINCE |
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Effective date of registration: 20130221 Address after: 310051 Binjiang District Jiangnan Road, Zhejiang, No. 96, No. Patentee after: Sinochem Lantian Co., Ltd. Patentee after: Zhejiang Lantian Environment Protecting Sci-Tech Co., Ltd. Address before: Hangzhou City, Zhejiang province 310012 Moganshan Road No. 639 building two Deyuan Patentee before: Zhejiang Lantian Environment Protecting Sci-Tech Co., Ltd. |