CN102001912A - Method for synthesizing 3,3,3-trifluoropropene - Google Patents
Method for synthesizing 3,3,3-trifluoropropene Download PDFInfo
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- CN102001912A CN102001912A CN201010528771XA CN201010528771A CN102001912A CN 102001912 A CN102001912 A CN 102001912A CN 201010528771X A CN201010528771X A CN 201010528771XA CN 201010528771 A CN201010528771 A CN 201010528771A CN 102001912 A CN102001912 A CN 102001912A
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- propylene
- reaction
- chloro
- hydrogen fluoride
- trifluoro propene
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Abstract
The invention discloses a method for preparing 3,3,3-trifluoropropene by performing gas phase fluorination on 1,1,3-trichloro-1-propylene and/or 1,1,1-trichloro-2-propylene by using anhydrous hydrogen fluoride. The method comprises the following step of: performing gas phase fluorination and catalytic reaction on the anhydrous hydrogen fluoride and the 1,1,3-trichloro-1-propylene and/or the 1,1,1-trichloro-2-propylene in the presence of a fluorination catalyst to obtain the 3,3,3-trifluoropropene, wherein the reaction temperature is between 200 and 350 DEG C; the reaction pressure is normal pressure; the reaction space velocity is 500 to 3,000h<->; and the molar ratio of the anhydrous hydrogen fluoride to the 1,1,3-trichloro-1-propylene and/or the 1,1,1-trichloro-2-propylene is 6:1 to 50:1. The method has the advantages of simple production equipment, easily controllable process parameters, high product purity, smaller investment and the like.
Description
Technical field
The present invention relates to a kind of 3,3, the synthetic method of 3-trifluoro propene.
Background technology
3,3, the 3-trifluoro propene is the basic raw material of synthetic trifluoropropyl siloxane and the contour performance macromolecular material of fluorosilicon oil, is the intermediate of producing agricultural chemicals, medicine etc., or the surrogate of freonll-11.
3,3, obtain after 3-trifluoro propene and the dimethyl dichlorosilane (DMCS) addition 3,3,3-trifluoro propyl dimethyl dichlorosilane (DMCS), the trifluoropropyl siloxane that obtains after hydrolysis, cracking, polymerization not only has the performance of silicon rubber high-low temperature resistant (55～205 ℃), and has characteristics such as viton fuel oil resistance, resistance to chemical attack, can be rated as one of best synthetic rubber of world today's over-all properties.Fields such as Aeronautics and Astronautics, automobile, medical science now have been widely used in.
3,3, can also obtain the hydroxyl fluorosilicon oil after the hydrolysis of 3-trifluoro propyl dimethyl dichlorosilane (DMCS), the condensation.This silicone oil also because it contains a large amount of silicon hydroxyls, therefore has very big chemical activity, thereby makes it have purposes widely except that having high-low temperature resistant, fuel resistance energy.As can be used as molecular weight regulator, generate with the organic monomer grafting and have the instrument thing of property, the constitution controller of making the hot sulfurization trifluoropropyl siloxane, fabric hydrophobic oleophobic finishing composition, organic solvent defoamer, cosmetics additive etc.
US 2,787, and 646 disclose and a kind ofly utilize hydrogen fluoride liquid-phase fluorination 1,1 under the catalyst compounded catalysis of antimony trifluoride and trifluoro antimony butter, and 3-three chloro-1-propylene are synthetic 3,3, the method for 3-trifluoro propene.But, be uncertain to a certain extent thereby cause reaction result because the composition of catalyzer can change in the reaction process.
US 4,220, and 608 disclose a kind ofly at the organic amine catalyzer, under monoamine, monoamine salt or the catalysis of alkylene diamine, utilize anhydrous hydrogen fluoride to fluoridize 1,1, and 3-three chloro-1-propylene are synthetic 3,3, the method for 3-trifluoro propene.
CN 1,345, and 709 disclose and a kind ofly fluoridize 1,1 by anhydrous hydrogen fluoride, 3-three chloro-1-propylene production 3,3, the on-catalytic liquid phase method of 3-trifluoro propene.
US 4,465, and 786 disclose under a kind of catalysis of the oxygen fluorine cpd at chromium, fluoridize 1,1,1 with anhydrous hydrogen fluoride, and 3-tetrachloro propane is synthetic 3,3, the method for 3-trifluoro propene.
Summary of the invention
The purpose of this invention is to provide a kind of 3,3, the synthetic method of 3-trifluoro propene.
3,3, the synthetic method of 3-trifluoro propene is in the presence of fluorination catalyst, anhydrous hydrogen fluoride is with 1,1,3-three chloro-1-propylene and/or 1,1,1-three chloro-2-propylene carry out the gas phase fluorination catalyzed reaction, obtain 3,3, the 3-trifluoro propene, temperature of reaction is 200～350 ℃, and reaction pressure is a normal pressure, and reaction velocity is 500～3000h
-1, anhydrous hydrogen fluoride is with 1,1,3-three chloro-1-propylene and/or 1,1, and the mol ratio of 1-three chloro-2-propylene is 6: 1～50: 1.
Fluorination catalyst is one or more of the fluorochemical of chromium, aluminium, zinc, cobalt, magnesium, indium etc. or fluorine oxide.The Preparation of catalysts step is that the water-soluble salt of chromium, aluminium, zinc, cobalt, magnesium, indium etc. such as nitrate or muriate are dissolved in water, the adding precipitation agent reacts and obtains oxyhydroxide, washing, drying, roasting, granulation, compression molding after filtration,, at a certain temperature, feed anhydrous hydrogen fluoride and carry out activation treatment, make fluorination catalyst.The active catalyzer that reduces can adopt continuously or periodically bubbling air or oxygen, hydrogen, anhydrous hydrogen fluoride come to carry out surface decarburization, activated catalyst again to the catalyzer of inactivation.
The following reaction of main generation in the reactor:
CCl
2＝CHCH
2Cl+3HF→CF
3CH＝CH
2+3HCl
CCl
2＝CHCH
2Cl+3HF→CF
3CH
2CH
2Cl+2HCl
CCl
3C＝CH
2+3HF→CF
3CH＝CH
2+3HCl
Temperature of reaction is for raw material 1,1,3-three chloro-1-propylene and/or 1,1, and 1-three chloro-2-propylene conversion and 3,3, the selectivity of 3-trifluoro propene has significant effects.Temperature is high more, can make the initial activity of catalyzer high more on the one hand, but carbon distribution speed is also fast more, causes catalyzer to quicken inactivation, and transformation efficiency descends fast; Also can make on the other hand and fluoridize material 1,1,3-three chloro-1-propylene and 1,1, the probability of 1-three chloro-2-propylene generation polymerization side reactions increases, and can cause the carbon distribution of catalyst surface, shortens life of catalyst.But temperature is crossed to hang down and can be caused conversion of raw material low excessively again.So range of reaction temperature of the present invention is controlled at 200～350 ℃, preferred 220～300 ℃.
Conversion of raw material and selectivity descend with the increase of air speed.This is owing to the increase with reaction velocity, and reaction mass is with shortening the duration of contact of catalyzer; And the organic materials by catalyst surface in the unit time increases, and then corresponding carbon distribution speed also increases, and has influenced the action effect and the work-ing life of catalyzer.Can reduce carbon distribution though lower reaction velocity, improve transformation efficiency and selectivity, can reduce the yield of unit time inner catalyst greatly, reduce the economy of reaction.The air speed that the present invention is fit to is 500～3000h
-1, preferred 1000～2000h
-1
Increase the reaction density of anhydrous hydrogen fluoride, promptly improve anhydrous hydrogen fluoride with 1,1,3-three chloro-1-propylene and/or 1,1, the mol ratio of 1-three chloro-2-propylene helps the generation of organic conversion and product.In addition, anhydrous hydrogen fluoride is with 1,1,3-three chloro-1-propylene and/or 1,1, and the mol ratio of 1-three chloro-2-propylene is big more, and the inductive phase of catalyzer is also short more, and life of catalyst is long more, but the cost that the anhydrous hydrogen fluoride later separation reclaims also can increase.Anhydrous hydrogen fluoride is with 1,1, and 3-three chloro-1-propylene and/or 1,1 when the mol ratio of 1-three chloro-2-propylene is too small, can shorten life of catalyst greatly.The anhydrous hydrogen fluoride that the present invention is fit to is with 1,1,3-three chloro-1-propylene and/or 1,1, and the mol ratio of 1-three chloro-2-propylene is 6: 1～50: 1, preferred 10: 1～24: 1.
Reaction pressure also has significant effects to this method, because 1,1,3-three chloro-1-propylene and 1,1, the boiling point of 1-three chloro-2-propylene and fluorinated intermediates thereof is all than higher, therefore boosting to cause that material is easier to be deposited on the catalyst surface, causes carbon distribution, reduces catalyst life; In addition, this reaction is the reaction that volume amplifies, and pressure boost is unfavorable for the carrying out that react.And negative-pressure operation can increase process cost and difficulty.Therefore the suitable pressure of this reaction is normal pressure.
Synthesis condition of the present invention is comparatively gentle, and operational condition elasticity is big: temperature of reaction can be selected 200～350 ℃, and optimum is 220～300 ℃; Reaction velocity can be selected 500～3000h
-1, optimum is 1000～2000h
-11,1,3-three chloro-1-propylene can be selected 6: 1～50: 1 with hydrofluoric mol ratio, and optimum is 10: 1～24: 1.With this understanding, the organic transformation efficiency of reactor outlet and 3,3, the selectivity of 3-trifluoro propene all can reach more than 95%.
It is simple that the present invention has a production unit; Technical process is short; Processing parameter control easily; Processing safety is better; Catalyst life is long; The reaction conversion ratio height; Good reaction selectivity; The product purity advantages of higher.
Embodiment
By the following examples the present invention is carried out more specific description, but the present invention is not limited to described embodiment.
Embodiment 1
In stainless steel gas phase fluorination device (φ 20mm * 1000mm, 316L stainless steel), add the 200mL chromium-based catalysts, through super-dry, activation treatment.Raw material 1,1,3-three chloro-1-propylene and anhydrous hydrogen fluoride (be called for short AHF) advanced to enter reactor after the thermal pretreatment and carry out fluoridation, at AHF/1, and 1,3-three chloro-1-propylene=15: 1,250 ℃ of temperature of reaction, reactor air speed 1000h
-1By the analysis reactor outlet material form draw 1,1,3-three chloro-1-propylene conversions are 100%, 3,3, the selectivity of 3-trifluoro propene is 96.5%.
Comparative example 2-5:
Operation steps by example 1 keeps other reaction conditions constant, and control reaction temperature is 200～350 ℃ respectively, to reactor outlet material sampling analysis 1,1, and 3-three chloro-1-propylene conversions and 3,3, the selectivity of 3-trifluoro propene.Data see Table 1.
Table 1 temperature of reaction is to the influence of reaction
| Embodiment | Temperature of reaction ℃ | 1,1,3-three chloro-1-propylene conversion % | 3,3,3-trifluoro propene selectivity % |
| 2? | 200? | 98.5? | 93.7? |
| 3? | 220? | 100? | 94.5? |
| 4? | 300? | 100? | 96.8? |
| 5? | 350? | 100? | 96.5? |
The comparative example 6～9:
Operation steps by example 1 keeps other reaction conditions constant, and controlling reaction velocity respectively is 500～3000h
-1, reactor outlet material sampling analysis 1,1,3-three chloro-1-propylene conversions and 3,3, the selectivity of 3-trifluoro propene, data see Table 2.
Table 2 air speed is to the influence of reaction
| Embodiment | Air speed h -1 | 1,1,3-three chloro-1-propylene conversion % | 3,3,3-trifluoro propene selectivity % |
| 6? | 500? | 100? | 98.3? |
| 7? | 1000? | 100? | 95.4? |
| 8? | 2000? | 100? | 94.6? |
| 9? | 3000? | 98.5? | 92.3? |
The comparative example 10～13:
Operation steps by example 1 keeps other reaction conditions constant, and control material respectively and joined 6: 1～50: 1, reactor outlet material sampling analysis 1,1,3-three chloro-1-propylene conversions and 3,3, the selectivity of 3-trifluoro propene, data see Table 3.
Table 3 mol ratio is to the influence of reaction
| Embodiment | AHF/ (1,1,3-three chloro-1-propylene) | 1,1,3-three chloro-1-propylene conversion % | 3,3,3-trifluoro propene selectivity % |
| 10? | 6∶1? | 98.7? | 85.6? |
| 11? | 10∶1? | 99.8? | 93.7? |
| 12? | 24∶1? | 100? | 97.8? |
| 13? | 50∶1? | 100? | 98.5? |
The comparative example 14～15:
Operation steps by example 1 keeps other reaction conditions constant, adopts different raw materials respectively, 250 ℃ of temperature of reaction, and reactor air speed 1000h
-1, at anhydrous hydrogen fluoride and material molar ratio=15: 1 reactor outlet material sampling analysis 1,1,3-three chloro-1-propylene conversions and 3,3, the selectivity of 3-trifluoro propene, data see Table 3.
Table 4 raw material is to the influence of reaction
Claims (5)
1. one kind 3,3, the synthetic method of 3-trifluoro propene, it is characterized in that, anhydrous hydrogen fluoride in the presence of fluorination catalyst with 1,1,3-three chloro-1-propylene and/or 1,1,1-three chloro-2-propylene carry out the gas phase fluorination catalyzed reaction, obtain 3,3, the 3-trifluoro propene, temperature of reaction is 200～350 ℃, reaction pressure is a normal pressure, and reaction velocity is 500～3000h
-1, anhydrous hydrogen fluoride is with 1,1,3-three chloro-1-propylene and/or 1,1, and the mol ratio of 1-three chloro-2-propylene is 6: 1～50: 1.
2. according to claim 1 a kind of 3,3, the synthetic method of 3-trifluoro propene is characterized in that described fluorination catalyst is one or more of the fluorochemical of chromium, aluminium, zinc, cobalt, magnesium, indium etc. or fluorine oxide.
3. according to claim 1 a kind of 3,3, the 3-trifluoro propene synthetic method, it is characterized in that described temperature of reaction is 220～300 ℃.
4. according to claim 1 a kind of 3,3, the synthetic method of 3-trifluoro propene is characterized in that, described reaction velocity is 1000～2000h
-1
5. according to claim 1 a kind of 3,3, the synthetic method of 3-trifluoro propene is characterized in that, described anhydrous hydrogen fluoride is with 1,1,3-three chloro-1-propylene and/or 1,1, and the mol ratio of 1-three chloro-2-propylene is 10: 1～24: 1.
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Cited By (3)
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|---|---|---|---|---|
| CN102631938A (en) * | 2012-03-08 | 2012-08-15 | 浙江三美化工股份有限公司 | Catalyst for synthesizing 2-3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene and preparation method thereof |
| WO2020014130A1 (en) * | 2018-07-09 | 2020-01-16 | The Chemours Company Fc, Llc | Compositions and methods for an integrated 2,3,3,3-tetrafluoropropene manufacturing process |
| US11261146B2 (en) * | 2018-10-04 | 2022-03-01 | Srf Limited | Preparation of 2,3,3,3-tetrafluoropropene and intermediates thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102631938A (en) * | 2012-03-08 | 2012-08-15 | 浙江三美化工股份有限公司 | Catalyst for synthesizing 2-3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene and preparation method thereof |
| CN102631938B (en) * | 2012-03-08 | 2013-09-18 | 浙江三美化工股份有限公司 | Catalyst for synthesizing 2-3,3,3-tetrafluoropropene from 2-chloro-3,3,3-trifluoropropene and preparation method thereof |
| WO2020014130A1 (en) * | 2018-07-09 | 2020-01-16 | The Chemours Company Fc, Llc | Compositions and methods for an integrated 2,3,3,3-tetrafluoropropene manufacturing process |
| CN112384490A (en) * | 2018-07-09 | 2021-02-19 | 科慕埃弗西有限公司 | Compositions and methods for integrated 2, 3, 3, 3-tetrafluoropropene manufacturing processes |
| US11261146B2 (en) * | 2018-10-04 | 2022-03-01 | Srf Limited | Preparation of 2,3,3,3-tetrafluoropropene and intermediates thereof |
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