CN103073386B - Preparation method of 2, 3, 3, 3-tetrafluoropropylene - Google Patents
Preparation method of 2, 3, 3, 3-tetrafluoropropylene Download PDFInfo
- Publication number
- CN103073386B CN103073386B CN201210594509.4A CN201210594509A CN103073386B CN 103073386 B CN103073386 B CN 103073386B CN 201210594509 A CN201210594509 A CN 201210594509A CN 103073386 B CN103073386 B CN 103073386B
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyzer
- preparation
- air speed
- tetrafluoeopropene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of 2, 3, 3, 3-tetrafluoropropylene. The preparation method comprises the following steps: (a) under the action of a catalyst, hydrogen fluoride and 1, 1, 2, 3-tetrachloropropene are mixed at the molar ratio of (15-30):1 and react at the reaction temperature of 150-280 DEG C and the airspeed of 300-1,000h<-1>, and impurities are separated to obtain 1, 2-dichloro-3, 3, 3-trifluoropropane; (b) under the action of the catalyst, hydrogen fluoride and 1, 2-dichloro-3, 3, 3-trifluoropropane obtained in the step (a) are mixed at the molar ratio of (8-15):1 and react at the reaction temperature of 250-350 DEG C and the airspeed of 500-800h<-1>, and impurities are separated to obtain 1, 1, 1, 2, 3-perfluoropropane; and (c) under the action of the catalyst, 1, 1, 1, 2, 3-perfluoropropane obtained in the step (b) is subject to dehydrofluorination at the reaction temperature of 300-350 DEG C and the airspeed of 300-500h<-1>, and impurities are separated to obtain 2, 3, 3, 3-tetrafluoropropylene. The preparation method has the advantages of simple process, mild reaction conditions, high yield and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of 2,3,3,3-tetrafluoeopropene, relate in particular to one with 1,1,2,3 – tetrachloro propylene are raw material, and three step gas phase catalytic reactions are prepared the method for 2,3,3,3-tetrafluoeopropene.
Background technology
The latent value of 2,3,3,3-tetrafluoeopropene (HFO-1234yf) ozone-depleting is zero, and the latent value of Greenhouse effect is 4, has good environmental performance.LCCP(lifetime climate performance) lower than HFC-134a, atmosphere resolvent is identical with HFC-134a, and its system performance is better than HFC-134a, is considered to the best substitute of HFC-134a.If select HFO-1234yf to substitute HFC-134a refrigeration agent, car manufactures just can continue to continue to use former MAC (Mobile Air-Conditioning) system.So HFO-1234yf is considered to the best substitute of young mobile refrigeration agent, accepted by car manufactures in West Europe at present, started progressively to promote in 2011 years.
It is multiple 2,3,3 that prior art discloses, the syntheti c route of 3-tetrafluoeopropene (HFO-1234yf), wherein with l, l, 2,3-tetrachloro propylene (HCC-1230xa) is raw material, and after fluoridizing, the method such as dehydrohalogenation is prepared target product HFO-1234yf, is a comparatively study route for focus.
China Patent Publication No. CN102056875A, open day on May 11st, 2011, denomination of invention: preparation 1,1,1-tri-is fluoro-2, the method for 3-propylene dichloride, this application case provides one to prepare 1,1,1-tri-fluoro-2, the method of 3-propylene dichloride (F243db), described method comprises: under the existence of catalyzer, make 3,3,3-trifluoro propene contacts with chlorine, and wherein said catalyzer comprises activated carbon, aluminum oxide and/or transition metal oxide.Its weak point is: the raw material trifluoro propene that this route is selected is expensive, more difficult acquisition.
China Patent Publication No. CN102056876A, open day on May 11st, 2011, denomination of invention: one is prepared the method for 2,3,3,3-tetrafluoeopropene (HFO-1234yf).This invention provides one to prepare 2,3,3, the method of 3-tetrafluoeopropene (HFO-1234yf), comprise: (a), under the existence of zinc/chromium oxide catalyst, make 1,1,1-tri-is fluoro-2, and 3-propylene dichloride (F243db) contacts with production CF with hydrogen fluoride (HF)
3cHFCH
2the compound of X, wherein X is Cl or F, and (b) makes formula CF
3cHFCH
2the compound dehydrohalogenation of X is to produce 1234yf; Wherein step (a) is carried out under the absolute pressure of the temperature of-70 ~ 400 DEG C and 0 ~ 30 bar under gas phase and/or liquid phase, and HF/ organism is 1:1 ~ 100:1; Step (b) is carried out under the absolute pressure of the temperature of-70 ~ 1000 DEG C and 0 ~ 30 bar under gas phase and/or liquid phase, and HF/ organism is 0.01:1 ~ 50:1.Its weak point is: reaction pressure is high, and temperature is high, the easy carbon distribution inactivation of catalyzer, and liquid phase reaction yield is not high.
China Patent Publication No. CN102603460A, July 25 2012 publication date, denomination of invention: a kind of 2-chloro-1,1, the preparation method's of 1,2-tetrafluoropropane, this application case discloses a kind of 2-chloro-1,1, the preparation method of 1,2-tetrafluoropropane, with 1,1,2,3-tetrachloro propylene is raw material, adopts the synthetic 2-chloro-1,1 of liquid phase method, 1,2-tetrafluoropropane, 2-chloro-1,1,1,2-tetrafluoropropane is the intermediate product of synthetic HFO-1234yf.This process is divided into three steps, all adopts liquid phase method, and reaction yield is not high, and by product is many.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, provide that a kind of technique is simple, reaction conditions is gentle, yield is high, cost is low 2,3,3, the preparation method of 3-tetrafluoeopropene.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
(a) under the effect of catalyzer, by hydrogen fluoride and 1,1, after the 15～30:1 mixing in molar ratio of 2,3 – tetrachloro propylene, be 150～280 DEG C in temperature of reaction, air speed is 300～1000h
-1condition under react, it is chloro-3,3 that separating impurity obtains 1,2-bis-, 3-trifluoro propane;
(b) under the effect of catalyzer, hydrogen fluoride and step (a) are obtained 1,2-bis-is chloro-3,3,3-trifluoro propane (F243db) after 8～15:1 mixes in molar ratio, is 250～350 DEG C in temperature of reaction, air speed is 500～800h
-1condition under react, separating impurity obtains 1,1,1,2,3-pentafluoropropane;
(c) under the effect of catalyzer, step (b) is obtained 1,1,1,2,3-pentafluoropropane (F245eb) is 300～350 DEG C in temperature of reaction, air speed is 300～500h
-1condition under dehydrofluorination, separating impurity obtains 2,3,3,3-tetrafluoeopropene.
Further:
Hydrogen fluoride and 1,1 described in step (a), the mol ratio of 2,3 – tetrachloro propylene is 15～20:1, and temperature of reaction is 150～240 DEG C, and air speed is 300～600h
-1.
The mol ratio of hydrogen fluoride described in step (b) and chloro-3,3, the 3 trifluoro propane of 1,2-bis-is 8～12:1, and temperature of reaction is 250～320 DEG C, and air speed is 500～600h
-1.
Temperature of reaction described in step (c) is 300～320 DEG C, and air speed is 300～400h
-1.
In step (a), due to 1,1,2,3 – tetrachloro propylene are alkene, and temperature of reaction is too high, and byproduct of reaction increases, and catalyzer knot carbon speed is accelerated, and causes catalyzer to accelerate inactivation; Temperature of reaction is too low, and the transformation efficiency of 1,1,2,3 – tetrachloro propylene is not high, and therefore the temperature of reaction in the present invention is 150～280 DEG C, preferably 150～240 DEG C; Air speed is too low, the overstand of reaction mass in reactor, reaction generate 1,2-bis-is chloro-3,3,3-trifluoro propane further reaction to generate 2-chloro-1,1,1-trifluoro propene, therefore the air speed in the present invention is 300～1000h
-1, be preferably 300～600h
-1; Not too high in order to control the focus of reaction, hydrogen fluoride is wanted a large amount of excessive heats of taking away, therefore hydrogen fluoride and 1,1 in the present invention, and the mol ratio of 2,3 – tetrachloro propylene is 15～30:1, preferred molar ratio is 15～20:1.
Temperature of reaction is too low in step (b), can generate a large amount of 2-chloro-1,1,1,3-tetrafluoropropane, and excess Temperature, sintering of catalyst, active decline, therefore the temperature of reaction in the present invention is 250～350 DEG C, is preferably 250～320 DEG C; Air speed is excessive, and material and catalyzer are too short duration of contact, also can generate a large amount of 2-chloro-1,1,1,3-tetrafluoropropane, and therefore the air speed in the present invention is 500～800h
-1, be preferably 500～600h
-1.
Step (c) is dehydrofluorination, and temperature is high, and 1,1,1,2,3-pentafluoropropane transformation efficiency is high, but can generate a small amount of by product, and the selectivity of 2,3,3,3-tetrafluoeopropene is not high, and temperature is high, the easy inactivation of catalyzer; The air speed of reaction increases, and the transformation efficiency of 1,1,1,2,3-pentafluoropropane reduces, and air speed reduces, and improves the transformation efficiency of 1,1,1,2,3-pentafluoropropane, but can reduce the yield of unit time inner catalyst, reduces the economy of reaction.Therefore the temperature of reaction in the present invention is 300～350 DEG C, is preferably 300～320 DEG C; Air speed is 300～500h
-1, preferably 300～400h
-1.
In step of the present invention (a), used catalyst can adopt general fluorination catalyst.Aluminum oxide floods the catalyzer taking chromium as active ingredient as known in the art, preferably adopts activated alumina dipping chromium, zinc and magnesium.Wherein the preparation method of catalyzer can adopt the method for the preparation of fluorination catalyst known in the art, and as by soluble in water the salt of chromium, zinc and magnesium, activated alumina impregnated in above salts solution, and then drying, roasting prepare catalyzer.
In step of the present invention (b), used catalyst can adopt general fluorination catalyst.Chromium-based catalysts as known in the art, auxiliary other metal component, preferably adopts Zn-CrF
3.Wherein the preparation method of catalyzer can adopt the method for the preparation of fluorination catalyst known in the art, as the salts solution of chromium and zinc is reacted with basic solution, makes the oxyhydroxide of chromium and zinc, makes catalyzer through super-dry, roasting, compressing tablet.
In step of the present invention (c), used catalyst can adopt general Dehydrofluorination catalyst.Metal fluoride as known in the art: aluminum fluoride, the chromic oxide of fluoridizing, metal load on chromium fluoride, metal load is in the aluminum oxide of fluoridizing; Can also gac, three dimensional matrix carbonaceous material is as carrier etc.In addition Dehydrofluorination catalyst includes but not limited to the fluorochemical of fluorochemical, magnesium and zinc mixture or the fluorochemical of magnesium and aluminium mixture of magnesium, also comprises oxide compound and the oxyfluoride fluoridized.Preferably adopt Zn-Ni/CrF
3wherein the preparation method of catalyzer can adopt the method for the preparation of fluorination catalyst known in the art, and as by soluble in water the salt of zinc and nickel, chromium fluoride impregnated in above salts solution, and then drying, roasting prepare catalyzer.
The present invention has the following advantages:
1, raw material is easy to get, and technical process is simple, and cost is low;
2, adopt gas-solid catalysis, the liquid phase method route three wastes are few relatively, reaction conditions gentleness;
3, yield is high, product selectivity good.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not only confined to following examples.
Embodiment 1
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
It is chloro-3,3 that (1) 1,1,2,3 – tetrachloro propylene and hydrogen fluoride reaction obtain 1,2-bis-, 3-trifluoro propane (F243db), and catalyzer is activated alumina dipping chromium, zinc and magnesium.
In the 316L reaction tubes I of φ 30 × 2.5, pack this catalyzer 100ml (51 grams) into, be warmed up to 350 DEG C, pass into HF and activate 15 hours, cool to 200 DEG C, then start the reaction that feeds intake, 1,1,2,3 – tetrachloro propylene adopt Micro-metering Pumps to squeeze into reactor, after HF gasification through the control of inflow-rate of water turbine meter, HF and 1,1,2, the mol ratio of 3 – tetrachloro propylene is 20:1, and air speed is 500h
-1, obtain containing chloro-3,3,3 trifluoro propane (F243db, the CF of 1,2-bis-
3cHClCH
2cl) reaction product, by reaction product through washing, separate, that dry, rectifying obtain 1,2-bis-is chloro-3,3,3-trifluoro propane, its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | F1230xa | CF 3CHClCH 2Cl | CF 3CCl=CH 2 | Other |
| Content | 1.2% | 95.6% | 1.5% | 1.7% |
Other comprises: CF
3cHFCH
2cl, CF
3cHClCH
2f
(2) in the 316L reaction tubes II of φ 30 × 2.5, pack Zn-CrF into
3catalyzer 100ml (72 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cool to 320 DEG C, then step (1) is obtained 1,2-bis-chloro-3,3,3-trifluoro propane (F243db) and ammonium acid fluoride enter reactor according to mol ratio 1:10, and air speed is 600h
-1, obtain containing 1,1,1,2,3-pentafluoropropane (F245eb, CF
3cHFCH
2f) reaction product, obtains 1,1,1,2,3-pentafluoropropane by reaction product through washing, alkali cleaning, dry, rectifying, and its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | CF 3CHClCH 2Cl | CF 3CHFCH 2F | CF 3CHClCH 2F | Other |
| Content | 35.5% | 58.6% | 4.2% | 1.7% |
Other product comprises: CF
3cHFCH
2cl, CF
3cF=CH
2, CF
3cF
2cH
3
(3) in the 316L reaction tubes III of φ 30 × 2.5, pack Zn-Ni/CrF into
3catalyzer 100ml (82 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cools to 310 DEG C, then step (2) is obtained 1,1,1,2,3-pentafluoropropane (F245eb) enters reactor, air speed is 300h
-1, obtain the reaction product that contains 2,3,3,3-tetrafluoeopropene (HFO-1234yf), reaction product is obtained to 2,3,3,3-tetrafluoeopropene through washing, alkali cleaning, dry, rectifying, its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | CF 3CHFCH 2F | CF 3CF=CH 2 | CF 3CH=CHF |
| Content | 68.6% | 30.8% | 0.6% |
Embodiment 2
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
(1) 1,1,2,3 – tetrachloro propylene and hydrogen fluoride reaction obtain chloro-3,3, the 3 trifluoro propane (F243db) of 1,2-bis-, and catalyzer is activated alumina dipping chromium, zinc and magnesium.
In the 316L reaction tubes I of φ 30 × 2.5, pack this catalyzer 100ml (51 grams) into, be warmed up to 350 DEG C, pass into HF and activate 15 hours, cool to 150 DEG C, then start the reaction that feeds intake, 1,1,2,3 – tetrachloro propylene adopt Micro-metering Pumps to squeeze into reactor, after HF gasification through the control of inflow-rate of water turbine meter, HF and 1,1,2, the mol ratio of 3 – tetrachloro propylene is 15:1, and air speed is 300h
-1, obtain containing chloro-3,3,3 trifluoro propane (F243db, the CF of 1,2-bis-
3cHClCH
2cl) reaction product, by reaction product through washing, separate, dry, rectifying obtain 1,2 two chloro-3,3,3 trifluoro propane, its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | F1230xa | CF 3CHClCH 2Cl | CF 3CCl=CH 2 | Other |
| Content | 30.6% | 68.3% | 0.8% | 0.3% |
Other comprises: CF
3cHFCH
2cl, CF
3cHClCH
2f
(2) in the 316L reaction tubes II of φ 30 × 2.5, pack Zn-CrF into
3catalyzer 100ml (72 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cool to 250 DEG C, then step (1) is obtained 1,2 two chloro-3,3,3-trifluoro propane (F243db) and ammonium acid fluoride enter reactor according to mol ratio 1:8, and air speed is 500h
-1, obtain containing 1,1,1,2,3-pentafluoropropane (F245eb, CF
3cHFCH
2f) reaction product, obtains 1,1,1,2,3-pentafluoropropane by reaction product through washing, alkali cleaning, dry, rectifying, and its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | CF 3CHClCH 2Cl | CF 3CHFCH 2F | CF 3CF 2CH 3 | Other |
| Content | 64.7% | 25.6% | 1.3% | 8.4% |
Other product comprises: CF
3cHFCH
2cl, CF
3cF=CH
2, CF
3cF
2cH
3
(3) in the 316L reaction tubes III of φ 30 × 2.5, pack Zn-Ni/CrF into
3catalyzer 100ml (82 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cools to 300 DEG C, then step (2) is obtained 1,1,1,2,3-pentafluoropropane (F245eb) enters reactor, air speed is 500h
-1, obtain the reaction product that contains 2,3,3,3-tetrafluoeopropene (HFO-1234yf), reaction product is obtained to 2,3,3,3-tetrafluoeopropene through washing, alkali cleaning, dry, rectifying, its purity is 99.5%.By to reactor outlet sampling analysis, result is as following table:
| Component | CF 3CHFCH 2F | CF 3CF=CH 2 | CF 3CH=CHF |
| Content | 75.4% | 23.3% | 1.3% |
Embodiment 3
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
It is chloro-3,3 that (1) 1,1,2,3 – tetrachloro propylene and hydrogen fluoride reaction obtain 1,2-bis-, 3-trifluoro propane (F243db), and catalyzer is activated alumina dipping chromium, zinc and magnesium.
In the 316L reaction tubes I of φ 30 × 2.5, pack this catalyzer 100ml (51 grams) into, be warmed up to 350 DEG C, pass into HF and activate 15 hours, cool to 280 DEG C, then start the reaction that feeds intake, 1,1,2,3 – tetrachloro propylene adopt Micro-metering Pumps to squeeze into reactor, after HF gasification through the control of inflow-rate of water turbine meter, HF and 1,1,2, the mol ratio of 3 – tetrachloro propylene is 30:1, and air speed is 1000h
-1, obtain containing 1,2-bis-chloro-3,3,3-trifluoro propane (F243db, CF
3cHClCH
2cl) reaction product, by reaction product through washing, separate, dry, rectifying obtain chloro-3,3, the 3 trifluoro propane of 1,2-bis-, its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | F1230xa | CF 3CHClCH 2Cl | CF 3CCl=CH 2 | Other |
| Content | 0.9% | 94.2% | 3.6% | 1.3% |
Other comprises: CF
3cHFCH
2cl, CF
3cHClCH
2f
(2) in the 316L reaction tubes II of φ 30 × 2.5, pack Zn-CrF into
3catalyzer 100ml (72 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cool to 350 DEG C, then step (1) is obtained 1,2-bis-chloro-3,3,3-trifluoro propane (F243db) and ammonium acid fluoride enter reactor according to mol ratio 1:15, and air speed is 800h
-1, obtain containing 1,1,1,2,3-pentafluoropropane (F245eb, CF
3cHFCH
2f) reaction product, obtains 1,1,1,2,3-pentafluoropropane by reaction product through washing, alkali cleaning, dry, rectifying, and its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | CF 3CHClCH 2Cl | CF 3CHFCH 2F | CF 3CF 2CH 3 | Other |
| Content | 31.8% | 61.3% | 2.0% | 4.9% |
Other product comprises: CF
3cHFCH
2cl, CF
3cF=CH
2, CF
3cF
2cH
3
(3) in the 316L reaction tubes III of φ 30 × 2.5, pack Zn-Ni/CrF into
3catalyzer 100ml (82 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cools to 350 DEG C, then step (2) is obtained 1,1,1,2,3-pentafluoropropane (F245eb) enters reactor, air speed is 400h
-1, obtain the reaction product that contains 2,3,3,3-tetrafluoeopropene (HFO-1234yf), reaction product is obtained to 2,3,3,3-tetrafluoeopropene through washing, alkali cleaning, dry, rectifying, its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | CF 3CHFCH 2F | CF 3CF=CH 2 | CF 3CH=CHF |
| Content | 54.5% | 42.8% | 2.7% |
Embodiment 4
A kind of preparation method of 2,3,3,3-tetrafluoeopropene, comprises the following steps:
It is chloro-3,3 that (1) 1,1,2,3 – tetrachloro propylene and hydrogen fluoride reaction obtain 1,2-bis-, 3-trifluoro propane (F243db), and catalyzer is activated alumina dipping chromium, zinc and magnesium.
In the 316L reaction tubes I of φ 30 × 2.5, pack this catalyzer 100ml (51 grams) into, be warmed up to 350 DEG C, pass into HF and activate 15 hours, cool to 250 DEG C, then start the reaction that feeds intake, 1,1,2,3 – tetrachloro propylene adopt Micro-metering Pumps to squeeze into reactor, after HF gasification through the control of inflow-rate of water turbine meter, HF and 1,1,2, the mol ratio of 3 – tetrachloro propylene is 20:1, and air speed is 500h
-1, obtain containing chloro-3,3,3 trifluoro propane (F243db, the CF of 1,2-bis-
3cHClCH
2cl) reaction product, by reaction product through washing, separate, dry, rectifying obtain chloro-3,3, the 3 trifluoro propane of 1,2-bis-, its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | F1230xa | CF 3CHClCH 2Cl | CF 3CCl=CH 2 | Other |
| Content | 0.1% | 97.2% | 2.1% | 0.6% |
Other comprises: CF
3cHFCH
2cl, CF
3cHClCH
2f
(2) in the 316L reaction tubes II of φ 30 × 2.5, pack Zn-CrF into
3catalyzer 100ml (72 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cool to 300 DEG C, then step (1) is obtained 1,2-bis-chloro-3,3,3-trifluoro propane (F243db) and ammonium acid fluoride enter reactor according to mol ratio 1:10, and air speed is 600h
-1, obtain containing 1,1,1,2,3-pentafluoropropane (F245eb, CF
3cHFCH
2f) reaction product, obtains 1,1,1,2,3-pentafluoropropane by reaction product through washing, alkali cleaning, dry, rectifying, and its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | CF 3CHClCH 2Cl | CF 3CHFCH 2F | CF 3CF 2CH 3 | Other |
| Content | 40.3% | 55.1% | 1.5% | 3.1% |
Other product comprises: CF
3cHFCH
2cl, CF
3cF=CH
2, CF
3cF
2cH
3
(3) in the 316L reaction tubes III of φ 30 × 2.5, pack Zn-Ni/CrF into
3catalyzer 100ml (82 grams), is warmed up to 350 DEG C, passes into HF and activates 15 hours, cools to 310 DEG C, then step (2) is obtained 1,1,1,2,3-pentafluoropropane (F245eb) enters reactor, air speed is 500h
-1, obtain the reaction product that contains 2,3,3,3-tetrafluoeopropene (HFO-1234yf), reaction product is obtained to 2,3,3,3-tetrafluoeopropene through washing, alkali cleaning, dry, rectifying, its purity is 99.5%.By to reactor outlet sampling analysis, result is as follows:
| Component | CF 3CHFCH 2F | CF 3CF=CH 2 | CF 3CH=CHF |
| Content | 70.8% | 25.4% | 3.8% |
Claims (4)
1. one kind 2,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that, comprises the following steps:
(a) under the effect of catalyzer, by hydrogen fluoride and 1,1, after the 15～30:1 mixing in molar ratio of 2,3 – tetrachloro propylene, be 150～280 DEG C in temperature of reaction, air speed is 300～1000h
-1condition under react, it is chloro-3,3 that separating impurity obtains 1,2-bis-, 3-trifluoro propane, wherein catalyzer is activated alumina dipping chromium, zinc and magnesium;
(b) at Zn-CrF
3under the effect of catalyzer, hydrogen fluoride and step (a) are obtained 1,2-bis-is chloro-3,3,3-trifluoro propane after 8～15:1 mixes in molar ratio, is 250～350 DEG C in temperature of reaction, air speed is 500～800h
-1condition under react, separating impurity obtains 1,1,1,2,3-pentafluoropropane;
(c) at Zn-Ni/CrF
3under the effect of catalyzer, step (b) is obtained 1,1,1,2,3-pentafluoropropane is 300～350 DEG C in temperature of reaction, air speed is 300～500h
-1condition under dehydrofluorination, separating impurity obtains 2,3,3,3-tetrafluoeopropene.
2. according to claim 12,3,3, the preparation method of 3-tetrafluoeopropene, it is characterized in that the hydrogen fluoride and 1,1 described in step (a), 2, the mol ratio of 3 – tetrachloro propylene is 15～20:1, and temperature of reaction is 150～240 DEG C, and air speed is 300～600h
-1.
3. according to claim 12,3,3, the preparation method of 3-tetrafluoeopropene, it is characterized in that hydrogen fluoride described in step (b) and 1,2-bis-chloro-3,3, the mol ratio of 3-trifluoro propane is 8～12:1, and temperature of reaction is 250～320 DEG C, and air speed is 500～600h
-1.
4. according to claim 12,3,3, the preparation method of 3-tetrafluoeopropene, is characterized in that the temperature of reaction described in step (c) is 300～320 DEG C, and air speed is 300～400h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594509.4A CN103073386B (en) | 2012-12-31 | 2012-12-31 | Preparation method of 2, 3, 3, 3-tetrafluoropropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210594509.4A CN103073386B (en) | 2012-12-31 | 2012-12-31 | Preparation method of 2, 3, 3, 3-tetrafluoropropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103073386A CN103073386A (en) | 2013-05-01 |
| CN103073386B true CN103073386B (en) | 2014-08-20 |
Family
ID=48150110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210594509.4A Active CN103073386B (en) | 2012-12-31 | 2012-12-31 | Preparation method of 2, 3, 3, 3-tetrafluoropropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103073386B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661438A (en) * | 2014-09-26 | 2017-05-10 | 大金工业株式会社 | Halo-olefin composition and use therefor |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8398882B2 (en) | 2006-10-31 | 2013-03-19 | E I Du Pont De Nemours And Company | Processes for the production of fluoropropanes and halopropenes and azeotropic compositions of 2-chloro-3,3,3-trifluoro-1-propene with HF and of 1,1,1,2,2-pentafluoropropane with HF |
| WO2019003848A1 (en) * | 2017-06-30 | 2019-01-03 | セントラル硝子株式会社 | Method for producing 1,3-dichloro-3,3-difluoropropene |
| JP7287965B2 (en) * | 2019-11-13 | 2023-06-06 | フジアン ヨンジン テクノロジー カンパニー リミテッド | A new synthetic method for 2,3,3,3-tetrafluoropropene (1234yf) and 2,3-dichloro-1,1,1-trifluoropropane (243db) |
| CN112592254B (en) * | 2020-12-21 | 2023-12-26 | 江苏三美化工有限公司 | System for preparing 2, 3-tetrafluoropropene and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2334490T3 (en) * | 2000-02-02 | 2010-03-11 | Daikin Industries, Ltd. | PROCESS TO PRODUCE A FLUORATED HYDROCARBON. |
| US7674939B2 (en) * | 2004-04-29 | 2010-03-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US7560602B2 (en) * | 2005-11-03 | 2009-07-14 | Honeywell International Inc. | Process for manufacture of fluorinated olefins |
| GB0806389D0 (en) * | 2008-04-09 | 2008-05-14 | Ineos Fluor Holdings Ltd | Process |
| CN102267869A (en) * | 2011-05-27 | 2011-12-07 | 山东东岳高分子材料有限公司 | Synthetic method of 2,3,3,3-tetrafluoropropene |
| CN102351637B (en) * | 2011-08-31 | 2013-10-23 | 浙江师范大学 | Method for preparing 2,3,3,3-tetrafluoropropene |
| CN102584520B (en) * | 2011-12-30 | 2013-11-27 | 浙江师范大学 | Preparation method of 1,3,3,3-tetrafluoropropene |
-
2012
- 2012-12-31 CN CN201210594509.4A patent/CN103073386B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106661438A (en) * | 2014-09-26 | 2017-05-10 | 大金工业株式会社 | Halo-olefin composition and use therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103073386A (en) | 2013-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073386B (en) | Preparation method of 2, 3, 3, 3-tetrafluoropropylene | |
| CN102001911B (en) | Method for preparing 2,3,3,3-tetrafluoropropene | |
| CN102351637A (en) | Method for preparing 2,3,3,3-tetrafluoropropene | |
| CN103827066A (en) | Method for manufacturing 2,3,3,3-tetrafluoropropene | |
| CN103880590B (en) | A kind of technique preparing 1,3,3,3-tetrafluoropropene | |
| CN103537305B (en) | Catalyst used in HFC-245fa cracking and combined production of HFC-1234ze and HFC-1234yf, and preparation method thereof | |
| CN102105423A (en) | Process for preparing 2,3,3,3-tetrafluoropropene | |
| CN104710274A (en) | Process for co-producing 1,3,3,3-tetrafluoropropene and/or 2,3,3,3-tetrafluoropropene | |
| CN102836722B (en) | Catalyst used in preparation of fluorine-containing olefin through dehydrohalogenation of halohydrofluoroalkane and preparation method of catalyst | |
| CN103418367A (en) | Catalyst used for preparing fluorinated alkene with chloro-fluoro alkane and preparation method thereof | |
| CN102267869A (en) | Synthetic method of 2,3,3,3-tetrafluoropropene | |
| CN104151131B (en) | A kind of preparation method of 2,3,3,3-tetrafluoeopropene | |
| CN106256429A (en) | The aluminum fluoride catalyst of a kind of high-specific surface area and application thereof | |
| CN103880589A (en) | Process for co-producing HFO-1234ze and HFC-245fa | |
| CN103319303B (en) | Method for simultaneously preparing 1,1,1,2-tetrafluoroethane and difluoromethane | |
| CN105130743A (en) | Production method of 2,3,3,3-tetrafluoropropene | |
| CN104710273B (en) | A kind of preparation method of trifluoro-ethylene | |
| CN103288589A (en) | Method for co-production of trifluoroethylene and hydrogen fluoride | |
| CN102698779B (en) | Catalyst for co-producing HCFC-123, HCFC-124 and HFC-125 and preparation method | |
| CN107739294A (en) | The method that gas phase dehydrofluorination prepares hydrogen fluorine cyclopentene | |
| CN103214342B (en) | Synthetic method of 1,1,1,3,3-perfluoropropane | |
| CN102698778B (en) | Catalyst for preparing vinyl fluoride and 1,1-difluoroethane by using acetylene fluoride and preparation method for catalyst | |
| CN104926596B (en) | A kind of method that micro passage reaction continuously prepares bromomethane | |
| CN103449958A (en) | Synthesis method of 2-chloro-3,3,3-trifluoropropene | |
| CN102895967A (en) | Catalyst for producing HFC-32 vapor phase method and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |