CN102442881B - Preparation method of 2-chloro-3, 3, 3-trifluoropropene - Google Patents
Preparation method of 2-chloro-3, 3, 3-trifluoropropene Download PDFInfo
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- CN102442881B CN102442881B CN201110379740.7A CN201110379740A CN102442881B CN 102442881 B CN102442881 B CN 102442881B CN 201110379740 A CN201110379740 A CN 201110379740A CN 102442881 B CN102442881 B CN 102442881B
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Abstract
The invention discloses a preparation method of 2-chloro-3, 3, 3-trifluoropropene. With 1, 1, 2-trichloro-3-fluoropropene as a raw material, the method comprises the following steps of: in the presence of a ferric iron supported catalyst, introducing hydrogen fluoride and 1, 1, 2-trichloro-3-fluoropropene in a mole ratio of 5-30:1, controlling a contact time at 2-20 seconds and a reaction temperature at 160DEG C-240DEG C. The method of the invention is mainly used for synthesis of 2-chloro-3, 3, 3-trifluoropropene.
Description
Technical field
The present invention relates to a kind of 2-chloro-3,3, the preparation method of 3-trifluoro propene (HCFC-1233xf), relate in particular to a kind of with 1, the chloro-3-fluorine of 1,2-tri-propylene (HCFC-1231) is raw material, and under the existence of fluorination catalyst, gas phase fluorination obtains 2-chloro-3, the preparation method of 3,3-trifluoro propene.
Background technology
2-chloro-3,3,3 ,-trifluoropropene (HCFC-1233xf) is a kind of raw material for the production of 2,3,3,3-tetrafluoeopropene (HFO-1234yf).For example US Patent No. 20070197842 discloses a kind of preparation method of 2-chloro-3,3,3 ,-trifluoropropene, the method with 2,3,3,3-tetrachloro propylene or 1,1,2,3-tetrachloro propylene for raw material, at reactor top and middle part filling FeCl
3/ C catalyzer, bottom filling Cr
2o
3catalyzer, reactor top and middle part temperature of reaction are 120～220 ℃, reactor lower part temperature of reaction is 270～500 ℃, gas phase fluorination 1,1,2,3-tetrachloro propylene is prepared HCFC-1233xf, and its yield is 85%.Gas phase fluorination 2,3,3,3-tetrachloro propylene is prepared HCFC-1233xf, and its yield is 79%.Two kinds of catalyzer of the method use and HCFC-1233xf yield are lower.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency existing in background technology, provides a kind of a kind of catalyzer of only using, the preparation method of the 2-chloro-3,3,3 ,-trifluoropropene that yield is higher.
The preparation method of HCFC-1233xf of the present invention, comprises the following steps: with 1,1, the chloro-3-fluorine of 2-tri-propylene is raw material, under ferric iron loaded catalyst exists, passes into hydrogen fluoride and 1, the chloro-3-fluorine of 1,2-tri-propylene gas, be 0.5～30 second duration of contact, 160～240 ℃ of temperature of reaction, obtain 2-chloro-3,3,3-trifluoro propene, wherein the mol ratio of hydrogen fluoride and the chloro-3-fluorine of 1,1,2-tri-propylene is 3～20: 1.
Under the existence of ferric iron loaded catalyst of the present invention, preferably 180 ℃～200 ℃ of the temperature of reaction of the synthetic HCFC-1233xf of HF and the chloro-3-fluorine of 1,1,2-tri-propylene.
Can select in scope widely the duration of contact of reaction, is generally 2 seconds～20 seconds, preferably 5 seconds～10 seconds.
The amount of HF at least should be stoichiometric quantity, and the molar ratio range of general HF and the chloro-3-fluorine of 1,1,2-tri-propylene is 5～30: 1, and preferably 10～20: 1.
Reaction pressure is little on the impact of reaction, is all very suitable under the condition of normal atmosphere and pressurization.
In reaction process, unreacted hydrogen fluoride can recycle.
The carrier of ferric iron loaded catalyst of the present invention is the conventional carrier in this area, and for example carrier can be Calcium Fluoride (Fluorspan), aluminum oxide, chromium sesquioxide, aluminum fluoride, gac or magnesium fluoride.
The present invention's ferric iron loaded catalyst used, ferric content is 5%～20% of support of the catalyst weight, preferably 10%～15%.
Type of reactor for fluoridation is not crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor also can be used to the present invention.
Method of the present invention is only a kind of ferric iron loaded catalyst with catalyzer, and two kinds of catalyzer that method in documents adopts are simultaneously respectively FeCl
3/ C catalyzer and Cr
2o
3catalyzer; The preparation method of 2-chloro-3,3,3 ,-trifluoropropene of the present invention has higher reaction yield, its HCFC-1233xf reaction yield can reach 99.2%, and the yield of method in documents, its gas phase fluorination 1,1,2,3-tetrachloro propylene is prepared HCFC-1233xf reaction yield and is up to 85%, its gas phase fluorination 2,3, it is 79% that 3,3-tetrachloro propylene is prepared HCFC-1233xf reaction yield.
Embodiment
The invention will be further described in conjunction with the embodiments, but do not limit the scope of the invention.
The preparation of ferric iron compound loaded catalyst
The present invention's ferric iron loaded catalyst used adopts pickling process preparation, using iron trichloride in water-soluble or organic solvent as steeping fluid, then by carrier impregnation in this steeping fluid, drying, roasting and activation step obtain ferric iron loaded catalyst of the present invention.Available carrier comprises Calcium Fluoride (Fluorspan), aluminum oxide, chromium sesquioxide, aluminum fluoride, gac or magnesium fluoride etc.
For example: by 29.04g iron trichloride (FeCl
3) be dissolved in 100ml distilled water and be made into steeping fluid, then by 100g Calcium Fluoride (Fluorspan) (CaF
2) carrier is placed in steeping fluid, floods after 5 hours, 60 ℃ of evaporating water on Rotary Evaporators, make ferric iron content and are 10% ferric iron compound loaded catalyst presoma of support of the catalyst weight.By the 400 ℃ of roastings 8 hours in retort furnace of this presoma, then pack tubular reactor into, be warming up to 200 ℃, passing into hydrogen fluoride gas fluoridizes 1 hour, then with 1 ℃/min temperature rise rate, be warming up to 350 ℃, continue to fluoridize 8 hours, make ferric iron compound loaded catalyst.
Embodiment 1
In the carbon steel pipe that is 38mm at internal diameter, add the above-mentioned ferric iron compound loaded catalyst making, pass into HF and 1,1,180 ℃ of the chloro-3-fluorine of 2-tri-propylene react, and controlling duration of contact is 5 seconds, after reaction 20h, HF and 1, the mol ratio of the chloro-3-fluorine of 1,2-tri-propylene is 10: 1, and reaction product is removed after HCl and HF through washing, alkali cleaning, with gas chromatographic analysis 1, the transformation efficiency of the chloro-3-fluorine of 1,2-tri-propylene and the selectivity of HCFC-1233xf, the results are shown in Table 1.
Embodiment 2
Operation substantially the same manner as Example 1, difference is to change temperature of reaction into 200 ℃, reaction result is in Table 1.
Embodiment 3
Operation substantially the same manner as Example 1, difference is to change temperature of reaction into 160 ℃, reaction result is in Table 1.
Embodiment 4
Operation substantially the same manner as Example 1, difference is to change temperature of reaction into 240 ℃, reaction result is in Table 1.
Table 1
CF wherein
2clCCl=CH
2(HCFC-1232), CF
3cFClCH
3(HCFC-244bb), other product comprises CF
3cHClCH
2f (HCFC-244db), CF
3cHFCH
2cl (HCFC-244cb), CF
3cHFCH
2f (HFC-245eb) etc.
Embodiment 5
Operation substantially the same manner as Example 1, difference is that the mol ratio of control HF and the chloro-3-fluorine of 1,1,2-tri-propylene is 5: 1, reaction result is in Table 2.
Embodiment 6
Operation substantially the same manner as Example 1, difference is that the mol ratio of control HF and the chloro-3-fluorine of 1,1,2-tri-propylene is 20: 1, reaction result is in Table 2.
Embodiment 7
Operation substantially the same manner as Example 1, difference is that the mol ratio of control HF and the chloro-3-fluorine of 1,1,2-tri-propylene is 30: 1, reaction result is in Table 2.
Table 2
CF wherein
2clCCl=CH
2(HCFC-1232), CF
3cFClCH
3(HCFC-244bb), other product comprises CF
3cHClCH
2f (HCFC-244db), CF
3cHFCH
2cl (HCFC-244cb), CF
3cHFCH
2f (HFC-245eb) etc.
Embodiment 8
Operation substantially the same manner as Example 1, difference is to change 2 seconds duration of contact into, reaction result is in Table 3.
Embodiment 9
Operation substantially the same manner as Example 1, difference is to change 10 seconds duration of contact into, reaction result is in Table 2.
Embodiment 10
Operation substantially the same manner as Example 1, difference is to change 20 seconds duration of contact into, reaction result is in Table 2.
Table 3
CF wherein
2clCCl=CH
2(HCFC-1232), CF
3cFClCH
3(HCFC-244bb), other product comprises CF
3cHClCH
2f (HCFC-244db), CF
3cHFCH
2cl (HCFC-244cb), CF
3cHFCH
2f (HFC-245eb) etc.
Embodiment 11
Operation substantially the same manner as Example 1, difference is by 5.81g FeCl
3be dissolved in 100ml distilled water as steeping fluid, make ferric iron content and be 5% Fe of support of the catalyst weight
3+/ CaF
2fluorination catalyst, reaction result is in Table 2.
Embodiment 12
Operation substantially the same manner as Example 1, difference is by 43.56g FeCl
3be dissolved in 100ml distilled water as steeping fluid, make ferric iron content and be 15% Fe of support of the catalyst weight
3+/ CaF
2fluorination catalyst, reaction result is in Table 2.
Embodiment 13
Operation substantially the same manner as Example 1, difference is by 58.08g FeCl
3be dissolved in 100ml distilled water as steeping fluid, make ferric iron content and be 20% Fe of support of the catalyst weight
3+/ CaF
2fluorination catalyst, reaction result is in Table 2.
Table 4
CF wherein
2clCCl=CH
2(HCFC-1232), CF
3cFClCH
3(HCFC-244bb), other product comprises CF
3cHClCH
2f (HCFC-244db), CF
3cHFCH
2cl (HCFC-244cb), CF
3cHFCH
2f (HFC-245eb) etc.
Embodiment 14
Operation substantially the same manner as Example 1, difference is by CaF
2carrier becomes aluminum fluoride, and reaction result is in Table 5.
Embodiment 15
Operation substantially the same manner as Example 1, difference is by CaF
2carrier becomes magnesium fluoride, and reaction result is in Table 5.
Embodiment 16
Operation substantially the same manner as Example 1, difference is by CaF
2carrier becomes aluminum oxide, and reaction result is in Table 5.
Embodiment 17
Operation substantially the same manner as Example 1, difference is by CaF
2carrier becomes chromium sesquioxide, and reaction result is in Table 5.
Table 5
CF wherein
2clCCl=CH
2(HCFC-1232), CF
3cFClCH
3(HCFC-244bb), other product comprises CF
3cHClCH
2f (HCFC-244db), CF
3cHFCH
2cl (HCFC-244cb), CF
3cHFCH
2f (HFC-245eb) etc.
Claims (2)
1. the preparation method of a 2-chloro-3,3,3 ,-trifluoropropene, the method comprises the following steps: with the chloro-3-fluorine of 1,1,2-tri-propylene for raw material, under ferric iron compound loaded catalyst exists, pass into hydrogen fluoride and 1,1, the chloro-3-fluorine of 2-tri-propylene gas, reaction conditions is: be 2～20 seconds duration of contact, 160～240 ℃ of temperature of reaction, wherein hydrogen fluoride and 1, the mol ratio of the chloro-3-fluorine of 1,2-tri-propylene is 5～30: 1; The ferric content of ferric iron loaded catalyst is 5%～20% of support of the catalyst weight.
According to claim 1 to described 2-chloro-3,3, the preparation method of 3-trifluoro propene, it is characterized in that described reaction conditions is: be 5～10 seconds duration of contact, 180～200 ℃ of temperature of reaction, hydrogen fluoride and 1,1, the mol ratio of the chloro-3-fluorine of 2-tri-propylene is 10～20: 1, and the ferric content of ferric iron loaded catalyst is 10%～15% of support of the catalyst weight.
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| FR3047240B1 (en) * | 2016-01-28 | 2019-09-27 | Arkema France | PROCESS FOR THE PRODUCTION OF 2-CHLORO-3,3,3-TRIFLUOROPROPENE |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168494A (en) * | 2007-11-27 | 2008-04-30 | 常熟三爱富中昊化工新材料有限公司 | Preparation method for chlorotrifluoropropylene |
| CN101597209A (en) * | 2008-03-20 | 2009-12-09 | 霍尼韦尔国际公司 | Be used to prepare 2,3,3, the integrated process of 3-tetrafluoeopropene |
| WO2011077191A1 (en) * | 2009-12-23 | 2011-06-30 | Arkema France | Catalytic gas phase fluorination of 1230xa to 1234yf |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101168494A (en) * | 2007-11-27 | 2008-04-30 | 常熟三爱富中昊化工新材料有限公司 | Preparation method for chlorotrifluoropropylene |
| CN101597209A (en) * | 2008-03-20 | 2009-12-09 | 霍尼韦尔国际公司 | Be used to prepare 2,3,3, the integrated process of 3-tetrafluoeopropene |
| WO2011077191A1 (en) * | 2009-12-23 | 2011-06-30 | Arkema France | Catalytic gas phase fluorination of 1230xa to 1234yf |
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Effective date of registration: 20160519 Address after: 255300 Zhoucun City, Shandong province constant access road, No. 979, Patentee after: Shandong Huaan Modern Environmental Protection Technology Co., Ltd. Address before: 710065 Shaanxi province Xi'an Yanta District Zhang eight road No. 168 Patentee before: Xi'an Inst. of Modern Chemistry |