CN102001910A - Method for preparing 2,3,3,3-tetrafluoropropene - Google Patents
Method for preparing 2,3,3,3-tetrafluoropropene Download PDFInfo
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- CN102001910A CN102001910A CN2010102869600A CN201010286960A CN102001910A CN 102001910 A CN102001910 A CN 102001910A CN 2010102869600 A CN2010102869600 A CN 2010102869600A CN 201010286960 A CN201010286960 A CN 201010286960A CN 102001910 A CN102001910 A CN 102001910A
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Abstract
The invention discloses a method for preparing 2,3,3,3-tetrafluoropropene, comprising the following steps: a. in the presence of a fluorinated catalyst, hydrogen fluoride and 1,1,2,3-tetrafluoropropene enter into a first reactor to react; b. in the presence of the fluorinated catalyst, 2-chloro-3,3,3 trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane, 1,1,1,2,2-pentafluoropropane and hydrogen fluoride enter into a second reactor to react; c. the product flows obtained in the steps a and b enter into a first distillation tower to be separated; the tower top components are hydrogen chloride and 2,3,3,3-tetrafluoropropene which break away from the system and others are column reactor components; and d. the column reactor components in the step c enter into a second distillation tower to be separated; the column reactor components include 2-chloro-3,3,3 trifluoropropene and 2-chloro-1,1,1,2-tetrafluoropropane which are recycled to the second reactor; and the tower top components, including hydrogen fluoride and 1,1,1,2,2-pentafluoropropane, are recycled to the first reactor or/and the second reactor to be used.
Description
Technical field
The present invention relates to a kind of 2,3,3, the preparation method of 3-tetrafluoeopropene (HFO-1234yf) relates in particular to a kind of in the presence of fluorination catalyst, with 1,1,1,2,2-pentachloropropane (HCC-240ab) or 2,3,3,3-tetrachloro propylene is a raw material, obtains 2,3 through two step gas phase fluorination, 3, the preparation method of 3-tetrafluoeopropene.
Background technology
At present, 1,1,1,2-Tetrafluoroethane (HFC-134a) is widely used in the mobile air conditioner refrigeration system, value (GWP) is 1430 because its Greenhouse effect are dived, and can cause global warming, needs the new needs of substitute to conform of exploitation.
2,3,3,3-tetrafluoeopropene, the ozone depletion value (ODP) of diving is zero, and GWP is 4, and atmospheric lifetime is 11 days only, has good physical and chemical performance, is considered to directly substitute the economical scheme of HFC-134a.U.S. Pat 2009024009 discloses the method for a kind of synthetic HFO-1234yf.This method is with 1,1,2, and 3-tetrachloro propylene or HCC-240db are raw material, at first at Cr
2O
3Under the existence of catalyzer, carry out HF gas phase fluorination 1,1,2 in first reactor, 3-tetrachloro propylene obtains 2-chloro-3,3, and 3-trifluoro propene (HCFC-1233xf) is then at SbCl
5Effect down, liquid-phase fluorination HCFC-1233xf obtains 2-chloro-1,1,1 in second reactor, 2-tetrafluoropropane (HCFC-244bb), at last in the 3rd reactor HCFC-244bb at CsCl/MgF
2Exist down, 350 ℃~550 ℃ dehydrochlorinations obtain HFO-1234yf.But this method reactions steps is more, total three-step reaction, and also the reaction of second step is liquid phase reaction, needs isolation of intermediate products HCFC-244bb, as the raw material of three-step reaction.。
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiency that exists in the background technology, provides a kind of with 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene is a raw material, need not the separation of intermediate product, reactions steps less 2,3,3, the preparation method of 3-tetrafluoeopropene.
In order to solve the problems of the technologies described above, the present invention is with 1,1,1,2,2-pentachloropropane (HCC-240ab) or 2,3,3, and 3-tetrachloro propylene is a raw material, adopts the gas phase catalytic fluorination legal system to be equipped with HFO-1234yf, the principal reaction of generation is as follows:
CCl
3CCl
2CH
3+3HF——→CF
3CCl=CH
2+4HCl (1)
CCl
3CCl=CH
2+3HF——→CF
3CCl=CH
2+3HCl (2)
CF
3CCl=CH
2+HF——→CF
3CFClCH
3 (3)
CF
3CFClCH
3——→CF
3CF=CH
2+HCl (4)
The main side reaction that takes place:
CF
3CFClCH
3+HF——→CF
3CF
2CH
3+HCl (5)
The present invention adopts two reactors, and first reactor mainly carries out hydrogen fluoride (HF) and fluoridizes HCC-240ab or 2,3,3, the reaction of 3-tetrachloro propylene, react (1) and (2) is under proper reaction conditions, HCC-240ab or 2,3,3,3-tetrachloro propylene conversion 〉=90%, even can reach 100%, primary product is HCFC-1233xf; Second reactor mainly carries out the reaction of reaction that HF fluoridizes HCFC-1233xf and HCFC-244bb, HFC-245cb dehydrochlorination, (3) and (4) react, HCFC-244bb can take place simultaneously fluoridize generation 1,1,1,2, the side reaction (5) of 2-pentafluoropropane (HFC-245cb) and HFO-1234yf and HF addition generate the side reaction (6) of HFC-245cb.The present invention loops back in second reactor reaction to generate more HFO-1234yf with intermediate product HCFC-244bb and HFC-245cb.
The invention provides a kind ofly 2,3,3, the preparation method of 3-tetrafluoeopropene may further comprise the steps:
A. hydrogen fluoride, 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene enters first reactor, reacts in the presence of fluorination catalyst, and reaction conditions is: reaction pressure 0.1MPa~1.0MPa, hydrogen fluoride and 1,1,1,2,2-pentachloropropane or 2,3,3, the mol ratio 5~20 of 3-tetrachloro propylene; 2 seconds~30 seconds duration of contact; 220 ℃~350 ℃ of temperature of reaction; Comprise 2-chloro-3,3,3 trifluoro propenes, the 2-chloro-1,1,1 that reaction generates, 2-tetrafluoropropane, 1,1,1,2,2-pentafluoropropane, hydrogenchloride and unreacted hydrogen fluoride and 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene in the product stream that obtains;
B.2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1, and 2-tetrafluoropropane and 1,1,1,2,2-pentafluoropropane and hydrogen fluoride enter second reactor, react in the presence of fluorination catalyst, and reaction conditions is: reaction pressure 0.1MPa~1.0MPa; Hydrogen fluoride and 2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1,2-tetrafluoropropane and 1,1,1,2, the 2-pentafluoropropane, or with 2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1,2-tetrafluoropropane and 2,3,3, the mol ratio 2~15 of 3-tetrachloro propylene total amount; 5 seconds~30 seconds duration of contact; 300 ℃~380 ℃ of temperature of reaction; Comprise 2,3,3,3-tetrafluoeopropene, 1,1,1,2,2-pentafluoropropane, 2-chloro-1,1,1,2-tetrafluoropropane, 2-chloro-3,3,3-trifluoro propene and hydrogenchloride and hydrogen fluoride in the product stream;
C. the product of step a flows to into first distillation tower and separates, tower still component comprises hydrogen fluoride, HCFC-1233xf, HCFC-244bb, HFC-245cb, HFO-1234yf and unreacted 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene, the cat head component is a hydrogenchloride, breaks away from reactive system, enters acid making system and makes hydrochloric acid;
D. the tower still component of step c enters phase separator and is separated, phase separation temperature is-30 ℃~10 ℃, 1,1,1 of phase separator lower floor, 2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene is circulated to first reactor, and the hydrogen fluoride on phase separator upper strata, HCFC-1233xf, HCFC-244bb, HFC-245cb and HFO-1234yf enter second column with the product of step b stream to be separated.
E. after-fractionating Tata still component 2-chloro-3,3,3-trifluoro propene, 2-chloro-1,1,1,2-tetrafluoropropane and hydrogen fluoride are circulated to second reactor, cat head component hydrogenchloride, 1,1,1,2,2-pentafluoropropane and 2,3,3, the 3-tetrafluoeopropene enters the 3rd distillation tower and separates;
F. the 3rd distills Tata still component 1,1,1,2, and the 2-pentafluoropropane is circulated to second reactor, cat head component hydrogenchloride and 2,3,3, the 3-tetrafluoeopropene breaks away from reactive system, enters the purifying products system, through technologies such as deacidification, dehydration, rectifying, obtain target product 2,3,3, the 3-tetrafluoeopropene.
The reaction conditions of the present invention's first reactor is preferably: reaction pressure 0.3~0.6MPa, hydrogen fluoride and 1,1,2, the mol ratio 10~15 of 3-tetrachloro propylene; 6 seconds~10 seconds duration of contact; 260 ℃~300 ℃ of temperature of reaction; The reaction conditions of second reactor is preferably: reaction pressure 0.3MPa~0.6MPa; Hydrogen fluoride and 2-chloro-3,3,3-trifluoro propene, 2-chloro-1,1,1,2-tetrafluoropropane and 1,1,1,2,2-pentafluoropropane or 2,3,3, the mol ratio 5~8 of 3-tetrachloro propylene total amount; 10 seconds~15 seconds duration of contact; 330 ℃~360 ℃ of temperature of reaction.
The present invention can suitably select according to the working pressure of the level of equipment, general facilities, reactive system and the isolating composition of desire etc. to the operational condition of distillation tower without limits.Working pressure is 0.1MPa~1.0MPa, preferred 0.3MPa~0.6MPa.Generally speaking, for easy and simple to handle, the working pressure of distillation tower is consistent with reactive system.Tower top temperature and tower still temperature are by working pressure and material component decision thereof.
Among the present invention, fresh HF raw material can or enter reactive system by first reactor, second reactor simultaneously by any one reactor in first reactor, second reactor.
The present invention to the catalyzer in the fluoridation without limits, any known fluorination catalyst all is applicable to the present invention, for example: chromic oxide, chromium fluoride, fluorizated chromic oxide, aluminum fluoride, fluorizated aluminum oxide, be carried on chromic oxide on gac, aluminum fluoride, the magnesium fluoride, contain chromic oxide and the activated carbon supported SbCl of multiple metal (as Zn, Co, Ni, Ge, In etc.)
5Or TiCl
4Deng.The fluorination catalyst difference that adopts, reaction conditions difference then comprises the mol ratio of temperature of reaction, reaction pressure, duration of contact and material.The preferential chromium-based fluorination catalyst that contains Al, Zn, Mg, Ni metal powder that adopts of the present invention, catalytic activity is good, the selectivity height, regenerability is good, and entire life is long.Chinese patent CN1651137A is seen in the preparation that contains the chromium-based catalysts of Al, Zn, Mg, Ni metal powder.
The type of reactor that the present invention is used for fluoridation is not crucial, any suitable gas phase fluorination device all is applicable to the present invention, and the present invention preferentially selects the material calandria type fixed bed reactor made of nickel and alloy (comprising Hastelloy, Inconel, Incoloy and Monel) thereof for example with anti-hydrogen fluoride corrosion effect for use.
Advantage of the present invention:
Of the present invention 2,3,3,3-tetrafluoeopropene preparation method is with 1,1,1,2,2-pentachloropropane (HCC-240ab) or 2,3,3,3-tetrachloro propylene is a raw material, the gas phase catalytic fluorination successive reaction, avoided second step liquid-phase fluorination process of prior art and the sepn process of intermediate product HCFC-244bb, reactions steps is less, and reactions steps of the present invention was two steps.And the reactions steps of the method for documents was three steps.
Description of drawings
Fig. 1 represents 2,3,3, preparation technology's schema of 3-tetrafluoeopropene.
Label meaning in Fig. 1 is as follows.Pipeline: 1,2,4,6,7,9,11,13,14,15,16,17,19 and 20; First reactor: 3; First distillation tower: 5; Phase separator: 8; Second column: 10; The 3rd distillation tower: 12; Second reactor: 18.
Embodiment
The present invention is described in more detail with reference to accompanying drawing.Fresh HCC-240ab or 2,3,3, the mixture of 3-tetrachloro propylene and HF is through pipeline 1, enter in first reactor 3 that is filled with fluorination catalyst by pipeline 2 with the logistics that recycles through pipeline 20 and to react, the reaction product pipeline 4 of flowing through enters first distillation tower 5 and separates.
The first distillation tower cat head component is that HCl enters acid making system by pipeline 6 and makes hydrochloric acid, tower still component is HF, HCFC-1233xf, HCFC-244bb, HFC-245cb, HFO-1234yf and unreacted HCC-240ab or 2,3,3,3-tetrachloro propylene, by pipeline 7, enter phase separator 8 and be separated; The unconverted HCC-240ab of phase separator lower floor or 2,3,3,3-tetrachloro propylene, enter first reactor via pipeline 21 circulations and continue reaction, the phase separator upper materials comprises HF, HCFC-1233xf and a spot of HCFC-244bb, HFC-245cb, HFO-1234yf, enters second column 10 by pipeline 9 with the second reactor outlet material pipeline 19 and separates.
The tower still component of second column is that HF, HCFC-1233xf, HCFC-244bb and small amount of H FC-245cb enter second reactor reaction by pipeline 15; The cat head component of second column is HFC-245cb, HFO-1234yf, HCl and small amount of H F, enters the 3rd distillation tower 12 by pipeline 11 and separates.
The 3rd distillation tower cat head component is HFO-1234yf and HCl, enters the purifying products system by pipeline 14, by obtaining the HFO-1234yf product after deacidification, dehydration, the rectification process; The 3rd distillation Tata still component is HFC-245cb, a spot of HF and section H FO-1234yf, by pipeline 13 with enter second reactor 18 after the tower still of second column mixes by pipeline 15 round-robin logistics and carry out second and go on foot and react.Reacting product stream enters second column 10 by pipeline 19 to be separated.The fresh HCC-240ab that adds or 2,3,3,3-tetrachloro propylene enters first reactor through pipeline 1, and the fresh HF that adds enters first reactor and second reactor respectively through pipeline 1,16.
Embodiment 1
At internal diameter is to add 60 milliliters of chromium-based fluorination catalysts that contain Al, Zn, Mg, Ni in the carbon steel pipe of 38mm, and method for preparing catalyst is seen Chinese patent CN1651137A.First reactor is warming up to 260 ℃, feeds HF and 1,1,1,2,2-pentachloropropane (HCC-240ab) is reacted, and the mol ratio of control HF and HCC-240ab is 10, be 6 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is after washing, alkali cleaning, alkali drying are removed HCl and HF, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 1.
Embodiment 2
Operation substantially the same manner as Example 1, different is changes the temperature of reaction of first reactor into 220 ℃, the results are shown in Table 1.
Embodiment 3
Operation substantially the same manner as Example 1, different is changes the temperature of reaction of first reactor into 300 ℃, the results are shown in Table 1.
Embodiment 4
Operation substantially the same manner as Example 1, different is changes the temperature of reaction of first reactor into 350 ℃, the results are shown in Table 1.
Embodiment 5
Operation substantially the same manner as Example 1, different is to change 2 seconds duration of contact into, the results are shown in Table 1.
Embodiment 6
Operation substantially the same manner as Example 1, different is to change 10 seconds duration of contact into, the results are shown in Table 1.
Embodiment 7
With basic 1 identical operations of embodiment, different is to change 30 seconds duration of contact into, the results are shown in Table 1.
Embodiment 8
Operation substantially the same manner as Example 1, different is changes the mol ratio of HF and HCC-240ab into 5, the results are shown in Table 1.
Embodiment 9
Operation substantially the same manner as Example 1, different is changes the mol ratio of HF and HCC-240ab into 15, the results are shown in Table 1.
Embodiment 10
Operation substantially the same manner as Example 1, different is changes the mol ratio of HF and HCC-240ab into 20, the results are shown in Table 1.
Embodiment 11
Operation substantially the same manner as Example 1, different is to change reaction pressure into 0.3MPa, the results are shown in Table 1.
Embodiment 12
Operation substantially the same manner as Example 1, different is to change reaction pressure into 0.6MPa, the results are shown in Table 1.
Embodiment 13
Operation substantially the same manner as Example 1, different is to change reaction pressure into 1.0MPa, the results are shown in Table 1.
Embodiment 14
Operation substantially the same manner as Example 1, different is with raw material 1,1,1,2, and the 2-pentachloropropane changes 2,3,3 into, and 3-tetrachloro propylene reacts, and the results are shown in Table 1.
Table 1
Other product comprises CF
3CFClCH
3(HCFC-244bb), CF
3CF
2CH
3(HFC-245cb) and the trace CF
3CHClCHF
2(HCFC-244db), CF
3CHFCH
2F (HFC-245eb) etc.
Embodiment 15
At internal diameter is to add 50 milliliters of chromium-based fluorination catalysts that contain Al, Zn, Mg, Ni in the carbon steel pipe of 38mm, method for preparing catalyst is seen Chinese patent CN1651137A, second reactor is warming up to 360 ℃, feeding HF and HCFC-1233xf reacts, the mol ratio of control HF and HCFC-1233xf is 5, be 10 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is after HCl and HF are removed in washing, alkali cleaning, with organic composition in the gas chromatographic analysis reaction product, the results are shown in Table 2.
Embodiment 16
With basic 15 identical operations of embodiment, different is changes the temperature of reaction of second reactor into 300 ℃, the results are shown in Table 2.
Embodiment 17
With basic 15 identical operations of embodiment, different is changes the temperature of reaction of second reactor into 330 ℃, the results are shown in Table 2.
Embodiment 18
With embodiment 15 identical operations, different is changes the temperature of reaction of second reactor into 380 ℃, the results are shown in Table 2.
Embodiment 19
With basic 15 identical operations of embodiment, different is to change 5 seconds duration of contact into, the results are shown in Table 2.
Embodiment 20
With basic 15 identical operations of embodiment, different is to change 15 seconds duration of contact into, the results are shown in Table 2.
Embodiment 21
With basic 15 identical operations of embodiment, different is to change 30 seconds duration of contact into, the results are shown in Table 2.
Embodiment 22
With basic 15 identical operations of embodiment, different mol ratios with HF and HCFC-1233xf change 2 into and the results are shown in Table 2.
Embodiment 23
With basic 15 identical operations of embodiment, different mol ratios with HF and HCFC-1233xf change 8 into, the results are shown in Table 2.
Embodiment 24
With basic 15 identical operations of embodiment, different mol ratios with HF and HCFC-1233xf change 15 into, the results are shown in Table 2.
Embodiment 25
With basic 15 identical operations of embodiment, different change reaction pressure into 0.3MPa, the results are shown in Table 2.
Embodiment 26
Operation substantially the same manner as Example 15, different change reaction pressure into 0.6MPa, the results are shown in Table 2.
Embodiment 27
Operation substantially the same manner as Example 15, different change reaction pressure into 1.0MPa, the results are shown in Table 2.
Table 2
Other product comprises CF
3CFClCH
3(HCFC-244bb), CF
3CF
2CH
3(HFC-245cb) and the trace CF
3CHClCHF
2(HCFC-244db), CF
3CHFCH
2F (HFC-245eb) etc.
Embodiment 27
At internal diameter is to add 50 milliliters in the carbon steel pipe of 38mm to contain Al, Zn, Mg, the chromium-based fluorination catalyst of Ni, method for preparing catalyst is seen Chinese patent CN1651137A, be warming up to 360 ℃, feed HCFC-1233xf, HCFC-244bb, HFC-245cb and HF react, control HFC-245cb, the molar ratio of HCFC-244bb and HCFC-1233xf 0.1: 0.2: 1, HF and mol ratio (HCFC-1233xf+HCFC-244bb+HFC-245cb) are 5, be 10 seconds duration of contact, reaction pressure 0.1MPa, behind the reaction 20h, reaction product is through washing, after HCl and HF are removed in alkali cleaning,, the results are shown in Table 3 with organic composition in the gas chromatographic analysis reaction product.
Embodiment 28
Operation substantially the same manner as Example 27, different molar ratios with HFC-245cb, HCFC-244bb and HCFC-1233xf change 0.2: 0.5: 1 into, the results are shown in Table 3.
Embodiment 29
Operation substantially the same manner as Example 27, different molar ratios with HFC-245cb, HCFC-244bb and HCFC-1233xf change 0.5: 0.1: 1 into, the results are shown in Table 3.
Embodiment 30
Operation substantially the same manner as Example 27, different molar ratios with HF ℃-245cb, HCFC-244bb and HCFC-1233xf change 0.5: 0.5: 1 into, the results are shown in Table 3.
Table 3
Other product comprises CF
3CFClCH
3(HCFC-244bb), CF
3CF
2CH
3(HFC-245cb) and the trace CF
3CHClCHF
2(HCFC-244db), CF
3CHFCH
2F (HFC-245eb) etc.
Claims (2)
1. one kind 2,3,3, the preparation method of 3-tetrafluoeopropene, this method be with 1,1,1,2,2-pentachloropropane or 2,3,3, and 3-tetrachloro propylene is a raw material, may further comprise the steps:
A. hydrogen fluoride, 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene enters first reactor, reacts in the presence of fluorination catalyst, and reaction conditions is: reaction pressure 0.1MPa~1.0MPa, hydrogen fluoride and 1,1,1,2,2-pentachloropropane or 2,3,3, the mol ratio 5~20 of 3-tetrachloro propylene; 2 seconds~30 seconds duration of contact; 220 ℃~350 ℃ of temperature of reaction; Comprise 2-chloro-3,3,3 trifluoro propenes, the 2-chloro-1,1,1 that reaction generates, 2-tetrafluoropropane, 1,1,1,2,2-pentafluoropropane, hydrogenchloride and unreacted hydrogen fluoride and 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene in the product stream that obtains;
B.2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1, and 2-tetrafluoropropane and 1,1,1,2,2-pentafluoropropane and hydrogen fluoride enter second reactor, react in the presence of fluorination catalyst, and reaction conditions is: reaction pressure 0.1MPa~1.0MPa; Hydrogen fluoride and 2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1,2-tetrafluoropropane and 1,1,1,2, the 2-pentafluoropropane, or with 2-chloro-3,3,3 trifluoro propenes, 2-chloro-1,1,1,2-tetrafluoropropane and 2,3,3, the mol ratio 2~15 of 3-tetrachloro propylene total amount; 5 seconds~30 seconds duration of contact; 300 ℃~380 ℃ of temperature of reaction; Comprise 2,3,3,3-tetrafluoeopropene, 1,1,1,2,2-pentafluoropropane, 2-chloro-1,1,1,2-tetrafluoropropane, 2-chloro-3,3,3-trifluoro propene and hydrogenchloride and hydrogen fluoride in the product stream;
C. the product of step a flows to into first distillation tower and separates, tower still component comprises hydrogen fluoride, HCFC-1233xf, HCFC-244bb, HF ℃-245cb, HFO-1234yf and unreacted 1,1,1,2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene, the cat head component is a hydrogenchloride, breaks away from reactive system, enters acid making system and makes hydrochloric acid;
D. the tower still component of step c enters phase separator and is separated, phase separation temperature is-30 ℃~10 ℃, 1,1,1 of phase separator lower floor, 2,2-pentachloropropane or 2,3,3,3-tetrachloro propylene is circulated to first reactor, and the hydrogen fluoride on phase separator upper strata, HCFC-1233xf, HCFC-244bb, HFC-245cb and HFO-1234yf enter second column with the product of step b stream to be separated.
E. after-fractionating Tata still component 2-chloro-3,3,3-trifluoro propene, 2-chloro-1,1,1,2-tetrafluoropropane and hydrogen fluoride are circulated to second reactor, cat head component hydrogenchloride, 1,1,1,2,2-pentafluoropropane and 2,3,3, the 3-tetrafluoeopropene enters the 3rd distillation tower and separates;
F. the 3rd distills Tata still component 1,1,1,2, and the 2-pentafluoropropane is circulated to second reactor, cat head component hydrogenchloride and 2,3,3, the 3-tetrafluoeopropene breaks away from reactive system, enters the purifying products system, through technologies such as deacidification, dehydration, rectifying, obtain target product 2,3,3, the 3-tetrafluoeopropene.
2. according to claim 12,3,3, the preparation method of 3-tetrafluoeopropene, the reaction conditions that it is characterized in that first reactor described in the step a is: reaction pressure 0.3MPa~0.6MPa, hydrogen fluoride and 1,1,1,2,2-pentachloropropane or 2,3,3, the mol ratio 10~15 of 3-tetrachloro propylene; 6 seconds~10 seconds duration of contact; 260 ℃~300 ℃ of temperature of reaction; The reaction conditions of second reactor described in the step b is: reaction pressure 0.3MPa~0.6MPa; Hydrogen fluoride and 2-chloro-3,3,3-trifluoro propene, 2-chloro-1,1,1,2-tetrafluoropropane and 1,1,1,2, the mol ratio 5~8 of 2-pentafluoropropane total amount; 10 seconds~15 seconds duration of contact; 330 ℃~360 ℃ of temperature of reaction.
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CN105026349A (en) * | 2013-03-12 | 2015-11-04 | 霍尼韦尔国际公司 | A method for mitigating HFC-245CB formation during hcfo-1233XF hydrofluorination to HCFC-244BB |
US9296670B2 (en) | 2012-02-10 | 2016-03-29 | The Chemours Company Fc, Llc | Process for the manufacture of 2,3,3,3-tetrafluoropropene |
CN105481636A (en) * | 2015-11-11 | 2016-04-13 | 西安近代化学研究所 | Method for synthesizing 1,1,1,2,2-pentafluoropropane |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101028992A (en) * | 2007-04-11 | 2007-09-05 | 西安近代化学研究所 | Method for producing 1,1,1,3-tetrafluoroethylene |
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 |
-
2010
- 2010-09-20 CN CN 201010286960 patent/CN102001910B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101028992A (en) * | 2007-04-11 | 2007-09-05 | 西安近代化学研究所 | Method for producing 1,1,1,3-tetrafluoroethylene |
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 |
Non-Patent Citations (2)
Title |
---|
杨刚,等: "HFO-1234yf合成的研究进展", 《有机氟工业》, no. 3, 31 December 2009 (2009-12-31), pages 12 - 15 * |
苏刚: "2,3,3,3-四氟丙烯专利研究", 《有机氟工业》, no. 2, 31 December 2009 (2009-12-31), pages 35 - 44 * |
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