CN103508843A - Method for preparing 1, 2-dichloro-3, 3, 3-trifluoropropene by gas-phase fluorination - Google Patents
Method for preparing 1, 2-dichloro-3, 3, 3-trifluoropropene by gas-phase fluorination Download PDFInfo
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- CN103508843A CN103508843A CN201310462309.8A CN201310462309A CN103508843A CN 103508843 A CN103508843 A CN 103508843A CN 201310462309 A CN201310462309 A CN 201310462309A CN 103508843 A CN103508843 A CN 103508843A
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Abstract
The invention discloses a method for preparing 1, 2-dichloro-3, 3, 3-trifluoropropene by gas-phase fluorination. Specifically, the method involves the gas-phase catalytic fluorination reaction between a compound with the general formula CF(3-x)ClxCH(2-y)ClyCH(3-z)Clz and hydrogen fluoride in the presence of a fluorination catalyst so as to generate 1, 2-dichloro-3, 3, 3-trifluoropropene, wherein in the general formula, x = 0, 1, 2, 3; y = 1, 2; z = 1, 2, and y+z=3. The method disclosed by the invention is mainly used to prepare 1, 2-dichloro-3, 3, 3-trifluoropropene.
Description
Technical field
The present invention relates to a kind ofly 1,2-bis-is chloro-3,3, and the preparation method of 3-trifluoro propene (HCFO-1223xd), relates in particular to Compound C F
3-xcl
xcH
2-ycl
ycH
3-zcl
z(x=0,1,2,3; Y=1,2; Z=1,2 and y+z=3) under the existence of fluorination catalyst, carry out gas phase catalytic fluorination with hydrogen fluoride and react the method that generates HCFO-1223xd.
Background technology
In recent years, generally believed that fully halogenated Chlorofluorocarbons (CFCs) (CFCs) has serious harm to earth's ozone layer, therefore, the safer equivalent material that hydrocarbon compoud containing fluorine industry has contained diversion still less or replaced without chlorine to exploitation, for example hydrogen chlorine fluoroolefin (HCFOs), hydrogen fluorohydrocarbon (HFCs), HF hydrocarbon (HFOs).
1,2-bis-is chloro-3,3, and 3-trifluoro propene (HCFO-1223xd) can be used as raw material and the intermediate of the various fluorocarbons of preparation, as cis 1,1,1,4,4,4-hexafluoro-2-butylene (cis-HCFO-1336), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 2,3,3,3-tetrafluoeopropene (HFO-1234yf), also can be used as producing the fluorochemical monomer of polymkeric substance, can be used as in addition introducing CF to functional fluoropolymer material
3the raw material of unit structure block and medicine intermediate are used.
WO9745388 discloses a kind of fluorine chloropropane and has reacted with fluorine antimony chloride the method for preparing HFC-245fa, and HCFO-1223xd is as a kind of intermediate product, and content changes in 0.2%~13.3% scope, and selectivity is low.
It is a kind of 1,1 that US2009043118 discloses, and 1-trifluoro propene (HFO-1243zf) is under the existence of catalysts for gas phase fluorination, with hydrogen fluoride (HF), chlorine (Cl
2) generate can be used as heat transfer composition comprise HFO-1234yf, 2,3-bis-chloro-1,1,1-trifluoro propane (HCFC-243db), 2-are chloro-1,1,1-trifluoro propene (HCFO-1233xf), 2-chloro-1, the method of the composition of 1,1,2-tetrafluoropropane (HCFC-244bb).But in the reaction of this chlorofluorination, reaction raw materials 1,1,1-trifluoro propene is difficult to obtain, and the HCFO-1223xd content generating changes in 0%~20.2% scope, and selectivity is low.
The disclosed HCFO-1223xd of above-mentioned patent synthesizes a small amount of by product generating in hydrogen fluorohydrocarbon, HF hydrocarbon and occurs as just this area, also there is no at present the open preparation method for HCFO-1223xd, thus need badly set up that a kind of raw material is easy to get, the preparation method of high conversion and highly selective.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of raw material is easy to get, transformation efficiency is high, selectivity is high gas phase fluorination to prepare 1,2-bis-chloro-3,3, the method for 3-trifluoro propene.
In order to realize object of the present invention, the invention provides a kind of gas phase fluorination, to prepare 1,2-bis-chloro-3,3, and the method for 3-trifluoro propene, is characterized in that, under the existence of fluorination catalyst, general formula is CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound react with hydrogen fluoride generation gas phase catalytic fluorination that to generate 1,2-bis-chloro-3,3,3-trifluoro propene, x=0 in compound general formula wherein, 1,2,3; Y=1,2; Z=1,2; And y+z=3;
Reaction conditions is: 180 ℃~450 ℃ of temperature of reaction; Hydrogen fluoride and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio (1~30): 1; Reaction contact time 0.5 second~60 seconds.
Other technologies of the present invention are characterized as:
Described fluorination catalyst is loaded catalyst, comprises carrier and active ingredient, and wherein carrier is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or the activated carbon fluoridized; Active ingredient is Mo
6+, V
5+, Zr
4+, Ti
4+or Sn
4+, and the content of active ingredient is 1~10% of fluorination catalyst quality.
Described active ingredient is Sn
4+.
Described temperature of reaction is 200 ℃~350 ℃.
Described temperature of reaction is 280 ℃~320 ℃.
Described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (3~20): 1.
Described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (5~15): 1.
Described reaction contact time is 3 seconds~30 seconds.
Described CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound is selected from CCl
3cCl
2cH
2cl, CFCl
2cCl
2cH
2cl, CF
2clCCl
2cH
2cl, CF
3cCl
2cH
2cl, CCl
3cHClCHCl
2, CFCl
2cHClCHCl
2, CF
2clCHClCHCl
2or CF
3cHClCHCl
2.
Described CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound is selected from CCl
3cCl
2cH
2cl or CCl
3cHClCHCl
2.
Compared with prior art, the present invention adopts under the existence of fluorination catalyst, hydrogen fluoride and formula CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound carries out gas phase catalytic fluorination reaction at 280 ℃~320 ℃, reaction raw materials can be selected in relative broad range, is easy to obtain, simultaneously can high conversion, highly selective prepares HCFO-1223xd, under more excellent condition, transformation efficiency can reach 100%, and selectivity can reach 99.0%.
Accompanying drawing explanation
Fig. 1 is the GC-MS collection of illustrative plates of target product HCFO-1223xd in embodiment 1.
Embodiment
Fluorination catalyst in the present invention is loaded catalyst, and carrier is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or the activated carbon fluoridized; Active ingredient is Mo
6+, V
5+, Zr
4+, Ti
4+or Sn
4+, and the content of active ingredient is approximately 1%~10% of fluorination catalyst quality, preferably Sn
4+.In addition, the carrier that is applicable to loaded catalyst of the present invention can be also the chromic oxide of fluoridizing, the aluminum oxide of fluoridizing, and active ingredient also can be Nb
5+, Ta
5+, Sb
5+, Ge
4+, Mn
4+, In
3+, Fe
3+, Ni
2+, Co
2+, Zn
2+, or their mixture.
Temperature of reaction of the present invention is the important factor that affects this gas phase fluorination catalyzed reaction, select suitable temperature can highly selective, the acquisition target product HCFO-1223xd of high conversion.Certainly fluorination reaction temperature also has close contacting with the composition of reaction raw materials and catalyzer, and temperature of reaction of the present invention can be selected in wider scope, is 180 ℃~450 ℃, and preferably 200 ℃~350 ℃, more preferably 280 ℃~320 ℃.When temperature exceeds the upper of this temperature range, prescribe a time limit, the selectivity of HCFO-1223xd is by disadvantageous minimizing, and the corrosion of reactor will be tending towards accelerating.When temperature, lower than the lower of this temperature range, prescribe a time limit, the conversion rate of compound will adversely reduce in fact.Especially when reaction is carried out higher than the temperature of 450 ℃, can produce carbide and adhere to or be deposited on reaction tube wall or filler, stop up gradually the inside of reactor.Can be by reaction being suspended and toward passing into oxygen in reactor or air removes the carbide residue in reaction tubes under this situation.
HF of the present invention selects substantially water-free hydrogen fluoride, and wherein sulphur content is less than 300ppm, preferably moisture content is lower than the HF of 0.05wt%, and more preferably moisture content is lower than the HF of 0.02wt%, can accelerator activator inactivation if sulphur content is higher, and this inactivation is difficult for regeneration.HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zthe mol ratio of compound is 1~50:1, preferred 3~20:1, and more preferably 5~15:1, excessive in reaction process, unreacted hydrogen fluoride can recycle in Returning reactor after conventional processing mode is processed.Reaction contact time of the present invention can be selected in wider scope, is generally 0.5 second~60 seconds, and preferably 3 seconds~30 seconds, more preferably 5 seconds~15 seconds.
Formula of CF of the present invention
3-xcl
xcH
2-ycl
ycH
3-zcl
zcorresponding compound, comprises CCl
3cCl
2cH
2cl, CFCl
2cCl
2cH
2cl, CF
2clCCl
2cH
2cl, CF
3cCl
2cH
2cl, CCl
3cHClCHCl
2, CFCl
2cHClCHCl
2, CF
2clCHClCHCl
2and CF
3cHClCHCl
2, preferred CCl
3cCl
2cH
2cl and CCl
3cHClCHCl
2.
In the present invention, reaction pressure is less on this fluoridation impact, to not restriction of the pressure in reaction process, as long as the beds that above-mentioned initial compounds and hydrogen fluoride can both enter reactor with gas phase just can, can select working pressure easily according to the material of conversion unit, anticorrosive and withstand voltage degree, under normal atmosphere and pressurized conditions, be all suitable, preferred 100~1000Kpa.
Reaction in the present invention can be carried out in any reactor that is suitable for gas phase fluorination.Preferably, described reactor is to be manufactured by the material of the corrosive nature of tolerance hydrogen fluoride and catalyzer, Hastelloy (Hastalloy) for example, inconel (Inconel), Monel metal (Monel) and in be lined with the container of fluoropolymer.Fluorination reactor type in the present invention neither be crucial, can use tubular reactor, fluidized-bed reactor etc.In addition, adiabatic reactor or isothermal reactor also can be used to the present invention.
In embodiment of the present invention, preferred process flow is to pass through beds downwards.Before each use, preferably catalyzer is dry, preheating and activation.After long-time use, in reactor, by catalyst regeneration, can be regularly also favourable on the spot.Pre-treatment can be undertaken by catalyzer being heated in nitrogen or other inert gas flows to approximately 200 ℃ to approximately 380 ℃.Then catalyzer can be processed and activate to obtain high catalyst activity with the hydrogen fluoride stream through a large amount of excessive nitrogen dilutions.The regeneration of catalyzer can be carried out under the following conditions: make air or with the air of nitrogen dilution at approximately 100 ℃ to approximately 380 ℃, preferably the temperature of approximately 150 ℃ to approximately 365 ℃ is by catalyzer, lasting approximately 8 hours to approximately 3 days, this depended on the size of reactor.
Below by specific embodiment, the present invention is described in further detail
Analytical instrument: extra large glad GC-930 type gas chromatograph, the 30m DB-5(50m * 0.32mm of Agilent company) capillary chromatographic column; ITQ700(ion trap): Thermofisher scientific, the GASPRO(60m * 0.25mm of Agilent company) capillary chromatographic column.
Chromatographic condition: 40 ℃ of initial column temperatures, keep 5min, with the temperature rise rate of 10 ℃/min, rise to 180 ℃, keep 3min; 220 ℃ of temperature of vaporization chamber, splitting ratio is 50.
Ion trap mass spectrometry condition: filament emission current 70A; Mass scanning scope 10-350amu; Full scan mode, 10 micro scanning/seconds of sweep velocity; Multiplier voltage 1556V; 220 ℃ of transmission line temperature, carrier gas is helium.
The preparation of fluorination catalyst: by a certain amount of SnCl
4be dissolved in the distilled water of hcl acidifying and be made into steeping fluid, then by AlF
3carrier is placed in steeping fluid, floods after 5 hours, and 60 ℃ of evaporating water on Rotary Evaporators, make the Sn of certain tin content
4+/ AlF
3fluorination catalyst.
Embodiment 1:
In the nickel pipe fixed-bed tube reactor that is 38mm at internal diameter, pack the 5%Sn that 60ml makes into
4+/ AlF
3catalyzer (active ingredient Sn
4+content be Sn
4+/ AlF
3catalyst quality 5%), and to catalyzer be dried, preheating and activation.To be activated complete, at 260 ℃, pass into HF and CCl
3cCl
2cH
2cl reacts under normal atmosphere (normal pressure), and the mol ratio of controlling both is 10:1, and be 8 seconds duration of contact, reaction product is removed after HCl and HF through washing, alkali cleaning, with gas-chromatography and mass spectroscopy reaction result, when generating HCFO-1223xd, also with a small amount of CF
3cFClCH
2cl, CF
3cCl=CHF by product occurs, in Table 1.
Target product HCFO-1223xd characterizes and identifies through GC-MS, as shown in Figure 1.
Fig. 1 mass spectrum result and peak ownership thereof are as follows: this material exists molecular ion peak, and m/z164:m/z166:m/z168=9:6:1 is the isotopic peak ratio containing two Cl; M/z145:m/z147:m/z149=9:6:1[(M-F)+]; M/z129:m/z131=3:1[(M-Cl)+], be the isotopic peak ratio containing a Cl, lose rationally; M/z85(+CClF
2) for due to fluorine migration, m/z69(+CF
3) and m/z95(CCl=CHCl+) be complementary ion, it is chloro-3,3 that compound name is called 1,2-bis-, and 3-trifluoropropyl is rare.
Embodiment 2~6:
Embodiment 2~6 prepares 1 according to preparation method identical in embodiment 1,2-bis-chloro-3,3,3-trifluoro propene, difference is that the temperature of reaction in embodiment 1 is 260 ℃, and temperature of reaction in embodiment 2~6 is followed successively by 280 ℃, 290 ℃, 300 ℃, 310 ℃, 330 ℃, the reaction result of embodiment 2~6 is as shown in table 1.
Table 1
Embodiment | Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) |
1 | 260 | 50.4 | 98.1 |
2 | 280 | 82.6 | 98.5 |
3 | 290 | 100 | 99.0 |
4 | 300 | 100 | 99.2 |
5 | 310 | 100 | 97.0 |
6 | 330 | 100 | 96.4 |
Embodiment 7~11:
It is chloro-3,3 that embodiment 7~11 prepares 1,2-bis-according to preparation method identical in embodiment 1,3-trifluoro propene, and difference is that the reaction raw materials in embodiment 1 is CCl
3cCl
2cH
2cl, temperature of reaction is 260 ℃, and reaction raw materials in embodiment 7~11 is followed successively by CFCl
2cCl
2cH
2cl, CF
2clCCl
2cH
2cl, CF
3cCl
2cH
2cl, CCl
3cHClCHCl
2, CF
2clCHClCHCl
2, when with CCl
3cHClCHCl
2during as reaction raw materials, HF and CCl
3cHClCHCl
2mol ratio be 15:1, temperature of reaction is 300 ℃.
The reaction result of embodiment 7~11 is as shown in table 2.
Table 2
Embodiment | Reaction raw materials | Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) |
7 | CFCl 2CCl 2CH 2Cl | 300 | 100 | 97.6 |
8 | CF 2ClCCl 2CH 2Cl | 300 | 93.2 | 98.2 |
9 | CF 3CCl 2CH 2Cl | 300 | 84.5 | 99.4 |
10 | CCl 3CHClCHCl 2 | 300 | 100 | 92.1 |
11 | CF 2ClCHClCHCl 2 | 300 | 96.3 | 94.5 |
Embodiment 12~15:
It is chloro-3,3 that embodiment 12~15 prepares 1,2-bis-according to preparation method identical in embodiment 1,3-trifluoro propene, and difference is HF and the CCl in embodiment 1
3cCl
2cH
2the mol ratio of Cl is 10:1, and temperature of reaction is 260 ℃, and both mol ratios in embodiment 12~15 are followed successively by 5:1,15:1,20:1,30:1, and temperature of reaction is 300 ℃.
The reaction result of embodiment 12~15 is as shown in table 3.
Table 3
Embodiment | Mol ratio | Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) |
12 | 5:1 | 300 | 100 | 98.5 |
13 | 15:1 | 300 | 100 | 98.9 |
14 | 20:1 | 300 | 100 | 97.2 |
15 | 30:1 | 300 | 100 | 97.3 |
Embodiment 16~19:
Embodiment 16~19 prepares 1 according to preparation method identical in embodiment 1,2-bis-chloro-3,3,3-trifluoro propene, difference is that be 8s the duration of contact in embodiment 1, temperature of reaction is 260 ℃, and duration of contact in embodiment 16~19 is followed successively by 5s, 10s, 15s, 30s, and temperature of reaction is 300 ℃.
The reaction result of embodiment 16~19 is as shown in table 4.
Table 4
Embodiment | Duration of contact (s) | Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) |
16 | 5 | 300 | 90.5 | 99.0 |
17 | 10 | 300 | 100 | 98.9 |
18 | 15 | 300 | 100 | 98.3 |
19 | 30 | 300 | 100 | 95.1 |
It is chloro-3,3 that embodiment 20~28 prepares 1,2-bis-according to preparation method identical in embodiment 1,3-trifluoro propene, and difference is the Sn that the catalyzer in embodiment 1 is 5%
4+/ AlF
3, temperature of reaction is 260 ℃, and catalyzer in embodiment 20~28 is followed successively by 5%Sn
4+/ MgF
2, 5%Sn
4+/ Al
2o
3, 5%Sn
4+/ Cr
2o
3, 2%Sn
4+/ AlF
3, 10%Sn
4+/ AlF
3, 5%Zr
4+/ AlF
3, 5%Ti
4+/ AlF
3, 5%V
5+/ AlF
3, 5%Mo
6+/ AlF
3, temperature of reaction is 300 ℃.
The reaction result of embodiment 20~28 is as shown in table 5.
Table 5
Embodiment | Catalyzer | Temperature of reaction (℃) | Transformation efficiency (%) | Selectivity (%) |
20 | 5%Sn 4+/MgF 2 | 300 | 100 | 95.3 |
21 | 5%Sn 4+/Al 2O 3 | 300 | 100 | 98.2 |
22 | 5%Sn 4+/Cr 2O 3 | 300 | 100 | 96.7 |
23 | 2%Sn 4+/AlF 3 | 300 | 97.5 | 98.9 |
24 | 10%Sn 4+/AlF 3 | 300 | 100 | 97.2 |
25 | 5%Zr 4+/AlF 3 | 300 | 100 | 95.4 |
26 | 5%Ti 4+/AlF 3 | 300 | 100 | 98.5 |
27 | 5%V 5+/AlF 3 | 300 | 100 | 96.2 |
28 | 5%Mo 6+/AlF 3 | 300 | 100 | 94.7 |
The above, be only part embodiment of the present invention, not the present invention done to any pro forma restriction, any simple modification that every foundation technical spirit of the present invention is done above-described embodiment, equivalent variations and modification, all belong within the scope of technical solution of the present invention.
Claims (10)
1. it is chloro-3,3 that a gas phase fluorination is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, under the existence of fluorination catalyst, general formula is CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound react with hydrogen fluoride generation gas phase catalytic fluorination that to generate 1,2-bis-chloro-3,3,3-trifluoro propene, x=0 in compound general formula wherein, 1,2,3; Y=1,2; Z=1,2; And y+z=3;
Reaction conditions is: 180 ℃~450 ℃ of temperature of reaction; Hydrogen fluoride and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio (1~30): 1; Reaction contact time 0.5 second~60 seconds.
2. gas phase fluorination according to claim 1 is prepared 1,2-bis-chloro-3,3, the method of 3-trifluoro propene, is characterized in that, fluorination catalyst is loaded catalyst, comprise carrier and active ingredient, wherein carrier is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or the activated carbon fluoridized; Active ingredient is Mo
6+, V
5+, Zr
4+, Ti
4+or Sn
4+, and the content of active ingredient is 1~10% of fluorination catalyst quality.
3. it is chloro-3,3 that gas phase fluorination according to claim 2 is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, described active ingredient is Sn
4+.
4. it is chloro-3,3 that gas phase fluorination according to claim 1 and 2 is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, described temperature of reaction is 200 ℃~350 ℃.
5. it is chloro-3,3 that gas phase fluorination according to claim 1 and 2 is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, described temperature of reaction is 280 ℃~320 ℃.
6. according to the gas phase fluorination described in claim 1,2,3 or 4, prepare 1,2-bis-chloro-3,3, the method for 3-trifluoro propene, is characterized in that, described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (3~20): 1.
7. according to the gas phase fluorination described in claim 1,2,3 or 4, prepare 1,2-bis-chloro-3,3, the method for 3-trifluoro propene, is characterized in that, described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (5~15): 1.
8. according to the gas phase fluorination described in claim 1,2,3 or 4, prepare 1,2-bis-chloro-3,3, the method for 3-trifluoro propene, is characterized in that, described reaction contact time is 3 seconds~30 seconds.
9. it is chloro-3,3 that gas phase fluorination according to claim 1 is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, general formula CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound is selected from CCl
3cCl
2cH
2cl, CFCl
2cCl
2cH
2cl, CF
2clCCl
2cH
2cl, CF
3cCl
2cH
2cl, CCl
3cHClCHCl
2, CFCl
2cHClCHCl
2, CF
2clCHClCHCl
2or CF
3cHClCHCl
2.
10. it is chloro-3,3 that gas phase fluorination according to claim 1 is prepared 1,2-bis-, and the method for 3-trifluoro propene, is characterized in that, general formula CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound is selected from CCl
3cCl
2cH
2cl or CCl
3cHClCHCl
2.
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CN105753637A (en) * | 2014-12-13 | 2016-07-13 | 西安近代化学研究所 | Preparation method of trans-1, 2-dichloro-3, 3, 3-trifluoropropene |
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CN107126965B (en) * | 2017-04-18 | 2020-07-10 | 北京宇极科技发展有限公司 | Tungsten-based catalyst |
CN107126948B (en) * | 2017-04-18 | 2020-07-10 | 北京宇极科技发展有限公司 | Molybdenum-based catalyst |
CN112194557A (en) * | 2020-06-09 | 2021-01-08 | 浙江省化工研究院有限公司 | Process for preparing 1, 1-dichloro-3, 3, 3-trifluoropropene and 1, 2-dichloro-3, 3, 3-trifluoropropene |
CN112194557B (en) * | 2020-06-09 | 2022-05-24 | 浙江省化工研究院有限公司 | Process for preparing 1, 1-dichloro-3, 3, 3-trifluoropropene and 1, 2-dichloro-3, 3, 3-trifluoropropene |
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