CN103508843B - A kind of gas phase fluorination prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis- - Google Patents
A kind of gas phase fluorination prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis- Download PDFInfo
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- CN103508843B CN103508843B CN201310462309.8A CN201310462309A CN103508843B CN 103508843 B CN103508843 B CN 103508843B CN 201310462309 A CN201310462309 A CN 201310462309A CN 103508843 B CN103508843 B CN 103508843B
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Abstract
The invention discloses a kind of method that gas phase fluorination prepares chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, specifically, it relates to general formula is CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound in the presence of a fluorination catalyst, react chloro-3,3, the 3-trifluoro propenes of generation 1,2-bis-with hydrogen fluoride generation gas phase catalytic fluorination, wherein x=0 in compound formula, 1,2,3; Y=1,2; Z=1,2; And y+z=3.The present invention is mainly for the preparation of chloro-3,3, the 3-trifluoro propenes of 1,2-bis-.
Description
Technical field
The present invention relates to the preparation method of chloro-3,3, the 3-trifluoro propenes (HCFO-1223xd) of a kind of 1,2-bis-, particularly relate 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) in the presence of a fluorination catalyst, carry out gas phase catalytic fluorination with hydrogen fluoride and react the method generating HCFO-1223xd.
Background technology
In recent years, generally believe that fully halogenated Chlorofluorocarbons (CFCs) (CFCs) has serious harm to earth's ozone layer, therefore, diversion to exploitation is contained safer equivalent material that is less or that replace without chlorine by hydrocarbon compoud containing fluorine industry, such as hydrogen chlorine fluoroolefin (HCFOs), hydrogen fluorohydrocarbon (HFCs), HF hydrocarbon (HFOs).
Chloro-3,3, the 3-trifluoro propenes (HCFO-1223xd) of 1,2-bis-can be used as the raw material and intermediate of preparing various fluorocarbon, 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 the fluorochemical monomer producing polymkeric substance, can be used as in addition introducing CF to functional fluoropolymer material
3the raw material of unit structure block and medicine intermediate use.
WO9745388 discloses a kind of fluorine chloropropane and fluorine antimony chloride reacts the method 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.
US2009043118 discloses a kind of 1,1,1-trifluoro propene (HFO-1243zf) 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, chloro-1,1, the 1-trifluoro propene (HCFO-1233xf) of 1-trifluoro propane (HCFC-243db), 2-, 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 generated changes in 0% ~ 20.2% scope, and selectivity is low.
A small amount of by product that HCFO-1223xd disclosed in above-mentioned patent generates in this area synthesis hydrogen fluorohydrocarbon, HF hydrocarbon occurs, the at present also open preparation method for HCFO-1223xd, therefore needs badly and sets 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 the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-.
In order to realize object of the present invention, the invention provides a kind of method that gas phase fluorination prepares chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it is characterized in that, in the presence of a fluorination catalyst, general formula is CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound and hydrogen fluoride generation gas phase catalytic fluorination react chloro-3,3, the 3-trifluoro propenes of generation 1,2-bis-, wherein x=0 in compound formula, 1,2,3; Y=1,2; Z=1,2; And y+z=3;
Reaction conditions is: temperature of reaction 180 DEG C ~ 450 DEG C; 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, wherein the carrier activated carbon that is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or fluoridizes; 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 DEG C ~ 350 DEG C.
Described temperature of reaction is 280 DEG C ~ 320 DEG C.
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 in the presence of a 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 DEG C ~ 320 DEG C, reaction raw materials can be selected in relative broad range, is easy to obtain, and simultaneously high conversion, highly selective can prepare 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, the activated carbon that carrier is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or fluoridizes; Active ingredient is Mo
6+, V
5+, Zr
4+, Ti
4+or Sn
4+, and the content of active ingredient is about 1% ~ 10%, preferred Sn of fluorination catalyst quality
4+.In addition, the carrier being applicable to loaded catalyst of the present invention also can be the chromic oxide fluoridized, the aluminum oxide fluoridized, 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 affecting this gas phase fluorination catalyzed reaction, select suitable temperature can highly selective, high conversion acquisition target product HCFO-1223xd.Certain 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 DEG C ~ 450 DEG C, preferably 200 DEG C ~ 350 DEG C, more preferably 280 DEG C ~ 320 DEG C.Prescribe a time limit when temperature exceeds the upper of this temperature range, the selectivity of HCFO-1223xd is by disadvantageous minimizing, and the corrosion of reactor will be tending towards accelerating.When temperature is prescribed a time limit lower than the lower of this temperature range, the conversion rate of compound will adversely reduce in fact.Especially when react carry out higher than the temperature of 450 DEG C time, carbide can be produced and adhere to or be deposited on reaction tube wall or filler, block the inside of reactor gradually.In this condition can by reaction be suspended and pass into oxygen or air in reactor and removes carbide residue in reaction tubes.
HF of the present invention selects substantially water-free hydrogen fluoride, and wherein sulphur content is less than 300ppm, preferred moisture content is lower than the HF of 0.05wt%, and more preferably moisture content is lower than the HF of 0.02wt%, if sulphur content is higher, can accelerator activator inactivation, and also this inactivation not easily regenerates.HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zthe mol ratio of compound is 1 ~ 50:1, preferably 3 ~ 20:1, more preferably 5 ~ 15:1, and excessive in reaction process, unreacted hydrogen fluoride can recycle in Returning reactor after the processing mode process of routine.Reaction contact time of the present invention can be selected in wider scope, is generally 0.5 second ~ 60 seconds, 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 the impact of this fluoridation, pressure in reaction process is not limited, as long as the beds that above-mentioned initial compounds and hydrogen fluoride can both enter reactor with gas phase just can, working pressure easily can be selected according to the material of conversion unit, anticorrosive and withstand voltage degree, all suitable under normal atmosphere and pressurized conditions, preferably 100 ~ 1000Kpa.
Reaction in the present invention can be carried out in the reactor of gas phase fluorination in any being suitable for.Preferably, described reactor is manufactured by the material of the corrosive nature tolerating hydrogen fluoride and catalyzer, such as Hastelloy (Hastalloy), inconel (Inconel), Monel metal (Monel) and the interior container being lined with 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 passes downwardly through beds.Before every use, preferably by catalyzer drying, preheating and activation.After a long time use, also can be regularly favourable on the spot by catalyst regeneration in reactor.Pre-treatment can be undertaken by being heated in nitrogen or other inert gas flows by catalyzer about 200 DEG C to about 380 DEG C.Then catalyzer can carry out activating to obtain high catalyst activity with the hydrogen fluoride stream process through nitrogen dilution excessive in a large number.The regeneration of catalyzer can be carried out under the following conditions: make air or with the air of nitrogen dilution at about 100 DEG C to about 380 DEG C, preferably the temperature of about 150 DEG C to about 365 DEG C is by catalyzer, and continue about 8 little of about 3 days, this depends 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, Agilent company 30m DB-5(50m × 0.32mm) capillary chromatographic column; ITQ700(ion trap): Thermofisher scientific, Agilent company GASPRO(60m × 0.25mm) capillary chromatographic column.
Chromatographic condition: initial column temperature 40 DEG C, keeps 5min, rises to 180 DEG C with the temperature rise rate of 10 DEG C/min, keeps 3min; Temperature of vaporization chamber 220 DEG C, splitting ratio is 50.
Ion trap mass spectrometry condition: filament emission current 70A; Mass scan range 10-350amu; Full scan mode, sweep velocity 10 micro scannings/second; Multiplier voltage 1556V; Transmission line temperature 220 DEG C, 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, on a rotary evaporator 60 DEG C of evaporating water, the Sn of obtained certain Theil indices
4+/ AlF
3fluorination catalyst.
Embodiment 1:
Be in the nickel pipe fixed-bed tube reactor of 38mm at internal diameter, load the 5%Sn that 60ml is obtained
4+/ AlF
3catalyzer (active ingredient Sn
4+content be Sn
4+/ AlF
35% of catalyst quality), and drying, preheating and activation are carried out to catalyzer.To be activated complete, at 260 DEG C, pass into HF and CCl
3cCl
2cH
2cl reacts under normal atmosphere (normal pressure), and the mol ratio of both control is 10:1, and duration of contact is 8 seconds, reaction product is after washing, alkali cleaning removing HCl and HF, with gas-chromatography and mass spectroscopy reaction result, while generation HCFO-1223xd, also with a small amount of CF
3cFClCH
2cl, CF
3cCl=CHF by product occurs, in table 1.
Target product HCFO-1223xd through GC-MS characterization, as shown in Figure 1.
Fig. 1 mass spectral results and peak thereof belong to as follows: this material exists molecular ion peak, m/z164:m/z166:m/z168=9:6:1, are 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)+] is the isotopic peak ratio containing a Cl, loses rationally; M/z85(+CClF
2) caused by fluorine migration, m/z69(+CF
3) and m/z95(CCl=CHCl+) be complementary ion, compound name is called that chloro-3,3, the 3-trifluoropropyl of 1,2-bis-are 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 the temperature of reaction in embodiment 1 is 260 DEG C, and the temperature of reaction in embodiment 2 ~ 6 is followed successively by 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 330 DEG C, the reaction result of embodiment 2 ~ 6 is as shown in table 1.
Table 1
| Embodiment | Temperature of reaction (DEG C) | 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:
Embodiment 7 ~ 11 prepares chloro-3,3, the 3-trifluoro propenes of 1,2-bis-according to preparation method identical in embodiment 1, and difference is the reaction raw materials in embodiment 1 is CCl
3cCl
2cH
2cl, temperature of reaction is 260 DEG C, and the 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 DEG C.
The reaction result of embodiment 7 ~ 11 is as shown in table 2.
Table 2
| Embodiment | Reaction raw materials | Temperature of reaction (DEG C) | 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:
Embodiment 12 ~ 15 prepares chloro-3,3, the 3-trifluoro propenes of 1,2-bis-according to preparation method identical in embodiment 1, 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 DEG C, 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 DEG C.
The reaction result of embodiment 12 ~ 15 is as shown in table 3.
Table 3
| Embodiment | Mol ratio | Temperature of reaction (DEG C) | 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 the duration of contact in embodiment 1 is 8s, temperature of reaction is 260 DEG C, and is followed successively by 5s, 10s, 15s, 30s the duration of contact in embodiment 16 ~ 19, and temperature of reaction is 300 DEG C.
The reaction result of embodiment 16 ~ 19 is as shown in table 4.
Table 4
| Embodiment | Duration of contact (s) | Temperature of reaction (DEG C) | 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 |
Embodiment 20 ~ 28:
Embodiment 20 ~ 28 prepares chloro-3,3, the 3-trifluoro propenes of 1,2-bis-according to preparation method identical in embodiment 1, and difference is the catalyzer in embodiment 1 is the Sn of 5%
4+/ AlF
3, temperature of reaction is 260 DEG C, and the 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 DEG C.
The reaction result of embodiment 20 ~ 28 is as shown in table 5.
Table 5
| Embodiment | Catalyzer | Temperature of reaction (DEG C) | 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 section Example of the present invention, not any pro forma restriction done to the present invention, every any simple amendment above-described embodiment done according to technical spirit of the present invention, equivalent variations and modification, all belong within the scope of technical solution of the present invention.
Claims (7)
1. a gas phase fluorination prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, and it is characterized in that, in the presence of a fluorination catalyst, general formula is CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zcompound and hydrogen fluoride generation gas phase catalytic fluorination react chloro-3,3, the 3-trifluoro propenes of generation 1,2-bis-, wherein x=0 in compound formula, 1,2,3; Y=1,2; Z=1,2; And y+z=3;
Reaction conditions is: temperature of reaction 280 DEG C ~ 330 DEG C; Hydrogen fluoride and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio (1 ~ 30): 1; Reaction contact time 3 seconds ~ 30 seconds;
Described fluorination catalyst is loaded catalyst, comprises carrier and active ingredient, wherein the carrier activated carbon that is chromic oxide, aluminum oxide, aluminum fluoride, magnesium fluoride or fluoridizes; 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.
2. gas phase fluorination according to claim 1 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it is characterized in that, described active ingredient is Sn
4+.
3. gas phase fluorination according to claim 1 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it is characterized in that, described temperature of reaction is 280 DEG C ~ 320 DEG C.
4. the gas phase fluorination according to claim 1,2 or 3 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it is characterized in that, described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (3 ~ 20): 1.
5. the gas phase fluorination according to claim 1,2 or 3 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it is characterized in that, described HF and CF
3-xcl
xcH
2-ycl
ycH
3-zcl
zmol ratio be (5 ~ 15): 1.
6. gas phase fluorination according to claim 1 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it 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.
7. gas phase fluorination according to claim 1 prepares the method for chloro-3,3, the 3-trifluoro propenes of 1,2-bis-, it 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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| CN105753637B (en) * | 2014-12-13 | 2017-12-22 | 西安近代化学研究所 | The preparation method of the trans trifluoro propene of 1,2 dichloro 3,3,3 |
| CN107213889B (en) * | 2017-04-18 | 2020-07-03 | 北京宇极科技发展有限公司 | Preparation of molybdenum-base and tungsten-base fluorine-chlorine exchange catalyst by blending method |
| CN107126948B (en) * | 2017-04-18 | 2020-07-10 | 北京宇极科技发展有限公司 | Molybdenum-based catalyst |
| CN107126965B (en) * | 2017-04-18 | 2020-07-10 | 北京宇极科技发展有限公司 | Tungsten-based catalyst |
| CN107126954B8 (en) * | 2017-04-18 | 2020-05-05 | 北京宇极科技发展有限公司 | Impregnation method for preparing molybdenum-based and tungsten-based fluorine-chlorine exchange catalyst |
| 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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