CN105753639A - Preparation method of 2,3,3,3-tetrafluoropropene - Google Patents
Preparation method of 2,3,3,3-tetrafluoropropene Download PDFInfo
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Abstract
The invention discloses a preparation method of 2,3,3,3-tetrafluoropropene; the preparation method includes the steps: a, in the presence of a composite catalyst, carrying out a gas phase fluorination reaction of a compound represented by the general formula of CF3-xClxCF2-yClyCH2Cl with hydrogen fluoride through two series-connection reactors to generate 1,2,3-trichloro-1,1,2-trifluoropropane, wherein in the compound general formula, x=1, 2 or 3, y=1 or 2, and 3<=(x+y)<=5; b, carrying out a dechloridation reaction of 1,2,3-trichloro-1,1,2-trifluoropropane to generate 3-chloro-2,3,3-trifluoropropylene; and c, in the presence of a fluorination catalyst, carrying out a gas phase fluorination reaction of 3-chloro-2,3,3-trifluoropropylene with hydrogen fluoride to generate 2,3,3,3-tetrafluoropropene. The preparation method is mainly used for preparation of 2,3,3,3-tetrafluoropropene.
Description
Technical field
The preparation method that the present invention relates to a kind of HF hydrocarbon, the preparation method particularly relating to a kind of 2,3,3,3-tetrafluoropropenes (HFO-1234yf).
Background technology
Compared with Chlorofluorocarbons (CFCs) (CFCs), HCFC (HCFCs), hydrogen fluorohydrocarbon (HFCs), HF hydrocarbon (HFOs) is not chloride, earth's ozone layer is not threatened, there is the latent value of low greenhouse effect simultaneously, become the emphasis of hydrofluorocarbons industrial research at present.2,3,3,3-tetrafluoropropene, i.e. HFO-1234yf, as the one (HFOs) of HF hydrocarbon, the latent value of ozone depletion is 0, greenhouse effect dive value be 4, can as cold-producing medium, extinguishing chemical, heat transfer medium, propellant, foaming agent, foaming agent, gas medium, biocide carrier, polymer monomer, remove granule fluid, carrier gas flow, grinding and polishing agent, replace desiccant and electricity periodic duty fluid, be widely used.
WO2009153493 discloses one with 1,1,1,2,2,3-HFC-236fa (HFC-236cb) for raw material, and the method preparing HFO-1234yf, first the method is at hydrogen and catalyst n i-Cr/AlF3Existence under, HFC-236cb dehydrofluorination generates 1,2,3,3,3-pentafluoropropene (HFO-1225ye), then HFO-1225ye hydrogenation obtains 1,1,1,2,3-pentafluoropropanes (HFC-245eb), finally obtain HFO-1234yf through dehydrofluorination more in the presence of hydrogen.
US20110190554 discloses one with 1,1,2,3,3,3-hexafluoropropene (HFP) for initiation material, the method that hydrogenated, dehydrofluorination, hydrogenation, dehydrofluorination four-step reaction synthesize HFO-1234yf.
In above two synthetic method, reaction raw materials not easily obtains, relatively costly, and need to pass into be at least stoichiometric hydrogen, hydrogenation step, in order to effectively control the exothermicity of reaction, often adopts higher mol ratio, in addition, passing into excessive hydrogen at a higher temperature and also can increase associated safety risk, condition is harsh, is unfavorable for industrialized production.
US2011207975 discloses the method that one is Material synthesis HFO-1234yf with 1,1,2,3-tetrachloropropylene (TCP) or 1,1,1,2,3-pentachloropropane (HCC-240db).The method is first at Cr2O3Under the existence of catalyst, the first reactor carries out HF gas phase fluorination TCP or HCC-240db, obtain 2-chloro-3,3,3 ,-trifluoropropene (HCFC-1233xf), then at SbCl5Under effect, in the second reactor, liquid-phase fluorination HCFC-1233xf obtains 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), finally carries out HCFC-244bb dehydrochlorination reaction in the 3rd reactor and obtains HFO-1234yf.
WO2012099776 discloses the method being prepared HFO-1234yf by TCP through HCFC-1233xf, HCFC-244bb with three steps integrated.
WO2009125199 discloses a kind of method being prepared HFO-1234yf through HCFC-1233xf, HCFC-244bb by 2,3-bis-chloro-1,1,1-trifluoro propane (HCFC-243db).
In above-mentioned preparation method, first, relate to Cr2O3, aluminium oxide or fluorided alumina load Cr2O3Deng chromium-based catalysts, in fact, the application of HFCs commercial production mostly also is chromium-based catalysts, and these compounds containing chromium, catalyst, digestive tract and the kidney of people can be caused damage, especially high valence chrome has strong carcinogenesis especially, with in use procedure, human and environment is unfriendly producing, and all can cause serious harm.Secondly, also intermediate HCFC-1233xf and HCFC-244bb has been all referred to, but both halogenated hydrocarbons boiling points are close, there is the characteristic of class azeotropic, and all easy and HF formation azeotropic mixture, there is the problem being difficult to separate, their mixture cannot realize efficiently separating by standard technology, conventional method, particularly when it forms a kind of binary azeotrope or Azeotrope-like composition.In addition have found that when carrying out HCFC-244bb dehydrochlorination and preparing HFO-1234yf, HCFO-1233xf, HF impurity wherein contained can have a strong impact on life-span and the selectivity of product of dehydrochlorination catalyst, be easily caused HFO-1234yf optionally reduce, the shortening of the reduction of catalyst activity and catalyst life.
Although the method preparing HFO-1234yf disclosed at present is more, but there is such as severe reaction conditions, catalyst is unfriendly to environment, reaction intermediate be difficult to separate and cause energy consumption, cost increase, target product selectivity is low waits deficiency, therefore, significantly more efficient preparation method is existed to Continual Improvement and demand.
Summary of the invention
It is an object of the invention to overcome the deficiency existed in background technology, it is provided that the preparation method of 2,3,3, the 3-tetrafluoropropenes (HFO-1234yf) that a kind of intermediate is easily isolated, catalyst is environmentally friendly, reaction condition is gentle.
The present invention is with formula CF3-xClxCF2-yClyCH2Cl compound is initiation material, generates 2,3,3,3-tetrafluoropropenes (HFO-1234yf) through gas phase fluorination, dechlorination, gas phase fluorination three-step reaction, and course of reaction is as follows:
In order to realize the purpose of the present invention, the preparation method of 2,3,3,3-tetrafluoropropenes provided by the invention, comprise the following steps:
A, formula are CF3-xClxCF2-yClyCH2The compound of Cl in the presence of a fluorination catalyst, through two tandem reactors, carries out gas phase fluorination with fluohydric acid gas and generates 1,2,3-tri-chloro-1,1,2-trifluoro propane, wherein in compound formula x=1,2,3；Y=1,2, and 3≤x+y≤5；In two tandem reactors, the reaction condition of the first reactor is: reaction temperature 220 DEG C～260 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2Mol ratio 5～the 20:1 of Cl, reaction contact time 0.5～20 second；In two tandem reactors, the reaction condition of the second reactor is: reaction temperature 280 DEG C～320 DEG C, the mol ratio 10～20:1 of fluohydric acid gas and the first reactor organic product, reaction contact time 5～30 seconds；
B, 1,2,3-tri-chloro-1,1,2-trifluoro propane, under the existence of dechlorination catalyst Cu-V-Mg-F, carry out gas phase dechlorination reaction with hydrogen and generate chloro-2,3, the 3-trifluoro propenes of 3-；Gas phase dechlorination reaction condition is: reaction temperature 200 DEG C～300 DEG C, the mol ratio 0～1:1 of hydrogen and 1,2,3-tri-chloro-1,1,2-trifluoro propane, 1～30 second time of contact；
The chloro-2,3,3-trifluoro propene of c, 3-is at FeF3/MgF2Under the existence of catalyst, carry out gas phase fluorination with fluohydric acid gas and generate 2,3,3,3-tetrafluoropropenes；Gas phase fluorination condition is: reaction temperature 160 DEG C～240 DEG C, the mol ratio 10～20:1 of fluohydric acid gas and chloro-2,3, the 3-trifluoro propenes of 3-, 0.1～10 second time of contact.
Formula CF described in step a3-xClxCF2-yClyCH2Cl compound is selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl、CF2ClCCl2CH2Cl、CCl3CFClCH2Cl or CFCl2CFClCH2Cl。
Formula CF described in step a3-xClxCF2-yClyCH2Cl compound is CCl3CCl2CH2Cl。
Fluorination catalyst described in step a is Zn-A-B-C composite catalyst, wherein, A is the VIIIth race's element, one or more combinations in Ni, Fe, Co, B is High field side injection, one or more combinations in Zr, Y, La, C is alkali earth metal, the one in Mg, Ca, Ba；The mol ratio of Zn, A, B, C is (0.3～2): (0.6～5): (0.1～1): (2～9), it is preferable that (0.5～1): (1～4): (0.5～1): (4～8).
Zn-A-B-C composite catalyst described in step a is Zn-Fe-La-Mg composite catalyst, and wherein the mol ratio of Zn, Fe, La, Mg is 0.5:2:0.5:7；The preparation method of this catalyst includes: reacted with precipitant by the mixed solution of a certain proportion of tri-kinds of metal soluble-salts of Zn, Fe, La, pH controls at 7.5-9.5, stir, precipitate, filter and dry, again by mixed to the oxide of a certain amount of magnesium, hydroxide or carbonate uniformly, again at 200 DEG C-500 DEG C, no less than three thermogrades when, carry out baking inphases, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C.
Tandem reactor described in step a is two tandem reactors being incremented by according to the reaction temperature equipped with same catalyst of material flow direction series arrangement, and it is 60 DEG C～80 DEG C that reaction temperature is incremented by amplitude.
In dechlorination catalyst Cu-V-Mg-F described in step b, the mol ratio of Cu, V, Mg three is 4:1:5.The preparation method being suitable for this catalyst has the method for preparing catalyst such as infusion process, coprecipitation, blending method, sol-gel process.Certainly this dechlorination reaction can also be in protonic solvent, the liquid phase dechlorination reaction of HCFC-233bc and reducing agent effect.
FeF described in step c3/MgF2In catalyst, the mol ratio of both Fe, Mg is 1:9,2:8,7:3 or 4:6.
Two tandem reactors in step a of the present invention are the tandem reactors being incremented by successively according to two reaction temperatures equipped with same catalyst of material flow direction series arrangement；Can according to need to arranging static mixer, heat exchanger to improve reaction effect between tandem reactor；The gas phase entrance of static mixer makes up line with fluohydric acid gas and connects, and liquid phase entrance connects with adjacent upper stage reactor liquid phase material outlet line, exports and the reactor inlet connection of adjacent subordinate；The product of each reactor optionally enters later separation workshop section and/or enters at least one in remaining reaction device；The conversion ratio of each reactor, products distribution control mainly through reaction temperature, the time of staying, material proportion, and the primary product stream of the first reactor is CFCl2CCl2CH2Cl(HCFC-231bc)、CF2ClCCl2CH2Cl (HCFC-232ac), HF, HCl, the primary product of the second reactor is CF2ClCFClCH2Cl (HCFC-233bc), when after the catalysqt deactivation in a reactor in tandem reactor, this reactor can be isolated from this device and carry out catalyst regeneration operation.
Reaction in step a of the present invention can carry out in any reactor being suitable for gas phase fluorination.The fluorination reactor type of step a neither be crucial, it is possible to use tubular reactor, fluidized-bed reactor etc..It addition, adiabatic reactor or isothermal reactor also can be used.
In step b of the present invention, in gas phase dechlorination reaction, the mol ratio of hydrogen and HCFC-233bc is the key factor affecting this reaction, when passing into excessive hydrogen, although reaction can realize converting completely, but the selectivity of target product substantially reduces, the mol ratio that hydrogen is suitable for HCFC-233bc is (0～1): 1, preferably (0.1～0.5): 1, more preferably (0.1～0.3): 1, the mode that passes into of hydrogen can be can also be off and on, semi-continuously continuously.
The pretreatment of the dechlorination catalyst in step b of the present invention can be undertaken by being heated in nitrogen or other inert gas flows by catalyst about 200 DEG C to about 380 DEG C.Then catalyst can process with the fluohydric acid gas stream through nitrogen dilution excessive in a large number and carry out activating to obtain high catalyst activity.The regeneration of catalyst can carry out under the following conditions, makes air or with the air of nitrogen dilution at about 100 DEG C to about 380 DEG C, it is preferable that the temperature of about 150 DEG C to about 365 DEG C passes through catalyst, continues about 8 hours to about 3 days, and this depends on the size of reactor.
Advantages of the present invention: compared with prior art, an advantage of the invention is that it provides a kind of effective method preparing HFO-1234yf, there is intermediate simultaneously and be easily isolated, in intermediate 1,2, chloro-1,1, the 2-trifluoro propane of 3-tri-and 3-chloro-2,3,3-trifluoro propene boiling point differs greatly, about 40 DEG C, it is easy to separate；Catalysts is not related to containing chromium compound, and human and environment is friendly；The feature that reaction condition is gentle, gas-phase reaction temperature is also less than 340 DEG C；Compared with documents patent WO2009153493 and US20110190554, dechlorination reaction of the present invention realizes under a small amount of hydrogen existent condition, it is not necessary to stoichiometric hydrogen.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail
Analytical tool: extra large glad GC-930 type gas chromatograph, Agilent company 30mDB-5 (50m × 0.32mm) capillary chromatographic column；ITQ700 (ion trap): Thermofisherscientific, 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 heating rate of 10 DEG C/min, keeps 3min；Temperature of vaporization chamber 220 DEG C, split ratio is 50.
Ion trap mass spectrometry condition: filament emission current 70A；Mass scan range 10-350amu；Full scan mode, scanning speed 10 micro scannings/second；Multiplier voltage 1556V；Transmission line temperature 220 DEG C, carrier gas is helium.
Embodiment 1:
The preparation of catalyst: by a certain proportion of Zn (NO3)2·6H2O、FeCl3、La(NO3)3·6H2O is mixed into 2mol/L aqueous solution, then at 20 DEG C-40 DEG C, dripping mass fraction when being stirred continuously is the ammonia of 15%, regulating pH is about 8.0, reacts 8h, filters, dry 2h at 120 DEG C again, then by mixed for a certain amount of magnesium oxide uniformly, then at 200 DEG C roasting 1h, 5 DEG C/min rises to 320 DEG C, roasting 2h, then 10 DEG C/min rises to 450 DEG C, roasting 4h, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C, about need 36h.
In the fixed-bed tube reactor that internal diameter is 38mm, load the above-mentioned Zn-Fe-La-Mg composite catalyst of 50ml, wherein the mol ratio of Zn, Fe, La, Mg is 0.5:2:0.5:7, and catalyst is dried, then at 250 DEG C, by HF and CCl3CCl2CH2Cl (HCC-230ab, it is abbreviated as 230ab) pass into the first reactor R1, controlling both mol ratios is 10:1, and time of contact is 15s, first product stream enters the second reactor reaction R2, second temperature of reactor is 300 DEG C, and HF and organic mol ratio are 15:1, and time of contact is 20 seconds, each reaction is all reacting under atmospheric pressure (normal pressure), product is after washing, alkali cleaning remove HCl and HF, and with gas chromatogram and mass spectral analysis, the first product stream is mainly CF2ClCHClCHCl2(HCFC-231ab is abbreviated as 232da), CF2ClCCl2CH2Cl (HCFC-232ac is abbreviated as 232ac), the second product stream is mainly CF2ClCFClCH2Cl (HCFC-233bc is abbreviated as 233bc), reaction result is in Table 1.
Embodiment 2～4:
Embodiment 2～4 prepares HCFC-233bc according to method identical in embodiment 1, the difference is that the reaction temperature of R1, R2 respectively 250 DEG C, 300 DEG C in embodiment 1, and in embodiment 2～4, the reaction temperature of R1, R2, reaction result are as shown in table 1.
Table 1
Embodiment 5～7:
Embodiment 5～7 prepares HCFC-233bc according to method identical in embodiment 1, be followed successively by 10:1 the difference is that the HF in R1, R2 in embodiment 1 and organic materials proportioning (mol ratio), 15:1, time of contact respectively 15s, 20s in R1, R2, and in embodiment 5～7, HF and organic materials proportioning, time of contact, reaction result is as shown in table 2, and wherein the conversion ratio of 230ab is 100%.
Table 2
Embodiment 8～11:
Embodiment 8～11 prepares HCFC-233bc according to method identical in embodiment 1, institute the difference is that in embodiment 1 catalyst Z n, Fe, La, Mg mol ratio be 0.5；2:0.5:7, and in embodiment 8～11, four mol ratios respectively 0.3:4:0.7:5,0.6:1:0.4:8,1:2:1:6,2；5:0.5:2.5, reaction result is as shown in table 3.
Table 3
Embodiment 12～16:
Embodiment 12～16 prepares HCFC-2233bc according to method identical in embodiment 1, the difference is that the catalyst in embodiment 1 be Zn-Fe-La-Mg composite catalyst, and the catalyst in embodiment 12～16 Zn-Ni-La-Mg, Zn-Fe-Zr-Mg, Zn-Ni-La-Ca, Zn-Co-Zr-Ca, Zn-Co-Y-Ba successively, reaction result is in Table 4.
Table 4
Embodiment 17:
The preparation of catalyst: by a certain percentage, by V2O5It is added to Mg (NO3)2·6H2O and Cu (NO3)2·3H2In the mixed aqueous solution of O, add the ammonium hydrogencarbonate that mass fraction is 10%, regulate pH and control to be about 9, about 5h, scrubbed rear centrifugation, again at 120 DEG C dry, then at 200 DEG C roasting 1h, 5 DEG C/min rises to 300 DEG C, roasting 2h, then 5 DEG C/min rises to 450 DEG C, roasting 4h, finally pass sequentially through again fluohydric acid gas, Hydrogen activation process obtain.
In the fixed-bed tube reactor that internal diameter is 38mm, loading 50ml containing above-mentioned Cu-V-Mg-F catalyst, wherein the mol ratio of Cu, V, Mg three is 4:1:5, passes into H at 280 DEG C2, after two hours, passing into HCFC-233bc and react under atmospheric pressure (normal pressure), the mol ratio controlling both is 0.3:1, and time of contact is 30 seconds, and with gas chromatogram, mass spectral analysis reaction result, result is in Table 5.
Embodiment 18～21:
Embodiment 18～21 prepares HCFO-1233yf according to the method that embodiment 17 is identical, the difference is that the reaction temperature in embodiment 17 be 280 DEG C, and in embodiment 18～21, reaction temperature is followed successively by 200 DEG C, 240 DEG C, 320 DEG C, and reaction result is as shown in table 5.
Table 5
Embodiment 22～24:
Embodiment 22～24 prepares HCFO-1233yf according to method identical in embodiment 17, institute is the difference is that in embodiment 17 catalyst, the mol ratio of Cu, V, Mg three is 4:1:5, and in embodiment 22～24 in catalyst, three mole is followed successively by 2:1:7,3:1:6,3:2:5, reaction result is as shown in table 6.
Table 6
Embodiment 25～27:
Embodiment 25～27 prepares HCFO-1233yf according to method identical in embodiment 17, institute is the difference is that in embodiment 17, and the mol ratio of hydrogen and HCFC-234bb is 0.3:1, and in embodiment 25～27, both are followed successively by 0.1:1,0.5:1,1:1 at mol ratio, and reaction result is as shown in table 7.
Table 7
Embodiment 28～30:
Embodiment 28～30 prepares HCFO-1233yf according to method identical in embodiment 17, institute the difference is that in embodiment 17 time of contact be 20s, and in embodiment 28～30, time of contact respectively 5s, 10s, 30s, result is in Table 8.
Table 8
Embodiment 31:
The preparation of catalyst: by a certain percentage, accurately weighs a certain amount of Fe (NO3)2·9H2O and Mg (NO3)2·6H2O, is dissolved in dehydrated alcohol, then under constantly stirring, is dropped to by the alcoholic solution of above-mentioned mixing in the HF solution of 40%, about 1h, precipitates, filters, washs and dry, rises to 350 DEG C of roasting 1～4h with the heating rate of 10 DEG C/min in Muffle furnace.
In the fixed-bed tube reactor that internal diameter is 38mm, load the above-mentioned FeF of 50ml3/MgF2Catalyst, wherein, the wherein mol ratio 2:8 of Fe, Mg, catalyst is dried, then at 150 DEG C, passes into HF and 3-chloro-2,3,3-trifluoro propylene, reacts under atmospheric pressure (normal pressure), and both mol ratios are 15:1, time of contact is 10 seconds, product is after washing, alkali cleaning remove HCl and HF, and through mass spectrum, gas chromatographic analysis, reaction result is in Table 9.
Embodiment 32～34:
Embodiment 32～34 prepares HFO-1234yf according to method identical in embodiment 31, the difference is that the reaction temperature in embodiment 31 be 200 DEG C, and the reaction temperature in embodiment 32～34 is followed successively by 160 DEG C, 180 DEG C, 240 DEG C, and reaction result is as shown in table 9.
Table 9
Embodiment 35～37:
Embodiment 35～37 prepares HFO-1234yf according to method identical in embodiment 31, the difference is that in the catalyst in embodiment 31, the mol ratio of both Fe, Mg is 2:8, and in the catalyst in embodiment 35～37 both mole be followed successively by 1:9,3:7,4:6, reaction result is in Table 10.
Table 10
Embodiment 38～39:
Embodiment 38～39 prepares HFO-1234yf according to preparation method identical in embodiment 31, the difference is that the mol ratio of HF and the HCFO-1233yf in embodiment 31 be 15:1, and both mol ratios in embodiment 38,39 are followed successively by 10:1,20:1, result is as shown in table 11.
Table 11
Embodiment 40～42:
Embodiment 40～42 prepares HFO-1234yf according to preparation method identical in embodiment 31, the difference is that the time of contact in embodiment 31 be 10s, and be followed successively by 3s, 5s, 20s the time of contact in embodiment 40～42, reaction result is as shown in table 12.
Table 12
Claims (8)
1. the preparation method of a tetrafluoropropene, it is characterised in that comprise the following steps:
A, formula are CF3-xClxCF2-yClyCH2The compound of Cl in the presence of a fluorination catalyst, through two tandem reactors, carries out gas phase fluorination with fluohydric acid gas and generates 1,2,3-tri-chloro-1,1,2-trifluoro propane, wherein in compound formula x=1,2,3；Y=1,2, and 3≤x+y≤5；In two tandem reactors, the reaction condition of the first reactor is: reaction temperature 220 DEG C～260 DEG C, fluohydric acid gas and CF3-xClxCF2-yClyCH2Mol ratio 5～the 20:1 of Cl, reaction contact time 0.5～20 second；In two tandem reactors, the reaction condition of the second reactor is: reaction temperature 280 DEG C～320 DEG C, the mol ratio 10～20:1 of fluohydric acid gas and the first reactor organic product, reaction contact time 5～30 seconds；
B, 1,2,3-tri-chloro-1,1,2-trifluoro propane, under the existence of dechlorination catalyst Cu-V-Mg-F, carry out gas phase dechlorination reaction with hydrogen and generate chloro-2,3, the 3-trifluoro propenes of 3-；Gas phase dechlorination reaction condition is: reaction temperature 200 DEG C～300 DEG C, the mol ratio 0～1:1 of hydrogen and 1,2,3-tri-chloro-1,1,2-trifluoro propane, 1～30 second time of contact；
The chloro-2,3,3-trifluoro propene of c, 3-is at FeF3/MgF2Under the existence of catalyst, carry out gas phase fluorination with fluohydric acid gas and generate 2,3,3,3-tetrafluoropropenes；Gas phase fluorination condition is: reaction temperature 160 DEG C～240 DEG C, the mol ratio 10～20:1 of fluohydric acid gas and chloro-2,3, the 3-trifluoro propenes of 3-, 0.1～10 second time of contact.
2. the preparation method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that the formula CF described in step a3-xClxCF2-yClyCH2Cl compound is selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl、CF2ClCCl2CH2Cl、CCl3CFClCH2Cl or CFCl2CFClCH2Cl。
3. the preparation method of 2,3,3,3-tetrafluoropropenes according to claim 2, it is characterised in that the formula CF described in step a3-xClxCF2-yClyCH2Cl compound is CCl3CCl2CH2Cl。
4. according to claim 12,3,3, the preparation method of 3-tetrafluoropropene, it is characterized in that, the fluorination catalyst described in step a is Zn-A-B-C composite catalyst, wherein, A is group VIII element, one or more combinations in Ni, Fe, Co, B is High field side injection, one or more combinations in Zr, Y, La, C is alkali earth metal, the one in Mg, Ca, Ba；The mol ratio of Zn, A, B, C is (0.3～2): (0.6～5): (0.1～1): (2～9).
5. the preparation method of 2,3,3,3-tetrafluoropropenes according to claim 4, it is characterised in that the Zn-A-B-C composite catalyst described in step a is Zn-Fe-La-Mg composite catalyst, wherein the mol ratio of Zn, Fe, La, Mg is 0.5:2:0.5:7；The preparation method of this catalyst includes: reacted with precipitant by the mixed solution of a certain proportion of tri-kinds of metal soluble-salts of Zn, Fe, La, pH controls at 7.5-9.5, stir, precipitate, filter and dry, again by mixed to the oxide of a certain amount of magnesium, hydroxide or carbonate uniformly, again at 200 DEG C-500 DEG C, no less than three thermogrades when, carry out baking inphases, finally obtain then through fluohydric acid gas activation processing at 200 DEG C-380 DEG C.
6. according to claim 12,3,3, the preparation method of 3-tetrafluoropropene, it is characterized in that, tandem reactor described in step a is two tandem reactors being incremented by according to the reaction temperature equipped with same catalyst of material flow direction series arrangement, and it is 60 DEG C～80 DEG C that reaction temperature is incremented by amplitude.
7. the preparation method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that in dechlorination catalyst Cu-V-Mg-F described in step b, the mol ratio of Cu, V, Mg three is 4:1:5.
8. the preparation method of 2,3,3,3-tetrafluoropropenes according to claim 1, it is characterised in that FeF described in step c3/MgF2In catalyst, the mol ratio of both Fe, Mg is 1:9,2:8,7:3 or 4:6.
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| CN107721809A (en) * | 2017-10-19 | 2018-02-23 | 浙江衢化氟化学有限公司 | A kind of co-production of 2,3,3,3 tetrafluoropropene and trans 1,3,3,3 tetrafluoropropene |
| CN111558386A (en) * | 2020-04-10 | 2020-08-21 | 西安近代化学研究所 | Iron fluoride-based catalyst for synthesizing hydrofluoroolefin by gas phase fluorination and preparation method and application thereof |
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| CN111558386B (en) * | 2020-04-10 | 2023-05-12 | 西安近代化学研究所 | Ferric fluoride-based catalyst for synthesizing hydro-fluoroolefin by gas phase fluorination, preparation method and application thereof |
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