CN105753639B - A kind of preparation method of 2,3,3,3- tetrafluoropropenes - Google Patents
A kind of preparation method of 2,3,3,3- tetrafluoropropenes Download PDFInfo
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- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical class FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000460 chlorine Substances 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006298 dechlorination reaction Methods 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- USCSECLOSDIOTA-UHFFFAOYSA-N 1-chloro-2,3,3-trifluoroprop-1-ene Chemical class FC(F)C(F)=CCl USCSECLOSDIOTA-UHFFFAOYSA-N 0.000 claims description 5
- 229910019077 Mg—F Inorganic materials 0.000 claims description 5
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 238000001994 activation Methods 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- VTCJDIFVBGRFCD-UHFFFAOYSA-N 1,2,3-trichloro-1,1,3-trifluoropropane Chemical compound FC(Cl)C(Cl)C(F)(F)Cl VTCJDIFVBGRFCD-UHFFFAOYSA-N 0.000 claims 1
- VTOPKRLXDFCFGJ-UHFFFAOYSA-N 3-chloro-2,3,3-trifluoroprop-1-ene Chemical class FC(=C)C(F)(F)Cl VTOPKRLXDFCFGJ-UHFFFAOYSA-N 0.000 claims 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims 1
- 229910021472 group 8 element Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 230000011218 segmentation Effects 0.000 claims 1
- JMRIJKGIVGYIAD-UHFFFAOYSA-N 2,3,3-trifluoroprop-1-ene Chemical compound FC(F)C(F)=C JMRIJKGIVGYIAD-UHFFFAOYSA-N 0.000 abstract description 3
- HHRQYHKSSIGXJV-UHFFFAOYSA-N 1,1,2-trifluoropropane Chemical compound CC(F)C(F)F HHRQYHKSSIGXJV-UHFFFAOYSA-N 0.000 abstract 2
- 238000000034 method Methods 0.000 description 24
- 239000012071 phase Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical class CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- SUAMPXQALWYDBK-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluoropropane Chemical compound FCC(F)(F)C(F)(F)F SUAMPXQALWYDBK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 description 3
- 238000005796 dehydrofluorination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZDCWZRQSHBQRGN-UHFFFAOYSA-N 1,1,1,2,3-pentafluoropropane Chemical compound FCC(F)C(F)(F)F ZDCWZRQSHBQRGN-UHFFFAOYSA-N 0.000 description 2
- HFHVCPIWDWKEOX-UHFFFAOYSA-N 1,2,2,3-tetrachloro-1,1-difluoropropane Chemical compound FC(F)(Cl)C(Cl)(Cl)CCl HFHVCPIWDWKEOX-UHFFFAOYSA-N 0.000 description 2
- BAROULROTHNRTG-UHFFFAOYSA-N 1,2,3-trichloro-1,1,2-trifluoropropane Chemical compound FC(F)(Cl)C(F)(Cl)CCl BAROULROTHNRTG-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZXPCCXXSNUIVNK-UHFFFAOYSA-N 1,1,1,2,3-pentachloropropane Chemical class ClCC(Cl)C(Cl)(Cl)Cl ZXPCCXXSNUIVNK-UHFFFAOYSA-N 0.000 description 1
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical class ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 description 1
- DMUPYMORYHFFCT-UHFFFAOYSA-N 1,2,3,3,3-pentafluoroprop-1-ene Chemical class FC=C(F)C(F)(F)F DMUPYMORYHFFCT-UHFFFAOYSA-N 0.000 description 1
- LOCOMRPWMOCMPV-UHFFFAOYSA-N 2,3-dichloro-1,1,1,2-tetrafluoropropane Chemical compound FC(F)(F)C(F)(Cl)CCl LOCOMRPWMOCMPV-UHFFFAOYSA-N 0.000 description 1
- QJMGASHUZRHZBT-UHFFFAOYSA-N 2,3-dichloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Cl)CCl QJMGASHUZRHZBT-UHFFFAOYSA-N 0.000 description 1
- OQISUJXQFPPARX-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Cl)=C OQISUJXQFPPARX-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- -1 hydrogen fluoride 2,3,3,3- tetrafluoropropenes Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005040 ion trap Methods 0.000 description 1
- 238000000534 ion trap mass spectrometry Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of 2,3,3,3 tetrafluoropropenes, including：A, general formula is CF3‑xClxCF2‑yClyCH2The compound of Cl is in the presence of composite catalyst, through two tandem reactors, carries out gas phase fluorination with hydrogen fluoride and generates 1,2,3 trichlorine, 1,1,2 trifluoro propane, wherein x=1 in compound formula, and 2,3；Y=1,2, and 3≤x+y≤5；B, the dechlorinated reaction of 1,2,3 trichlorine, 1,1,2 trifluoro propane generates 3 chlorine, 2,3,3 trifluoro propene；C, 3 chlorine, 2,3,3 trifluoro propene in the presence of a fluorination catalyst, carries out gas phase fluorination with hydrogen fluoride and generates 2,3,3,3 tetrafluoropropenes.Present invention is mainly used for prepare 2,3,3,3 tetrafluoropropenes.
Description
Technical field
The present invention relates to a kind of preparation methods of HF hydrocarbon, more particularly to 2,3,3,3- tetrafluoropropene (HFO- of one kind
Preparation method 1234yf).
Background technology
Compared with chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbon (HFCs), HF hydrocarbon (HFOs) is free of chlorine,
It does not threaten to earth's ozone layer, while there are low greenhouse effects to dive value, have become the weight of hydrofluorocarbons industrial research at present
Point.2,3,3,3- tetrafluoropropenes, i.e. HFO-1234yf, as one kind (HFOs) of HF hydrocarbon, the latent value of ozone depletion is 0, temperature
Effect latent value in room is 4, can be used as refrigerant, extinguishing chemical, heat transfer medium, propellant, foaming agent, foaming agent, gas medium, sterilizing
Agent carrier, polymer monomer remove granule fluid, carrier gas flow, grinding with polishing agent, replace drier and electric cycle operation stream
Body is widely used.
WO2009153493 discloses one kind with 1,1,1,2,2,3- hexafluoropropane (HFC-236cb) as raw material, prepares
The method of HFO-1234yf, this method are in hydrogen and catalyst n i-Cr/AlF first3In the presence of, HFC-236cb defluorinates
Hydrogen generates 1,2,3,3,3- pentafluoropropenes (HFO-1225ye), and then HFO-1225ye adds hydrogen to obtain 1,1,1,2,3- pentafluoropropane
(HFC-245eb), finally HFO-1234yf is obtained through dehydrofluorination in the presence of hydrogen again.
US20110190554 disclose it is a kind of with 1,1,2,3,3,3- hexafluoropropene (HFP) for starting material, it is hydrogenated,
The method of dehydrofluorination plus hydrogen, dehydrofluorination four-step reaction synthesis HFO-1234yf.
In above two synthetic method, reaction raw materials are not easy to obtain, and cost is higher, and need to be passed through at least chemistry meter
The hydrogen of amount, hydrogenation step often use higher molar ratio, in addition, higher to effectively control the exothermicity of reaction
At a temperature of be passed through excessive hydrogen and can also increase associated safety risk, condition is harsh, is unfavorable for industrialized production.
US2011207975 discloses one kind with 1,1,2,3- tetrachloropropylenes (TCP) or 1,1,1,2,3- pentachloropropanes
(HCC-240db) method for being Material synthesis HFO-1234yf.This method is first in Cr2O3It is anti-first in the presence of catalyst
Progress HF gas phase fluorination TCP or HCC-240db in device is answered, obtains 2- chloro-3,3,3 ,-trifluoropropenes (HCFC-1233xf), so
Afterwards in SbCl5Under effect, liquid-phase fluorination HCFC-1233xf obtains 2- chloro-1,1,1,2-tetrafluoropropanes in the second reactor
(HCFC-244bb), HCFC-244bb dehydrochlorination reactions are finally carried out in third reactor obtain HFO-1234yf.
WO2012099776 is disclosed to be prepared by TCP through HCFC-1233xf, HCFC-244bb with three steps of integration
The method of HFO-1234yf.
WO2009125199 discloses one kind by bis- chloro- 1,1,1- trifluoros propane (HCFC-243db) of 2,3- through HCFC-
The method that 1233xf, HCFC-244bb prepare HFO-1234yf.
In the above preparation method, first, Cr is related to2O3, aluminium oxide or fluorided alumina load Cr2O3Equal chromium base
Catalyst, in fact, be also mostly chromium-based catalysts in the application of HFCs industrial productions, and these compounds containing chromium, catalyst, meeting
The alimentary canal and kidney of people are damaged, especially high valence chrome is even more to have strong carcinogenesis, right in the production and use process
Human and environment is unfriendly, can all cause to seriously endanger.Secondly, intermediate HCFC-1233xf and HCFC- have also been all referred to
244bb, but both halogenated hydrocarbons boiling points are close, have azeotrope-like characteristic, and easily form azeotropic mixture with HF, there are difficulties
The problem of to detach, their mixture cannot achieve by standard technology, conventional method and efficiently separate, especially when it
When forming a kind of binary azeotrope or Azeotrope-like ingredient.In addition it has found that and is carrying out HCFC-244bb dehydrochlorination preparations
When HFO-1234yf, wherein HCFO-1233xf, HF impurity contained can seriously affect service life and the production of dehydrochlorination catalyst
Object selectivity, easily leads to the reduction of HFO-1234yf selectivity, the reduction of catalyst activity and the shortening of catalyst life.
Although the presently disclosed method for preparing HFO-1234yf is more, there is such as severe reaction conditions, urge
Agent is unfriendly to environment, reaction intermediate be difficult to separation and caused by energy consumption, cost increase, target product selectivity it is low it is equal not
Foot, therefore, for significantly more efficient preparation method, there are sustained improvements and demand.
Invention content
It is insufficient it is an object of the invention to overcome present in background technology, a kind of intermediate is provided and is easily isolated, is catalyzed
The preparation method for the 2,3,3,3- tetrafluoropropenes (HFO-1234yf) that agent is environmentally friendly, reaction condition is mild.
The present invention is with formula CF3-xClxCF2-yClyCH2Cl compounds are starting material, through gas phase fluorination, dechlorination, gas phase fluorination
Three-step reaction generates 2,3,3,3- tetrafluoropropenes (HFO-1234yf), and reaction process is as follows：
In order to achieve the object of the present invention, provided by the invention 2, the preparation method of 3,3,3- tetrafluoropropenes, including it is following
Step：
A, general formula is CF3-xClxCF2-yClyCH2The compound of Cl in the presence of a fluorination catalyst, through two cascade reactions
Device carries out gas phase fluorination with hydrogen fluoride and generates 1,2,3- tri- chloro- 1,1,2- trifluoro propane, wherein x=in compound formula
1,2,3；Y=1,2, and 3≤x+y≤5；The reaction condition of first reactor is in two tandem reactors：220 DEG C of reaction temperature
~260 DEG C, hydrogen fluoride and CF3-xClxCF2-yClyCH2The molar ratio 5~20 of Cl：1, reaction contact time 0.5~20 second；Two
The reaction condition of second reactor is in tandem reactor：280 DEG C~320 DEG C of reaction temperature, hydrogen fluoride has with first reactor
The molar ratio 10~20 of machine product：1, reaction contact time 5~30 seconds；
B, 1,2,3- tri- chloro- 1,1,2- trifluoro propane is in the presence of dechlorination catalyst Cu-V-Mg-F, with hydrogen into promoting the circulation of qi
Phase dechlorination reaction generates the chloro- 2,3,3- trifluoro propenes of 3-；Gas phase dechlorination reaction condition is：200 DEG C~300 DEG C of reaction temperature, hydrogen
The molar ratio 0~1 of gas and tri- chloro- 1,1,2- trifluoros propane of 1,2,3-:1,1~30 second time of contact；
C, the chloro- 2,3,3- trifluoro propenes of 3- are in FeF3/MgF2In the presence of catalyst, it is anti-to carry out gas phase fluorination with hydrogen fluoride
2,3,3,3- tetrafluoropropenes should be generated；Gas phase fluorination condition is：160 DEG C~240 DEG C of reaction temperature, hydrogen fluoride is chloro- with 3-
The molar ratio 10~20 of 2,3,3- trifluoro propenes:1,0.1~10 second time of contact.
Formula CF described in step a3-xClxCF2-yClyCH2Cl compounds are selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl、
CF2ClCCl2CH2Cl、CCl3CFClCH2Cl or CFCl2CFClCH2Cl。
Formula CF described in step a3-xClxCF2-yClyCH2Cl compounds are CCl3CCl2CH2Cl。
Fluorination catalyst described in step a is Zn-A-B-C composite catalysts, wherein A be the VIIIth race's element, selected from Ni,
One or more of Fe, Co are combined, and B is High field side injection, selected from one or more of Zr, Y, La combination, C
For alkali earth metal, one kind in Mg, Ca, Ba；The molar ratio of Zn, A, B, C are (0.3~2):(0.6~5):(0.1
~1):(2~9), preferably (0.5~1):(1~4):(0.5~1):(4~8).
Zn-A-B-C composite catalysts described in step a are Zn-Fe-La-Mg composite catalysts, wherein Zn, Fe, La, Mg
Four molar ratio is 0.5:2:0.5:7；The preparation method of the catalyst includes：By tri- kinds of metals of a certain proportion of Zn, Fe, La
The mixed solution of soluble-salt is reacted with precipitating reagent, and pH controls are stirred, precipitated, filtering and is dry, then will be certain in 7.5-9.5
The oxide, hydroxide or carbonate for measuring magnesium are mixed uniformly, then at 200 DEG C -500 DEG C, in no less than three temperature
Baking inphases are carried out under conditions of gradient, finally perfluorinated hydrogen activation process at 200 DEG C -380 DEG C obtains again.
Tandem reactor described in step a is the reaction equipped with same catalyst according to material flow direction series arrangement
Two tandem reactors of temperature increment, it is 60 DEG C~80 DEG C that reaction temperature, which is incremented by amplitude,.
The molar ratio of Cu, V, Mg three are 4 in dechlorination catalyst Cu-V-Mg-F described in step b：1：5.It is suitable for the catalysis
The preparation method of agent has the method for preparing catalyst such as infusion process, coprecipitation, blending method, sol-gel method.Certain dechlorination is anti-
It should can also be the liquid phase dechlorination reaction of HCFC-233bc and reducing agent effect in protonic solvent.
FeF described in step c3/MgF2The molar ratio of both Fe, Mg are 1 in catalyst：9、2：8、7：3 or 4：6.
Two tandem reactors in step a of the present invention are that identical catalysis is housed according to material flow direction series arrangement
Two reaction temperatures of agent tandem reactor incremented by successively；Between tandem reactor can according to need can be arranged static mixer,
Heat exchanger is to improve reaction effect；The gas phase entrance of static mixer makes up line with hydrogen fluoride to be connected to, liquid phase entrance with it is adjacent
Upper stage reactor liquid phase material outlet line connection, outlet is connected to adjacent subordinate's reactor inlet；The product of each reactor
At least one of optionally enter later separation workshop section and/or enter remaining reaction device；The conversion ratio of each reactor,
Product distribution is mainly controlled by reaction temperature, residence time, material proportion, and the primary product stream of first reactor is
CFCl2CCl2CH2Cl(HCFC-231bc)、CF2ClCCl2CH2Cl (HCFC-232ac), HF, HCl, the main production of second reactor
Object is CF2ClCFClCH2Cl (HCFC-233bc), after catalyst inactivation in a reactor in tandem reactor, can be from
The reactor is isolated in the device and carries out catalyst regeneration operation.
Reaction in step a of the present invention can carry out in any reactor for being suitable for gas phase fluorination.Step a's
Fluorination reactor type can use tubular reactor, fluidized-bed reactor etc. nor key.In addition, adiabatic reactor or
Isothermal reactor also can be used.
Hydrogen and the molar ratio of HCFC-233bc are the key that influence this to react in gas phase dechlorination reaction in step b of the present invention
Factor, when being passed through excessive hydrogen, although reaction may be implemented to convert completely, the selectivity of target product obviously drops
Low, hydrogen is (0~1) with molar ratio suitable HCFC-233bc:1, preferably (0.1~0.5):1, more preferable (0.1~0.3):
1, hydrogen be passed through mode can be can also be intermittently, semi-continuously continuously.
The pretreatment of dechlorination catalyst in step b of the present invention can by by catalyst in nitrogen or other inert gases
About 200 DEG C are heated in stream to about 380 DEG C to carry out.Then catalyst can be used through a large amount of excessive diluted hydrogen fluoride of nitrogen
Stream process is activated to obtain high catalyst activity.The regeneration of catalyst can carry out under the following conditions, make air or use
For the diluted air of nitrogen at about 100 DEG C to about 380 DEG C, preferably from about 150 DEG C to about 365 DEG C of temperature lasts about 8 by catalyst
Hour, this depended on the size of reactor to about 3 days.
Advantages of the present invention：Compared with the prior art, the advantages of the present invention are as follows provide a kind of effectively preparation HFO-
The method of 1234yf, while there is intermediate to be easily isolated, 1,2,3- tri- chloro- 1 in intermediate, 1,2- trifluoro propane and 3- are chloro-
2,3,3- trifluoro propene boiling points differ greatly, and about 40 DEG C, are easily isolated；Catalysts are not related to containing chromium compound, to people and ring
Border is friendly；The mild feature of reaction condition, gas phase reaction temperature are also no more than 340 DEG C；With documents patent
WO2009153493 is compared with US20110190554, is realized under the conditions of dechlorination reaction of the present invention is existing for a small amount of hydrogen, no
Need the hydrogen of stoichiometry.
Specific implementation mode
Below by specific embodiment, invention is further described in detail
Analytical instrument：The glad GC-930 types gas chromatograph in sea, agilent company 30m DB-5 (50m × 0.32mm) capillary
Chromatographic column；ITQ 700 (ion trap)：Thermofisher scientific, agilent company GASPRO (60m × 0.25mm)
Capillary chromatographic column.
Chromatographic condition：40 DEG C of initial column temperature keeps 5min, rises to 180 DEG C with the heating rate of 10 DEG C/min, keeps
3min；220 DEG C of temperature of vaporization chamber, split ratio 50.
Ion trap mass spectrometry condition：Filament emission current 70A；Mass scan range 10-350amu；Full scan mode, scanning
10 micro scannings of speed/second；Multiplier voltage 1556V；220 DEG C of transmission line temperature, 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 solutions, then the ammonium hydroxide that mass fraction is 15% is added dropwise at 20 DEG C -40 DEG C, under conditions of being stirred continuously, it is 8.0 to adjust pH
8h, filtering, then the dry 2h at 120 DEG C are reacted in left and right, then a certain amount of magnesia is mixed uniformly, then are roasted at 200 DEG C
Burn 1h, 5 DEG C/min rises to 320 DEG C, roasts 2h, and then 10 DEG C/min rises to 450 DEG C, roasts 4h, finally again perfluorinated hydrogen 200
Activation process obtains at DEG C -380 DEG C, about needs 36h.
In the fixed-bed tube reactor that internal diameter is 38mm, the above-mentioned Zn-Fe-La-Mg composite catalysts of 50ml are packed into,
The molar ratio of middle Zn, Fe, La, Mg are 0.5:2:0.5:7, and catalyst is dried and then at 250 DEG C, by HF
And CCl3CCl2CH2Cl (HCC-230ab is abbreviated as 230ab) is passed through first reactor R1, and both control molar ratio is 10:1, it connects
It is 15s to touch the time, and the first product stream enters second reactor reaction R2, and second reactor temperature is 300 DEG C, HF and organic matter
Molar ratio is 15:1, time of contact is 20 seconds, and each reaction is reacted under atmospheric pressure (normal pressure), and reaction product is through water
It washes, after alkali cleaning removing HCl and HF, with gas-chromatography 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 are mainly
CF2ClCFClCH2Cl (HCFC-233bc is abbreviated as 233bc), reaction result is shown in Table 1.
Embodiment 2~4：
Embodiment 2~4 prepares HCFC-233bc according to identical method in embodiment 1, except that in embodiment 1
The reaction temperature of R1, R2 are respectively 250 DEG C, 300 DEG C, and in embodiment 2~4, the reaction temperature of R1, R2, reaction result such as table 1
It is shown.
Table 1
Embodiment 5~7：
Embodiment 5~7 prepares HCFC-233bc according to identical method in embodiment 1, except that in embodiment 1
HF and organic materials proportioning (molar ratio) in R1, R2 are followed successively by 10:1,15:1, R1, in R2 time of contact be respectively 15s,
20s, and in embodiment 5~7, HF is matched with organic materials, and time of contact, reaction result is as shown in table 2, and wherein 230ab's turns
Rate is 100%.
Table 2
Embodiment 8~11：
Embodiment 8~11 prepares HCFC-233bc according to identical method in embodiment 1, except that in embodiment 1
Catalyst Z n, Fe, La, Mg molar ratio is 0.5；2：0.5：7, and in embodiment 8~11, four molar ratios are 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 identical method in embodiment 1, except that embodiment 1
In catalyst be Zn-Fe-La-Mg composite catalysts, and the catalyst in embodiment 12~16 Zn-Ni-La-Mg, Zn- successively
Fe-Zr-Mg, Zn-Ni-La-Ca, Zn-Co-Zr-Ca, Zn-Co-Y-Ba, reaction result are shown 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)2·3H2The mixing water of O
In solution, it is 10% ammonium hydrogencarbonate to add mass fraction, and it is about 9, about 5h to adjust pH controls, is centrifuged after washed, then
It is dried at 120 DEG C, then roasts 1h at 200 DEG C, 5 DEG C/min rises to 300 DEG C, roasts 2h, and then 5 DEG C/min rises to 450 DEG C, roasting
4h is burnt, finally passes sequentially through hydrogen fluoride again, Hydrogen activation handles to obtain.
In the fixed-bed tube reactor that internal diameter is 38mm, it is packed into 50ml and contains above-mentioned Cu-V-Mg-F catalyst, wherein
The molar ratio of Cu, V, Mg three are 4：1：5, it is passed through H at 280 DEG C2, after two hours, it is (normal in atmospheric pressure to be passed through HCFC-233bc
Pressure) under reacted, the molar ratio both controlled is 0.3:1, time of contact is 30 seconds, is reacted with gas-chromatography, mass spectral analysis
As a result, the results are shown in Table 5.
Embodiment 18~21：
Embodiment 18~21 prepares HCFO-1233yf according to 17 identical method of embodiment, except that embodiment 17
In reaction temperature be 280 DEG C, and in embodiment 18~21, reaction temperature is followed successively by 200 DEG C, 240 DEG C, 320 DEG C, reaction result
As shown in table 5.
Table 5
Embodiment 22~24：
Embodiment 22~24 prepares HCFO-1233yf according to identical method in embodiment 17, except that embodiment
In 17 catalyst, the molar ratio of Cu, V, Mg three are 4：1：5, and in embodiment 22~24 in catalyst, three mole successively
It is 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 identical method in embodiment 17, except that embodiment
In 17, the molar ratio of hydrogen and HCFC-234bb are 0.3:1, and in embodiment 25~27, the two molar ratio is followed successively by 0.1:1、
0.5:1、1:1, reaction result is as shown in table 7.
Table 7
Embodiment 28~30：
Embodiment 28~30 prepares HCFO-1233yf according to identical method in embodiment 17, except that embodiment
Time of contact is 20s in 17, and in embodiment 28~30, time of contact is respectively 5s, 10s, 30s, the results are shown in Table 8.
Table 8
Embodiment 31：
The preparation of catalyst：By a certain percentage, a certain amount of Fe (NO are accurately weighed3)2·9H2O and Mg (NO3)2·6H2O,
It is dissolved in absolute ethyl alcohol, then under continuous stirring, the ethanol solution of above-mentioned mixing is added dropwise in 40% HF solution, about
1h is precipitated, is filtered, washed and dried, and 350 DEG C of 1~4h of roasting are risen to the heating rate of 10 DEG C/min in Muffle furnace.
In the fixed-bed tube reactor that internal diameter is 38mm, it is packed into the above-mentioned FeF of 50ml3/MgF2Catalyst, wherein wherein
The molar ratio 2 of Fe, Mg:8, catalyst is dried, then at 150 DEG C, is passed through chloro- 2,3,3- trifluoro propylenes of HF and 3-,
It is reacted under atmospheric pressure (normal pressure), the molar ratio of the two is 15:1, time of contact is 10 seconds, and reaction product is through washing, alkali cleaning
After removing HCl and HF, through mass spectrum, gas chromatographic analysis, reaction result is shown in Table 9.
Embodiment 32~34：
Embodiment 32~34 prepares HFO-1234yf according to identical method in embodiment 31, except that embodiment 31
In reaction temperature 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, reaction knot
Fruit is as shown in table 9.
Table 9
Embodiment 35~37：
Embodiment 35~37 prepares HFO-1234yf according to identical method in embodiment 31, except that embodiment 31
In catalyst in, the molar ratio of both Fe, Mg is 2：8, and both in the catalyst in embodiment 35~37 mole successively
It is 1：9、3：7、4：6, reaction result is shown in Table 10.
Table 10
Embodiment 38~39：
Embodiment 38~39 prepares HFO-1234yf according to identical preparation method in embodiment 31, except that implementing
The molar ratio of HF and HCFO-1233yf in example 31 are 15:1, and the two molar ratio in embodiment 38,39 is followed successively by 10:1、
20:1, as a result as shown in table 11.
Table 11
Embodiment 40~42：
Embodiment 40~42 prepares HFO-1234yf according to identical preparation method in embodiment 31, except that implementing
Time of contact in example 31 is 10s, and the time of contact in embodiment 40~42 is followed successively by 3s, 5s, 20s, reaction result such as table
Shown in 12.
Table 12
Claims (5)
1. the preparation method of 2,3,3,3- tetrafluoropropene of one kind, which is characterized in that include the following steps：
A, general formula is CF3-xClxCF2-yClyCH2The compound of Cl in the presence of a fluorination catalyst, through two differential responses temperature
Tandem reactor, with hydrogen fluoride carry out gas phase fluorination generate 1,2,3- tri- chloro- 1,1,3- trifluoro propane, wherein compound
X=1,2,3 in general formula；Y=1,2, and 3≤x+y≤5；The reaction condition of first reactor is in two tandem reactors：Reaction
220 DEG C~260 DEG C of temperature, hydrogen fluoride and CF3-xClxCF2-yClyCH2The molar ratio 5~20 of Cl：1, reaction contact time 1~20
Second；The reaction condition of second reactor is in two tandem reactors：280 DEG C~320 DEG C of reaction temperature, hydrogen fluoride and first is instead
Answer the molar ratio 10~20 of device organic product：1, reaction contact time 5~30 seconds；
The fluorination catalyst is Zn-A-B-C composite catalysts, wherein A is group VIII element, in Ni, Fe, Co
One or more kinds of combinations, B is High field side injection, and selected from one or more of Zr, Y, La combination, C is alkaline earth
Metallic element, one kind in Mg, Ca, Ba；The molar ratio of Zn, A, B, C are (0.3~2):(0.6~5):(0.1~1):(2
~9)；
B, 1,2,3- tri- chloro- 1, it is de- that 1,2- trifluoro propane carries out gas phase in the presence of dechlorination catalyst Cu-V-Mg-F, with hydrogen
Chlorine reaction generates 3- chloro- 2,3,3- trifluoro propenes, and gas phase dechlorination reaction condition is：200 DEG C~300 DEG C of reaction temperature, hydrogen with
The molar ratio 0.1~1 of tri- chloro- 1,1,2- trifluoros propane of 1,2,3-:1,5~30 seconds times of contact；
The molar ratio of Cu, V, Mg three are 4 in the dechlorination catalyst Cu-V-Mg-F：1：5；
C, the chloro- 2,3,3- trifluoro propenes of 3- are in FeF3/MgF2In the presence of catalyst, gas phase fluorination life is carried out with hydrogen fluoride
At 2,3,3,3- tetrafluoropropenes, gas phase fluorination condition is：160 DEG C~240 DEG C of reaction temperature, hydrogen fluoride and 3- chloro- 2,3,
The molar ratio 10~20 of 3- trifluoro propenes:1,10 seconds times of contact；
The FeF3/MgF2The molar ratio of both Fe, Mg are 1 in catalyst：9 or 2：8 or 7：3 or 4：6.
2. according to claim 12, the preparation method of 3,3,3- tetrafluoropropenes, which is characterized in that the formula described in step a
CF3-xClxCF2-yClyCH2Cl compounds are selected from CCl3CCl2CH2Cl、CFCl2CCl2CH2Cl、CF2ClCCl2CH2Cl、
CCl3CFClCH2Cl、CFCl2CFClCH2Cl。
3. according to claim 22, the preparation method of 3,3,3- tetrafluoropropenes, which is characterized in that the formula described in step a
CF3-xClxCF2-yClyCH2Cl compounds are CCl3CCl2CH2Cl。
4. according to claim 12, the preparation method of 3,3,3- tetrafluoropropenes, which is characterized in that the Zn- described in step a
A-B-C composite catalysts are Zn-Fe-La-Mg composite catalysts, and wherein the molar ratio of Zn, Fe, La, Mg are 0.5:2:
0.5:7；The preparation method of the catalyst includes：By the mixed solution of tri- kinds of metal soluble-salts of a certain proportion of Zn, Fe, La with
Precipitating reagent reacts, and pH controls are in 7.5-9.5, stirring, precipitation, filtering and dry, then by the oxide of a certain amount of magnesium, hydroxide
Or carbonate is mixed uniformly, then at 200 DEG C -500 DEG C, segmentation roasting is carried out under conditions of no less than three temperature gradients
It burns, finally perfluorinated hydrogen activation process at 200 DEG C -380 DEG C obtains again.
5. according to claim 12, the preparation method of 3,3,3- tetrafluoropropenes, which is characterized in that the string described in step a
Connection reactor is anti-according to two incremental series connection of the reaction temperature equipped with same catalyst of material flow direction series arrangement
Device is answered, it is 60 DEG C~80 DEG C that reaction temperature, which is incremented by amplitude,.
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