US20190047925A1 - Method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene - Google Patents
Method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene Download PDFInfo
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- US20190047925A1 US20190047925A1 US16/079,085 US201716079085A US2019047925A1 US 20190047925 A1 US20190047925 A1 US 20190047925A1 US 201716079085 A US201716079085 A US 201716079085A US 2019047925 A1 US2019047925 A1 US 2019047925A1
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- reactor
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- hfo
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- tetrafluoropropene
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- 238000000034 method Methods 0.000 title claims abstract description 53
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 title claims abstract description 45
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 title claims abstract description 39
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 15
- VVWFZKBKXPXGBH-UHFFFAOYSA-N 1,1,1,3,3-pentachloropropane Chemical compound ClC(Cl)CC(Cl)(Cl)Cl VVWFZKBKXPXGBH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 15
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- BUQMVYQMVLAYRU-UHFFFAOYSA-N 1,1,2,3-tetrachloropropane Chemical compound ClCC(Cl)C(Cl)Cl BUQMVYQMVLAYRU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- UMGQVBVEWTXECF-UHFFFAOYSA-N 1,1,2,3-tetrachloroprop-1-ene Chemical compound ClCC(Cl)=C(Cl)Cl UMGQVBVEWTXECF-UHFFFAOYSA-N 0.000 abstract description 19
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 45
- 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 28
- 238000004458 analytical method Methods 0.000 description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 150000002894 organic compounds Chemical class 0.000 description 12
- 239000007791 liquid phase Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 8
- -1 antimony halide Chemical class 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- GXBPITKCTXKSEI-UHFFFAOYSA-N [Cr].[Mg].[Zn] Chemical compound [Cr].[Mg].[Zn] GXBPITKCTXKSEI-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- FDOPVENYMZRARC-UHFFFAOYSA-N 1,1,1,2,2-pentafluoropropane Chemical compound CC(F)(F)C(F)(F)F FDOPVENYMZRARC-UHFFFAOYSA-N 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005796 dehydrofluorination reaction Methods 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229960004065 perflutren Drugs 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PGJHURKAWUJHLJ-UHFFFAOYSA-N 1,1,2,3-tetrafluoroprop-1-ene Chemical compound FCC(F)=C(F)F PGJHURKAWUJHLJ-UHFFFAOYSA-N 0.000 description 2
- PNWJILFKWURCIR-UHFFFAOYSA-N 1-chloro-1,3,3,3-tetrafluoroprop-1-ene Chemical compound FC(Cl)=CC(F)(F)F PNWJILFKWURCIR-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
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Definitions
- This invention relates to a preparation method of alkenes containing fluorine and alkenes containing fluorine and chlorine, in particular to a method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene.
- Hydrofluoroolefins such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze), are important fourth-generation refrigerants and foamer.
- HFO-1234yf has a boiling point of ⁇ 29.5° C., a GWP value of 4 and an atmospheric life of about 10 days.
- HFO-1234yf can serve as a refrigerant, an extinguisher, a propellant, a foamer, a foaming agent, a fluid carrier, a polishing abradant, and a dynamic circulating medium.
- HFO-1234yf A preferable prospected application of the HFO-1234yf is in the refrigerant field, as a fourth-generation refrigerant, replacing 1,1,1,2-tetrafluoroethane (HFC-134a).
- Two types of HFO-1234ze are available, namely Z type and E type.
- the Z-type has a boiling point of 9° C.
- the E-type has a boiling point of ⁇ 19° C.
- the GWP value is 6.
- the Z-type may serve as foamer, and the E type may be mixed with other substances to serve as a refrigerant.
- HFO-1233zd 1-chloro-,3,3,3-trifluoropropene, is abbreviated as LBA, has a boiling point of 19° C., an atmospheric life of 26 days, an ODP value of approximately zero, and a GWP value of ⁇ 5, and is the first choice of a new-generation of environmentally-friendly foamer.
- HFO-1233zd is applicable to foaming polyurethane heat-insulating materials in fields such as household appliances, building insulation, cold-chain transmission and industrial insulation, and is the optimal foamer for replacing CFC, HCFC, HFC and other non-fluorocarbon foamer.
- HFO-1233zd Compared with the existing foamer systems (HFC-245fa and cyclopentane), HFO-1233zd has higher performance in the aspects of heat conductivity coefficient and overall energy consumption level. In comparison with the same type refrigerators using HFC-245fa and cyclopentane system, the heat conductivity coefficient of HFO-1233zd is reduced by 7% (in comparison with the HFC-245fa system) and by 12% (in comparison with the cyclopentane system), and the overall energy consumption is reduced by 3% (in comparison with HFC-245fa) and 7% (in comparison with cyclopentane).
- HFO-1234yf can be prepared by three methods with industrial prospects, namely the 3,3,3-trifluoropropene method, hexafluoropropylene method, and 1,1,2,3-tetrachloropropene (TCP) method.
- the 3,3,3-trifluoropropene method has a long line, lots of waste water, waste gas and waste solids, and high product cost; the 1,1,2,3-tetrachloropropene method features fewer reaction steps and a high utilization rate of raw materials; and the hexafluoropropylene method has a long preparation line and a low total yield.
- Other preparation processes are all derived from the intermediate materials of the above mentioned three methods.
- HFO-1234ze preparation methods with the industrial prospects include a 1,1,1,3,3-perfluoropropane (HFC-245fa) gas-phase HF-elimination method and a 1-chloro-3,3,3-trifluoropropene HF-addition method.
- HFC-245fa 1,1,1,3,3-perfluoropropane
- Chinese Patent Publication No. CN201180052804A published on Jul. 3, 2013 and titled with “Integrated Method for Co-production of Trans-1-Chloro-3,3,3-Trifluoropropene, Trans-1,3,3,3-Tetrafluoropropene, and 1,1,1,3,3-Perfluoropropane,” disclosed an integrated method for co-production of (E) 1-chloro-3,3,3-trifluoropropene, (E) 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane using a single chlorinated hydrocarbon raw material, namely 1,1,1,3,3-pentachloropropane (HCC-240fa).
- HCC-240fa 1,1,1,3,3-pentachloropropane
- the method includes a combined liquid phase or gas phase reaction/purification operation for directly producing (E) 1-chloro-3,3,3-trifluoropropene (1233zd(E)).
- 1233zd(E) and hydrogen fluoride (HF) contact each other under the presence of a catalyst to perform a reaction with a high conversion rate and high selectivity to generate 1,1,1,3,3-perfluoropropane (HCC-240fa).
- the third reactor is used to remove the hydrogen fluoride from the HFC-245fa through contacting a high alkaline solution in a liquid phase or using a dehydrofluorination catalyst in a gas phase to generate (E)1,3,3,3-tetrafluoropropene (1234ze(E)).
- one or more extraction processes may be carried out to recover the 1234ze(E) product.
- the defects are found in the liquid-phase fluorination and liquid-phase dehydrofluorination processes, including a short reaction catalyst life, a lot of process waste liquid and high environmentally-friendly processing cost.
- HFO-1234yf 2,3,3,3-tetrafluoropropene
- TC 1,1,2,3-tetrachloropropene
- HFC-245cb 1,1,1,2,2-pentafluoropropane
- HFC-245cb is generated during the process.
- HCFO-1233xf and HFC-245cb cannot generate HFO-1234yf at the same time, and HFO-1234yf is synthesized through two-step reaction.
- the method includes: reacting 1,1,2,3-tetrachloropropene and a first fluorinated reagent to generate 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and a first intermediate composition of a first chlorine-containing side product; reacting the first intermediate composition of the first chlorine-containing side product and a second fluorinated reagent to generate 2-chloro-1,1,2,2-tetrachloropropene (HCFC-244bb) and a second intermediate composition of a second chlorine-containing side product; catalyzing at least part of the HCFC-244bb and eliminating the hydrogen chloride to generate 2,3,3,3-tetrafluoropropene.
- HCFO-1233xf 2-chloro-3,3,3-trifluoropropene
- HCFC-244bb 2-chloro-1,1,2,2-tetrachloropropene
- This process synthesizes the 2,3,3,3-tetrafluoropropene using three steps.
- HCFO-1233xf is converted into HCFC-244bb in a liquid-phase reactor.
- the catalyst is antimony halide.
- the reactor adopts TFE or PFA as the inner lining. The defect is that the reactor is seriously corroded inside and bulged. It is difficult to select equipment.
- the third step namely saponification, generates a huge amount of waste water, waste gas and waste solids, and has a low yield.
- this invention provides a method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. This method is simple in process, low in investment, low in energy consumption and high in catalyst conversion rate.
- a method for co-production of 1-chloro-3,3,3-,trifluoropropene, 2,3,3,3-,tetrafluoropropene and 1,3,3,3-,tetrafluoropropene includes the following steps:
- Hydrogen fluoride and 1,1,1,3,3-pentachloropropane are preheated and then directed into a first reactor in a molar ratio of 9-15:1.
- the first reactor includes two sections, namely an upper section and a lower section.
- the upper section is filled with an aluminum oxide supported chromium metal catalyst, and the lower section is filled with a chromic oxide supported indium metal catalyst.
- the hydrogen fluoride and the 1,1,1,3,3-pentachloropropane are reacted in the upper section of the first reactor at a temperature of 200-400° C. and at an air flow rate of 300-1,000 h ⁇ 1 .
- the reaction product thereof enters the lower section of the first reactor to continuously react with the 1,1,2,3-tetrachloropropane, and the molar ratio of the 1,1,2,3-tetrachloropropane to the hydrogen fluoride is 3-5:9. A reaction product of the first reactor is obtained.
- step (b) The reaction product of the first reactor obtained in step (a) is directly directed into a second reactor, and the reaction product of the first reactor catalyzed by a catalyst of the second reactor at a temperature of 250-450° C. and at an air flow rate of 500-1,500 h ⁇ 1 .
- a reaction product of the second reactor is obtained.
- step (c) The reaction product of the second reactor obtained in step (b) is directed into a hydrogen chloride tower to perform separation to obtain a tower bottom fraction and an tower top fraction of the hydrogen chloride tower.
- the tower top fraction is hydrogen chloride.
- the hydrogen chloride is refined to obtain hydrochloric acid;
- the tower bottom fraction of the hydrogen chloride tower is sequentially passed through a water washing tower, an alkaline washing tower and a drying tower to remove hydrogen fluoride and hydrogen chloride, and then enter a first rectifying tower to perform rectification.
- a tower bottom fraction and a tower top fraction of the first rectifying tower are obtained.
- the tower bottom fraction of the first rectifying tower is directed into a second rectifying tower for separation to obtain a product of 1-chloro-3,3,3-trifluoropropene and a tower top fraction of the second rectifying tower.
- the tower top fraction of the first rectifying tower is direct into a third rectifying tower for separation to obtain a product of 2,3,3,3-tetrafluoropropene at the top of the third rectifying tower and a 1,3,3,3-tetrafluoropropene product at the bottom of the third rectifying tower.
- the tower top fraction of the second rectifying tower obtained in step (e) may be circulated to reenter the second reactor.
- the molar ratio of the hydrogen fluoride to the 1,1,1,3,3-pentachloropropane is preferably 9-12:1; the reaction temperature is preferably 250-320° C. and the air flow rate is preferably 500-800 h ⁇ 1 .
- the reaction temperature is preferably 300-400° C.
- the air flow rate is preferably 800-1,200 h ⁇ 1 .
- the loading amount of chromium in the aluminum oxide supported chromium metal catalyst is 5-15 wt % (wt %, weight percentage content).
- the loading amount of indium in the chromic oxide supported indium metal catalyst is 3-10 wt %.
- the catalyst in the second reactor comprises the following ingredients in mass percentage: 70-80% of chromium oxide, 10-15% of magnesium oxide, and 5-15% of zinc oxide.
- the first reactor is divided into two sections, an upper section and a lower section.
- the upper section is filled with hydrogen fluoride and 1,1,1,3,3-pentachloropropane from the top
- the lower section is filled with 1,1,2,3-tetrachloropropene. Since the reaction of 1,1,2,3-tetrachloropropene and the HF is a strong exothermic reaction, so that the reacting materials in the upper section may carry heat away, without affecting the conversion rate of the 1,1,2,3-tetrachloropropene.
- the reaction temperature has a large influence on the activity of the catalyst and the selectivity of products. The increased reaction temperature helps to enhance the activity of the catalyst.
- the temperature of the upper section of the first reactor of this invention is selected to be 200-400° C., preferably 250-320° C., and the needed temperature of the lower section of the first reactor depends on the heat of the materials in the upper section brought into.
- a fluorine-chlorine exchange reaction and an addition reaction of alkenes occur in the first reactor.
- the catalyst in the upper section of the first reactor is aluminum oxide supported chromium metal, and the catalyst in the lower section is chromic oxide supported indium metal.
- the catalyst in the upper section uses aluminum oxide as the support, and is capable of preventing quick reduction of the specific area of the catalyst due to strong heat release during reaction between the hydrogen fluoride and the 1,1,1,3,3-pentachloropropane, and the addition of chromium increases the activity of the catalyst.
- the catalyst in the lower section uses chromic oxide as the support to load indium metal, further enhancing the activity of the catalyst, and ensuring that the 1,1,1,3,3-pentachloropropane and the 1,1,2,3-tetrachloropropene may be completely converted under proper temperature conditions.
- the molar ratio has a relatively large influence on the reaction.
- the HF required by the reactions in the upper and lower sections of the first reactor is imported from the upper section. Theoretically, 5 moles of HF are needed for the reaction of each mole of the 1,1,1,3,3-pentachloropropane in the upper section, and 3-4 moles of HF are needed for the reaction of each mole of the 1,1,2,3-tetrachloropropene in the lower section.
- a huge amount of HF in the upper section can carry heat away, and the reaction heat in the lower section is supplied by and brought away by the upper section, and comprehensive utilization of the heat and reducing energy consumption is thus realized.
- the molar ratio of the HF to the 1,1,1,3,3-pentachloropropane is controlled to be 9-15:1, preferably 9-12:1.
- HFO-1233zd and HCFO-1233xf perform a fluorine-chlorine exchange reaction with the HF. Temperature is a main factor that determines the reaction. If the temperature is too high, it leads to higher conversion rates of the HFO-1233zd and HCFO-1233xf, higher yields of HFO-1234ze and HFO-1234yf, and a lower yield of co-produced HFO-1233zd, and the catalyst is deactivated due to fast carbon deposition.
- reaction temperature can be adjusted according to the demands of the market and products.
- the reaction temperature of the second reactor of this invention is selected to be 250-450° C., preferably 300-400° C.
- the main cause of deactivating the catalyst in the two-step reaction is carbon deposition, resulting in a reduction in the specific area and micropores of the catalyst.
- the activity of the catalyst can be recovered by a method of regeneration. At a temperature of 330-380° C., air and nitrogen gas are directed in a ratio to remove the carbon deposited on the surface of the catalyst.
- the catalysts in the upper and lower sections of the first reactor of this invention are prepared by methods known in the prior art.
- the aluminum oxide support is immersed in a chromium solution with a certain concentration; after reaching a certain loading amount, the obtained substance is dried and calcined to obtain a catalyst precursor; and the catalyst precursor is fluorinated to obtain the catalyst for the upper section.
- the chromic oxide support is immersed in indium solution with a certain concentration; after reaching a certain loading amount, the obtained substance is dried and calcined to obtain the catalyst precursor; and the catalyst precursor is fluorinated to obtain the catalyst for the lower section.
- the catalyst used in the second reactor may be a catalyst which takes chromic oxide known in the art as the active ingredient.
- the catalyst is prepared using the steps: reacting nitrates of chromium, magnesium and zinc with a precipitant to generate suspended hydroxide solids; filtering, obtaining oxides of chromium, magnesium and zinc after washing, drying and calcining; obtaining the catalyst precursor by pelleting, pressing and molding; and obtaining the catalyst by fluorinating.
- the activation of the catalyst may proceed in other reactors.
- the first reactor and the second reactor in this invention may be isothermal or heat-insulating type reactors.
- the material of the reactors may select a material resistant to acid corrosion, for example, Inconel.
- this invention has the following advantages:
- the first reactor is filled with two different types of catalysts, so that two reactions may occur at the same time to simplify the process flow.
- High conversion rate By adjusting the reaction temperature, the conversion rates of HCC-240fa and 1,1,2,3-tetrachloropropene may reach 100%.
- the lower section of the first reactor is not required to be heated from the outside, and the heat required by the reaction is supplied by the material coming from the upper section to realize comprehensive heat utilization and reducing energy consumption.
- a set of devices can produce three products, namely HFO-1233zd, HFO-1234yf and HFO-1234ze, and the product ratios can be flexibly adjusted according to the demands of the market, thereby obviously reducing investments in the devices.
- FIG. 1 is a process flowchart of this invention.
- the process flow of this invention can be seen in FIG. 1 .
- the first reactor is divided into two sections, namely an upper section and a lower section, each filled with a different catalyst.
- Raw materials, hydrogen fluoride and HCC-240fa are input in a certain molar ratio into a preheater 1 via a pipeline 11 to be preheated, and then enter the top of the upper section of a first reactor 2 via a pipeline 12.
- 1,1,2,3-tetrachloropropene is input into the lower section of the first reactor 2, and a mixture of HFO-1233zd, HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained after reaction.
- the mixture is directly input into a second reactor 3 via a pipeline 13 without separation.
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained and enters a hydrogen chloride tower 4 via a pipeline 14 to obtain a tower bottom fraction and an tower top fraction.
- the tower top fraction of the hydrogen chloride tower 4 is hydrogen chloride, and the hydrogen chloride is separately refined to obtain hydrochloric acid.
- the tower bottom fraction enters a water washing tower 5 via a pipeline 15 to be washed with water, then enters an alkaline washing tower 6 via a pipeline 16 to be washed with alkali, next enters a drying tower 7 via a pipeline 17 to be dried to obtain a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd.
- the mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd enters a first rectifying tower 8 via a pipeline 18 to obtain a tower bottom fraction and an tower top fraction.
- the tower top fraction of the first rectifying tower 8 includes HFO-1234yf and HFO-1234ze, and enters a third rectifying tower 10 via a pipeline 21.
- a product HFO-1234yf is obtained at the top of the third rectifying tower 10
- a product HFO-1234ze is obtained in the tower bottom of the third rectifying tower 10.
- the tower bottom fraction of the first rectifying tower 8 enters a second rectifying tower 9 via a pipeline 19 to be separated to obtain a tower bottom fraction and an tower top fraction of the second rectifying tower 9.
- the fraction at the top of the second rectifying tower 9 mainly includes HCFO-1233xf and carries a small amount of HFO-1233zd, and is circulated to enter the second reactor.
- a product HFO-1233zd is obtained in the tower bottom of the second rectifying tower 9.
- the first reactor is heated to a temperature of 350° C., while HF and nitrogen gas are input to perform activation for 50 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min.
- the second reactor is heated to a temperature of 350° C., while HF and nitrogen gas are input to perform activation for 40 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min. In this way, the activation of the catalysts in the two reactors is completed.
- the first reactor and the second reactor are heated, a temperature increase rate is 1° C./min from room temperature to 150° C., and a temperature increase rate is 0.5° C./min when the temperature is above 150° C.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1.
- the temperature of the upper section of the first reactor is controlled to be 280° C.
- the air flow rate is controlled to be 500 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 1 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300° C., and the air flow rate is 800 h ⁇ 1 .
- the temperature of the second reactor is 300° C.
- the air flow rate is 800 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 1 after gas chromatography analysis.
- the activation method of the catalysts is the same as that in Embodiment 1.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1.
- the temperature of the upper section of the first reactor is controlled to be 300° C.
- the air flow rate is controlled to be 600 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 5:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 2 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 320° C., and the air flow rate is 800 h ⁇ 1 .
- the temperature of the second reactor is 320° C.
- the air flow rate is 800 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 2 after gas chromatography analysis.
- the activation method of the catalysts is the same as that in Embodiment 1.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 15:1.
- the temperature of the upper section of the first reactor is controlled to be 320° C.
- the air flow rate is controlled to be 1000 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 3:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 3 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 350° C., and the air flow rate is 1200 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 3 after gas chromatography analysis.
- the activation method of the catalysts is the same as that in Embodiment 1.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 12:1.
- the temperature of the upper section of the first reactor is controlled to be 400° C.
- the air flow rate is controlled to be 300 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 4 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 400° C., and the air flow rate is 500 h ⁇ 1 .
- the temperature of the second reactor is 400° C.
- the air flow rate is 500 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 4 after gas chromatography analysis.
- the activation method of the catalysts is the same as that in Embodiment 1.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1.
- the temperature of the upper section of the first reactor is controlled to be 300° C.
- the air flow rate is controlled to be 500 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 5 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 330° C., and the air flow rate is 600 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 5 after gas chromatography analysis.
- the activation method of the catalysts is the same as that in Embodiment 1.
- HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1.
- the temperature of the upper section of the first reactor is controlled to be 300° C.
- the air flow rate is controlled to be 600 h ⁇ 1
- the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9.
- a mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 6 after gas chromatography analysis.
- the mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300° C., and the air flow rate is 700 h ⁇ 1 .
- a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained.
- Composition of organic compounds are shown in Table 6 after gas chromatography analysis.
Abstract
Description
- 1. Field of this Invention
- This invention relates to a preparation method of alkenes containing fluorine and alkenes containing fluorine and chlorine, in particular to a method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene.
- Hydrofluoroolefins (HFOs), such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze), are important fourth-generation refrigerants and foamer. HFO-1234yf has a boiling point of −29.5° C., a GWP value of 4 and an atmospheric life of about 10 days. HFO-1234yf can serve as a refrigerant, an extinguisher, a propellant, a foamer, a foaming agent, a fluid carrier, a polishing abradant, and a dynamic circulating medium. A preferable prospected application of the HFO-1234yf is in the refrigerant field, as a fourth-generation refrigerant, replacing 1,1,1,2-tetrafluoroethane (HFC-134a). Two types of HFO-1234ze are available, namely Z type and E type. The Z-type has a boiling point of 9° C., and the E-type has a boiling point of −19° C. The GWP value is 6. The Z-type may serve as foamer, and the E type may be mixed with other substances to serve as a refrigerant.
- HFO-1233zd, 1-chloro-,3,3,3-trifluoropropene, is abbreviated as LBA, has a boiling point of 19° C., an atmospheric life of 26 days, an ODP value of approximately zero, and a GWP value of <5, and is the first choice of a new-generation of environmentally-friendly foamer. HFO-1233zd is applicable to foaming polyurethane heat-insulating materials in fields such as household appliances, building insulation, cold-chain transmission and industrial insulation, and is the optimal foamer for replacing CFC, HCFC, HFC and other non-fluorocarbon foamer. Compared with the existing foamer systems (HFC-245fa and cyclopentane), HFO-1233zd has higher performance in the aspects of heat conductivity coefficient and overall energy consumption level. In comparison with the same type refrigerators using HFC-245fa and cyclopentane system, the heat conductivity coefficient of HFO-1233zd is reduced by 7% (in comparison with the HFC-245fa system) and by 12% (in comparison with the cyclopentane system), and the overall energy consumption is reduced by 3% (in comparison with HFC-245fa) and 7% (in comparison with cyclopentane).
- HFO-1234yf can be prepared by three methods with industrial prospects, namely the 3,3,3-trifluoropropene method, hexafluoropropylene method, and 1,1,2,3-tetrachloropropene (TCP) method. The 3,3,3-trifluoropropene method has a long line, lots of waste water, waste gas and waste solids, and high product cost; the 1,1,2,3-tetrachloropropene method features fewer reaction steps and a high utilization rate of raw materials; and the hexafluoropropylene method has a long preparation line and a low total yield. Other preparation processes are all derived from the intermediate materials of the above mentioned three methods.
- Two HFO-1234ze preparation methods with the industrial prospects include a 1,1,1,3,3-perfluoropropane (HFC-245fa) gas-phase HF-elimination method and a 1-chloro-3,3,3-trifluoropropene HF-addition method.
- For example, Chinese Patent Publication No. CN201180052804A, published on Jul. 3, 2013 and titled with “Integrated Method for Co-production of Trans-1-Chloro-3,3,3-Trifluoropropene, Trans-1,3,3,3-Tetrafluoropropene, and 1,1,1,3,3-Perfluoropropane,” disclosed an integrated method for co-production of (E) 1-chloro-3,3,3-trifluoropropene, (E) 1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane using a single chlorinated hydrocarbon raw material, namely 1,1,1,3,3-pentachloropropane (HCC-240fa). The method includes a combined liquid phase or gas phase reaction/purification operation for directly producing (E) 1-chloro-3,3,3-trifluoropropene (1233zd(E)). In a second liquid-phase fluorination reactor, 1233zd(E) and hydrogen fluoride (HF) contact each other under the presence of a catalyst to perform a reaction with a high conversion rate and high selectivity to generate 1,1,1,3,3-perfluoropropane (HCC-240fa). The third reactor is used to remove the hydrogen fluoride from the HFC-245fa through contacting a high alkaline solution in a liquid phase or using a dehydrofluorination catalyst in a gas phase to generate (E)1,3,3,3-tetrafluoropropene (1234ze(E)). After this operation, one or more extraction processes may be carried out to recover the 1234ze(E) product. The defects are found in the liquid-phase fluorination and liquid-phase dehydrofluorination processes, including a short reaction catalyst life, a lot of process waste liquid and high environmentally-friendly processing cost.
- For example, Chinese Patent Publication No. CN201180027570A, published on Feb. 25, 2015 and titled with “Comprehensive Method for Co-production of Trans-1-Chloro-3,3,3-Trifluoropropene and Trans-1,3,3,3-Tetrafluoropropene,” disclosed a comprehensive manufacturing method in combination with liquid-phase reactions and purification operations. According to the disclosed method, the trans-1-chloro-3,3,3-trifluoropropene and 3-chloro-1,1,1,3-tetrafluoropropene, which are precursors for manufacturing trans-1,3,3,3-tetrafluoropropene, are produced directly. Mixtures of co-products are easily separated through conventional distillation, and then hydrogen chloride is eliminated from the 3-chloro-1,1,1,3-tetrafluoropropene through contacting a high alkaline solution in a liquid phase or using a dehydrofluorination catalyst in a gas phase to produce the trans-1,3,3,3-tetrafluoropropene. The defects are found in the liquid-phase fluorination and liquid-phase dehydrofluorination processes, including a short reaction catalyst life, a lot of process waste liquid and high environmentally-friendly processing cost.
- For example, Chinese Patent Publication No. CN102686543A, published on Sep. 19, 2012 and titled with “Gas Fluorination of 1230xa to 1234yf,” relates to a method for preparation of 2,3,3,3-tetrafluoropropene (HFO-1234yf), including (1) allowing 1,1,2,3-tetrachloropropene (TC) to contact hydrogen fluoride in a gas phase with the existence of a fluorination catalyst; (2) separating the reaction mixture to obtain 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and 1,1,1,2,2-pentafluoropropane (HFC-245cb), and inputting HCFO-1233xf and HFC-245cb into a reactor to generate HFO-1234yf. The defect is that some HFC-245cb is generated during the process. During the reaction process, a problem of balancing with HFO-1234yf occurred. Within the catalyst system, HCFO-1233xf and HFC-245cb cannot generate HFO-1234yf at the same time, and HFO-1234yf is synthesized through two-step reaction.
- For example, Chinese Patent Publication No. CN101597209A, published on Sep. 9, 2009 and titled with “Integrated Method for Preparation of 2,3,3,3-Tetrafluoropropene” provides an integrated method for preparing 2,3,3,3-tetrafluoropropene. The method includes: reacting 1,1,2,3-tetrachloropropene and a first fluorinated reagent to generate 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) and a first intermediate composition of a first chlorine-containing side product; reacting the first intermediate composition of the first chlorine-containing side product and a second fluorinated reagent to generate 2-chloro-1,1,2,2-tetrachloropropene (HCFC-244bb) and a second intermediate composition of a second chlorine-containing side product; catalyzing at least part of the HCFC-244bb and eliminating the hydrogen chloride to generate 2,3,3,3-tetrafluoropropene. This process synthesizes the 2,3,3,3-tetrafluoropropene using three steps. HCFO-1233xf is converted into HCFC-244bb in a liquid-phase reactor. The catalyst is antimony halide. The reactor adopts TFE or PFA as the inner lining. The defect is that the reactor is seriously corroded inside and bulged. It is difficult to select equipment. The third step, namely saponification, generates a huge amount of waste water, waste gas and waste solids, and has a low yield.
- Aiming at defects in the prior arts, this invention provides a method for co-production of 1-chloro-3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. This method is simple in process, low in investment, low in energy consumption and high in catalyst conversion rate.
- In order to solve the above technical problems, this invention adopts the following technical solution: a method for co-production of 1-chloro-3,3,3-,trifluoropropene, 2,3,3,3-,tetrafluoropropene and 1,3,3,3-,tetrafluoropropene includes the following steps:
- (a) Hydrogen fluoride and 1,1,1,3,3-pentachloropropane (HCC-240fa) are preheated and then directed into a first reactor in a molar ratio of 9-15:1. The first reactor includes two sections, namely an upper section and a lower section. The upper section is filled with an aluminum oxide supported chromium metal catalyst, and the lower section is filled with a chromic oxide supported indium metal catalyst. The hydrogen fluoride and the 1,1,1,3,3-pentachloropropane are reacted in the upper section of the first reactor at a temperature of 200-400° C. and at an air flow rate of 300-1,000 h−1. The reaction product thereof enters the lower section of the first reactor to continuously react with the 1,1,2,3-tetrachloropropane, and the molar ratio of the 1,1,2,3-tetrachloropropane to the hydrogen fluoride is 3-5:9. A reaction product of the first reactor is obtained.
- (b) The reaction product of the first reactor obtained in step (a) is directly directed into a second reactor, and the reaction product of the first reactor catalyzed by a catalyst of the second reactor at a temperature of 250-450° C. and at an air flow rate of 500-1,500 h−1. A reaction product of the second reactor is obtained.
- (c) The reaction product of the second reactor obtained in step (b) is directed into a hydrogen chloride tower to perform separation to obtain a tower bottom fraction and an tower top fraction of the hydrogen chloride tower. The tower top fraction is hydrogen chloride. The hydrogen chloride is refined to obtain hydrochloric acid;
- (d) The tower bottom fraction of the hydrogen chloride tower is sequentially passed through a water washing tower, an alkaline washing tower and a drying tower to remove hydrogen fluoride and hydrogen chloride, and then enter a first rectifying tower to perform rectification. A tower bottom fraction and a tower top fraction of the first rectifying tower are obtained.
- (e) The tower bottom fraction of the first rectifying tower is directed into a second rectifying tower for separation to obtain a product of 1-chloro-3,3,3-trifluoropropene and a tower top fraction of the second rectifying tower. The tower top fraction of the first rectifying tower is direct into a third rectifying tower for separation to obtain a product of 2,3,3,3-tetrafluoropropene at the top of the third rectifying tower and a 1,3,3,3-tetrafluoropropene product at the bottom of the third rectifying tower.
- As a preferable embodiment of this invention, the tower top fraction of the second rectifying tower obtained in step (e) may be circulated to reenter the second reactor.
- As a preferable embodiment of this invention, in step (a), the molar ratio of the hydrogen fluoride to the 1,1,1,3,3-pentachloropropane is preferably 9-12:1; the reaction temperature is preferably 250-320° C. and the air flow rate is preferably 500-800 h−1.
- As a preferable embodiment of this invention, in step (b), the reaction temperature is preferably 300-400° C., and the air flow rate is preferably 800-1,200 h−1.
- As a preferable embodiment of this invention, in step (a), the loading amount of chromium in the aluminum oxide supported chromium metal catalyst is 5-15 wt % (wt %, weight percentage content).
- As a preferable embodiment of this invention, in step (a), the loading amount of indium in the chromic oxide supported indium metal catalyst is 3-10 wt %.
- As a preferable embodiment of this invention, in step (b), the catalyst in the second reactor comprises the following ingredients in mass percentage: 70-80% of chromium oxide, 10-15% of magnesium oxide, and 5-15% of zinc oxide.
- In this invention, the first reactor is divided into two sections, an upper section and a lower section. The upper section is filled with hydrogen fluoride and 1,1,1,3,3-pentachloropropane from the top, and the lower section is filled with 1,1,2,3-tetrachloropropene. Since the reaction of 1,1,2,3-tetrachloropropene and the HF is a strong exothermic reaction, so that the reacting materials in the upper section may carry heat away, without affecting the conversion rate of the 1,1,2,3-tetrachloropropene. The reaction temperature has a large influence on the activity of the catalyst and the selectivity of products. The increased reaction temperature helps to enhance the activity of the catalyst. Proper control over the reaction temperature may allow the conversion rate of the 1,1,1,3,3-pentachloropropane and the 1,1,2,3-tetrachloropropene to reach 100%. Therefore, the temperature of the upper section of the first reactor of this invention is selected to be 200-400° C., preferably 250-320° C., and the needed temperature of the lower section of the first reactor depends on the heat of the materials in the upper section brought into.
- A fluorine-chlorine exchange reaction and an addition reaction of alkenes occur in the first reactor. The catalyst in the upper section of the first reactor is aluminum oxide supported chromium metal, and the catalyst in the lower section is chromic oxide supported indium metal. The catalyst in the upper section uses aluminum oxide as the support, and is capable of preventing quick reduction of the specific area of the catalyst due to strong heat release during reaction between the hydrogen fluoride and the 1,1,1,3,3-pentachloropropane, and the addition of chromium increases the activity of the catalyst. The catalyst in the lower section uses chromic oxide as the support to load indium metal, further enhancing the activity of the catalyst, and ensuring that the 1,1,1,3,3-pentachloropropane and the 1,1,2,3-tetrachloropropene may be completely converted under proper temperature conditions.
- The molar ratio has a relatively large influence on the reaction. The HF required by the reactions in the upper and lower sections of the first reactor is imported from the upper section. Theoretically, 5 moles of HF are needed for the reaction of each mole of the 1,1,1,3,3-pentachloropropane in the upper section, and 3-4 moles of HF are needed for the reaction of each mole of the 1,1,2,3-tetrachloropropene in the lower section. A huge amount of HF in the upper section can carry heat away, and the reaction heat in the lower section is supplied by and brought away by the upper section, and comprehensive utilization of the heat and reducing energy consumption is thus realized. However, excessive HF results in an increase in the amount of acid-washing aqueous alkaline waste. Therefore, in this invention, the molar ratio of the HF to the 1,1,1,3,3-pentachloropropane is controlled to be 9-15:1, preferably 9-12:1.
- In the second reactor, HFO-1233zd and HCFO-1233xf perform a fluorine-chlorine exchange reaction with the HF. Temperature is a main factor that determines the reaction. If the temperature is too high, it leads to higher conversion rates of the HFO-1233zd and HCFO-1233xf, higher yields of HFO-1234ze and HFO-1234yf, and a lower yield of co-produced HFO-1233zd, and the catalyst is deactivated due to fast carbon deposition. If the temperature is too low, it leads to lower conversion rates of the HFO-1233zd and HCFO-1233xf, a larger amount of HCFO-1233xf returned back into the reactor, a higher yield of HFO-1233zd, lower yields of HFO-1234ze and HFO-1234yf. Therefore, the reaction temperature can be adjusted according to the demands of the market and products. The reaction temperature of the second reactor of this invention is selected to be 250-450° C., preferably 300-400° C.
- In this invention, the main cause of deactivating the catalyst in the two-step reaction is carbon deposition, resulting in a reduction in the specific area and micropores of the catalyst. The activity of the catalyst can be recovered by a method of regeneration. At a temperature of 330-380° C., air and nitrogen gas are directed in a ratio to remove the carbon deposited on the surface of the catalyst.
- The catalysts in the upper and lower sections of the first reactor of this invention are prepared by methods known in the prior art. The aluminum oxide support is immersed in a chromium solution with a certain concentration; after reaching a certain loading amount, the obtained substance is dried and calcined to obtain a catalyst precursor; and the catalyst precursor is fluorinated to obtain the catalyst for the upper section. The chromic oxide support is immersed in indium solution with a certain concentration; after reaching a certain loading amount, the obtained substance is dried and calcined to obtain the catalyst precursor; and the catalyst precursor is fluorinated to obtain the catalyst for the lower section. The catalyst used in the second reactor may be a catalyst which takes chromic oxide known in the art as the active ingredient. The catalyst is prepared using the steps: reacting nitrates of chromium, magnesium and zinc with a precipitant to generate suspended hydroxide solids; filtering, obtaining oxides of chromium, magnesium and zinc after washing, drying and calcining; obtaining the catalyst precursor by pelleting, pressing and molding; and obtaining the catalyst by fluorinating. The activation of the catalyst may proceed in other reactors.
- The first reactor and the second reactor in this invention may be isothermal or heat-insulating type reactors. The material of the reactors may select a material resistant to acid corrosion, for example, Inconel.
- Compared with the prior art, this invention has the following advantages:
- 1. Simple process: The first reactor is filled with two different types of catalysts, so that two reactions may occur at the same time to simplify the process flow.
- 2. High conversion rate: By adjusting the reaction temperature, the conversion rates of HCC-240fa and 1,1,2,3-tetrachloropropene may reach 100%.
- 3. Low energy consumption: The lower section of the first reactor is not required to be heated from the outside, and the heat required by the reaction is supplied by the material coming from the upper section to realize comprehensive heat utilization and reducing energy consumption.
- 4. Small investment, and high operation flexibility: A set of devices can produce three products, namely HFO-1233zd, HFO-1234yf and HFO-1234ze, and the product ratios can be flexibly adjusted according to the demands of the market, thereby obviously reducing investments in the devices.
-
FIG. 1 is a process flowchart of this invention. - As shown in the FIGURE, 1—preheater; 2—first reactor; 3—second reactor; 4—hydrogen chloride tower; 5—water washing tower; 6—alkaline washing tower; 7—drying tower; 8—first rectifying tower; 9—second rectifying tower; 10—third rectifying tower; 11—21 pipelines.
- The process flow of this invention can be seen in
FIG. 1 . The first reactor is divided into two sections, namely an upper section and a lower section, each filled with a different catalyst. Raw materials, hydrogen fluoride and HCC-240fa, are input in a certain molar ratio into apreheater 1 via apipeline 11 to be preheated, and then enter the top of the upper section of afirst reactor 2 via apipeline 12. 1,1,2,3-tetrachloropropene is input into the lower section of thefirst reactor 2, and a mixture of HFO-1233zd, HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained after reaction. The mixture is directly input into asecond reactor 3 via apipeline 13 without separation. After reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained and enters ahydrogen chloride tower 4 via apipeline 14 to obtain a tower bottom fraction and an tower top fraction. The tower top fraction of thehydrogen chloride tower 4 is hydrogen chloride, and the hydrogen chloride is separately refined to obtain hydrochloric acid. The tower bottom fraction enters awater washing tower 5 via apipeline 15 to be washed with water, then enters analkaline washing tower 6 via apipeline 16 to be washed with alkali, next enters a dryingtower 7 via apipeline 17 to be dried to obtain a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd. The mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf and HFO-1233zd enters afirst rectifying tower 8 via apipeline 18 to obtain a tower bottom fraction and an tower top fraction. The tower top fraction of thefirst rectifying tower 8 includes HFO-1234yf and HFO-1234ze, and enters athird rectifying tower 10 via apipeline 21. A product HFO-1234yf is obtained at the top of thethird rectifying tower 10, and a product HFO-1234ze is obtained in the tower bottom of thethird rectifying tower 10. The tower bottom fraction of thefirst rectifying tower 8 enters asecond rectifying tower 9 via apipeline 19 to be separated to obtain a tower bottom fraction and an tower top fraction of thesecond rectifying tower 9. The fraction at the top of thesecond rectifying tower 9 mainly includes HCFO-1233xf and carries a small amount of HFO-1233zd, and is circulated to enter the second reactor. A product HFO-1233zd is obtained in the tower bottom of thesecond rectifying tower 9. - This invention is described in further detail in conjunction with embodiments. However, this invention is not merely limited to the following embodiments.
- First, 100 mL of Cr2O3/In catalyst (3 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 10% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.
- Then, the first reactor is heated to a temperature of 350° C., while HF and nitrogen gas are input to perform activation for 50 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min. The second reactor is heated to a temperature of 350° C., while HF and nitrogen gas are input to perform activation for 40 hours at an HF flow rate of 100 g/h and a nitrogen flow rate of 1.5 L/min. In this way, the activation of the catalysts in the two reactors is completed. The first reactor and the second reactor are heated, a temperature increase rate is 1° C./min from room temperature to 150° C., and a temperature increase rate is 0.5° C./min when the temperature is above 150° C.
- Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1. The temperature of the upper section of the first reactor is controlled to be 280° C., the air flow rate is controlled to be 500 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 1 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300° C., and the air flow rate is 800 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 1 after gas chromatography analysis.
-
TABLE 1 Composition of Organics at the reactor exit in Embodiment 1fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 1.5 55 43.4 0.1 Second reactor (%) 22.5 28.6 18.5 30.3 0.1 - First, 100 mL of Cr2O3/In catalyst (5 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (15 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 70% of chromic oxide, 15% of magnesium oxide, and 15% of zinc oxide) is placed into a second reactor.
- The activation method of the catalysts is the same as that in
Embodiment 1. - Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1. The temperature of the upper section of the first reactor is controlled to be 300° C., the air flow rate is controlled to be 600 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 5:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 2 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 320° C., and the air flow rate is 800 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 2 after gas chromatography analysis.
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TABLE 2 Composition of Organics at the reactor exit in Embodiment 2fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 1.8 46.9 51.2 0.1 Second reactor (%) 25.8 31.6 17.1 25.3 0.2 - First, 100 mL of Cr2O3/In catalyst (10 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (5 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 12% of magnesium oxide, and 8% of zinc oxide) is placed into a second reactor.
- The activation method of the catalysts is the same as that in
Embodiment 1. - Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 15:1. The temperature of the upper section of the first reactor is controlled to be 320° C., the air flow rate is controlled to be 1000 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 3:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 3 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 350° C., and the air flow rate is 1200 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 3 after gas chromatography analysis.
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TABLE 3 Composition of Organics at the reactor exit in Embodiment 3fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 2.7 38.6 58.5 0.2 Second reactor (%) 31.3 29.4 16.6 22.6 0.1 - First, 100 mL of Cr2O3/In catalyst (8 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (8 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 15% of magnesium oxide, and 5% of zinc oxide) is placed into a second reactor.
- The activation method of the catalysts is the same as that in
Embodiment 1. - Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 12:1. The temperature of the upper section of the first reactor is controlled to be 400° C., the air flow rate is controlled to be 300 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 4 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 400° C., and the air flow rate is 500 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 4 after gas chromatography analysis.
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TABLE 4 Composition of Organics at the reactor exit in Embodiment 4fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 3.1 44.5 52.3 0.1 Second reactor (%) 28.6 25.3 18.2 27.8 0.1 - First, 100 mL of Cr2O3/In catalyst (6 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 80% of chromic oxide, 10% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.
- The activation method of the catalysts is the same as that in
Embodiment 1. - Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 10:1. The temperature of the upper section of the first reactor is controlled to be 300° C., the air flow rate is controlled to be 500 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 5 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 330° C., and the air flow rate is 600 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 5 after gas chromatography analysis.
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TABLE 5 Composition of Organics at the reactor exit in Embodiment 5fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 1.0 52.8 46.1 0.1 Second reactor (%) 15.3 22.5 31.2 31 0 - First, 100 mL of Cr2O3/In catalyst (8 wt % In loading amount) is placed in the lower section of a first reactor, and 100 mL of Al2O3/Cr catalyst (10 wt % of Cr loading amount) is placed in the upper section of the first reactor. Next, 200 mL of chromium-magnesium-zinc catalyst (the catalyst includes, in mass percentage, 75% of chromic oxide, 15% of magnesium oxide, and 10% of zinc oxide) is placed into a second reactor.
- The activation method of the catalysts is the same as that in
Embodiment 1. - Subsequently, materials are fed for reaction. The HF and HCC-240fa are input into a preheater to be preheated, where the molar ratio of the HF to HCC-240fa is 9:1. The temperature of the upper section of the first reactor is controlled to be 300° C., the air flow rate is controlled to be 600 h−1, the molar ratio of the 1,1,2,3-tetrachloropropene to the HF is 4:9. A mixture of HFO-1233zd, a small amount of HFO-1234ze, HCFO-1233xf, hydrogen chloride and hydrogen fluoride is obtained in the first reactor. Composition of organic compounds are shown in Table 6 after gas chromatography analysis. The mixture coming from the outlet of the first reactor directly enters the second reactor, where the temperature of the second reactor is 300° C., and the air flow rate is 700 h−1. After a reaction, a mixture of HFO-1234yf, HFO-1234ze, HCFO-1233xf, HFO-1233zd, hydrogen chloride and hydrogen fluoride is obtained. Composition of organic compounds are shown in Table 6 after gas chromatography analysis.
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TABLE 6 Composition of Organics at the reactor exit in Embodiment 6fraction HFO- HFO- HFO- HCFO- Reactor 1234yf 1234ze 1233zd 1233xf Others First reactor (%) 0 1.2 48.5 50.2 0.1 Second reactor (%) 20.1 25.3 20.4 34 0.2
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US20200039902A1 (en) * | 2017-07-24 | 2020-02-06 | Zhejiang Quhua Fluor-Chemistry Co Ltd | Method for co-producing low-carbon foaming agents |
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US11913681B2 (en) | 2018-10-26 | 2024-02-27 | The Chemours Company Fc, Llc | HFO-1234ZE, HFO-1225ZC and HFO-1234YF compositions and processes for producing and using the compositions |
US11927373B2 (en) | 2018-10-26 | 2024-03-12 | The Chemours Company Fc, Llc | HFO-1234ze, HFO-1225zc and HFO-1234yf compositions and processes for producing and using the compositions |
CN114276208A (en) * | 2021-11-26 | 2022-04-05 | 西安近代化学研究所 | Production equipment and production method of 1,1,1,2,3,3, 3-heptafluoropropane |
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