CN111635291A - Preparation process of monochlorodifluoromethane - Google Patents
Preparation process of monochlorodifluoromethane Download PDFInfo
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- CN111635291A CN111635291A CN202010517438.2A CN202010517438A CN111635291A CN 111635291 A CN111635291 A CN 111635291A CN 202010517438 A CN202010517438 A CN 202010517438A CN 111635291 A CN111635291 A CN 111635291A
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- trifluoromethane
- reaction
- chlorine
- trichloromethane
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- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims abstract description 266
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000002994 raw material Substances 0.000 claims abstract description 55
- 238000000926 separation method Methods 0.000 claims abstract description 55
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 47
- 239000000460 chlorine Substances 0.000 claims abstract description 46
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 46
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229960001701 chloroform Drugs 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 26
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 24
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 20
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000654 additive Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- RZSJYVBYLBNFGQ-UHFFFAOYSA-N difluoromethane hydrochloride Chemical compound FCF.Cl RZSJYVBYLBNFGQ-UHFFFAOYSA-N 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 36
- 230000003197 catalytic effect Effects 0.000 claims description 34
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 23
- 239000006227 byproduct Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 150000001805 chlorine compounds Chemical group 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- LOZOAPSBGHOALW-UHFFFAOYSA-N 1h-imidazol-1-ium;1,1,2,2-tetrafluoroethanesulfonate Chemical compound [NH2+]1C=CN=C1.[O-]S(=O)(=O)C(F)(F)C(F)F LOZOAPSBGHOALW-UHFFFAOYSA-N 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- TYWBQDXFYZUNHV-UHFFFAOYSA-N pyridine 1,1,2,2-tetrafluoroethanesulfonic acid Chemical compound FC(C(S(=O)(=O)O)(F)F)F.N1=CC=CC=C1 TYWBQDXFYZUNHV-UHFFFAOYSA-N 0.000 claims description 3
- KZWJWYFPLXRYIL-UHFFFAOYSA-M 1,1,2,2-tetrafluoroethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)F KZWJWYFPLXRYIL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000000306 component Substances 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- KZWJWYFPLXRYIL-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)F KZWJWYFPLXRYIL-UHFFFAOYSA-N 0.000 abstract 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 50
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 238000001035 drying Methods 0.000 description 19
- 238000003682 fluorination reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000002243 precursor Substances 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 12
- 238000002791 soaking Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 11
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 229910052772 Samarium Inorganic materials 0.000 description 3
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
-
- B01J35/613—
-
- B01J35/647—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/40—Improvements relating to fluorochloro hydrocarbon, e.g. chlorodifluoromethane [HCFC-22] production
Abstract
The invention discloses a preparation process for producing a difluorochloromethane product with high added value by taking trifluoromethane, trichloromethane and chlorine as raw materials, wherein the preparation process uses a microchannel reactor, effectively promotes the reaction of the trifluoromethane and the chlorine and the reaction of the trifluoromethane and the trichloromethane by setting active components, carriers, metal doping components and rare earth additives with specific types and proportions, and adopts multilevel micro/mesoporous Cr2O3The carrier is used for promoting the exchange reaction of fluorine and chlorine and further improving the performance of the catalyst, during the reaction, the excess amount of trifluoromethane is selected to promote the full conversion of trichloromethane and chlorine, and simultaneously, in a subsequent separation system, proper extraction liquid tetrafluoroborate or tetrafluoroethanesulfonic acid is selectedAnd acid salt, namely, the trifluoromethane is fully extracted and recovered and is used as a reaction raw material, and the reaction raw material is circularly fed into the initial reactor, so that the full utilization of the raw material is promoted.
Description
Technical Field
The invention relates to a preparation process of difluorochloromethane, in particular to a preparation process for producing difluorochloromethane products with high added value by taking trifluoromethane, trichloromethane and chlorine as raw materials to react in the presence of a catalyst.
Background
The chlorodifluoromethane is named as freon-22 (HCFC-22), the Ozone Depletion Potential (ODP) is 0.05, the GWP is 1780, the chlorodifluoromethane is the most widely used HCFC substance, is mainly applied to foaming agents, aerosols, refrigerants and other chemical product raw materials, and the production and consumption of the chlorodifluoromethane are developed rapidly in China.
Trifluoromethane (CHF)3) Also called fluoroform, which is a byproduct of industrial preparation of chlorodifluoromethane (HCFC-22), the content of the generated HCFC-22 is about 1.5 to 3 weight percent, and the annual output in China is about 1.3 to 1.5 ten thousand tons.
CHCl3+2HF→CHClF2+2HCl
CHClF in the course of the reaction2Continued fluorination produces CHF as a by-product3。
Trifluoromethane is a very high potential greenhouse effect (equivalent to CO)214800 times of the standard value) and long-life greenhouse gases, with the increase of the accumulation amount in the atmosphere, the ecological hidden trouble is being formed, and the treatment and the conversion and the utilization of the trifluoromethane are not slow.
Currently, trifluoromethane has been regulated to be emitted internationally and is targeted for carbon trading. The traditional treatment methods for trifluoromethane are mainly thermal incineration, plasma treatment and strong base decomposition. The methods not only can not obtain economic benefits, but also can consume a large amount of energy, and have the defects of high cost, high energy consumption, environmental pollution and the like, so that the exploration of an environment-friendly and sustainable method for utilizing the trifluoromethane as a raw material is very important and critical.
The separation and recovery of the by-product trifluoromethane of the chlorodifluoromethane (HCFC-22) have been studied, the recovery mostly adopts the membrane separation, rectification, absorption tower and other processes, and the problems of complex recovery equipment, high cost or purity to be improved still exist.
The patent application CN102101651B discloses a recovery method of a difluoromethane chloride byproduct trifluoromethane, which comprises the steps of inputting an organic mixture of difluoromethane chloride and hydrogen chloride obtained in the production of difluoromethane chloride into an internally-refluxing hydrogen chloride tower, strictly controlling the pressure of the hydrogen chloride tower to be 1.4-1.6 MPa, and the temperature of the tower top to be-20 to-5 ℃; collecting crude hydrogen chloride from the tower top; the crude hydrogen chloride sequentially passes through a first-stage graphite absorber, a second-stage graphite absorber and a third-stage graphite absorber which are connected in series, and the hydrogen chloride is collected in a concentrated hydrochloric acid storage tank; and the trifluoromethane in the crude hydrogen chloride is collected from the top of the third-stage graphite absorber because the crude hydrogen chloride is insoluble in water, is input into a trifluoromethane recovery system through a pipeline, and is subjected to buffer compression and rectification to prepare the trifluoromethane with the purity of more than 99 vol%.
Patent application CN101239884A discloses a method for separating a mixed gas of difluoromethane chloride and trifluoromethane by using a membrane, which comprises the steps of enabling the mixed gas of difluoromethane chloride and trifluoromethane which cannot be separated after condensation in the process of producing a refrigerant R22 to pass through a gas membrane separation device at ambient temperature under certain pressure, enabling the difluoromethane chloride to preferentially permeate and pass through a gas separation membrane to reach the other side, dividing the mixed gas into two streams by the gas separation membrane, compressing the enriched difluoromethane chloride permeate gas and then refluxing into a condensation tower, recovering the cooled and liquefied difluoromethane chloride as a product, and directly sending the high-concentration trifluoromethane permeate gas to a torch for combustion after reaching the standard through detection. The gas separation membrane is a dissolving-analyzing membrane made of high polymer materials and is formed by compounding a rubber-state high polymer coating and a glass-state high polymer supporting layer.
The patent application CN100424057C discloses a method for separating and recovering trifluoromethane, which comprises the steps of producing difluorochloromethane vent gas, compressing the gas by a compressor, then entering a degassing tower, separating in the degassing tower to obtain a crude product of trifluoromethane and difluorochloromethane, wherein the temperature of the degassing tower is 20-50 ℃, and the pressure of the degassing tower is 3.5-5.5 MPa; the crude trifluoromethane enters a rectifying tower, the temperature of the rectifying tower is 20-50 ℃, the pressure is 3.5-5.5 MPa, and the crude trifluoromethane is rectified to obtain the trifluoromethane with the purity of 99.5-100%; and cooling and liquefying by a finished product condenser, and collecting in a trifluoromethane finished product tank.
The conversion and reuse of the by-product trifluoromethane of difluoromethane chloride (HCFC-22) mainly comprises the following steps: the hydrogenolysis method is used for preparing difluoromethane, the bromination method is used for preparing trifluorobromomethane, tetrafluoroethylene and hexafluoropropylene are prepared by single cracking under the high temperature condition, and 1, 1-difluoroethylene and the like are prepared by co-cracking with methane. However, the method is usually carried out better under the action of a catalyst, and the use of a suitable catalyst can reduce the reaction temperature, thereby reducing side reactions and byproducts, and improving the conversion rate of raw materials and the selectivity of target products, so that the preparation and selection of the catalyst become important for research.
Patent application US2003/0166981 discloses the production of a mixture of Tetrafluoroethylene (TFE), Hexafluoropropylene (HFP), pentafluoroethane (HFC-125), heptafluoropropane (HFC-227EA) using pyrolysis of trifluoromethane with difluoromethane chloride at a temperature of 690-775 ℃ in the presence of gold as a catalyst. The molar ratio of trifluoromethane to difluoromethane chloride is at least 5:1 to about 2: 1. however, like the above method, the pyrolysis temperature is high and the reaction conditions are severe.
Patent application CN104628513B discloses a method for resource utilization of trifluoromethane, wherein trifluoromethane and one or more halogenated hydrocarbons are mixed and converted into a product containing difluorochloromethane under the action of a catalyst, unreacted trifluoromethane and other reaction products circularly enter a reactor to participate in the reaction, and the catalyst is Cr2O3，Sm2O3/MgO，La2O3/Al2O3Partially fluorinatedOf Cr (C)2O3，Cr2O3The catalyst comprises graphite and Fe/activated carbon, wherein the halohydrocarbon is RCHaXbFc, R in the formula is H, alkyl or chlorofluorocarbon containing halogen molecules, X is Cl or Br, a is more than or equal to 0 and less than or equal to 2, b is more than or equal to 1 and less than or equal to 3, c is more than or equal to 0 and less than or equal to 2, and the catalyst auxiliary agent is La or Sm.
The patent application CN103467239B discloses a method for preparing difluoromethane chloride by cracking trifluoromethane, which comprises the steps of mixing raw materials of trifluoromethane and methane chloride according to the molar ratio of 0.1-10, putting the mixture into a reactor filled with a catalyst, staying for 3-30 seconds at the temperature of 150-350 ℃ for cracking reaction to obtain a mixture containing trifluoromethane, methane chloride, monofluorodichloromethane and difluoromethane chloride, directly separating the difluoromethane chloride, reacting the separated monofluorodichloromethane with hydrogen fluoride to produce difluoromethane chloride, and continuously taking the separated trifluoromethane and methane chloride as a reaction mixture after separation and recovery. The catalyst is metal fluoride of magnesium, aluminum, zinc and chromium or the mixture of the metal fluorides. The raw material contains chlorine, and the molar ratio of the trifluoromethane to the chlorine is 1.
The method has the problems of complex process for separating and purifying the trifluoromethane or low purity, poor product selectivity for producing the difluoromethane chloride, low conversion rate and the like. Through intensive research, the invention improves the operability of the purification of the trifluoromethane raw material by arranging a special extracting agent and an extracting process, reduces the purification cost and promotes the circulation of the raw material. Thereby carrying out resource utilization on the trifluoromethane and converting the trifluoromethane into a compound with higher value. The preparation process for producing the difluorochloromethane with high added value by using the trifluoromethane, the trichloromethane and the chlorine as raw materials and adopting the microchannel reactor can effectively reduce the production cost, improve the economic benefit and simultaneously have remarkable social benefit.
Disclosure of Invention
The invention provides a preparation process for producing difluorochloromethane by using trifluoromethane, trichloromethane and chlorine as raw materials.
The following reactions occur in a reaction system taking trifluoromethane, trichloromethane and chlorine as raw materials, wherein the target reactions are as follows:
2CHF3+CHCl3+Cl2→CHClF2+CHFCl2+CF4+HCl(1)
side reactions which may also occur therein are as follows:
CHF3+Cl2→CCl2F2+HF (2)
CHF3+Cl2→CClF3+HCl (3)
CHF3unavoidable side reactions occur during the conversion process, such as CHF3Conversion to CCl2F2And CClF3. The proper catalyst can control the occurrence of side reaction, thereby reducing by-products and improving the conversion rate of raw materials and the selectivity of target products. Therefore, catalyst preparation and selection is of critical importance.
The catalytic system of the invention contains a main catalyst, a metal doping component and a rare earth auxiliary agent.
The main catalyst comprises the active components of chlorides, carbonates, nitrates, acetates or sulfates corresponding to chromium, aluminum and magnesium metals commonly used for fluorine-chlorine exchange reaction and Cr loaded in a multi-stage micro/mesoporous2O3The above.
For Cr containing a certain proportion of microporous structure2O3Vector, studies showed that: the large and medium pores with the aperture larger than 2nm have diffusion function; can adsorb halohydrocarbon reactant, promotes fluorine-chlorine exchange reaction, is microporous with pore diameter less than 2nm, and simultaneously avoids the problem that the pore diameter is small and limits reactant molecules to diffuse to active center on the surface of catalyst, the invention adopts multi-stage micro/mesoporous Cr2O3Thereby having the advantages of both mesopores and micropores.
And the activity of the catalyst can be greatly influenced by selecting proper micropore and mesopore proportion. The invention uses a specific surface and pore size analyzer to measure BET specific surface area and BJH pore size distribution, and utilizes N at liquid nitrogen temperature (77K)2And (4) measuring by an adsorption method, and respectively calculating the specific surface area and pore size distribution according to a BET model and a BJH model. Before testing, the samples were subjected to heat treatment under vacuum (80 ℃ C.)And 2 hours, so as to remove water and other impurities adsorbed on the surface of the material. More preferably, the specific surface area of the catalyst carrier is 15-120 m2(iv)/g, more preferably 56 to 120m2(ii)/g; the average pore diameter is 0.2-12 nm. Further, 10-70% of the pores have a diameter of 0.2-2 nm, and 10-50% of the pores have a diameter of 15-50 nm; preferably, 40-70% of the pores have a diameter of 0.2-2 nm; 10-20% of the pores have a diameter of 15-50 nm.
Preferably, the mass ratio of the carrier to the active component of the main catalyst is 100: (0.5 to 25); preferably, the mass ratio of the carrier to the active component of the main catalyst is 100: (0.8 to 20).
The catalytic system of the invention is preferably added with a metal doping component and a rare earth promoter. The metal doping component is one or a combination of more of Co, Ni, Ru, Rh, Pd, Pt, Ag and Au; the rare earth additive is one or more of oxides of rare earth elements or chlorides, carbonates, nitrates, acetates and sulfates thereof, preferably oxides and chlorides, and further preferably the rare earth elements are La and/or Sm. The particle size distribution of the solid particles of the catalytic system is within the range of 200-800 meshes, and preferably 300-500 meshes.
In the catalytic system provided by the invention, the ratio of the main catalyst, the metal doping component and the rare earth additive meets the requirement that the main catalyst, the metal doping component and the rare earth additive can be used for resource utilization of trifluoromethane. As a preferred technical solution, the mass ratio of the main catalyst, the metal doping component and the rare earth additive is (1:0.01:0.02) - (1:0.3:0.6), and further preferably: the mass ratio of the main catalyst, the metal doping component and the rare earth additive is (1:0.01:0.02) - (1:0.05: 0.09).
The catalytic system formed by the main catalyst, the metal doping component and the rare earth additive has the following requirements: the catalyst needs to be in sufficient, even excess, to achieve optimal selectivity and conversion. The physical properties are not limited, and may be, for example, round balls, tablets, and granules.
The invention also provides a preparation method of the catalytic system, which comprises the following steps:
the main catalyst is prepared by adopting an impregnation method, and the specific preparation method comprises the following steps: adding deionized water into active component metal salt, stirring and dissolving to obtain metal salt solution, namely dipping solution; and (3) soaking the dried carrier in a soaking solution at room temperature for 3-8 h, filtering, drying in a drying oven at 110-120 ℃ for 8-13 h to obtain a precursor, roasting the precursor in an inert gas atmosphere, and roasting at 500 ℃ for 5h to obtain the main catalyst. Wherein, the inert gas is preferably argon or helium.
The addition method of the metal doping component and the rare earth additive adopts the conventional method for preparing the existing catalyst, such as: physically grinding the catalyst with a main body catalyst, or doping by a coprecipitation method metal salt solution precursor wet mixing method or an impregnation method and then roasting.
The catalytic system of the invention is pretreated by fluorination, preferably by HF, before use. The specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst, a metal doping component and a rare earth auxiliary agent) in a catalyst reactor, and introducing an HF-inert gas mixture with a molar ratio of (3-8): 1, wherein the preferred molar ratio is (5-7): 1, preferably an inert gas such as helium, argon. The fluorination pretreatment temperature is 180-380 ℃, and preferably 240-360 ℃; the fluorination treatment is carried out for 15 to 400 minutes, preferably 140 to 220 minutes.
The invention provides a preparation process for producing a difluoromethane chloride product by taking trifluoromethane, trichloromethane and chlorine as raw materials, which comprises the following specific steps:
step 1), sending a mixed gas (1) containing a trifluoromethane byproduct obtained by preparing monochlorodifluoromethane (HCFC-22) into an extraction separation tower, and purifying to obtain a high-purity trifluoromethane gas (2);
the extract in the extraction separation column is selected from tetrafluoroborate, tetrafluoroethanesulfonate, preferably imidazole tetrafluoroborate, imidazole tetrafluoroethanesulfonate, pyridine tetrafluoroborate or pyridine tetrafluoroethanesulfonate, and more preferably 1-butyl-3-methylimidazole tetrafluoroborate.
The extraction pressure is 0.1 MPa-2.5 MPa, the extraction temperature is 5-50 ℃, and the preferred temperature is 15-35 ℃. The extract absorbs more than 80% of the trifluoromethane in the gaseous mixture, ideally, substantially all of the trifluoromethane is absorbed by the extractant, the extractant containing the absorbed trifluoromethane can be heated in the stripping tower to release the trifluoromethane and realize the regeneration of the extractant, and the extractant after the extraction can be recycled to the extraction separation tower for reuse. The extraction liquid of the invention has high extraction precision, can effectively remove impurities to obtain high-purity trifluoromethane (more than 99 percent), has recyclable performance and reduces the production cost.
And 2), feeding the extracted and purified high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, introducing trichloromethane and chlorine, and reacting in the presence of the catalytic system to obtain a reaction product stream (3) containing the difluorochloromethane.
The reaction temperature in the microchannel reactor is 200-260 ℃, the reaction pressure is 0.5-3 Mpa, and the materials are ensured to be in a gas-liquid mixed state.
The amount of the raw material trifluoromethane is in excess, and the molar ratio of trifluoromethane to chloroform to chlorine gas is preferably (1:0.6:1) to (12:0.6:1), more preferably (2.5:0.6:1) to (6:0.6: 1).
The reaction of trifluoromethane, trichloromethane and chlorine to form difluoromethane chloride is shown in the formula (1), the reaction is exothermic, the reaction temperature is high, the temperature is easy to be out of control, and chlorine and possibly generated hydrogen chloride gas have certain dangerousness. The reaction of the present invention cannot be carried out at 200 ℃ or lower, and therefore, the present reaction system has strict requirements for precise control of temperature. The microchannel reactor has thousands of microchannels, so that the microchannel reactor has extremely large specific surface area which can reach hundreds of even thousands of times of the specific surface area of a common reaction kettle, thereby having excellent heat transfer and mass transfer capacity, and the optimal heat transfer coefficient can reach 30 kW/(m)2K), the reactant in the microchannel can carry out efficient heat exchange with the wall surface, the temperature uniformity is good, and the reaction zone is close to constant temperature, so that the heat to be released can be efficiently conducted in time and absorbed instantly, thereby ensuring that the reaction temperature fluctuation is small and stable, and being beneficial to the stable proceeding of chemical reaction.
The faces of the reaction channels of the microchannel reactor are defined by the reaction channel walls. The walls can be made of hard materials, so that the durability, the corrosion resistance, the high temperature resistance, the high pressure resistance and the good heat conductivity are better ensured. The hard material can be selected from: ceramics, metals, metal alloys, preferably the hard material is stainless steel or monel.
The equivalent diameter range of the micro-channel reactor is 50-700 mu m, and each micro-channel reactor comprises 100-8000 process channels. Not only has small channel size, but also has channel diversity, and the channel cross section can have any shape, such as but not limited to the following: circular, semicircular, elongated, square, trapezoidal, triangular, hourglass, V-shaped, S-shaped, star-shaped, octagonal, and the like, with hourglass, S-shaped, star-shaped, and octagonal preferred. The cross-sectional shape or size of the microchannel may vary in the length direction, with the length of the channel being 0.5 to 50m, preferably 5 to 30 m.
And 3) feeding the reaction product flow (3) containing the difluorochloromethane into a separation system, and separating to obtain the target product difluorochloromethane, wherein the separation system comprises a plurality of separation towers, a standing tank and an extraction separation tower. And (3) feeding the reaction product flow (3) of the microchannel reactor into a separation tower, rectifying and separating to obtain a target product of difluoro-monochloromethane, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane serving as a raw material into the microchannel reactor.
Compared with the prior art, the invention has the following technical characteristics and beneficial effects:
1. the difluoromethane monochloride product with high added value is produced by taking the trifluoromethane, the trichloromethane and the chlorine as raw materials, so that the resource utilization of the by-product trifluoromethane is promoted, and remarkable economic benefit and social benefit are generated.
2. By setting specific types and proportions of active components, carriers, metal doping components and rare earth additives, the reaction of trifluoromethane, trichloromethane and chlorine is effectively promoted, the selectivity of a target product, namely difluorochloromethane, is improved, and the occurrence of side reactions is reduced; adopts multi-stage micro/mesoporous Cr2O3And the catalyst performance is further improved by the carrier.
3. For the arrangement of reaction raw materials, the excessive amount of the trifluoromethane is selected to promote the sufficient conversion of chlorine and trichloromethane, and meanwhile, in a subsequent separation system, proper extraction liquid of imidazole tetrafluoroborate, imidazole tetrafluoroethanesulfonate, pyridine tetrafluoroborate or pyridine tetrafluoroethanesulfonate is selected to fully extract and recover the trifluoromethane and serve as the reaction raw materials to circularly enter an initial reactor, so that the purity of the raw materials is improved, the sufficient utilization of the raw materials is promoted, and the production cost is effectively reduced.
4. The microchannel reactor is selected as a reaction generating device, and suitable reaction process conditions are explored through multiple tests, so that the uniformity of the reaction temperature is improved, the stable reaction is ensured, and the safety of process operation is improved.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing difluoromethane chloride according to the embodiment of the present invention.
Detailed Description
The technical solution and effects of the present invention will be further described below by way of specific embodiments. The following embodiments are merely illustrative of the present invention, and the present invention is not limited to the following embodiments or examples. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
Example 1:
preparing a main catalyst by adopting an impregnation method: adding deionized water into nitrate of an active component Al, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying the multi-stage micro/mesoporous Cr2O3And (3) soaking the carrier in the soaking solution at room temperature for 4h, then filtering, putting the carrier into a drying oven for drying at 114 ℃ for 8h to obtain a precursor, roasting the precursor under inert gas argon, and roasting at 500 ℃ for 4h to obtain the main catalyst. Wherein, the multi-level micro/mesoporous Cr2O3Has a specific surface area of 86.5m2(ii)/g, the average pore diameter is 9.5nm, 55.2% of the pores have a diameter of 0.2 to 2nm, and 14.5% of the pores have a diameter of 15 to 50 nm.
Through physically grinding and mixing with a main catalyst, a metal doping component of 2 wt% Ru and a rare earth additive of 5 wt% Sm are added2O3、1wt％SmCl3The addition amount of the catalyst is the main catalystIs 100%.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst, a metal doping component and a rare earth auxiliary agent) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Example 2:
preparing a main catalyst by adopting an impregnation method: adding deionized water into sulfate of an active component Mg, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying the multi-stage micro/mesoporous Cr2O3Dipping the mixture in the dipping solution for 4h at room temperature, then filtering, putting the mixture into a drying oven to be dried for 8h at 114 ℃ to obtain a precursor, finally roasting the precursor under inert gas argon, and roasting for 4h at 500 ℃ to obtain the main catalyst. Wherein, the multi-level micro/mesoporous Cr2O3The specific surface area of the carrier was 85.8m2(ii)/g, the average pore diameter is 9.5nm, 55.2% of the pores have a diameter of 0.2 to 2nm, and 14.5% of the pores have a diameter of 15 to 50 nm.
Through physically grinding and mixing with a main catalyst, a metal doping component of 2 wt% Pd and a rare earth additive of 3 wt% La are added2O3、2wt％LaCl3The amounts added are all based on 100% by mass of the main catalyst.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst, a metal doping component and a rare earth auxiliary agent) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Comparative example 1:
preparing a main catalyst by adopting an impregnation method: adding deionized water into nitrate of an active component Al, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying Al containing a certain proportion of microporous structure2O3Soaking the carrier in the soaking solution at room temperature for 4h, filtering, drying in a drying oven at 114 ℃ for 8h to obtain a precursor, roasting the precursor under inert gas argon, and roasting at 500 ℃ for 4h to obtain the catalyst.
By reacting withPhysically grinding and mixing the main catalyst, and adding 5 wt% of Sm into the main catalyst2O3、1wt％SmCl3The amounts added are all based on 100% by mass of the main catalyst.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst and a rare earth auxiliary agent) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Comparative example 2:
preparing a main catalyst by adopting an impregnation method: adding deionized water into sulfate of an active component Mg, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying Al containing a certain proportion of microporous structure2O3Soaking the carrier in the soaking solution at room temperature for 4h, filtering, drying in a drying oven at 114 ℃ for 8h to obtain a precursor, roasting the precursor under inert gas argon, and roasting at 500 ℃ for 4h to obtain the catalyst.
Through physical grinding and mixing with the main catalyst, 2 wt% of Pd as a metal doping component is added, and the addition amount is calculated by taking the mass of the main catalyst as 100%.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst and a metal doping component) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Comparative example 3:
preparing a main catalyst by adopting an impregnation method: adding deionized water into nitrate of an active component Al, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying the mesoporous Cr2O3Soaking the carrier in the soaking solution at room temperature for 4h, filtering, drying in a drying oven at 114 ℃ for 8h to obtain a precursor, roasting the precursor under inert gas argon, and roasting at 500 ℃ for 4h to obtain the catalyst. Wherein, the mesoporous Cr2O3Has a specific surface area of 84.6m2The pore diameter is 15-50 nm.
Adding metal doping group by physical grinding and mixing with the main catalyst2 wt% of Ru and 5 wt% of Sm as rare earth additive2O3、1wt％SmCl3The amounts added are all based on 100% by mass of the main catalyst.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst, a metal doping component and a rare earth auxiliary agent) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Comparative example 4:
preparing a main catalyst by adopting an impregnation method: adding deionized water into nitrate of an active component Al, stirring and dissolving to obtain a metal salt solution, namely an impregnation solution; drying the microporous Cr2O3Soaking the carrier in the soaking solution at room temperature for 4h, filtering, drying in a drying oven at 114 ℃ for 8h to obtain a precursor, roasting the precursor under inert gas argon, and roasting at 500 ℃ for 4h to obtain the catalyst. Wherein, the micropore Cr2O3Has a specific surface area of 87.7m2(ii)/g, the pore diameter is 0.2 to 2 nm.
Through physically grinding and mixing with a main catalyst, a metal doping component of 2 wt% Ru and a rare earth additive of 5 wt% Sm are added2O3、1wt％SmCl3The amounts added are all based on 100% by mass of the main catalyst.
The catalytic system is subjected to fluorination pretreatment before use, and the specific pretreatment mode is as follows: placing a catalytic system (containing a main catalyst, a metal doping component and a rare earth auxiliary agent) in a catalyst reactor, introducing HF-argon mixed gas with a molar ratio of 5:1, and carrying out fluorination treatment at 270 ℃ for 230 minutes.
Example 3
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) as a reaction raw material into a microchannel reactor, adding trichloromethane and chlorine, and reacting in the presence of the catalytic system of the embodiment 1 to obtain a reaction product stream (3) containing difluorochloromethane, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
Example 4
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) as a reaction raw material into a microchannel reactor, introducing chlorine gas, and reacting in the presence of the catalytic system of the embodiment 2 to obtain a reaction product stream (3) containing difluoromethane chloride, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine gas is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
Example 5
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, introducing chlorine gas, and reacting in the presence of the catalytic system of the comparative example 1 to obtain a reaction product stream (3) containing difluoromethane chloride, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine gas is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
Example 6
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, introducing chlorine gas, and reacting in the presence of the catalytic system of the comparative example 2 to obtain a reaction product stream (3) containing difluoromethane chloride, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine gas is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
Example 7
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), feeding mixed gas (1) containing a trifluoromethane byproduct into a microchannel reactor as a reaction raw material, introducing chlorine, and reacting in the presence of the catalytic system of example 1 to obtain a reaction product stream (3) containing difluoromethane chloride, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of trifluoromethane to trichloromethane to chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, and separating to obtain the target product difluoromethane chloride.
Example 8
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), feeding mixed gas (1) containing a trifluoromethane byproduct into a microchannel reactor as a reaction raw material, introducing chlorine, and reacting in the presence of the catalytic system of the embodiment 2 to obtain a reaction product stream (3) containing difluoromethane chloride, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of trifluoromethane to trichloromethane to chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, and separating to obtain the target product difluoromethane chloride.
Example 9
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) as a reaction raw material into a tubular reactor which is replaced by protective gas nitrogen, adding trichloromethane and chlorine, and reacting in the presence of the catalytic system of the embodiment 1 to obtain a reaction product stream (3) containing difluoromonochloromethane, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, and separating to obtain the target product difluoromethane chloride.
Example 10
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) as a reaction raw material into a tubular reactor which is replaced by protective gas nitrogen, adding trichloromethane and chlorine, and reacting in the presence of the catalytic system of the embodiment 1 to obtain a reaction product stream (3) containing difluoromonochloromethane, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, and separating to obtain the target product difluoromethane chloride. And (3) returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to the microchannel reactor in the step 2).
Example 11
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, adding trichloromethane and chlorine, and reacting in the presence of the catalytic system of the comparative example 3 to obtain a reaction product stream (3) containing difluorochloromethane, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
Example 12
The method for producing the difluorochloromethane product by using the trifluoromethane, the trichloromethane and the chlorine as the raw materials comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is pyridine tetrafluoroborate; step 2), feeding the high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, adding trichloromethane and chlorine, and reacting in the presence of the catalytic system of the comparative example 4 to obtain a reaction product stream (3) containing difluorochloromethane, wherein the heating temperature of the reactor is 230 ℃, and the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is 3:0.6: 1; and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, returning the excessive trifluoromethane to the extraction separation tower in the step 1), purifying and recycling the excessive trifluoromethane as a raw material to enter the microchannel reactor in the step 2).
The selected time interval length is 20 hours, the amount of the reaction raw materials is measured, and the gas chromatograph is used for detecting and analyzing the reaction products of the examples 3-12, and the detection results are shown in tables 1 and 2:
TABLE 1
| Detecting items | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Selectivity to difluoromethane chloride | 61.1％ | 60.2％ | 31.6％ | 34.5％ | 59.8％ |
| Conversion of trifluoromethane | 75.7％ | 74.8％ | 64.7％ | 63.1％ | 41.5％ |
| Conversion of chlorine | 79.8％ | 78.7％ | 60.3％ | 60.5％ | 77.3％ |
| Conversion of chloroform | 70.1％ | 69.8％ | 50.3％ | 52.1％ | 68.8％ |
TABLE 2
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention.
Claims (10)
1. A preparation process for producing a chlorodifluoromethane product by taking trifluoromethane, trichloromethane and chlorine as raw materials is characterized in that: the method comprises the following steps:
step 1), sending mixed gas (1) containing a trifluoromethane byproduct into an extraction separation tower, and purifying to obtain high-purity trifluoromethane gas (2), wherein an extraction liquid in the extraction separation tower is selected from tetrafluoroborate and tetrafluoroethanesulfonate;
step 2), feeding the high-purity trifluoromethane gas (2) serving as a reaction raw material into a microchannel reactor, adding chlorine and trichloromethane, and reacting in the presence of a catalytic system to obtain a reaction product stream (3) containing difluorochloromethane, wherein the catalytic system contains a main catalyst, a metal doping component and a rare earth auxiliary agent; the main catalyst comprises a carrier and an active component, wherein the carrier is multi-stage micro/mesoporous Cr2O3The pore size distribution has the following characteristics: 40-70% of the pores have the diameter of 0.2-2 nm, and 10-20% of the pores have the diameter of 15-50 nm;
and 3) feeding the reaction product flow (3) containing the difluoromethane chloride into a separation system, separating to obtain a target product difluoromethane chloride, and returning the excessive trifluoromethane to the extraction separation tower in the step 1).
2. The process according to claim 1, characterized in that: the mass ratio of the carrier to the active component of the main catalyst is 100: (0.5 to 25).
3. The process according to claim 2, characterized in that: the multi-stage micro/mesoporous Cr2O3The specific surface area of (A) is 15 to 120m2(ii)/g, the average pore diameter is 0.2 to 12 nm.
4. The process according to claim 3, characterized in that: in the catalytic system, the active component of the main catalyst is chloride, carbonate, nitrate, acetate or sulfate corresponding to chromium, aluminum and magnesium metals.
5. The process according to claim 2, characterized in that: the metal doping component is one or a combination of more of Co, Ni, Ru, Rh, Pd, Pt, Ag and Au.
6. The process according to claim 2, characterized in that: the rare earth auxiliary agent is an oxide or chloride of La and/or Sm.
7. The production process according to any one of claims 1 to 6, characterized in that: the mass ratio of the main catalyst, the metal doping component and the rare earth additive is (1:0.01:0.02) - (1:0.3: 0.6).
8. The process according to claim 1, characterized in that: the extract is selected from imidazole tetrafluoroborate, imidazole tetrafluoroethanesulfonate, pyridine tetrafluoroborate or pyridine tetrafluoroethanesulfonate.
9. The process according to claim 1, characterized in that: the equivalent diameter of the channel of the microchannel reactor is 50-700 mu m, each microchannel reactor comprises 100-8000 process channels, and the shape of the section of the channel is selected from hourglass shape, S shape, star shape or octagon shape.
10. The process according to claim 1, characterized in that: in the step 2), the molar ratio of the trifluoromethane to the trichloromethane to the chlorine is (1:0.6:1) to (12:0.6: 1).
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