CN111960916B - 一种r23资源化利用方法 - Google Patents
一种r23资源化利用方法 Download PDFInfo
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- CN111960916B CN111960916B CN202010517435.9A CN202010517435A CN111960916B CN 111960916 B CN111960916 B CN 111960916B CN 202010517435 A CN202010517435 A CN 202010517435A CN 111960916 B CN111960916 B CN 111960916B
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- catalyst
- fluorination
- fluorination catalyst
- equal
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 59
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011777 magnesium Substances 0.000 claims abstract description 19
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 17
- 239000011575 calcium Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims abstract description 8
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 19
- 150000001348 alkyl chlorides Chemical class 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 60
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910000859 α-Fe Inorganic materials 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 6
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical group [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical group O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000004323 potassium nitrate Substances 0.000 description 4
- 235000010333 potassium nitrate Nutrition 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- -1 lanthanide metal oxide Chemical class 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QAERDLQYXMEHEB-UHFFFAOYSA-N 1,1,3,3,3-pentafluoroprop-1-ene Chemical compound FC(F)=CC(F)(F)F QAERDLQYXMEHEB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 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
- 235000014304 histidine Nutrition 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- OPNWGGRJSXYWRA-UHFFFAOYSA-M 1-butylpyridin-1-ium;hydrogen sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+]1=CC=CC=C1 OPNWGGRJSXYWRA-UHFFFAOYSA-M 0.000 description 1
- KPPZVGULRLEVCE-UHFFFAOYSA-N 2-butylpyridine sulfuric acid Chemical compound S(=O)(=O)(O)O.C(CCC)C1=NC=CC=C1 KPPZVGULRLEVCE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 1
- RZSJYVBYLBNFGQ-UHFFFAOYSA-N difluoromethane hydrochloride Chemical compound FCF.Cl RZSJYVBYLBNFGQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite 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
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time 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
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8435—Antimony
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- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- B01J35/613—10-100 m2/g
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- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C01G49/10—Halides
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Abstract
本发明提供一种R23资源化利用方法,所述方法包括:在氟化催化剂作用下,R23与氯代烷烃发生氟化反应,所述氟化催化剂包括氧化铁或氧化铁和氟化铁的混合物,所述氧化铁为α‑Fe2O3和γ‑Fe2O3的混合晶型。氟化催化剂还包括其它活性组分,其它活性组分选自锑、锌、镁、钙中至少一种。本发明的氟化催化剂不含重金属铬,污染少,在各组分的协同作用下,能很好的实现R23与氯代烷烃的反应,在较温和条件下实现R23的高效转化。
Description
技术领域
本发明涉及HFC-23的资源化利用,具体涉及HFC-23与氯代烷烃反应实现HFC-23资源化利用的方法。
背景技术
HFC-23(CHF3,三氟甲烷,R23),是生产HCFC-22(CHClF2,二氟一氯甲烷,R22)不可避免的副产物,具有较强的温室效应,其GWP值高达14800,在国际上已经被控制排放,并被作为碳交易对象。一般工业上采用焚烧的方法处理三氟甲烷,将其彻底锻烧分解成氟化氢、二氧化碳等物质。但焚烧处理需要配备专用的焚烧设备,投资大,且分解产物氟化氢易对腐蚀设备。如果能够将三氟甲烷进行资源化利用,使其转变成其他有用的化合物,将具有重要的经济效益。
专利US3009966A公开了在700-1090℃下三氟甲烷热解制备TFE和六氟丙烯(HFP)的方法。
专利CN104628514A报道了在一定比例的O2的存在下、在镧系金属氧化物催化剂作用下、甲烷和三氟甲烷进行热裂解反应生成偏氟乙烯的方法。
专利CN107434759B公开了一种1,1,3,3,3-五氟丙烯的制备方法,包括两步反应,先使CF3X和CH2=CF2反应得到CF3CH2CF2X(X独立地选自Br或Cl),再使CF3CH2CF2X脱HX得到1,1,3,3,3-五氟丙烯,所述CF3X由CHF3与Br2、CaBr2或Cl2经气相反应得到,从而实现高GWP值物质HFC-23的资源化利用。
专利CN104628513B公开一种三氟甲烷资源化利用的方法,其特征在于将三氟甲烷和一种或者几种卤代烃混合,在催化剂作用下转化成含二氟一氯甲烷的产物,未反应的三氟甲烷和其他反应产物循环进入反应器再参与反应,催化剂为Cr2O3,Sm2O3/MgO,La2O3/Al2O3,部分氟化的Cr2O3,Cr2O3/石墨及Fe/活性炭,所述的卤代烃为RCHaXbFc,式中R为H、烷基或含卤素分子的氟氯烃,X为Cl或Br,0≤a≤2,1≤b≤3,0≤c≤2,催化剂助剂为La或Sm。
CN110833837A公开了一种用于三氟甲烷资源化利用的催化剂,包括选自铬、铝、镁氧化物或氟化物中的至少一种的主催化剂和选自Cr、Mg、Al、Ni、Co、Zn、Fe、Cu、In、Mn、La、Ce、Sm氧化物或氟化物中的至少一种的助催化剂。该专利还公开了所述催化剂的制备方法。
在利用R23进行氟氯交换反应时,现有技术中大多是R23与卤代甲烷发生反应,烷烃数量越多,用R23进行氟氯交换反应越困难。
发明内容
本发明提供一种R23资源化方法,该方法采用R23为原料,在催化剂存在下对氯代烷烃进行氟化,实现了R23的资源化利用。
本发明提供一种R23资源化利用方法,所述方法包括:
在氟化催化剂作用下,R23与氯代烷烃发生氟化反应,所述氟化催化剂包括氧化铁或氧化铁和氟化铁(FeF3)的混合物,所述氧化铁为α-Fe2O3和γ-Fe2O3的混合晶型,所述氯代烷烃为CxHyClz,式中1≤x≤2,1≤z≤3,y+z=2x+2,且x=2时,z≠3。
本发明方法中,所述氟化催化剂还包括其它活性组分,其它活性组分选自锑、锌、镁、钙中至少一种。
本发明的氯代烷烃包括CHCl3、CH2Cl2、CH3CH2Cl、CH3CHCl2。
本发明的可能产物包括HCFC-22,CHCl2F,CH2ClF,CH2F2,CH3CH2F,CH3CHF2,CH3CHClF。
本发明催化剂氧化铁中α-Fe2O3和γ-Fe2O3晶型的摩尔比为1:5-5:1,进一步优选为1:2-2:1。
当本发明催化剂含有氟化铁时,FeF3与Fe2O3的摩尔比为1:2-1:5。
所述氧化铁可同时作为氟化催化剂的载体。优选地,本发明中氧化铁的比表面积为80-125m2/g,平均孔径为10-15nm。
进一步优选地,本发明中氧化铁的孔径分布集中,80%以上的孔径为5-20nm;更优选地,90%以上的孔径为5-20nm,此处百分含量表示质量百分含量。在本发明的氧化铁的比表面积、孔径下,有效的减少了微孔烧结现象的产生,提高了R23的转化率。
本发明氟化催化剂中铁元素与其它活性组分元素总和的摩尔比为1:0.05-0.8,进一步优选为1:0.2-0.5,此处其它活性组分元素总和的指当其它活性组分至少含有两种元素时,为各元素摩尔数的总和;优选地,其它活性组分元素至少一种为锑,进一步优选地,其他活性组分选自镁、锌、锑、钙中的至少两种。其中,其它活性组分为镁和锑时,镁和锑元素的摩尔比为1:0.1-0.5;其它活性组分为锌和锑时,锌和锑元素的摩尔比为1:0.1-0.5;其它活性组分为钙、锌和锑时,钙、锌和锑元素的摩尔比为1:0.5-1:0.1-0.5;其它活性组分为镁、锌和锑时,镁、锌和锑的元素摩尔比为1:0.5-1:0.1-0.5;其它活性组分为镁、钙和锑时,镁、钙和锑元素的摩尔比为1:0.5-1:0.1-0.5。本发明的氟化催化剂在各组分的协同作用下,能很好的实现R23与氯代甲烷和氯代乙烷的反应,R23转化率高,反应容易进行。
本发明的R23资源化利用方法中,氟化反应优先在气相中进行,R23与氯代烷烃的摩尔比为1:1-1:5,优选为1:1.5-1:3;反应温度为200-400℃,优选为300-380℃;反应压力为0.3-0.8Mpa;反应时间为5s-100s,优选为10s-80s。
在上述反应条件下,原料R23和产物具有高的转化率和选择性。
本发明还提供一种用于R23资源化利用的催化剂,所述氟化催化剂包括氧化铁,所述氧化铁为α-Fe2O3和γ-Fe2O3的混合晶型,氟化催化剂还包括其它活性组分,所述其它活性组分选自镁、锌、锑、钙中至少一种,所述催化剂用于催化R23与氯代烷烃的反应,所述氯代烷烃为CxHyClz,式中1≤x≤2,1≤z≤3,y+z=2x+2,且x=2时,z≠3。
本发明中α-Fe2O3的制备方法,包括以下步骤:
将三价铁盐、表面活性剂溶解到乙二醇和乙二胺的溶液中,制备得到混合液,其中乙二胺与乙二醇体积比为0.6-0.9:1;混合液在170-200℃反应24h,制备得到沉淀物,沉淀物经洗涤干燥,在200-250℃下,焙烧2-3h,制备得到α-Fe2O3。三价铁盐与表面活性剂的质量比为25-50:1。所述三价铁盐可选自三氯化铁、硫酸铁、硝酸铁等。所述表面活性剂为1-(4-磺酸基)丁基吡啶硫酸氢盐,N-甲基-N-癸基-2-吡咯烷酮溴化盐。制备的α-Fe2O3的比表面积为80-125m2/g,平均孔径为10-15nm。
本发明中γ-Fe2O3的制备方法,包括以下步骤:
以体积比1∶1-3的乙醇胺和1,3-丙二醇为混合溶剂,加入硫酸亚铁、硝酸钾、组氨酸,在反应釜中140-150℃反应12-26小时,所得产物经磁铁吸附,水洗干燥,得到由γ-Fe2O3;其中,硫酸亚铁、硝酸钾和组氨酸的质量比为1∶0.2-0.7∶0.3-0.5。制备的γ-Fe2O3的比表面积80-125m2/g,平均孔径为10-15nm。
本发明的FeF3的制备,包括以下步骤,将一定量的Fe(NO3)3溶于乙醇溶液中,在40-60℃搅拌下,向其中缓慢滴加0.5mol/LHF酸,控制溶液pH值在5.0-6.0之间,待完全沉淀后,在50℃下,静置12小时,经过滤、洗涤,60℃蒸干水分,在马弗炉中300℃焙烧5小时,制得FeF3。
本发明氟化催化剂的制备可采用催化剂制备的常规方法,如浸渍法,沉淀法,机械混合法等。
本领域人员已知的,R23的C-F非常稳定,而烷烃链越长,C-Cl键能越高,氟氯交换反应越不容易发生,而采用本发明的催化剂可以很好的实现R23与氯代甲烷和乙烷的氟氯交换反应。
本发明采用R23作为氟化反应的原料,实现了R23的资源化利用,具有重要的经济效益和社会效益。
本发明的氟化催化剂不含重金属铬,污染少,在各组分的协同作用下,能很好的实现R23与氯代甲烷和氯代乙烷的反应,在较温和条件下实现R23的高效转化。
本发明的氟化催化剂中的氧化铁,包含α-Fe2O3和γ-Fe2O3混合晶型,在作为活性成分的同时,又可作为其它活性成分的载体,对活性组分具有优异的分散性能,催化活性高,稳定性高,原料R23的转化率高,产物选择性高。
在本发明的氧化铁的比表面积、孔径下,有效的减少了微孔烧结现象的产生,提高了R23的转化率。
附图说明
图1为本发明制备例1制备的α-Fe2O3晶型和γ-Fe2O3晶型的X射线衍射图。
具体实施方式
下面结合实施例对本发明做进一步的说明,需要说明的是,下述实施例仅是用于说明,本发明的保护范围并不限于此。本领域技术人员根据本发明的推导所做出的各种变化均应在本申请权利要求所要求的保护范围之内。
一、催化剂制备
制备例1
将FeCl3、1-(4-磺酸基)丁基吡啶硫酸氢盐溶解到乙二醇和乙二胺的溶液中,制备得到混合液,其中乙二胺与乙二醇体积比为4:5,混合液在180℃反应24h,制备得到沉淀物,沉淀物经洗涤干燥,在200-250℃下,焙烧2-3h,制备得到α-Fe2O3。FeCl3与表面活性剂的质量比为40-1。采用比表面积及孔结构测试仪分析制备的α-Fe2O3的比表面积为89m2/g,平均孔径为13nm,92%以上的孔径为5-20nm,如附图1所示。
以体积比1∶3的乙醇胺和1,3-丙二醇为混合溶剂,加入硫酸亚铁、硝酸钾、组氨酸,在反应釜中140℃反应20小时,所得产物经磁铁吸附,水洗干燥,得到由γ-Fe2O3;其中,硫酸亚铁、硝酸钾和组氨酸的质量比为1∶0.5∶0.4。采用比表面积及孔结构测试仪分析制备的γ-Fe2O3的比表面积为85m2/g,平均孔径为12nm,90%以上的孔径为5-20nm,如附图1所示。
将Sb2O3与制备得到的α-Fe2O3与γ-Fe2O3按所需比例球磨混合,搅拌混合均匀,然后压片或挤出成型,得到Sb-含α-Fe2O3和γ-Fe2O3的Fe2O3前驱体。将该催化剂前驱体在氮气气氛下,200℃焙烧2h,接着升温至350℃,焙烧3h,制得Sb-含α-Fe2O3和γ-Fe2O3氟化催化剂。其中,铁:锑元素的摩尔比为1:0.3,α-Fe2O3和γ-Fe2O3的摩尔比为1:1。
制备例2
按照制备1的方法制备Zn-含α-Fe2O3和γ-Fe2O3的Fe2O3氟化催化剂,不同的是用ZnO代替Sb2O3。
制备例3
按照制备1的方法制备Mg-含α-Fe2O3和γ-Fe2O3的Fe2O3氟化催化剂,不同的是用MgO代替Sb2O3。
制备例4
按照制备例1的方法制备Zn/Sb-含α-Fe2O3和γ-Fe2O3的Fe2O3氟化催化剂,不同的是方法还包括称一定量的Zn(NO3)2溶于一定量水中,滴加入制备得到含Sb-含α-Fe2O3和γ-Fe2O3的Fe2O3的氟化催化剂前驱体中,70℃浸渍16h,120℃干燥10h,得到催化剂前驱体。将该催化剂前驱体在氮气气氛下,200℃焙烧2h,接着升温至350℃,焙烧3h,制得氟化催化剂,其中铁:锌、锑元素的摩尔比为1:0.2:0.1。
制备例5
按照制备例4的方法制备Mg/Ca-含α-Fe2O3和γ-Fe2O3的Fe2O3氟化催化剂,不同的是MgO代替Sb2O3,Ca(NO3)2代替Zn(NO3)2,其中铁:镁、钙元素的摩尔比为1:0.2:0.1。
制备例6
按照制备例4的方法制备Mg/Ca/Sb-含α-Fe2O3和γ-Fe2O3的Fe2O3氟化催化剂,不同的是Mg(NO3)2和Ca(NO3)2代替Zn(NO3)2,其中铁:镁:钙:锑元素的摩尔比为1:0.15:0.075:0.075。
制备例7
按照制备例1的方法制备Sb-含FeF3、α-Fe2O3和γ-Fe2O3氟化催化剂,不同的是,还包括FeF3的制备,包括以下步骤,将所需量的Fe(NO3)3溶于乙醇溶液中,在60℃搅拌下,向其中缓慢滴加0.5mol/LHF酸,控制溶液pH值在5.0-6.0之间,待完全沉淀后,在50℃下,静置12小时,经过滤、洗涤,60℃蒸干水分,在马弗炉中300℃焙烧5小时,制得FeF3;Sb2O3与制备得到的FeF3、α-Fe2O3、γ-Fe2O3按所需比例球磨混合,其中,铁:锑元素的摩尔比为1:0.3,FeF3、α-Fe2O3和γ-Fe2O3的摩尔比为0.5:1:1。
对比制备例1
按照制备例4的方法制备Zn/Sb-α-Fe2O3氟化催化剂,不同的是催化剂中不含γ-Fe2O3。
对比制备例2
按照制备例4的方法制备Zn/Sb-γ-Fe2O3氟化催化剂,不同的是催化剂中不含α-Fe2O3。
对比制备例3
按照制备例4的方法制备Zn/Sb-Fe2O3(含有α,γ,β三种晶型)催化剂,不同的是Fe2O3含有α,γ,β三种晶型,含有三种晶型的Fe2O3,可通过市售购买。
对比制备例4
按照制备例7的方法制备Sb-FeF3氟化催化剂,不同的是,催化剂中不含有α-Fe2O3和γ-Fe2O3催化剂。
二、催化剂应用
实施例1
氟化催化剂的预处理过程为氟化氢和氮气混合气氛,250℃下氟化处理4小时。将R23和CH3CH2Cl以摩尔比1:2通入装有经过预处理的制备例1制备的氟化催化剂的反应器中,在温度360℃,反应压力0.6Mpa,停留时间20s。反应生成的产物经洗涤、精馏提纯等处理后即得到二氟一氯甲烷,CH3CH2F,经气相色谱分析R23的转化率及二氟一氯甲烷,CH3CH2F的选择性见表1。
实施例2
按照实施例1的方法,不同的是,用制备例2制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例3
按照实施例1的方法,不同的是,用制备例3制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例4
按照实施例1的方法,不同的是,用制备例4制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例5
按照实施例1的方法,不同的是,用制备例5制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例6
按照实施例1的方法,不同的是,用制备例6制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例7
按照实施例1的方法,不同的是,用CH3CHCl2代替CH3CH2Cl为原料。
实施例8
按照实施例1的方法,不同的是,用氯仿代替CH3CH2Cl为原料。
实施例9
按照实施例4的方法,不同的是,用氯仿代替CH3CH2Cl为原料。
实施例10
按照实施例5的方法,不同的是,用氯仿代替CH3CH2Cl为原料。
实施例11
按照实施例4的方法,不同的是,用CH2Cl2代替CH3CH2Cl为原料。
实施例12
按照实施例1的方法,不同的是,用制备例7制备的氟化催化剂代替制备例1制备的氟化催化剂。
实施例13
按照实施例12的方法,不同的是,用氯仿代替CH3CH2Cl为原料。
对比例1
按照实施例1的方法,不同的是,用对比制备例1的氟化催化剂代替制备例1制备的氟化催化剂。
对比例2
按照实施例1的方法,不同的是,用对比制备例2的氟化催化剂代替制备例1制备的氟化催化剂。
对比例3
按照实施例1的方法,不同的是,用对比制备例3的氟化催化剂代替制备例1制备的氟化催化剂。
对比例4
按照实施例1的方法,不同的是,用对比制备例4的氟化催化剂代替制备例1制备的氟化催化剂。
表1
Claims (9)
1.一种R23资源化利用的方法,其特征在于,所述方法包括:
在氟化催化剂作用下,R23与氯代烷烃发生氟化反应,所述氟化催化剂包括氧化铁或氧化铁和氟化铁的混合物,所述氧化铁为α-Fe2O3和γ-Fe2O3的混合晶型,所述氯代烷烃为CxHyClz,式中1≤x≤2,1≤z≤3,y+z=2x+2,且x=2时,z≠3;
所述氟化催化剂还包括其它活性组分,所述其它活性组分选自锑、锌、镁、钙中至少一种。
2.根据权利要求1所述的方法,其特征在于,所述氧化铁的比表面积为80-125m2/g,平均孔径为10-15nm。
3.根据权利要求2所述的方法,其特征在于,所述氧化铁中,氧化铁的孔径分布集中,80%以上的孔径为5-20nm。
4.根据权利要求1所述的方法,其特征在于,所述氟化催化剂中铁元素与其它活性组分的摩尔比为1:0.05-0.8。
5.根据权利要求1所述的方法,其特征在于,所述其它活性组分至少一种为锑。
6.根据权利要求1所述的方法,其特征在于,R23与氯代烷烃的摩尔比为1:1-1:5。
7.根据权利要求1所述的方法,其特征在于,所述反应在气相中进行,反应温度为200-400℃,反应压力为0.3-0.8MPa。
8.一种用于R23资源化利用的催化剂,其特征在于,所述催化剂包括氧化铁,所述氧化铁为α-Fe2O3和γ-Fe2O3的混合晶型,催化剂还包括其它活性组分,所述其它活性组分选自镁、锌、锑、钙中至少一种,所述催化剂用于催化R23与氯代烷烃的反应,所述氯代烷烃为CxHyClz,式中1≤x≤2,1≤z≤3,y+z=2x+2,且x=2时,z≠3。
9.根据权利要求8所述的催化剂,其特征在于,所述氧化铁的比表面积为80-125m2/g,平均孔径为10-15nm。
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