CN105688890B - A kind of fluorination catalyst and preparation method thereof - Google Patents
A kind of fluorination catalyst and preparation method thereof Download PDFInfo
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- CN105688890B CN105688890B CN201610070645.1A CN201610070645A CN105688890B CN 105688890 B CN105688890 B CN 105688890B CN 201610070645 A CN201610070645 A CN 201610070645A CN 105688890 B CN105688890 B CN 105688890B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 23
- 239000011737 fluorine Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 230000032683 aging Effects 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 239000002585 base Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical group CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 abstract description 5
- JYHHXQKTNJXLFU-UHFFFAOYSA-N C(C)Cl.[F] Chemical compound C(C)Cl.[F] JYHHXQKTNJXLFU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 230000008859 change Effects 0.000 description 19
- 238000001914 filtration Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 17
- 239000000908 ammonium hydroxide Substances 0.000 description 17
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 16
- 238000000643 oven drying Methods 0.000 description 16
- 239000012266 salt solution Substances 0.000 description 16
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 15
- 239000011636 chromium(III) chloride Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- -1 bromo quaternary ammonium salt Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 4
- 229920001213 Polysorbate 20 Polymers 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019804 NbCl5 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 description 1
- CYXIKYKBLDZZNW-UHFFFAOYSA-N 2-Chloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)CCl CYXIKYKBLDZZNW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019406 chloropentafluoroethane Nutrition 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 238000009702 powder compression Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—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
- B01J23/84—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- 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
- B01J23/70—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
- B01J23/84—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
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
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- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of fluorination catalysts and preparation method thereof, the fluorination catalyst is mainly prepared by metal chromic salts, metal promoter, * surfactant, the pore volume of the presoma of the fluorination catalyst is 0.30-0.53ml/g, average pore size is 4.0-6.0nm, wherein the molar ratio of metal chromic salts and metal promoter is 1:0.003-0.3, and the molar ratio of metal chromic salts and surfactant is 1:0.0001%-0.5%.The present invention adds surfactant by addition metal promoter or while adding metal promoter to be modified to catalyst, metal promoter is adjustable catalyst pore structure, synthesize the fluorination catalyst with preferable aperture structure, the fluorination catalyst has good catalytic performance during catalysis prepares pentafluoroethane, the yield and selectivity of product are all higher, and the purity is high of product, five fluorine monochlorethane of by-product are substantially reduced.
Description
Technical field
The present invention relates to a kind of fluorination catalysts and its preparation method and application, and in particular to one kind is used for halogenated hydrocarbons and fluorine
Change the catalyst of the gas phase fluorination of hydrogen, in particular for being catalyzed the catalyst and preparation method thereof for preparing R125.
Background technique
In fluorine chemical field, since the Ozone Depletion Potential (ODP) of hydrogen fluorohydrocarbon (HFCs) is 0, global warming potential
Value (GWP) is smaller, and refrigeration performance is similar to fluorochlorohydrocarbon (CFCs), is the ideal substitute of CFCs, is widely used in large-scale quotient
Industry refrigerant, foaming agent, extinguishing chemical etc..Gas phase exchange chloride for fluoride is the key reaction of selective synthesis fluorochemical,
Since its is simple and easy to do, economical and practical, have many advantages, such as that pollution is few easy to operate, oneself is through being widely used in the industrial production of hydrofluorocarbon
In the process.Common gas phase fluorination is such as:
CF3CH2Cl+HF→CF3CH2F(HFC-134a)+HCl
CCl2=CCl2+HF→CF3CHF2(HFC-125)+HCl
Since F/Cl exchange reaction is thermodynamically obstructed, effective catalyst is generally required to reduce the activation energy of reaction,
Accelerate reaction rate, to reach acceptable reaction rate.Therefore fluorination catalyst rises emphatically in F/Cl exchange reaction
It acts on.The selection and research of fluorination catalyst, have a very important significance.Catalysts for gas phase fluorination is in the process route
Core, efficient fluorination catalyst can be very good to solve the problems, such as that target product selectivity is low, thus largely
Improve the yield of target product.The catalyst being typically used in gas phase fluorination is urging using chromium as main active component
Agent.So far, the method for improving catalyst performance is usually to pass through to increase specific surface area of catalyst or addition assistant metal
It carries out.
Chinese patent CN101417816A discloses a kind of chromium system fluorination catalyst oxidation of precursor chromium of high-specific surface area
Preparation method, this method is by the way that organic additive to be dissolved in soluble chromium salting liquid, then is precipitated with precipitating reagent and fluorine is made
Change catalyst Cr2O3·nH2O (0 < n < 3), although this method effectively increases Cr2O3·nH2The specific surface area of O (0 < n < 3), and
Preparation process is simple to operation, tests favorable reproducibility, but the specific surface area of chromium-based catalysts synthesized in the document still compared with
It is low, and the relevant parameter in the hole without disclosing the catalyst, also without disclosing the catalyst in terms of catalysis prepares hydrofluorocarbon
Catalytic performance parameter.It does not evaluate using data, does not refer to influence of the organic additive to Catalyst Pore Structure Parameters.China
Patent CN103143344B discloses a kind of high than table chromium-based fluorination catalyst and preparation method thereof, and the patent was by preparing
Polyethylene glycol is added in the solution of other metal ions of chromium base and the second active constituent that Cheng Zhongxiang contains the first active constituent
The organic compounding agent to be formed is compounded with ionic liquid to prepare chromium-based fluorination catalyst.Although the specific surface area of catalyst obviously increases
Greatly, but the patent is on the one hand without the pore structure relevant parameter of open catalyst, does not also refer to the pore structure of the catalyst to fluorine
Change the influence of catalysis reaction, in addition catalyst synthesized in the patent prepares pentafluoroethane (HFC-125 or R125) in catalysis
When selective highest also only have 70.70, still do not meet the existing market requirement highly selective to fluorination catalyst.Due to mesh
It is preceding during synthesizing R125, the boiling point and R125 phase of generated five fluorine monochlorethane of by-product (R115 or CFC-115)
Closely, and there are azeotropisms, it is difficult to and it is isolated with common distillation technology, is usually isolated purification with extraction fractional distillation,
To largely improve its energy consumption and cost in industrial separation purification process, therefore it is badly in need of synthesizing a kind of be catalyzed at present
There is more highly selective catalyst in terms of preparing R125.
Summary of the invention
Smaller for catalyst pore structure in the prior art, active lower, catalysis prepares the by-product in R125 reaction
The problems such as R115 is selectively excessively high, the present invention provides a kind of chromium-based fluorination catalysts, by adding in catalyst preparation process
Add metal promoter or adds metal promoter and surfactant simultaneously to adjust the pore structure parameter of catalyst, so that catalyst exists
In pore forming process, the catalyst for being suitble to the pore structure of R125 gas phase fluorination is formed.And it is applied to the gas phase fluorine of R125
It is combined in reaction.The catalyst has good catalytic performance, and the yield and selectivity of target product are higher, and product
Purity is fine, and by-product R115 is substantially reduced.
On the one hand technical solution of the present invention provides a kind of fluorination catalyst, which is characterized in that the fluorination catalyst
The presoma of agent is mainly prepared by metal chromic salts, metal promoter, and wherein the molar ratio of metal chromic salts and metal promoter is 1:
0.003-0.3, the pore volume of the fluorination catalyst presoma are 0.30-0.52ml/g, average pore size 4.0-6.0nm.
The method provided according to the above technical scheme, the metal promoter be selected from Zn, Ni, Mg, Al, La, Ce, Co, Nd,
Fe, Ca, In, Cu, Ag, Hg, at least two；In certain embodiments of the present invention, in the metal promoter at least
One kind being selected from La, Ce, Co, Nd, Fe, Ca, In, Cu, Ag or Hg.In certain embodiments of the present invention, the metal promoter
At least one of be selected from La, Ce, Co, Nd, In, Cu, Ag or Hg.In other embodiments of the invention, the metal
At least one of auxiliary agent is selected from La, Co, Nd, Fe, Ca, In, Cu, Ag or Hg.
In certain embodiments of the present invention, the molar ratio of the metal chromic salts and metal promoter is 1:0.032-
0.28.In other of the invention embodiments, the molar ratio of the metal chromic salts and metal promoter is 0.008,0.01,
0.015、0.025、0.04、0.05、0.06、0.07、0.08、0.09、0.1、0.13、0.16、0.18、0.2、0.23、0.25、
0.26 or 0.28.
In certain embodiments of the present invention, the pore volume of the fluorination catalyst presoma is 0.4015-
0.5202ml/g, average pore size 4.723-5.843nm.In other embodiments of the invention, fluorination catalyst forerunner
The pore volume of body be 0.35ml/g, 0.36ml/g, 0.37ml/g, 0.38ml/g, 0.39ml/g, 0.41ml/g, 0.42ml/g,
0.43ml/g, 0.44ml/g, 0.45ml/g, 0.46ml/g, 0.47ml/g, 0.48ml/g, 0.49ml/g or 0.50ml/g.At it
In its some embodiment, the average pore size of fluorination catalyst presoma is 4.2nm, 4.4nm, 4.6nm, 4.8nm, 5.0nm,
5.3nm, 5.5nm, 5.7nm or 5.9nm.
In certain embodiments of the present invention, the metal chromic salts is selected from chromic nitrate, chromium chloride, chromium sulfate or chromium
Alum.
It in certain embodiments of the present invention, further include surfactant in the presoma of the fluorination catalyst.
In certain embodiments of the present invention, the surfactant be selected from perfluorinated nonene oxygroup benzene sulfonic acid sodium salt (OBS),
Hexafluoropropylene oxide tripolymer base amine-oxides, bromo quaternary ammonium salt, both sexes carboxylic acid ammonium, Tween-20 or polyethylene glycol.In some implementations
In mode, the surfactant is selected from bromo quaternary ammonium salt, both sexes carboxylic acid ammonium, Tween-20 or polyethylene glycol.In other realities
It applies in mode, the surfactant is selected from OBS or hexafluoropropylene oxide tripolymer base amine-oxides.
In certain embodiments of the present invention, metal chromic salts and surfactant in the presoma of the fluorination catalyst
Molar ratio be 1:0.0001%-0.5%.In certain embodiments of the present invention, the presoma of the fluorination catalyst
The molar ratio of middle metal chromic salts and surfactant is 1:0.005%, 1:0.008%, 1:0.01%, 1:0.02%, 1:
0.03%, 1:0.05%, 1:0.08%, 1:0.1%, 1:0.14%, 1:0.18%, 1:0.22%, 1:0.25%, 1:0.3%,
1:0.35%, 1:0.4%, 1:0.42%, 1:0.45% or 1:0.5%.
On the other hand technical solution of the present invention provides a kind of method for preparing above-mentioned fluorination catalyst, feature exists
In, comprising the following steps:
1) mixed solution is obtained after dissolving metal chromic salts, metal promoter, * surfactant in a solvent；
2) solution that pH value is 8-12 is obtained after mixing mixed solution described in step 1) and alkaline solution, after to be aging,
Sediment is filtered, washed to neutral re-dry, after high-temperature roasting by pulverizing and sieving, compression molding is up to complex catalyst precursor
Body；
3) presoma described in step 2) is fitted into reactor, is passed through the mixed gas of inert gas and HF in 200-
It is fluorinated at 400 DEG C, fluorination catalyst is made.
In certain embodiments of the present invention, graphite additive is added with when tabletting in powder, wherein the quality of graphite
For the 1-5% of gross mass.In some embodiments, the quality of graphite is 1.5%, 2.0%, 2.5%, the 3% of gross mass.?
In other embodiments, the quality of graphite is gross mass 3.5%, 4%, 4.5% or 5%.
In certain embodiments of the present invention, alkaline solution is ammonium hydroxide.
In certain embodiments of the present invention, mixed solution is mixed under the stirring rate of 20-1000rpm in step 1)
Even, and the time of aging is 8-300min.In some embodiments, in step 1) mixed solution be 50rpm,
100rpm、150rpm、200rpm、250rpm、300rpm、400rpm、500rpm、600rpm、700rpm、800rpm、900rpm、
It is mixed under the stirring rate of 950rpm or 1000rpm.In other embodiments, the time of aging be 10min, 15min,
20min、30min、40min、50min、60min、70min、80min、90min、100min、120min、140min、160min、
180min, 210min, 240min, 270min or 300min.
In certain embodiments of the present invention, the solvent is water.In certain embodiments of the present invention, solvent
The mass ratio of water and chromic salts is 15-25:1.In some embodiments, the mass ratio of aqueous solvent and chromic salts be 16:1,18:1,
20:1.And in other embodiments of the invention, the mass ratio of aqueous solvent and chromic salts is 22:1,23:1 or 24:1.
In certain embodiments of the present invention, the roasting is to carry out in inert gas, and the temperature roasted is
350-400 DEG C, calcining time 2-8h.In some embodiments, the temperature of roasting is 360 DEG C, 370 DEG C, 380 DEG C, 385
DEG C, 390 DEG C, 395 DEG C or 400 DEG C；In other embodiments, calcining time 7h, 6h, 5h, 5.5h, 4h, 3h or 2h.
Technical solution of the present invention provides application of the above-mentioned fluorination catalyst in terms of catalysis prepares hydrogen fluorohydrocarbon, special
Sign is, the gas phase fluorination for halogenated hydrocarbons and hydrogen fluoride.
Technical solution of the present invention additionally provides application of the above-mentioned fluorination catalyst in terms of catalysis prepares R125, feature
It is, is prepared in the fluorination reaction of R125 for being catalyzed.
Water used in embodiments of the present invention is deionized water.
" the both sexes carboxylic acid ammonium " in the present invention is a kind of surface-active simultaneously with two kinds of ionic natures of yin, yang
Agent.Its structural formula general formula such as Formulas I:
Heretofore described " hexafluoropropylene oxide tripolymer base amine-oxides " refer to be chemical formula be CF3(CF2)2O[CF
(CF3)CF2O]nCF(CF3)CONH(CH2)kNO(CmH2m+1)2A kind of compound, wherein n is the integer of 1-60, and k is 1-15
Integer, m are the integer of 1-10.It, will be representated by above-mentioned chemical formula according to the variation of n, k and m in the present invention in order to facilitate differentiation
Compound nomenclature is NnKkMm, wherein n is the integer of 1-60, and k is the integer of 1-15, and m is the integer of 1-10；Work as n=3, k=
When 2, m=4, N3K2M4Chemical formula is represented as CF3(CF2)2O[CF(CF3)CF2O]3CF(CF3)CONH(CH2)2NO(C4H9)2Change
Object is closed, works as n=30, when k=12, m=9, N30K12M9Chemical formula is represented as CF3(CF2)2O[CF(CF3)CF2O]30CF(CF3)
CONH(CH2)12NO(C9H19)2Compound, and so on.
* A in the present invention indicates that may contain A in component may also be free of A, such as: " by metal chromic salts, metal promoted
Agent, * surfactant dissolve in water after mixed solution " expression " must mix after dissolving metal chromic salts, metal promoter in water
Close solution " or " mixed solution is obtained after dissolving metal chromic salts, metal promoter, surfactant in water ".
Heretofore described " inert gas " refers in roasting and the fluorinated gas for not participating in reaction in the process, such as
Nitrogen, argon gas etc..
Drying of the present invention, referring to makes water or solvent gasification in material by means of energy, and takes away steam generated
Process.Drying mode used by some embodiments of the invention is drying drying.It should be pointed out that can achieve same effect
Drying means further include but be not limited to drying, vacuum drying, freeze-drying, pneumatic conveying drying, microwave drying, infrared drying and
Dielectric dry etc., in certain embodiments of the present invention, the temperature of the drying are 90-120 DEG C, and the dry time is 5-
30h。
Term " washing " of the present invention refers to through certain effect to weaken or eliminate between impurity and material
Interaction, makes the combination of impurity and material be changed into the combination of impurity and solvent, is finally detached from impurity and material.The present invention
Some embodiments in refer to the process of and rinsed material to pH ≈ 7 with water, ethyl alcohol.
Terminology used in the present invention " filtering " indicate under gravity or other external forces by medium by fluid with it is non-
The operation of fluid separation, the medium includes but is not limited to filter paper, gauze, filter core, semi-permeable membrane, strainer etc., theoretically, containing more
The material of pore structure can become the medium of filtering；The equipment of filtering includes but is not limited to vacuum or decompressor, pressurization dress
It sets, centrifugal device etc..
Unless explicitly stated otherwise in contrast, otherwise, all ranges that the present invention quotes include end value.For example, " roasting
Temperature is 350-400 DEG C ", indicate that the value range of temperature when roasting is 350 DEG C≤T≤400 DEG C.
Terminology used in the present invention "or" indicates that alternative can combine them if applicable, that is,
It says, term "or" includes each listed independent alternative and their combination.For example, " the surfactant choosing
From perfluorinated nonene oxygroup benzene sulfonic acid sodium salt (OBS), hexafluoropropylene oxide tripolymer base amine-oxides, bromo quaternary ammonium salt, both sexes carboxylic acid ammonium,
Tween-20 or polyethylene glycol " indicates that surfactant can be perfluorinated nonene oxygroup benzene sulfonic acid sodium salt, hexafluoropropylene oxide tripolymer
Base amine-oxides, bromo quaternary ammonium salt, both sexes carboxylic acid ammonium, Tween-20 or polyethylene glycol one of, be also possible to its more than one
Combination.
Terminology used in the present invention "one" or "an" describes element and component described herein.It does so only
It is for convenience, and to provide general meaning to the scope of the present invention.This description should be read to include one or extremely
It is one few, and the odd number also includes plural number, unless it is obvious that it is meant otherwise.
Number in the present invention is approximation, no matter whether uses the wordings such as " about " or " about ".The numerical value of number has
It is possible that the differences such as 1%, 2%, 5%, 7%, 8%, 10%.It is any to have whenever disclosing a number with N value
The number of N+/- 1%, N+/- 2%, N+/- 3%, N+/- 5%, N+/- 7%, N+/- 8% or the value of N+/- 10% can be by clearly public
It opens, adds deduct wherein " +/- " refers to, and the range between N-10% to N+10% is also disclosed.
Unless otherwise defined, the otherwise meaning of all scientific and technical terminologies used herein and common skill of the art
As art personnel are generally understood.Although similar or equivalent method and material also can be used with approach described herein and material
In the implementation or test of embodiment of the present invention, but suitable method and material is described below.What is be mentioned above is all
Publication, patent application, patent and other bibliography are incorporated herein in a manner of being cited in full text, and remove non-quoted physical segment
It falls.If conflict occurs, it is subject to this specification and its included definition.In addition, material, method and embodiment are only illustrative
, it is no intended to it is limited.
In industrial catalyst, the state of catalyst pore structure be influence catalyst catalytic performance an important factor for one of.
The pore structure of catalyst is larger, this is conducive to the mass transfer and diabatic process of catalysis reaction, but it will affect reaction mass anti-
The time contacted during answering with activated centre；Catalyst pore structure is smaller, this is conducive to extend in material and catalyst activity
The time of contact of the heart, but the heat generated in reaction product and reaction process will be not easy to export, this will cause a series of pairs
The generation of reaction, to directly affect the selectivity of target product.Present invention discover that for the fluorination catalyst of precipitation method preparation,
When the average pore size of its presoma is 4-8nm, especially when the average pore size of its presoma is 5-6nm, catalyst tool
There is very high catalytic activity.When the average pore size of the presoma of fluorination catalyst is less than 4nm, since lesser aperture is internally expanded
It dissipates and leads to active decline；When the average pore size of the presoma of fluorination catalyst is greater than 8nm, the specific surface area of catalyst is substantially
Degree declines and is unfavorable for reacting.
The beneficial effects of the present invention are:
1) surfactant used in the present invention can be reduced the collapsing of catalyst micropore in roasting process, can be abundant
Adjusting catalyst precursor pore structure size, increase catalyst average pore size；
2) fluorination catalyst prepared in the present invention adds various metals auxiliary agent on the basis of chromium base or adds gold simultaneously
Belong to auxiliary agent and surfactant, synthesized catalyst still had greater activity using 3 months or more, i.e., synthesized by the present invention
Catalyst have a longer life expectancy；Catalyst catalytic activity also with higher synthesized by the present invention simultaneously, is conducive to mention
The yield of high target product, to can largely reduce energy consumption, save the cost in commercial process.
3) the catalyst catalytic activity with higher in the present invention, and can be in the catalysis preparation process of hydrogen fluorohydrocarbon
The effective conversion ratio for improving reactant, reduces the content of by-product, to obtain the product of higher yields and selectivity；
4) fluorination catalyst synthesized in the present invention is greatly improving target product during catalysis prepares R125
The generation that R115 is reduced while the yield of R125 overcomes generated by-product during synthesizing R125 at present
The boiling point of R115 is close with HFC-125, and there are azeotropisms, it is difficult to is isolated, and can only used with common distillation technology
Extraction fractional distillation is isolated the problems such as purification, thus largely improve its energy consumption in industrial separation purification process and at
This, so that avoiding the separation process of subsequent complexity, reducing industrial energy consumption and production cost while having also obtained Gao Pin
The R125 product of matter.
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred implementation side
Formula.It should be pointed out that for those skilled in the art on the basis of the inventive concept, several deformations for making and
It improves, belongs to protection scope of the present invention, in order to further describe the present invention, illustrate combined with specific embodiments below.
Comparative example 1
By 500g CrCl3·6H2O、2.4g ZnCl2It is dissolved in 11.45L deionized water, adjusting reaction kettle revolving speed is
400r/min mixes mixed salt solution with ammonium hydroxide to pH value of solution=9.5 in kettle, continues to filter washing after stirring aging 90min
Sample is obtained, roaster is transferred to after plunging the sample into 120 DEG C of oven drying 10h, in N2360 DEG C of roasting 7h in atmosphere, after roasting
Sample comminution be sieved and be added 2% graphite (mass fraction), form uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 288.33m2/ g, pore volume are
0.3115ml/g, average pore size 4.322nm.
Embodiment 1
By 500g CrCl3·6H2O、2.4g ZnCl2、1.876×10-4The OBS of M is dissolved in 11.45L deionized water,
Adjusting reaction kettle revolving speed is 400r/min, and mixed salt solution is mixed with ammonium hydroxide to pH value of solution=9.5 in kettle, continues to stir aging
Filtering washing obtains sample after 90min, plunges the sample into 105 DEG C of oven dryings and is transferred to roaster afterwards for 24 hours, in N2395 in atmosphere
DEG C roasting 3h, the sample comminution after roasting be sieved and is added 2% graphite (mass fraction), pressed powder molding that will be uniformly mixed
Obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 335.876m2/ g, pore volume
For 0.4232ml/g, average pore size 4.988nm.
Embodiment 2
By 500g CrCl3·6H2O、0.13g ZnCl2、3.48g LaCl3、45.5g AlCl3Be dissolved in 11.45L go from
In sub- water, adjusting reaction kettle revolving speed is 400r/min, and mixed salt solution is mixed with ammonium hydroxide to solution PH=9.5 in kettle, is continued
Filtering washing obtains sample after stirring aging 90min, roaster is transferred to after plunging the sample into 140 DEG C of oven drying 5h, in N2Gas
400 DEG C of roasting 2h in atmosphere, the sample comminution after roasting are sieved and are added 2% graphite (mass fraction), by uniformly mixed powder
Compression molding obtains catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 310.885m2/ g, pore volume
For 0.4492ml/g, average pore size 4.723nm.
Embodiment 3
By 500g CrCl3·6H2O、13.94g LaCl3、12.51g AlCl3、27.31g Co(NO3)2、1.23g
NiCl2It is dissolved in 7.5L deionized water, adjusting reaction kettle revolving speed is 1000r/min, and mixed salt solution is mixed in kettle with ammonium hydroxide
PH value of solution=8 are bonded to, continues filtering washing after stirring aging 8min and obtains sample, after plunging the sample into 120 DEG C of oven drying 10h
It is transferred to roaster, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 1% graphite (mass fraction),
It forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 200 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 320.575m2/ g, pore volume
For 0.4220ml/g, average pore size 4.982nm.
Embodiment 4
By 500g CrCl3·6H2O、36.54g ZnCl2、2.73g Co(NO3)2、22.30g NiCl2、0.25g NbCl5
It is dissolved in 10L deionized water, adjusting reaction kettle revolving speed is 100r/min, and mixed salt solution is mixed with ammonium hydroxide to solution in kettle
PH=11 continues filtering washing after stirring aging 20min and obtains sample, is transferred to roasting after plunging the sample into 120 DEG C of oven drying 10h
Furnace is burnt, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 3% graphite (mass fraction), will mix
Uniform pressed powder forms to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 260 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 345.885m2/ g, pore volume
For 0.4122ml/g, average pore size 4.983nm.
Embodiment 5
By 500g CrCl3·6H2O、0.13g AlCl3、2.19g ZrCl4、34.95g CeCl2、20.75g InCl3It is molten
For solution in 10L deionized water, adjusting reaction kettle revolving speed is 300r/min, and mixed salt solution is mixed with ammonium hydroxide to pH value of solution in kettle
=8.5, continue filtering washing after stirring aging 200min and obtain sample, is transferred to roasting after plunging the sample into 120 DEG C of oven drying 10h
Furnace is burnt, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 3% graphite (mass fraction), will mix
Uniform pressed powder forms to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 280 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 356.885m2/ g, pore volume
For 0.4492ml/g, average pore size 5.350nm.
Embodiment 6
By 500g CrCl3·6H2O、42.3g MgCl2、21.86g ZrCl4、3.49g CeCl2、0.21g InCl3Dissolution
In 10L deionized water, adjusting reaction kettle revolving speed is 600r/min, mixed salt solution is mixed in kettle with ammonium hydroxide to pH value of solution=
9, continue filtering washing after stirring aging 30min and obtain sample, is transferred to roaster after plunging the sample into 120 DEG C of oven drying 10h,
In N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 4% graphite (mass fraction), will be uniformly mixed
Pressed powder form to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 300 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 361.885m2/ g, pore volume
For 0.4503ml/g, average pore size 5.260nm.
Embodiment 7
By 500g CrCl3·6H2O、12.8g MgCl2、15.22g FeCl3、11.14g MnCl4、8.3g InCl3Dissolution
In 10L deionized water, adjusting reaction kettle revolving speed is 900r/min, mixed salt solution is mixed in kettle with ammonium hydroxide to pH value of solution=
9.5, continue filtering washing after stirring aging 180min and obtain sample, is transferred to roasting after plunging the sample into 120 DEG C of oven drying 10h
Furnace, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 4% graphite (mass fraction), and mixing is equal
Even pressed powder forms to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 365.825m2/ g, pore volume
For 0.4692ml/g, average pore size 5.250nm.
Embodiment 8
By 500g CrCl3·6H2O、5.64g Co(NO3)2、0.09g MgCl2、7.43g MnCl4、9.6×10-5M's
OBS is dissolved in 12.5L deionized water, and adjusting reaction kettle revolving speed is 20r/min, mixed salt solution is mixed in kettle with ammonium hydroxide to
PH value of solution=12 continue filtering washing after stirring aging 300min and obtain sample, after plunging the sample into 120 DEG C of oven drying 10h
It is transferred to roaster, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 5% graphite (mass fraction),
It forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 400 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 340.885m2/ g, pore volume
For 0.4392ml/g, average pore size 5.220nm.
Embodiment 9
By 500g CrCl3·6H2O、6.09g FeCl3、1.86g MgCl2、0.10g CaCl2It is dissolved in 10L deionized water
In, adjusting reaction kettle revolving speed is 300r/min, and mixed salt solution is mixed with ammonium hydroxide to pH value of solution=8.5 in kettle, continues to stir
Filtering washing obtains sample after aging 250min, roaster is transferred to after plunging the sample into 120 DEG C of oven drying 10h, in N2Atmosphere
In 360 DEG C of roasting 7h, the sample comminution after roasting is sieved and is added 4% graphite (mass fraction), powder pressure that will be uniformly mixed
Sheetmolding obtains catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 385.869m2/ g, pore volume
For 0.4782ml/g, average pore size 5.251nm.
Embodiment 10
By 500g CrCl3·6H2O、0.15g FeCl3、8.92g NiCl2、25.35g NbCl5It is dissolved in 10L deionization
In water, adjusting reaction kettle revolving speed is 600r/min, and mixed salt solution is mixed with ammonium hydroxide to pH value of solution=11.5 in kettle, continues to stir
Filtering washing obtains sample after mixing aging 30min, roaster is transferred to after plunging the sample into 120 DEG C of oven drying 10h, in N2Atmosphere
In 360 DEG C of roasting 7h, the sample comminution after roasting is sieved and is added 4% graphite (mass fraction), powder pressure that will be uniformly mixed
Sheetmolding obtains catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 379.538m2/ g, pore volume
For 0.4518ml/g, average pore size 5.210nm.
Embodiment 11
By 500g CrCl3·6H2O、4.16g CaCl2、34.84g LaCl3、10.14g NbCl5、5.6×10-5M's
OBS is dissolved in 10L deionized water, and adjusting reaction kettle revolving speed is 500r/min, mixed salt solution is mixed in kettle with ammonium hydroxide to
PH value of solution=10.5 continue filtering washing after stirring aging 50min and obtain sample, after plunging the sample into 120 DEG C of oven drying 10h
It is transferred to roaster, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and are added 3% graphite (mass fraction),
It forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 402.631m2/ g, pore volume
For 0.5092ml/g, average pore size 5.512nm.
Embodiment 12
By 500g CrCl3·6H2O、8.75g ZrCl4、13.98g CeCl2、10.41g CaCl、5.6×10-5M's
N15K5M3It is dissolved in 10L deionized water, adjusting reaction kettle revolving speed is 600r/min, and mixed salt solution is mixed in kettle with ammonium hydroxide
To solution PH=10, continues filtering washing after stirring aging 180min and obtain sample, plunge the sample into 120 DEG C of oven drying 10h
After be transferred to roaster, in N2360 DEG C of roasting 7h in atmosphere, the sample comminution after roasting are sieved and 3% graphite (quality point are added
Number), it forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 410.885m2/ g, pore volume
For 0.5132ml/g, average pore size 5.622nm.
Embodiment 13
By 500gCrCl3·6H2O、0.13g ZnCl2、3.48gLaCl3、45.5gAlCl3、1.87×10-4The N of M5K10M7
Be dissolved in 11.45L deionized water, adjusting reaction kettle revolving speed is 400r/min, mixed salt solution is mixed in kettle with ammonium hydroxide to
PH value of solution=9.5 continue filtering washing after stirring aging 90min and obtain sample, after plunging the sample into 105 DEG C of oven dryings for 24 hours
It is transferred to roaster, in N2390 DEG C of roasting 4h in atmosphere, the sample comminution after roasting are sieved and are added 2% graphite (mass fraction),
It forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 412.803m2/ g, pore volume
For 0.5202ml/g, average pore size 5.843nm.
Embodiment 14
By 500g CrCl3·6H2O、3.5g ZnCl2、3.3g NiCl2、2.73g Co(NO3)、25.8g AlCl3Dissolution
In 11.45L deionized water, adjusting reaction kettle revolving speed is 400r/min, and mixed salt solution is mixed with ammonium hydroxide to solution in kettle
PH=9.5 continues filtering washing after stirring aging 90min and obtains sample, is transferred to roasting after plunging the sample into 90 DEG C of oven drying 30h
Furnace is burnt, in N2380 DEG C of roasting 5h in atmosphere, the sample comminution after roasting are sieved and are added 2% graphite (mass fraction), will mix
Uniform pressed powder forms to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 375.842m2/ g, pore volume
For 0.4988ml/g, average pore size 5.451nm.
Embodiment 15
By 500g CrCl3·6H2O、3.5g ZnCl2、3.3g NiCl2、2.73g Co(NO3)、25.8g AlCl3、0.98
×10-4M N8K5M9Be dissolved in 11.45L deionized water, adjusting reaction kettle revolving speed be 400r/min, by mixed salt solution in kettle
It is interior to mix with ammonium hydroxide to pH value of solution=9.5, continue filtering washing after stirring aging 90min and obtain sample, plunges the sample into 90 DEG C
It is transferred to roaster after oven drying 30h, in N2370 DEG C of roasting 6h, the sample comminution after roasting are sieved and 2% stone are added in atmosphere
Black (mass fraction) forms uniformly mixed pressed powder to obtain catalyst precursor.
Then above-mentioned catalyst precursor is fitted into reactor, is passed through the mixed gas of the nitrogen and HF fluorine at 350 DEG C
Change, fluorination catalyst is made.
Specific surface area and pore structure tester is used to analyze the specific surface area of its presoma as 402.308m2/ g, pore volume
For 0.5145ml/g, average pore size 5.766nm.
Embodiment 16
Respectively by institute in comparative example 1, embodiment 1, embodiment 2, embodiment 8, embodiment 13, embodiment 14 and embodiment 15
The fluorination catalyst of preparation is used to synthesize the evaluation experimental of R125, and evaluation condition is as follows: being packed into 90ml fluorination in self-control fixed bed
Catalyst, reaction temperature control are 350 DEG C.R123 and HF are passed through in reactor, the flow of R123 is 20g/h, and HF flow is
40g/h.R123 and HF enters reactor reaction after mixing, and product gas washing, alkali cleaning use gas-chromatography after removing HCl and HF
Analysis.The conversion ratio and R124, R125 of R123 is selectively shown in Table 1.
Evaluation experimental result of 1 fluorination catalyst of table to synthesis R125
Fluorination catalyst provided in the present invention, the synthesis after being synthesized under specific process conditions, to R125
Preparation has preferable catalytic action, and the conversion ratio of R123 may be up to 98.20%, and for selectivity up to 88.47%, yield can also be high
Up to 86.87%.
Claims (8)
1. a kind of fluorination catalyst, which is characterized in that the presoma of the fluorination catalyst is mainly by metal chromic salts, metal promoted
Agent, surfactant are prepared, and wherein the molar ratio of metal chromic salts and metal promoter is 1:0.003-0.3, and the fluorination is urged
The pore volume of agent presoma is 0.30-0.53ml/g, average pore size 4.0-6.0nm；
The metal promoter is selected from tri- kinds of Zn, La and Al of combination or tetra- kinds of Zn, Ni, Co and Al of combination；
The surfactant is selected from perfluorinated nonene oxygroup benzene sulfonic acid sodium salt or hexafluoropropylene oxide tripolymer base amine-oxides；The fluorine
Changing the molar ratio of metal chromic salts and surfactant in the presoma of catalyst is 1:0.0001%-0.5%.
2. a kind of method for preparing fluorination catalyst as described in claim 1, which comprises the following steps:
1) mixed solution is obtained after dissolving metal chromic salts, metal promoter, surfactant in a solvent；
2) solution that pH value is 8-12 is obtained after mixing above-mentioned mixed solution and alkaline solution to be filtered, washed after standing aging
Sediment to neutral re-dry, after high-temperature roasting by pulverizing and sieving, compression molding is up to catalyst precursor；
3) above-mentioned presoma is fitted into reactor, the mixed gas for being passed through inert gas and HF is fluorinated at 200-400 DEG C, system
Obtain fluorination catalyst；
The metal promoter is selected from tri- kinds of Zn, La and Al of combination or tetra- kinds of Zn, Ni, Co and Al of combination；
The surfactant is selected from perfluorinated nonene oxygroup benzene sulfonic acid sodium salt or hexafluoropropylene oxide tripolymer base amine-oxides；The fluorine
Changing the molar ratio of metal chromic salts and surfactant in the presoma of catalyst is 1:0.0001%-0.5%.
3. preparation method according to claim 2, which is characterized in that graphite additive is added with when tabletting in powder,
The quality of middle graphite is the 1-5% of gross mass.
4. preparation method according to claim 2, which is characterized in that mixed solution is in 20-1000rpm in step 2)
The time for mixing under stirring rate, and standing aging is 8-300min.
5. preparation method according to claim 2, which is characterized in that the solvent is water, and the quality of water and chromic salts
Than for 15-25:1.
6. preparation method according to claim 2, which is characterized in that the roasting be carry out in inert gas, and
The temperature of roasting is 350-400 DEG C, time 2-8h.
7. the application that a kind of fluorination catalyst catalysis described in claim 1 prepares hydrogen fluorohydrocarbon, which is characterized in that for halogenated
The gas phase fluorination of hydrocarbon and hydrogen fluoride.
8. the application that a kind of catalysis of the fluorination catalyst described in claim 1 prepares R125, which is characterized in that for being catalyzed preparation
In the fluorination reaction of R125.
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| GB201615197D0 (en) * | 2016-09-07 | 2016-10-19 | Mexichem Fluor Sa De Cv | Catalyst and process using the catalyst |
| GB201615209D0 (en) | 2016-09-07 | 2016-10-19 | Mexichem Fluor Sa De Cv | Catalyst and process using the catalyst |
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| CN109569674B (en) * | 2018-11-06 | 2019-10-18 | 东莞东阳光科研发有限公司 | A kind of fluorination catalyst and its preparation method and application |
| CN110496615A (en) * | 2019-08-23 | 2019-11-26 | 江苏蓝色星球环保科技股份有限公司 | A kind of preparation method of catalysts for gas phase fluorination |
| CN110586144A (en) * | 2019-08-28 | 2019-12-20 | 东莞东阳光科研发有限公司 | Film catalyst precursor, film catalyst, preparation method and application thereof |
| CN112264057A (en) * | 2020-10-09 | 2021-01-26 | 南北兄弟药业投资有限公司 | Nano fluorination catalyst for preparing R152a and preparation method thereof |
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