CN108057435A - A kind of preparation method of catalysts for gas phase fluorination - Google Patents
A kind of preparation method of catalysts for gas phase fluorination Download PDFInfo
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- CN108057435A CN108057435A CN201711103893.2A CN201711103893A CN108057435A CN 108057435 A CN108057435 A CN 108057435A CN 201711103893 A CN201711103893 A CN 201711103893A CN 108057435 A CN108057435 A CN 108057435A
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- gas phase
- catalysts
- phase fluorination
- preparation
- organic matter
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- 238000003682 fluorination reaction Methods 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 42
- 239000005416 organic matter Substances 0.000 claims abstract description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 91
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 235000019441 ethanol Nutrition 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 150000001720 carbohydrates Chemical class 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- OLGONLPBKFPQNS-UHFFFAOYSA-M sodium 2-(4-phenylphenyl)butanoate Chemical compound [Na+].CCC(C([O-])=O)c1ccc(cc1)-c1ccccc1 OLGONLPBKFPQNS-UHFFFAOYSA-M 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229940107816 ammonium iodide Drugs 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 235000014633 carbohydrates Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011975 tartaric acid Substances 0.000 description 5
- 235000002906 tartaric acid Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 235000012501 ammonium carbonate Nutrition 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- -1 for example Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QZXRMXMYYOEUSZ-UHFFFAOYSA-N C(C1CO1)C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC Chemical group C(C1CO1)C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QZXRMXMYYOEUSZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002249 LaCl3 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
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical class [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- OIDPCXKPHYRNKH-UHFFFAOYSA-J chrome alum Chemical compound [K]OS(=O)(=O)O[Cr]1OS(=O)(=O)O1 OIDPCXKPHYRNKH-UHFFFAOYSA-J 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001845 chromium compounds Chemical class 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
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000011636 chromium(III) chloride Substances 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
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- GUCZRMHEUZDIJR-UHFFFAOYSA-N dimethyl-(oxiran-2-ylmethyl)-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1CO1 GUCZRMHEUZDIJR-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- 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
- 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
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/038—Precipitation; Co-precipitation to form slurries or suspensions, e.g. a washcoat
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of catalysts for gas phase fluorination, including：Nanocrystalline gamma-alumina powder, unformed chromium oxide powder, organic matter II and graphite are uniformly mixed, compression molding obtains catalysts for gas phase fluorination presoma；Above-mentioned catalysts for gas phase fluorination precursor is fluorinated to obtain catalysts for gas phase fluorination.Wherein, nanocrystalline gamma-alumina powder is prepared using aqueous gel sol method, and added with organic matter I.The organic matter I and organic matter II can be played the role of pore-creating by thermal decomposition volatilization, so as to get catalysts for gas phase fluorination fluorination after still with higher specific surface area, show high activity and high stability, the preparation particularly suitable for R134a products.
Description
Technical field
The present invention relates to the preparation methods of fluorination catalyst, and in particular to a kind of for halogenated hydrocarbons and the gas phase fluorine of hydrogen fluoride
Change the preparation method of the catalyst of reaction, the preparation method of the catalysts for gas phase fluorination of R134a is prepared in particular for catalysis.
Background technology
Research in recent years finds that (Ozone Depletion Potential (ODP) of (HFCs) is 0 to fluorohydrocarbon, global warming potential
(GWP) it is smaller, it is widely used in large scale business refrigerant, foaming agent, extinguishing chemical etc..Existing market mainstream environment friendly refrigerating fluid
The key production technology thereof of (R125, R134a, R1234yf) product is gas phase fluorination catalytic reaction process, and catalysts for gas phase fluorination is
Produce fluorohydrocarbon (core in (HFCs) process route, and catalysts for gas phase fluorination mainly using chromium base solid catalyst or
Aluminium base solid catalyst；Numerous studies find that pore volume, aperture and the specific surface area of fluorination catalyst catalytic activity and catalyst have
Much relations.In general, high-specific surface area, high pore volume, suitable aperture can effectively improve activity and the selection of catalyst
Property.Catalysts for gas phase fluorination is only fluorinated state and just shows high catalytic activity and highly selective, but catalysts for gas phase fluorination forerunner
Mainly there is rather than be fluorinated state in the form of the oxide in body, thus need before the reaction to catalysts for gas phase fluorination presoma into
Row fluorination activation process, and be fluorinated highly exothermic phenomenon in activation process and directly result in the increase of catalyst crystal grain, specific surface area
It is greatly reduced etc. as a result, so as to cause obtaining the problems such as fluorination catalyst activity is relatively low, stability is poor, regeneration activating is frequent,
Therefore exploitation high temperature resistant, there is important meanings for the catalysts for gas phase fluorination of high-specific surface area.
There are many researchs in relation to improving catalysts for gas phase fluorination specific surface area in the prior art.Such as Chinese patent CN
101214449A Lv Jian disclose fluorination catalyst and preparation method thereof, are 40-80 in mass ratio in the patent:10-30:10-
Aluminium compound, trivalent chromium compound and ammonium compounds are blended 30 ratios, and fluorination catalyst, patent profit is made in roasting, fluorination
It is prepared with blend technique, the specific surface area of gained fluorination catalyst is promoted.But above-mentioned preparation method urges fluorination
The specific surface area of agent promotes limitation, and the specific surface area of the fluorination catalyst after activation is all in 100m2/ below g, and it is not right
Refrigerant product R134a carries out concrete application, and effect is unknown.
The content of the invention
After fluorination activation process being carried out for catalysts for gas phase fluorination presoma in the prior art, large specific surface area
Width reduces, and so as to cause the problems such as fluorination catalyst activity is relatively low, stability is poor, regeneration activating is frequent is obtained, the present invention carries
For a kind of preparation method of new catalysts for gas phase fluorination, still there is higher ratio after obtained catalysts for gas phase fluorination fluorination
Surface area shows high activity and high stability, the preparation particularly suitable for R134a products.
In order to achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of catalysts for gas phase fluorination, which is characterized in that including：
S1：Nanocrystalline gama-alumina powder, unformed chromium oxide powder, organic matter II and graphite are uniformly mixed, tabletting
Shaping obtains catalysts for gas phase fluorination presoma；
S2：Above-mentioned catalysts for gas phase fluorination precursor is fluorinated to obtain catalysts for gas phase fluorination.
Further, unformed chromium oxide powder described in step S1, nanocrystalline gama-alumina powder, organic matter II, stone
The mass ratio of ink is 65-98.8:1-15:0.1-10:0.1-10.
Further, organic matter II described in step S1 is selected from amphoteric cellulose, polyethyleneoxide diamine, quaternary ammonium type iodate
One or more in ammonium, polyethylene glycol, polyvinylpyrrolidone.
Further, nanocrystalline gama-alumina powder is prepared by following methods described in step S1：By metallic aluminium
Salt, metal promoter, organic matter I are added in solvent, stirring and dissolving and condensing reflux, then the aqueous solution of precipitating reagent is added dropwise, reaction,
Crystallization obtains lyosol, is then dried to obtain solid gel, finally roasts and nanocrystalline gama-alumina powder is made；Wherein,
The test metal of the organic matter I accounts for the 1-20% of aluminium salt quality.
Further, the metal promoter includes alkaline-earth metal and rare metal, and the alkaline-earth metal is selected from Mg, Ca, Ba
In one or more, one or more of the rare metal in La, Y, Ce.
Further, the organic matter I includes alcohol, organic acid and carbohydrate, and the alcohol, organic acid, the mass ratio of carbohydrate are
10-30:40-80:10-30。
Further, the one kind of the alcohol in ethyl alcohol, ethylene glycol, propyl alcohol, glycerine, isopropanol, butanol, butanediol
Or more than one；One or more of the organic acid in acetic acid, tartaric acid, citric acid；The carbohydrate is selected from Portugal
One or more in grape sugar, sucrose, fructose.
Further, the time control that precipitant solution is added dropwise is in 1-60min；The drying condition is：First 25
~50 DEG C of 8~12h of vacuum drying, are then dried in vacuo 2-4h at 110 DEG C again；The roasting condition is：Under nitrogen atmosphere
350-550 DEG C of roasting 3-8h.
On the other hand, the present invention also provides catalysts for gas phase fluorination prepared by the preparation method of above-mentioned catalysts for gas phase fluorination
And application of the catalysts for gas phase fluorination in catalysis prepares the fluorination reaction of R134a.
Invention is detailed
1st, the preparation of nanocrystalline gama-alumina powder
The nanocrystalline gama-alumina powder used in the preparation method of the above-mentioned catalysts for gas phase fluorination of the present invention is by following system
Preparation Method obtains：Metal aluminum salt, metal promoter, organic matter I are added in solvent, stirring and dissolving and condensing reflux, then are added dropwise
Precipitant solution, reaction, crystallization obtain lyosol, are then dried to obtain solid gel, and the obtained nanocrystalline γ of finally roasting-
Alumina powder.
Further, the metal promoter includes alkaline-earth metal and rare metal, and the alkaline-earth metal is selected from Mg, Ca, Ba
In one or more, one or more of the rare metal in La, Y, Ce.
Preferably, the metal promoter is the mixture of Mg and La.But said combination is not limited to, other alkaline-earth metal and dilute
There is the combination of metal, for example, Mg and Ce, Ba and La, Mg and Y, Ca and La, etc., can be used for the present invention.
Further, the quality of the organic matter I accounts for the 1-20% of Metal aluminum salt quality, preferably 1-10%, more excellent
Choosing is 1~8%, is particularly preferred to be 2~5%.
Further, the organic matter I includes alcohol, organic acid and carbohydrate, and the alcohol, organic acid, the mass ratio of carbohydrate are
10-30:40-80:10-30, preferably 15-30:50-70:10-25, more preferably 20-30:55-65:15-20.
Further, the one kind of the alcohol in ethyl alcohol, ethylene glycol, propyl alcohol, glycerine, isopropanol, butanol, butanediol
Or more than one；One or more of the organic acid in acetic acid, tartaric acid, citric acid；The carbohydrate is selected from Portugal
One or more in grape sugar, sucrose, fructose.
Preferably, the organic matter I is the mixture of isopropanol, tartaric acid and glucose.
Further, the time control of the aqueous solution that precipitating reagent is added dropwise is in 1-60min, and preferred control is in 2-
50min, preferred control is in 5-30min.
Further, one or more of the precipitating reagent in ammonium hydroxide, ammonium carbonate, urea.
Further, the drying condition of the lyosol is：8~12h first is dried in vacuo at 25~50 DEG C, is then existed again
110 DEG C of vacuum drying 2-4h.
Further, the condition of the roasting is：Under nitrogen atmosphere 3-8h is roasted at 350-550 DEG C.
2nd, the preparation of unformed chromium oxide powder
The unformed chromium oxide powder used in the preparation method of the above-mentioned catalysts for gas phase fluorination of the present invention can be used any
It is prepared by conventional method.
Preferably, the unformed chromium oxide powder is obtained by following preparation method：
Metal chromic salts, metal promoter, organic matter I is soluble in water, and stirring and dissolving is sharp into metal mixed salt solution at room temperature
The metal mixed salt solution is added in precipitating reagent aqueous solution with peristaltic pump, aging, filtering, dry, roasting are made unformed
Chrome oxide particle, pulverize and sieve (40~120 mesh) unformed chromium oxide powder.
Further, the metal chromic salts is selected from chromic nitrate, chromium chloride, chromium sulfate or chrome alum.
Further, one or more of the metal promoter in Zn, Mg, Al, Fe, Co, Ni, La.
Preferably, the metal promoter is Mg, Al, Zn and La.
Further, the quality of the organic matter I accounts for the 1-10% of chromic salts quality, and preferably 1~8%, more preferably
For 2~5%.
Further, the organic matter I be alcohol, organic acid and carbohydrate mixture, the alcohol, organic acid, the matter of carbohydrate
Amount is than being 10-30:40-80:10-30, preferably 15-30:50-70:10-25, more preferably 20-30:55-65:15-
20。
Further, the one kind of the alcohol in ethyl alcohol, ethylene glycol, propyl alcohol, glycerine, isopropanol, butanol, butanediol
Or more than one；One or more of the organic acid in acetic acid, tartaric acid, citric acid；The carbohydrate is selected from Portugal
One or more in grape sugar, sucrose, fructose.
Preferably, the organic matter I is the mixture of ethyl alcohol, citric acid and sucrose.
Further, one or more of the precipitating reagent in ammonium hydroxide, ammonium carbonate, urea.
Further, the drying condition is：100-120 DEG C of dry 12h.
Further, the roasting carries out in inert gas, and calcination temperature is 200-400 DEG C, roasting time 3-
10h。
3rd, the preparation of catalysts for gas phase fluorination
The preparation method of the catalysts for gas phase fluorination includes：By nanocrystalline gama-alumina powder, unformed chromium oxide powder
End, organic matter II and graphite are uniformly mixed, and compression molding obtains catalyst precursor；Catalyst precursor is fluorinated to obtain gas phase
Fluorination catalyst.
Further, the unformed chromium oxide powder, nanocrystalline gama-alumina powder, organic matter II, the quality of graphite
Than for 65-98.8:1-15:0.1-10:0.1-10, preferably 75~93.8:5~12:0.2~5:1~8, more preferably
81~90:8~12:0.5~2:1.5~5.
Further, the organic matter II is selected from amphoteric cellulose, polyethyleneoxide diamine, quaternary ammonium type ammonium iodide, poly- second two
One or more in alcohol, polyvinylpyrrolidone (PVP).
Preferably, the amphoteric cellulose is quaternary ammonium type carboxymethyl cellulose, and the quaternary ammonium type carboxymethyl cellulose is selected from
Glycidyl trioctylmethylammonium chloride-carboxymethyl cellulose (EPTO-CMC), glycidyl dimethyl tetradecyl ammonium chloride-carboxylic first
One kind in base cellulose (MEQ-CMC), trimethyl lignin ammonium chloride-carboxymethyl cellulose (TLQAS-CMC) or it is a kind of with
On.
Preferably, the quaternary ammonium type carboxymethyl cellulose is EPTO-CMC.
But the above-mentioned quaternary ammonium type carboxymethyl cellulose enumerated is not limited to, other are commonly used in the art to can reach same effect
Amphoteric cellulose can also be used for the present invention.
Preferably, the quaternary ammonium type ammonium iodide is N- [3- (p- perfluorinated nonene oxygroups benzoyl) propyl]-N, N, N- tri-
Methylpyridinium iodide ammonium.But it is not limited to above-mentioned N- [3- (p- perfluorinated nonene oxygroups benzoyl) propyl]-N, N enumerated, N- trimethyls
Ammonium iodide, other quaternary ammonium type ammonium iodides that can reach same effect commonly used in the art can also be used for the present invention.
Further, the fluorination is carried out under the mixed gas of inert gas and HF, fluorination temperature for 300~
400℃.Preferably, it is 300~350 DEG C to be fluorinated temperature.
4th, catalysts for gas phase fluorination
Catalysts for gas phase fluorination, the ratio table of the catalysts for gas phase fluorination are obtained by the preparation method that is provided in the present invention
Area is 130~150m2/g.In some embodiments, the specific surface area of catalysts for gas phase fluorination is 130m2/g、135m2/g、
140m2/ g or 145m2/g。
Term defines
" water " used in embodiments of the present invention is deionized water.
Heretofore described " inert gas " refers to the gas for not participating in reaction during roasting and fluorination, such as
Nitrogen, argon gas etc..
Drying of the present invention refers to energy is borrowed to make water or solvent gasification in material, and takes away generated steam
Process.Drying mode is drying drying used by some embodiments of the present invention.It should be pointed out that same effect can be reached
Drying means further include but be not limited to drying drying, vacuum drying, freeze-drying, pneumatic conveying drying, microwave drying, infrared ray are done
Dry and dielectric dry etc..
Term " washing " of the present invention refers to through certain effect weaken or eliminate between impurity and material
Interaction, makes the combination of impurity and material be changed into the combination of impurity and solvent, and impurity is finally made to depart from material.The present invention
Some embodiments in refer to the process of be rinsed material to pH ≈ 7 with water, ethyl alcohol.
Terminology used in the present invention " filtering " represent gravity or other external force effect under by medium by fluid with it is non-
The separated operation of fluid, the medium include but 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 not limited to vacuum or decompressor, pressurization dress
It puts, centrifugal device etc..
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention quotes include end value.For example, " roasting 3-
8h ", the value range for representing roasting time are 3h≤roasting time≤8h.
Terminology used in the present invention "one" or " one kind " describes element and component described herein.It so does 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 a number with N values is disclosed
The number that N+/- 1%, N+/- 2%, N+/- 3%, N+/- 5%, N+/- 7%, N+/- 8% or N+/- 10% are worth can be by clearly public
It opens, wherein " +/- " refers to add deduct, and the scope 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 use 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, except non-quoted physical segment
Fall.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.
The beneficial effects of the present invention are：
1) present invention adds organic matter I and metal promoted when preparing nanocrystalline gama-alumina powder and unformed chromium oxide
Agent, on the one hand, organic matter I can make precipitation particles and metal promoter high degree of dispersion, prevent that precipitation particles is excessively heavy in precipitation process
The reunion rate formed sediment with metal promoter during exothermic heat of reaction；On the other hand, firing stage, organic matter I are heated volatilization, play pore-creating
Effect, while metal promoter can effectively reduce duct and cave in rate；The two synergistic effect is conducive to catalyst after high-temperature process
Still keep high-specific surface area, original aperture and pattern；
2) in the preparation method of catalysts for gas phase fluorination provided by the invention, organic matter II is added, the organic matter II can
To be played the role of pore-creating and lubrication adhesive effect by thermal decomposition volatilization, activity and the service life of catalysts for gas phase fluorination are carried；
3) when catalyst prepared by the present invention is applied to the preparation of R134a, high activity, high stability are shown, the catalysis
After agent successive reaction 1050h, the conversion ratio of raw material R133a stills remain in 27% or so.
Description of the drawings
Fig. 1：The life diagram for the catalysts for gas phase fluorination that embodiment 3 is prepared with comparative example 3
Specific embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferably implemented
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation design, several deformations for making and
It improves, protection scope of the present invention is belonged to, in order to further describe the present invention, below in conjunction with the accompanying drawings with for specific embodiment
It is bright.
The preparation of the nanocrystalline gama-alumina powder of embodiment 1-1
By 25.03g Al (NO3)3·9H2O、1.35g MgCl2、0.21gLaCl3, 1g organic matters I (0.26g isopropanols+
0.56g tartaric acid+0.18g glucose) it is dissolved in 500mL alcohol solvents, the reflow treatment 2h under 80 DEG C of stirrings, then carbonic acid is added dropwise
Aqueous ammonium, time for adding 10min, then crystallization 12h under reaction temperature is maintained to obtain lyosol, then by lyosol 110
DEG C vacuum drying 12h obtain solid gel, finally 550 DEG C roast 3h nanocrystalline gama-alumina powder is made, it is standby as carrier
With.
The preparation of the nanocrystalline gama-alumina powder of embodiment 1-2
By 25.03g Al (NO3)3·9H2O is dissolved in 500mL alcohol solvents, the reflow treatment 2h under 80 DEG C of stirrings, then is dripped
Add ammonium carbonate solution, time for adding 10min, then crystallization 12h is maintained under reaction temperature to obtain lyosol, then by lyosol
12h is dried in vacuo at 110 DEG C and obtains solid gel, and finally roasting 3h at 550 DEG C is made nanocrystalline gama-alumina powder.
The preparation of 2 unformed chromium oxide powder of embodiment
Weigh 50.02g CrCl3·6H2O、1.85gMgCl2、2.81g AlCl3、1.53gZnCl3、0.21g LaCl3、
2.49g organic matters I (0.68g ethyl alcohol+1.42g citric acid+0.39g sucrose) is dissolved in 900mL deionized waters, obtains salt-mixture
Solution mixes the mixing salt solution to pH value of solution=10 with ammonium hydroxide, and filtering washing obtains sample, sample is placed in baking oven 110
DEG C dry 6h, after be transferred to roaster, in N2350 DEG C of high-temperature roasting 3h in atmosphere, the sample comminution sieving after roasting, obtain unformed
Chromium oxide powder, it is spare.
Embodiment 3
By 92% unformed chromium oxide powder, the 5% nanocrystalline gama-alumina powder prepared by embodiment 1-1,1%
EPTO-CMC, 2% graphite mixed pressuring plate are molded to obtain catalysts for gas phase fluorination presoma；It then will be before the catalysts for gas phase fluorination
It drives body to be fitted into reactor, the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, and catalysts for gas phase fluorination is made.
Embodiment 4
85% unformed chromium oxide powder, the 10% nanocrystalline gama-alumina powder prepared by embodiment 1-1,2% are gathered
Ethylene oxide diamines, 3% graphite mixed pressuring plate are molded to obtain catalysts for gas phase fluorination presoma；Then by the catalysts for gas phase fluorination
Presoma is fitted into reactor, and the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, and catalysts for gas phase fluorination is made.
Embodiment 5
By 81% unformed chromium oxide powder, the 13% nanocrystalline gama-alumina powder prepared by embodiment 1-1,1% season
Ammonium type ammonium iodide, 5% graphite mixed pressuring plate are molded to obtain catalysts for gas phase fluorination presoma；Then by the catalysts for gas phase fluorination
Presoma is fitted into reactor, and the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, and catalysts for gas phase fluorination is made.
Comparative example 1
By 92% unformed chromium oxide powder, the 5% nanocrystalline gama-alumina powder prepared by embodiment 1-2,1%
EPTO-CMC, 2% graphite mixed pressuring plate shaping catalysts for gas phase fluorination presoma；Then by the catalysts for gas phase fluorination presoma
It is fitted into reactor, the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, and catalysts for gas phase fluorination is made.
Comparative example 2
By 97% unformed chromium oxide powder, 1%EPTO-CMC, 2% graphite mixed pressuring plate shaping catalysts for gas phase fluorination
Presoma；Then the catalysts for gas phase fluorination presoma is fitted into reactor, be passed through at 350 DEG C of the mixed gas of nitrogen and HF
Fluorination, is made catalysts for gas phase fluorination.
Comparative example 3
By 98% unformed chromium oxide compounds, 2% graphite mixed pressuring plate shaping catalysts for gas phase fluorination presoma；Then
The catalysts for gas phase fluorination presoma is fitted into reactor, the mixed gas for being passed through nitrogen and HF is fluorinated at 350 DEG C, is made
Catalysts for gas phase fluorination.
6 performance test of embodiment and evaluation
The catalysts for gas phase fluorination prepared by embodiment 3-5, comparative example 1-3 is surveyed using specific surface area and pore structure respectively
Examination instrument analyzes its reference area, and test result is shown in Table 1.
The evaluation that catalysts for gas phase fluorination prepared by embodiment 3-5, comparative example 1-3 is used to synthesize to R134a respectively is real
It tests, evaluation condition is as follows：The 20mL catalysts for gas phase fluorination prepared is attached in self-control fixed bed reactors, reaction temperature control
For 310-360 DEG C.R133a and HF are passed through into reactor, the flow of R133a is 30g/h, and HF flows are 62g/h.R133a and
For HF after mixing into reactor reaction, product gas washing, alkali cleaning use gas chromatographic analysis after removing HCl and HF.R133a's
Conversion ratio and R134a are selectively shown in Table 2.
The catalysts for gas phase fluorination prepared to embodiment 3 and comparative example 3 carries out life test, and test result is shown in attached drawing 1.
The specific surface area of 1 catalysts for gas phase fluorination of table
| Number | Nanocrystalline gama-alumina | Organic matter II | Specific surface area, m2/g |
| Embodiment 3 | It is prepared by embodiment 1-1 | EPTO-CMC | 140.85 |
| Embodiment 4 | It is prepared by embodiment 1-1 | Polyethyleneoxide diamine | 144.11 |
| Embodiment 5 | It is prepared by embodiment 1-1 | Quaternary ammonium type ammonium iodide | 136.75 |
| Comparative example 1 | It is prepared by embodiment 1-2 | EPTO-CMC | 103.12 |
| Comparative example 2 | / | EPTO-CMC | 109.64 |
| Comparative example 3 | / | / | 89.38 |
From data in table 1, it is up to by the specific surface area of the embodiment 3-5 catalysts for gas phase fluorination prepared
136.75m2/ more than g, compared with comparative example 1-3, the specific surface area of the catalysts for gas phase fluorination of the preparation of embodiment 3 is by 100m2/
G or so is increased to 140m2/g.Show still be kept after high-temperature process by catalysts for gas phase fluorination prepared by embodiment
High-specific surface area.
2 catalysts for gas phase fluorination of table is to the evaluation experimental result of synthesis R134a
From data in table 2, compared with comparative example, during the catalysts for gas phase fluorination catalytic reaction prepared by embodiment,
The conversion ratio of R133a is increased to more than 30% by 26%, shows the activity of catalysts for gas phase fluorination prepared by the embodiment of the present invention
Higher.
From Fig. 1 test results, during catalysts for gas phase fluorination catalytic reaction prepared by embodiment 3, successive reaction 1050h
Afterwards, the conversion ratio of raw material R133a stills remain in 27% or so, and catalysts for gas phase fluorination catalytic reaction prepared by comparative example 3
When, the conversion ratio of raw material R133a has decreased to 20%, shows the catalytic activity of catalysts for gas phase fluorination prepared by embodiment 3 more
Stablize, longer life expectancy.
Claims (10)
1. a kind of preparation method of catalysts for gas phase fluorination, which is characterized in that including：
S1：Nanocrystalline gama-alumina powder, unformed chromium oxide powder, organic matter II and graphite are uniformly mixed, compression molding
Obtain catalysts for gas phase fluorination presoma；
S2：Above-mentioned catalysts for gas phase fluorination precursor is fluorinated to obtain catalysts for gas phase fluorination.
2. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that without fixed described in step S1
Type chromium oxide powder, nanocrystalline gama-alumina powder, organic matter II, the mass ratio of graphite are 65-98.8:1-15:0.1-10:
0.1-10。
3. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that organic described in step S1
The one kind of object II in amphoteric cellulose, polyethyleneoxide diamine, quaternary ammonium type ammonium iodide, polyethylene glycol, polyvinylpyrrolidone
Or more than one.
4. the preparation method of catalysts for gas phase fluorination according to claim 1, which is characterized in that nanometer described in step S1
Brilliant gama-alumina powder is prepared by following methods：Metal aluminum salt, metal promoter, organic matter I are added in solvent, stirred
Dissolving and condensing reflux are mixed, then the aqueous solution of precipitating reagent is added dropwise, reaction, crystallization obtain lyosol, be then dried to obtain solid
Gel finally roasts and nanocrystalline gama-alumina powder is made；Wherein, the quality of the organic matter I accounts for the 1- of Metal aluminum salt quality
20%.
5. the preparation method of catalysts for gas phase fluorination according to claim 4, which is characterized in that the metal promoter includes
Alkaline-earth metal and rare metal, one or more of the alkaline-earth metal in Mg, Ca, Ba, the rare metal choosing
From the one or more in La, Y, Ce.
6. the preparation method of catalysts for gas phase fluorination according to claim 4, which is characterized in that the organic matter I includes
Alcohol, organic acid and carbohydrate, the alcohol, organic acid, the mass ratio of carbohydrate are 10-30:40-80:10-30.
7. the preparation method of catalysts for gas phase fluorination according to claim 6, which is characterized in that the alcohol be selected from ethyl alcohol,
One or more in ethylene glycol, propyl alcohol, glycerine, isopropanol, butanol, butanediol；The organic acid is selected from acetic acid, wine
One or more in stone acid, citric acid；One or more of the carbohydrate in glucose, sucrose, fructose.
8. the preparation method of catalysts for gas phase fluorination according to claim 4, which is characterized in that the dropwise addition precipitating reagent is molten
The time control of liquid is in 1-60min；The drying condition is：8~12h first is dried in vacuo at 25~50 DEG C, then again at 110 DEG C
It is dried in vacuo 2-4h；The roasting condition is：Under nitrogen atmosphere 3-8h is roasted at 350-550 DEG C.
9. the gas phase fluorination prepared according to the preparation method of claim 1-8 any one of them catalysts for gas phase fluorination is catalyzed
Agent.
10. the application of the catalysts for gas phase fluorination described in claim 9, which is characterized in that the catalysts for gas phase fluorination is used for
Catalysis is prepared in the fluorination reaction of R134a.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590493A (en) * | 2019-09-24 | 2019-12-20 | 浙江三美化工股份有限公司 | Preparation method of high-purity hexafluoroethane |
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