CN108067260A - A kind of preparation method of core-shell catalyst for methane zirconyl oxyhalides - Google Patents
A kind of preparation method of core-shell catalyst for methane zirconyl oxyhalides Download PDFInfo
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- CN108067260A CN108067260A CN201610990982.2A CN201610990982A CN108067260A CN 108067260 A CN108067260 A CN 108067260A CN 201610990982 A CN201610990982 A CN 201610990982A CN 108067260 A CN108067260 A CN 108067260A
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- silica
- zinc
- methane
- catalyst
- solid acid
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011258 core-shell material Substances 0.000 title claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 238
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 116
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 116
- 239000011701 zinc Substances 0.000 claims abstract description 116
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 107
- 238000001035 drying Methods 0.000 claims abstract description 83
- 239000011973 solid acid Substances 0.000 claims abstract description 79
- 239000002253 acid Substances 0.000 claims abstract description 74
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 61
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 61
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 60
- 239000011593 sulfur Substances 0.000 claims abstract description 60
- 230000032683 aging Effects 0.000 claims abstract description 56
- 239000002002 slurry Substances 0.000 claims abstract description 56
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims abstract description 29
- 239000007921 spray Substances 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 239000007853 buffer solution Substances 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 114
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 14
- 239000005695 Ammonium acetate Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229940043376 ammonium acetate Drugs 0.000 claims description 14
- 235000019257 ammonium acetate Nutrition 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- -1 wherein Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 abstract description 14
- 238000011156 evaluation Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- 238000007598 dipping method Methods 0.000 description 17
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 15
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 10
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 10
- 238000002407 reforming Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 description 5
- 229960001763 zinc sulfate Drugs 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002420 LaOCl Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical class O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 229910021485 fumed silica Inorganic materials 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- NLOAOXIUYAGBGO-UHFFFAOYSA-N C.[O] Chemical compound C.[O] NLOAOXIUYAGBGO-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000007138 Deacon process reaction Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- LEMJKBQFTSWJDG-UHFFFAOYSA-N O(Cl)Cl.C Chemical compound O(Cl)Cl.C LEMJKBQFTSWJDG-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UEJSULFMZBPUJW-UHFFFAOYSA-N bromomethane methane Chemical compound C.CBr UEJSULFMZBPUJW-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940044927 ceric oxide Drugs 0.000 description 1
- 229940060038 chlorine Drugs 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/154—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of saturated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of preparation method of the core-shell catalyst for methane zirconyl oxyhalides, includes the following steps：（1）Using the buffer solution oxide impregnation silicon of ammonium salt-containing, modified silicon oxide is then made after aging, drying, calcination process；（2）Zinc is supported on step（1）On modified silicon oxide obtained, the silica of zinc supported is made after drying, roasting（3）Zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid；（4）Use step（3）The aluminum hydroxide slurry of the sulfur acid zirconium solid acid of preparation sprays the silica of zinc supported, and methane zirconyl oxyhalides catalyst is made after drying, roasting.Catalyst prepared by this method can improve the conversion ratio of methane and the selectivity of target product halide simultaneously, it is suppressed that the deep oxidation of halide, and then significantly improve the yield of halide.
Description
Technical field
The present invention relates to a kind of preparation methods of the core-shell catalyst for methane zirconyl oxyhalides, relate in particular to one kind
Low temperature high activity, be used alternately for methane zirconyl oxyhalides core-shell catalyst preparation method.
Background technology
Methane is not direct with halogen reaction but by the use of HCl, HBr or metal halide as halogen source, in the presence of oxygen
The process for carrying out reaction generation halide is known as zirconyl oxyhalides reaction.This method is earliest applied to HCl catalysis oxidation preparing chlorine gas
Industrial production is known as Deacon processes.
The methane zirconyl oxyhalides of early stage are reacted mainly using HCl as halogen source, and catalyst is mainly with CuCl2For active component,
Bromhead etc.（Bromhead J, Font-Freide J J, Westlake D J. Process for the
production of methyl or ethyl mono-chloride or bromide. EP. Patent, 0117731.
1984-09-05）CuCl on alumina2Oxychlorination catalyst is made.Conner etc.（Conner W C Jr,
Pieters W J M, Gates W, et al. The oxyhydrochlorination of methane on fumed
silica-based Cu, K, La catalysts: II. Gas phase stoichiometry. Appl Catal,
1984, 11(1): 49-58；Conner W C Jr, Pieters W J M, Signorelli A J. The
oxyhydrochlorination of methane on fumed silica-based Cu, K, La catalysts:
III. Bulk&surface analysis. Appl. Catal., 1984, 11(1): 59-71）In CuCl2Catalyst base
Dystectic alkali metal chloride KCl or rare-earth metal chloride LaCl is with the addition of on plinth3Auxiliary agent is made, uses it to rugged catalyst
Activity, so as to reduce because of CuCl2Catalyst loss caused by low boiling point obtains higher methane conversion, catalytic effect
Also stablize relatively, but also result in the rise of more chloromethane selectivity.
US 6452058 is disclosed as CuCl2The rare-earth metal chloride LaCl of main auxiliary agent3Have for oxi-chlorination
Good catalytic activity, has synthesized porous LaOCl, catalyst has good catalytic performance, is 400 in reaction temperature
DEG C, methane conversion has reached 12%, and the selectivity of monochloro methane is then 55%.
For La base catalyst, Lercher etc.（ Podkolzin S G, Stangland E E, Lercher J A,
et al. Methyl Chloride Production from Methane over Lanthanum-Based
Catalysts. J. Am. Chem. Soc., 2007, 129(9): 2569-2576）Further research has been done, has been synthesized
Catalyst LaOCl/LaCl3In 540 DEG C, gas composition V（CH4）:V（HCl）:V（O2）:V（N2）=2:1:1:Under conditions of 0.5, methane
Conversion ratio 13.3%, monochloro methane selectivity 62.6%, and catalyst has good stability.Lercher is also further ground
Reaction mechanism is studied carefully, La is to make the metal that oxi-chlorination occurs for methane and itself valence state is constant, he thinks that reaction is being catalyzed
Redox reaction, O occur for agent surface2The Cl on activated catalyst surface forms OCl, and OCl becomes after playing activation to methane
The mutual inversion of phases of Cl, Cl and OCl, enables oxi-chlorination to carry out.
Wang Ye etc.（Transformation of methane to propylene:a two step reaction
route catalyzed by modified CeO2 nanocrystals and zeolites [J]. Angewendte
Chemie Internation Edition, 2012, 51: 2438-2442；Ceric oxide nanorod loads palladium oxide and oxygen
Methane oxychloride reaction [D] Xiamen University on change Mn catalyst, 2013.）Use urging using rare earth element ce as key component
Agent has oxi-chlorination prominent activity.Catalyst activity component is CeO2And it can modify and be made through the second component
Cerium based bi-component composite oxides, be carried on (SiO on different carriers2、Al2O3、MgO、ZrO2、TiO2Deng).It is in temperature
480℃、CH4：HCl：O2：N2：He = 4:2:1:1.5:1.5th, under conditions of 40 mL/min of air speed, CH3Cl selectivity and yield
Up to 66% and 8%, 55% selectivity of the LaOCl better than Lercher, 6.6% yield.In dual-component catalyst with iron mixed effect
Preferably, 15%wtFeOx-CeO2Nanometer rods react 100 h CH4Conversion ratio 23%, CH3Cl selectivity 74%.Ce in cerium base catalyst3 +And Ce4+Between valence state conversion and cycle in oxi-chlorination activate HCl play an important role, HCl is through O2Activate the work of generation
Property Cl, active Cl and methane reaction generate monochloro methane, the Ce being reduced3+Again by O2It is oxidized to Ce4+Complete catalytic cycle.Research
It has also been found that the crystal face that the form of catalyst is exposure significantly affects the activity of catalyst, highest activity is { 100 }
Face, it is secondary it is high be { 110 } face, and the activity in { 111 } face is minimum（Using oxygen as the epoxidation of propylene of oxidant on copper-based catalysts
With methane oxychloride reaction [D] Xiamen University on cerium base catalyst, 2012.）.
CN201310216352.6 disclose it is a kind of prepare bromomethane and the catalyst of CO for bromine oxidation of methane, it is described to urge
Agent includes main active component and carrier, wherein the main active component is selected from FePO4、Fe2P2O7And Fe3(P2O7)2In one
Kind is several, and the carrier is selected from TiC-SiC and TiO2One or more of-SiC, and the weight of the main active component
1.0~50.0% that content is the catalyst weight are measured, the catalyst, will be containing main active component by using infusion process
Maceration extract is supported on carrier, through drying, roasting after be made, the catalyst under normal pressure and 400-800 DEG C of reaction condition,
It is capable of the mixture high activity of catalytic methane, oxygen and HBr aqueous solutions, is converted into bromomethane and CO with high selectivity.It is described to urge
Agent has good performance, without not sent out on substantially inactivation and catalyst in the tandem reaction sequence when small more than 1400
Raw carbon distribution.
CN201110198638.7 discloses a kind of methane oxychloride chloromethanes and bromine oxidation of methane bromomethane.It is described
Cerium base catalyst is reacted suitable for methane zirconyl oxyhalides, and the cerium base catalyst can be CeO2, cerium based bi-component composite oxides
Or support type cerium base oxide catalyst etc..The cerium base catalyst can efficiently, steadily catalytic methane zirconyl oxyhalides be reacted, including
Oxychloride reacts and bromine oxidation reaction, generates chloromethanes and bromomethane.The cerium base catalyst can efficient catalytic reactant for reforming
CH4, HCl, O2Carry out oxychloride reaction generation product CH3Cl and CH2Cl2；The cerium base catalyst can also Efficient Conversion CH4, HBr
(H2O), O2Carry out bromine oxidation reaction generation CH3Br, CH2Br2。
Methane zirconyl oxyhalides reaction in the prior art has the following technical problems that high temperature is conducive to improve the conversion ratio of methane,
But the halide of generation can be made to be particularly halide deep oxidation generation CO or CO2, significantly reduce halide
Selectivity, the yield for causing halide is relatively low, therefore develop at the same there is higher methane conversion and halide select
The methane zirconyl oxyhalides catalysts of selecting property are of great significance.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation side of core-shell catalyst for methane zirconyl oxyhalides
Method.Catalyst prepared by this method can improve the conversion ratio of methane and the selectivity of target product halide simultaneously, inhibit
The deep oxidation of halide, and then significantly improve the yield of halide.
A kind of preparation method of core-shell catalyst for methane zirconyl oxyhalides, includes the following steps：
（1）Using the buffer solution oxide impregnation silicon of ammonium salt-containing, then it is made modified oxidized after aging, drying, calcination process
Silicon；
（2）Zinc is supported on step（1）On modified silicon oxide obtained, the silica of zinc supported is made after drying, roasting
（3）Zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid；
（4）Use step（3）The aluminum hydroxide slurry of the sulfur acid zirconium solid acid of preparation sprays the silica of zinc supported, through drying,
Methane zirconyl oxyhalides catalyst is made after roasting.
The above method prepare methane zirconyl oxyhalides catalyst have nucleocapsid, core be zinc supported silica, shell be containing
The aluminium oxide of zirconium sulfate solid acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 10:
1-2:1, it is preferably 8:1-5:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight content
It is preferably 8wt%-15wt%, on the basis of the silica weight of zinc supported, content of the zinc in terms of oxide is for 5wt%-10wt%
5wt%-30wt%, preferably 10 wt%-25wt%.
Catalyst prepared by the above method, the thickness of the shell is 5 μm -200 μm, is preferably 10 μm -150 μm, more into one
Step is preferably 15 μm -100 μm.
Catalyst prepared by the above method, the silica of the zinc supported can be spherical or bar shaped, preferably spherical；Load
The silica equivalent diameter of zinc is 1mm-5mm, preferably 2mm-5mm, preferably 2mm-3mm.
The above method, step（1）The buffer solution ammonium of middle ammonium salt-containing is aqueous solution, and salt can be selected from ammonium acetate, formic acid
One or more of ammonium, ammonium carbonate, ammonium hydrogen carbonate etc..The weight concentration of ammonium salt is 1%-35% in buffer solution, is preferably 5%-
20%.Aging temperature is 50-95 DEG C, is preferably 60 ~ 80 DEG C, ageing time 0.5-10h, preferably 2-5h.Drying temperature after aging
For 90-150 DEG C, drying time 0.5-36h, the dry 8-24h preferably at 100-120 DEG C.Roasting roasts at 280-500 DEG C
When 2-15 is small, when roasting 3-5 is small preferably at 300-450 DEG C.Silica is handled using the buffer solution of ammonium salt-containing, is conducive to oxygen
SiClx adsorption halogen acids, and then promote zirconyl oxyhalides reaction.
The above method, step（2）Routine techniques can be used in the preparation of the silica of middle zinc supported, including zinc is supported on oxygen
Either method in SiClx.It is specific to can be used the compound dip loading containing zinc in molded silica or by the chemical combination containing zinc
Then the silica of zinc supported is made with silica powder kneading and compacting in object through drying and roasting.City may be employed in the silica
It sells commodity or is prepared according to the prior art, the compound of the zinc supported can be zinc nitrate, zinc sulfate, zinc bromide, chlorine
Change one or more of zinc.The drying time is 1-5h, and preferably 2-4h, drying temperature is 90-150 DEG C, preferably 100-130
℃；The roasting time is 3-8h, and preferably 4-6h, temperature is 300-600 DEG C, preferably 400-500 DEG C.
The above method, step（3）Described in zirconium sulfate solid acid using commercial goods or according to prior art system
It is standby.The aluminum hydroxide slurry generally uses boehmite slurries.Boehmite also known as monohydrate alumina or vacation
Boehmite, molecular formula AlOOHnH2O（n=0.08-0.62）.For the no spy of the preparation method of aluminum hydroxide slurry
Other restriction, can be various methods commonly used in the art, such as can be aluminium alcoholates Hydrolyze method, aluminium salt or aluminate acid system or
Alkaline process, NaA1O2Solution is passed through CO2Carbonizatin method etc..Specific operating method is known to those skilled in the art, herein no longer
It repeats.
The above method, step（3）The middle aluminum hydroxide slurry with sulfur acid zirconium solid acid spray zinc supported silica it
Before, it is preferred to use vapor volume content is 1%-15%, and the vapor nitrogen mixture of preferably 1%-5% is to the silica of zinc supported
It being handled, treatment temperature is 150-300 DEG C, preferably 180-200 DEG C, processing time 5-30min, preferably 5-15 min, into
The preferred 5-10 min of one step.Result of study shows that silica can be improved using above-mentioned processing mode in the silica table of zinc supported
For the hydroxy radical content in face simultaneously without the hydroxy radical content inside improving, the aluminum hydroxide slurry for enabling sulfur acid zirconium solid acid is uniform
Spray around the silica of zinc supported, while the enough silicon oxide surfaces with zinc supported of hydrogen-oxygen bond energy of aluminium hydroxide are rich in
Hydroxyl is bonded, and is that duct is mutually got around regulations, is improved the activity of catalyst and the selectivity of target product.
The above method, step（4）Described in drying time be 1-5h, preferably 2-4h, drying temperature be 90-150 DEG C, preferably
100-130℃；The roasting time is 3-8h, and preferably 4-6h, temperature is 300-600 DEG C, preferably 400-500 DEG C.
The application of catalyst prepared by the above method in the conversion of methane zirconyl oxyhalides, using fixed-bed process, with methane, oxygen
Gas, halogen acids are reactant or carry out methane under the effect of the catalyst as reactant using methane, oxygen, aqueous solution of halogen acid
Zirconyl oxyhalides convert, and reaction temperature is 250-600 DEG C, and preferably 300-450 DEG C, methane, halogen acids, the input material volume ratio of oxygen are
(3-5):(1-3):1, the flow of methane is 10-50ml/min, preferably 20-40ml/min.The haloid acid for hydrogen chloride or
Hydrogen bromide or its aqueous solution, preferably aqueous solution of hydrogen bromide.
Result of study show methane zirconyl oxyhalides conversion reaction be related to methane-steam reforming, methane oxidation,
The many reactions of halide deep oxidation, cause the selectivity of halide can not effectively to improve.Prepared by the present invention has
The catalyst of nucleocapsid can be realized to above-mentioned the difference of the sensitivity of differential responses with the different component of core-shell structure
The relation control of reaction.The silica of the specifically kernel zinc supported of catalyst is more advantageous to progress halogen acids and is converted into halogen
The reaction of free radical and a small amount of methane halogenation reaction occurs, shell is substantially carried out methane for the aluminium oxide of sulfur acid zirconium solid acid
Halogenation, the halogen radical of interior karyogenesis can be diffused rapidly to progress methane halogenating reaction in shell, generate halogenated hydrocarbons
Rapidly diffuse into the outside of catalyst afterwards, it is therefore prevented that it is further aoxidized, and significantly improves the selectivity and methane of halogenated hydrocarbons
Conversion ratio.
Specific embodiment
A kind of methane zirconyl oxyhalides reforming catalyst and preparation method thereof is further illustrated the present invention with reference to embodiment
With using functions and effects, but following embodiment is not construed as limiting the invention.Transmission may be employed in the catalyst of the present invention
The means such as electron microscopic observation, electron diffraction analysis and Elemental Composition analysis confirm its nucleocapsid structure, and measure its center and shell
Composition.Catalyst core shell structure it is definite it is specific with the following method：Use Japanese 2100 LaB6 high scores of JEOL companies JEM
Distinguish transmission electron microscope, 0.23 nm of resolution ratio, the X ray energy dispersion spectroscopy instrument equipped with EDAX companies（EDX）, sample is placed in agate
It is fully ground in Nao mortars, then ultrasonic wave disperses 20 min in absolute ethyl alcohol.2-3 drop suspensions is taken to drop in copper mesh support
On micro-grid carbon film, TEM observations, electron diffraction analysis and Elemental Composition analysis are carried out to sample after sample drying.
Embodiment 1
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Zinc nitrate solution is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 2h, and drying temperature is 130 DEG C；The roasting time 4h, temperature is 400 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the silica of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 6h, temperature
It spends for 400 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 8wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell is 15 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, evaluation condition is as follows：Methane oxygen bromination reaction is fixed in normal pressure
It is carried out in bed microreactor.10ml 20-40 mesh catalyst is taken to be fitted into crystal reaction tube, catalyst bed is made to be located at heating
In the middle part of stove, bed fills quartz sand up and down.Reaction gas adjusts flow, the flow peristaltic pump control of hydrobromic acid with mass flowmenter
System.Temperature programming is to 350 DEG C under nitrogen protection, after constant temperature, by methane, halogen acids, oxygen, nitrogen by volume 4：
2：1：1 is passed through in reactor, and the flow of methane is 30ml/min.Tail gas divides SP- after washing, drying with north after reaction 2h
3420A type gas-chromatography on-line analyses.Evaluation result is shown in Table 1
Embodiment 2
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping salt ammonium bicarbonate aqueous solution, ammonium bicarbonate aqueous solution weight concentration are 20%.Aging temperature
For 60 DEG C, ageing time 5h, drying temperature is dry 8h at 100 DEG C after aging, when roasting that roasting 3 is small at 450 DEG C；
Prepare the silica of zinc supported：Solution of zinc sulfate is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature is 450 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the silica of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature
It spends for 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 3
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper formic acid aqueous ammonium, the weight concentration of formic acid aqueous ammonium is 10%, and aging temperature is 70 DEG C, always
The change time is 3.5h, and drying temperature is dry 15h at 110 DEG C after aging.Roasting at 380 DEG C roasting 4 it is small when；
Prepare the silica of zinc supported：Bromide solutions are impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 4h, temperature is 500 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 3mm；
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, hydrolysis temperature
Degree control is at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature control is at 90 DEG C -95 DEG C, aging
Time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the silica of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature
It spends for 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 5：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 15wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell is 60 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 4
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium carbonate solution, the weight concentration of ammonium carbonate solution is 20%.Aging temperature is 80
DEG C, ageing time 2h, drying temperature is 100 DEG C after aging, drying time 14h.Roasting at 350 DEG C roasting 4 it is small when；
Prepare the silica of zinc supported：Solution of zinc sulfate is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature is 450 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；Use volume content for 1% vapor nitrogen
Gaseous mixture carries out the silica of zinc supported hydro-thermal process, and treatment temperature is 200 DEG C, processing time 10min.
Aluminum hydroxide slurry is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:1 mixing, water
Temperature control is solved at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carries out aging, aging temperature is controlled at 90 DEG C -95 DEG C,
Ageing time is 18h, obtains the aluminum hydroxide slurry that solid content is 21.3wt%.
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain sulfur acid zirconium solid acid
Then aluminum hydroxide slurry sprays the silica of zinc supported with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, through drying, roasting
Methane zirconyl oxyhalides reforming catalyst is made afterwards, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature
It spends for 450 DEG C.
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 5
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Zinc nitrate solution is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 2h, and drying temperature is 130 DEG C；The roasting time 4h, temperature is 400 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；Using being passed through dioxy into sodium aluminate solution
Change the preparing aluminum hydroxide through carbonization slurries of carbon gas：30wt%CO will be contained2CO2/N2Gaseous mixture is passed through in sodium aluminate solution,
At 30 DEG C carry out plastic reaction, control reaction end pH be 10.5-11.0, after the completion of reaction, aging, at 60 DEG C through go from
Sub- water washing is 6.5 to filtrate pH, obtains the aluminum hydroxide slurry that solid content is 31.2wt%；
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the silica of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 6h, temperature are
400℃。
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 8wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 25wt%；The thickness of the shell is 15 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 6
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Solution of zinc sulfate is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature is 450 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the silica of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 7
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Bromide solutions are impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 4h, and drying temperature is 100 DEG C；The roasting time 4h, temperature is 500 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 3mm；
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：30wt%CO will be contained2
CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, and it is 10.5- to control reaction end pH
11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, obtains solid content as 31.2wt%
Aluminum hydroxide slurry；
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the silica of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 5：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 15wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 10wt%；The thickness of the shell is 60 μm.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
Embodiment 8
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Solution of zinc sulfate is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 3h, and drying temperature is 120 DEG C；The roasting time 5h, temperature is 450 DEG C, described
The silica of zinc supported is spherical shape, and the silica equivalent diameter of zinc supported is 2mm；Use volume content for 5% vapor nitrogen
Gaseous mixture carries out the silica of zinc supported hydro-thermal process, and treatment temperature is 200 DEG C, processing time 10min.
Using the preparing aluminum hydroxide through carbonization slurries that carbon dioxide is passed through into sodium aluminate solution：It will contain
30wt%CO2CO2/N2Gaseous mixture is passed through in sodium aluminate solution, and plastic reaction is carried out at 30 DEG C, controls the reaction end pH to be
10.5-11.0, after the completion of reaction, aging, it is 6.5 to be washed at 60 DEG C through deionized water to filtrate pH, and obtaining solid content is
The aluminum hydroxide slurry of 31.2wt%；
Spray process：Suitable zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the hydrogen-oxygen of sulfur acid zirconium solid acid
Change aluminium paste liquid, the silica of zinc supported is then sprayed with the aluminum hydroxide slurry of sulfur acid zirconium solid acid, made after drying, roasting
Methane zirconyl oxyhalides reforming catalyst is obtained, the drying time is 3h, and drying temperature is 100 DEG C；The roasting time 4h, temperature are
450℃。
Catalyst property is as follows：The catalyst has nucleocapsid, and core is the silica of zinc supported, and shell is consolidated for sulfur acid zirconium
The aluminium oxide of body acid, wherein, the weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 7：1；With sulfur-bearing
On the basis of the weight of the aluminium oxide of sour zirconium solid acid, zirconium sulfate solid acid weight content is 11wt%, with the silica weight of zinc supported
On the basis of amount, zinc is using the content that oxide is counted as 15wt%；The thickness of the shell is 30 μm.
Comparative example 1
The preparation of modified silicon oxide：Using equi-volume impregnating in silica（Commercial goods, property are as follows：Specific surface 335m2/
G, pore volume 0.86ml/g）Upper dipping ammonium acetate aqueous solution, ammonium acetate aqueous solution mass concentration are 5%, and aging temperature is 80 DEG C,
Ageing time is 2h, and drying temperature is 150 DEG C after aging, drying time for 24 hours, roast at 300 DEG C roasting 3 it is small when；
Prepare the silica of zinc supported：Zinc nitrate solution is impregnated on modified silicon oxide using equi-volume impregnating, dipping is laggard
Row is dry, roasting, and the drying time is 2h, and drying temperature is 130 DEG C；The roasting time 4h, temperature is 400 DEG C, described
The silica of zinc supported is powder
The aluminium oxide of zirconium sulfate solid acid modification is prepared using aluminium isopropoxide Hydrolyze method：By water and aluminium isopropoxide in molar ratio 120:
1 mixing, hydrolysis temperature are controlled at 80 DEG C -85 DEG C, after making aluminium isopropoxide hydrolysis 1.5h, carry out aging, aging temperature is controlled 90
DEG C -95 DEG C, ageing time 18h, the aluminum hydroxide slurry that solid content is 21.3wt% is obtained, by suitable zirconium sulfate solid acid
It is mixed with aluminum hydroxide slurry, obtains the aluminum hydroxide slurry of sulfur acid zirconium solid acid, sulphur is made after filtered, dry, roasting
The aluminium oxide that sour zirconium solid acid is modified；
Aluminium oxide and the silica powder kneading and compacting of zinc supported that zirconium sulfate solid acid is modified are made and urge through drying, roasting
Agent.The weight ratio of the silica of zinc supported and the aluminium oxide of sulfur acid zirconium solid acid is 8 in catalyst：1；Consolidated with sulfur acid zirconium
On the basis of the weight of the aluminium oxide of body acid, zirconium sulfate solid acid weight content is 8wt%, using the silica weight of zinc supported as base
Standard, zinc is using the content that oxide is counted as 25wt%, and the composition of catalyst is the same as embodiment 1.
Methane zirconyl oxyhalides evaluation is carried out to above-mentioned catalyst, for evaluation condition with embodiment 1, evaluation result is shown in Table 1.
1 different catalysts of table are used for methane oxygen bromination reaction result
Claims (15)
1. a kind of preparation method of core-shell catalyst for methane zirconyl oxyhalides, includes the following steps：
（1）Using the buffer solution oxide impregnation silicon of ammonium salt-containing, then it is made modified oxidized after aging, drying, calcination process
Silicon；
（2）Zinc is supported on step（1）On modified silicon oxide obtained, the silica of zinc supported is made after drying, roasting
（3）Zirconium sulfate solid acid and aluminum hydroxide slurry are mixed, obtain the aluminum hydroxide slurry of sulfur acid zirconium solid acid；
（4）Use step（3）The aluminum hydroxide slurry of the sulfur acid zirconium solid acid of preparation sprays the silica of zinc supported, through drying,
Methane zirconyl oxyhalides catalyst is made after roasting.
2. according to the method described in claim 1, it is characterized in that：The methane zirconyl oxyhalides catalyst has nucleocapsid,
Core is the silica of zinc supported, and shell is the aluminium oxide of sulfur acid zirconium solid acid, wherein, silica and the sulfur acid zirconium of zinc supported are consolidated
The weight ratio of the aluminium oxide of body acid is 10:1-2:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate is solid
Body acid weight content is 5wt%-10wt%, and on the basis of the silica weight of zinc supported, zinc is using the content that oxide is counted as 5wt%-
30wt%。
3. according to the method described in claim 2, it is characterized in that：The silica of zinc supported and the oxygen of sulfur acid zirconium solid acid
The weight ratio for changing aluminium is 8:1-5:1；On the basis of the weight of the aluminium oxide of sulfur acid zirconium solid acid, zirconium sulfate solid acid weight contains
It measures as 8wt%-15wt%, zinc is using the content that oxide is counted as 10 wt%-25wt%.
4. according to the method described in claim 2, it is characterized in that：The thickness of the shell is 5 μm -200 μm, the oxidation of zinc supported
The a diameter of 1mm-5mm of silicon equivalent weight.
5. according to the method described in claim 4, it is characterized in that：The thickness of the shell is 10 μm -150 μm,
The silica equivalent diameter of the zinc supported is 2mm-5mm.
6. according to the method described in claim 1, it is characterized in that：Step（1）The buffer solution ammonium of middle ammonium salt-containing is aqueous solution,
Salt is selected from one or more of ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate etc., the weight concentration of ammonium salt in buffer solution
For 1%-35%, aging temperature is 50-95 DEG C, ageing time 0.5-10h, and drying temperature is 90-150 DEG C after aging, when dry
Between for 0.5-36h, roast roasted at 280-500 DEG C 2-15 it is small when.
7. according to the method described in claim 6, it is characterized in that：The weight concentration of ammonium salt is 5%-20% in buffer solution, always
It is 60 ~ 80 DEG C, ageing time 2-5h to change temperature, dries 8-24h after aging at 100-120 DEG C, is roasted at 300-450 DEG C
When 3-5 is small.
8. according to the method described in claim 1, it is characterized in that：Step（2）The preparation of the silica of middle zinc supported is using normal
Rule technology, including the either method being supported on zinc on silica.
9. according to the method described in claim 8, it is characterized in that：Using the compound dip loading of zinc will be contained in shaped alumina
Silicon or by the compound containing zinc with silica powder kneading and compacting, the silica of zinc supported is then made through drying and roasting.
10. according to the method described in claim 1, it is characterized in that：Step（2）The drying time be 1-5h, drying temperature
For 90-150 DEG C；The roasting time is 3-8h, and temperature is 400-500 DEG C.
11. according to the method described in claim 1, it is characterized in that：Step（3）Described in zirconium sulfate solid acid use commercially available business
Product are prepared according to the prior art, and the aluminum hydroxide slurry uses boehmite slurries.
12. according to the method described in claim 1, it is characterized in that：Step（3）The middle aluminium hydroxide with sulfur acid zirconium solid acid
Before slurries spray the silica of zinc supported, use vapor volume content as 1%-15%, vapor nitrogen mixture to negative
The silica for carrying zinc is handled, and treatment temperature is 150-300 DEG C, processing time 5-30min.
13. according to the method for claim 12, it is characterised in that：Use vapor of the vapor volume content for 1%-5%
Nitrogen mixture handles the silica of zinc supported, and treatment temperature is 180-200 DEG C, and processing time is 5-15 min.
14. according to the method described in claim 1, it is characterized in that：Step（4）Described in drying time be 2-4h, dry temperature
It spends for 100-130 DEG C；The roasting time be 3-8h, 400-500 DEG C of calcination temperature.
15. application of any catalyst of claim 1 to 14 in the conversion of methane zirconyl oxyhalides, it is characterised in that：Using fixed bed
Technique, using methane, oxygen, halogen acids as reactant or using methane, oxygen, aqueous solution of halogen acid be reactant in catalyst
Effect is lower to carry out methane zirconyl oxyhalides conversion, and reaction temperature is 250-600 DEG C, and methane, halogen acids, the input material volume ratio of oxygen are
(3-5):(1-3):1, the flow of methane is 10-50ml/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718017A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Shell-core catalyst and preparation method and application thereof |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146519A (en) * | 1982-02-25 | 1983-09-01 | Mitsubishi Gas Chem Co Inc | Preparation of methyl chloride and ammonia |
| CN101850244A (en) * | 2010-06-08 | 2010-10-06 | 浙江大学 | Preparation method of Al2O3-SiO3 solid acid catalyst in nuclear shell structure |
| CN102344339A (en) * | 2011-07-15 | 2012-02-08 | 厦门大学 | Application of cerium-based catalyst in methane oxyhalogenation methods used for preparing halogenated methane |
| CN104399465A (en) * | 2014-11-12 | 2015-03-11 | 石河子大学 | Core-shell catalyst and preparation method and application thereof |
| CN104624210A (en) * | 2013-11-07 | 2015-05-20 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method and application thereof and method for preparing isobutene from halogenated methane |
-
2016
- 2016-11-11 CN CN201610990982.2A patent/CN108067260B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58146519A (en) * | 1982-02-25 | 1983-09-01 | Mitsubishi Gas Chem Co Inc | Preparation of methyl chloride and ammonia |
| CN101850244A (en) * | 2010-06-08 | 2010-10-06 | 浙江大学 | Preparation method of Al2O3-SiO3 solid acid catalyst in nuclear shell structure |
| CN102344339A (en) * | 2011-07-15 | 2012-02-08 | 厦门大学 | Application of cerium-based catalyst in methane oxyhalogenation methods used for preparing halogenated methane |
| CN104624210A (en) * | 2013-11-07 | 2015-05-20 | 中国石油化工股份有限公司 | Supported catalyst as well as preparation method and application thereof and method for preparing isobutene from halogenated methane |
| CN104399465A (en) * | 2014-11-12 | 2015-03-11 | 石河子大学 | Core-shell catalyst and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112718017A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Shell-core catalyst and preparation method and application thereof |
| CN112718017B (en) * | 2019-10-28 | 2022-08-12 | 中国石油化工股份有限公司 | Shell-core catalyst and preparation method and application thereof |
| CN114797904A (en) * | 2022-04-15 | 2022-07-29 | 新奥科技发展有限公司 | Application of supported sodium catalyst in catalytic coal gasification reaction |
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