WO2020082195A1 - Ultra high selective hydrogenation catalyst and preparation thereof - Google Patents
Ultra high selective hydrogenation catalyst and preparation thereof Download PDFInfo
- Publication number
- WO2020082195A1 WO2020082195A1 PCT/CN2018/111132 CN2018111132W WO2020082195A1 WO 2020082195 A1 WO2020082195 A1 WO 2020082195A1 CN 2018111132 W CN2018111132 W CN 2018111132W WO 2020082195 A1 WO2020082195 A1 WO 2020082195A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- solution
- mixture
- carrier
- auxiliary agent
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 133
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 34
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 22
- 239000003607 modifier Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005751 Copper oxide Substances 0.000 claims description 6
- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
- -1 polyoxyethylene methacrylate Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 26
- 229910021641 deionized water Inorganic materials 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004876 x-ray fluorescence Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- RNRTZBLTXKBUMF-UHFFFAOYSA-N O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O RNRTZBLTXKBUMF-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a catalyst highly selective for hydrogenation of oxalate to ethylene glycol and preparation thereof.
- Ethylene glycol is an important organic chemical raw material widely used in the synthesis of polyester, polyester resin, moisture absorbent, plasticizer and surfactant.
- Chinese ethylene glycol consumption continues to rise, domestic production capacity is insufficient, and the relationship between supply and demand is tight.
- the present invention provides a highly selective catalyst for hydrogenation of an oxalate to ethylene and preparation thereof.
- a highly selective hydrogenation catalyst for hydrogenating an oxalate to ethylene glycol comprises an active component, an auxiliary agent and a carrier.
- the active component comprises copper or an oxide thereof.
- the auxiliary agent is a metal selected from the group consisting of Ni, B, Bi, Fe, Ce, Mo, Sn, Co, La, Y, Nd, V and W, an oxide thereof, or a combination thereof.
- the carrier is selected from the group consisting of silicon, aluminum, zirconium, titanium and an oxide thereof.
- the catalyst may have a selectivity of at least 91%for ethylene glycol at a weight space velocity of oxalate 5-20 h -1 .
- the catalyst may have a specific surface area of 250-900 m 2 /g.
- the catalyst may have a pore volume of 0.4-1.3 cm 3 /g.
- the catalyst may have an average pore diameter is 3-25 nm.
- the active component may be a copper oxide, and the catalyst may comprise 10-50 or 20-40 wt%of the copper oxide.
- the catalyst may comprise 1-15 or 2-10 wt%of the auxiliary agent.
- the catalyst may comprise 50-90 or 50-80 wt%of the carrier.
- a process for preparing the catalyst comprises: mixing a carrier precursor solution with a modifier solution to form a first mixture; adding an active metal precursor solution and an auxiliary agent precursor solution to the first mixture to form a second mixture; adding a precipitating agent solution to the second mixture to form a third mixture; stirring vigorously and aging the third mixture, whereby precipitates are formed; isolating the precipitates; and washing, drying and baking the isolated precipitates.
- a catalyst is formed for catalyzing hydrogenation of an oxalate to ethylene glycol.
- the process may further comprise activating the catalyst.
- the process may further comprise stirring the first mixture for 0.5-5h.
- the third mixture may be aged at 60-100 °C for 4-24h.
- the active metal precursor solution may comprise Cu (NO 3 ) 2 , CuCl2, Cu (CH 3 COO) 2 , or a combination thereof, and has a pH of 1.0-7.0.
- the auxiliary agent precursor solution may comprise Ni (NO 3 ) 2 , HBO 3 , BiNO 3 , Fe (NO 3 ) 3 , Ce (NO) 3 , Na 2 MoO 4 , (NH 4 ) 6 Mo 7 O 24 , SnCl 4 , Co (NO 3 ) 2 , La (NO 3 ) 3 , Y (NO 3 ) 3 , Nd (NO 3 ) 3 , NH 4 VO 3 , (NH 4 ) 6 H 2 W 12 O 40 , or a combination thereof, and has a pH of 1.0-7.0.
- the carrier precursor solution may comprise Na 2 SiO 3 , tetraethyl orthosilicate, silica sol, Al (NO 3 ) 3 , aluminum sol, ZrOCl 2 , Zr (NO 3 ) 4 , butyl titanate, TiCl 4 or a combination thereof, and has a pH of 1.0-7.0.
- the precipitating agent solution may comprise urea, ammonia water, sodium carbonate, potassium carbonate, ammonium carbonate, ethylenediamine or a combination thereof.
- the modifier solution may comprise starch, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, methyltrimethoxysilane, vinyltriethoxysilane, cetyltrimethylammonium bromide, polyoxyethylene methacrylate, or a combination thereof.
- the present invention provides a catalyst for hydrogenation of an oxalate to ethylene glycol and preparation thereof.
- the catalyst comprises an active component, an auxiliary agent and a carrier.
- the invention was made based on the inventors’surprising discoveries that selection of a suitable auxiliary agent to promote the interaction between copper as an active component and the carrier and the use of a modifier to improve the structure of the catalyst contribute to the high activity of the catalyst in catalyzing hydrogenation of an oxalate to ethylene glycol and the high selectivity of the catalyst for ethylene glycol.
- a catalyst is provided for a hydrogenation reaction, for example, an ester hydrogenation reaction of an oxalate to ethylene glycol.
- the catalyst comprises an active component, an auxiliary agent and a carrier.
- the oxalate may be dimethyl oxalate or diethyl oxalate.
- active component refers to a substance in the catalyst that catalyzes hydrogenation of an oxalate to ethylene glycol.
- the active component may be copper or an oxide thereof.
- the active component may account for about 10-50 or 20-40 wt%of the catalyst.
- active metal precursor refers to a substance in an active metal precursor solution used to provide the active component in the catalyst.
- the active metal precursor may be a soluble salt of the active metal copper, for example, Cu (NO 3 ) 2 , CuCl 2 , or Cu (CH 3 COO) 2 .
- An active metal precursor solution may be an aqueous solution comprising the active metal precursor at a concentration in the range of, for example, 5-30 wt%, based on the total weight of the solution.
- the active metal precursor solution may have a pH in the range of about 1.0-7.0.
- auxiliary agent refers to a substance in the catalyst that promote the interaction between an active component and a carrier in a catalyst.
- the auxiliary agent may be a metal selected from the group consisting of Ni, B, Bi, Fe, Ce, Mo, Sn, Co, La, Y, Nd, V and W, an oxide thereof, and a combination thereof.
- the auxiliary agent may account for about 1-15 or 2-10 wt%of the catalyst.
- auxiliary agent precursor refers to a substance in an auxiliary agent precursor solution used to provide the auxiliary agent in the catalyst.
- the auxiliary agent precursor may be a soluble salt or other soluble substance of the auxiliary metal, for example, Ni (NO 3 ) 2 , HBO 3 , BiNO 3 , Fe (NO 3 ) 3 , Ce (NO) 3 , Na 2 MoO 4 , (NH 4 ) 6 Mo 7 O 24 , SnCl 4 , Co (NO 3 ) 2 , La (NO 3 ) 3 , Y (NO 3 ) 3 , Nd (NO 3 ) 3 , NH 4 VO 3 and (NH 4 ) 6 H 2 W 12 O 40 .
- An auxiliary agent precursor solution may be an aqueous solution comprising the auxiliary agent precursor at a concentration in the range of, for example, 2-20 wt%, based on the total weight of the solution.
- the pH of the auxiliary agent precursor solution may be in the range of about 1.0-7.0.
- carrier refers to a substance in the catalyst that provides support for the active component and the auxiliary agent.
- the carrier is Si, Al, Zr, Ti, an oxide thereof, or a combination thereof.
- the carrier accounts for about 50-90 or 50-80 wt%of the catalyst.
- carrier precursor used herein refers to a substance in the carrier precursor solution used to provide a carrier in the catalyst.
- the carrier precursor may be a soluble salt or other soluble substance of the carrier, for example, Na 2 SiO 3 , tetraethyl orthosilicate, silica sol, Al (NO 3 ) 3 , aluminum sol, ZrOCl 2 , Zr (NO 3 ) 4 , butyl titanate or TiCl 4 .
- a carrier precursor solution may be an aqueous solution comprising the carrier precursor at a concentration in the range of, for example, 20-60 wt%, based on the total weight of the solution.
- the carrier precursor solution may have a PH in the range of about 1.0-7.0.
- precipitating agent refers to an agent that reacts with a precursor of the combination of the active metal, the auxiliary agent and the carrier to form precipitates.
- the precipitating agent may be a soluble carbonate, a soluble hydroxide, or a substance that hydrolyzes to generate hydroxide, carbonate or bicarbonate under certain conditions.
- the precipitating agents include urea, ammonia water, sodium carbonate, potassium carbonate, ammonium carbonate, ethylenediamine, and a combination thereof.
- a precipitating agent solution may be an aqueous solution comprising the precipitating agent at a concentration in the range of, for example, 10-50 wt%, based on the total weight of the solution.
- the precipitating agent solution may have a pH in the range of about 6.0-11.0.
- modifier refers to a substance that modifies the structure of the carrier precursor by, for example, changing a surface group and/or adjusting pores to form the carrier in the catalyst.
- the modifier may be selected from the group consisting of water-soluble polymers, silane coupling agents and surfactants.
- examples of the modifiers include starch, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, methyltrimethoxysilane, vinyltriethoxysilane, cetyltrimethylammonium bromide, polyoxyethylene methacrylate, and a combination thereof.
- a modifier solution may be an aqueous solution comprising the modifier at a concentration in the range of, for example, 0.1-5.0 wt%, based on the total weight of the solution.
- the modifier solution may have a PH in the range of about 3.0-8.0.
- a process for preparing the catalyst of the present invention comprises mixing a carrier precursor solution with a modifier solution to form a first mixture; adding an active metal precursor solution and an auxiliary agent precursor solution to the first mixture to form a second mixture; adding a precipitating agent solution to the second mixture to form a third mixture; stirring vigorously and aging, for example, by heating, the third mixture to form precipitates; isolating the precipitates from the third mixture; and washing, drying and baking the isolated precipitates to obtain a catalyst for catalyzing hydrogenation of an oxalate to ethylene glycol.
- a carrier precursor solution is mixed with a modifier solution for about 0.5-5.0 hours (h) to form a first mixture.
- An active metal precursor solution and an auxiliary agent precursor solution are added to the first mixture to form a second mixture.
- a precipitating agent solution is added slowly to the second mixture to form a third mixture.
- the third mixture is stirred vigorously and aged at 60-100 °C for 4-24 h to form precipitates.
- the precipitates are then isolated from the third mixture by filtering.
- the isolated precipitates are washed, dried at 60-120 °C for 6-24 h, and baked at 300-600 °C for 2-8 h.
- a catalyst for catalyzing hydrogenation of an oxalate to ethylene glycol is obtained.
- the catalyst must be activated before use in a hydrogenation reaction.
- the catalyst may be activated by hydrogen under normal atmospheric pressure and an activation temperature.
- the activation temperature may be raised from room temperature to 300 °Cat 1 °C per min and then be maintained for 6-12h.
- a method for hydrogenate an oxalate to ethylene glycol comprises a hydrogenation reaction of an ester with hydrogen at a reaction temperature and under a reaction pressure.
- the reaction temperature may be in the range of about 150-250 °C.
- the reaction pressure may be in the range of about 1.5-3.5 MPa.
- the hydrogen and the ester may have a molar ratio in the range from about 30: 1 to 150: 1.
- the oxalate may be introduced into the reaction at a flow rate of 0.5-20 h -1 .
- auxiliary agent promotes the interaction between the active component copper and the carrier, and thus improves the stability of the catalyst and avoids sintering of the catalyst during long-term use.
- the auxiliary agent may neutralize surface acidity or alkalinity of the carrier and effectively avoid the occurrence of side reactions.
- the modifier is introduced to graft the carrier so that a surface group of the catalyst carrier is changed, thereby affecting the agglomeration behavior of the carrier during precipitation and adjusting the microstructure of the carrier.
- the modifier decomposes and generates many pores.
- the catalyst generates many micropores, improving the pore size and specific surface area, and further improving the activity and selectivity of the catalyst.
- the average pore size of the catalyst may be in the range of about 3-25 nm.
- the average pore volume of the catalyst may be in the range of about 0.4-1.3 cm 3 /g.
- the specific surface area of the catalyst may be in the range of about 250-900 m 2 /g.
- the catalyst of the present invention has a significant improvement in the conversion rate and selectivity of the catalyst in hydrogenation of oxalate to ethylene glycol.
- the reaction temperature may be lower during the hydrogenation reaction, the hydrogen to ester ratio may be lower, the liquid hourly space velocity is larger, and the purity of the ethylene glycol produced according to this invention may be higher.
- conversion rate refers to the percentage of an oxalate that is converted to one or more desirable or undesirable products.
- the conversion rate of the catalyst according to this invention may 98-100 %at a weight space velocity of oxalate 5-20 h -1 .
- the conversion rate may be improved by at least about 1 %using the catalyst of the present invention as compared with that using a catalyst prepared by the same process except without a modifier and/or an auxiliary agent.
- selectivity refers to the percentage of an oxalate that is converted to one or more desirable products relative to the portion of the oxalate that is converted to one or more desirable or undesirable products.
- the selectivity of the catalyst according to this invention may in the range of about 91-99.5 %at a weight space velocity of oxalate 5-20 h -1 .
- the selectivity for ethylene glycol may be improved by at least about 5 %using the catalyst of the present invention as compared with that using a catalyst prepared by the same process except without a modifier, an auxiliary agent or a combination thereof.
- weight space velocity refers to the weight of oxalate treated per unit mass of a catalyst per unit time.
- Ultra-high selectivity hydrogenation catalyst 1 was prepared according to a preparation method comprising the following steps:
- composition hydrogenation catalyst 1 by X-ray fluorescence (XRF) was 25%CuO-10%NiO-65%SiO 2 .
- Hydrogenation catalyst 2 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 2 by XRF was 20%CuO-9%CeO 2 -71%SiO 2 .
- Hydrogenation catalyst 3 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 3 by XRF was 50%CuO-1%MoO 3 -49%Al 2 O 3 .
- Hydrogenation catalyst 4 was prepared according to a preparation method comprising the following steps:
- the composition of hydrogenation catalyst 4 was 28%CuO-9%Fe 2 O 3 -63%ZrO 2 .
- Hydrogenation catalyst 5 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 5 by XRF test was 42%CuO-6%Bi 2 O 3 -52%ZrO 2 .
- Hydrogenation catalyst 6 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 6 by XRF was 30%CuO-4%CeO2-50%SiO2/6%TiO2.
- Hydrogenation catalyst 7 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 7 by XRF test was 40%CuO-5%Fe 2 O 3 -50%SiO 2 /5ZrO 2 .
- Hydrogenation catalyst 8 was prepared according to a preparation method comprising the following steps:
- composition of hydrogenation catalyst 8 by XRF test was 32%CuO-7%B 2 O 3 -55%SiO 2 /6Al 2 O 3 .
- Comparative hydrogenation catalyst 1 was prepared according to the method described in Example 1 except that step 4 was removed.
- the composition of comparative hydrogenation catalyst 1 remains to be 25%CuO-10%NiO-65%SiO 2 .
- Comparative hydrogenation catalyst 1 was prepared according to the method described in Example 1 except that nickel nitrate hexahydrate was removed from step 1.
- Comparative hydrogenation catalyst 1 was prepared according to the method described in Example 1 except that nickel nitrate hexahydrate was removed from step 1 and that step 4 was removed.
- Each catalyst prepared in Examples 1-11 were crushed to 40-60 mesh particles after tableting, and placed into a fixed window reactor having an inner diameter of 8 mm. Electric heating was used. The catalyst was reduced by hydrogen under normal atmospheric pressure before the reaction, and the hydrogen flow rate was 100 ml/min. The reduction temperature increased to 300 °C from a normal temperature at a rate of 2 °C /min. Then the temperature was maintained for 12 h before the temperature was lowered to the reaction temperature, and the feed evaluation started.
- the catalyst performance was evaluated by using dimethyl oxalate as a raw material and methanol as a solvent.
- the EBT test results of each catalyst are shown in Table 1.
- the reaction results for the preparation of ethylene glycol using each catalyst are shown in Table 2.
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Abstract
Description
Claims (20)
- A highly selective hydrogenation catalyst for hydrogenating an oxalate to ethylene glycol, comprising an active component, an auxiliary agent and a carrier, wherein the active component comprises copper or an oxide thereof, wherein the auxiliary agent is a metal selected from the group consisting of Ni, B, Bi, Fe, Ce, Mo, Sn, Co, La, Y, Nd, V and W, an oxide thereof, and a combination thereof, and wherein the carrier is selected from the group consisting of silicon, aluminum, zirconium, titanium and an oxide thereof.
- The catalyst of claim 1, wherein the catalyst has a selectivity of at least 91 %for ethylene glycol at a weight space velocity of oxalate 5-20 h -1.
- The catalyst of claim 1, wherein the catalyst has a specific surface area of 250-900 m 2/g.
- The catalyst of claim 1, wherein the catalyst has a pore volume of 0.4-1.3 cm 3/g.
- The catalyst of claim 1, wherein the catalyst has an average pore diameter is 3-25 nm.
- The catalyst of claim 1, wherein the active component is copper oxide, wherein the catalyst comprises 10-50 wt%of the copper oxide.
- The catalyst of claim 1, wherein the active component is copper oxide and comprises 20-40 wt%of the copper oxide.
- The catalyst of claim 1, wherein the catalyst comprises 1-15 wt%of the auxiliary agent.
- The catalyst of claim 1, wherein the catalyst comprises 2-10 wt%of the auxiliary agent.
- The catalyst of claim 1, wherein the catalyst comprises 50-90 wt%of the carrier.
- The catalyst of claim 1, wherein the catalyst comprises 50-80 wt%of the carrier.
- A process for preparing the catalyst of claim 1, comprising:(a) mixing a carrier precursor solution with a modifier solution to form a first mixture;(b) adding an active metal precursor solution and an auxiliary agent precursor solution to the first mixture to form a second mixture;(c) adding a precipitating agent solution to the second mixture to form a third mixture;(d) stirring vigorously and aging the third mixture, whereby precipitates are formed;(e) isolating the precipitates; and(f) washing, drying and baking the isolated precipitates, whereby a catalyst is formed for catalyzing hydrogenation of an oxalate to ethylene glycol.
- The process of claim 12, further comprising stirring the first mixture for 0.5-5h.
- The process of claim 12, wherein the third mixture is aged at 60-100 ℃ for 4-24h.
- The process of claim 12, wherein the active metal precursor solution comprises Cu (NO 3) 2, CuCl2, Cu (CH 3COO) 2, or a combination thereof, and wherein the active metal precursor solution has a pH of 1.0-7.0.
- The process of claim 12, wherein the auxiliary agent precursor solution comprises Ni (NO 3) 2, HBO 3, BiNO 3, Fe (NO 3) 3, Ce (NO) 3, Na 2MoO 4, (NH 4) 6Mo 7O 24, SnCl 4, Co (NO 3) 2, La (NO 3) 3, Y (NO 3) 3, Nd (NO 3) 3, NH 4VO 3, (NH 4) 6H 2W 12O 40, or a combination thereof and has a pH of 1.0-7.0.
- The process of claim 12, wherein the carrier precursor solution comprises Na 2SiO 3, tetraethyl orthosilicate, silica sol, Al (NO 3) 3, aluminum sol, ZrOCl 2, Zr (NO 3) 4, butyl titanate, TiCl 4 or a combination thereof and has a pH of 1.0-7.0.
- The process of claim 12, wherein the precipitating agent solution comprises urea, ammonia water, sodium carbonate, potassium carbonate, ammonium carbonate, ethylenediamine or a combination thereof.
- The process of claim 12, wherein the modifier solution comprises starch, polyvinylpyrrolidone, polyethylene glycol, polyacrylamide, methyltrimethoxysilane, vinyltriethoxysilane, cetyltrimethylammonium bromide, polyoxyethylene methacrylate, or a combination thereof.
- The process of claim 12, further comprising activating the catalyst.
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CN118002204A (en) * | 2024-04-10 | 2024-05-10 | 烟台百川汇通科技有限公司 | Granular catalyst based on naphtha reforming method and preparation method thereof |
CN118002204B (en) * | 2024-04-10 | 2024-06-04 | 烟台百川汇通科技有限公司 | Granular catalyst based on naphtha reforming method and preparation method thereof |
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CN111569876A (en) * | 2020-04-29 | 2020-08-25 | 厦门大学 | Hydrogenation catalyst, preparation method and application thereof |
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