CN111054337B - Catalyst for preparing ethylene glycol from biomass - Google Patents
Catalyst for preparing ethylene glycol from biomass Download PDFInfo
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- CN111054337B CN111054337B CN201811201452.0A CN201811201452A CN111054337B CN 111054337 B CN111054337 B CN 111054337B CN 201811201452 A CN201811201452 A CN 201811201452A CN 111054337 B CN111054337 B CN 111054337B
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- catalyst
- reaction
- ethylene glycol
- biomass
- water
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 239000003054 catalyst Substances 0.000 title claims abstract description 185
- 239000002028 Biomass Substances 0.000 title claims abstract description 34
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000011973 solid acid Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 316
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 106
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 90
- 239000001257 hydrogen Substances 0.000 claims description 79
- 229910052739 hydrogen Inorganic materials 0.000 claims description 79
- 238000000034 method Methods 0.000 claims description 53
- 229920002678 cellulose Polymers 0.000 claims description 52
- 239000001913 cellulose Substances 0.000 claims description 52
- 238000002360 preparation method Methods 0.000 claims description 48
- 238000005470 impregnation Methods 0.000 claims description 32
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 13
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229920002670 Fructan Polymers 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000002016 disaccharides Chemical class 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 229920001221 xylan Polymers 0.000 claims description 2
- 150000004823 xylans Chemical class 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 43
- 239000010955 niobium Substances 0.000 description 52
- 235000010980 cellulose Nutrition 0.000 description 51
- 239000007787 solid Substances 0.000 description 46
- 238000001035 drying Methods 0.000 description 45
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 40
- 238000005303 weighing Methods 0.000 description 40
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 37
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 37
- 239000008108 microcrystalline cellulose Substances 0.000 description 37
- 229940016286 microcrystalline cellulose Drugs 0.000 description 37
- 238000001914 filtration Methods 0.000 description 36
- 239000007795 chemical reaction product Substances 0.000 description 35
- 238000004445 quantitative analysis Methods 0.000 description 35
- 239000008367 deionised water Substances 0.000 description 34
- 229910021641 deionized water Inorganic materials 0.000 description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 31
- 238000010438 heat treatment Methods 0.000 description 27
- 238000007789 sealing Methods 0.000 description 27
- 238000011049 filling Methods 0.000 description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- 238000000227 grinding Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- 230000032683 aging Effects 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- OSYUGTCJVMTNTO-UHFFFAOYSA-D oxalate;tantalum(5+) Chemical compound [Ta+5].[Ta+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O OSYUGTCJVMTNTO-UHFFFAOYSA-D 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- VUWVDWMFBFJOCE-UHFFFAOYSA-N niobium(5+);oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Ta+5] VUWVDWMFBFJOCE-UHFFFAOYSA-N 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 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 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- RHDUVDHGVHBHCL-UHFFFAOYSA-N niobium tantalum Chemical compound [Nb].[Ta] RHDUVDHGVHBHCL-UHFFFAOYSA-N 0.000 description 2
- ABLLXXOPOBEPIU-UHFFFAOYSA-N niobium vanadium Chemical compound [V].[Nb] ABLLXXOPOBEPIU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- STQOGYGOERBIDF-UHFFFAOYSA-N tantalum vanadium Chemical compound [V].[V].[Ta] STQOGYGOERBIDF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- JUEKGDNOZQEDDO-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[V+5].[Nb+5] Chemical compound [O--].[O--].[O--].[O--].[O--].[V+5].[Nb+5] JUEKGDNOZQEDDO-UHFFFAOYSA-N 0.000 description 1
- MAXQLERHKYESIW-UHFFFAOYSA-N [O-2].[V+5].[Ta+5].[O-2].[O-2].[O-2].[O-2] Chemical compound [O-2].[V+5].[Ta+5].[O-2].[O-2].[O-2].[O-2] MAXQLERHKYESIW-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- B01J35/19—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Abstract
The invention relates to a catalyst for preparing ethylene glycol from biomass, which mainly solves the problem of low efficiency in preparing biomass-based ethylene glycol in the prior art. According to the invention, a multi-component catalytic system is adopted, and the multi-component catalytic system comprises a supported metal catalyst I and a supported tungsten trioxide catalyst II, wherein the supported tungsten trioxide catalyst II is a supported oxide solid acid, and the supported oxide solid acid is an oxide of at least one element in a group VB.
Description
Technical Field
The invention relates to the field of biomass utilization, and mainly relates to a catalyst for preparing ethylene glycol from biomass.
Background
Ethylene glycol is an important basic organic raw material, is mainly used for producing polyethylene terephthalate, polyethylene naphthalate, motor vehicle antifreeze, unsaturated polyester resin, nonionic surfactant, plasticizer and the like, and has wide application.
The current technical routes adopted by the industrial production of glycol comprise a petroleum raw material route and a coal-to-glycol route. The petroleum feedstock route produces ethylene oxide from the epoxidation of petroleum-based ethylene feedstocks, and the ethylene oxide is then hydrated to produce ethylene glycol products. In the route of preparing glycol from coal, coal is firstly gasified into synthesis gas, then gas-phase coupling is carried out to synthesize dimethyl oxalate, and then dimethyl oxalate is hydrogenated to prepare glycol products. Both routes rely on fossil resources, but the storage of fossil resources is limited and non-renewable, and an alternative route for the production of ethylene glycol needs to be found. Among them, biomass is the only renewable resource that can replace fossil raw materials to provide chemicals for human beings. The route for producing the ethylene glycol by using the biomass can increase the yield of the ethylene glycol and has the advantages of rich raw material resources, flexible process route, energy conservation, emission reduction and the like. Therefore, the development of a catalytic system capable of efficiently catalyzing the biomass raw material to be converted into the ethylene glycol is of great significance.
The method has multiple routes for preparing the ethylene glycol from the biomass raw material, and compared with the route for preparing the ethylene glycol through a sugar alcohol intermediate, the route for preparing the ethylene glycol through direct catalytic hydrocracking reaction of cellulose/hemicellulose, starch, saccharides and the like is simpler, and the selectivity of the ethylene glycol is higher; the conversion of non-edible biomass raw materials such as cellulose to prepare ethylene glycol is the focus of current research because the ethylene glycol does not compete with human grains. In 2008, researchers at the institute of chemical and physical sciences reported that tungsten carbide promoted with metallic nickel directly catalyzes the conversion of cellulose into ethylene glycol (Direct catalytic conversion of cellulose into ethylene glycol-catalyzed structural carbonate catalysts, angew. Chem. Int. Ed.2008,47, 8510-8513). CN101723802A discloses a method for preparing glycol from cellulose, which takes cellulose as a reaction raw material, takes metal states, carbides, nitrides and phosphides of VIII group transition metals of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium, platinum, molybdenum and tungsten as catalytic active components to form a multi-metal catalyst, and realizes the preparation of glycol from cellulose with high efficiency, high selectivity and high yield through a one-step catalytic conversion process under the hydrothermal condition of 120-300 ℃ and hydrogen pressure of 1-12 MPa. CN 101768050A discloses a process for the production of ethylene glycol and 1, 2-propylene glycol by hydrolysis of cellulose under hot water conditions (200-250 ℃ C.) by introducing WO 3 Of the load typeWO 3 And the Ru/C catalyst provides acidity to promote cellulose hydrolysis, converts a hydrolysis intermediate product into a low-carbon substance and hydrogenates the low-carbon substance to obtain ethylene glycol and 1, 2-propylene glycol.
The research shows that in the process of preparing the biomass ethylene glycol, the supported metal catalyst and the tungsten trioxide catalyst supported by the VB group element oxide are used, so that the conversion efficiency of biomass is improved, and the catalyst can be recycled; meanwhile, the method has low requirements on reaction equipment, and is a new green, low-carbon and environment-friendly method.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the efficiency of catalytic conversion of ethylene glycol by biomass is low in the prior art, and a multi-component catalyst for preparing biomass-based ethylene glycol is provided. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem. The third technical problem to be solved by the invention is to adopt a catalyst corresponding to the solution of one of the technical problems to a method for preparing the ethylene glycol by using the biomass.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing ethylene glycol from biomass comprises a supported metal catalyst I and a supported tungsten trioxide catalyst II, wherein the supported tungsten trioxide catalyst II is a supported oxide solid acid, and the supported oxide solid acid is an oxide of at least one element selected from group VB; the ratio of the content of metal in the catalyst I to the content of tungsten trioxide in the catalyst II used in the reaction is in the range of 0.0001 to 1000 by weight.
In the above technical solution, the catalyst for preparing ethylene glycol from biomass is provided, wherein the raw material biomass is selected from at least one of cellulose, starch, hemicellulose, fructan, xylan and disaccharide, but is not limited thereto; wherein the cellulose includes microcrystalline cellulose and cellulose from lignocellulosic biomass.
In the technical scheme, the carrier of the supported metal catalyst I is selected from at least one of carbon materials or oxide carriers; the supported metal component of the catalyst I is selected from at least one of VIII and VIIB.
In the above technical scheme, the metal component supported by the catalyst I is preferably used together by group VIII and VIIB.
In the technical scheme, the metal components loaded by the catalyst I are preferably Ru and Mn; or Ru and Re; or mixed oxides of Ni and Re.
In the technical scheme, the content of the metal component loaded by the catalyst I is 0.03-50%, preferably 0.05-40%, and more preferably 0.08-30% of the weight of the catalyst I.
According to the technical scheme adopted by the invention, the oxide solid acid is selected from at least one oxide of V, nb and Ta.
In the above technical solution, preferably, the oxide solid acid is a mixed oxide of Nb and Ta, or a mixed oxide of Nb and V, or a mixed oxide of Ta and V.
Wherein the molar ratio of Nb to Ta or Nb to V or Ta to V is (0.05-20): 1, and more preferably (0.1-10): 1. The oxide solid acid Nb and Ta or Nb and V or Ta and V is used together, and an unexpected synergistic effect is achieved on improving the yield of the target product ethylene glycol in the reaction of preparing ethylene glycol from biomass.
In the technical scheme, the content of the tungsten trioxide in the catalyst II is 0.1-80% of the weight of the catalyst II, preferably 1-60%, and more preferably 3-50%.
The ratio of the content of metal in catalyst I to the content of tungsten trioxide in catalyst II used in the reaction is in the range of 0.0003 to 500.
In the technical scheme, the supported metal catalyst in the multi-component catalyst and the oxide solid acid-supported tungsten trioxide catalyst are jointly used, so that an unexpected synergistic effect is better played for improving the yield of ethylene glycol in the reaction of preparing the biomass ethylene glycol.
To solve the second technical problem, the technical solution adopted by the present invention comprises the following:
a) The preparation method of the catalyst I comprises an impregnation method, a precipitation method, an ion exchange method and a liquid phase reduction method;
b) The preparation method of the solid acid as the carrier oxide of the catalyst II comprises a precipitation method, a hydrolysis method, a solvothermal method, a direct roasting method and a sol-gel method;
c) The preparation method of the catalyst II comprises an impregnation method and a precipitation method.
In order to solve the third technical problem, the invention adopts the technical scheme that the catalyst I and the catalyst II in the scheme are adopted, water is used as a solvent, hydrogen is filled into a high-pressure reaction kettle before the reaction, and the initial hydrogen pressure is 1-10MPa, preferably 2-8MPa; the reaction temperature is 120-300 ℃, preferably 150-260 ℃, and the biomass raw material is converted into the glycol under the action of the combined catalyst.
In the technical scheme, the reaction steps for preparing the ethylene glycol by catalytic conversion of the biomass are as follows: adding a required catalyst and a certain amount of reactants into a 100mL high-pressure reaction kettle, adding a required amount of water, sealing the kettle, introducing hydrogen for replacement, and filling hydrogen to the target pressure; heating to the target temperature, reacting for a certain time, and cooling after the reaction is finished. After cooling to room temperature, the solid and the reaction solution were separated by filtration, and the filtrate was fixed to volume and then quantified. The reaction solution was subjected to gas chromatography after silylation, and each product was quantitatively analyzed by using HP-1ms (30 m.times.0.25 mm. Times.0.25 μm)) column and FID detector, and using the internal standard method.
The conversion of biomass and the selectivity and yield of ethylene glycol were calculated according to the following formulas:
ethylene glycol yield = biomass conversion × ethylene glycol selectivity
The multi-component catalyst formed by coupling the supported metal catalyst and the oxide solid acid supported tungsten trioxide catalyst is applied to the reaction of preparing ethylene glycol from biomass, so that the green and efficient conversion of the biomass raw material to ethylene glycol is realized. The oxide solid acid is used as a carrier of the tungsten trioxide, so that the acidity of the catalyst under the reaction condition is increased, the reaction temperature can be reduced, the reaction time can be shortened, and the conversion of the biomass raw material can be accelerated. Meanwhile, liquid acid is not required to be added in the method, so that the discharge of acid liquor and environmental pollution are avoided, and the method is a green and environment-friendly process; and the solid acid catalyst can be reused, so that the economy is improved, and the industrialization is facilitated.
When the catalyst provided by the invention is used in the reaction of preparing ethylene glycol from cellulose, the conversion rate of the cellulose reaches 56.7% and the selectivity of the ethylene glycol is 33.1% at a lower temperature; the catalyst has good performance and high stability, and achieves good technical effect.
The invention is further illustrated by the following examples, without restricting the inventive content to these examples.
Detailed Description
[ example 1 ]
1% Ru/C catalyst was prepared by isochoric impregnation: taking 1.35mL of 0.0732mol/L RuCl 3 Adding 1.5g of deionized water into the aqueous solution, shaking uniformly, adding 0.99g of activated carbon, shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally reducing by using hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst is prepared by adopting an impregnation method: dissolving niobium oxalate in deionized water, then dropwise adding strong ammonia water under stirring to generate white precipitate until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain Nb 2 O 5 A solid acid; weighing 0.6977g ammonium metatungstate, dissolving in 1.4g deionized water, adding 1.4g treated carrier Nb 2 O 5 Shaking to mix well, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration.
Mixing a certain amount of reaction liquid with an internal standard solution, derivatizing part of the mixed solution by utilizing hexamethyldisilazane and trimethylchlorosilane, and carrying out quantitative analysis by adopting gas chromatography. The conversion of cellulose and the selectivity and yield of ethylene glycol were calculated according to the above formula. The evaluation results are shown in Table 1.
[ example 2 ]
1% Ru/C catalyst preparation method as in example 1.
40％WO 3 /Nb 2 O 5 The catalyst is prepared by an impregnation method: carrier Nb 2 O 5 The preparation method of (1) is the same as example 1; 0.9303g of ammonium metatungstate was weighed and dissolved in 1.2g of deionized water, and 1.2g of the treated carrier Nb was added after ammonium metatungstate was completely dissolved 2 O 5 Shaking to mix well, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.375g 40% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 3 ]
1% Ru/C catalyst preparation method as in example 1.
50％WO 3 /Nb 2 O 5 The catalyst is prepared by an impregnation method: carrier Nb 2 O 5 The preparation method of (1) is the same as example 1; 1.1629g of ammonium metatungstate was weighed and dissolved in 1g of deionized water, and 1.0g of the treated carrier Nb was added after the ammonium metatungstate was completely dissolved 2 O 5 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.3g 50% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 4 ]
1% Ru/C catalyst preparation method same as example 1.
5％WO 3 /Nb 2 O 5 The catalyst is prepared by adopting an impregnation method: carrier Nb 2 O 5 The preparation method of (1) is the same as example 1; 0.2907g of ammonium metatungstate is weighed and dissolved in 5g of deionized water, and 4.75g of the treated carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 Shaking to mix well, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 1% Ru/C and 3.0g 5% 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1The results are shown in Table 1.
[ example 5 ]
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /Ta 2 O 5 The catalyst is prepared by adopting an impregnation method: : dissolving tantalum pentachloride in deionized water, stirring for hydrolysis, aging for 12h after generating white precipitate, filtering and washing until no chloride ion exists in the filtrate, drying in an oven at 80 ℃ for 12h to obtain amorphous hydrated tantalum oxide (Ta) 2 O 5 ·nH 2 O, and finally roasting at 500 ℃ for 3h in air atmosphere to obtain Ta 2 O 5 A solid acid; weighing 0.6977g ammonium metatungstate, dissolving in 1.4g deionized water, adding 1.4g treated carrier Ta 2 O 5 Shaking to mix well, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Ta 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 6 ]
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /V 2 O 5 The catalyst is prepared by adopting an impregnation method: taking ammonium metavanadate, putting the ammonium metavanadate into a quartz tube, and roasting the ammonium metavanadate for 3 hours at 500 ℃ in air atmosphere to obtain V 2 O 5 (ii) a Weighing 0.6977g ammonium metatungstate, dissolving in 1.4g deionized water, adding 1.4g treated carrier V after ammonium metatungstate is completely dissolved 2 O 5 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /V 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 7 ] A method for producing a polycarbonate
0.1% Ru/C catalyst was prepared by isochoric impregnation: taking 0.40mL of 0.0732mol/L RuCl 3 Adding 8.5g of deionized water into the aqueous solution, shaking uniformly, adding 2.956g of activated carbon, shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally reducing by using hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 2.0g of 0.1% of Ru/C and 0.5g of 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 8 ]
8% Ru/C catalyst was prepared by isochoric impregnation: 2.0mL of 0.366mol/L RuCl is taken 3 Adding 0.5g of deionized water into the aqueous solution, shaking uniformly, adding 0.85g of activated carbon, shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally reducing by using hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.025g 8% Ru/C and 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 9 ] A method for producing a polycarbonate
1％Ru/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: taking 1.35mL of 0.0732mol/L RuCl 3 0.99g of Al was added to the aqueous solution of (1) 2 O 3 Shaking until mixed well, drying at room temperature until most water is evaporated, continuing to dry in the oven at 110 ℃ overnight, and finally reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/Al 2 O 3 And 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 10 ]
1％Pd/TiO 2 The catalyst is prepared by adopting an isochoric impregnation method: 0.0167g of PdCl are taken 2 Is dissolved in 1.5g of hydrochloric acid aqueous solution, and 0.992g of TiO is added 2 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, and finally roasting under air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Pd/TiO 2 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 11 ] A method for producing a polycarbonate
10％Ni/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 0.99g of nickel nitrate hexahydrate is dissolved in 1.5g of deionized water, and 1.8g of Al is added after complete dissolution 2 O 3 Shaking to mix evenly, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally roasting under air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 1.0g of 10% Ni/Al 2 O 3 And 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 12 ] A method for producing a polycarbonate
30％Ni/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 1.49g of nickel nitrate hexahydrate is dissolved in 1.6g of deionized water, and 0.7g of Al is added after complete dissolution 2 O 3 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, and continuously drying in an oven at 110 DEG CAnd finally, roasting under air and then reducing by hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.4g 30% Ni/Al 2 O 3 And 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 13 ] to prepare a suspension
10％Co/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 0.99g of cobalt nitrate hexahydrate is dissolved in 1.5g of deionized water, and after complete dissolution, 1.8g of Al is added 2 O 3 Shaking to mix evenly, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally roasting in air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 1.0g of 10% Co/Al 2 O 3 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 14 ]
0.9％Ru-0.1％Mn/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 1.20mL of 0.0732mol/LRuCl was taken 3 And 0.064g of the aqueous solution of (2)The 5% manganese nitrate aqueous solution was mixed well, and then 0.978g of Al was added 2 O 3 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, and finally roasting under air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method was the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 0.9% Ru-0.1% 2 O 3 And 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 15 ]
0.8％Ru-0.2％Mn/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: taking 1.00mL of 0.0732mol/L RuCl 3 The aqueous solution of (1) and 0.121g of a 5% manganese nitrate aqueous solution were mixed uniformly, and 0.917g of Al was added 2 O 3 Shaking to mix evenly, drying at room temperature until most of water is evaporated, continuing to dry overnight in a 110 ℃ oven, and finally roasting in air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 0.8% Ru-0.2% 2 O 3 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction is carried out in the same wayExample 1, the results are shown in table 1.
[ example 16 ]
0.9% Ru-0.1% Re/C catalyst was prepared by isochoric impregnation: taking 2.00mL of 0.0732mol/L RuCl 3 2.4mg of ammonium perrhenate is weighed, added into 2.0g of deionized water, mixed evenly, added with 1.630g of active carbon, shaken to be mixed evenly, dried at room temperature until most of water is evaporated, continuously dried in an oven at 110 ℃ for one night, and finally reduced by hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 0.9% of Ru-0.1% by weight, re/C and 0.5g 30% by weight of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 17 ] to provide
0.8% Ru-0.2% Re/C catalyst by isochoric impregnation: taking 1.00mL of 0.0732mol/L RuCl 3 2.7mg of ammonium perrhenate is weighed and added into 1.5g of deionized water, the mixture is mixed evenly, then 0.917g of active carbon is added, the mixture is shaken until the mixture is mixed evenly, the mixture is dried at room temperature until most of water is evaporated, the drying is continued in an oven at 110 ℃ for overnight, and finally the mixture is reduced by hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 0.8% Ru-0.2% 2 O 3 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, and heating to the temperatureThe reaction was carried out at 220 ℃ for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 18 ]
0.9％Pd-0.1％Re/TiO 2 The catalyst is prepared by adopting an isochoric impregnation method: 0.015g of PdCl is taken 2 Is dissolved in 1.5g of aqueous hydrochloric acid, 41.4mg of ammonium perrhenate are weighed out, dissolved and mixed, and 0.99g of TiO is added 2 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuously drying in an oven at 110 ℃ overnight, and finally roasting under air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 0.9% of the content of Pd-0.1% 2 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 19 ]
9％Ni-1％Re/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 0.892g of nickel nitrate hexahydrate and 0.0288g of ammonium perrhenate are respectively weighed and dissolved in 1.5g of deionized water, and after complete dissolution and uniform mixing, 1.8g of Al is added 2 O 3 Shaking to mix evenly, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally roasting in air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method was the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose and 1.0g of 9%Ni-1％Re/Al 2 O 3 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 20 ]
8％Ni-2％Re/Al 2 O 3 The catalyst is prepared by adopting an isochoric impregnation method: 0.792g of nickel nitrate hexahydrate and 0.0576g of ammonium perrhenate are respectively weighed and dissolved in 1.5g of deionized water, and after complete dissolution and uniform mixing, 1.8g of Al is added 2 O 3 Shaking to mix evenly, drying at room temperature until most water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally roasting under air and then reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method is the same as in example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 1.0g of 8% of Re/Al 2 O 3 And 0.5g 30% WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 21 ] to provide
1% Ru/C catalyst preparation method same as example 1.
Niobium tantalum mixed oxide (niobium tantalum molar ratio of 1/9) supported tungsten trioxide catalyst, with a tungsten trioxide loading of 30%, catalyst reported as 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9) (the same applies below). The preparation method comprises the following steps: firstly, niobium oxalate and tantalum oxalate are dissolved in proportion (Nb/Ta =1/9, molar ratio) to removeAdding concentrated ammonia water dropwise into ionized water under stirring to generate precipitate until the pH value of the solution is 10, stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in a drying oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h in air atmosphere to obtain niobium tantalum oxide Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9), shaking until the mixture is mixed uniformly, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, and roasting at 500 ℃ for 3h in an air atmosphere after grinding.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9) catalyst was added to a high pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times with hydrogen, charged with hydrogen gas to 6MPa, heated to 220 ℃ and reacted for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 22 ]
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 The (Nb/Ta = 3/7) catalyst was prepared by impregnation: firstly, dissolving niobium oxalate and tantalum oxalate in proportion (Nb/Ta =3/7, molar ratio) in deionized water, then dropwise adding concentrated ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain niobium tantalum oxide Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 3/7). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 -Ta 2 O 5 (Nb/Ta = 3/7), shaking until mixed well, drying at room temperature until most of water has evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 3/7) catalyst was added to a high pressure reactor (100 mL) containing 40mL of water, the reactor was sealed, then replaced three times with hydrogen, charged with hydrogen to 6MPa, heated to 220 ℃ and reacted for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 23 ]
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 5/5) the catalyst was prepared by impregnation: firstly, dissolving niobium oxalate and tantalum oxalate in proportion (Nb/Ta =5/5, molar ratio) in deionized water, then dropwise adding concentrated ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain niobium tantalum oxide Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 5/5). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 -Ta 2 O 5 (Nb/Ta = 5/5), shaking until mixed well, drying at room temperature until most of water has evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and calcining at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 5/5) catalyst was charged into a high pressure autoclave (100 mL) containing 40mL of waterIn the method, the reaction kettle is sealed, then hydrogen is introduced for three times for replacement, hydrogen is filled to 6MPa, the temperature is raised to 220 ℃, and the reaction is carried out for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 24 ] A method for producing a polycarbonate
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 7/3) the catalyst was prepared by impregnation: firstly, dissolving niobium oxalate and tantalum oxalate in proportion (Nb/Ta =7/3, molar ratio) in deionized water, then dropwise adding concentrated ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain niobium tantalum oxide Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 7/3). Weighing 0.6977g of ammonium metatungstate, dissolving in 1.4g of deionized water, adding 1.4g of carrier Nb after ammonium metatungstate is completely dissolved 2 O 5 -Ta 2 O 5 (Nb/Ta = 7/3), shaking until mixed well, drying at room temperature until most of water has evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 7/3) catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then, hydrogen gas was introduced for three times for replacement, hydrogen gas was introduced to 6MPa, the temperature was raised to 220 ℃, and the reaction was carried out for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 25 ]
1% Ru/C catalyst preparation method as in example 1.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1) the catalyst was prepared by impregnation: firstly, dissolving niobium oxalate and tantalum oxalate in proportion (Nb/Ta =9/1, molar ratio) in deionized water, then dropwise adding concentrated ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain niobium tantalum oxide Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1), shaking until mixed well, drying at room temperature until most of water has evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 500 ℃ for 3h in an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then replaced three times with hydrogen, charged with hydrogen gas to 6MPa, heated to 220 ℃ and reacted for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 26 ]
1% Ru/C catalyst preparation method same as example 1.
Niobium vanadium mixed oxide (niobium vanadium molar ratio of 9/1) supported tungsten trioxide catalyst, wherein the tungsten trioxide loading is 30%, the catalyst is noted as 30% 3 /Nb 2 O 5 -V 2 O 5 (Nb/V = 9/1). The preparation method comprises the following steps: firstly, dissolving niobium oxalate and sodium metavanadate in proportion (Nb/V =9/1, mol ratio) in deionized water, then dropwise adding strong ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally drying at 500 ℃ in an air atmosphereRoasting for 3 hours to obtain niobium vanadium oxide Nb 2 O 5 -V 2 O 5 (Nb/V = 9/1). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Nb is added after the ammonium metatungstate is completely dissolved 2 O 5 -V 2 O 5 (Nb/V = 9/1), shaking until mixed well, drying at room temperature until most of the water has evaporated, continuing to dry overnight in an oven at 110 ℃, grinding, and calcining at 500 ℃ for 3h under an air atmosphere.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Nb 2 O 5 -V 2 O 5 (Nb/V = 9/1) the catalyst was charged into a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then, after three times of replacement by introducing hydrogen gas, the vessel was charged with hydrogen gas to 6MPa, and the temperature was raised to 220 ℃ to react for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 27 ]
1% Ru/C catalyst preparation method same as example 1.
Tantalum vanadium mixed oxide (tantalum vanadium molar ratio 9/1) supported tungsten trioxide catalyst, with a tungsten trioxide loading of 30%, the catalyst being noted 30% WO 3 /Ta 2 O 5 -V 2 O 5 (Ta/V = 9/1). The preparation method comprises the following steps: firstly, dissolving tantalum oxalate and sodium metavanadate in proportion (Ta/V =9/1, molar ratio) in deionized water, then dropwise adding concentrated ammonia water under stirring to generate precipitation until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain tantalum vanadium oxide Ta 2 O 5 -V 2 O 5 (Ta/V = 9/1). Then 0.6977g of ammonium metatungstate is weighed and dissolved in 1.4g of deionized water, and 1.4g of carrier Ta is added after the ammonium metatungstate is completely dissolved 2 O 5 -V 2 O 5 (Ta/V = 9/1), shaking until the mixture is uniformly mixed, and continuing to perform drying at 110 ℃ until most of water is evaporated at room temperatureDrying in an oven overnight, grinding, and roasting at 500 deg.C for 3h in air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /Ta 2 O 5 -V 2 O 5 (Nb/V = 9/1) the catalyst was charged into a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then, after three times of replacement by introducing hydrogen gas, the vessel was charged with hydrogen gas to 6MPa, and the temperature was raised to 220 ℃ to react for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 28 ]
0.9% Ru-0.1% by weight of Re/C catalyst preparation method as in example 16.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9) the catalyst was prepared in the same manner as in example 21.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 0.9% Ru-0.1% Re/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 1/9) catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then, hydrogen gas was introduced for three times for replacement, hydrogen gas was introduced to 6MPa, the temperature was raised to 220 ℃, and the reaction was carried out for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 28 ]
0.9% Ru-0.1% by weight of Re/C catalyst preparation method as in example 16.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 5/5) catalyst was prepared in the same manner as in example 23.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 0.9% Ru-0.1% Re/C and 0.5g 30% 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta＝5/5) adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ example 30 ] to provide
0.9% Ru-0.1% Re/C catalyst preparation method same as in example 16.
30％WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1) the catalyst was prepared in the same manner as in example 25.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 0.2g 0.9% of Ru-0.1% by weight, re/C and 0.5g 30% by weight of WO 3 /Nb 2 O 5 -Ta 2 O 5 (Nb/Ta = 9/1) the catalyst was added to a high-pressure reaction vessel (100 mL) containing 40mL of water, the reaction vessel was closed, then, hydrogen gas was introduced for three times for replacement, hydrogen gas was introduced to 6MPa, the temperature was raised to 220 ℃ and the reaction was carried out for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 1
1% Ru/C catalyst preparation method same as example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose and 0.2g 1% Ru/C catalyst, adding into a high pressure reaction kettle (100 mL) containing 40mL water, sealing the reaction kettle, introducing hydrogen gas for replacement for three times, charging hydrogen gas to 6MPa, heating to 220 deg.C, and reacting for 30min. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 2
1% Ru/C catalyst preparation method same as example 1.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.15g WO 3 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
1% Ru/C catalyst preparation method as in example 1.
Nb 2 O 5 The catalyst is prepared by a precipitation method: dissolving niobium oxalate in deionized water, then dropwise adding strong ammonia water under stirring to generate white precipitate until the pH value of the solution is 10, then stirring and aging for 12h, filtering and washing until the filtrate is neutral, drying the solid in an oven at 110 ℃ overnight, and finally roasting at 500 ℃ for 3h under the air atmosphere to obtain Nb 2 O 5 A solid acid.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.35g Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 4
1% Ru/C catalyst preparation method same as example 1.
30％WO 3 /SiO 2 The catalyst is prepared by adopting an isochoric impregnation method: mixing SiO 2 Placing the powder in air, and roasting at 500 ℃ for 3h to obtain a carrier before impregnation; weighing 0.6977g ammonium metatungstate, dissolving in 6g deionized water, adding 1.4g treated carrier SiO 2 Shaking until the mixture is uniformly mixed, drying at room temperature until most of water is evaporated, continuing to dry in an oven at 110 ℃ overnight, grinding, and roasting at 400 ℃ for 3h in an air atmosphere.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is a closed reactionThe reaction is carried out in a kettle. Weighing 1.0g microcrystalline cellulose, 0.2g 1% Ru/C and 0.5g 30% 3 /SiO 2 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction, the temperature is reduced, and the solid and the reaction solution (reaction product) are separated by filtration. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
Comparative example 5
0.2％Mn-2％Re/Al 2 O 3 The preparation method adopts an isochoric impregnation method: 0.261g of the prepared 5% manganese nitrate aqueous solution and 0.0576g of ammonium perrhenate were weighed, dissolved in 2.0g of deionized water and mixed, and then 1.956g of Al was added 2 O 3 Shaking until mixed evenly, drying at room temperature until most water is evaporated, continuing to dry in the oven at 110 ℃ overnight, and finally reducing with hydrogen.
30％WO 3 /Nb 2 O 5 The catalyst preparation method was the same as in example 1.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. Weighing 1.0g of microcrystalline cellulose, 1.0g of 0.2% of Mn-2% Re/Al 2 O 3 And 0.5g 30% of WO 3 /Nb 2 O 5 Adding the catalyst into a high-pressure reaction kettle (100 mL) filled with 40mL of water, sealing the reaction kettle, introducing hydrogen for three times for replacement, filling hydrogen to 6MPa, heating to 220 ℃, and reacting for 30 minutes. After the reaction is finished, the temperature is reduced, and solid and reaction liquid (reaction product) are filtered and separated. The quantitative method of the reaction was the same as in example 1, and the results are shown in Table 1.
TABLE 1
The reaction conditions are as follows: 1.0g microcrystalline cellulose, 40mL water, 6MPa H 2 ，220℃，30min。
[ examples 31 to 35 ]
The catalyst obtained in example 29 was recovered and subjected to catalyst cycling reaction 5 times to obtain examples 31-35, and the results are shown in Table 2.
TABLE 2
| Number of cycles | Conversion rate/%) | Ethylene glycol selectivity/%) | Ethylene glycol yield/% | |
| Example 29 | - | 56.7 | 33.1 | 18.8 |
| Example 31 | 1 time of | 57.2 | 32.5 | 18.6 |
| Example 32 | 2 times (one time) | 55.6 | 32.5 | 18.1 |
| Example 33 | 3 times of | 55.1 | 32.3 | 17.8 |
| Example 34 | 4 times (twice) | 53.9 | 31.9 | 17.2 |
| Example 35 | 5 times (twice) | 54.3 | 32.0 | 17.4 |
Reaction conditions are as follows: 1.0g cellulose, 40mL water, 6MPa H 2 At 220 deg.C, reaction for 30min.
[ examples 36 to 40 ]
The combined catalyst prepared in example 29 was used in the reaction for preparing ethylene glycol from other biomass raw materials, and the results are shown in table 3.
TABLE 3
The reaction conditions are as follows: 1.0g starting material, 40mL water, 6MPa H 2 At 220 deg.C, reaction for 30min.
Claims (8)
1. A catalyst for preparing ethylene glycol from biomass comprises a supported metal catalyst I and a supported tungsten trioxide catalyst II, wherein the supported metal component of the catalyst I is selected from Ru and Mn, or Ru and Re, or a mixed oxide of Ni and Re, the supported metal component of the catalyst I is selected from mixed oxides of Nb and Ta, or mixed oxides of Nb and V, or mixed oxides of Ta and V, and the content of tungsten trioxide in the catalyst II is 5-80% of the weight of the catalyst II; the ratio of the content of metal in the catalyst I to the content of tungsten trioxide in the catalyst II used in the reaction is between 0.0001 and 1000 by weight.
2. The catalyst of claim 1, wherein the feedstock biomass is selected from at least one of cellulose, starch, hemicellulose, fructan, xylan, and disaccharide.
3. The catalyst according to claim 1, wherein the support of catalyst I is selected from at least one of carbon material or oxide support.
4. The catalyst according to claim 1, wherein the content of the metal component supported by the catalyst I is 0.03-50% by weight of the catalyst I.
5. The catalyst of claim 1, wherein the content of tungsten trioxide in the catalyst II is 30-60% by weight of the catalyst II.
6. The catalyst according to claim 1, wherein the ratio of the content of metal in catalyst I to the content of tungsten trioxide in catalyst II used in the reaction is between 0.0003 and 500, calculated as a weight ratio.
7. A method for preparing the catalyst for preparing ethylene glycol by using biomass according to any one of claims 1 to 6, characterized in that:
a) The preparation method of the catalyst I comprises an impregnation method, a precipitation method, an ion exchange method and a liquid phase reduction method;
b) The preparation method of the carrier oxide solid acid of the catalyst II comprises a precipitation method, a hydrolysis method, a solvothermal method, a direct roasting method and a sol-gel method;
c) The preparation method of the catalyst II comprises an impregnation method and a precipitation method.
8. A method for preparing ethylene glycol by biomass adopts any one catalyst as described in claims 1-6, and is characterized in that water is used as a solvent, hydrogen is filled into a high-pressure reaction kettle before reaction, the initial hydrogen pressure is 1-10MPa, the reaction temperature is 120-300 ℃, and the biomass is converted into the ethylene glycol under the action of the catalyst.
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