CN111054336A - Catalyst for preparing biomass-based ethylene glycol and preparation method thereof - Google Patents
Catalyst for preparing biomass-based ethylene glycol and preparation method thereof Download PDFInfo
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- CN111054336A CN111054336A CN201811201448.4A CN201811201448A CN111054336A CN 111054336 A CN111054336 A CN 111054336A CN 201811201448 A CN201811201448 A CN 201811201448A CN 111054336 A CN111054336 A CN 111054336A
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- Prior art keywords
- catalyst
- reaction
- ethylene glycol
- preparing
- biomass
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 239000003054 catalyst Substances 0.000 title claims abstract description 134
- 239000002028 Biomass Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011973 solid acid Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 215
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000001257 hydrogen Substances 0.000 claims description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 40
- 229920002678 cellulose Polymers 0.000 claims description 38
- 239000001913 cellulose Substances 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 19
- 229920001400 block copolymer Polymers 0.000 claims description 18
- 229910052707 ruthenium Inorganic materials 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 6
- 229920002488 Hemicellulose Polymers 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 claims description 2
- 150000008163 sugars Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 31
- 239000000243 solution Substances 0.000 description 57
- 239000010955 niobium Substances 0.000 description 56
- 235000010980 cellulose Nutrition 0.000 description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- 238000003756 stirring Methods 0.000 description 28
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 24
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 24
- 239000008108 microcrystalline cellulose Substances 0.000 description 24
- 229940016286 microcrystalline cellulose Drugs 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 238000001914 filtration Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 239000007795 chemical reaction product Substances 0.000 description 21
- 238000004445 quantitative analysis Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 20
- 238000011049 filling Methods 0.000 description 19
- 238000007789 sealing Methods 0.000 description 19
- 239000002994 raw material Substances 0.000 description 15
- 230000008859 change Effects 0.000 description 13
- 238000005303 weighing Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910019804 NbCl5 Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910004537 TaCl5 Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001720 carbohydrates Chemical class 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005846 sugar alcohols Chemical class 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution 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
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 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 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 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
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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
- 239000013589 supplement Substances 0.000 description 1
- 229920000428 triblock copolymer Polymers 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
- 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
- 229920001221 xylan Polymers 0.000 description 1
- 150000004823 xylans Chemical class 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
- B01J23/70—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
-
- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/70—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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- 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 biomass-based ethylene glycol and a preparation method thereof, and mainly solves the problem of low efficiency of the catalyst for preparing the biomass-based ethylene glycol in the prior art. The invention adopts a multi-component catalytic system, which comprises a supported metal catalyst I and a mesoporous M-W-O oxide solid acid catalyst II, wherein M is at least one element selected from Nb and Ta.
Description
Technical Field
The invention relates to the field of biomass utilization, and mainly relates to a catalyst for preparing biomass-based ethylene glycol and a preparation method thereof.
Background
The ethylene glycol is used as a bulk chemical, and can be widely used for producing polyethylene terephthalate, polyethylene naphthalate, motor vehicle antifreeze, unsaturated polyester resin, nonionic surfactant, plasticizer and other fields.
The current technical routes adopted by the industrial production of glycol comprise a petroleum raw material route and a coal-to-glycol route. Both routes rely on fossil resources, but the storage amount of the fossil resources is limited and the fossil resources are non-renewable, and with the exhaustion of the fossil resources, a sustainable development route for producing the ethylene glycol is searched to supplement the existing route. Compared with other renewable energy sources such as wind energy, nuclear energy and the like, biomass is the only renewable organic carbon source which can provide chemicals for human beings. The biomass is used for producing the ethylene glycol, so that the yield of the ethylene glycol can be increased, and the method 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 for preparing the ethylene glycol by using the biomass raw material mainly comprises three routes; in the first route, biomass is fermented to prepare bioethanol, ethanol is dehydrated to prepare ethylene, and the ethylene is epoxidized and hydrated to prepare ethylene glycol; the second route is that the biomass raw material is firstly prepared into saccharides, the saccharides are hydrogenated into sugar alcohol, and the sugar alcohol is then hydrogenated and cracked to prepare glycol; the third route is that the biomass raw material is treated to obtain cellulose/hemicellulose, starch or saccharides and the like, and then the cellulose/hemicellulose, the starch or the saccharides and the like are directly hydrocracked to prepare the ethylene glycol. The first route mainly links up the existing petrochemical technology and is the route which is popularized and applied most at present. Compared with the second route, the third route has fewer steps for preparing the ethylene glycol by direct catalytic hydrocracking without a sugar alcohol intermediate, and meanwhile, the selectivity of the target product ethylene glycol is higher, and the method is more efficient and energy-saving and receives more and more attention. 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 the use of nickel-promoted tungsten carbide to directly catalyze the conversion of cellulose to ethylene glycol (direct catalytic conversion of cellulose into ethylene glycol-promoter-carbon carbide catalysts, acquisition. CN101723802A discloses a method for preparing glycol from cellulose, which takes cellulose as a reaction raw material, takes metal state, carbide, nitride and phosphide 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 conditions of 120-300 ℃ and 1-12MPa of hydrogen pressure. CN 104119207A discloses a method for preparing ethylene glycol by catalytic conversion of carbohydrate, which takes carbohydrate as a reaction raw material, water as a solvent, a catalyst which is composed of a simple substance or a compound of lanthanum and one or more than two of VIII transition metals of iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum as a composite catalyst, and the ethylene glycol is prepared by one-step catalytic conversion process under the hydrothermal conditions of 120-300 ℃ and 1-13MPa of hydrogen pressure.
The research shows that in the process of preparing the biomass-based ethylene glycol, the supported metal catalyst and the mesoporous M-W-O oxide solid acid catalyst are used, so that the conversion efficiency of the biomass is improved, the requirement on reaction equipment is low, and the catalyst system is a novel green, low-carbon and environment-friendly catalyst system.
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 a method for preparing biomass-based ethylene glycol by adopting a catalyst corresponding to the solution of one of the technical problems.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing biomass-based ethylene glycol comprises a supported metal catalyst I and a mesoporous M-W-O oxide solid acid catalyst II, wherein M is at least one element selected from Nb and Ta.
In the above technical solution, the catalyst is used for preparing ethylene glycol from biomass, wherein the raw material biomass is selected from at least one of cellulose, starch, hemicellulose, and sugar, 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 is at least one selected from the group consisting of Ru, Pd, and Ni.
In the technical scheme, the content of the loaded metal component is 0.01-50%, preferably 0.03-40%, and more preferably 0.06-30% of the weight of the catalyst I.
According to the technical scheme adopted by the invention, M in the mesoporous M-W-O oxide solid acid catalyst II is at least one selected from Nb and Ta.
In the above technical solution, preferably, M in the mesoporous M-W-O oxide solid acid catalyst II is selected from Nb and Ta.
In the technical scheme, Nb, Ta and W are selected and used together in the mesoporous oxide solid acid catalyst II, and an unexpected synergistic effect is achieved on the improvement of the yield of a target product ethylene glycol in the reaction of preparing the biomass-based ethylene glycol.
In the technical scheme, in the mesoporous M-W-O oxide solid acid catalyst II, the molar ratio of W to M is (0.01-49):1, preferably (0.05-24):1, and more preferably (0.10-19): 1.
In the above technical solution, the ratio of the content of the metal in the catalyst I used in the reaction process to the content of the tungsten trioxide in the catalyst II is in the range of 0.0001 to 1000, preferably 0.0005 to 800.
In the technical scheme, the supported metal catalyst and the mesoporous M-W-O oxide solid acid catalyst are jointly used, so that unexpected synergistic effect on improving the yield of ethylene glycol in the reaction of preparing the biomass-based ethylene glycol is achieved.
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 catalyst II is a template method.
In the technical scheme, the template agent in the preparation process of the catalyst II comprises a block copolymer and stearic acid.
In the above technical scheme, the block copolymer template is selected from at least one of P-123, F-127, L-121, F-108, P-103, F-88 and P-85, preferably the mixed block copolymer is selected from L-121 and P-123.
In the above technical solution, the solvent used for the block copolymer is at least one selected from ethanol, n-propanol and n-butanol, and preferably the solvent is mixed.
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 2-8 MPa; the reaction temperature is 120-300 ℃, preferably 150-260 ℃, and the biomass raw material is catalyzed and converted into the glycol under the action of the combined catalyst.
In the technical scheme, the reaction for preparing the biomass-based ethylene glycol through catalytic conversion comprises the following steps: 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 formula:
yield of ethylene glycol-biomass conversion x ethylene glycol selectivity
In the invention, a multi-component catalyst formed by coupling a supported metal catalyst and mesoporous M-W-O oxide solid acid is applied to the reaction for preparing biomass-based ethylene glycol, so that the biomass raw material is efficiently converted into ethylene glycol. The mesoporous M-W-O oxide solid acid plays a role in catalyzing reactants or reaction intermediates to prepare ethylene glycol by breaking C-C bonds, increases the acidity of a solution under reaction conditions, accelerates the conversion of biomass raw materials, and is beneficial to reducing the reaction temperature or shortening the reaction time. 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 mesoporous oxide 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 57.7% and the selectivity of the ethylene glycol is 33.9% at a lower temperature; the catalyst has good performance and high stability, and obtains good technical effect.
The invention is further illustrated by the following examples, without restricting the inventive content to these examples.
Detailed Description
[ example 1 ]
The 1% Ru/C catalyst is prepared by an isochoric impregnation method: 1.35mL of 0.0732mol/L RuCl was taken3Adding 1.5g of deionized water into the aqueous solution, shaking uniformly, and adding0.99g of activated carbon, shaking until uniform mixing, drying at room temperature until most of the water has evaporated, continuing to dry in an oven at 110 ℃ overnight, and finally reducing with hydrogen.
A mesoporous Nb-W-O oxide solid acid catalyst, wherein W/Nb (molar ratio) is 5/5 and is recorded as mes-Nb5W5. The preparation process comprises the following steps: with the triblock copolymer L-121(HO (CH)2CH2O)5-(CH2CH(CH3)O)70-(CH2CH2O)5H) Is a template agent. 1.0g L-121 was dissolved in 10g of anhydrous n-propanol and 1.190g of WCl was added with vigorous stirring6And 0.811gNbCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb5W5。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-Nb are weighed out5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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.
[ examples 2 to 11 ]
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
mes-Ta5W5Catalyst preparation the procedure of example 1 was followed, with variation of the template or solvent used.
The mes-Ta is prepared under different coupling conditions of 1 percent Ru/C5W5The reaction conditions of the catalyst for preparing ethylene glycol by catalytic conversion of cellulose are the same as those of example 1, and the reaction results are shown in Table 1.
[ example 12 ]
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
A mesoporous Nb-W-O oxide solid acid catalyst, wherein W/Nb (molar ratio) is 1/9 and is recorded as mes-Nb9W1. The preparation process comprises the following steps: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 0.238g WCl was added with vigorous stirring6And 1.459g NbCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb9W1。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-Nb are weighed out9W1Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 13 ]
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
A mesoporous Nb-W-O oxide solid acid catalyst, wherein W/Nb (molar ratio) is 3/7 and is recorded as mes-Nb7W3. The preparation process comprises the following steps: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 0.714g WCl was added with vigorous stirring6And 1.135g NbCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution is homogenizedSpread on a culture dish and placed for 1h at room temperature to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb7W3。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-Nb are weighed out7W3Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 14 ]
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
A mesoporous Nb-W-O oxide solid acid catalyst, wherein W/Nb (molar ratio) is 7/3 and is recorded as mes-Nb3W7. The preparation process comprises the following steps: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.666g WCl was added with vigorous stirring6And 0.486g NbCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb3W7。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-Nb are weighed out3W7Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 15 ]
The 0.1% Ru/C catalyst is prepared by a method of constant volume impregnation: 0.40mL of 0.0732mol/L RuCl was taken38.5g of deionized water is added into the aqueous solution, the mixture is shaken evenly, 2.956g of active carbon is added into the mixture, the mixture is shaken till 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.
mes-Nb5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6And 0.811g NbCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb5W5。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 2.0g of 0.1% Ru/C and 0.3g of mes-Nb are weighed out5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 16 ]
The 8% Ru/C catalyst is prepared by adopting an isochoric impregnation method: 2.0mL of 0.366mol/L RuCl was taken3Adding 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.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
The reaction for preparing the glycol by the catalytic conversion of the cellulose is in a closed reactionCarried out in a kettle. 1.0g of microcrystalline cellulose, 0.025g of 8% Ru/C and 0.3g of mes-Nb are weighed out5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 17 ]
1％Ru/Al2O3The catalyst is prepared by adopting an isochoric impregnation method: 1.35mL of 0.0732mol/L RuCl was taken30.99g of Al was added to the aqueous solution of (1)2O3Shaking 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.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
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/Al2O3And 0.3g mes-Nb5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 18 ]
The 1% Pd/C catalyst is prepared by adopting an isochoric impregnation method: 0.0167g of PdCl are taken2Dissolving in 2.5g of hydrochloric acid aqueous solution, adding 0.992g 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 with hydrogen.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose and 0.2g of 1% P were weighed outd/C and 0.3g mes-Nb5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 19 ]
10％Ni/Al2O3The 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 dissolution2O3Shaking 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.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
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 1.0g 10% Ni/Al2O3And 0.3g mes-Nb5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 20 ]
30％Ni/Al2O3The 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 dissolution2O3Shaking 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.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
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,0.4g 30％Ni/Al2O3And 0.3g mes-Nb5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 21 ]
The 0.9 percent Ru-0.1 percent Pd/C catalyst is prepared by adopting an isochoric impregnation method: weighing 2.5mg of PdCl2Completely dissolve in 0.5g of dilute hydrochloric acid solution, and take 1.80mL 0.0732mol/L RuCl3The aqueous solution and 1.5g deionized water, to ensure uniform mixing, then adding 1.467g active carbon, shaking to mix uniformly, drying at room temperature until most water is evaporated, continuing drying in an oven at 110 ℃ overnight, and finally reducing with hydrogen.
mes-Nb5W5The catalyst was prepared in the same manner as in example 15.
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% Pd/C and 0.3g mes-Nb5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 22 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21.
mes-Ta5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6And 1.075g of TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. Uniformly spreading the obtained solution on a culture dishThen, the mixture was left at room temperature for 1 hour to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at 500 ℃ to prepare the mesoporous solid acid mes-Ta5W5。
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% Pd/C and 0.3g mes-Ta5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 23 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21.
mes-Nb0.5Ta4.5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol, and 1.190g WCl was added with vigorous stirring6、0.081g NbCl5And 0.967g of TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb0.5Ta4.5W5。
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% Pd/C and mes-Nb0.5Ta4.5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 24 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21.
mes-Nb1.5Ta3.5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6、0.243g NbCl5And 0.752g of TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb1.5Ta3.5W5。
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% Pd/C and 0.3g mes-Nb1.5Ta3.5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 25 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21.
mes-Nb2.5Ta2.5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6、0.405g NbCl5And 0.537g TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally horse at 500 deg.CRoasting for 3 hours in a muffle furnace to prepare mesoporous solid acid mes-Nb2.5Ta2.5W5。
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% Pd/C and 0.3g mes-Nb2.5Ta2.5W5(W/Nb/Ta is 1/0.5/0.5) the catalyst was charged into a high-pressure reaction vessel (100mL) containing 40mL of water, the reaction vessel was closed, then replaced with hydrogen gas three times, 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 2.
[ example 26 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21.
mes-Nb3.5Ta1.5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6、0.567g NbCl5And 0.322g of TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb3.5Ta1.5W5。
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% Pd/C and 0.3g mes-Nb3.5Ta1.5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
[ example 27 ]
The catalyst was prepared from 0.9% Ru to 0.1% Pd/C as in example 21. mes-Nb4.5Ta0.5W5The preparation process of the solid acid catalyst is as follows: the mixed block copolymer L-121 and P-123 are used as templates. 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 1.190g WCl was added with vigorous stirring6、0.729g NbCl5And 0.107g of TaCl5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare the mesoporous solid acid mes-Nb4.5Ta0.5W5。
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% Pd/C and 0.3g mes-Nb4.5Ta0.5W5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
Comparative example 1
The preparation of the 1% Ru/C catalyst was carried out 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. 1.0g of microcrystalline cellulose and 0.2g of 1% Ru/C catalyst are weighed and added into a high-pressure reaction kettle (100mL) filled with 40mL of water, the reaction kettle is sealed, then hydrogen is introduced for replacement for three times, hydrogen is filled to 6MPa, the temperature is raised to 220 ℃, and the reaction is 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 2.
Comparative example 2
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
mes-WO3The preparation process of the catalyst is as follows: 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol and 2.379g WCl was added with vigorous stirring6. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to prepare solid acid mes-WO3。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-WO were weighed out3Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
Comparative example 3
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
mes-Nb2O5The preparation process of the catalyst is as follows: : 0.25g L-121 and 0.75g P-123 were dissolved in a solvent of 2g ethanol mixed with 8g n-propanol, 1.621g NbCl was added with vigorous stirring5. To the solution, which did not change color, 0.54g of water was added dropwise with constant stirring. The obtained solution was spread evenly on a petri dish and left to stand at room temperature for 1h to form a sol. The sol was then dried in an oven at 50 ℃ for 5 days. Finally, roasting the mixture for 3 hours in a muffle furnace at the temperature of 500 ℃ to obtain solid acid mes-Nb2O5。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of mes-Nb are weighed out2O5Adding the catalyst into a high-pressure reaction kettle (100mL) 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 2.
Comparative example 4
The preparation of the 1% Ru/C catalyst was carried out as in example 1.
Non-mesoporous WO3-Nb2O5(W/Nb-1/1) namely WO3-Nb2O5(W/Nb ═ 1/1) the catalyst was prepared using a mixed heating method: 1.478g of ammonium metatungstate and 2.950g of niobium oxalate are dissolved in 100ml of deionized water, and the mixture is heated to 80 ℃ under stirring to ensure that the precursor is completely dissolved; evaporating water to dryness at 100 ℃ under the condition of strongly ensuring strong stirring to obtain solid powder; drying the solid at 120 deg.C for 12 hr, and calcining at 500 deg.C in air atmosphere for 3 hr to obtain solid acid WO3-Nb2O5(W/Nb＝1/1)。
The reaction for preparing the ethylene glycol by the catalytic conversion of the cellulose is carried out in a closed reaction kettle. 1.0g of microcrystalline cellulose, 0.2g of 1% Ru/C and 0.3g of bulk WO were weighed out3-Nb2O5(W/Nb ═ 1/1) the catalyst was charged in a high-pressure reactor (100mL) containing 40mL of water, the reactor was closed, then, hydrogen gas was introduced into the reactor to replace it three times, then, hydrogen gas was introduced into the reactor 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 2.
TABLE 1
Reaction conditions are as follows: 1.0g microcrystalline cellulose, 40mL water, 0.2g 1% Ru/C, 0.3g mes-Nb5W5，6MPa H2，220℃，30min。
TABLE 2
Reaction conditions are as follows: 1.0g microcrystalline cellulose, 40mL water, 6MPa H2，220℃，30min。
[ examples 28 to 30 ]
The catalyst obtained in example 25 was recovered and subjected to cyclic reaction 3 times to obtain examples 28 to 30, and the results are shown in Table 3.
TABLE 3
| Number of cycles | Conversion rate/% | Ethylene glycol selectivity/%) | Ethylene glycol yield/% | |
| Example 25 | - | 57.7 | 33.9 | 19.6 |
| Example 28 | 1 time of | 57.8 | 33.4 | 19.3 |
| Example 29 | 2 times (one time) | 56.9 | 33.6 | 19.1 |
| Example 30 | 3 times of | 56.0 | 33.1 | 18.5 |
Reaction conditions are as follows: 1.0g cellulose, 40mL water, 6MPa H2At 220 deg.C, reaction for 30 min.
[ examples 31 to 34 ]
The combined catalyst prepared in example 25 was used in the reaction for preparing ethylene glycol from other biomass raw materials, and the results are shown in table 4.
TABLE 4
| Raw materials | Conversion rate/% | Ethylene glycol selectivity/%) | Ethylene glycol yield/% | |
| Example 31 | Starch | 84.6 | 38.2 | 32.3 |
| Example 32 | Hemicellulose | 90.7 | 29.5 | 26.8 |
| Example 33 | Xylan | 95.2 | 20.9 | 19.9 |
| Example 34 | Glucose | 100.0 | 35.6 | 35.6 |
Reaction conditions are as follows: 1.0g of starting material, 40mL of water, 6MPa H2At 220 deg.C, reaction for 30 min.
Claims (12)
1. A catalyst for preparing biomass-based ethylene glycol comprises a supported metal catalyst I and a mesoporous M-W-O oxide solid acid catalyst II, wherein M is at least one element selected from Nb and Ta.
2. The catalyst of claim 1, wherein the feedstock biomass is selected from at least one of cellulose, starch, hemicellulose, and sugars.
3. Catalyst I according to claim 1, characterized in that the support of catalyst I is selected from at least one of carbon material or oxide support; the supported metal component is at least one of Ru, Pd and Ni.
4. The catalyst I according to claim 3, characterized in that the supported metal component is present in an amount of 0.03% to 50% by weight of the catalyst I.
5. Catalyst I according to claim 3, characterized in that the metal components supported by catalyst I are Ru and Pd.
6. The catalyst of claim 5, wherein in catalyst II, W: M is (0.01-49):1 in terms of mole ratio.
7. The catalyst according to claim 1, characterized in that 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 0.0001-1000 by weight ratio.
8. A method for preparing a catalyst for preparing biomass-based ethylene glycol according to any one of claims 1 to 7, wherein the catalyst is used
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 catalyst II is a template method.
9. The method of claim 8, wherein the template agent used in the method for preparing the catalyst II comprises a block copolymer and stearic acid.
10. The method of claim 9, wherein the catalyst II is prepared using a block copolymer as a template, wherein the block copolymer is at least one selected from the group consisting of P-123, F-127, L-121, F-108, P-103, F-88, and P-85.
11. The method of claim 10, wherein the solvent used for the block copolymer is at least one selected from the group consisting of ethanol, n-propanol and n-butanol.
12. A method for preparing biomass-based ethylene glycol by using the catalyst of any one of the combinations in claims 1-11, which is characterized in that water is used as a solvent, hydrogen is filled into a high-pressure reaction kettle before the reaction, the initial hydrogen pressure is 1-10MPa, the reaction temperature is 120-300 ℃, and biomass is converted into ethylene glycol under the action of a multi-component catalyst.
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