CN109999880A - N doping porous carbon supported bimetal catalyst as well as preparation method and application thereof - Google Patents
N doping porous carbon supported bimetal catalyst as well as preparation method and application thereof Download PDFInfo
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- CN109999880A CN109999880A CN201910317149.5A CN201910317149A CN109999880A CN 109999880 A CN109999880 A CN 109999880A CN 201910317149 A CN201910317149 A CN 201910317149A CN 109999880 A CN109999880 A CN 109999880A
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- catalyst
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- porous carbon
- doping
- nitrogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 105
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002028 Biomass Substances 0.000 claims abstract description 23
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000005580 one pot reaction Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000811 xylitol Substances 0.000 claims abstract description 9
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims abstract description 9
- 229960002675 xylitol Drugs 0.000 claims abstract description 9
- 235000010447 xylitol Nutrition 0.000 claims abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 229910000510 noble metal Inorganic materials 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 12
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 12
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 12
- 239000011425 bamboo Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 4
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 4
- 229920002488 Hemicellulose Polymers 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 235000009337 Spinacia oleracea Nutrition 0.000 claims description 4
- 244000300264 Spinacia oleracea Species 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001720 carbohydrates Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- -1 metals salt Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 240000005528 Arctium lappa Species 0.000 claims description 2
- 235000003130 Arctium lappa Nutrition 0.000 claims description 2
- 235000008078 Arctium minus Nutrition 0.000 claims description 2
- 244000003416 Asparagus officinalis Species 0.000 claims description 2
- 235000005340 Asparagus officinalis Nutrition 0.000 claims description 2
- 235000017647 Brassica oleracea var italica Nutrition 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 241000245665 Taraxacum Species 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 3
- 240000000491 Corchorus aestuans Species 0.000 claims 1
- 235000011777 Corchorus aestuans Nutrition 0.000 claims 1
- 235000010862 Corchorus capsularis Nutrition 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 210000004885 white matter Anatomy 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 11
- 239000000920 calcium hydroxide Substances 0.000 description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 11
- 238000004587 chromatography analysis Methods 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 241001330002 Bambuseae Species 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007327 hydrogenolysis reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 229910019891 RuCl3 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000005255 carburizing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses one kind using N doping biology base porous carbon as carrier, passes through one pot process bimetallic-carbon-based bifunctional catalyst of N doping and its preparation method and application.The catalyst can be used for the biomass efficients selective hydrogenations such as catalysis biological base sorbierite, xylitol, cellulose, lignocellulosic and prepare the low alcohols such as glycol.Catalyst according to the invention is that raw material prepare porous nitrogen-doped carbon material using cheap, renewable biomass, is not needed by adding itrogenous organic substance as nitrogen source nitrogen doped, environmentally protective, cheap.The metal-supported catalyst of preparation is used to have excellent catalytic activity, stability and selectivity in aqueous phase system when catalysis biomass selective hydrogenation.Also, product separates simply with catalyst, and ethylene glycol and the yield of propylene glycol may be up to 85% or more in product, and reaction step is few, mild condition, easy to operate, has a extensive future.
Description
Technical field
The invention belongs to field of fine chemical, are related to one kind using N doping biology base porous carbon as carrier, pass through one kettle way
Synthesize the carbon-based bifunctional catalyst of bimetallic-N doping, the catalyst for catalysis biological base sorbierite, xylitol, cellulose,
The biomass efficients selective hydrogenation such as lignocellulosic prepares the low alcohols such as glycol and the preparation method and use of the catalyst
On the way.
Background technique
Ethylene glycol and propylene glycol are widely used in artificial synthesized polyester resin, change as a kind of high valuable chemicals
The fields such as cosmetic, medical industry and pharmacy industry.Currently, industrially main is still original with the downstream product of petroleum cracking and coal
Material produces ethylene glycol and propylene glycol by harsh conditions such as conventional catalyst hydrogenolysis.Traditional industry synthetic route raw material not only height
The problems such as relying on petroleum, coal, and reaction route is complicated, generating a large amount of pollutants.With the growing tension of global fossil resource, benefit
Ethylene glycol and propylene glycol are prepared with reproducible agriculture and forestry organic waste material resource, not only can solve the Dependence Problem to fossil resource,
The resource utilization that agriculture and forestry organic waste material can also be improved is expected to become the alternative route of conventional petroleum, Coal Chemical Industry Route.
Currently, prepared in the low alcohols catalyst system such as ethylene glycol, propylene glycol by raw material of biomass, frequently with catalyst
The metals such as including Ni, Cu, Ru, Pt, Au, Pd, Rh, carrier include silica, active carbon, carbon nanotube, zeolite molecular sieve etc..
Zhou Xinggui teaches the carbon nanotube of team's exploitation and graphene composite carrier passes through incipient impregnation load ruthenium, and post-processing etc.
The catalyst of technique synthesis, realizes sorb alcohol conversion of the highest less than 70% under the conditions of 220 DEG C, 8MPa
(Chin.J.Catal.,35(2014)692).Zhang Yi teaches the silica supports load ruthenium and tungsten of team's exploitation, 200 DEG C,
50h is reacted under the conditions of 4MPa, realizes 100% conversion ratio of glucose, and ethylene glycol and propylene glycol are selectively no more than 70%
(App.Catal.B, 242 (2019) 100).The silica supports that Liu Haichao teaches team's exploitation are loaded by coprecipitation
Copper is catalyzed xylitol, realizes that ethylene glycol and propylene glycol are selectively no more than 65% under the conditions of 200 DEG C, 6MPa
(App.Catal.B,147(2014)377).It has reported in document, heterogeneous catalyst mainly passes through coprecipitation, incipient impregnation
The multi-step synthesis such as method, complex steps, efficiency is lower, is unfavorable for the synthesis of catalyst needed for industry is amplified from now on.
The present invention develops one kettle way process for synthetic catalyst, using rich protein-contg biomass as raw material, passes through a step water
Thermal method prepares the catalyst of N doping porous carbon supported bi-metallic.Synthetic method is simple, and porous by selection N doping
Carbon does carrier, supported bi-metallic.The transition metal of load keeps biomass polynary by the soda acid position of adjusting catalyst support surface
The C-C key of alcohol is selectively broken, and noble metal provides hydrogenation activity position, improves the selectivity of target product.Preparation gained is difunctional
Catalyst not only greatly improves the conversion ratio and selectivity of product of reactant, also reduces the temperature (< 200 of catalysis reaction
DEG C) and pressure (< 4MPa), process is environmentally protective, safety easy to operate.Therefore, it develops a kind of convieniently synthesized, living to aqueous systems height
Property and highly selective heterogeneous catalyst for ethylene glycol, propylene glycol and other low alcohols production have great meaning
Justice.
Summary of the invention
For above-mentioned the problems of the prior art, purpose according to the present invention, it is desirable to provide a kind of with N doping biology
Sill is realized more to biomass by one pot of hydro-thermal method synthesising biological base N doping porous carbon load type bimetal catalyst
The high activity and highly selective catalysis of the pure and mild polynary selective hydrogenolysis of sugar of member.
The loaded catalyst is by the noble metal of 0.5-20wt% and the transition metal element of 1-30wt% and 50-
The biology base nitrogen-doped porous carbon material carrier of 98.5wt% is constituted.
Wherein the specific surface area of the biology base nitrogen-doped porous carbon material carrier is 150-1500m2/ g, nitrogen content 1-
10wt%.
The noble metal is selected from one of palladium, gold, platinum, ruthenium, rhodium, iridium or a variety of noble metals, preferably
Palladium, platinum or ruthenium；The transition metal element is selected from one of iron, copper, tungsten, chromium, manganese, cobalt, nickel or a variety of transition metal member
Element, preferably tungsten, manganese or cobalt.
It is porous carbon-supported that according to the present invention another is designed to provide a kind of one pot process biology base N doping
The preparation method of bimetallic catalyst, the preparation method include the following steps:
1) biological material is dry, it is ground into fine powder；
2) fine powder obtained in step 1) and noble metal, transition metal precursor solution are distributed in water；
3) mixture for obtaining step 2) is transferred in reaction kettle, is heated to 100-300 DEG C under hydrothermal reaction condition,
It is preferred that 150-250 DEG C, 1-56 hours are kept the temperature, cooling, washing obtains brown solid；
4) brown solid obtained in step 3) is dried, ground, then in tube furnace under inert atmosphere protection
It is roasted, maturing temperature is 200-1500 DEG C, keeps the temperature 1-100 hours；After tube furnace is cooled to room temperature, sample is taken
Out to get the N doping porous carbon load type bimetal catalyst prepared to one kettle way.
Wherein, the biological material described in step 1) is the plant rich in protein, includes fruits of elm, Folium Taraxacum, Huang
In at least one of sesame slices, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli, preferably spinach, bamboo shoots at least
One kind being used as carbon source and nitrogen source simultaneously.
Wherein, the noble metal precursor liquid solution described in step 2), presoma can be in ruthenium, palladium, platinum, rhodium and iridium
One or more metal salts, such as hydrochloride, sulfate, nitrate etc.；Transition metal precursor can for iron, copper, manganese, nickel and
One or more metal salts, such as hydrochloride, sulfate, nitrate of tungsten etc..Noble metal described in step 2) and transition metal
Presoma and the proportional amount of powdered biomass are 1~30wt%.
The maturing temperature described in step 4) is 200-1500 DEG C, and preferably 500-100 DEG C, the inert gas is nitrogen
One of gas, argon gas and helium are a variety of, and soaking time is preferably 5-30 hours.
The one-pot preparation thereof does not use activator or other nitrogen source materials, only with biological material and bears
Carrying metal only needs a step to complete.
Another purpose according to the present invention is to provide using aqueous biochemical matter raw material and/or carbohydrate as raw material,
The method for adding hydrogen to prepare ethylene glycol and propylene glycol in the presence of the biology base N doping porous carbon load type bimetal catalyst.
Preferably, the biomass material and/or carbohydrate be preferably sorbierite, glucose, xylitol, xylose,
One of cellulose, hemicellulose, timber, bamboo wood are a variety of.
It the described method comprises the following steps: a certain amount of biomass being added in autoclave high-pressure reactor, the support type is urged
Agent, deionized water are filled with 0.1-10MPa hydrogen after closed, reacted at 100-350 DEG C, after reaction 0.5-48 hours,
It is cooled to room temperature, filtering reacting liquid, separating catalyst.Gained product liquid isolates the mixing such as ethylene glycol and propylene glycol through rectifying
Dihydric alcohol.
Preferably, the loaded catalyst dosage is the 0.1-100wt%, preferably 1- of biomass dosage
20wt%；Water consumption is 10-200 times, preferably 10-100 times of biomass dosage；Reaction pressure is 0.1-20MPa, preferably
1-8MPa；Reaction temperature is 50-250 DEG C, preferably 100-200 DEG C；Reaction time is 0.5-48 hours, and preferably 1-10 is small
When.
Preferably, N doping porous carbon load type bimetal catalyst produced according to the present invention is selected using aqueous biochemical matter
The method that property adds hydrogen to prepare ethylene glycol and propylene glycol, reaction temperature is preferably 120-250 DEG C in the method, and Hydrogen Vapor Pressure is preferred
For 1-8MPa, the reaction time is preferably 1-10 hours, and the yield of ethylene glycol and propylene glycol may be up to 85%, the biology of use
The specific surface area of base N doping porous carbon load type bimetal catalyst is about 350-850m2/ g, nitrogen content are about 4-10%, institute
Stating the maturing temperature in the preparation method of biology base N doping porous carbon load type bimetal catalyst is 500-900 DEG C.
Beneficial effect
The present invention has the advantage that compared with prior art
1, the use of cheap, renewable biomass is that raw material prepares porous nitrogen-doped carbon material, does not need nitrogenous by adding
Organic matter is as nitrogen source nitrogen doped.In addition, the present invention passes through the porous N doping load type double-metal of one kettle way one-step synthesis
Catalyst is avoided using multistage methods carried metal elements such as incipient impregnations.Also, raw materials used is renewable resource,
It is widely distributed, it is environmentally protective, it is simple and easy to get, it is cheap.Synthetic method is an environmentally protective step hydrothermal synthesis method, preparation tool
There is the N doping porous carbon load type bimetal catalyst of bigger serface, abundant porosity, nano metal good dispersion.
2, metal-supported catalyst of the present invention is used in aqueous phase system when catalysis biomass selective hydrogenation,
With excellent catalytic activity, stability and selectivity.Also, product separates simply with catalyst, ethylene glycol and third in product
The yield of glycol may be up to 85% or more, and reaction step is few, and mild condition is easy to operate, have a extensive future.
Detailed description of the invention
Fig. 1 is N doping porous carbon supported bimetal catalyst Ru-W/NC- prepared by present invention preparation embodiment 1
800TEM test chart.
Fig. 2 is N doping porous carbon load type bimetal catalyst Ru-W/NC-700 prepared by present invention preparation embodiment 1
The BET result of (preparation embodiment 4), Ru-W/NC-800 (preparation embodiment 1), Ru-W/NC-900 (preparation embodiment 5).
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The present invention loads double catalysis using the biomass of N doping as raw material, by one kettle way hydrothermal synthesis N doping porous carbon
Agent, the catalyst by 0.5-20wt% noble metal 1-30wt% transition metal element and 50-98.5wt% biology
Base nitrogen-doped porous carbon material carrier is constituted, and it is raw to can be used for sorbierite, xylitol, xylose, cellulose, hemicellulose, bamboo wood etc.
Substance selectivity hydrogenolysis prepares the low alcohols product such as ethylene glycol, propylene glycol.All raw materials of the catalyst are renewable resource,
It is widely distributed, it is environmentally protective, it is simple and easy to get, it is resourceful, it is cheap, and catalyst can be recycled, stability is good.According to
The load type bimetal catalyst of one pot process of the invention, by taking sorb raw polyol as an example, biomass-based sorbierite is mild
Under the conditions of selective hydrogenolysis prepare the yield of ethylene glycol and propylene glycol up to 85% or more, sorb alcohol conversion is greater than 99%.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.Unless stated otherwise, reagent and instrument used in the following embodiment are commercially available product.
Characterize instrument:
1) transmission electron microscope: model H-7650, manufacturer are Hitachi Hitachi, Ltd
2) elemental analyser: model Vario-EL-cube, manufacturer are Elementary company, Germany
3) physical adsorption appearance: model Autosorb iQ, manufacturer are U.S. Kang Ta company
The synthesis of catalyst
Prepare embodiment 1: one pot process nitrogen-doped porous carbon material support type Ru-W catalyst (Ru-W/NC-800)
Preparation
The bamboo shoots that 1kg is cleaned up cut into pieces, dry, obtain solid and are ground into a powder.Take 2g powder, with 18mL go from
Sub- water, 0.28mL RuCl3Solution (5wt%) mixing, is added 0.0972g ammonium metatungstate (AMT), the above mixture is mixed equal
It is transferred in water heating kettle after even, in 180 DEG C of reaction 6h, is filtered, washed, it is dry, obtain brown solid.The solid that will be obtained later
Be put in tube furnace and roasted in a nitrogen atmosphere to 800 DEG C, keep the temperature 1 hour to get to N doping porous carbon load catalyst,
It is indicated with Ru-W/NC-800.
Fig. 1 is the TEM figure of the Ru-W catalyst loaded according to N doping porous carbon manufactured in the present embodiment, as shown in Figure 1,
Ru nano particle is dispersed in carbon material surface, granular size about 3nm in the material.Its specific surface area is 435m2/ g, by
BET, which analyzes the visible catalyst, has hierarchical porous structure and different maturing temperatures to catalyst Ru-W/NC-700 (preparation implementation
Example 4), the influence of Ru-W/NC-800 (preparation embodiment 1) and Ru-W/NC-900 (preparing embodiment 5) specific surface area (see Fig. 2).
Prepare embodiment 2: multistep processes synthesizes the system of nitrogen-doped porous carbon material support type Ru-W catalyst (HRu-W/NC)
It is standby
2g bamboo powder is taken, is transferred in water heating kettle after mixing with 18mL deionized water, in 180 DEG C of reaction 6h, filters, wash
It washs, it is dry, obtain brown solid hydro-thermal carbon.
1g hydro-thermal carbon is taken, with 4mL deionized water, 0.28mL RuCl3Solution (5wt%) and 0.0972g AMT mixing,
25 DEG C of temperature stand 3h.50 DEG C of dry 12h are roasted, 800 in a nitrogen atmosphere by being put in tube furnace after the grinding of the above mixture
DEG C range inside holding 1 hour.Sample is taken out to get the N doping porous carbon synthesized to multistep processes after tube furnace drops to room temperature
The catalyst of load, is indicated with HRu-W/NC.
Prepare embodiment 3: the system of the activated carbon supported type Ru-W catalyst of equi-volume impregnating composite commodityization (Ru-W@AC)
It is standby
1g commercial activated charcoal (purchased from Norit company) is taken, with 4mL deionized water, 0.28mL RuCl3Solution (5wt%)
It is mixed with 0.0972g AMT, stands 3h, 50 DEG C of dry 12h in 25 DEG C of temperature, will be put in tube furnace after the grinding of the above mixture
Roast in a nitrogen atmosphere, 800 DEG C range inside holding 1 hour.Sample is taken out to get equal bodies are arrived after tube furnace drops to room temperature
The catalyst of product Immesion active carbon load, is indicated with Ru-W@AC.
Prepare embodiment 4: one pot process nitrogen-doped porous carbon material support type Ru-W catalyst (Ru-W/NC-700)
Preparation
It is other porous according to the preparation identical method of embodiment 1 preparation doping other than carburizing temperature is changed to 700 DEG C
Catalysts supported on carbon, specific surface area 557m2/ g (see Fig. 2), is indicated with Ru-W/NC-700.
Prepare embodiment 5: one pot process nitrogen-doped porous carbon material support type Ru-W catalyst (Ru-W/NC-900)
Preparation
Other than carburizing temperature is changed to 900 DEG C, other according to the preparation identical method of embodiment 1, to prepare N doping more
Hole catalysts supported on carbon, specific surface area 413m2/ g (see Fig. 2), is indicated with Ru-W/NC-900.
Prepare embodiment 6: the preparation of one pot process nitrogen-doped porous carbon material supported Ru catalysts (Ru/NC-800)
Other than not adding AMT, other according to the preparation identical method of embodiment 1, to prepare N doping porous carbon-supported
Catalyst is indicated with Ru/NC-800.
Prepare embodiment 7: the preparation of one pot process nitrogen-doped porous carbon material support type W catalyst (W/NC-800)
It is other to prepare N doping porous carbon according to the preparation identical method of embodiment 1 other than not adding ruthenium trichloride
Loaded catalyst is indicated with W/NC-800.
Embodiment 1: the Catalyzed by Pt/M Bimetallic Nano sorbierite selectivity of nitrogen-doped carbon material load nanometer ruthenium and tungsten is utilized
The method that hydrogenolysis prepares ethylene glycol and propylene glycol.It the steps include:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 1
Ru-W catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 6 hours, be cooled to room
Temperature, filtering reacting liquid carry out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorb alcohol conversion is in water phase
100%, the yield of ethylene glycol and propylene glycol is 85%.
Embodiment 2:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 4 and makes
Standby Ru-W catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 6 hours, be cooled to
Room temperature, filtering reacting liquid carry out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorb alcohol conversion in water phase
It is 99% or more, the yield of ethylene glycol and propylene glycol is 63%.
Embodiment 3:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 5 and makes
Standby Ru-W catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 6 hours, cooling
To room temperature, filtering reacting liquid carries out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorbierite converts in water phase
Rate is 99% or more, and the yield of ethylene glycol and propylene glycol is 72%.
Embodiment 4:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 2 and makes
Standby Ru-W catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 6 hours, cooling
To room temperature, filtering reacting liquid carries out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorbierite converts in water phase
Rate is 90%, and it is 51% that the yield of ethylene glycol and propylene glycol, which is greater than,.
Embodiment 5:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 3 and makes
The carbon material supported Ru-W catalyst of standby business, 20mL deionized water are passed through 4MPa hydrogen, carry out at 200 DEG C anti-after closed
It answers, reacts 6 hours, be cooled to room temperature, filtering reacting liquid, gas-chromatography and liquid-phase chromatographic analysis are carried out to reaction solution.As a result table
Sorb alcohol conversion is 80% in bright water phase, and the yield of ethylene glycol and propylene glycol is 35%.
Embodiment 6:
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 6 and makes
Standby Ru catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 6 hours, be cooled to
Room temperature, filtering reacting liquid carry out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorb alcohol conversion in water phase
It is 52%, the yield of ethylene glycol and propylene glycol is 35%.
Embodiment 7
It is put into 2g sorbierite and 0.2g calcium hydroxide in autoclave high-pressure reactor, 0.1g preparation is added and implements to prepare in 7
W catalyst, 20mL deionized water is passed through 6MPa hydrogen, reacted at 200 DEG C after closed, react 6 hours, be cooled to room
Temperature, filtering reacting liquid carry out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that sorb alcohol conversion is in water phase
90%, the yield of ethylene glycol and propylene glycol is 15%.
Embodiment 8
It is put into 4g xylitol and 0.3g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 1 and makes
Standby Ru-W catalyst, 40mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 3 hours, cooling
To room temperature, filtering reacting liquid carries out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that xylitol conversion in water phase
Rate is 95%, and the yield of ethylene glycol and propylene glycol is 82%.
Embodiment 9
It is put into 2g glucose and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.1g preparation embodiment 1 and makes
Standby Ru-W catalyst, 20mL deionized water are passed through 4MPa hydrogen, are reacted at 200 DEG C after closed, react 30 hours, cold
But to room temperature, filtering reacting liquid carries out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that glucose turns in water phase
Rate is 100%, and the yield of ethylene glycol and propylene glycol is 80%.
Embodiment 10
It is put into 0.5g cellulose and 0.2g calcium hydroxide in autoclave high-pressure reactor, is added in 0.2g preparation embodiment 1
The Ru-W catalyst of preparation, 50mL deionized water are passed through 5MPa hydrogen, are reacted at 240 DEG C after closed, react 2 hours, cold
But to room temperature, filtering reacting liquid carries out gas-chromatography and liquid-phase chromatographic analysis to reaction solution.The result shows that cellulose conversion ratio is
98%, the yield of ethylene glycol and propylene glycol is 75%.
Embodiment 11
By 5g bamboo powder 800 revs/min ball milling 20 hours in a planetary ball mill, 1g is put into autoclave high-pressure reactor
The Ru-W catalyst prepared in 0.4g preparation embodiment 1,100mL deionization is added in bamboo powder and 0.6g calcium hydroxide after ball milling
Water is passed through 6MPa hydrogen, is reacted at 240 DEG C after closed, react 4 hours, be cooled to room temperature, filtering reacting liquid, to reaction
Liquid carries out gas-chromatography and liquid-phase chromatographic analysis.The result shows that cellulose conversion ratio is 80% in bamboo powder in water phase, hemicellulose
Conversion ratio is 95%, and the yield of ethylene glycol and propylene glycol is 65%.
Embodiment 12
After reaction, the heterogeneous catalyst in embodiment 1 is centrifugated, is used for circulation experiment, other reaction conditions
It is identical as the reaction condition in embodiment 1.After recycling 50 secondary responses, with gas-chromatography and liquid chromatogram measuring experiment knot
Fruit, sorb alcohol conversion are 95%, and reaction product yield is not substantially change.Illustrate that catalyst stabilization is good, is easy to be recycled.
Embodiment 1 and 4 with multi-step synthetic methods the experimental results showed that compare, the load of one pot process N doping porous carbon
Bimetallic catalyst, not only synthetic method is simple, but also metal Ru particle size dispersion on carrier is uniform, provides more active sites
Point, catalytic activity are high.Embodiment 1 and 5 is the experiment results show that nitrogen in double-function catalyzing agent carrier, in catalyst
In water phase polyol systems, there is great effect to the raising of catalyst activity, the nitrogen on carrier can not only be adjusted
Save carrier surface soda acid position, moreover it is possible to adjust electronics transfer between active catalyst sites, improve catalyst activity.
The experimental data of comparative example 1,6,7 can be seen that the transition metal element energy loaded on N doping porous carbon
The conversion ratio for improving sorbierite provides acidic site, and adsorption reaction object is simultaneously selectively broken C-C key in sorbierite, and noble metal is made
For hydrogenation activity position, the selectivity of target product is improved.Above-mentioned experiment shows to make by the collaboration of noble metal and transition metal
With, the hydrogenation reaction of the biomass such as sorbierite can be not only significantly improved, but also can be distributed with the hydrogenation products of modulation sorbierite,
Ethylene glycol and propylene glycol is set to become primary product.Embodiment 1-10 is the experiment results show that bimetallic association on N doping porous carbon
With catalytic action reactant can be not only significantly improved with the biomass selectivity hydrogenolysis such as efficient catalytic sorbierite, xylitol
Conversion ratio and selectivity of product, also reduce reaction temperature and pressure.Wherein, sorbierite selective hydrogenation conversion ratio is greater than
99%, the yield of ethylene glycol and propylene glycol is greater than 85%.
Claims (10)
1. one kind passes through one pot of hydro-thermal method synthesising biological base N doping porous carbon load type double-metal with N doping bio-based materials
Catalyst, the loaded catalyst is by the noble metal of 0.5-20wt% and the transition metal element of 1-30wt% and 50-
The biology base nitrogen-doped porous carbon material carrier of 98.5wt% is constituted.
2. catalyst according to claim 1, which is characterized in that the ratio of the biology base nitrogen-doped porous carbon material carrier
Surface area is 150-1500m2/ g, nitrogen content 1-10wt%.
3. catalyst according to claim 1, which is characterized in that the noble metal be selected from palladium, gold, platinum, ruthenium,
One of rhodium, iridium or a variety of noble metals, preferably palladium, platinum or ruthenium；The transition metal element be selected from iron, copper, tungsten,
One of chromium, manganese, cobalt, nickel or a variety of transition metal elements, preferably tungsten, manganese or cobalt.
4. a kind of one pot process biology base N doping porous carbon load type bimetal catalyst according to claim 1
Preparation method, the preparation method include the following steps:
1) biological material is dry, it is ground into fine powder；
2) fine powder obtained in step 1) and noble metal, transition metal precursor solution are distributed in water；
3) mixture for obtaining step 2) is transferred in reaction kettle, 100-300 DEG C is heated under hydrothermal reaction condition, preferably
150-250 DEG C, 1-56 hours are kept the temperature, cooling, washing obtains brown solid；
4) brown solid obtained in step 3) is dried, ground, then carried out under inert atmosphere protection in tube furnace
Roasting, maturing temperature are 200-1500 DEG C, keep the temperature 1-100 hours；After tube furnace is cooled to room temperature, sample is taken out, i.e.,
Obtain the N doping porous carbon load type bimetal catalyst of one kettle way preparation.
5. the preparation method according to claim 4, which is characterized in that the biological material described in step 1) is rich in egg
The plant of white matter, comprising in fruits of elm, Folium Taraxacum, roundpod jute leaf, burdock leaf, asparagus, bamboo shoots, Cauliflower, spinach, broccoli extremely
Few one kind, preferably at least one of spinach, bamboo shoots, are used as carbon source and nitrogen source simultaneously.
6. the preparation method according to claim 4, which is characterized in that the noble metal precursor liquid solution described in step 2),
Its presoma can be one of ruthenium, palladium, platinum, rhodium and iridium or various metals salt, such as hydrochloride, sulfate, nitrate etc.；
Transition metal precursor can be one or more metal salts of iron, copper, manganese, nickel and tungsten, such as hydrochloride, sulfate, nitric acid
Salt etc.；Noble metal described in step 2) and transition metal precursor and the proportional amount of powdered biomass are 1~30wt%.
7. the preparation method according to claim 4, which is characterized in that the maturing temperature described in step 4) is 200-1500
DEG C, preferably 500-100 DEG C, the inert gas is one of nitrogen, argon gas and helium or a variety of, and soaking time is preferably
5-30 hours.
8. the preparation method according to claim 4, which is characterized in that the preparation method does not use activator or other nitrogen
Source material only needs a step to complete only with biological material and carried metal.
9. one kind using aqueous biochemical matter raw material and/or carbohydrate as raw material, is loaded in the biology base N doping porous carbon
The method for adding hydrogen to prepare ethylene glycol and propylene glycol in the presence of type bimetallic catalyst, the described method comprises the following steps: in autoclave
A certain amount of biomass is added in high-pressure reactor, the loaded catalyst, deionized water are filled with 0.1-10MPa hydrogen after closed
Gas is reacted at 100-350 DEG C, after reaction 0.5-48 hours, is cooled to room temperature, filtering reacting liquid, separating catalyst.Institute
It obtains product liquid and isolates the mixing dihydric alcohol such as ethylene glycol and propylene glycol through rectifying.
10. the method that according to claim 9 plus hydrogen prepares ethylene glycol and propylene glycol, which is characterized in that the biomass
Raw material and/or carbohydrate are preferably sorbierite, glucose, xylitol, xylose, cellulose, hemicellulose, timber, bamboo wood
One of or it is a variety of；
The loaded catalyst dosage is the 0.1-100wt%, preferably 1-20wt% of biomass dosage；Water consumption is made a living
10-200 times of substance dosage, preferably 10-100 times；Reaction pressure is 0.1-20MPa, preferably 1-8MPa；Reaction temperature is
50-250 DEG C, preferably 100-200 DEG C；Reaction time is 0.5-48 hours, preferably 1-10 hours；
Reaction temperature is preferably 120-250 DEG C in the method, and Hydrogen Vapor Pressure is preferably 1-8MPa, and the reaction time is preferably 1-10
Hour, the yield of ethylene glycol and propylene glycol may be up to 85%, the biology base N doping porous carbon load type double-metal of use
The specific surface area of catalyst is about 350-850m2/ g, nitrogen content are about 4-10%, and the biology base N doping is porous carbon-supported
Maturing temperature in the preparation method of bimetallic catalyst is 500-900 DEG C.
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