CN112206769A - Multi-walled carbon nanotube supported ruthenium catalyst and preparation and application thereof - Google Patents
Multi-walled carbon nanotube supported ruthenium catalyst and preparation and application thereof Download PDFInfo
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- CN112206769A CN112206769A CN202010994370.7A CN202010994370A CN112206769A CN 112206769 A CN112206769 A CN 112206769A CN 202010994370 A CN202010994370 A CN 202010994370A CN 112206769 A CN112206769 A CN 112206769A
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- walled carbon
- catalyst
- carbon nanotube
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- nitric acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 239000002048 multi walled nanotube Substances 0.000 title claims abstract description 88
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 116
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 66
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 66
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000005846 sugar alcohols Chemical class 0.000 claims abstract description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 27
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 27
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 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 abstract description 8
- 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 abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims abstract description 7
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims abstract description 7
- 229930182830 galactose Natural products 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 13
- 150000004676 glycans Chemical class 0.000 claims description 12
- 229920001282 polysaccharide Polymers 0.000 claims description 12
- 239000005017 polysaccharide Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
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- 230000001376 precipitating effect Effects 0.000 claims description 2
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 22
- 235000000346 sugar Nutrition 0.000 abstract description 19
- 239000000758 substrate Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 150000008163 sugars Chemical class 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 19
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 18
- 239000000811 xylitol Substances 0.000 description 18
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 18
- 235000010447 xylitol Nutrition 0.000 description 18
- 229960002675 xylitol Drugs 0.000 description 18
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- 239000011148 porous material Substances 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- FBPFZTCFMRRESA-GUCUJZIJSA-N galactitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-GUCUJZIJSA-N 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- 230000003914 insulin secretion Effects 0.000 description 1
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- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 230000000638 stimulation Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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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
-
- 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
- B01J23/42—Platinum
-
- 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
-
- 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
- B01J23/464—Rhodium
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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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- B01J35/393—
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- B01J35/396—
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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
- B01J37/0207—Pretreatment of the support
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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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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a multiwalled carbon nanotube supported ruthenium catalyst, and a preparation method and application thereof, wherein the catalyst is obtained by taking multiwalled carbon nanotubes treated by nitric acid as a carrier, taking ruthenium trichloride as a precursor and/or taking sodium borohydride as a reducing agent and carrying out immersion reduction in ethanol; the mass loading of ruthenium is 1-5%. The catalyst is suitable for the hydrogenation process of various sugars such as xylose, arabinose, glucose, mannose, galactose and the like, and has good universality; moreover, the method can realize high conversion rate of the substrate and high selectivity of the product under the conditions of less catalyst dosage, lower reaction temperature and pressure, and is beneficial to popularization; the stability is good, the recovery is facilitated, the repeated recycling can be realized, the yield of the sugar alcohol is still over 95 percent after the sugar alcohol is recycled to 5 batches, the stability of the catalyst is good, and the comprehensive utilization cost is greatly reduced.
Description
(I) technical field
The invention relates to the technical field of fine chemical engineering, in particular to a multiwalled carbon nanotube supported ruthenium catalyst, a preparation method thereof and application thereof in production of series sugar alcohols.
(II) background of the invention
The sugar alcohol is a polyol produced by reducing aldehyde and ketocarbonyl groups of a saccharide to hydroxyl groups. The sugar alcohol has moderate sweetness and low calorific value, is not suitable to be used as a nutrient source of oral microorganisms, and can be used as a novel green and healthy sweetener and a food additive. The sugar alcohol has no influence on insulin secretion and no fluctuation of blood sugar, and can be used as adjuvant therapeutic agent and special nutritional agent for patients with diabetes. In addition, the sugar alcohol has certain hygroscopicity, has no stimulation to skin, can be used as a moisture regulator, and is applied to the cosmetic industry. In recent years, the application field of the sugar alcohol is continuously expanded, and the market prospect is very wide.
The main method for the industrial production of sugar alcohol is to use Raney nickel or modified Raney nickel as a catalyst to carry out hydrogenation reduction on sugar under the conditions of high temperature and high pressure. However, raney nickel has poor catalytic activity, and requires higher reaction temperature and pressure to realize high conversion rate of substrate sugar and high selectivity of sugar alcohol; secondly, raney nickel tends to leach into the hydrogenated liquid during use, increasing the separation cost of sugar alcohol production. Therefore, the novel catalyst with stable preparation performance, high catalytic activity and wide application is applied to the preparation process of the sugar alcohol, and has very important significance for large-scale production of the sugar alcohol.
Patent CN105859522A discloses a process for preparing a series of sugar alcohols by reducing glucose, fructose, galactose, xylose and arabinose by using a universal noble metal catalyst, wherein formate is used as a hydrogen donor in the reaction, the reaction is green and environment-friendly, but the selectivity of the catalyst is not ideal, and the yield of the sugar alcohol is low between 44 and 83 percent. At present, there is no report on the efficiency and the application of the catalyst in various sugar hydrogenation catalysts. Patent CN101591222B discloses a preparation method of a co-supported catalyst and a method for preparing sorbitol by glucose hydrogenation, wherein the method co-supports metal nickel and another transition metal on a molecular sieve or Al2O3、SiO2、TiO2MgO, amorphous aluminum silicate and the like on the carrier to prepare the co-supported catalyst, and the yield of the sorbitol>98 percent. However, the catalyst preparation process of the present invention requiresThe energy consumption and the production cost are high when the reaction is carried out under the hydrogen pressure of 2.0-8.0MPa and the temperature of 300-500 ℃. The catalyst is only suitable for preparing sorbitol, and the catalytic efficiency and selectivity of the catalyst to other sugar alcohols are not clear.
In conclusion, the existing production process for sugar alcohol still has the problems of high reaction temperature and pressure, poor catalyst universality, high comprehensive production cost, poor catalyst stability and the like.
Disclosure of the invention
The invention aims to provide a multiwalled carbon nanotube supported ruthenium catalyst, and preparation and application thereof.
The technical scheme adopted by the invention is as follows:
the invention provides a multiwalled carbon nanotube loaded ruthenium catalyst, which is obtained by taking multiwalled carbon nanotubes treated by nitric acid as a carrier, taking ruthenium trichloride (the mass content of ruthenium is 39.97%) as a precursor and/or (with or without a reducing agent) taking sodium borohydride as a reducing agent and immersing in ethanol for reduction; the negative mass loading capacity of ruthenium is 1-5%.
Further, the mass ratio of the ruthenium trichloride to the carrier is 1:5-100 (preferably 1:7-96), the mass ratio of the sodium borohydride to the ruthenium trichloride is 0-5:1, preferably 1-5:1, most preferably 2:1, 0 means no sodium borohydride is added.
Further, the nitric acid treatment method of the multi-walled carbon nanotube comprises the following steps: adding multi-walled carbon nanotubes (MWCNTs) into concentrated nitric acid (with the mass concentration of 65-68%), refluxing at the constant temperature of 110 ℃ for 10h, cooling, filtering, washing a filter cake with distilled water until a washing liquid is neutral (the pH value is 7.0), and drying (preferably drying under the vacuum condition of 60 ℃) to obtain the carbon nanotubes treated by the nitric acid.
Further, the multi-walled carbon nanotube supported ruthenium catalyst is prepared by the following method: (1) adding multi-walled carbon nanotubes (MWCNTs) into concentrated nitric acid, refluxing at a constant temperature of 110 ℃ for 10h, cooling, filtering, washing a filter cake with distilled water until a washing solution is neutral (the pH value is 7.0), and drying (preferably drying under a vacuum condition at 60 ℃) to obtain the multi-walled carbon nanotubes treated by nitric acid; (2) adding ruthenium trichloride and the multi-walled carbon nano-tube treated by nitric acid in the step (1) into ethanol, stirring for 2h at room temperature under the protection of nitrogen, and/or adding sodium borohydride serving as a reducing agent, soaking for 10h at room temperature, centrifuging (preferably at 8000rpm for 10min), and drying (preferably drying at 60 ℃ under vacuum condition) to obtain the multi-walled carbon nano-tube supported ruthenium catalyst, namely the supported Ru/MWCNTs catalyst.
Further, the mass concentration of the concentrated nitric acid in the step (1) is 65-68%, and the volume dosage of the concentrated nitric acid is 20-50mL/g, preferably 20mL/g, calculated by the weight of the multi-wall carbon nano tube.
Further, adding sodium borohydride in the step (2) in the form of 1mol/L sodium borohydride aqueous solution; the ratio of the amount of sodium borohydride to the amount of ruthenium trichloride material is 0-5:1, preferably 2: 1.
Further, the mass ratio of the ruthenium trichloride to the multi-walled carbon nano-tube treated by the nitric acid in the step (2) is 1:5-100 (preferably 1:7.6), and the volume dosage of the ethanol is 100-800mL/g (preferably 160mL/g) calculated by the weight of the ruthenium trichloride.
The invention also provides an application of the multiwalled carbon nanotube loaded ruthenium catalyst in preparation of sugar alcohol by catalyzing polysaccharide, and the application method comprises the following steps: adding a multiwalled carbon nanotube loaded ruthenium catalyst into a polysaccharide aqueous solution, reacting (preferably for 120min) under the conditions that the hydrogen pressure is 1.0-4.0MPa, the temperature is 80-120 ℃, and the rotating speed is 300-700rpm, centrifuging the reaction solution after the reaction is completed, precipitating and recovering the catalyst, and separating and purifying the supernatant to obtain the sugar alcohol; the mass concentration of the polysaccharide aqueous solution is 5-25% (preferably 10%), and the mass ratio of the polysaccharide to the catalyst in the polysaccharide aqueous solution is 1:10-50, preferably 1: 20.
Further, the reaction conditions are preferably a hydrogen pressure of 3.0MPa, a temperature of 100 ℃ and 110 ℃ and a rotation speed of 500 rpm.
Further, the polysaccharide is xylose, arabinose, glucose, mannose or galactose.
Further, the catalyst recovery method comprises the following steps: after the reaction, the reaction solution is centrifuged (preferably at 8000rpm for 10min), and the precipitate is washed three times with ultrapure water and then dried under vacuum at 60 ℃ to recover the catalyst.
The method takes multi-walled carbon nano-tubes treated by nitric acid as a carrier, takes ruthenium trichloride as a precursor, adopts the immersion reduction in an ethanol system, and controls the Ru on the surface of the catalyst by optimizing the addition of a sodium borohydride reducing agent0And Ru3+In which Ru0Dissociation of hydrogen into active hydrogen, Ru3+The catalyst is favorable for combining carbonyl in substrate sugar molecules, and the carbonyl and the substrate sugar molecules have synergistic effect, so that the prepared catalyst can efficiently catalyze the hydrogenation activity. The supported catalyst is further applied to the hydrogenation process of series sugars such as xylose, arabinose, glucose, mannose, galactose and the like to prepare corresponding sugar alcohol, and the catalyst is recycled.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a multiwalled carbon nanotube supported ruthenium catalyst, and preparation and application thereof in sugar alcohol production0And Ru3+The proportion is high-efficiency cooperated with the selective adsorption and hydrogenation process of the sugar molecule carbonyl, so that the high-efficiency preparation of the sugar alcohol is realized. The catalyst is suitable for the hydrogenation process of various sugars such as xylose, arabinose, glucose, mannose, galactose and the like, and has good universality; and can realize high conversion rate of the substrate and high selectivity of the product under the conditions of less catalyst dosage, lower reaction temperature and pressure, and is beneficial to popularization. The catalyst has good stability, is beneficial to recovery, can be recycled for many times, has the yield of sugar alcohol of more than 95 percent after being recycled to 5 batches, has good stability, and greatly reduces the comprehensive utilization cost.
(IV) description of the drawings
FIG. 1 RuCl for ICP characterization and analysis of inductively coupled plasma emission spectrometer3A standard curve.
Fig. 2 shows a nitrogen adsorption-desorption curve (a) and a pore size-pore volume distribution curve (b) of the catalyst.
FIG. 3 TEM image (a) and particle size distribution (b) of the catalyst.
FIG. 4C 1s (a) and Ru 3p (b) XPS spectra of catalyst.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be equivalents thereof, and they fall within the scope of the claims.
The multi-walled carbon nanotube of the embodiment of the invention is purchased from Aladdin reagent Co, Ltd, and has an inner diameter of 5-10nm and an outer diameter of 20-40 nm. In the embodiment of the invention, the mass content of ruthenium in the ruthenium trichloride is 39.97%. In the examples of the present invention, the theoretical loading amount of ruthenium is equal to the mass of ruthenium in ruthenium trichloride/the total mass of the carrier and ruthenium × 100%.
The room temperature of the invention is 25-30 ℃.
Example 1: preparation and characterization of Ru/MWCNTs catalyst
(1) Preparation of multi-walled carbon nanotubes after nitric acid treatment
Weighing 5.0 g of multi-walled carbon nanotubes (MWCNTs), placing the weighed 5.0 g of multi-walled carbon nanotubes (MWCNTs) in a 250mL round-bottom flask, adding 100mL of concentrated nitric acid (65-68%), installing a reflux condenser tube, heating to 110 ℃ by using an oil bath, refluxing for 10h at a constant temperature under a stirring condition, cooling, filtering, washing a filter cake by using distilled water until the pH value of a washing liquid is neutral (the pH value is 7), and then drying for 12h at 60 ℃ in a vacuum oven to obtain 4.9g of the multi-walled carbon nanotubes after the nitric acid treatment.
(2) Preparation of different nanotube-supported metal catalysts
Preparation of Ru/MWCNTs catalyst: adding 0.125g (0.6mmol) of ruthenium trichloride and 0.95g of multi-walled carbon nano-tube treated by nitric acid into 20mL of ethanol, stirring at room temperature for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride aqueous solution serving as a reducing agent, continuing to soak at room temperature for 10h, then centrifuging at 8000rpm for 10min, and drying at 60 ℃ under vacuum condition to obtain the supported Ru/MWCNTs catalyst.
Preparation of Pt/MWCNTs catalyst: dissolving 0.50g of chloroplatinic acid and 0.95g of multi-walled carbon nano-tube treated by nitric acid in 20mL of ethanol, stirring for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride serving as a reducing agent, continuously soaking at room temperature for 10h, centrifuging at 8000rpm for 10min, and drying at 60 ℃ under a vacuum condition to obtain the supported Pt/MWCNTs catalyst.
Preparation of Pd/MWCNTs catalyst: dissolving 0.30g of chloroplatinic acid and 0.95g of multi-walled carbon nano-tube treated by nitric acid in 20mL of ethanol, stirring for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride serving as a reducing agent, continuously soaking at room temperature for 10h, centrifuging at 8000rpm for 10min, and drying at 60 ℃ under a vacuum condition to obtain the supported Pd/MWCNTs catalyst.
Preparation of Rh/MWCNTs catalyst: dissolving 0.25g of rhodium chloride and 0.95g of multi-walled carbon nano-tube treated by nitric acid in 20mL of ethanol, stirring for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride serving as a reducing agent, continuously soaking at room temperature for 10h, centrifuging for 10min at 8000rpm, and drying at 60 ℃ under a vacuum condition to obtain the supported Rh/MWCNTs catalyst.
Preparation of Ni/MWCNTs catalyst: dissolving 0.43g of nickel chloride and 0.95g of multi-walled carbon nano-tube treated by nitric acid in 20mL of ethanol, stirring for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride serving as a reducing agent, continuously soaking at room temperature for 10h, centrifuging for 10min at 8000rpm, and drying at 60 ℃ under a vacuum condition to obtain the supported Ni/MWCNTs catalyst.
(3) Catalytic activity of different nanotube-supported metal catalysts
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose aqueous solution with the mass concentration of 10%, transferring the xylose aqueous solution into a 100mL reaction kettle, respectively adding 0.3g of each catalyst prepared by the method (2), and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to be 100 ℃, stirring the mixture at a rotating speed of 500rpm, and filling hydrogen to 3.0MPa after the temperature is stable to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
2. Method for detecting substrate sugar and product sugar alcohol
mu.L of the reaction product before sealing the reaction vessel and 20. mu.L of the product after hydrogenation reaction were each taken, diluted to 1mL with ultrapure water, and the concentration of sugar in the reaction product, the residual concentration of sugar in the product, and the concentration of sugar alcohol in the product were measured by high performance liquid chromatography.
The high performance liquid chromatography apparatus used for detection is a waters system 2414 differential detector, the chromatographic column is an Aminex HPX-87H column (300X 7.8mM), and the mobile phase is 5mM H2SO4Flow rate 0.6mL/min, column temperature: 60.0 ℃, injection volume: 20 μ L.
The conversion of sugars and the selectivity of sugar alcohols are calculated as follows:
yield of sugar alcohol as sugar conversion rate x selectivity of sugar alcohol
The effect of different supported metal catalysts is shown in table 1, when the supported metal is Ru, the xylose conversion rate is 99.8%, the xylitol yield is 98.7%, and the catalytic effect is the best.
TABLE 1 influence of different Supported Metal catalysts on xylose conversion and xylitol yield
Example 2: preparation and characterization of Ru/MWCNTs catalyst
1. Preparation of Ru/MWCNTs catalyst
(1) Preparing the multi-wall carbon nano tube after nitric acid treatment: weighing 5.0 g of multi-walled carbon nanotubes (MWCNTs), placing the weighed 5.0 g of multi-walled carbon nanotubes (MWCNTs) in a 250mL round-bottom flask, adding 100mL of concentrated nitric acid (65-68%), installing a reflux condenser tube, heating to 110 ℃ by using an oil bath, refluxing for 10h at a constant temperature under a stirring condition, cooling, filtering, washing a filter cake by using distilled water until the pH value of a washing liquid is neutral (the pH value is 7), and then drying for 12h at 60 ℃ in a vacuum oven to obtain 4.9g of the multi-walled carbon nanotubes after the nitric acid treatment.
(2) Preparation of Ru/MWCNTs catalyst: adding 0.125g (0.6mmol) of ruthenium trichloride and 0.95g of multi-walled carbon nano-tube treated by nitric acid into 20mL of ethanol, stirring at room temperature for 2h under the protection of nitrogen, adding 1mL of 1mol/L sodium borohydride aqueous solution serving as a reducing agent, continuing to soak at room temperature for 10h, then centrifuging at 8000rpm for 10min, and drying at 60 ℃ under a vacuum condition to obtain 1.0g of supported Ru/MWCNTs catalyst, wherein the theoretical mass loading of Ru is 5%.
2. Characterization of the Ru/MWCNTs catalyst
(1) Characterization of the actual load of Ru elements
ICP characterization is carried out on the catalyst by adopting an inductively coupled plasma emission spectrometer Optima 8300DV, and RuCl is adopted3A standard sample containing 0%, 0.05%, 0.2%, 0.5%, 1.0%, 2.0% of Ru was prepared and the standard curve was determined, as shown in FIG. 1. The catalyst is further characterized, and the actual mass loading of the Ru element is 4.76%.
(2) Morphology characterization of catalysts
1) Nitrogen physical adsorption desorption method (BET)
And (2) respectively taking the Ru/MWCNTs catalyst prepared in the step (1), the raw material MWCNTs and the pretreated multi-wall carbon nanotube carrier (marked as MWCNTs-1) as samples to be detected, and detecting the specific surface area and the pore structure of the samples. Specific surface area and pore distribution were measured by nitrogen adsorption under liquid nitrogen (77K) using a Micromerics ASAP 2010 chemical physical adsorption apparatus from Mack, USA. During the test, the sample is firstly vacuumized at 150 ℃ and treated for 10 hours under the vacuum condition to completely remove the physically adsorbed water molecules in the sample. The adsorption-desorption isotherms (a in fig. 2) and pore size distribution curves (b in fig. 2) of the catalyst samples were further determined.
2) Transmission Electron Microscope (TEM)
And (3) taking the Ru/MWCNTs catalyst prepared in the step (1) as a catalyst sample.
Transmission electron microscopy, dark field-scanning transmission electron image (HAADF-STEM) observation was performed by a field emission transmission electron microscope (FEI, Talos-S) at an accelerating voltage of 200 kV. The preparation steps of the transmission electron microscope sample are as follows: 0.02g of catalyst sample is taken and prepared into suspension with 10mL of absolute ethyl alcohol, the suspension is placed into an ultrasonic cleaner for ultrasonic treatment for 10min after being fully mixed, and the catalyst is fully dispersed, and the result is shown in figure 3. It can be seen from a in fig. 3 that the metallic ruthenium nanoparticles are uniformly loaded on the surface of the activated carbon, and no obvious agglomeration phenomenon exists, and it can be seen from b in fig. 3 that the particle size distribution of the metal is narrow, and the average particle size is 2.39 nm.
(3) Valence state characterization of catalysts
And (3) taking the Ru/MWCNTs catalyst prepared in the step (1) as a sample.
The valence state of the elements on the surface of the catalyst was determined by Thermo Scientific K-Alpha + type X-ray photoelectron spectrometer (XPS), and the binding energy of all elements was corrected with contaminated carbon C1s (284.8eV), and the results are shown in FIG. 4. According to the fitting result, Ru in the catalyst0And Ru3+Co-exist of Ru061.6% of Ru3+In the proportion of 38.4%, wherein Ru0Is favorable for dissociating hydrogen into active hydrogen, Ru3+The catalyst is beneficial to being combined with carbonyl of substrate sugar, and the catalyst has higher activity due to the synergistic effect of the two.
Example 3: preparation of catalysts with different sodium borohydride addition amounts and hydrogenation activity test
1. Effect of the hydrogenation Activity of the catalyst
In example 2, the adding ratio of the sodium borohydride to the ruthenium trichloride is changed to be 0, 1: 1. 2: 1. 3: 1. 4: 1. 5:1, wherein 0 means no sodium borohydride is added. Otherwise, the same procedure as in example 2 was followed, using the procedure of example 2, to obtain 6 parts of Ru/MWCNTs catalysts, which were respectively identified as catalysts 0, 1, 2, 3, 4 and 5.
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose aqueous solution with the mass concentration of 10%, transferring the xylose aqueous solution into a 100mL reaction kettle, respectively adding 0.3g of each Ru/MWCNTs catalyst prepared by the method, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to be 100 ℃, stirring the mixture at a rotating speed of 500rpm, and filling hydrogen to 3.0MPa after the temperature is stable to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
When the method of example 1 is adopted for detection, the effect of the catalyst is shown in table 2, and when the molar ratio of sodium borohydride to ruthenium trichloride is 2:1, when the catalyst Ru is present0/Ru3+The ratio is 1.60, the xylose conversion rate is 99.8%, the xylitol yield is 99.0%, and the catalytic effect is optimal.
TABLE 2 influence of molar ratio of sodium borohydride and ruthenium trichloride on xylose conversion and xylitol yield
Example 4: preparation of catalysts with different ruthenium loadings
In example 2, the addition amounts of ruthenium trichloride were respectively adjusted to 0.025g, 0.050g, 0.075g, 0.010g and 0.125g, the addition amounts of the corresponding pretreated carbon nanotube carriers were respectively adjusted to 0.99g, 0.98g, 0.97g, 0.96g and 0.95g, and the addition ratio of sodium borohydride to ruthenium trichloride was kept to 2:1, the other operations are the same as example 2, and the Ru/MWCNTs catalysts with the theoretical mass loading of 1%, 2%, 3%, 4% and 5% are respectively obtained by adopting the detection method of example 1.
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose aqueous solution with the mass concentration of 10%, transferring the xylose aqueous solution into a 100mL reaction kettle, respectively adding 0.3g of each Ru/MWCNTs catalyst prepared by the method, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to be 100 ℃, stirring the mixture at a rotating speed of 500rpm, and filling hydrogen to 3.0MPa after the temperature is stable to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished. When the catalyst effect is determined by the method of example 1, as shown in table 3, when the ruthenium loading rate is 5%, the xylose conversion rate is 99.8%, the xylitol yield is 99.2%, and the catalytic effect is the best.
TABLE 3 influence of ruthenium loading on xylose conversion and xylitol yield
Example 5: pressure condition optimization of xylose
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose solution with the mass concentration of 10%, transferring the xylose solution into a 100mL reaction kettle, adding 0.3g of the Ru/MWCNTs catalyst prepared by the method in the example 2, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to 110 ℃, stirring at a speed of 500rpm, and after the temperature is stable, filling hydrogen to 1.0-4.0MPa to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
The method of example 1 is adopted for detection, the conversion rate of xylose and the yield of xylitol under different pressure conditions are shown in table 4, the conversion rate of xylose and the yield of xylitol are gradually improved along with the increase of reaction pressure, when the pressure is increased to 3.0MPa, the influence of the reaction pressure on the conversion rate and the yield is not great, and the production cost can be reduced by selecting 3.0MPa as the reaction pressure.
TABLE 4 influence of reaction pressure on xylose conversion and xylitol yield
Example 6: optimization of xylose rotation speed conditions
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose aqueous solution with the mass concentration of 10%, transferring the xylose aqueous solution into a 100mL reaction kettle, adding 0.3g of the Ru/MWCNTs catalyst prepared by the method in the example 2, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. The temperature of the reaction kettle is adjusted to be 110 ℃, the stirring speed is 300-700rpm, and after the temperature is stable, hydrogen is filled to 3.0MPa, and the reaction is started. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
The method of example 1 is adopted for detection, the conversion rate of xylose and the yield of xylitol under different rotation speeds are shown in table 5, the conversion rate of xylose and the yield of xylitol are gradually improved along with the increase of the reaction rotation speed, when the rotation speed is increased to 500rpm, the influence of the reaction speed rotation speed on the conversion rate and the yield is not great, and the 500rpm is selected as the reaction rotation speed, so that the energy consumption in the sugar alcohol production process can be effectively saved, and the production cost is reduced.
TABLE 5 influence of reaction rotation speed on xylose conversion and xylitol yield
Example 7: initial concentration optimization of xylose
Weighing 3.0 g, 6.0g, 9.0 g, 12 g and 15g of anhydrous xylose, preparing 60mL of xylose aqueous solution with mass concentration of 5%, 10%, 15%, 20% and 25% by using ultrapure water respectively, transferring the xylose aqueous solution into a 100mL reaction kettle, adding 0.3g of the Ru/MWCNTs catalyst prepared by the method of example 1, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to 110 ℃, stirring at a speed of 500rpm, and after the temperature is stable, filling hydrogen to 3.0MPa to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
The method of example 1 was used to determine that the conversion rate of xylose and the yield of xylitol under different initial xylose concentrations are shown in Table 6, the conversion rate of xylose is high at lower xylose concentrations, the final conversion rate of xylitol is gradually reduced with the increase of substrate concentration, the conversion rate of catalyst is over 99% when the substrate concentration is 5-10%, and the conversion rate of xylose is only 79.9% when the substrate concentration is increased to 25%.
TABLE 6 influence of substrate concentration on xylose conversion and xylitol yield
Example 8: recycling of catalyst
Weighing 6.0g of anhydrous xylose, adding the anhydrous xylose into 54mL of ultrapure water, preparing 60mL of xylose aqueous solution with the mass concentration of 10%, transferring the xylose aqueous solution into a 100mL reaction kettle, adding 0.3g of the Ru/MWCNTs catalyst prepared by the method in the example 2, and sealing the reaction kettle. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. Adjusting the temperature of the reaction kettle to 110 ℃, stirring at a speed of 500rpm, and after the temperature is stable, filling hydrogen to 3.0MPa to start the reaction. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished. And (3) introducing the reaction product into a 50mL centrifuge tube, centrifuging at 8000rpm for 10min, and performing liquid chromatography detection on 20 mu L of supernatant to obtain the product with the xylose conversion rate of 100% and the xylitol selectivity of 99.6%. And (4) discarding the supernatant in the centrifuge tube, centrifugally washing the precipitate for three times by using ultrapure water, and drying the precipitate in vacuum at the temperature of 60 ℃. The dried Ru/MWCNTs catalyst is used for the next xylose hydrogenation reaction, and the reaction conditions are the same. After repeating the operation five times, the xylose conversion and xylitol yield of each batch were measured by ICP-OES (Agilent 720ES) as shown in table 7 for the supernatant centrifuged after the fifth time, and no leaching of ruthenium was detected.
TABLE 7 xylose conversion and xylitol yield during Ru/MWCNTs catalysis xylose hydrogenation process of different batches
Example 9: hydrogenation reaction of series sugar
6.0g of different sugars (arabinose, glucose, mannose and galactose) are respectively weighed, added into 54mL of ultrapure water, prepared into 60mL of 10% sugar water solution, transferred into a 100mL reaction kettle, added with 0.3g of the Ru/MWCNTs catalyst prepared by the method in the example 2, and sealed. The reaction kettle is replaced by nitrogen for three times, and air in the reaction kettle is removed. The temperature of the reaction kettle is respectively adjusted to be 100 ℃, 110 ℃, the stirring speed is 500rpm, and after the temperature is stable, hydrogen is filled to 3.0MPa, and the reaction is started. After 120min of reaction, the reaction kettle is quickly cooled, and when the temperature is reduced to room temperature, hydrogen is discharged, and the hydrogenation reaction is finished.
The yields of the respective sugar alcohols at 110 ℃ as measured by the method of example 1 are shown in Table 8. With the increase of the temperature, the yield of the sugar alcohol is continuously increased, and the optimized conditions are as follows: the yield of arabitol was 98.9% at 100 ℃, sorbitol was 98.1%, mannitol was 98.7% and galactitol was 98.6% at 110 ℃.
TABLE 8 yield of sugar alcohols under different temperature conditions
Claims (10)
1. A multi-walled carbon nanotube loaded ruthenium catalyst is characterized in that the catalyst is obtained by taking a multi-walled carbon nanotube treated by nitric acid as a carrier, taking ruthenium trichloride as a precursor and/or taking sodium borohydride as a reducing agent and immersing in ethanol for reduction; the mass loading of the ruthenium is 1-5%.
2. The multi-walled carbon nanotube-supported ruthenium catalyst according to claim 1, wherein the mass ratio of the ruthenium trichloride to the support is 1: 5-100; the mass ratio of the sodium borohydride to the ruthenium trichloride is 0-5: 1.
3. The multi-walled carbon nanotube-supported ruthenium catalyst according to claim 1, wherein the nitric acid treatment method of the multi-walled carbon nanotube comprises: adding the multi-walled carbon nanotube into concentrated nitric acid with the mass concentration of 65-68%, refluxing for 10h at the constant temperature of 110 ℃, cooling, filtering, washing a filter cake with distilled water until a washing liquid is neutral, and drying to obtain the multi-walled carbon nanotube treated by nitric acid.
4. The multi-walled carbon nanotube-supported ruthenium catalyst according to claim 1, wherein the multi-walled carbon nanotube-supported ruthenium catalyst is prepared by the following method: (1) adding the multi-walled carbon nanotube into concentrated nitric acid with the mass concentration of 65-68%, refluxing for 10h at the constant temperature of 110 ℃, cooling, filtering, washing a filter cake with distilled water until a washing liquid is neutral, and drying to obtain the multi-walled carbon nanotube treated by nitric acid; (2) adding ruthenium trichloride and the multi-walled carbon nano-tube treated by nitric acid in the step (1) into ethanol, stirring for 2h under the protection of nitrogen, and/or adding sodium borohydride serving as a reducing agent, soaking for 10h at room temperature, centrifuging, and drying to obtain the multi-walled carbon nano-tube supported ruthenium catalyst.
5. The multi-walled carbon nanotube-supported ruthenium catalyst according to claim 4, wherein the concentrated nitric acid is used in an amount of 20 to 50mL/g by volume based on the weight of the multi-walled carbon nanotube in the step (1).
6. The multi-walled carbon nanotube-supported ruthenium catalyst according to claim 4, wherein in the step (2), sodium borohydride is added in the form of 1mol/L aqueous solution of sodium borohydride; the mass ratio of the sodium borohydride to the ruthenium trichloride is 0-5: 1; the mass ratio of the ruthenium trichloride to the multi-walled carbon nano-tube treated by the nitric acid is 1:5-100, and the volume dosage of the ethanol is 100-800mL/g calculated by the weight of the ruthenium trichloride.
7. The application of the multi-walled carbon nanotube-loaded ruthenium catalyst in the preparation of sugar alcohol by catalyzing polysaccharide according to claim 1.
8. The use according to claim 7, characterized in that the method of application is: adding a multiwalled carbon nanotube loaded ruthenium catalyst into a polysaccharide aqueous solution, reacting under the conditions of hydrogen pressure of 1.0-4.0MPa, temperature of 80-120 ℃ and rotation speed of 300-700rpm, centrifuging the reaction solution after the reaction is completed, precipitating and recovering the catalyst, and separating and purifying supernatant to obtain the sugar alcohol.
9. The use according to claim 8, wherein the aqueous solution of polysaccharide has a concentration of 5 to 25% by mass, and the ratio of polysaccharide to catalyst in the aqueous solution of polysaccharide is 1:10 to 50 by mass.
10. Use according to claim 8, characterized in that the polysaccharide is xylose, arabinose, glucose, mannose or galactose.
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