CN112547106A - Carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture and preparation method and application thereof - Google Patents
Carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920005610 lignin Polymers 0.000 claims abstract description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 238000001035 drying Methods 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- CBOJBBMQJBVCMW-BTVCFUMJSA-N (2r,3r,4s,5r)-2-amino-3,4,5,6-tetrahydroxyhexanal;hydrochloride Chemical compound Cl.O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO CBOJBBMQJBVCMW-BTVCFUMJSA-N 0.000 claims description 9
- 229960001911 glucosamine hydrochloride Drugs 0.000 claims description 9
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 82
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 239000002923 metal particle Substances 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- UYXMBPVOGLUKIV-UHFFFAOYSA-N (2-methoxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC=CC=C1OC UYXMBPVOGLUKIV-UHFFFAOYSA-N 0.000 abstract description 2
- LBPOTMKNHGNDFG-UHFFFAOYSA-N 2,6-dimethoxy-3-propylphenol Chemical compound CCCc1ccc(OC)c(O)c1OC LBPOTMKNHGNDFG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 238000006731 degradation reaction Methods 0.000 description 36
- 230000015556 catabolic process Effects 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000007787 solid Substances 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 28
- 239000012075 bio-oil Substances 0.000 description 25
- 239000007788 liquid Substances 0.000 description 25
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 229940045348 brown mixture Drugs 0.000 description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 239000000126 substance Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- -1 monophenol compound Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 229910015711 MoOx Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241000124033 Salix Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/40—
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- B01J35/613—
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- B01J35/615—
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- B01J35/617—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
Abstract
The invention belongs to the technical field of metal solid catalysts, and particularly discloses a carbon-nitrogen material loaded nickel catalyst with adjustable mesoporous aperture, and a preparation method and application thereof. The invention adopts a hydrothermal synthesis process to pretreat a carbon source precursor and a template agent, and the template agent is well doped on a carbon carrier through a self-assembly process. The synthesized nickel-based composite nitrogen-doped carbon material nano catalyst carrier has the advantages of adjustable pore channel size, small metal particles, large specific surface area, uniform dispersion and no obvious agglomeration. Can efficiently depolymerize lignin to prepare single benzene ring compounds, has higher selectivity on propyl syringol and propyl guaiacol, has high catalyst circulation stability, and has the monophenol yield of 28.21 percent.
Description
Technical Field
The invention belongs to the technical field of metal solid catalysts, and particularly relates to a carbon-nitrogen material loaded nickel catalyst with adjustable mesoporous aperture, and a preparation method and application thereof.
Background
In the current society, the exhaustion of fossil resources and the environmental burden caused by the use of fossil resources require the society to seek sustainable alternative methods, and the large-scale development and efficient utilization of biomass energy are effective ways for solving the global energy crisis and environmental problems, and are also huge challenges faced by the current scientific and industrial fields. The lignin is a renewable natural aromatic ring polymer consisting of phenylpropane structural units, and the preparation of the monophenol compound by efficiently depolymerizing the lignin has great potential in the aspect of replacing fossil liquid fuel and bulk chemicals. The development of a catalyst with high catalytic activity, high product selectivity and good cycle stability is the key to improving the lignin depolymerization efficiency and further realizing industrialization.
At present, scholars at home and abroad have extensive research on depolymerization of lignin. The current major lignin depolymerization methods include catalytic thermal cracking, oxidative degradation, base catalytic degradation, and hydro-degradation, among others. The conversion efficiency of the hydrogenolysis lignin is better, and the efficiency is determined by the catalytic activity of the catalyst.
The metal catalyst for lignin depolymerization mainly comprises noble metals Pd, Pt and Rh and transition metals Ni, Fe and Mo. The Ling-Ping Xiao et al (ACS Catal.2017,7, 7535-sa 7542) group of topics reported a catalyst system prepared by attaching molybdenum oxide particles to multi-layered carbon nanotubes, which has high selectivity for phenolic compounds with unsaturated substituents, by attaching molybdenum oxide particles to multi-layered carbon nanotubes (MoOx/CNT). The subject group takes willow enzyme mild acidolysis lignin as a substrate, MoOx/CNT as a catalyst, methanol as a solvent and 3MPa hydrogen environment at 240 ℃ for 4h to obtain 33% of monophenol yield, the selectivity of unsaturated components reaches 47.2% of yield, and the product mainly has an S-shaped structure but is high in cost, so that the industrial application is limited. Penguru Chen (Bioresource Technology 226(2017) 125-131) et Al propose that lignin hydrolysis as raw material, ethanol as solvent, Ni/Al-SBA-15(20) (20 is Si/Al molar ratio) as catalyst are reacted at 300 deg.C for 4 hours, lignin liquefaction rate is 81.4%, monophenol yield is 21.9%, but a small amount of coke is generated in the final product. The subject group utilizes the ordered pore structure and larger pore diameter on SBA-15, can effectively inhibit the re-polymerization reaction, and can promote the degradation of lignin and the generation of saturated unstable intermediate products by adding aluminum and nickel into SBA-15. The subject group and the discovery that the addition of aluminum and nickel does not destroy the porous structure of the original scaffold, the increase in pore volume with the increase in silica-alumina ratio, the replacement of part of the silicon ions in the framework by aluminum ions, can increase the activity and acidity of SBA-15, the increase in catalyst acidity can promote the breaking of C-O bonds (such as β -O-4 and α -O-4 bonds), but too strong acidity can also promote the occurrence of the re-polymerization reaction to significantly increase the catalytic effect, but the final product still has a small amount of coke production while the large pore size catalyst favors the degradation of the organic solvent hydrolysis lignin and may inhibit the formation of carbon. Gomez-Cazalila, M. (Journal of Solid State Chemistry 180(2007) 1130) -1140) task group and the like synthesize the Y/Al-SBA-15 composite material by a two-step synthesis method under a mild acidic medium, and the composite material is shown to be rich in mesoporous and microporous which are mutually communicated in certain areas, so that the composite material has higher catalytic activity on the cracking reaction of small molecular hydrocarbons (such as isopropylbenzene) and large molecular hydrocarbons (such as 1,3, 5-triisopropylbenzene). In 2017, Sandy M.G. Lama (ACS Sustainable Chemistry & Engineering,2017,5(3):2415-2420) and the like firstly prepare a nitrogen-doped hierarchical porous carbon material by a molten salt method, load an active component Ni by a wet impregnation method for hydrogenolysis of alkali lignin, and react for 24h at the temperature of 150 ℃ to finally show excellent catalytic activity. The problem group finds that the pore size of the catalyst has certain influence on the catalytic efficiency, the larger pores are beneficial to the diffusion of lignin in the catalyst, and the lignin can more effectively reach the active Ni site, so that higher yield of monophenol is obtained. Although noble metal catalysts show excellent activity and efficiency in the depolymerization process of lignin, their use in lignin depolymerization is limited due to their expensive price and excessive hydrogenation of benzene rings. Noble metals are expensive, and compared with the noble metals, non-noble metals have catalytic hydrogenation effects and relatively low price, so that the application of non-noble metal catalysts in lignin hydrogenolysis is more and more attractive. The size of the pore channel of the catalyst carrier also has great influence on the depolymerization efficiency of lignin, and the smaller pore channel is not beneficial to the diffusion of lignin molecules in the catalyst, so that the agglomeration phenomenon occurs and the degradation effect is influenced. Therefore, the pore size of the catalyst carrier is regulated and controlled to find the pore size most suitable for lignin molecular diffusion, so that the mass transfer efficiency can be effectively improved, and the yield of monophenol is improved.
The Chinese patent application CN 108283933A discloses a preparation method of a catalytic hydrodechlorination Pd-M/NOMC catalyst. The nitrogen-doped NOMC is prepared by loading Pd nanoparticles by an impregnation method by using urea as a nitrogen source, resorcinol and 1,3, 5-trimethylbenzene as carbon sources and F127 as a soft template agent. The prepared ordered mesoporous carbon has ordered pore canal arrangement, larger pore volume and specific surface than common activated carbon, and more active sites on the surface. The Pd nano-particles are loaded by an impregnation method, the doping of nitrogen atoms improves the defect sites on the surface of the carbon material, so that the dispersion degree of the carbon-loaded Pd particles with uniform distribution and high stability is improved, and the addition of nitrogen changes the surface electrochemical state of the carbon material, so that the stability of the Pd nano-particles is improved. The catalyst shows higher Pd-based hydrodechlorination catalyst activity and stability in the degradation reaction of dichlorophenol. The Chinese patent CN 104028293A discloses a preparation method of a low-temperature nitrogen-doped graphene-loaded nano Pd hydrogenation catalyst. Graphite oxide is used as a raw material, ammonia water, ethylenediamine or urea is used as a nitrogen source, a nitrogen-doped carbon carrier is obtained through hydrothermal reaction, Pd nano-particles are loaded by an impregnation method to prepare the carbon-loaded Pd-based catalyst, and the nitrogen-doped graphene is used for loading Pd, so that the dispersion degree of the Pd nano-particles can be improved to a great extent by the action of lone pair electrons of nitrogen and metal Pd, and the loss of Pd can be reduced. The catalyst shows good catalytic activity and reusability in the hydrogenation reaction of olefin.
The nickel-based catalyst prepared by taking the metallic nickel as the active component has great potential for preparing monophenol compounds by lignin depolymerization from the comprehensive consideration of the lignin depolymerization activity and the raw material price. The nickel-based catalyst prepared by the traditional impregnation method needs long-time roasting and high-temperature reduction, and the prepared catalyst has the advantages of large nano particles, poor dispersity, easy agglomeration, easy loss of active components and poor stability. Thus, the movement of the movable member; the nitrogen element is doped into the carbon material, so that the acting force between the metal nickel and the carrier can be enhanced, the loss of metal particles in the catalytic process is greatly reduced, the recycling efficiency of the catalyst can be improved, and the method is a better method for solving the problems. On the other hand, most of the current catalyst carriers for lignin depolymerization have a microporous structure, the microporous structure is easy to block in the reaction process, the mass transfer effect is poor, and thus the catalyst has a short service life or low catalytic efficiency due to the re-polymerization phenomenon of reaction products, and the mesoporous molecular sieves, such as HZSM-5 and SBA-15, have small mesoporous diameters, are easy to block the pore channels, and have poor hydrothermal stability. Therefore, it is necessary to develop a catalyst loaded on a large-pore-size carrier which is low in price, high in catalytic efficiency, excellent in performance and most suitable for lignin macromolecule degradation, so as to meet the demand of lignin hydrogenation high-value utilization depolymerization.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture.
The invention also aims to provide the carbon-nitrogen material supported nickel catalyst with the adjustable mesoporous aperture, which is prepared by the method.
The invention further aims to provide application of the carbon-nitrogen material loaded nickel catalyst with the adjustable mesoporous aperture in lignin depolymerization by hydrogenation.
The purpose of the invention is realized by the following scheme:
a preparation method of a carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture comprises the following steps:
1) mixing a soluble carbon and nitrogen precursor with a template agent to form a uniform mixture, then carrying out hydrothermal reaction, and drying the obtained product for later use;
2) grinding the product obtained in the step 1), and then pyrolyzing the product under a protective atmosphere; then adding water and sodium hydroxide, stirring, carrying out suction filtration, and drying filter residues to obtain a nitrogen-doped carbon material carrier;
3) mixing and stirring soluble nickel salt water and the obtained nitrogen-doped carbon material carrier, then evaporating to dryness, and drying the obtained product to obtain the nickel-based composite nitrogen-doped carbon material nano catalyst;
4) the product obtained in the step 3) is fully ground and then is subjected to H2And reducing in a protective atmosphere to finally obtain the carbon-nitrogen material loaded nickel catalyst with adjustable mesoporous aperture.
The soluble carbon and nitrogen precursor in the step 1) is at least one of glucosamine hydrochloride, melamine and urea; the template agent is at least one of LUDOX @ AS-40, LUDOX @ HS-40 and LUDOX @ SM.
The mass ratio of the soluble carbon nitrogen precursor to the template agent in the step 1) is 1-8: 0-8, and the dosage of the template agent is not 0; preferably 1: 1.
Step 1), the hydrothermal reaction is carried out for 8-24h at the temperature rising rate of 10-60 ℃/min and the temperature rising to 140-200 ℃; preferably, the temperature is raised to 140-180 ℃ at the temperature raising rate of 20-30 ℃/min for reaction for 10-16 h.
Preferably, after the hydrothermal reaction in step 1) is completed, the product is further purified, specifically, washed by centrifugation with water and ethanol.
The pyrolysis procedure in the step 2) is to heat to 900 ℃ at the temperature of 700 ℃ at the speed of 3-8 ℃/min and keep the temperature for 1-4 h. Preferably, the temperature is raised to 800 ℃ at the speed of 5 ℃/min, and the constant temperature is kept for 2 h.
The mass-volume ratio of the product in the step 2) to water and sodium hydroxide is as follows: 0.1-2 g: 100-300 mL: 2-10 g.
And 2) performing suction filtration in the step of suction filtration until the pH value of the filtrate is below 8. The drying is carried out for 6-24 hours at 50-70 ℃.
The nickel salt in the step 3) is one or two of nickel nitrate hexahydrate and nickel acetate tetrahydrate; the concentration of the soluble nickel salt water is 0.006-0.012 g/ml, preferably 0.01 g/ml;
and 3) mixing the nickel salt water with a nitrogen-carbon material carrier in a volume-to-mass ratio of 10-30 mL: 0.3 g.
The evaporation in the step 3) is preferably carried out at 60-80 ℃, and the drying is preferably carried out at 50-70 ℃ for 6-24 h.
The reduction in the step 4) is specifically carried out for 2-8 h at 400-480 ℃, and preferably for 4h at 450 ℃. Said H2The flow rate of the protective atmosphere is 20-80 sccm.
A carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture is prepared by the method.
The carbon-nitrogen material loaded nickel catalyst with the adjustable mesoporous aperture is applied to lignin depolymerization by hydrogenation.
The surface of the catalyst prepared by the method is a compact network consisting of agglomerated nano particles, pores with uniform and adjustable sizes are formed on the carrier after the template agent is removed, the catalyst has a very high specific surface area and a developed pore structure, the metal nickel particles are small, the dispersion degree of active components is very high, and the circulation stability of the catalyst is high.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1) the invention adopts a hydrothermal synthesis process to pretreat a carbon source precursor and a template agent, and the template agent is well doped on a carbon carrier through a self-assembly process.
2) The pore canal size of the nickel-based composite nitrogen-doped carbon material nano catalyst carrier synthesized by the method can be regulated and controlled (7nm,12nm and 22nm) metal particlesSmall (5-20nm) and large specific surface area (70-830 m)2Per g) and is dispersed uniformly without obvious agglomeration.
3) The nickel-based composite nitrogen-doped carbon material nano catalyst synthesized by the invention can be used for preparing single benzene ring compounds by efficiently depolymerizing lignin, and has high selectivity on propyl syringol and propyl guaiacol and high catalyst cycle stability.
4) The nickel-based composite nitrogen-doped carbon material nano catalyst synthesized by the method can change the size of the template agent and the type of the carbon source to regulate the micro-morphology of the template agent, and change the pyrolysis temperature to regulate the size of nickel nano particles of the catalyst.
Drawings
FIG. 1 shows catalyst Ni/N1SEM (A) scanning Electron and TEM (B) Transmission Electron of HC (22)
FIG. 2 shows the catalyst Ni/N1XRD patterns (A) and N of HC (22)2Adsorption and desorption isotherm (B)
FIG. 3 shows catalyst N1EDS Spectroscopy of HC (22)
FIG. 4 shows catalyst N1SEM (A) diagram and N of HC (12)2Adsorption and desorption isotherm (B)
FIG. 5 shows catalyst N1SEM (A) diagram and N of HC (7)2Adsorption and desorption isotherm (B)
FIG. 6 shows catalyst N1SEM (A) diagram of HC (0) and N2Adsorption and desorption isotherm (B)
FIG. 7 shows SEM (A) scanning electron microscope and TEM (B) transmission electron microscope of catalyst Ni/HC (22)
FIG. 8 shows the Fe/N ratio of the catalyst1HC(22),Co/N1HC(22),Mo/N1XRD Pattern of HC (22)
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N1HC(22)。
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst1HC(22)。
FIG. 1 catalyst Ni/N1SEM (A) scanning Electron microscopy and TEM (B) for HC (22). It can be seen that the catalyst surface is a tight network composed of agglomerated nanoparticles, macropores exist between particles, the carrier has pores of 22nm with uniform size, and the average particle size of the nickel nanoparticles is about 7.55 nm.
FIG. 2 catalyst Ni/N1XRD patterns (A) and N of HC (22)2Adsorption and desorption isotherms (B). It can be seen that Ni in the catalyst exists in a simple substance form, and an obvious H4 type hysteresis loop exists in the absorption and desorption curve of the catalyst, which indicates that the material has a micropore and mesopore structure.
FIG. 3 catalyst N1EDS energy spectrum of HC (22). It can be seen that the templating agent in the catalyst was completely eluted,and the N element is successfully doped into the carbon skeleton.
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave1HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Example 2
1) In a 100ml beaker, 4g of LUDOX @ HS-40 was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N1HC(12)。
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 ℃ at the heating rate of 2 ℃/min under the Ar atmosphere, and keeping the temperature for 4 hours to obtain a black solid，H2The flow rate of/Ar was 60 sccm. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst1HC(12)。
FIG. 4 SEM images (A) and N of catalyst Ni/NHC (12)2Adsorption and desorption graph (B). The catalyst surface and Ni/N can be seen1HC (22) is consistent, and the size of pore channels on the surface of the catalyst is identical to that of a pore-forming agent and is about 12 nm. The absorption and desorption curves of the catalyst have obvious H4 type hysteresis loops, which indicates that the material has micropore and mesopore structures.
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave1HC (12), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Example 3
1) In a 100ml beaker, 4g of LUDOX @ SM was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300-500 rpm for 2h to form a homogeneous transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) And adding the obtained black solid powder into a 200ml beaker, adding 150ml of deionized water and 10g of sodium hydroxide, washing to be neutral, and drying the obtained filter residue in an oven at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon carrier, which is recorded as NHC (7).
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst1HC(7)。
FIG. 5 SEM image of catalyst Ni/NHC (7). The catalyst surface and Ni/N can be seen1HC (22) is consistent, and the size of pore channels on the surface of the catalyst is identical to that of a pore-forming agent and is about 7 nm. The absorption and desorption curves of the catalyst have obvious H4 type hysteresis loops, which indicates that the material has micropore and mesoporous structures.
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave1HC (7), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Example 4
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of melamine was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2h to form a homogeneous transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 200 ℃ at the heating rate of 10 ℃/min, and reacting for 8h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 900 ℃ at the heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N2HC(22)。
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst2HC(22)。
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave2HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Example 5
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of urea was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 140 ℃ at a heating rate of 10 ℃/min, and reacting for 24 hours to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 700 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N3HC(22)。
6) 0.16g of nickel acetate tetrahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst3HC(22)。
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave3HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 1
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of glucose was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) And adding the obtained black solid powder into a 200ml beaker, adding 150ml of deionized water and 10g of sodium hydroxide, washing to be neutral, and drying the obtained filter residue in an oven at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon carrier, which is recorded as HC (22).
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely the nickel-based composite nitrogen-doped carbon material nano catalyst Ni/HC (22).
FIG. 7 SEM (A) scanning Electron microscope and TEM (B) of catalyst Ni/HC (22). It can be seen that the catalyst carrier is spherical particles with a size of 1-5 μm, and only a small number of spherical pores are present on the surface of the catalyst, and the particle size of the metallic nickel nanoparticles is large, about 13.91 nm.
Performance testing
0.3g of lignin, 0.06g of Ni/HC (22) catalyst, 10ml of distilled water and 10ml of ethanol were added to a 100ml autoclave, and the mixture was stirred with N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 2
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) And adding the obtained black solid powder into a 200ml beaker, adding 150ml of deionized water and 10g of sodium hydroxide, washing to be neutral, and drying the obtained filter residue in an oven at 50 ℃ for 24 hours to obtain the nitrogen-doped carbon carrier, which is recorded as NHC (22).
6) 0.07g of ammonium heptamolybdate tetrahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. Namely the catalyst Mo/N1HC(22)。
FIG. 8 catalyst Mo/N1HC(22)，Fe/N1HC(22),Co/N1XRD pattern of HC (22). It can be seen that the molybdenum element is mainly MoO at the hydrogen reduction temperature of 450 DEG C2Exist in the form of (1).
Performance testing
0.3g of lignin and 0.06g of catalyst Mo/N are added into a 100ml high-pressure reaction kettle1HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. Using n-decane as an internal standard substance, and quantitatively detecting the yield of the bio-oil and the yield of monophenol obtained by lignin degradation by using a gas chromatography-mass spectrometerAnd (4) rate.
Comparative example 3
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N1HC(22)。
6) 0.24g of ferric nitrate nonahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated in an oil bath kettle at the temperature of 80 ℃ and then is put into an oven at the temperature of 50 ℃ for drying for 24 hours, and the black compound is obtained.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 ℃ at the heating rate of 2 ℃/min under the Ar atmosphere, and keeping the temperature for 4 hours to obtain a black solid. Namely the catalyst Fe/NHC (22).
FIG. 8 catalyst Mo/N1HC(22)，Fe/N1HC(22),Co/N1XRD pattern of HC (22). It can be seen that the iron element is mainly Fe at the hydrogen reduction temperature of 450 deg.C2O3Exist in the form of (1).
Performance testing
0.3g of lignin and 0.06g of catalyst Fe/N were added to a 100ml autoclave1HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. After the reaction is finished, cooling to room temperatureExtracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 4
1) In a 100ml beaker, 4g of LUDOX @ AS-40 was weighed, and 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300rpm to 500rpm for 2 hours to form a uniform transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 800 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 2 hours to obtain a black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N1HC(22)。
6) 0.16g of cobalt nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 deg.C at a rate of 2 deg.C/min under Ar atmosphere, and maintaining for 4H to obtain black solid, H2The flow rate of/Ar was 60 sccm. I.e. Co/N1HC(22)。
FIG. 8 catalyst Mo/N1HC(22)，Fe/N1HC(22),Co/N1XRD pattern of HC (22). It can be seen that the cobalt element exists mainly as simple substance of Co at the hydrogen reduction temperature of 450 c.
Performance testing
Adding the mixture into a 100ml high-pressure reaction kettle0.3g of lignin and 0.06g of catalyst Co/N were added1HC (22), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 5
1) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of activated carbon is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
2) The resulting compound is transferred to a tube furnace in H2Heating to 450 ℃ at the heating rate of 2 ℃/min under the Ar atmosphere, and keeping the temperature for 4 hours to obtain a black solid. Namely Ni/AC.
Performance testing
Adding 0.3g lignin, 0.06g catalyst Ni/AC, 10ml distilled water and 10ml ethanol into a 100ml high-pressure reaction kettle, adding N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 6
1) In a 100ml beaker, 4g of glucosamine hydrochloride was weighed into 50ml of distilled water and stirred at 300-500 rpm for 2h to form a homogeneous transparent mixture.
2) Transferring the mixture into a hydrothermal reaction kettle, heating to 160 ℃ at a heating rate of 10 ℃/min, and reacting for 12h to obtain a black-brown mixture.
3) And (3) drying the black-brown mixture in an oven at 50 ℃ for 24h to obtain a compound of the carbon-nitrogen precursor and the template agent.
4) Transferring the obtained compound into a tube furnace in N2Heating to 700 ℃ at a heating rate of 10 ℃/min and keeping the temperature for 2 hours to obtain black solid.
5) Adding the obtained black solid powder into a 200ml beaker, adding 150ml deionized water and 10g sodium hydroxide, washing to be neutral, putting the obtained filter residue into a 50 ℃ oven for drying for 24h to obtain the nitrogen-doped carbon carrier, and marking as N1HC(0)。
6) 0.16g of nickel nitrate hexahydrate is weighed in a 100ml beaker, 0.3g of the carrier is weighed and added into 20ml of deionized water, the mixture is heated and evaporated to dryness in an oil bath kettle at the temperature of 80 ℃, and then the mixture is placed in an oven at the temperature of 50 ℃ for drying for 24 hours to obtain a black compound.
7) The resulting compound is transferred to a tube furnace in H2Heating to 450 ℃ at the heating rate of 2 ℃/min under the Ar atmosphere, and keeping the temperature for 4 hours to obtain a black solid. Namely Ni/N serving as the nickel-based composite nitrogen-doped carbon material nano catalyst1HC(0)。
FIG. 6 catalyst Ni/N1SEM images (A) and N of HC (0)2Adsorption and desorption graph (B). From Ni/N1The SEM image (A) of HC (0) shows that the catalyst is a compact network composed of agglomerated nanoparticles, and a macroporous structure exists between the particles, but the surfaces of the particles are very smooth and have no pore structure, from N2The absorption and desorption curve chart (B) shows that the hysteresis loop is H4 type, which indicates that the material has micropore and mesopore structure.
Performance testing
0.3g of lignin and 0.06g of catalyst Ni/N were added to a 100ml autoclave1HC (0), 10ml distilled water, 10ml ethanol, N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
Comparative example 7
Lignin was degraded using commercial Pd/C catalysts.
Performance testing
Adding 0.3g lignin, 0.06g catalyst Pd/C, 10ml distilled water and 10ml ethanol into a 100ml high-pressure reaction kettle, adding N2Carrying out evacuation for three times, and then introducing 1MPa of H2The reaction is carried out for 120min under the conditions that the temperature is 300 ℃ and the rotating speed is 400 rpm. And cooling to room temperature after the reaction is finished, extracting the degradation liquid by using 60ml of ethyl acetate for three times, and carrying out rotary evaporation and drying on the extract liquid to obtain the bio-oil. And (3) quantitatively detecting the yield of the bio-oil and the yield of the monophenol obtained by lignin degradation by using the gas chromatography-mass spectrometer with n-decane as an internal standard substance.
TABLE 1 Lignin Bio-oil yield, monophenol yield and selectivity
Table 1 shows the activity evaluation data of the inventive examples and comparative examples on lignin degradation. As can be seen from Table 1, the catalyst prepared in the embodiment of the present invention has much higher activity than that of the comparative example (template agent with other diameter size), and shows excellent catalytic effect in lignin degradation reaction, the optimal mesoporous size (22nm) for lignin degradation is successfully screened, and the yield of monophenol reaches 28.21% at most. In the preparation process, the pore-forming effect of the template agent greatly improves the specific surface area of the catalyst carrier, the optimal pore diameter is more suitable for the degradation of lignin, the introduction of nitrogen is also beneficial to the dispersion of metal, the size of metal particles is obviously reduced, the effect of anchoring metal is successfully played, and the degradation efficiency of lignin is effectively improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture is characterized by comprising the following steps:
1) mixing a soluble carbon and nitrogen precursor with a template agent to form a uniform mixture, then carrying out hydrothermal reaction, and drying the obtained product for later use;
2) grinding the product obtained in the step 1), and then pyrolyzing the product under a protective atmosphere; then adding water and sodium hydroxide, stirring, carrying out suction filtration, and drying filter residues to obtain a nitrogen-doped carbon material carrier;
3) mixing and stirring soluble nickel salt water and the obtained nitrogen-doped carbon material carrier, then evaporating to dryness, and drying the obtained product to obtain the nickel-based composite nitrogen-doped carbon material nano catalyst;
4) the product obtained in the step 3) is fully ground and then is subjected to H2And reducing in a protective atmosphere to finally obtain the carbon-nitrogen material loaded nickel catalyst with adjustable mesoporous aperture.
2. The method of claim 1, wherein: the template agent in the step 1) is at least one of LUDOX @ AS-40, LUDOX @ HS-40 and LUDOX @ SM.
3. The method of claim 1, wherein: the soluble carbon-nitrogen precursor in the step 1) is at least one of glucosamine hydrochloride, melamine and urea.
4. The method of claim 1, wherein: the mass ratio of the soluble carbon nitrogen precursor to the template agent in the step 1) is 1-8: 0-8, and the dosage of the template agent is not 0.
5. The method of claim 1, wherein: the hydrothermal reaction in the step 1) is carried out at a heating rate of 10-60 ℃/min, and the temperature is raised to 140-200 ℃ for 8-24 h.
6. The method of claim 1, wherein: the mass-volume ratio of the product in the step 2) to water and sodium hydroxide is as follows: 0.1-2 g: 100-300 mL: 2-10 g.
7. The method of claim 1, wherein: the nickel salt in the step 3) is one or two of nickel nitrate hexahydrate and nickel acetate tetrahydrate; the concentration of the soluble nickel salt water is 0.006-0.012 g/ml.
8. The method of claim 1, wherein: the pyrolysis procedure in the step 2) is to heat up to 700 ℃ and 900 ℃ at the speed of 3-8 ℃/min and keep the temperature for 1-4 h; the reduction in the step 4) is specifically carried out for 2-8 h at 400-480 ℃; said H2The flow rate of the protective atmosphere is 20-80 sccm.
9. A carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture, which is prepared by the method of any one of claims 1 to 8.
10. The use of the mesoporous pore size controllable carbon and nitrogen material supported nickel catalyst according to claim 9 in lignin depolymerization by hydrogenation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113145121A (en) * | 2021-05-10 | 2021-07-23 | 中国矿业大学 | Nickel-carbon catalyst with high specific surface area and preparation method and application thereof |
| CN113385214A (en) * | 2021-07-05 | 2021-09-14 | 上海交通大学 | Method for preparing Co/3DNG catalyst and applying Co/3DNG catalyst to catalytic oxidation of lignin and beta-O-4 model compound thereof |
| CN113509934A (en) * | 2021-04-27 | 2021-10-19 | 浙江海洋大学 | Preparation method of high-dispersion supported transition metal catalyst |
| CN113559907A (en) * | 2021-07-23 | 2021-10-29 | 中国地质大学（武汉） | Nano-confinement nickel-based catalyst and preparation method and application thereof |
| CN114433163A (en) * | 2022-01-24 | 2022-05-06 | 广东工业大学 | In-situ modified and pore-controllable biochar-supported ruthenium catalyst, preparation method thereof and application thereof in lignin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263942A (en) * | 2013-06-05 | 2013-08-28 | 南京理工大学 | Preparation method and application of cobalt-loaded mesoporous graphite-phase carbon nitride visible-light-induced catalyst |
| CN105381812A (en) * | 2015-10-15 | 2016-03-09 | 中国科学院上海硅酸盐研究所 | Method for preparing composite semiconductor material with mesoporous structure |
| CN109364972A (en) * | 2018-10-30 | 2019-02-22 | 华南理工大学 | It is a kind of for the ruthenium base composite nitride carbon nanocatalyst and preparation method of lignin hydrodepolymerization and the application in lignin depolymerization |
| US20200239311A1 (en) * | 2020-01-14 | 2020-07-30 | Qatar University | Porous one-dimensional polymeric graphitic carbon nitride-based nanosystems for catalytic conversion of carbon monoxide and carbon dioxide under ambient conditions |
-
2020
- 2020-12-08 CN CN202011422882.2A patent/CN112547106A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263942A (en) * | 2013-06-05 | 2013-08-28 | 南京理工大学 | Preparation method and application of cobalt-loaded mesoporous graphite-phase carbon nitride visible-light-induced catalyst |
| CN105381812A (en) * | 2015-10-15 | 2016-03-09 | 中国科学院上海硅酸盐研究所 | Method for preparing composite semiconductor material with mesoporous structure |
| CN109364972A (en) * | 2018-10-30 | 2019-02-22 | 华南理工大学 | It is a kind of for the ruthenium base composite nitride carbon nanocatalyst and preparation method of lignin hydrodepolymerization and the application in lignin depolymerization |
| US20200239311A1 (en) * | 2020-01-14 | 2020-07-30 | Qatar University | Porous one-dimensional polymeric graphitic carbon nitride-based nanosystems for catalytic conversion of carbon monoxide and carbon dioxide under ambient conditions |
Non-Patent Citations (2)
| Title |
|---|
| SANDY M. G. LAMA ET AL.: "Efficiency of Ni Nanoparticles Supported on Hierarchical Porous Nitrogen-Doped Carbon for Hydrogenolysis of Kraft Lignin in Flow and Batch Systems", 《ACS SUSTAINABLE CHEM. ENG.》 * |
| 王文耀: "石墨烯氮化碳的官能化及其应用", 《中国学位论文全文数据库》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113509934A (en) * | 2021-04-27 | 2021-10-19 | 浙江海洋大学 | Preparation method of high-dispersion supported transition metal catalyst |
| CN113145121A (en) * | 2021-05-10 | 2021-07-23 | 中国矿业大学 | Nickel-carbon catalyst with high specific surface area and preparation method and application thereof |
| CN113145121B (en) * | 2021-05-10 | 2022-03-01 | 中国矿业大学 | Nickel-carbon catalyst with high specific surface area and preparation method and application thereof |
| CN113385214A (en) * | 2021-07-05 | 2021-09-14 | 上海交通大学 | Method for preparing Co/3DNG catalyst and applying Co/3DNG catalyst to catalytic oxidation of lignin and beta-O-4 model compound thereof |
| CN113385214B (en) * | 2021-07-05 | 2022-10-18 | 上海交通大学 | Method for preparing Co/3DNG catalyst and applying Co/3DNG catalyst to catalytic oxidation of lignin and beta-O-4 model compound thereof |
| CN113559907A (en) * | 2021-07-23 | 2021-10-29 | 中国地质大学（武汉） | Nano-confinement nickel-based catalyst and preparation method and application thereof |
| CN114433163A (en) * | 2022-01-24 | 2022-05-06 | 广东工业大学 | In-situ modified and pore-controllable biochar-supported ruthenium catalyst, preparation method thereof and application thereof in lignin |
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