CN114272932B - Nickel-cerium biochar catalyst and preparation method and application thereof - Google Patents
Nickel-cerium biochar catalyst and preparation method and application thereof Download PDFInfo
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- CN114272932B CN114272932B CN202111672123.6A CN202111672123A CN114272932B CN 114272932 B CN114272932 B CN 114272932B CN 202111672123 A CN202111672123 A CN 202111672123A CN 114272932 B CN114272932 B CN 114272932B
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- lignin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229920005610 lignin Polymers 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000011187 glycerol Nutrition 0.000 claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 3
- BYCKXMUEODWQNZ-UHFFFAOYSA-H cerium(3+);oxalate;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BYCKXMUEODWQNZ-UHFFFAOYSA-H 0.000 claims description 3
- JITPFBSJZPOLGT-UHFFFAOYSA-N cerium(3+);propan-2-olate Chemical compound [Ce+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] JITPFBSJZPOLGT-UHFFFAOYSA-N 0.000 claims description 3
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 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
- 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 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 abstract description 36
- 229960001867 guaiacol Drugs 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 35
- 239000007787 solid Substances 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 238000000227 grinding Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 5
- 235000017491 Bambusa tulda Nutrition 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000011425 bamboo Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to the field of lignin degradation, in particular to a nickel-cerium biochar catalyst, a preparation method and application thereof, wherein the nickel-cerium biochar catalyst comprises biochar serving as a carrier and active components loaded on the biochar, and the active components are nickel and cerium; the content of nickel is 1-10 wt%, the content of cerium is 1-10 wt%, and the balance is biochar. The application is that the nickel cerium biochar catalyst is applied to catalytic depolymerization lignin. The nickel cerium biochar catalyst disclosed by the invention has the advantages that the raw material for preparing the biochar is lignin, the natural world widely exists, the acquisition cost is low, the catalyst is renewable, the depolymerization cost can be effectively reduced, the catalyst is suitable for large-scale industrial application, and the catalyst is matched with a crude glycerin system, and is beneficial to green utilization of industrial byproducts of crude glycerin, so that the depolymerization efficiency of lignin is higher, the conversion rate of lignin can reach more than 78%, the selectivity of guaiacol and derivatives thereof exceeds 82%, and the selectivity of monomer guaiacol exceeds 41%.
Description
Technical Field
The invention relates to the field of lignin degradation, in particular to a nickel-cerium biochar catalyst and a preparation method and application thereof.
Background
The lignocellulose biomass mainly comprises cellulose, hemicellulose and lignin, wherein the lignin accounts for 15-20%, is the only non-fossil energy source for providing aryl compounds in nature, has rich and renewable content and low cost, and can be continuously converted into chemicals, fuels and carbon materials. Lignin is rarely utilized on a large scale due to its irregular polymeric structure and recalcitrance, and is considered waste in the pulp and paper industry and biorefinery processes. In most cases, the energy is directly burnt as low-value energy, so that not only is the resource wasted, but also the air is polluted. Starting from the improvement of the resource utilization rate, the catalytic depolymerization of lignin to prepare aromatic compounds with high added value can reduce the dependence on fossil energy, and can obtain higher economic benefit and contribute to environmental protection.
The efficient depolymerization of lignin requires a catalyst in which both a metal active site and an adsorption site coexist, C-O and C-C bonds are selectively broken, and adsorption of intermediate species prevents further depolymerization, but the problems existing at present are mainly concentrated on insufficient depolymerization and heteropolymerization of products. Ni metal has well known excellent hydrogenation performance, ce oxide has rich oxygen vacancies, and the oxygen vacancies are considered as important active sites in the lignin depolymerization process, so that the nickel-cerium bimetal is loaded on the biochar with the specific surface area and the defect site enriched, and the bimetal is beneficial to the synergistic catalysis of lignin.
At present, the chemical conversion method of the catalytic depolymerization lignin mainly comprises the following steps: the methods of catalytic pyrolysis, catalytic hydrogenolysis, catalytic oxidation and the like are mainly faced by catalytic pyrolysis: the small molecular yield is low, the catalyst is easy to coke and form carbon deposit, the product is complex and difficult to purify, the oxygen content of the product is high, the freezing point is high, and the product can not replace fossil fuel. The catalytic hydrogenolysis process mostly uses noble metal and molecular hydrogen, and has high cost and severe equipment requirements. The catalytic oxidation process can obviously reduce the activation energy to realize efficient depolymerization, but the use of the oxidant not only can cause excessive oxidation of the product, but also can increase the oxygen content of the depolymerized product, thereby being unfavorable for being used as commercial fuel.
Disclosure of Invention
In order to solve the defects in the background technology, the invention aims to provide a nickel-cerium biochar catalyst and a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme:
a nickel-cerium biochar catalyst comprises biochar serving as a carrier and an active component loaded on the biochar, wherein the active component is nickel and cerium;
the content of nickel is 1-10 wt%, the content of cerium is 1-10 wt%, and the balance is biochar.
Further, the preparation method comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and performing low-temperature calcination treatment to obtain a biochar carrier;
s2, dissolving precursor salts of nickel and cerium in deionized water to form a solution I, adding calcined biochar into the solution I, and heating and stirring to form a suspension II;
and S3, sequentially carrying out seal aging treatment, vacuum drying treatment and calcination treatment on the suspension II to obtain the nickel-cerium biochar catalyst.
Further, the dissolution of the lignin is carried out at 100-200 ℃ in nitrogen atmosphere, and the reaction time is 1-4 hours; the calcination of lignin is carried out at 200-400 ℃ in a carbon dioxide atmosphere for 1-4 h;
the solvent for dissolving the lignin is an organic solvent, including one of ethanol, ethylene glycol or dimethyl sulfoxide.
Further, the precursor salt of nickel comprises one of nickel acetylacetonate, anhydrous nickel carbonate, nickel nitrate hexahydrate and nickel acetate tetrahydrate;
the precursor salt of cerium comprises one of cerium carbonate, cerium nitrate hexahydrate, cerium isopropoxide, cerium acetylacetonate hydrate and cerium oxalate hydrate.
Further, the specific process of the seal aging treatment in S3 is: under the protection of nitrogen, the suspension II is in a slurry state, and is subjected to constant temperature treatment for 24-48 h at 50-65 ℃;
the vacuum drying treatment in S3 comprises the following specific steps: drying is carried out step by step, and the aged suspension is put into a metal bath to be dried for 8 to 16 hours at the temperature of between 60 and 110 ℃; then placing the mixture into a vacuum drying oven for drying for 24-36 h;
the specific process of the calcination treatment in S3 is as follows: and (3) under the nitrogen atmosphere, raising the temperature to 500-800 ℃ at the heating rate of 2-7 ℃/min, and performing constant temperature treatment for 2-6 h.
Further, the nickel-cerium biochar catalyst is applied to catalytic depolymerization of lignin, and the lignin and the nickel-cerium biochar catalyst are placed in a crude glycerin system for reaction.
Further, the crude glycerin is formed by compounding water and pure glycerin in different volume ratios, and the ratio of the water to the oil is 1-9: 1.
further, the specific steps of the application are that lignin and nickel cerium biochar catalyst are put into an intermittent high-pressure reaction kettle, coarse glycerin is added into the intermittent high-pressure reaction kettle, high-purity nitrogen with the pressure of 0.3-0.8 MPa is filled into the intermittent high-pressure reaction kettle, the temperature is raised from normal temperature to 240-320 ℃ at the heating rate of 2-7 ℃/min after stirring, and the reaction is carried out for 1-10 h at the temperature.
The invention has the beneficial effects that:
1. the nickel-cerium biochar catalyst has wide raw material sources, low cost, green and renewable performance, can effectively reduce the depolymerization cost, is suitable for large-scale industrial application, is beneficial to green utilization of industrial byproducts of crude glycerol, has higher conversion rate of depolymerized lignin, can reach more than 78%, and has selectivity of guaiacol and derivatives thereof exceeding 82%, wherein the selectivity of guaiacol exceeds 41%;
2. the nickel cerium biochar catalyst has rich carbon defects and large specific surface area, is favorable for anchoring metal nano particles, and ensures that the nickel metal particles are uniformly dispersed on cerium dioxide by the synergistic effect of nickel cerium bimetal, so that better reactive sites are obtained, and the depolymerization of lignin is promoted;
3. the method for degrading lignin by the cooperation of the crude glycerin system and the catalyst has the advantages of being low in cost, simple and easy to operate, high in practicability, environment-friendly and renewable, free of pollution and the like, is suitable for large-scale industrial application, is high in depolymerization lignin conversion rate, can reach more than 78%, and the selectivity of guaiacol and the derivatives thereof is more than 82%, wherein the monomer guaiacol selectivity is more than 41%, and the product is easy to separate and can be used in fine product chemical industry such as perfume, medicine and cosmetics, can improve the efficient and comprehensive utilization of lignin, reduces the dependence on fossil resources and has sustainable social benefits.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A nickel-cerium biochar catalyst comprises biochar serving as a carrier and an active component loaded on the biochar, wherein the active component is nickel and cerium;
the content of nickel is 1-10 wt%, the content of cerium is 1-10 wt%, and the balance is biochar.
A preparation method of a nickel cerium biochar catalyst, which comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and performing low-temperature calcination treatment to obtain a biochar carrier;
s2, dissolving precursor salts of nickel and cerium in deionized water to form a solution I, adding calcined biochar into the solution I, and heating and stirring to form a suspension II;
and S3, sequentially carrying out seal aging treatment, vacuum drying treatment and calcination treatment on the suspension II to obtain the nickel-cerium biochar catalyst.
Wherein, the dissolution of lignin is carried out at 100-200 ℃ under nitrogen atmosphere; the calcination of lignin is carried out at 200-400 ℃ under the carbon dioxide atmosphere;
the solvent for dissolving the lignin is an organic solvent, including one of ethanol, ethylene glycol or dimethyl sulfoxide.
The precursor salt of nickel comprises one of nickel acetylacetonate, anhydrous nickel carbonate, nickel nitrate hexahydrate and nickel acetate tetrahydrate; the precursor salt of cerium includes one of cerium carbonate, cerium nitrate hexahydrate, cerium isopropoxide, cerium acetylacetonate hydrate, and cerium oxalate hydrate.
The specific process of the seal aging treatment in the S3 is as follows: under the protection of nitrogen, the suspension II is in a slurry state, and is subjected to constant temperature treatment for 24-48 h at 50-65 ℃.
The vacuum drying treatment in S3 comprises the following specific steps: drying is carried out step by step, and the aged suspension is put into a metal bath to be dried for 8 to 16 hours at the temperature of between 60 and 110 ℃; and then the mixture is put into a vacuum drying oven to be dried for 24 to 36 hours.
The specific process of the calcination treatment in S3 is as follows: and (3) under the nitrogen atmosphere, raising the temperature to 500-800 ℃ at the heating rate of 2-7 ℃/min, and performing constant temperature treatment for 2-6 h.
The application of the nickel-cerium biochar catalyst is that the nickel-cerium biochar catalyst is applied to catalytic depolymerization of lignin, and the lignin and the nickel-cerium biochar catalyst are placed in a crude glycerin system for reaction.
Wherein, the ratio of water to oil of the crude glycerin is 1-9: 1, the crude glycerin system is provided by an intermittent high-pressure reaction kettle, the pressure is 6.5-10.0 MPa, and the temperature is 260-320 ℃.
Example 1
Preparation of nickel-cerium biochar catalyst and depolymerizing lignin by a crude glycerin system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation of the nickel cerium biochar catalyst comprises the following steps:
dissolving biochar raw material lignin in 50ml of ethylene glycol, reacting for 2 hours at a constant temperature in a reaction kettle under a nitrogen atmosphere and at 180 ℃ to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ under air to obtain a solid I; placing the solid I in a tube furnace, heating to 200 ℃ at a heating rate of 2 ℃/min, roasting for 1h in a CO2 atmosphere, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO) 3 ) 2 ·6H 2 O and 1.2386gCe (NO) 3 )3·6H 2 Placing O in a 250mL round bottom beaker, adding 100mL deionized water, and completely dissolving to form solution I; weighing 3.60g of calcined biochar, adding the calcined biochar into the solution I, and placing the solution I in a water bath kettle to stir at the constant temperature of 60 ℃ for 24 hours to form a suspension II; then the temperature of the suspension II is raised to 95 ℃, the solution is slowly evaporated to a slurry state by using a metal bath, then the mixture system in the state is sealed, and the mixture system is placed at 55 ℃ for standing and aging for 24 hours. Then evaporating the suspension II after the seal aging treatment in a metal bath to obtain a blocky solid; and (3) drying the obtained massive solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding and sieving, heating to 700 ℃ in a tube furnace at a heating rate of 5 ℃/min, and roasting in a nitrogen atmosphere for 4 hours to obtain the nickel-cerium biochar catalyst with the nickel content of 10wt.% and the cerium content of 10 wt.%.
2. The crude glycerol system is used for depolymerizing lignin in cooperation with a nickel-cerium biochar catalyst, and comprises the following steps:
1.0122g of bamboo lignin and 0.1042g of catalyst were placed in a 100mL batch autoclave, to which 30mL of crude glycerol (water-oil ratio 1:1) was added. Then 0.5MPa high-purity nitrogen is filled into the reactor. The reaction was preceded by stirring at 560rpm for 15 minutes and then by heating from ambient temperature 24℃to 280℃at a heating rate of 5℃per minute, at which temperature the reaction was carried out for 3 hours. And after the reaction is finished, rapidly putting the autoclave into an ice water bath or liquid nitrogen for quenching and cooling, and thus, the depolymerization of lignin can be completed.
And after the temperature is reduced to normal temperature, collecting a viscous product in the intermittent high-pressure reaction kettle, performing suction filtration by using a sand core funnel, separating solid from liquid, and repeatedly washing the solid product with an ethyl acetate solvent for a plurality of times. The solid phase product was taken out after multiple washes and dried in a 105 ℃ oven for 12h. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And carrying out vacuum rotary evaporation on the liquid phase component to finally obtain a depolymerization product, and carrying out GC-MS and GC qualitative and quantitative analysis on the depolymerization product. The lignin conversion rate can reach more than 59%, the selectivity of the guaiacol and the derivatives thereof exceeds 72%, and the guaiacol selectivity exceeds 26%.
Example 2
Preparation of nickel-cerium biochar catalyst and depolymerizing lignin by a crude glycerin system in cooperation with the nickel-cerium biochar catalyst.
1. The preparation of the nickel cerium biochar catalyst comprises the following steps:
dissolving biochar raw material lignin in 50ml of ethylene glycol, reacting for 3 hours at a constant temperature in a reaction kettle under a nitrogen atmosphere at 150 ℃ to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ under air to obtain a solid I; placing the solid I in a tube furnace, heating to 250 ℃ at a heating rate of 3 ℃/min, roasting for 2 hours in a CO2 atmosphere, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO) 3 ) 2 ·6H 2 O and 0.1239gCe (NO) 3 ) 3 ·6H 2 Placing O in a 250mL round bottom beaker, adding 100mL deionized water, and completely dissolving to form solution I; weighing 3.60g of calcined biochar, adding the calcined biochar into the solution I, and placing the solution I in a water bath kettle to stir at the constant temperature of 60 ℃ for 24 hours to form a suspension II; then the temperature of the suspension II is raised to 95 ℃, the solution is slowly evaporated to a slurry state by using a metal bath, then the mixture system in the state is sealed, and the mixture system is placed at 60 ℃ for standing and aging for 32 hours. Then evaporating the suspension II after the seal aging treatment in a metal bath to obtain a blocky solid; and (3) drying the obtained massive solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding and sieving, heating to 600 ℃ in a tube furnace at a heating rate of 2 ℃/min, and roasting in a nitrogen atmosphere for 3 hours to obtain the nickel-cerium biochar catalyst with the nickel content of 10wt.% and the cerium content of 1 wt.%.
2. The crude glycerol system is used for depolymerizing lignin in cooperation with a nickel-cerium biochar catalyst, and comprises the following steps:
1.0069g of bamboo lignin and 0.1012g of catalyst were placed in a 100mL batch autoclave, to which 30mL of crude glycerol (water-oil ratio 3:1) was added. Then 0.3MPa high-purity nitrogen is filled into the reactor. The reaction was preceded by stirring at 650rpm for 15 minutes and then by heating from ambient temperature 25℃to 260℃at a heating rate of 6℃per minute, at which temperature the reaction was carried out for 4 hours. And after the reaction is finished, rapidly putting the autoclave into an ice water bath or liquid nitrogen for quenching and cooling, and thus, the depolymerization of lignin can be completed.
And after the temperature is reduced to normal temperature, collecting a viscous product in the intermittent high-pressure reaction kettle, performing suction filtration by using a sand core funnel, separating solid from liquid, and repeatedly washing the solid product with an ethyl acetate solvent for a plurality of times. The solid phase product was taken out after multiple washes and dried in a 105 ℃ oven for 12h. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And carrying out vacuum rotary evaporation on the liquid phase component to finally obtain a depolymerization product, and carrying out GC-MS and GC qualitative and quantitative analysis on the depolymerization product. Calculated, the lignin conversion rate can reach more than 48%, the selectivity of the guaiacol and the derivatives thereof exceeds 62%, and the guaiacol selectivity exceeds 23%.
Example 3
Preparation of nickel-cerium biochar catalyst and depolymerizing lignin by a crude glycerin system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation of the nickel cerium biochar catalyst comprises the following steps:
dissolving biochar raw material lignin in 50ml of ethylene glycol, reacting for 4 hours at constant temperature in a reaction kettle under nitrogen atmosphere and at 200 ℃ to obtain black brown molten lignin solution, and spin-drying at 105 ℃ under air to obtain solid I; placing the solid I in a tubular furnace, heating to 300 ℃ at a heating rate of 4 ℃/min, roasting for 3 hours in a CO2 atmosphere, and grinding into powder to obtain a biochar carrier; weighing 0.9422gNi (NO) 3 ) 2 ·6H 2 O and 1.2383gCe (NO) 3 ) 3 ·6H 2 Placing O in a 250mL round bottom beaker, adding 100mL deionized water, and completely dissolving to form solution I; weighing 3.60g of calcined biochar, adding the calcined biochar into the solution I, and placing the solution I in a water bath kettle to stir at the constant temperature of 60 ℃ for 24 hours to form a suspension II; then the temperature of the suspension II is raised to 95 ℃, the solution is slowly evaporated to a slurry state by using a metal bath, then the mixture system in the state is sealed, and the mixture system is placed at 65 ℃ for standing and aging for 28 hours. Then evaporating the suspension II after the seal aging treatment in a metal bath to obtain a blocky solid; and (3) drying the obtained massive solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding and sieving, heating to 650 ℃ in a tube furnace at a heating rate of 6 ℃/min, and roasting in a nitrogen atmosphere for 4 hours to obtain the nickel-cerium biochar catalyst with the nickel content of 5wt.% and the cerium content of 10 wt.%.
2. The crude glycerol system is used for depolymerizing lignin in cooperation with a nickel-cerium biochar catalyst, and comprises the following steps:
1.0122g of bamboo lignin and 0.1042g of catalyst were placed in a 100mL batch autoclave, to which 30mL of crude glycerol (water-oil ratio 5:1) was added. Then 0.4MPa high-purity nitrogen is filled into the reactor. The reaction was preceded by stirring at 700rpm for 15 minutes and then by heating from ambient temperature 27℃to 310℃at a heating rate of 5℃per minute, at which temperature the reaction was carried out for 8 hours. And after the reaction is finished, rapidly putting the autoclave into an ice water bath or liquid nitrogen for quenching and cooling, and thus, the depolymerization of lignin can be completed.
And after the temperature is reduced to normal temperature, collecting a viscous product in the intermittent high-pressure reaction kettle, performing suction filtration by using a sand core funnel, separating solid from liquid, and repeatedly washing the solid product with an ethyl acetate solvent for a plurality of times. The solid phase product was taken out after multiple washes and dried in a 105 ℃ oven for 12h. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And carrying out vacuum rotary evaporation on the liquid phase component to finally obtain a depolymerization product, and carrying out GC-MS and GC qualitative and quantitative analysis on the depolymerization product. The lignin conversion rate can reach more than 66%, the selectivity of the guaiacol and the derivatives thereof exceeds 74%, and the selectivity of the guaiacol exceeds 29%.
Example 4
Preparation of nickel-cerium biochar catalyst and depolymerizing lignin by a crude glycerin system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation of the nickel cerium biochar catalyst comprises the following steps:
dissolving biochar raw material lignin in 50ml of ethylene glycol, reacting for 2.5 hours at a constant temperature in a reaction kettle under a nitrogen atmosphere and at 180 ℃ to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ under air to obtain a solid I; placing the solid I in a tube furnace, heating to 400 ℃ at a heating rate of 5 ℃/min, roasting for 1h in a CO2 atmosphere, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO) 3 ) 2 ·6H 2 O and 0.6197gCe (NO) 3 ) 3 ·6H 2 Placing O in a 250mL round bottom beaker, adding 100mL deionized water, and completely dissolving to form solution I; weighing 3.60g of calcined biochar, adding the calcined biochar into the solution I, and placing the solution I in a water bath kettle to stir at the constant temperature of 60 ℃ for 24 hours to form a suspension II; then the temperature of the suspension II is raised to 95 ℃, the solution is slowly evaporated to a slurry state by using a metal bath, then the mixture system in the state is sealed, and the mixture system is placed at 50 ℃ for standing and aging for 36 hours. Then evaporating the suspension II after the seal aging treatment in a metal bath to obtain a blocky solid; and (3) drying the obtained massive solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding, sieving, heating to 500 ℃ in a tube furnace at a heating rate of 3 ℃/min, and roasting in a nitrogen atmosphere for 5 hours to obtain the nickel-cerium biochar catalyst with the nickel content of 10% and the cerium content of 5 wt.%.
2. The crude glycerol system is used for depolymerizing lignin in cooperation with a nickel-cerium biochar catalyst, and comprises the following steps:
1.0103g of bamboo lignin and 0.1002g of catalyst were placed in a 100mL batch autoclave, to which 30mL of crude glycerol (water-oil ratio 6:1) was added. Then 0.7MPa high-purity nitrogen was charged therein. The reaction was preceded by stirring at 580rpm for 15 minutes and then by heating from ambient temperature 30℃to 290℃at a heating rate of 5℃per minute, at which temperature the reaction was carried out for 7 hours. And after the reaction is finished, rapidly putting the autoclave into an ice water bath or liquid nitrogen for quenching and cooling, and thus, the depolymerization of lignin can be completed.
And after the temperature is reduced to normal temperature, collecting a viscous product in the intermittent high-pressure reaction kettle, performing suction filtration by using a sand core funnel, separating solid from liquid, and repeatedly washing the solid product with an ethyl acetate solvent for a plurality of times. The solid phase product was taken out after multiple washes and dried in a 105 ℃ oven for 12h. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And carrying out vacuum rotary evaporation on the liquid phase component to finally obtain a depolymerization product, and carrying out GC-MS and GC qualitative and quantitative analysis on the depolymerization product. The lignin conversion rate can reach more than 72%, the selectivity of the guaiacol and the derivatives thereof exceeds 82%, and the guaiacol selectivity exceeds 41%.
Example 5
Preparation of nickel-cerium biochar catalyst and depolymerizing lignin by a crude glycerin system in cooperation with the nickel-cerium biochar catalyst.
1. The preparation of the nickel cerium biochar catalyst comprises the following steps:
dissolving biochar raw material lignin in 50ml of ethylene glycol, reacting for 3.5 hours at a constant temperature in a reaction kettle under a nitrogen atmosphere and at 180 ℃ to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ under air to obtain a solid I; placing the solid I in a tube furnace, heating to 350 ℃ at a heating rate of 3 ℃/min, roasting for 1h in a CO2 atmosphere, and grinding into powder to obtain a biochar carrier; weighing 0.1882gNi (NO) 3 )2·6H 2 O and 1.2390gCe (NO) 3 ) 3 ·6H 2 Placing O in a 250mL round bottom beaker, adding 100mL deionized water, and completely dissolving to form solution I; weighing 3.60g of calcined biochar, adding the calcined biochar into the solution I, and placing the solution I in a water bath kettle to stir at the constant temperature of 60 ℃ for 24 hours to form a suspension II; then the temperature of the suspension II is raised to 95 ℃, the solution is slowly evaporated to a slurry state by using a metal bath, then the mixture system in the state is sealed, and the mixture system is placed at 55 ℃ for standing and aging for 30 hours. Then evaporating the suspension II after the seal aging treatment in a metal bath to obtain a blocky solid; placing the obtained solid block in vacuumDrying for 12 hours at 105 ℃ in a drying oven, grinding, sieving, heating to 800 ℃ in a tube furnace at a heating rate of 7 ℃/min, and roasting for 2 hours in a nitrogen atmosphere to obtain the nickel-cerium biochar catalyst with the nickel content of 1% and the cerium content of 10 wt.%.
2. The crude glycerol system is used for depolymerizing lignin in cooperation with a nickel-cerium biochar catalyst, and comprises the following steps:
1.0113g of bamboo lignin and 0.1025g of catalyst were placed in a 100mL batch autoclave, to which 30mL of crude glycerol (water-to-oil ratio 9:1) was added. Then 0.5MPa high-purity nitrogen is filled into the reactor. The reaction was preceded by stirring at 620rpm for 15 minutes and then at a temperature increase rate of 5 c/min from ambient 28 c to 320 c, at which temperature the reaction was carried out for 10 hours. And after the reaction is finished, rapidly putting the autoclave into an ice water bath or liquid nitrogen for quenching and cooling, and thus, the depolymerization of lignin can be completed.
And after the temperature is reduced to normal temperature, collecting a viscous product in the intermittent high-pressure reaction kettle, performing suction filtration by using a sand core funnel, separating solid from liquid, and repeatedly washing the solid product with an ethyl acetate solvent for a plurality of times. The solid phase product was taken out after multiple washes and dried in a 105 ℃ oven for 12h. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And carrying out vacuum rotary evaporation on the liquid phase component to finally obtain a depolymerization product, and carrying out GC-MS and GC qualitative and quantitative analysis on the depolymerization product. The lignin conversion rate can reach more than 68%, the selectivity of the guaiacol and the derivatives thereof exceeds 79%, and the guaiacol selectivity exceeds 37%.
To sum up:
the method for degrading lignin by the cooperation of the crude glycerin system and the catalyst has the advantages of being low in cost, simple and easy to operate, high in practicability, environment-friendly and renewable, free of pollution and the like, is suitable for large-scale industrial application, is high in depolymerization lignin conversion rate, can reach more than 78%, and the selectivity of guaiacol and the derivatives thereof is more than 82%, wherein the monomer guaiacol selectivity is more than 41%, and the product is easy to separate and can be used in fine product chemical industry such as perfume, medicine and cosmetics, can improve the efficient and comprehensive utilization of lignin, reduces the dependence on fossil resources and has sustainable social benefits.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (5)
1. The nickel-cerium biochar catalyst is characterized by comprising biochar serving as a carrier and an active component loaded on the biochar, wherein the active component is nickel and cerium;
the content of nickel is 1-10 wt%, the content of cerium is 1-10 wt%, and the balance is biochar;
the preparation method of the nickel cerium biochar catalyst comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and performing low-temperature calcination treatment to obtain a biochar carrier;
s2, dissolving precursor salts of nickel and cerium in deionized water to form a solution I, adding the calcined biochar carrier into the solution I, and heating and stirring to form a suspension II;
s3, sequentially carrying out seal aging treatment, vacuum drying treatment and calcination treatment on the suspension II to obtain the nickel-cerium biochar catalyst;
the dissolution of lignin is carried out at 100-200 ℃ under nitrogen atmosphere, and the reaction time is 1-4 h; the calcination of lignin is carried out at 200-400 ℃ in a carbon dioxide atmosphere for 1-4 h;
the solvent for dissolving the lignin is one of ethanol, glycol or dimethyl sulfoxide;
the nickel-cerium biochar catalyst is applied to catalytic depolymerization of lignin, and the lignin and the nickel-cerium biochar catalyst are placed in a crude glycerin system for reaction.
2. The nickel cerium biochar catalyst according to claim 1, wherein the precursor salt of nickel comprises one of nickel acetylacetonate, anhydrous nickel carbonate, nickel nitrate hexahydrate, nickel acetate tetrahydrate;
the precursor salt of cerium comprises one of cerium carbonate, cerium nitrate hexahydrate, cerium isopropoxide, cerium acetylacetonate hydrate and cerium oxalate hydrate.
3. The nickel cerium biochar catalyst according to claim 1, wherein the specific process of the seal aging treatment in S3 is: under the protection of nitrogen, the suspension II is in a slurry state, and is subjected to constant temperature treatment for 24-48 h at 50-65 ℃;
the vacuum drying treatment in S3 comprises the following specific steps: drying is carried out step by step, and the aged suspension is put into a metal bath to be dried for 8 to 16 hours at the temperature of between 60 and 110 ℃; then placing the mixture into a vacuum drying oven for drying for 24-36 h;
the specific process of the calcination treatment in S3 is as follows: and (3) under the nitrogen atmosphere, raising the temperature to 500-800 ℃ at the heating rate of 2-7 ℃/min, and performing constant temperature treatment for 2-6 h.
4. The application of the nickel-cerium biochar catalyst according to claim 1, wherein the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, and the ratio of water to oil is 1-9: 1.
5. the use of the nickel-cerium biochar catalyst according to claim 4, wherein the specific steps of the use are that lignin and the nickel-cerium biochar catalyst are put into a batch high-pressure reaction kettle, coarse glycerin is added into the batch high-pressure reaction kettle, high-purity nitrogen with the pressure of 0.3-0.8 MPa is filled into the batch high-pressure reaction kettle, the batch high-purity glycerin is stirred and then is heated to 240-320 ℃ from normal temperature at a heating rate of 2-7 ℃/min, and the batch high-purity glycerin is reacted for 1-10 h at the temperature.
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| CN114272932A (en) | 2022-04-05 |
| GB2614343A (en) | 2023-07-05 |
| GB202202544D0 (en) | 2022-04-13 |
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