CN114272932A - 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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- CN114272932A CN114272932A CN202111672123.6A CN202111672123A CN114272932A CN 114272932 A CN114272932 A CN 114272932A CN 202111672123 A CN202111672123 A CN 202111672123A CN 114272932 A CN114272932 A CN 114272932A
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- cerium
- nickel
- biochar
- 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 60
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920005610 lignin Polymers 0.000 claims abstract description 82
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 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
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000003610 charcoal Substances 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 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
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000007789 sealing Methods 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
- 239000000203 mixture Substances 0.000 claims description 7
- 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
- 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
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 43
- 235000011187 glycerol Nutrition 0.000 description 33
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 32
- 239000007787 solid Substances 0.000 description 30
- 229960001867 guaiacol Drugs 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 10
- 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
- 238000005406 washing Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 230000008901 benefit Effects 0.000 description 6
- 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
- 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
- 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
- 238000000967 suction filtration Methods 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 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
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 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
- 230000002153 concerted effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 230000035484 reaction time Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002195 synergetic effect Effects 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
- 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
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (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, wherein 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 charcoal. The application is that the nickel-cerium biochar catalyst is applied to catalytic depolymerization of lignin. The raw material for preparing the biochar is lignin which widely exists in the natural world, has low acquisition cost and can be regenerated, the depolymerization cost can be effectively reduced, and the catalyst is suitable for large-scale industrial application.
Description
Technical Field
The invention relates to the field of lignin degradation, and particularly relates 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 providing aryl compounds in the nature, is rich in content, renewable and low in price, and can be continuously converted into chemicals, fuels and carbon materials. Lignin, which is rarely utilized on a large scale due to its irregular polymeric structure and recalcitrance, is considered a waste product in the pulp and paper industry and biorefinery processes. In most cases, the fuel is directly combusted as low-value energy, which not only causes resource waste but also pollutes air. From the aspect of improving the resource utilization rate, the aromatic compound with high added value is prepared by catalytic depolymerization of lignin, so that the dependence on fossil energy can be reduced, higher economic benefit can be obtained, and the method contributes to environmental protection.
The high-efficiency depolymerization of lignin needs a catalyst which has the coexistence of metal active sites and adsorption sites, selectively breaks C-O and C-C bonds, adsorbs intermediate species and prevents further depolymerization, but the existing problems mainly focus on insufficient depolymerization and excessive depolymerization products. Ni metal has well-known excellent hydrogenation performance, Ce oxide has abundant oxygen vacancies which are considered as important active sites in the depolymerization process of lignin, so that nickel-cerium bimetal is loaded on biochar with enriched specific surface area and defect sites, and the bimetallic concerted catalysis of the lignin is facilitated.
At present, the chemical conversion method for catalytically depolymerizing lignin mainly comprises the following steps: catalytic pyrolysis, catalytic hydrogenolysis, catalytic oxidation and other methods, and the catalytic pyrolysis mainly comprises the following steps: the yield of small molecules is low, the catalyst is easy to coke and form carbon deposition, the product is complex and difficult to purify, the oxygen content of the product is high, the freezing point is high, and fossil fuels cannot be replaced. The catalytic hydrogenolysis process mostly uses noble metal and molecular hydrogen, and has high cost and strict equipment requirement. The catalytic oxidation process can significantly reduce the activation energy and realize high-efficiency 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 depolymerization product, thus being not beneficial to the use as commercial fuel.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a nickel-cerium biochar catalyst, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a nickel-cerium biochar catalyst comprises biochar serving as a carrier and active components loaded on the biochar, wherein the active components are nickel and cerium;
the content of the nickel is 1-10 wt.%, the content of the cerium is 1-10 wt.%, and the balance is charcoal.
Further, the preparation method comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and calcining at a low temperature 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 sealing aging treatment, vacuum drying treatment and calcining treatment on the suspension II to obtain the nickel-cerium biochar catalyst.
Further, the lignin is dissolved at the temperature of 100-200 ℃ in a nitrogen atmosphere, and the reaction time is 1-4 h; calcining the lignin at 200-400 ℃ in a carbon dioxide atmosphere for 1-4 h;
the solvent for dissolving the lignin is 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 as follows: under the protection of nitrogen, treating the suspension II in a slurry state at a constant temperature of 50-65 ℃ for 24-48 h;
the specific process of the vacuum drying treatment in the S3 is as follows: drying is carried out step by step, and the aged suspension is placed in a metal bath to be dried for 8-16 h at the temperature of 60-110 ℃; then, drying the mixture in a vacuum drying oven for 24-36 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 temperature rise rate of 2-7 ℃/min, and carrying out 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 glycerol system for reaction.
Further, the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, wherein the ratio of the water to the oil is 1-9: 1.
further, the method comprises the specific steps of putting lignin and the nickel-cerium biochar catalyst into an intermittent high-pressure reaction kettle, adding crude glycerol, then filling 0.3-0.8 MPa high-purity nitrogen into the reaction kettle, stirring, raising the temperature from normal temperature to 240-320 ℃ at the temperature raising rate of 2-7 ℃/min, and reacting for 1-10 hours at the temperature.
The invention has the beneficial effects that:
1. the nickel-cerium biochar catalyst has wide sources of biochar raw materials, low cost, greenness and reproducibility, can effectively reduce depolymerization cost, and is suitable for large-scale industrial application, the nickel-cerium biochar catalyst and a crude glycerin system are beneficial to green utilization of industrial byproduct crude glycerin, the conversion rate of depolymerized lignin is high and can reach over 78%, the selectivity of guaiacol and derivatives thereof exceeds 82%, and the selectivity of guaiacol exceeds 41%;
2. according to the nickel-cerium biochar catalyst, the carbon carrier has rich carbon defects and a large specific surface area, metal nano particles are favorably anchored, and the nickel-cerium bimetal synergistic effect enables the metal particles of nickel to be uniformly dispersed on cerium dioxide, so that a better reaction active site is obtained, and depolymerization of lignin is promoted;
3. the method for degrading lignin by the cooperation of the crude glycerol system and the catalyst has the advantages of degrading lignin in crude glycerol, easily obtained reaction conditions, low cost, simple operation, strong practicability, environmental protection, reproducibility, no pollution and the like, is suitable for large-scale industrial application, has high conversion rate of depolymerized lignin, the conversion rate of which can reach more than 78 percent, and the selectivity of guaiacol and derivatives thereof exceeds 82 percent, wherein the selectivity of monomer guaiacol exceeds 41 percent, and the product is easy to separate, can be used in fine chemical industries such as spice, medicine, cosmetics and the like, can improve the efficient comprehensive utilization of lignin, simultaneously reduces the dependence on fossil resources, and has social benefits of sustainable development.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A nickel-cerium biochar catalyst comprises biochar serving as a carrier and active components loaded on the biochar, wherein the active components are nickel and cerium;
the content of the nickel is 1-10 wt.%, the content of the cerium is 1-10 wt.%, and the balance is charcoal.
A preparation method of a nickel-cerium biochar catalyst comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and calcining at a low temperature 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 sealing aging treatment, vacuum drying treatment and calcining treatment on the suspension II to obtain the nickel-cerium biochar catalyst.
Wherein, the dissolution of the lignin is carried out at 100-200 ℃ under the nitrogen atmosphere; the calcination of the lignin is carried out at the temperature of 200-400 ℃ in a carbon dioxide atmosphere;
the solvent for dissolving the lignin is 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 sealing aging treatment in the step S3 is as follows: and under the protection of nitrogen, treating the suspension II in a slurry state at a constant temperature of 50-65 ℃ for 24-48 h.
The specific process of the vacuum drying treatment in the S3 is as follows: drying is carried out step by step, and the aged suspension is placed in a metal bath to be dried for 8-16 h at the temperature of 60-110 ℃; and then putting the mixture into a vacuum drying oven to be dried 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 temperature rise rate of 2-7 ℃/min, and carrying out constant temperature treatment for 2-6 h.
The application of the nickel-cerium biochar catalyst is characterized in 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 water-oil ratio of the crude glycerol is 1-9: 1, a crude glycerol 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 a nickel-cerium biochar catalyst and depolymerization of lignin by a crude glycerol system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation method of the nickel-cerium biochar catalyst comprises the following steps:
dissolving biological charcoal raw material lignin in 50ml ethylene glycol, and performing nitrogen atmosphere 1Reacting in a reaction kettle at the constant temperature of 80 ℃ for 2 hours to obtain a black brown molten lignin solution, and spin-drying at the temperature of 105 ℃ in the air to obtain a solid I; putting the solid I into a tubular furnace, heating to 200 ℃ at the heating rate of 2 ℃/min, then roasting for 1h in the atmosphere of CO2, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO)3)2·6H2O and 1.2386gCe (NO)3)3·6H2Placing O in a 250mL round-bottom beaker, adding 100mL deionized water, and completely dissolving to form a solution I; weighing 3.60g of calcined biochar, adding the biochar into the solution I, and placing the biochar in a water bath kettle to stir for 24 hours at a constant temperature of 60 ℃ to form a suspension II; the suspension II is then brought to a temperature of 95 ℃ and the solution is slowly evaporated to a slurry state using a metal bath, and the mixture is then sealed and aged at 55 ℃ for 24 hours. Then, evaporating the suspension II subjected to the sealing aging treatment in a metal bath to dryness to obtain a blocky solid; and drying the obtained blocky solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding, sieving, heating to 700 ℃ in a tubular furnace at the 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 10 wt.% and the cerium content of 10 wt.%.
2. The method for depolymerizing lignin by using a crude glycerol system and a nickel-cerium biochar catalyst comprises the following steps:
1.0122g of bamboo lignin and 0.1042g of catalyst were put into a 100mL batch autoclave, and 30mL of crude glycerin (water-oil ratio 1:1) was added thereto. Then, 0.5MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring at 560rpm for 15 minutes before reaction, then increasing the temperature from 24 ℃ to 280 ℃ at the temperature increasing rate of 5 ℃/min, and reacting for 3 hours at the temperature. And after the reaction is finished, quickly placing the high-pressure kettle into ice water bath or liquid nitrogen for quenching and cooling, and finishing the depolymerization of the lignin.
And (3) cooling to normal temperature, collecting the viscous product in the batch high-pressure reaction kettle, performing suction filtration by using a sand core funnel to separate solid from liquid, and repeatedly washing the solid-phase product by using an ethyl acetate solvent. And taking out the solid-phase product after multiple times of washing, and drying the solid-phase product in a drying oven at 105 ℃ for 12 hours. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components contained in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And finally obtaining a depolymerized product by performing vacuum rotary evaporation on the liquid phase component, and performing qualitative and quantitative analysis on the depolymerized product by GC-MS and GC. The conversion rate of lignin can reach more than 59 percent by calculation, the selectivity of the guaiacol and the derivatives thereof exceeds 72 percent, wherein the selectivity of the guaiacol exceeds 26 percent.
Example 2
Preparation of a nickel-cerium biochar catalyst and depolymerization of lignin by the cooperation of a crude glycerol system and the nickel-cerium biochar catalyst.
1. The preparation method of the nickel-cerium biochar catalyst comprises the following steps:
dissolving a biochar raw material lignin in 50ml of ethylene glycol, reacting in a reaction kettle at a constant temperature of 150 ℃ for 3h in a nitrogen atmosphere to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ in the air to obtain a solid I; putting the solid I into a tubular furnace, heating to 250 ℃ at the heating rate of 3 ℃/min, then roasting for 2 hours in the atmosphere of CO2, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO)3)2·6H2O and 0.1239gCe (NO)3)3·6H2Placing O in a 250mL round-bottom beaker, adding 100mL deionized water, and completely dissolving to form a solution I; weighing 3.60g of calcined biochar, adding the biochar into the solution I, and placing the biochar in a water bath kettle to stir for 24 hours at a constant temperature of 60 ℃ to form a suspension II; then, the temperature of the suspension II was raised to 95 ℃, the solution was slowly evaporated to a slurry state by a metal bath, and then the mixed system in this state was sealed and left to stand and age at 60 ℃ for 32 hours. Then, evaporating the suspension II subjected to the sealing aging treatment in a metal bath to dryness to obtain a blocky solid; and drying the obtained blocky solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding, sieving, heating to 600 ℃ in a tubular furnace at the 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 10 wt.% and the cerium content of 1 wt.%.
2. The method for depolymerizing lignin by using a crude glycerol system and a nickel-cerium biochar catalyst comprises the following steps:
1.0069g of bamboo lignin and 0.1012g of catalyst were put into a 100mL batch autoclave, and 30mL of crude glycerin (water-oil ratio 3:1) was added thereto. Then, 0.3MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring for 15 minutes at 650rpm, then increasing the temperature from 25 ℃ to 260 ℃ at the heating rate of 6 ℃/min, and reacting for 4 hours at the temperature. And after the reaction is finished, quickly placing the high-pressure kettle into ice water bath or liquid nitrogen for quenching and cooling, and finishing the depolymerization of the lignin.
And (3) cooling to normal temperature, collecting the viscous product in the batch high-pressure reaction kettle, performing suction filtration by using a sand core funnel to separate solid from liquid, and repeatedly washing the solid-phase product by using an ethyl acetate solvent. And taking out the solid-phase product after multiple times of washing, and drying the solid-phase product in a drying oven at 105 ℃ for 12 hours. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components contained in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And finally obtaining a depolymerized product by performing vacuum rotary evaporation on the liquid phase component, and performing qualitative and quantitative analysis on the depolymerized product by GC-MS and GC. The conversion rate of the lignin can reach more than 48 percent by calculation, the selectivity of the guaiacol and the derivatives thereof exceeds 62 percent, wherein the selectivity of the guaiacol exceeds 23 percent.
Example 3
Preparation of a nickel-cerium biochar catalyst and depolymerization of lignin by a crude glycerol system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation method of the nickel-cerium biochar catalyst comprises the following steps:
dissolving a biochar raw material lignin in 50ml of ethylene glycol, reacting for 4 hours in a reaction kettle at a constant temperature of 200 ℃ in a nitrogen atmosphere to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ in the air to obtain a solid I; putting the solid I into a tubular furnace, heating to 300 ℃ at the heating rate of 4 ℃/min, then roasting for 3 hours in the atmosphere of CO2, and grinding into powder to obtain a biochar carrier; weighing 0.9422gNi (NO)3)2·6H2O and 1.2383gCe (NO)3)3·6H2Placing O in a 250mL round-bottom beaker, adding 100mL deionized water, and completely dissolving to form a solution I; 3.60g of calcined biochar is weighed, added into the solution I and placedStirring at the constant temperature of 60 ℃ for 24 hours in a water bath kettle to form a suspension II; the suspension II was then brought to a temperature of 95 ℃ and the solution was slowly evaporated to a slurry state using a metal bath, and the mixture in this state was then sealed and left to stand at 65 ℃ for aging for 28 hours. Then, evaporating the suspension II subjected to the sealing aging treatment in a metal bath to dryness to obtain a blocky solid; and drying the obtained blocky solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding, sieving, heating to 650 ℃ in a tubular furnace at the 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 5 wt.% and the cerium content of 10 wt.%.
2. The method for depolymerizing lignin by using a crude glycerol system and a nickel-cerium biochar catalyst comprises the following steps:
1.0122g of bamboo lignin and 0.1042g of catalyst were put into a 100mL batch autoclave, and 30mL of crude glycerin (water-oil ratio 5:1) was added thereto. Then, 0.4MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring at 700rpm for 15 minutes before reaction, then increasing the temperature from the normal temperature of 27 ℃ to 310 ℃ at the temperature increasing rate of 5 ℃/min, and reacting for 8 hours at the temperature. And after the reaction is finished, quickly placing the high-pressure kettle into ice water bath or liquid nitrogen for quenching and cooling, and finishing the depolymerization of the lignin.
And (3) cooling to normal temperature, collecting the viscous product in the batch high-pressure reaction kettle, performing suction filtration by using a sand core funnel to separate solid from liquid, and repeatedly washing the solid-phase product by using an ethyl acetate solvent. And taking out the solid-phase product after multiple times of washing, and drying the solid-phase product in a drying oven at 105 ℃ for 12 hours. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components contained in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And finally obtaining a depolymerized product by performing vacuum rotary evaporation on the liquid phase component, and performing qualitative and quantitative analysis on the depolymerized product by GC-MS and GC. The conversion rate of the lignin can reach more than 66 percent by calculation, the selectivity of the guaiacol and the derivatives thereof exceeds 74 percent, wherein the selectivity of the guaiacol exceeds 29 percent.
Example 4
Preparation of a nickel-cerium biochar catalyst and depolymerization of lignin by a crude glycerol system in cooperation with the nickel-cerium biochar catalyst:
1. the preparation method of the nickel-cerium biochar catalyst comprises the following steps:
dissolving a biochar raw material lignin in 50ml of ethylene glycol, reacting in a reaction kettle at a constant temperature of 180 ℃ for 2.5 hours in a nitrogen atmosphere to obtain a black brown molten lignin solution, and spin-drying at 105 ℃ in the air to obtain a solid I; putting the solid I into a tubular furnace, heating to 400 ℃ at the heating rate of 5 ℃/min, then roasting for 1h in the atmosphere of CO2, and grinding into powder to obtain a biochar carrier; weighing 1.8842gNi (NO)3)2·6H2O and 0.6197gCe (NO)3)3·6H2Placing O in a 250mL round-bottom beaker, adding 100mL deionized water, and completely dissolving to form a solution I; weighing 3.60g of calcined biochar, adding the biochar into the solution I, and placing the biochar in a water bath kettle to stir for 24 hours at a constant temperature of 60 ℃ to form a suspension II; the suspension II was then brought to a temperature of 95 ℃ and the solution was slowly evaporated to a slurry state using a metal bath, and the mixture in this state was then sealed and left to stand at 50 ℃ for aging for 36 hours. Then, evaporating the suspension II subjected to the sealing aging treatment in a metal bath to dryness to obtain a blocky solid; and drying the obtained massive solid in a vacuum drying oven at 105 ℃ for 12 hours, grinding, sieving, heating to 500 ℃ in a tubular furnace at the 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 method for depolymerizing lignin by using a crude glycerol system and a nickel-cerium biochar catalyst comprises the following steps:
1.0103g of bamboo lignin and 0.1002g of catalyst were put into a 100mL batch autoclave, and 30mL of crude glycerin (water-oil ratio 6:1) was added thereto. Then, 0.7MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring for 15 minutes at 580rpm, then increasing the temperature from 30 ℃ to 290 ℃ at the temperature increasing rate of 5 ℃/min, and reacting for 7 hours at the temperature. And after the reaction is finished, quickly placing the high-pressure kettle into ice water bath or liquid nitrogen for quenching and cooling, and finishing the depolymerization of the lignin.
And (3) cooling to normal temperature, collecting the viscous product in the batch high-pressure reaction kettle, performing suction filtration by using a sand core funnel to separate solid from liquid, and repeatedly washing the solid-phase product by using an ethyl acetate solvent. And taking out the solid-phase product after multiple times of washing, and drying the solid-phase product in a drying oven at 105 ℃ for 12 hours. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components contained in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And finally obtaining a depolymerized product by performing vacuum rotary evaporation on the liquid phase component, and performing qualitative and quantitative analysis on the depolymerized product by GC-MS and GC. The conversion rate of the lignin can reach more than 72 percent by calculation, the selectivity of the guaiacol and the derivatives thereof exceeds 82 percent, wherein the selectivity of the guaiacol exceeds 41 percent.
Example 5
Preparation of a nickel-cerium biochar catalyst and depolymerization of lignin by the cooperation of a crude glycerol system and the nickel-cerium biochar catalyst.
1. The preparation method of the nickel-cerium biochar catalyst comprises the following steps:
dissolving a biochar raw material lignin in 50ml of ethylene glycol, reacting in a reaction kettle at a constant temperature of 180 ℃ for 3.5 hours in a nitrogen atmosphere to obtain a dark brown molten lignin solution, and spin-drying at 105 ℃ in the air to obtain a solid I; putting the solid I into a tubular furnace, heating to 350 ℃ at the heating rate of 3 ℃/min, then roasting for 1h in the atmosphere of CO2, and grinding into powder to obtain a biochar carrier; weighing 0.1882gNi (NO)3)2·6H2O and 1.2390gCe (NO)3)3·6H2Placing O in a 250mL round-bottom beaker, adding 100mL deionized water, and completely dissolving to form a solution I; weighing 3.60g of calcined biochar, adding the biochar into the solution I, and placing the biochar in a water bath kettle to stir for 24 hours at a constant temperature of 60 ℃ to form a suspension II; the suspension II is then brought to a temperature of 95 ℃ and the solution is slowly evaporated to a slurry state using a metal bath, and the mixture is then sealed and aged at 55 ℃ for 30 hours. Then, evaporating the suspension II subjected to the sealing aging treatment in a metal bath to dryness to obtain a blocky solid; drying the obtained block solid in a vacuum drying oven at 105 deg.C for 12 hr, grinding, sieving, heating to 800 deg.C at a heating rate of 7 deg.C/min in a tubular furnace, and calcining in nitrogen atmosphere for 2 hr to obtain nickelA nickel-cerium biocarbon catalyst having a cerium content of 10 wt.% and a content of 1%.
2. The method for depolymerizing lignin by using a crude glycerol system and a nickel-cerium biochar catalyst comprises the following steps:
1.0113g of bamboo lignin and 0.1025g of catalyst are put into a 100mL batch autoclave, and 30mL of crude glycerol (water-oil ratio 9:1) is added into the autoclave. Then, 0.5MPa of high purity nitrogen was charged therein. The reaction is carried out by stirring for 15 minutes at 620rpm, then increasing the temperature from the normal temperature of 28 ℃ to 320 ℃ at the temperature increasing rate of 5 ℃/min, and reacting for 10 hours at the temperature. And after the reaction is finished, quickly placing the high-pressure kettle into ice water bath or liquid nitrogen for quenching and cooling, and finishing the depolymerization of the lignin.
And (3) cooling to normal temperature, collecting the viscous product in the batch high-pressure reaction kettle, performing suction filtration by using a sand core funnel to separate solid from liquid, and repeatedly washing the solid-phase product by using an ethyl acetate solvent. And taking out the solid-phase product after multiple times of washing, and drying the solid-phase product in a drying oven at 105 ℃ for 12 hours. Separating and extracting an upper oil phase by using a separating funnel, removing water and glycerin components contained in the oil phase by using excessive solid anhydrous sodium sulfate, and filtering to obtain a lignin liquid phase product. And finally obtaining a depolymerized product by performing vacuum rotary evaporation on the liquid phase component, and performing qualitative and quantitative analysis on the depolymerized product by GC-MS and GC. The conversion rate of the lignin can reach more than 68 percent through calculation, the selectivity of the guaiacol and the derivatives thereof exceeds 79 percent, wherein the selectivity of the guaiacol exceeds 37 percent.
In summary, the following steps:
the method for degrading lignin by the cooperation of the crude glycerol system and the catalyst has the advantages of degrading lignin in crude glycerol, easily obtained reaction conditions, low cost, simple operation, strong practicability, environmental protection, reproducibility, no pollution and the like, is suitable for large-scale industrial application, has high conversion rate of depolymerized lignin, the conversion rate of which can reach more than 78 percent, and the selectivity of guaiacol and derivatives thereof exceeds 82 percent, wherein the selectivity of monomer guaiacol exceeds 41 percent, and the product is easy to separate, can be used in fine chemical industries such as spice, medicine, cosmetics and the like, can improve the efficient comprehensive utilization of lignin, simultaneously reduces the dependence on fossil resources, and has social benefits of sustainable development.
The foregoing shows and describes the general principles, essential 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, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (8)
1. A nickel-cerium biochar catalyst is characterized by comprising biochar serving as a carrier and active components loaded on the biochar, wherein the active components are nickel and cerium;
the content of the nickel is 1-10 wt.%, the content of the cerium is 1-10 wt.%, and the balance is charcoal.
2. A method for preparing the nickel-cerium biochar catalyst according to claim 1, which comprises the following steps:
s1, dissolving lignin by using a low-temperature solvent and calcining at a low temperature 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 sealing aging treatment, vacuum drying treatment and calcining treatment on the suspension II to obtain the nickel-cerium biochar catalyst.
3. The method for preparing the nickel-cerium biochar catalyst according to claim 2, wherein the lignin is dissolved at 100-200 ℃ in a nitrogen atmosphere for 1-4 h; calcining the lignin at 200-400 ℃ in a carbon dioxide atmosphere for 1-4 h;
the solvent for dissolving the lignin is organic solvent, including one of ethanol, ethylene glycol or dimethyl sulfoxide.
4. The method for preparing the nickel-cerium biochar catalyst according to claim 2, wherein 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.
5. The method for preparing the nickel-cerium biochar catalyst according to claim 2, wherein the specific process of the sealing aging treatment in the step S3 is as follows: under the protection of nitrogen, treating the suspension II in a slurry state at a constant temperature of 50-65 ℃ for 24-48 h;
the specific process of the vacuum drying treatment in the S3 is as follows: drying is carried out step by step, and the aged suspension is placed in a metal bath to be dried for 8-16 h at the temperature of 60-110 ℃; then, drying the mixture in a vacuum drying oven for 24-36 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 temperature rise rate of 2-7 ℃/min, and carrying out constant temperature treatment for 2-6 h.
6. The use of the nickel-cerium biochar catalyst as claimed in claim 1 or 2, wherein the nickel-cerium biochar catalyst is used in catalytic depolymerization of lignin, and the lignin and the nickel-cerium biochar catalyst are placed in a crude glycerol system for reaction.
7. The application of the nickel-cerium biochar catalyst as claimed in claim 6, wherein the crude glycerol is prepared by compounding water and pure glycerol in different volume ratios, and the ratio of the water to the oil is 1-9: 1.
8. the application of the nickel-cerium biochar catalyst according to claim 7 is characterized in that the application comprises the specific steps of putting lignin and the nickel-cerium biochar catalyst into a batch-type high-pressure reaction kettle, adding crude glycerol, then filling 0.3-0.8 MPa high-purity nitrogen, stirring, raising the temperature from normal temperature to 240-320 ℃ at a temperature rise rate of 2-7 ℃/min, and reacting for 1-10 hours at the temperature.
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| CN114478201A (en) * | 2021-12-30 | 2022-05-13 | 安徽理工大学 | Production process for directionally preparing guaiacol and derivatives thereof from lignin |
| CN114931953A (en) * | 2022-06-02 | 2022-08-23 | 南昌大学 | Preparation method of catalyst for converting biomass into hydrocarbon compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478201A (en) * | 2021-12-30 | 2022-05-13 | 安徽理工大学 | Production process for directionally preparing guaiacol and derivatives thereof from lignin |
| GB2614344A (en) * | 2021-12-30 | 2023-07-05 | Univ Anhui Sci & Technology | Method for directional preparation of guaiacol and derivatives thereof from lignin |
| GB2614344B (en) * | 2021-12-30 | 2024-01-03 | Univ Anhui Sci & Technology | Method for directional preparation of guaiacol and derivatives thereof from lignin |
| CN114931953A (en) * | 2022-06-02 | 2022-08-23 | 南昌大学 | Preparation method of catalyst for converting biomass into hydrocarbon compound |
Also Published As
| Publication number | Publication date |
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| GB2614343A (en) | 2023-07-05 |
| CN114272932B (en) | 2023-11-07 |
| GB202202544D0 (en) | 2022-04-13 |
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