CN117431082B - Catalytic carbonization method of tar generated by biomass pyrolysis, carbon material and application - Google Patents
Catalytic carbonization method of tar generated by biomass pyrolysis, carbon material and application Download PDFInfo
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- CN117431082B CN117431082B CN202311692835.3A CN202311692835A CN117431082B CN 117431082 B CN117431082 B CN 117431082B CN 202311692835 A CN202311692835 A CN 202311692835A CN 117431082 B CN117431082 B CN 117431082B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 59
- 238000003763 carbonization Methods 0.000 title claims abstract description 48
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 40
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 83
- 239000002184 metal Substances 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000006260 foam Substances 0.000 claims abstract description 32
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- 239000010806 kitchen waste Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010902 straw Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 240000007049 Juglans regia Species 0.000 claims description 6
- 235000009496 Juglans regia Nutrition 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 235000020234 walnut Nutrition 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 241000609240 Ambelania acida Species 0.000 claims description 4
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 102000002322 Egg Proteins Human genes 0.000 claims description 4
- 108010000912 Egg Proteins Proteins 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 4
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 4
- 235000014676 Phragmites communis Nutrition 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 239000010905 bagasse Substances 0.000 claims description 4
- 210000003278 egg shell Anatomy 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 3
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 240000000560 Citrus x paradisi Species 0.000 claims 1
- 239000000976 ink Substances 0.000 claims 1
- 239000006262 metallic foam Substances 0.000 claims 1
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000011269 tar Substances 0.000 description 59
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 229910021385 hard carbon Inorganic materials 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005235 decoking Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 244000276331 Citrus maxima Species 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011273 tar residue Substances 0.000 description 3
- 235000001759 Citrus maxima Nutrition 0.000 description 2
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000035425 carbon utilization Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/06—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a catalytic carbonization method of tar generated by biomass pyrolysis, a carbon material and application thereof, belonging to the field of biomass utilization, wherein the method comprises the following steps: s1: treating foam metal or metal screen with high-valence metal salt solution, washing, drying, and performing heat treatment in reducing atmosphere to obtain metal catalyst material with metal loaded on the surface; s2: placing a biomass precursor in a first temperature zone of a double-temperature zone atmosphere furnace, placing the catalyst material prepared in the step S1 in a second temperature zone, and introducing a protective gas; s3: heating the second temperature zone to a temperature required by catalytic carbonization, starting the temperature programming of the first temperature zone, and carbonizing the tar generated in the pyrolysis carbonization process of the biomass precursor on the surface of the metal catalyst material to form a carbon material after contacting the metal catalyst material of the second temperature zone in the protection gas flow; solves the problems of low catalytic efficiency and catalyst deactivation existing in the prior art.
Description
Technical Field
The invention relates to the field of biomass utilization, in particular to a catalytic carbonization method of tar generated by biomass pyrolysis, a carbon material and application thereof.
Background
With the development of sodium ion batteries in recent years, the market demand for electrode materials is increasing, and particularly for negative electrode materials, commercial graphite negative electrodes of traditional lithium ion batteries cannot be used for sodium ion batteries, so that development of hard carbon materials suitable for sodium ion batteries is an important development point. Biomass is considered to be the most potential precursor of a negative electrode material of a sodium ion battery due to its low price, abundant resources and the characteristic of being able to form a hard carbon material by pyrolysis and carbonization.
However, during pyrolysis of biomass precursors, tar is inevitably generated, and the pyrolysis efficiency may be reduced because of the large influence of tar on a pyrolysis system, and furthermore, tar is usually in a gaseous state at 200 ℃ or higher, and is carried away from a heating zone along with a protection gas path or condensed at a lower temperature in a furnace chamber during pyrolysis of biomass, and is combined with dust, water and the like, so that the risk of blocking pipelines and equipment exists. In addition, tar contains linear hydrocarbons and aromatic compounds as main components, and is toxic and causes environmental pollution. Thus, the tar produced by pyrolysis needs to be treated. Common tar treatment methods are divided into a physical decoking method and a chemical decoking method, the physical decoking method can not completely remove tar, only the tar is converted from a gas phase into a liquid phase, collected for takeaway after enrichment, but the collected tar is a hydrocarbon mixture with extremely complex components, and the added value is extremely low; the chemical decoking method mainly adopts a catalyst to convert tar into usable small molecules, and the catalyst is often high in price and has the problem of deactivation although the tar problem can be fundamentally solved.
Disclosure of Invention
The invention provides a catalytic carbonization method of tar generated by biomass pyrolysis, a carbon material and application thereof, and solves the problems that the tar cannot be recovered, the catalytic efficiency and the carbon utilization rate are low in the prior art.
In order to solve the technical problem, the invention provides the following technical scheme:
a method for catalytic carbonization of tar produced by pyrolysis of biomass, comprising the steps of:
s1, treating foam metal or a metal screen with high-valence metal salt solution, washing, drying, and performing heat treatment in a reducing atmosphere to obtain a metal catalyst material with metal loaded on the surface;
s2, placing the biomass precursor in a first temperature zone of a double-temperature zone atmosphere furnace, placing the catalyst material prepared in the step S1 in a second temperature zone, and introducing protective gas;
s3, after the second temperature zone is heated to the temperature required by catalytic carbonization, starting the temperature programming of the first temperature zone, after tar generated in the pyrolysis carbonization process of the biomass precursor contacts with the metal catalyst material of the second temperature zone downstream of the protective gas flow, carbonizing the surface of the metal catalyst material to form a carbon material, cooling to room temperature, taking out and collecting the carbon material generated by biomass pyrolysis, and simultaneously taking out the catalyst and collecting the carbon material deposited on the catalyst.
Treating foam metal or metal screen with high-valence metal salt solution, wherein the surface of the foam metal or metal screen is oxidized, the high-valence metal salt is reduced to corresponding low-valence metal compound which is adhered to the surface of the foam metal or metal screen, washing and drying, and then performing heat treatment in a reducing atmosphere, wherein the low-valence metal compound adhered to the surface of the foam metal or metal screen and the surface oxide layer of the foam metal or metal screen are reduced to corresponding metal simple substances, so that a catalyst material with one metal surface loaded with the other metal is obtained;
the beneficial effects of adopting above-mentioned technical scheme are:
(1) The method is simple and convenient to operate, and is different from other methods for preparing catalyst main materials by growing supported metal particles in situ by using a precipitation method and preparing the catalyst main materials by using adhesive supported metal particles, the metal particles prepared by the method are more tightly combined with the foam metal or the metal screen, are not easy to fall off and are resistant to high temperature, and are more suitable for use scenes related to the invention; (2) The surface of the foam metal or the metal screen is directly treated by using a high-valence metal salt solution, and then the foam metal or the metal screen catalyst main body material with thin-layer metal particles attached in situ is obtained after the high-temperature treatment in a reducing atmosphere, and a large number of fine catalyst metal particles are loaded on the surface of the foam metal or the metal screen catalyst main body material, and when the catalyst metal particles are contacted with the gaseous tar, hydrocarbon substances in catalytic tar components are cracked and carbonized, and continuously carbonized and grown on the surface of the metal catalyst in a vapor deposition mode, and the fine metal particles bring a large specific surface area, so that the contact area between the metal catalyst particles and the gaseous tar is increased, and the catalytic carbonization efficiency is improved; (3) In the invention, the prepared metal catalyst is not used for realizing high-efficiency tar catalytic carbonization well, and a double-temperature-zone program control heating pyrolysis mode is necessary to be matched, because the biomass can generate tar in the heating carbonization process, and the temperature for generating the tar is different from the temperature at which the tar can be subjected to catalytic carbonization, so that the tar and the tar cannot be carried out in the same temperature zone; the invention designs a double-temperature-zone program control pyrolysis method, a biomass precursor to be pyrolyzed and carbonized is placed in a first temperature zone at the upstream of a protective gas, a prepared catalyst is placed in a second temperature zone at the downstream of the protective gas and is preheated to the temperature required by tar catalytic carbonization, and then the first temperature zone heating program is started, so that when the biomass in the first temperature zone is heated to a specific temperature to start to produce tar, the protective gas brings gaseous tar into the second temperature zone, the second temperature zone is already below the optimal temperature for tar catalytic carbonization, and at the moment, the gaseous tar is efficiently catalyzed and carbonized to be converted into carbon materials to be attached to the surface of the catalyst when contacting the surface of the catalyst.
Preferably, the biomass precursor is selected from one of kitchen waste oil, bagasse, coconut shells, oil residues, walnut shells, walnut peel, peanut shells, pomelo shells, vinasse, eggshell membranes, bean dregs, wheat straw, rice straw or reed stems.
Preferably, the foam metal is selected from one of foam nickel, foam copper, foam aluminum, foam titanium or foam iron, and the metal screen is selected from one of copper mesh, aluminum mesh, stainless steel mesh or titanium mesh.
Preferably, the high-valence metal salt is selected from one or more of potassium manganate, potassium permanganate, potassium ferrate, sodium manganate, sodium permanganate and sodium ferrate.
Preferably, the concentration of the high-valence metal salt solution is 0.1 mol/L to 5 mol/L.
The beneficial effects of adopting above-mentioned technical scheme are: the reaction rate of the low-concentration high-valence metal salt solution with the concentration lower than 0.1 mol/L and the foam metal or the metal screen is too slow, meanwhile, the reaction rate of the high-valence metal salt solution with the concentration ranging from 0.1 mol/L to 5 mol/L is suitable, the control is easy, the thickness of the metal particles loaded on the surface of the prepared catalyst main body material is properly and uniformly distributed, and the catalyst main body material is suitable for catalyzing the carbonization reaction of tar.
Preferably, the reducing atmosphere is hydrogen and the heat treatment temperature is 500 ℃ to 1000 ℃.
The beneficial effects of adopting above-mentioned technical scheme are: when a carbon-containing small molecular reducing gas such as acetylene is used for reduction treatment of foam metal or metal screen cloth treated by high valence salt solution, carbon is formed on the surface of the catalyst by catalytic carbonization, and the carbon material obtained by carbonizing the small molecular reducing gas such as acetylene cannot be applied, belongs to waste materials, is unfavorable for the surface structure of the catalyst, and is not formed by using hydrogen as a reducing atmosphere, so that the obtained catalyst main body material is very pure, and is unfavorable for the reduction of low valence metal compounds formed on the surface after the foam metal or metal screen cloth is treated by the high valence metal salt solution when the heat treatment temperature is lower than 500 ℃, and when the temperature is higher than 1000 ℃, the foam metal or the metal screen cloth is softened or partially melted to cause the strength to be greatly reduced, the catalyst main body material is easy to be damaged, the reaction rate is proper and easy to control when the heat treatment reduction is carried out within the temperature range of 500 ℃ to 1000 ℃, and the catalyst main body material is not easy to be damaged.
Preferably, the temperature required for the catalytic carbonization of the second temperature zone is 500 to 1200 ℃.
The beneficial effects of adopting above-mentioned technical scheme are: the tar is used as a mixture of hydrocarbon substances generated in the carbonization process of biomass, the components are complex, and the kitchen waste oil, bagasse, coconut shells, oil residues, walnut shells, peanut shells, shaddock shells, vinasse, eggshell membranes, bean dregs, wheat straws, rice straws and reed stems which are selected to be used in the invention have different tar components generated by carbonizing different biomass, and the different tar components have different temperatures during catalytic carbonization, so that the different second temperature zone catalytic carbonization temperatures are selected for different biomass to ensure that the tar is fully converted into carbon materials, and the temperature required by catalytic carbonization is in the range of 500-1200 ℃ for the biomass types.
Preferably, the metal catalyst material with metal supported on the surface is placed in the second temperature zone in a manner perpendicular to the direction of the air flow of the protective atmosphere, and 10 to 100 layers are simultaneously placed.
The beneficial effects of adopting above-mentioned technical scheme are: the catalyst material is placed vertically to make the catalyst fully contact with the air flow, increase the contact area of the catalyst and the gaseous tar, and maximally realize the catalytic carbonization efficiency, while 10 to 100 layers of catalyst materials are placed according to the amount of biomass, and the number of layers of catalyst materials is properly increased according to the increase of the amount of biomass to be carbonized, so that the tar is more fully converted into carbon material.
The carbon material obtained by the catalytic carbonization method of tar generated by biomass pyrolysis can be applied to the fields of conductive agents, lithium ion battery cathodes, sodium ion battery cathodes, printing ink and the like.
The beneficial effects of adopting above-mentioned technical scheme are: when the tar catalytic carbonization method is used, the catalyst material can induce tar to pyrolyze and carbonize on the surface of the tar and grow to form a nano rod-shaped carbon material, and the carbon material has high graphitization degree and good conductivity and also has good electrochemical performance when being used for a lithium ion battery cathode and a sodium ion battery cathode.
Compared with the prior art, the invention has the following advantages:
the method is characterized in that the metal-based catalyst developed by the method has the characteristic of cracking branched chain or annular hydrocarbon, tar generated by pyrolysis is catalyzed and carbonized after reaching the surface of the catalyst, carbon is generated on the surface of the catalyst, the purpose of removing the tar is achieved, and meanwhile, another carbon material generated by tar catalytic cracking is obtained, the carbon utilization rate in the process of preparing the hard carbon material from biomass is improved, and the additional value of a byproduct is also improved.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention. In the drawings:
FIG. 1 is a schematic diagram of a catalytic carbonization process and apparatus for producing tar by pyrolysis of biomass according to the present invention;
FIG. 2 is a surface scanning electron microscope image of the metal catalyst material in example 1;
FIGS. 3 (a) and 3 (b) are scanning electron microscope images of the catalyst of example 1 at different scales on the surface after the catalytic tar carbonization;
FIG. 4 is a scanning electron microscope image of the surface of the copper mesh of comparative example 1 after biomass pyrolysis;
FIG. 5 is a scanning electron microscope image of the surface of the catalyst after pyrolysis of biomass in comparative example 2;
fig. 6 is a constant current charge-discharge curve of the assembled battery in example 7.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
Example 1
As shown in fig. 1, a catalyst is prepared first, a copper mesh is treated by using a 5 mol/L potassium permanganate solution, washed and dried, then heat treatment is carried out at 800 ℃ in a hydrogen atmosphere to obtain a metal catalyst material with manganese supported on the surface, kitchen waste oil is used as a biomass precursor, the metal catalyst material is placed in a first temperature zone of a double-temperature zone atmosphere furnace, the prepared catalyst material is placed in a second temperature zone, argon is introduced, the temperature of the second temperature zone is raised to 1000 ℃, the temperature programming of the first temperature zone is started, tar generated in the biomass pyrolysis carbonization process contacts with a catalyst of a second temperature zone downstream of a protective gas flow, carbon materials are formed on the surface of the catalyst by carbonization, the hard carbon materials generated by biomass pyrolysis are taken out and collected after cooling to room temperature, and meanwhile, the catalyst is taken out and carbon materials deposited on the catalyst are collected.
Example 2
In the embodiment, firstly, a catalyst is prepared, a copper mesh is treated by using a 0.1 mol/L potassium permanganate solution, washed and dried, then the copper mesh is subjected to heat treatment at 500 ℃ in a hydrogen atmosphere to obtain a metal catalyst material with manganese loaded on the surface, kitchen waste oil is used as a biomass precursor, the kitchen waste oil is placed in a first temperature zone of a double-temperature-zone atmosphere furnace, the prepared catalyst material is placed in a second temperature zone, argon is introduced, the second temperature zone is heated to 1200 ℃, then the temperature programming of the first temperature zone is started, tar generated in the biomass pyrolysis carbonization process contacts with a catalyst of a second temperature zone downstream of a protective gas flow, then a carbon material is carbonized on the surface of the catalyst, the hard carbon material generated by biomass pyrolysis is taken out and collected after cooling to room temperature, and meanwhile, the catalyst is taken out and the carbon material deposited on the catalyst is collected.
Example 3
In the embodiment, firstly, a catalyst is prepared, a copper mesh is treated by 1 mol/L potassium permanganate solution, washed and dried, then heat treatment is carried out at 1000 ℃ in hydrogen atmosphere to obtain a metal catalyst material with manganese supported on the surface, kitchen waste oil is used as a biomass precursor, the metal catalyst material is placed in a first temperature zone of a double-temperature zone atmosphere furnace, the prepared catalyst material is placed in a second temperature zone, argon is introduced, the temperature of the second temperature zone is raised to 500 ℃, then the temperature programming of the first temperature zone is started, tar generated in the biomass pyrolysis carbonization process contacts with a catalyst of a second temperature zone downstream of a protective gas flow, then carbon materials are carbonized on the surface of the catalyst, the hard carbon materials generated by biomass pyrolysis are taken out and collected after cooling to room temperature, and meanwhile, the carbon materials deposited on the catalyst are collected.
Example 4
The difference between this example and example 1 is that nickel foam, copper foam, aluminum foam, titanium foam or iron foam or aluminum mesh, respectively, are used as catalyst supports instead of the copper mesh in example 1.
Example 5
This example differs from example 1 in that potassium manganate, potassium ferrate, sodium manganate, sodium permanganate, sodium ferrate, respectively, were used as catalyst carriers instead of potassium permanganate in example 1.
Example 6
The difference between this example and example 1 is that instead of the kitchen waste oil in example 1, the kitchen waste oil in example 1 is replaced with bagasse, coconut shells, oil residues, walnut shells, peanut shells, shaddock shells, distillers grains, eggshell membranes, bean dregs, wheat straw, rice straw, reed stems, and other kitchen waste materials.
Example 7
In this example, a sodium ion battery was assembled using the carbon material prepared in example 1 as a working electrode, sodium metal as a counter electrode, a glass fiber separator was used as a separator, and NaClO of 1M was used as a separator 4 The assembled battery was charge and discharge tested at 0.1C rate by dissolving in 1:1 by volume of ethylene carbonate and diethyl carbonate and adding 5. 5 wt% fluoroethylene carbonate solution as electrolyte.
Comparative example 1
In this comparative example, untreated copper mesh was directly used instead of the manganese-loaded metal catalyst material in example 1, the biomass precursor was placed in the first temperature zone of the double temperature zone atmosphere furnace, the copper mesh was placed in the second temperature zone, argon was introduced, the second temperature zone was warmed to 1000 ℃, the programmed warming of the first temperature zone was started, after biomass pyrolysis was completed, cooled to room temperature, and all the material was taken out.
Comparative example 2
In the comparative example, a catalyst is prepared first, a copper mesh is treated by using a 5 mol/L potassium permanganate solution, washed and dried, then heat treatment is carried out at 800 ℃ in a hydrogen atmosphere to obtain a metal catalyst material with manganese supported on the surface, a biomass precursor and the catalyst material are placed in the same temperature zone, the catalyst is positioned at the downstream of a gas flow relative to the biomass precursor, argon is introduced, a programmed temperature is started, the biomass pyrolysis is completed, and then the catalyst material is cooled to room temperature, and all the materials are taken out.
Characterization of the materials prepared in example 1 and comparative examples 1-2 is carried out, and fig. 2 is a surface scanning electron microscope image of the metal catalyst in example 1, and it can be seen from the image that after the metal screen is treated with the high-valence metal salt solution and treated with the reducing atmosphere, the surface of the prepared metal catalyst is loaded with a large amount of fine metal particles, so that the surface has a large specific surface area, and the contact area between the gaseous tar and the catalyst metal particles can be increased in the process of carbonizing the catalytic tar, thereby improving the catalytic efficiency. Fig. 3 is a scanning electron microscope image of the surface of the catalyst after the tar carbonization in example 1, and from fig. 3a, it can be seen that the catalyst has the effect of catalyzing the tar carbonization, new materials are generated on the surface of the copper mesh, fig. 3b shows that linear carbon materials are generated on the surface of the copper mesh, no obvious tar residue is observed at the tail end of a pipeline after the pyrolysis reaction is cooled to room temperature, so that the method can effectively remove the tar and convert the tar into the carbon materials. Fig. 4 is a scanning electron microscope image of the surface of the copper mesh after biomass pyrolysis in comparative example 1, and it can be seen from fig. 4 that no obvious substance is generated on the surface of the copper mesh, and meanwhile, obvious tar residue can be observed at the tail end of a pipeline after cooling to room temperature, which indicates that the blank copper mesh does not have the capability of catalyzing tar carbonization, and the surface of the blank copper mesh is loaded with manganese or iron. Fig. 5 is a scanning electron microscope image of the surface of the catalyst after biomass pyrolysis in comparative example 2, and it can be seen from fig. 5 that only a very small amount of carbon is generated on the surface, and meanwhile, after cooling to room temperature, the end of the pipeline can still observe obvious tar residue, which indicates that catalytic carbonization of tar cannot be effectively realized by using the same temperature zone.
The sodium ion battery assembled in example 7 was subjected to constant current charge and discharge test, and the result is shown in fig. 6, and when the carbon material produced by catalytic pyrolysis of tar obtained in the method in example 1 is used as a negative electrode of the sodium ion battery, the carbon material shows a reversible specific charge capacity of 320 mAh/g, and the initial coulomb efficiency reaches 88%, so that the carbon material has excellent negative electrode performance of the sodium ion battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A method for catalytic carbonization of tar produced by pyrolysis of biomass, comprising the steps of:
s1, treating foam metal or a metal screen with high-valence metal salt solution, washing, drying, and performing heat treatment in a reducing atmosphere to obtain a metal catalyst material with metal loaded on the surface; the reducing atmosphere is hydrogen, and the heat treatment temperature is 500-1000 ℃;
s2, placing the biomass precursor in a first temperature zone of a double-temperature zone atmosphere furnace, placing the catalyst material prepared in the step S1 in a second temperature zone, and introducing protective gas;
s3, after the second temperature zone is heated to the temperature required by catalytic carbonization, starting the temperature programming of the first temperature zone, after tar generated in the pyrolysis carbonization process of the biomass precursor contacts with the metal catalyst material of the second temperature zone downstream of the protective gas flow, carbonizing the surface of the metal catalyst material to form a carbon material, cooling to room temperature, taking out and collecting the carbon material generated by biomass pyrolysis, and simultaneously taking out the catalyst and collecting the carbon material deposited on the catalyst.
2. The method for catalytic carbonization of tar produced by pyrolysis of biomass according to claim 1, wherein the biomass precursor is selected from any one of kitchen waste oil, bagasse, coconut shells, oil residues, walnut shells, walnut peel, peanut shells, pomelo shells, distillers grains, eggshell membranes, bean dregs, wheat straw, rice straw, and reed stems.
3. The method for catalytic carbonization of tar produced by pyrolysis of biomass according to claim 1, wherein the metal foam is selected from one of nickel foam, copper foam, aluminum foam, titanium foam or iron foam, and the metal mesh is selected from one of copper mesh, aluminum mesh, stainless steel mesh or titanium mesh.
4. The catalytic carbonization method of tar produced by biomass pyrolysis according to claim 1, wherein the high-valence metal salt is selected from one or more of potassium manganate, potassium permanganate, potassium ferrate, sodium manganate, sodium permanganate or sodium ferrate.
5. The method for catalytic carbonization of tar produced by pyrolysis of biomass according to claim 1, characterized in that the concentration of the high-valence metal salt solution is 0.1 mol/L to 5 mol/L.
6. The method of catalytic carbonization of tar produced by pyrolysis of biomass as set forth in claim 1, characterized in that the temperature required for catalytic carbonization of the second temperature zone is 500 to 1200 ℃.
7. The method for catalytic carbonization of tar produced by pyrolysis of biomass according to claim 1, wherein the metal catalyst material with metal supported on the surface is placed in the second temperature zone in a manner perpendicular to the direction of the gas flow of the protective atmosphere and is placed in 10 to 100 layers simultaneously.
8. A carbon material obtainable by a catalytic carbonization process of tar produced by pyrolysis of biomass according to any one of claims 1 to 7.
9. The use of the carbon material of claim 8 in the fields of conductive agents, lithium ion battery cathodes, sodium ion battery cathodes and inks.
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