CN116835584A - Device and method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals - Google Patents
Device and method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000002028 Biomass Substances 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000126 substance Substances 0.000 title claims abstract description 30
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 52
- 238000000197 pyrolysis Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002918 waste heat Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims description 29
- 239000010949 copper Substances 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000003921 oil Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000012075 bio-oil Substances 0.000 claims description 13
- 239000003575 carbonaceous material Substances 0.000 claims description 13
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000003990 capacitor Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 copper modified activated carbon Chemical class 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 abstract description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002296 pyrolytic carbon Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000008901 benefit Effects 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 5
- 235000017491 Bambusa tulda Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 238000006479 redox reaction Methods 0.000 description 5
- 241000209128 Bambusa Species 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003487 electrochemical reaction Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 240000000231 Ficus thonningii Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 235000002566 Capsicum Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 240000008574 Capsicum frutescens Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241001412225 Firmiana simplex Species 0.000 description 1
- 240000005790 Oroxylum indicum Species 0.000 description 1
- 235000012920 Oroxylum indicum Nutrition 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 244000203593 Piper nigrum Species 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001390 capsicum minimum Substances 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a device and a method for co-producing biomass-based porous carbon and high-value nitrogenous chemicals. The specific products are the copper ion modified porous carbon and the nitrogen-rich biological oil. The co-production device comprises a grate pyrolysis furnace, a condenser, a tubular furnace, an acid washing tower, a drying tower and a waste heat transmission pipe. The co-production method is that agriculture and forestry waste is mixed with nitrogen and then enters a grate pyrolysis furnace for slow co-pyrolysis. And (3) pyrolyzing the biological oil to enter a biological oil storage tank through a condenser to obtain the high-value nitrogen-containing chemical. The pyrolytic carbon is subjected to activation, acid washing and mixing calcination with copper acetate in sequence to obtain the copper ion modified biomass-based porous carbon. By the device and the method, the agriculture and forestry biomass waste is simultaneously converted into high-value nitrogen-containing chemicals and high-performance biomass-based porous carbon, and the purpose of utilizing the high added value of the agriculture and forestry waste is achieved.
Description
Technical Field
The application relates to the field of high added value utilization of biomass, in particular to a device and a method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals.
Background
The biomass material has the advantages of sustainability, environmental protection, economy and the like. The agricultural and forestry waste has the advantages of environmental protection, low carbon emission, strong reproducibility, economic benefit, multifunction and the like in preparing the biochar and the biomass bio-oil, and the high value-added utilization of biomass resources such as the agricultural and forestry waste is a great research focus in the future.
The application fields of biomass are various, and sustainable development, resource recycling and environmental protection can be promoted. They have important significance in reducing greenhouse gas emissions, promoting agricultural sustainable development, promoting green chemical industry and the like. However, in the current research and actual production, the high value-added utilization of biomass is generally limited to one field such as biochar or bio-oil, and the high value utilization of biomass is not sufficiently achieved. Meanwhile, the existing biomass treatment process has the problems of complicated steps, long time consumption and the like. Therefore, development of an oil-carbon co-production preparation device and method which are low in cost, high in efficiency and capable of realizing biomass value to the greatest extent is very necessary.
Based on the method, the device is designed to simultaneously prepare high-value nitrogen-containing chemicals and biomass-based porous carbon by slowly pyrolyzing the agricultural and forestry waste, so that the high additional value utilization of the agricultural and forestry waste is fully realized.
Chinese patent (CN 111785535B) discloses a method for self-activating a carbon micro-tube electrode material with high specific capacitance, which comprises the steps of calcining and activating French phoenix tree fruits cultivated by a potash fertilizer at constant temperature to obtain a required material, and obtaining excellent electrochemical performance through the self-activating capability of potassium element of the material; chinese patent (CN 114751394A) discloses a preparation method of a nitrogen-doped pepper residue biomass porous carbon material. Taking capsicum residue as a raw material, urea as a nitrogen source, obtaining a carbon precursor through simple impregnation and heating, and obtaining a carbon material through high-temperature calcination by taking KOH as an activating agent; the Chinese patent (CN 113105907A) relates to the field of ethylene tar, in particular to an ethylene tar treatment device for combustion, and provides an ethylene tar treatment device for combustion, which realizes the treatment of ethylene tar before combustion, avoids the blockage of a pipeline by ethylene tar, collects carbon black which is fully combusted after the ethylene tar is combusted, avoids environmental pollution and improves the utilization effect of the ethylene tar; chinese patent (CN 116199205 a) discloses a preparation method and application of a porous carbon material. The preparation method comprises the steps of dissolving cobalt salt and an organic ligand in a solvent, putting a carbon material into the solvent, and carrying out hydrothermal reaction to obtain a ZIF-67/carbon material composite product; and annealing the ZIF-67/carbon material composite product to obtain the porous carbon material, wherein the ZIF-67 which is arranged in high density is grown on the growth substrate by a hydrothermal method, and the porous carbon material is generated by high-temperature carbonization, so that better electrochemical performance is obtained. .
Although the above-mentioned patent has achieved excellent effects in the field of biomass-based carbon materials or oil materials, it has achieved excellent results in terms of biomass utilization. However, in the production process, the potential of the value of the biomass material cannot be fully utilized, and the biomass material can be only converted into one of biochar or bio-oil, so that the value of the biomass cannot be fully exerted; in addition, the problems of high pollution and high energy consumption are commonly existed in the production process; meanwhile, the patent also has the problem of complex synthesis process of biomass-based materials.
Therefore, it is very necessary to develop a low-cost, green and efficient biomass utilization method in engineering, and for this reason, the co-production engineering device adopted in the patent realizes the co-preparation of biochar and bio-oil in one process, and fully utilizes the value of biomass materials.
Disclosure of Invention
The application adopts a co-production engineering device to finish a series of processes from biomass raw materials to copper ion modified biomass-based activated carbon and high-value nitrogen-containing chemicals in a system.
In order to achieve the above purpose, the application adopts the following technical scheme:
the agriculture and forestry waste is mixed with nitrogen source and then enters a grate pyrolysis furnace through a screw feeder for slow co-pyrolysis. And (3) enabling the pyrolysis bio-oil to enter a bio-oil storage tank through a condenser to obtain the biomass-based nitrogen-rich bio-oil. And activating pyrolytic carbon and zinc chloride at a high temperature to generate porous carbon, mixing the porous carbon with copper acetate, calcining and pickling to obtain the copper ion modified biomass-based porous carbon.
Further, biological oil generated by co-pyrolysis of the agricultural and forestry waste and the nitrogen source is collected by a condensing device.
Further, the co-production device comprises a waste heat transmission pipeline, and the waste heat transmission pipeline is used for transmitting heat in the first tubular furnace for activation to the grate pyrolysis furnace; and transmitting heat in the second tubular furnace for calcining the mixed metal copper activated carbon to a drying tower; the waste heat is fully utilized, and the economic benefit is improved.
Further, the device comprises a primary pyrolysis furnace, wherein the agricultural and forestry waste is co-pyrolyzed with a nitrogen source to generate nitrogen-rich biomass; transferring the obtained product into a tube furnace, and mixing with zinc chloride in a certain proportion to perform one-step activation; the obtained product is mixed with copper acetate again and is transferred to a tube furnace for low-temperature calcination to obtain the copper metal modified porous carbon material.
Furthermore, a spiral structure is arranged in a tubular furnace for mixing and calcining the activated carbon and the copper acetate in the device, so that better adhesion of copper ions to the activated carbon is facilitated, and the copper metal modified porous carbon material is obtained.
Further, the co-production device comprises a condenser and a biological oil collecting bottle, and the nitrogen-rich biological oil generated in the pyrolysis process is collected.
The preparation method of the metal copper modified biomass-based activated carbon and the high-value nitrogen-containing chemicals by adopting the co-production device comprises the following steps:
(1) A pyrolysis preparation stage: introducing inert gas into the grate pyrolysis furnace to fully preheat the pyrolysis furnace;
(2) Primary pyrolysis stage: screw feeder for feeding mixed powder of agricultural and forestry waste and nitrogen source to
Heating to 300-400 ℃ at a heating rate of 3-5 ℃/min, and maintaining at the temperature for 1h;
(3) Activation preparation stage: the obtained finished product nitrogen-rich biomass is mixed with zinc chloride in a proportion of 2:1-1:1
Combining and transferring to a tube furnace;
(4) Activation: mixing the nitrogen-rich biomass and zinc chloride, placing the mixture into a vertical tube furnace, heating to 700-900 ℃ at a heating rate of 3 ℃/min, and keeping for 1h;
(5) And (3) cleaning: transferring biomass obtained in the activation stage to a pickling tower to perform under 2mol/L hydrochloric acid
Acid washing, and then washing the activated carbon to be neutral by deionized water;
(6) Modification preparation stage: conveying the cleaned activated carbon to a drying device, and feeding
Adding a certain amount of copper acetate into the material machine, fully mixing and drying, and transferring the powder back to the tubular furnace;
(7) Modification: the heating rate of the finished product obtained by the process is 300-400 ℃ at 10 ℃/min
Calcining for 2 hours to obtain the metallic copper modified biomass-based activated carbon.
(8) Biological oil collection process: the biomass bio-oil obtained in the preliminary pyrolysis stage is obtained by condensation
The device is collected in a bottle to obtain the nitrogen-rich biological oil.
Furthermore, the prepared metal copper modified biomass-based activated carbon material has a higher specific surface area and an excellent pore structure, and meanwhile, as copper ions are modified on the surface of the activated carbon, in an electrochemical reaction, the activated carbon can obtain excellent electrochemical performance including high capacitance and excellent cycle stability through Faraday redox reaction of the copper ions, so that the activated carbon can be applied to the fields of manufacturing of capacitor pole pieces of super capacitors and the like; meanwhile, the obtained nitrogen-rich biological oil can be further purified to prepare nitrogen-rich chemicals.
Compared with the prior art, the application has the advantages and effects that:
(1) Agricultural and forestry waste bagasse, ficus microcarpa, algae, white-layer tree bark and other agricultural and forestry waste as main material
The biomass carbon source has the characteristics of low price, convenient collection, wide sources and the like, and the process required by raw material treatment is relatively simple.
(2) Through co-pyrolysis, agricultural and forestry waste is mixed with an external nitrogen source in a certain proportion, nitrogen-rich substances released by the nitrogen source in the pyrolysis process are captured by furfural-based substances generated by the biomass nitrogen source in the pyrolysis process, stable and rich nitrogen-rich functional groups are further formed in a biochar structure, and the stable and rich nitrogen-rich functional groups are fixed in the biochar to form the nitrogen-rich biochar.
(3) The metal compound and the nitrogen-rich biochar are mixed and then calcined together, metal ions are modified on the surface of the active carbon, and pseudo-capacitance is introduced into the double-electric-layer super capacitor based on the biomass-based active carbon material through Faraday redox reaction of the metal ions
(4) The utilization efficiency of biomass is improved by collecting the bio-oil in the pyrolysis process.
(5) And the waste heat transmission pipeline is improved, the waste heat of the tubular furnace is fully utilized and is utilized to the pyrolysis furnace and the drying tower, and the economic benefit is improved.
(6) The copper ion modified activated carbon and the biological oil liquid fuel are prepared simultaneously through the co-production device, so that the high additional value utilization of agricultural and forestry waste is realized, the production efficiency is improved, and the complicated process flow is avoided.
(7) The application is simple and easy to operate, has the advantages of environmental protection and high economic benefit, can be widely applied to the production of agricultural and forestry wastes in the field of super capacitors and the application field of bio-oil liquid fuel, and has wide application prospect.
Drawings
FIG. 1 is a diagram of an oil-carbon co-production preparation device based on metal copper doped biomass-based porous carbon as a supercapacitor material and methanol added biomass bio-oil;
in the figure: 1-a grate pyrolysis furnace; a 2-condenser; 3-a bio-oil collection tank; 4-a waste heat transmission pipeline; 5-a first tubular furnace; 6-an acid washing tower; 7-a drying tower; 8-second tubular furnace.
FIG. 2 is a constant current charge-discharge graph of the nitrogen-doped activated carbon material prepared in step six of example 1 obtained at a current density of 1A/g in a three-electrode system.
FIG. 3 is a constant current charge and discharge graph of the copper ion modified biomass-based activated carbon material prepared in example 1 obtained at a current density of 1A/g in a three-electrode system.
Detailed Description
The application is further described below. The following examples are only for more clearly illustrating the technical solution of the present application and are not intended to limit the scope of the present application.
As shown in fig. 1, the oil-carbon co-production device comprises a fire grate pyrolysis furnace 1, a condenser 2, a biological oil storage tank 3, a waste heat transmission pipeline 4, a first tubular furnace 5, an acid washing tower 6, a drying tower 7 and a second tubular furnace 8 for calcining mixed metal copper activated carbon; the grate pyrolysis furnace 1 is connected with the biological oil storage tank 3 through the condenser 2; the grate pyrolysis furnace 1 is connected with a first tubular furnace 5 through a waste heat transmission pipeline 4, and the first tubular furnace 5 is sequentially connected with an acid pickling tower 6, a drying tower 7 and a second tubular furnace 8 for calcining the mixed metal copper activated carbon; the method can be used for generating the biomass-based activated carbon modified by the metallic copper of the super capacitor and the high-value nitrogenous chemical in one step in the oil-carbon co-production device. Heat in the first tubular furnace for activation is conducted to a grate pyrolysis furnace by utilizing a waste heat transmission pipeline; and transmitting heat in the second tubular furnace for calcining the mixed metal copper activated carbon to a drying tower; waste heat is fully utilized; transferring the nitrogen-rich biomass obtained in the pyrolysis furnace to a tubular furnace for mixed combustion with an activating agent; and simultaneously, the biological oil is condensed and collected through a condenser and is subjected to subsequent operation.
Example 1
The embodiment relates to a co-production preparation method of copper ion modified biomass-based activated carbon and high-value nitrogen-containing chemicals, which comprises the following steps:
step one: crushing and cleaning the collected white-layer tree barks, drying the white-layer tree barks in a drying oven at 105 ℃ for 24 hours, crushing and grinding the white-layer tree barks, and sieving the white-layer tree barks with a 80-mesh sieve.
Step two: urea is used as a nitrogen source, and the urea is mixed with the white oroxylum bark powder obtained in the step one according to the proportion of 1:1.
Step three: transferring the agricultural and forestry waste and biomass nitrogen source mixed powder obtained in the second step through a screw feeder, placing the transferred powder in a grate pyrolysis furnace, introducing inert gas as shielding gas, heating to 400 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature at 400 ℃ for 1h.
Step four: and (3) collecting the biological oil obtained in the co-pyrolysis process in the step three through a condenser.
Step five: mixing the nitrogen-enriched biomass obtained in the step three with an activator zinc chloride in a ratio of 2:1, moving the mixture into a tube furnace, heating the mixture to 700 ℃ at a heating rate of 3 ℃/min under the protection of inert gas, and keeping the mixture for 1h.
Step six: and (3) washing the product after the activation in the step (V) by 2mol/L dilute hydrochloric acid and deionized water, and obtaining the nitrogen-doped active carbon.
Step seven: conveying the cleaned active carbon into a drying device, adding 32mg of copper acetate into the drying device through a feeder, fully mixing and drying, transferring the powder back to a tube furnace, and transferring the powder to a nitrogen atmosphere at 10 DEG C
The temperature rising rate per min is raised to 300 ℃ and calcined for 2 hours.
The implementation effect is as follows: the prepared metal copper modified biomass-based activated carbon has a higher specific surface area, and meanwhile, due to the modification effect of the metal copper, in an electrochemical reaction, a sample obtains excellent electrochemical performance through Faraday redox reaction of metal, and the sample comprises high capacitance and excellent cycle stability. The obtained nitrogen-rich biological oil can be used for extracting nitrogen-rich chemicals by distillation, fractionation and other modes.
The metal copper modification effect is obvious in electrochemical layering effect, the nitrogen-doped active carbon prepared in the step six, conductive carbon black and PTFE (polytetrafluoroethylene) are mixed according to the mass ratio of 8:1:1 to prepare an electrode material, and in a three-electrode system test, the specific capacitance is 140F/g when the current density is 1A/g (shown in figure 2); and the biomass-based activated carbon material modified by the seven-metal copper is mixed with carbon black and PTFE (polytetrafluoroethylene) according to the mass ratio of 8:1:1 to prepare an electrode material, wherein in a three-electrode system test, the specific capacitance is 280F/g when the current density is 1A/g (shown in figure 3).
Example 2
The embodiment relates to a co-production preparation method of copper ion modified biomass-based activated carbon and high-value nitrogen-containing chemicals, which comprises the following steps:
step one: crushing and cleaning the collected ficus microcarpa, drying in a drying oven at 105 ℃ for 24 hours, crushing and grinding, and sieving with a 80-mesh sieve.
Step two: urea is taken as a nitrogen source, and is mixed with the ficus microcarpa powder obtained in the step one according to the proportion of 1:1.
Step three: transferring the agricultural and forestry waste and biomass nitrogen source mixed powder obtained in the second step through a screw feeder, placing the transferred powder in a grate pyrolysis furnace, introducing inert gas as shielding gas, heating to 300 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature at 400 ℃ for 1h.
Step four: and (3) collecting the biological oil obtained in the co-pyrolysis process in the step three through a condenser.
Step five: mixing the nitrogen-enriched biomass obtained in the step three with an activator zinc chloride in a ratio of 1:1, moving the mixture into a tube furnace, heating the mixture to 800 ℃ at a heating rate of 3 ℃/min under the protection of inert gas, and keeping the mixture for 1h.
Step six: and (3) washing the product after the activation in the step (V) by 2mol/L dilute hydrochloric acid and deionized water, and obtaining the nitrogen-doped active carbon.
Step seven: conveying the cleaned active carbon into a drying device, adding 32mg of copper acetate into the drying device through a feeder, fully mixing and drying, transferring the powder back to a tube furnace, and transferring the powder to a nitrogen atmosphere at 10 DEG C
The temperature rising rate per min is raised to 300 ℃ and calcined for 2 hours.
The implementation effect is as follows: the prepared metal copper modified biomass-based activated carbon has higher specific surface area, meanwhile, due to the modification effect of the metal copper, in an electrochemical reaction, a sample obtains excellent electrochemical performance through Faraday redox reaction of metal, the sample comprises high capacitance and excellent cycle stability, the activated carbon can be applied to the fields of super capacitors and the like, and the specific capacitance of the metal copper modified biomass-based activated carbon material is 289F/g when the current density is 1A/g in a three-electrode system test. The obtained nitrogen-rich biological oil can be used for extracting nitrogen-rich chemicals by distillation, fractionation and other modes.
Example 3
The embodiment relates to a co-production preparation method of copper ion modified biomass-based activated carbon and high-value nitrogen-containing chemicals, which comprises the following steps:
step one: crushing and cleaning the collected bamboos, drying the bamboos in a drying oven at 105 ℃ for 24 hours, crushing and grinding the bamboos, and sieving the bamboos with a 80-mesh sieve.
Step two: mixing urea as nitrogen source with the bamboo powder obtained in the step one at a ratio of 1:1.
Step three: transferring the agricultural and forestry waste and biomass nitrogen source mixed powder obtained in the second step through a screw feeder, placing the transferred powder in a grate pyrolysis furnace, introducing inert gas as shielding gas, heating to 400 ℃ at a heating rate of 5 ℃/min, and maintaining the temperature at 400 ℃ for 1h.
Step four: and (3) collecting the biological oil obtained in the co-pyrolysis process in the step three through a condenser.
Step five: mixing the nitrogen-enriched biomass obtained in the step three with an activator zinc chloride in a ratio of 2:1, moving the mixture into a tube furnace, heating the mixture to 900 ℃ at a heating rate of 3 ℃/min under the protection of inert gas, and keeping the mixture for 1h.
Step six: and (3) washing the product after the activation in the step (V) by 2mol/L dilute hydrochloric acid and deionized water, and obtaining the nitrogen-doped active carbon.
Step seven: conveying the cleaned active carbon into a drying device, adding 32mg of copper acetate into the drying device through a feeder, fully mixing and drying, transferring the powder back to a tube furnace, and transferring the powder to a nitrogen atmosphere at 10 DEG C
The temperature rising rate per min is raised to 400 ℃ and calcined for 2 hours.
The implementation effect is as follows: the prepared metal copper modified biomass-based activated carbon has higher specific surface area, meanwhile, due to the modification effect of the metal copper, in the electrochemical reaction, a sample obtains excellent electrochemical performance through Faraday redox reaction of metal, the sample comprises high capacitance and excellent cycle stability, and the activated carbon can be applied to the fields of super capacitors and the like, wherein the metal copper modified biomass-based activated carbon material has a specific capacitance of 274F/g when the current density is 1A/g in a three-electrode system test. The obtained nitrogen-rich biological oil can be used for extracting nitrogen-rich chemicals by distillation, fractionation and other modes.
It should be noted that the above embodiments are merely illustrative of the technical solutions of the present application, and various modifications and equivalents of the present application are possible to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for co-producing biomass-based porous carbon and high-value nitrogenous chemicals is characterized in that agricultural and forestry waste is taken as a carbon source, an additional nitrogen source is added, the two are uniformly mixed, then the nitrogen-rich biochar is obtained through slow co-pyrolysis, and high-value nitrogenous bio-oil is obtained through collection of a condensing device; the nitrogen-rich biochar and zinc chloride are activated at high temperature by a one-step method to generate active carbon; mixing the obtained activated carbon with copper acetate, calcining at low temperature, and modifying the activated carbon with metallic copper to introduce pseudo-capacitance characteristics, so as to obtain the biomass-based activated carbon with excellent pore structure and electrochemical characteristics; and cleaning and drying the obtained activated carbon to obtain the metal copper modified porous carbon material.
2. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 1, wherein the agricultural and forestry waste is dried and crushed and then passes through a 80-mesh sieve; the mass ratio of the agricultural and forestry waste to the external nitrogen source is 2:1-1:1.
3. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 1, wherein biomass and a nitrogen source are subjected to low-temperature co-pyrolysis in a tube furnace after being uniformly mixed, are heated to 300-400 ℃ at a heating rate of 3-5 ℃/min under the protection of inert gas nitrogen, and are maintained at the temperature for 1h, so that the nitrogen-rich biochar is obtained.
4. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 1, wherein the nitrogen-rich biomass and zinc chloride in the activation stage are mixed and placed in a vertical tube furnace, and are heated to 700-900 ℃ at a heating rate of 3 ℃/min, and are kept for 1h; the activated carbon is mixed with copper acetate after acid washing, water washing and drying and calcined in an air atmosphere at a heating rate of 10 ℃/min for 2 hours at 300-400 ℃.
5. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 4, wherein the mass ratio of the nitrogen-rich biomass to zinc chloride in the activation stage is 2:1-1:1.
6. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 4, wherein copper acetate is added into the secondary treatment tube furnace, and the copper acetate and the activated carbon are mixed in a mass ratio of 1:10-1:5 and subjected to metal modification to obtain pseudocapacitance characteristics; the activated carbon and the copper acetate are fully mixed in the tubular furnace through a spiral stirrer.
7. The method for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to claim 4, wherein the active material obtained by the preparation method of the metal copper modified active carbon has rich nitrogen-containing functional groups, excellent electrochemical performance and obvious pseudocapacitance characteristics outside an electric double layer structure;
the biomass-based nitrogen-rich biological oil has low viscosity, and the preparation process is environment-friendly.
8. The method for co-producing biomass-based porous carbon and high value nitrogen-containing chemicals of claim 1, wherein the mixing of forestry and agricultural residues with a nitrogen source to the production of metallic copper modified activated carbon is accomplished in a single integrated system; meanwhile, biological oil generated in the co-pyrolysis process of the agricultural and forestry waste and the nitrogen source is collected through a condenser of the co-production device, and the biological oil is obtained.
9. The device for co-producing biomass-based porous carbon and high-value nitrogen-containing chemicals according to any one of claims 1 to 8, characterized in that the oil-carbon co-production device comprises a grate pyrolysis furnace (1), a condenser (2), a biological oil storage tank (3), a waste heat transmission pipeline (4), a first tubular furnace (5), an acid washing tower (6), a drying tower (7) and a second tubular furnace (8) for calcining mixed metal copper activated carbon; the grate pyrolysis furnace (1) is connected with the biological oil storage tank (3) through the condenser (2); the grate pyrolysis furnace (1) is connected with a first tubular furnace (5) through a waste heat transmission pipeline (4), and the first tubular furnace (5) is sequentially connected with an acid pickling tower (6), a drying tower (7) and a second tubular furnace (8) for calcining the mixed metal copper activated carbon; the method can be used for generating the biomass-based activated carbon modified by the metallic copper of the super capacitor and the high-value nitrogenous chemical in one step in the oil-carbon co-production device.
10. The apparatus of claim 9, wherein the heat of the first tube furnace for activation is transferred to the grate pyrolysis furnace by means of a waste heat transfer conduit; and transmitting heat in the second tubular furnace for calcining the mixed metal copper activated carbon to a drying tower; waste heat is fully utilized;
transferring the nitrogen-rich biomass obtained in the pyrolysis furnace to a tubular furnace for mixed combustion with an activating agent; and simultaneously, the biological oil is condensed and collected through a condenser and is subjected to subsequent operation.
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