CN116374990A - Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid - Google Patents
Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid Download PDFInfo
- Publication number
- CN116374990A CN116374990A CN202310214730.0A CN202310214730A CN116374990A CN 116374990 A CN116374990 A CN 116374990A CN 202310214730 A CN202310214730 A CN 202310214730A CN 116374990 A CN116374990 A CN 116374990A
- Authority
- CN
- China
- Prior art keywords
- formic acid
- biomass
- block
- pore carbon
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 150
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 title claims abstract description 30
- 239000011148 porous material Substances 0.000 title claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 229920002522 Wood fibre Polymers 0.000 claims abstract description 33
- 239000002025 wood fiber Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- 239000002023 wood Substances 0.000 claims description 30
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 25
- 239000012498 ultrapure water Substances 0.000 claims description 25
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 24
- 238000007865 diluting Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 235000019270 ammonium chloride Nutrition 0.000 claims description 12
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000010908 plant waste Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims 1
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 32
- 239000003054 catalyst Substances 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 20
- 229920005610 lignin Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 241000219927 Eucalyptus Species 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 238000010306 acid treatment Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229920002488 Hemicellulose Polymers 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000710013 Lily symptomless virus Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Chemical group CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000035425 carbon utilization Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002373 hemiacetals Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention discloses a method for preparing powder/block biomass grade pore carbon by pretreating lignocellulose biomass with formic acid. The method comprises the following steps: adding the wood fiber raw material into formic acid solution, and reacting for 1-12 h at room temperature-90 ℃; solid-liquid separation, washing and drying filter residues to obtain a product of the second treatment, wherein formic acid solution in filtrate can be recovered; and then uniformly mixing and grinding the nitrogen source and the obtained product, and carrying out pyrolysis carbonization for 1-3 hours at 800-1000 ℃ to obtain the nitrogen-doped hierarchical pore carbon material. The raw materials used in the invention are common and cheap wood fiber materials, the experimental steps are simple, the raw materials are prevented from being transferred in the process, the integral utilization of all components of wood fiber is ensured, biomass resources are utilized to a great extent, and the powder/block carbon catalyst with strong catalytic performance is prepared. The preparation method has simple process and low cost, and has good economic and environmental benefits.
Description
Technical Field
The invention belongs to the field of biomass material resource utilization, and particularly relates to a method for preparing powder/block biomass grade pore carbon by pretreating lignocellulose biomass with formic acid.
Background
The most main energy source raw materials in the current industrial production are fossil energy sources such as coal, petroleum and natural gas, and the rapid development of the industry aggravates the consumption of mineral resources, so that the problems of energy shortage, raw material reserves reduction, environmental pollution and the like are caused, and the environment and energy pressure caused by the problems force people to seek a sustainable development mode to extract green and environment-friendly raw materials. In addition, due to the increasing demand for energy, research is increasingly focused on the search for stable and efficient energy storage devices. The cathode electrocatalyst is an important component of a zinc-air battery of an energy storage device, noble metal platinum is the most common commercial cathode electrocatalyst at present, has good catalytic performance, can show stable and good catalytic performance in an acidic electrolyte environment and an alkaline electrolyte environment, but has rare noble metal reserves and high price, so that it is important to find materials with abundant and renewable raw materials, low development cost and good electrocatalytic performance.
The wood fiber raw material has the characteristics of large reserve, low toxicity, reproducibility, rich carbon content and the like. Catalysts using lignocellulosic raw materials as carbon sources are receiving more and more attention, and the interrelation between structural units of lignocellulosic components is more conducive to the generation of pore and network-like structures of carbon materials, to electron transfer and mass transfer processes in electrochemical processes, and to providing more active sites for electrocatalysis, thereby improving electrocatalytic performance. The wood fiber is fully utilized, so that the utilization rate of the wood fiber is improved, and the problems of cost, pollution, chemical use and the like brought in the separation process are reduced. Research into effective and environmentally friendly pretreatment techniques is an important prerequisite for the development and utilization of lignocellulosic materials.
The hierarchical pore carbon material is an effective electrocatalyst, has the characteristics of high specific surface area, stable electrochemical property, wide sources and the like, and has good performances in the aspects of electrocatalytic oxygen reduction, electrolysis of water to produce hydrogen, electrolysis of water to produce oxygen reaction and the like. Improving the surface structure of the catalyst and improving the performance of the electrocatalytic reaction by doping heteroatoms such as sulfur, nitrogen, phosphorus and the like is one of important strategies for researching and synthesizing carbon-based catalysts with excellent electrochemical performance and catalytic effect. In general, the preparation method of the electrode material has complicated process, conductive carriers such as carbon cloth and carbon paper are needed to be used for being unfavorable for the stability of the material, and mass transfer and gas transfer of the electrode material are hindered in the long-time reaction process, so that the integrated electrode preparation method is required to be developed for reducing the mass loss and the performance attenuation of the electrode material in the catalysis process.
Currently, chemical vapor deposition, chemical treatment, pyrolysis, and the like techniques have been used to prepare carbon-based materials. Chemical vapor deposition is easy to realize specific structural design, but often involves more steps, is complex and is expensive; some synthesis processes, such as in-situ growth processes, can well control the morphology, density and hybrid structure of the product, but the process is complex and can also affect the specific surface area and conductivity of the material. The method of preparing the porous carbon material by chemical treatment is limited in terms of selectively introducing chemical components, maintaining mechanical integrity of the material, but is relatively easy to mass-produce. The method for pretreating the lignocellulose biomass by formic acid degrades part of hemicellulose and lignin, damages tight connection among the hemicellulose, the lignin and the cellulose, is beneficial to doping of subsequent hetero atoms, and retains a carbon structure of the biomass as much as possible in the pyrolysis process, so that the maximization of the biomass carbon utilization rate is realized, the process is simple, and the large-scale application can be realized.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention provides a method for preparing powder/block biomass grade pore carbon by pretreating lignocellulose biomass with formic acid. The method has simple process and controllable conditions, and the prepared nonmetallic carbon-based electrocatalyst has excellent oxygen reduction performance.
The invention aims at realizing the following technical scheme:
a method for preparing powder/block biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid comprises the following steps: adding the wood fiber raw material into formic acid solution, and reacting for 1-12 h at the room temperature to 90 ℃; after the reaction is finished, carrying out solid-liquid separation, washing filter residues with water and drying to obtain a product of the second treatment, wherein formic acid solution in filtrate can be recovered; and then uniformly mixing and grinding the mixture with a nitrogen source and the obtained product, and then pyrolyzing and carbonizing the mixture at 800-1000 ℃ for 1-3 hours to obtain the nitrogen-doped hierarchical pore carbon material, namely the powder/block biomass hierarchical pore carbon.
According to the preparation method, firstly, the lignocellulose raw material is pretreated by formic acid, lignin and hemicellulose are partially degraded, so that intermolecular hydrogen bonds of cellulose and ether bonds connecting the cellulose and the lignin are broken, structures such as a benzyl ether bond, a phenyl glycosidic bond, a hemiacetal or an acetal bond and the like between the lignin and the hemicellulose are damaged, the subsequent penetration of heteroatoms from the surface and in-situ doping into the lignocellulose are facilitated, and the biomass carbon isopore structure powder/block catalyst with active sites and catalytic functions is obtained after high-temperature pyrolysis treatment.
The wood fiber raw material is agriculture and forestry crops or agriculture and forestry crop wastes and the like, including but not limited to wood, bamboo, corncob, crop straw, bagasse or artificial boards and the like.
The nitrogen source is ammonium chloride, urea or melamine; the pyrolysis carbonization time is preferably 2 hours.
The method specifically comprises the following steps:
1) Mechanically cutting the wood fiber raw material into powder or blocks with proper size to obtain the wood fiber raw material for formic acid pretreatment;
2) Mixing the wood fiber raw material obtained in the step 1) with a formic acid solution, wherein the solid-to-liquid ratio of the wood fiber raw material to the formic acid solution is 1:5 to 1:30 (g/mL), pretreating for 1-12 h at the temperature of between room temperature and 90 ℃ to obtain a solid-liquid mixture;
3) Diluting formic acid in the solid-liquid mixture in the step 2), and separating the solid-liquid mixture to obtain solid residues;
4) Washing the solid residue in the step 3) with ultrapure water or ethanol, washing the solid residue to be neutral with ultrapure water, and drying the solid residue to obtain a product of the second treatment;
5) Taking the product treated for the second time in the step 4) as a precursor, fully grinding the precursor and a nitrogen source, wherein the mass of the nitrogen source is 5-20 times of that of the product treated for the second time; and (3) in a nitrogen atmosphere, pyrolyzing and carbonizing for 1-3 hours at 800-1000 ℃ in a tube furnace to obtain the powder/block biomass grade pore carbon.
Further, in the step 1), the particle size of the powder is 20-200 meshes; the length and width of the block ranges from 0.5cm to 1m, and the thickness ranges from 1mm to 3cm.
Further, the pretreatment conditions in step 2) are as follows: the mass concentration of the formic acid solution is 80-99%, and the stirring speed is 100-400 rpm.
Further, in the step 3), ultrapure water or ethanol is added to dilute the formic acid to 2-5 times of the volume, so that the formic acid is prevented from being volatilized easily and corroding instruments in the separation process.
Further, the drying condition in the step 4) is that liquid nitrogen is frozen and dried to constant weight.
Further, in the step 5), the temperature rising rate is 5-10 ℃/min under the condition that the flow rate of the nitrogen is 10-50 mL/min.
Compared with the prior art, the invention has the following advantages:
1) The formic acid pretreatment method is simple and convenient to operate, has stronger degradation capability on cellulose, hemicellulose and lignin, and has the maximum degradation effect on lignin, wherein the cellulose content is reduced by at least 2% and the hemicellulose content is reduced by at least 2% compared with the cellulose content before and after the formic acid pretreatment, and the lignin is reduced by at least 3%.
2) The treatment condition is mild and moderate, the operation is carried out at normal pressure, the energy consumption is small, and the reagent used in the treatment process can be recycled.
3) The hierarchical pore carbon material prepared by the heteroatom doping method has larger controllability and simple operation.
4) The nitrogen-doped carbon catalyst has large specific surface area (the specific surface area of a block body can reach 1000 m) 2 And/g) is higher than the above, the electrochemical performance is stable, the catalytic activity to the oxygen reduction reaction is stronger, and the catalyst can be applied to the energy fields of zinc-air batteries and the like.
Drawings
Figure 1 is an SEM image (magnification 250) of a log cross section of example 9.
FIG. 2 is an SEM image of a cross section of carbonized eucalyptus wood of example 9 (magnification of 1X 10) 4 Multiple). The inner wall of the pipeline of carbonized eucalyptus is smoother.
FIG. 3 is an SEM image of a cross section of a wood block subjected to formic acid pretreatment of example 9 (magnification of 2.5X10) 3 Multiple).
Fig. 4 is an SEM image (magnification 400) of a cross section of the carbonized wood block subjected to formic acid degradation treatment of example 9. The inner wall of the treated carbonized wood block pipeline generates a small amount of pores.
FIG. 5 is a formic acid pretreated wood of example 1Infrared spectrogram of the powder. 1240cm -1 The peak at which the methoxy group of lignin was reduced or disappeared in the treatment of example 1 indicated that lignin was partially or mostly removed.
FIG. 6 is an electrocatalytic oxygen reduction CV diagram of the nitrogen doped powdered carbon based catalyst prepared in example 1. In contrast to the N2 saturated electrolyte test, the sample was tested at O 2 A significant redox peak appears in the saturated electrolyte.
Fig. 7 is a comparison of oxygen reduced LSVs of the nitrogen doped powdered carbon based catalyst prepared in example 1 and a commercial platinum carbon catalyst. The half-wave potential of the sample is similar to that of the commercial platinum carbon catalyst, which indicates that the sample has similar oxygen reduction performance to that of the commercial platinum carbon catalyst.
Fig. 8 is a graph showing the cell performance (power density, cycle stability) of the nitrogen-doped bulk carbon-based catalyst prepared in example 9. The stability of the block catalyst was kept relatively stable over 150h of cycle test.
FIG. 9 is a BET plot of the wood block of example 9.
Fig. 10 is a physical diagram of the nitrogen-doped bulk carbon-based catalyst prepared in example 9.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 10mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 9% before and after treatment. Weighing and weighing0.3g of the product was thoroughly ground with 4.5g of ammonium chloride at 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 2
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 5mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and carrying out normal-pressure treatment for 1h; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 7% before and after treatment. Weighing 0.3g of the product, fully grinding with 4.5g of ammonium chloride, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 3
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 20mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and carrying out normal-pressure treatment for 1h; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 7% before and after treatment. Weighing 0.3g of the product, fully grinding with 4.5g of ammonium chloride, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 4
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 30mL of 98% formic acid solution, and placing in pretreatment for burningIn the bottle, a constant-temperature water bath is started, the reaction temperature is set to 60 ℃, the stirring speed is 200rpm, and the normal pressure treatment is carried out for 1h; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 7% before and after treatment. Weighing 0.3g of the product, fully grinding with 4.5g of ammonium chloride, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 5
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 10mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 9% before and after treatment. Weighing 0.3g of the product, fully grinding with 4.5g of ammonium chloride, and standing for 15mL min -1 And (3) carrying out pyrolysis at 800 ℃ in a tube furnace for 2h under the nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 6
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 10mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 9% before and after treatment. Weighing 0.3g of the productThe product was sufficiently ground with 4.5g of ammonium chloride at 15mL min -1 And (3) carrying out pyrolysis at 1000 ℃ in a tube furnace for 2h under the nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 7
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 10mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 9% before and after treatment. Weighing 0.3g of the product, fully grinding with 4.5g of urea, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 8
Mechanically crushing eucalyptus wood to 80 meshes to obtain a wood fiber raw material for formic acid treatment; weighing 2g of crushed wood fiber raw material, adding 10mL of 98% formic acid solution into a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, separating the solid-liquid mixture to obtain solid residues, washing the solid residues with ultrapure water or ethanol, washing the solid residues with ultrapure water to be neutral, and drying the solid residues at 60 ℃ to obtain the product of the second step reaction. The lignin content of the product is reduced by 9% before and after treatment. Weighing 0.3g of the product and 4.5g of melamine, grinding thoroughly, and grinding for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped powder carbon-based catalyst.
Example 9
Mechanically cutting eucalyptus wood to a proper size to obtain a bulk lignocellulosic feedstock for formic acid pretreatment; selecting 1cm×1cm×5mm wood block (about 1 g) and adding 98% formic acid solution (solid-liquid ratio is1:5, g/mL) is placed in a pretreatment flask, a constant-temperature water bath is started, the reaction temperature is set to 60 ℃, the stirring speed is 200rpm, and the pretreatment is carried out for 1h under normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, taking out the treated block, washing the block to be neutral by ultrapure water or ethanol, and drying the block at 60 ℃ to obtain the wood block for the second step reaction. Weighing 15 times of ammonium chloride and wood blocks, fully dispersing in a closed container, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped block carbon-based catalyst.
Example 10
Mechanically cutting eucalyptus wood to a proper size to obtain a bulk lignocellulosic feedstock for formic acid pretreatment; selecting 4cm multiplied by 3mm wood blocks (about 3g in mass), adding 98% formic acid solution (solid-liquid ratio is 1:5, g/mL), placing in a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, taking out the treated block, washing the block to be neutral by ultrapure water or ethanol, and drying the block at 60 ℃ to obtain the wood block for the second step reaction. Weighing 15 times of ammonium chloride and wood blocks, fully dispersing in a closed container, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped block carbon-based catalyst.
Example 11
Mechanically cutting the lignocellulosic biomass to a suitable size to obtain a bulk lignocellulosic feedstock for formic acid pretreatment; selecting 50cm multiplied by 3cm wood blocks (about 40g in mass), adding 98% formic acid solution (solid-liquid ratio is 1:5, g/mL), placing in a pretreatment flask, starting a constant-temperature water bath, setting the reaction temperature to 60 ℃, stirring at 200rpm, and treating for 1h at normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, taking out the treated block, washing the block to be neutral by ultrapure water or ethanol, and drying the block at 60 ℃ to obtain the wood block for the second step reaction. Weighing 15 times of ammonium chloride and wood blocks, fully dispersing in a closed container, and standing for 15mL min -1 Pyrolysis in a tube furnace at 900 ℃ in nitrogen atmosphere for carbonization 2And h, obtaining the nitrogen-doped bulk carbon-based catalyst.
Example 12
Mechanically cutting the lignocellulosic biomass to a suitable size to obtain a bulk lignocellulosic feedstock for formic acid pretreatment; 1m multiplied by 3cm of wood blocks (about 80g in mass) are selected, 98% formic acid solution (solid-liquid mass ratio is 1:5, g/mL) is added into a pretreatment flask, a constant-temperature water bath is started, the reaction temperature is set to 60 ℃, the stirring speed is 200rpm, and the pretreatment is carried out for 1h under normal pressure; diluting formic acid in the mixture after the reaction is finished, cooling to room temperature, taking out the treated block, washing the block to be neutral by ultrapure water or ethanol, and drying the block at 60 ℃ to obtain the wood block for the second step reaction. Weighing 15 times of ammonium chloride and wood blocks, fully dispersing in a closed container, and standing for 15mL min -1 And (3) carrying out pyrolysis at 900 ℃ for 2 hours in a tube furnace in a nitrogen atmosphere to obtain the nitrogen-doped block carbon-based catalyst.
Table 1 shows the specific surface areas of the nitrogen-doped powdered carbon-based catalysts prepared in examples 1-4.
TABLE 1
| Sample of | Specific surface area (m) 2 g -1 ) |
| Example 1 | 776 |
| Example 2 | 666 |
| Example 3 | 745 |
| Example 4 | 674 |
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. A method for preparing powder/block biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid, which is characterized by comprising the following steps: adding the wood fiber raw material into formic acid solution, and reacting for 1-12 h at the room temperature to 90 ℃; after the reaction is finished, carrying out solid-liquid separation, and washing and drying filter residues to obtain a product of the second treatment; and then uniformly mixing and grinding the mixture with a nitrogen source and the obtained product, and then pyrolyzing and carbonizing the mixture at 800-1000 ℃ for 1-3 hours to obtain the nitrogen-doped hierarchical pore carbon material, namely the powder/block biomass hierarchical pore carbon.
2. The method for preparing the powdery/massive biomass grade pore carbon by pretreating the lignocellulosic biomass with formic acid according to claim 1, wherein the lignocellulosic raw material is agriculture and forestry crops or agriculture and forestry crop wastes, including but not limited to wood, bamboo, corncob, crop straw, bagasse or artificial boards.
3. The method for preparing powdery/bulk biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid of claim 1, wherein the nitrogen source is ammonium chloride, urea or melamine.
4. The method for preparing powder/block biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid of claim 1, wherein the pyrolysis carbonization time is 2h.
5. A method for preparing powder/bulk biomass grade pore carbon from formic acid pretreated lignocellulosic biomass as claimed in any one of claims 1 to 4, comprising the steps of:
1) Mechanically cutting the wood fiber raw material into powder or blocks with proper size to obtain the wood fiber raw material for formic acid pretreatment;
2) Mixing the wood fiber raw material obtained in the step 1) with a formic acid solution, wherein the solid-to-liquid ratio of the wood fiber raw material to the formic acid solution is 1:5 to 1:30g/mL, and pretreating at room temperature to 90 ℃ for 1 to 12 hours to obtain a solid-liquid mixture;
3) Diluting formic acid in the solid-liquid mixture in the step 2), and separating the solid-liquid mixture to obtain solid residues;
4) Washing the solid residue in the step 3) with ultrapure water or ethanol, washing the solid residue to be neutral with ultrapure water, and drying the solid residue to obtain a product of the second treatment;
5) Taking the product treated for the second time in the step 4) as a precursor, fully grinding the precursor and a nitrogen source, wherein the mass of the nitrogen source is 5-20 times of that of the product treated for the second time; and (3) in a nitrogen atmosphere, pyrolyzing and carbonizing for 1-3 hours at 800-1000 ℃ in a tube furnace to obtain the powder/block biomass grade pore carbon.
6. The method for preparing powder/block biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid according to claim 5, wherein the particle size of the powder in step 1) is 20-200 mesh; the length and width of the block ranges from 0.5cm to 1m, and the thickness ranges from 1mm to 3cm.
7. The method for preparing powdery/bulk biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid of claim 5, wherein the pretreatment conditions in step 2) are as follows: the mass concentration of the formic acid solution is 80-99%, and the stirring speed is 100-400 rpm.
8. The method for preparing powdery/bulk biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid of claim 5, wherein the drying condition in step 4) is liquid nitrogen freeze drying to constant weight.
9. The method for preparing powder/block biomass grade pore carbon by pretreating lignocellulosic biomass with formic acid according to claim 5, wherein in step 5), the heating rate is 5-10 ℃/min under the condition that the nitrogen flow rate is 10-50 mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310214730.0A CN116374990A (en) | 2023-03-08 | 2023-03-08 | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310214730.0A CN116374990A (en) | 2023-03-08 | 2023-03-08 | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116374990A true CN116374990A (en) | 2023-07-04 |
Family
ID=86960634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310214730.0A Pending CN116374990A (en) | 2023-03-08 | 2023-03-08 | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116374990A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220566A (en) * | 2007-12-19 | 2008-07-16 | 天津大学 | Method for separating lignocellulose-containing biomass with methanoic acid |
| CN106191135A (en) * | 2016-07-15 | 2016-12-07 | 东莞深圳清华大学研究院创新中心 | Lignocellulose is the biorefinery method of raw material coproduction multi-product |
| CN106601490A (en) * | 2016-06-21 | 2017-04-26 | 中国科学院青岛生物能源与过程研究所 | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof |
| CN110684204A (en) * | 2019-09-23 | 2020-01-14 | 广东工业大学 | Method for separating wood fiber by organic acid and homologously preparing furfural |
| CN114976063A (en) * | 2022-04-27 | 2022-08-30 | 华南理工大学 | Nitrogen-doped biomass carbon-based bifunctional catalyst and preparation method and application thereof |
-
2023
- 2023-03-08 CN CN202310214730.0A patent/CN116374990A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220566A (en) * | 2007-12-19 | 2008-07-16 | 天津大学 | Method for separating lignocellulose-containing biomass with methanoic acid |
| CN106601490A (en) * | 2016-06-21 | 2017-04-26 | 中国科学院青岛生物能源与过程研究所 | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof |
| CN106191135A (en) * | 2016-07-15 | 2016-12-07 | 东莞深圳清华大学研究院创新中心 | Lignocellulose is the biorefinery method of raw material coproduction multi-product |
| CN110684204A (en) * | 2019-09-23 | 2020-01-14 | 广东工业大学 | Method for separating wood fiber by organic acid and homologously preparing furfural |
| CN114976063A (en) * | 2022-04-27 | 2022-08-30 | 华南理工大学 | Nitrogen-doped biomass carbon-based bifunctional catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Lignocellulosic biomass as sustainable feedstock and materials for power generation and energy storage | |
| CN109037704B (en) | Nitrogen-doped 3D porous carbon material and preparation method and application thereof | |
| CN112499613B (en) | Preparation method of nitrogen and phosphorus doped porous carbon for wide pH range oxygen reduction electrocatalysis | |
| CN108117073B (en) | Method for preparing porous carbon material by using water hyacinth and application | |
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| Xu et al. | Green conversion of Ganoderma lucidum residues to electrode materials for supercapacitors | |
| CN107089659B (en) | Radio frequency plasma is modifies quickly to prepare enzymolysis xylogen base richness nitrogen active carbon method | |
| CN111017927A (en) | Preparation and application method of nitrogen-doped porous carbon based on straw hydrothermal carbonization | |
| CN107697913B (en) | Preparation method of walnut shell-based high-capacitance graded porous carbon | |
| Li et al. | Lignocellulosic biomass for ethanol production and preparation of activated carbon applied for supercapacitor | |
| CN105762372A (en) | Method for preparing microbial fuel cell anode electrodes from agricultural wastes | |
| CN114538408B (en) | Method for preparing high-electrocatalytic active biochar by micro-oxygen pyrolysis | |
| CN105152170A (en) | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor | |
| CN109019598A (en) | A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance | |
| Xu et al. | Towards a waste-free biorefinery: A cascade valorization of bamboo for efficient fractionation, enzymatic hydrolysis and lithium-sulfur cathode | |
| CN112133572A (en) | Three-dimensional porous biomass carbon material used as supercapacitor and preparation method thereof | |
| Wang et al. | Self‑nitrogen-doped carbon materials derived from microalgae by lipid extraction pretreatment: Highly efficient catalyst for the oxygen reduction reaction | |
| CN112194132B (en) | Preparation method and application of iron-modified carbon microsphere/carbon nanosheet composite porous carbon based on moso bamboo hydrothermal carbonization | |
| Wang et al. | Cellulose degradation of cottonseed meal derived porous carbon for supercapacitor | |
| CN112635202A (en) | Nickel cobaltate @ graphene @ China fir composite material electrode and preparation method and application thereof | |
| CN115497749B (en) | Tobacco stem-based porous carbon material, preparation method thereof and application thereof in super capacitor | |
| CN116374990A (en) | Method for preparing powder/block biomass grade pore carbon by pretreatment of lignocellulose biomass with formic acid | |
| CN113178589B (en) | Microbial fuel cell cathode, preparation method thereof and microbial fuel cell | |
| CN109755039A (en) | A kind of manganese oxide composite material preparation method based on red bayberry biomass carbon sill and application | |
| Al et al. | Oxygen-rich precursors via glycerol organosolv treatment: Preparation of activated carbon from hazelnut shell and its structural components for possible use in electrodes for supercapacitors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |