CN109701493B - Preparation method of nitrogen-doped biochar - Google Patents
Preparation method of nitrogen-doped biochar Download PDFInfo
- Publication number
- CN109701493B CN109701493B CN201910147971.1A CN201910147971A CN109701493B CN 109701493 B CN109701493 B CN 109701493B CN 201910147971 A CN201910147971 A CN 201910147971A CN 109701493 B CN109701493 B CN 109701493B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- biochar
- hydrothermal reaction
- plant waste
- preparation
- 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.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 36
- 239000010908 plant waste Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000011592 zinc chloride Substances 0.000 claims abstract description 20
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 25
- 235000009024 Ceanothus sanguineus Nutrition 0.000 claims description 21
- 240000003553 Leptospermum scoparium Species 0.000 claims description 21
- 235000015459 Lycium barbarum Nutrition 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 235000013399 edible fruits Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 244000269722 Thea sinensis Species 0.000 claims 2
- 238000010298 pulverizing process Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 229920002488 Hemicellulose Polymers 0.000 abstract description 3
- 238000005899 aromatization reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229920002678 cellulose Polymers 0.000 abstract description 3
- 239000001913 cellulose Substances 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 241001122767 Theaceae Species 0.000 description 23
- 235000013616 tea Nutrition 0.000 description 23
- 239000000126 substance Substances 0.000 description 21
- 239000007787 solid Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000007873 sieving Methods 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960001948 caffeine Drugs 0.000 description 2
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 235000020334 white tea Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 210000004102 animal cell Anatomy 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000008558 metabolic pathway by substance Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
本发明提供了一种氮掺杂生物炭的制备方法，属于炭材料技术领域。本发明将预处理后的植物废料、氯化铵、氯化锌和水混合，进行水热反应，得到氮掺杂生物炭。本发明以预处理后的植物废料为主要原料，实现了废弃资源再利用，节约了资源，改善了生态环境；氯化铵在水热反应过程中分解为氯化氢和氨气，这两者形成高压气氛，将氮原子压入生物炭中形成氮掺杂生物炭；氯化锌可以脱除植物废料中纤维素和半纤维素中的水分子，促进芳香化和生物炭的形成以及提高生物炭的孔隙率。采用本发明的制备方法具有原料来源广泛、制备方法简便、成本低、耗能低、氮掺杂率高以及绿色安全的优点。The invention provides a preparation method of nitrogen-doped biochar, belonging to the technical field of carbon materials. In the present invention, the pretreated plant waste, ammonium chloride, zinc chloride and water are mixed, and a hydrothermal reaction is carried out to obtain nitrogen-doped biochar. The invention uses the pretreated plant waste as the main raw material, realizes the reuse of waste resources, saves resources and improves the ecological environment; ammonium chloride is decomposed into hydrogen chloride and ammonia gas in the process of hydrothermal reaction, and the two form high pressure Atmosphere, nitrogen atoms are pressed into biochar to form nitrogen-doped biochar; zinc chloride can remove water molecules in cellulose and hemicellulose in plant waste, promote aromatization and the formation of biochar, and improve biochar Porosity. The preparation method of the invention has the advantages of wide raw material sources, simple and convenient preparation method, low cost, low energy consumption, high nitrogen doping rate and green safety.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a preparation method of nitrogen-doped biochar.
Background
The biochar is a solid product with stable property and fine texture formed by pyrolyzing and carbonizing biomass under the condition of complete or partial hypoxia and relatively low temperature (<700 ℃). Biochar is mainly divided into two types, one type is derived from excrement, animal fur, animal cells, tissues and the like generated by animals, the raw materials contain a large amount of high molecular substances such as oxygen-containing functional groups, proteins and the like, and the internal components are complex, and the processes in the treatment process are multiple, so that extensive and intensive research is not carried out; the other is from rice straw, pericarp, seeds and the like, the main components of the raw materials are cellulose, hemicellulose and lignin, after pyrolysis and carbonization, the main components are carbon, hydrogen, oxygen and other metal impurities, and the contents of nitrogen, phosphorus and sulfur are small, so that the preparation is easy. The biochar has good adsorbability and stability due to the fact that the biochar has a rich pore structure, a stable aliphatic chain structure and a highly aromatic structure on the surface, and therefore the biochar is widely applied to the aspects of soil improvement, ecological restoration, volatile gas fixation and the like. The main advantages of biochar are high yield and low cost compared to traditional activated carbon materials.
The nitrogen-doped biochar has the advantages of high nitrogen content, high adsorbability, high energy storage performance, high catalytic performance, low cost, easiness in preparation, high stability and wide attention from people in the fields of energy storage electrode materials and environmental remediation.
Chinese patent CN201710501592.9 discloses a preparation method of nitrogen-doped biochar, which specifically comprises the steps of roasting lotus flower stems serving as a material and urea serving as a nitrogen source twice in a tubular furnace, wherein the roasting temperature is 300-900 ℃; chinese patent CN201810451659.7 discloses a method for preparing nitrogen-doped biochar, which specifically comprises the steps of taking cotton seed hulls as raw materials, mixing the cotton seed hulls with potassium hydroxide, urea and water according to a certain proportion, and roasting in a tubular furnace at 800 ℃ under the protection of nitrogen. The preparation method of the nitrogen-doped biochar takes urea as a nitrogen source, has high production cost, needs high-temperature roasting and consumes more energy.
Disclosure of Invention
The invention aims to provide a preparation method of nitrogen-doped biochar, and the preparation method provided by the invention has the advantages of wide raw material source, simplicity and convenience in preparation method, low cost, low energy consumption, high nitrogen doping rate, greenness and safety.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of nitrogen-doped biochar, which comprises the steps of mixing pretreated plant waste, ammonium chloride, zinc chloride and water, and carrying out hydrothermal reaction to obtain the nitrogen-doped biochar.
Preferably, the plant waste comprises one or more of tea tree branches and leaves, tea tree flowers, tea tree fruits and tea processing residues.
Preferably, the pre-treatment comprises drying and crushing; the drying temperature is 60-80 ℃, and the drying time is 6-12 h; the size of the pretreated plant waste is 40-80 meshes.
Preferably, the ratio of the amount of the pretreated plant waste to the amount of water is 1 kg: (15-40) L.
Preferably, the mass ratio of the pretreated plant waste to ammonium chloride is 1: (0.1 to 3).
Preferably, the mass ratio of the pretreated plant waste to the zinc chloride is 1: (0.02-0.5).
Preferably, the mixing is carried out under the condition of stirring at room temperature, the temperature of the room temperature is 15-30 ℃, the stirring speed is 100-400 rpm, and the stirring time is 2-24 hours.
Preferably, the temperature of the hydrothermal reaction is 120-280 ℃; the pressure of the hydrothermal reaction is 0.5-10 MPa; the time of the hydrothermal reaction is 0.5-2 h.
Preferably, the hydrothermal reaction is carried out under a stirring condition, and the stirring speed is 100-400 rpm.
Preferably, the hydrothermal reaction further comprises solid-liquid separation, washing and drying.
The invention provides a preparation method of nitrogen-doped biochar, which comprises the steps of mixing pretreated plant waste, ammonium chloride, zinc chloride and water, and carrying out hydrothermal reaction to obtain the nitrogen-doped biochar. The invention takes the pretreated plant waste as the main raw material, realizes the reutilization of waste resources, saves the resources and improves the ecological environment; decomposing ammonium chloride into hydrogen chloride and ammonia gas in the hydrothermal reaction process, wherein the hydrogen chloride and the ammonia gas form high-pressure atmosphere, and nitrogen atoms are pressed into the biochar to form nitrogen-doped biochar; the zinc chloride promotes aromatization and biochar formation by removing water molecules in cellulose and hemicellulose in the plant waste, and in addition, the zinc chloride is beneficial to improving the porosity of the biochar. According to the embodiment, the nitrogen-doped biochar with the nitrogen doping amount of 0.9-10% can be prepared at 120-280 ℃, and the preparation method has the advantages of wide raw material source, simple preparation method, low cost, low energy consumption, high nitrogen doping rate, greenness and safety.
Detailed Description
The invention provides a preparation method of nitrogen-doped biochar, which comprises the steps of mixing pretreated plant waste, ammonium chloride, zinc chloride and water, and carrying out hydrothermal reaction to obtain the nitrogen-doped biochar.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the plant waste preferably comprises one or more of tea tree branches and leaves, tea flowers, tea tree fruits and tea processing residues, and more preferably Shaan tea No. 1 tea branches and leaves, Shaan tea No. 1 tea flowers and fruits, Anji white tea branches and leaves or tea processing residues. The tea tree substance metabolism is special, wherein the amino acid content accounts for 1-4% of the dry weight of the tea tree, the caffeine content accounts for 2-4% of the dry weight of the tea tree, and the amino acid and the caffeine are nitrogen-containing compounds, so that the nitrogen-doped biochar is prepared by taking one or more of tea tree branches and leaves, tea flowers, tea tree fruits and tea processing residues as raw materials.
In the invention, the pretreatment of the plant waste preferably comprises drying and crushing, and the drying temperature is preferably 60-80 ℃; the drying time is preferably 6-12 hours, and more preferably 8-10 hours. The crushing equipment and specific parameters are not particularly limited, and the plant waste with the size of 40-80 meshes is preferably obtained.
After the pretreated plant waste is obtained, the pretreated plant waste, ammonium chloride, zinc chloride and water are mixed for hydrothermal reaction to obtain the nitrogen-doped biochar. In the present invention, the ratio of the amount of the pretreated plant waste to the amount of water is preferably 1 kg: (15-40) L, more preferably 1 kg: (20-30) L; the mass ratio of the pretreated plant waste to the ammonium chloride is preferably 1: (0.1 to 3), more preferably 1: (2-3); the mass ratio of the pretreated plant waste to the zinc chloride is preferably 1: (0.02 to 0.5), more preferably 1: (0.3-0.5).
In the invention, the mixing is preferably carried out under the condition of room-temperature stirring, the temperature of the room temperature is preferably 15-30 ℃, and the stirring speed is preferably 100-400 rpm, and more preferably 200-300 rpm; the stirring time is preferably 2-24 hours, and more preferably 8-12 hours.
In the invention, the temperature of the hydrothermal reaction is preferably 120-280 ℃, and more preferably 240-280 ℃; the heating rate of the hydrothermal reaction is preferably 1-10 ℃/min, and more preferably 2-6 ℃/min; the time of the hydrothermal reaction is preferably 0.5-2 h, more preferably 1-2 h, and timing is started when the temperature reaches 120-280 ℃; the pressure of the hydrothermal reaction is preferably 0.5-10 MPa, more preferably 3.6-10 MPa, in the invention, as the hydrothermal reaction proceeds, ammonium chloride is decomposed into hydrogen chloride and ammonia gas, the pressure of the system is increased, and the pressure applied by the equipment is adjusted to keep the pressure of the reaction system at 0.5-10 MPa. In the present invention, the hydrothermal reaction is preferably carried out under a stirring condition, and the stirring speed is preferably 100 to 400rpm, and more preferably 300 to 400 rpm.
In the hydrothermal reaction process, the ammonium chloride is decomposed into hydrogen chloride and ammonia gas, the hydrogen chloride and the ammonia gas form high-pressure atmosphere, and nitrogen atoms are pressed into the biochar to form nitrogen-doped biochar; meanwhile, the zinc chloride has the functions of catalytic dehydroxylation and dehydration, so that hydrogen and oxygen in the raw material are released in the form of water vapor to form a porous structure, aromatization and biochar formation can be promoted, and the porosity of the biochar is improved. Compared with the prior art, the invention takes the ammonium chloride as the nitrogen source, the price of urea per ton is 2000 yuan, and the price of ammonium chloride per ton is 650 yuan, so the cost can be reduced by more than 2/3; in the prior art, nitrogen-doped raw materials are prepared by roasting at a high temperature of 800-1000 ℃, and the invention adopts a mixed solution of ammonium chloride and zinc chloride to treat plant waste, so that the high-nitrogen-doped biochar can be prepared at a temperature of 120-280 ℃, and the energy consumption is obviously reduced.
In the present invention, the hydrothermal reaction preferably further includes solid-liquid separation, washing and drying. In the present invention, the solid-liquid separation means preferably includes filtration or centrifugation. In the present invention, the filtration is preferably vacuum filtration, and the degree of vacuum of the vacuum filtration is preferably-0.01 to-2 MPa, more preferably-0.06 to-0.5 MPa. In the invention, the rotation speed of the centrifugation is preferably 1000-5000 rpm, and more preferably 3000-5000 rpm; the time for centrifugation is preferably 15-30 min, and more preferably 15-20 min.
According to the invention, the mixed solution obtained by the hydrothermal reaction is subjected to solid-liquid separation to obtain a solid substance, and the obtained solid substance is preferably washed and dried. In the present invention, the washing is preferably water washing, and the water is preferably deionized water; in the present invention, the number of washing is not particularly limited, and the obtained washing solution is preferably neutral. According to the invention, through washing, on one hand, reaction liquid in the reaction process is removed, and on the other hand, the pH value of the nitrogen-doped activated carbon is adjusted, so that the nitrogen-doped activated carbon is beneficial to exerting a larger adsorption or loading effect in subsequent application.
In the invention, the drying temperature is preferably 60-120 ℃, and more preferably 60-80 ℃; the drying time is preferably 6-12 h, and more preferably 8-10 h; the heating rate of the drying is preferably 0.5-10 ℃/min, and more preferably 1-5 ℃/min.
In the invention, the average pore radius of the nitrogen-doped biochar is preferably 5-20 nm, and the pore volume is preferably 0.01-0.5 cm3The nitrogen doping amount is preferably 0.9 to 10%, more preferably 2.3 to 10%.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Drying the branches and leaves of No. 1 Shaanxi tea for 6h at 80 ℃, crushing and then sieving with a 40-mesh sieve, wherein the obtained undersize is a tea branch and leaf sample;
mixing 1kg of the tea branch and leaf sample with 3kg of ammonium chloride, 0.5kg of zinc chloride and 25L of water, stirring for 24h at 25 ℃ and the rotation speed of 300rpm, then adding the mixed solution into a high-temperature high-pressure reaction kettle, heating to 280 ℃ at the heating rate of 2 ℃/min, and carrying out hydrothermal reaction for 2h at the rotation speed of 400rpm, wherein the pressure is 10 MPa;
centrifuging the mixed solution obtained by the hydrothermal reaction for 15min at the rotating speed of 5000rpm to obtain a solid substance; washing the solid substance with deionized water until the washing solution is neutral, placing the washed solid substance in an oven, heating to 60 deg.C at a temperature rise rate of 1 deg.C/min, and drying for 10 hr to obtain solid substance with average pore radius of 5nm and pore volume of 0.4cm3The nitrogen content of the tea tree waste nitrogen-doped biochar is 10% through detection of an element analyzer.
Example 2
Drying the flowers and fruits of No. 1 tea of Shaanxi tea for 8h at 80 ℃, crushing and then sieving with a 60-mesh sieve, wherein the obtained undersize is a tea tree sample;
mixing 1kg of the tea tree sample with 2kg of ammonium chloride, 0.3kg of zinc chloride and 25L of water, stirring for 2h at 25 ℃ and the rotation speed of 300rpm, adding the mixed solution into a high-temperature high-pressure reaction kettle, heating to 240 ℃ at the heating rate of 3 ℃/min, and carrying out hydrothermal reaction for 0.5h at the rotation speed of 400rpm, wherein the pressure is 6.2 MPa;
centrifuging the mixed solution obtained by the hydrothermal reaction for 15min at the rotating speed of 4000rpm to obtain a solid substance; washing the solid substance with deionized water until the washing solution is neutral, placing the washed solid substance in an oven, heating to 80 deg.C at a temperature rise rate of 5 deg.C/min, and drying for 8 hr to obtain solid substance with average pore radius of 20nm and pore volume of 0.5cm3The tea tree waste nitrogen is doped with biochar per gram,the nitrogen content in the tea tree waste nitrogen-doped biochar detected by an element analyzer is 8.2%.
Example 3
Drying branches and leaves of Anji white tea for 10 hours at the temperature of 60 ℃, crushing, and sieving by a 60-mesh sieve to obtain undersize products which are tea branch and leaf samples;
mixing 1kg of the tea branch and leaf sample with 1kg of ammonium chloride, 0.1kg of zinc chloride and 30L of water, stirring for 12h at 30 ℃ and the rotation speed of 300rpm, adding the mixed solution into a high-temperature high-pressure reaction kettle, heating to 200 ℃ at the heating rate of 6 ℃/min, and carrying out hydrothermal reaction for 1.5h at the rotation speed of 300rpm, wherein the pressure is 3.6 MPa;
centrifuging the mixed solution obtained by the hydrothermal reaction at the rotating speed of 3000rpm for 20min to obtain a solid substance; washing the solid substance with deionized water until the washing solution is neutral, placing the washed solid substance in an oven, heating to 80 deg.C at a temperature rise rate of 0.5 deg.C/min, and drying for 8 hr to obtain the final product with average pore radius of 10nm and pore volume of 0.2cm3The nitrogen content of the tea tree waste nitrogen-doped biochar is 6.7 percent through the detection of an element analyzer.
Example 4
Drying the tea processing residues at 60 ℃ for 10h, crushing and sieving by a 40-mesh sieve to obtain undersize products which are tea residue samples;
mixing 1kg of the tea residue sample with 0.5kg of ammonium chloride, 0.05kg of zinc chloride and 40L of water, stirring for 8h at 20 ℃ and the rotation speed of 300rpm, adding the mixed solution into a high-temperature high-pressure reaction kettle, heating to 160 ℃ at the heating rate of 10 ℃/min, and carrying out hydrothermal reaction for 1h at the rotation speed of 200rpm, wherein the pressure is 2.4 MPa;
centrifuging the mixed solution obtained by the hydrothermal reaction for 25min at the rotating speed of 2000rpm to obtain a solid substance; washing the solid substance with deionized water until the washing solution is neutral, placing the washed solid substance in an oven, heating to 100 deg.C at a temperature rising rate of 10 deg.C/min, and drying for 6 hr to obtain the final product with average pore radius of 15nm and pore volume of 0.1cm3The tea tree waste nitrogen-doped biochar is detected by an element analyzerThe nitrogen content of the obtained tea tree waste nitrogen-doped biochar is 2.3%.
Example 5
Drying the tea processing residues at 60 ℃ for 12h, crushing and sieving by a 80-mesh sieve to obtain undersize products which are tea residue samples;
mixing 1kg of the tea residue sample with 0.1kg of ammonium chloride, 0.02kg of zinc chloride and 15L of water, stirring for 4h at the temperature of 15 ℃ and the rotation speed of 300rpm, adding the mixed solution into a high-temperature high-pressure reaction kettle, heating to 120 ℃ at the heating speed of 5 ℃/min, and carrying out hydrothermal reaction for 0.5h at the rotation speed of 100rpm, wherein the pressure is 0.5 MPa;
centrifuging the mixed solution obtained by the hydrothermal reaction for 30min at the rotating speed of 1000rpm to obtain a solid substance; washing the solid substance with deionized water until the washing solution is neutral, placing the washed solid substance in an oven, heating to 120 deg.C at a temperature rising rate of 8 deg.C/min, and drying for 8 hr to obtain solid substance with average pore radius of 12nm and pore volume of 0.01cm3The nitrogen content of the tea tree waste nitrogen-doped biochar is 0.9 percent.
According to the embodiments, the high-nitrogen-doped biochar with the nitrogen doping amount of 0.9-10% can be prepared by treating the plant waste material with the ammonium chloride as the nitrogen source and the zinc chloride at the temperature of 120-280 ℃, so that the energy consumption is obviously reduced, the production cost is reduced on the premise of realizing the high-nitrogen doping, and the method is suitable for industrial large-scale production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The preparation method of the nitrogen-doped biochar is characterized by comprising the following steps of: mixing the pretreated plant waste, ammonium chloride, zinc chloride and water, carrying out hydrothermal reaction, carrying out solid-liquid separation, washing and drying to obtain nitrogen-doped biochar;
the plant waste comprises one or more of tea tree branches and leaves, tea flowers, tea tree fruits and tea processing residues; the pressure of the hydrothermal reaction is 0.5-10 MPa; the temperature of the hydrothermal reaction is 120-280 ℃; the time of the hydrothermal reaction is 0.5-2 h;
the average pore radius of the nitrogen-doped biochar is 5-20 nm, and the pore volume is 0.01-0.5 cm3The nitrogen doping amount is 0.9-10%.
2. The production method according to claim 1, wherein the pretreatment comprises drying and pulverization; the drying temperature is 60-80 ℃, and the drying time is 6-12 h; the size of the pretreated plant waste is 40-80 meshes.
3. The method according to claim 1, wherein the ratio of the amount of the pretreated plant waste to the amount of water is 1 kg: (15-40) L.
4. The preparation method according to claim 1, wherein the mass ratio of the pretreated plant waste to the ammonium chloride is 1: (0.1 to 3).
5. The preparation method according to claim 1, wherein the mass ratio of the pretreated plant waste to the zinc chloride is 1: (0.02-0.5).
6. The method according to claim 1, wherein the mixing is carried out under stirring conditions at room temperature, wherein the temperature at room temperature is 15 to 30 ℃, the stirring speed is 100 to 400rpm, and the stirring time is 2 to 24 hours.
7. The method according to claim 1, wherein the hydrothermal reaction is carried out under stirring at a speed of 100 to 400 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147971.1A CN109701493B (en) | 2019-02-28 | 2019-02-28 | Preparation method of nitrogen-doped biochar |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147971.1A CN109701493B (en) | 2019-02-28 | 2019-02-28 | Preparation method of nitrogen-doped biochar |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109701493A CN109701493A (en) | 2019-05-03 |
| CN109701493B true CN109701493B (en) | 2021-09-17 |
Family
ID=66265233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910147971.1A Active CN109701493B (en) | 2019-02-28 | 2019-02-28 | Preparation method of nitrogen-doped biochar |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109701493B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111111739B (en) * | 2020-01-17 | 2022-10-25 | 齐鲁工业大学 | Preparation of nitrogen-doped biochar material and method for improving dark fermentation hydrogen production performance |
| CN111574957B (en) * | 2020-05-13 | 2023-03-31 | 中国科学院合肥物质科学研究院 | Wave-absorbing material based on biological waste and magnetic material waste and preparation method thereof |
| CN112093789A (en) * | 2020-06-16 | 2020-12-18 | 广东省农业科学院茶叶研究所 | A method for preparing biochar based on tea garden waste and biochar |
| CN113233457A (en) * | 2021-06-29 | 2021-08-10 | 华中科技大学 | Nitrogen-doped porous carbon material prepared from traditional Chinese medicine residues, and preparation method and application thereof |
| CN114709427A (en) * | 2022-05-05 | 2022-07-05 | 河南师范大学 | Preparation method of nitrogen-sulfur co-doped hierarchical porous carbon catalyst with acid-alkali-oxygen-resistant reduction catalysis performance |
| CN115043479B (en) * | 2022-05-17 | 2024-02-27 | 山西财经大学 | Nitrogen-doped biochar as well as preparation method and application thereof |
| CN114804069A (en) * | 2022-05-20 | 2022-07-29 | 南京工业大学 | Method for preparing nitrogen-doped porous carbon material by gas-phase stripping of lignin and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN106179440A (en) * | 2016-06-24 | 2016-12-07 | 浙江大学 | N doping multi-stage porous charcoal and its preparation method and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL261828B2 (en) * | 2016-03-19 | 2025-05-01 | Kiverdi Inc | Microorganisms and artificial ecosystems for the production of protein, food and useful co-products from C1 substrates |
| CN106000303B (en) * | 2016-06-01 | 2019-01-04 | 湖南农业大学 | It is a kind of using pomelo peel preparation charcoal, preparation method and applications |
| CN106865543B (en) * | 2017-01-25 | 2019-03-08 | 北京凯风泰智能技术研究有限公司 | A kind of cotton stalk anaerobic steam charing method |
| CN108516916A (en) * | 2018-06-04 | 2018-09-11 | 芜湖通农生态农业有限公司 | A kind of flowers are slow-release fertilizer dedicated |
-
2019
- 2019-02-28 CN CN201910147971.1A patent/CN109701493B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183341A (en) * | 2013-04-02 | 2013-07-03 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN106179440A (en) * | 2016-06-24 | 2016-12-07 | 浙江大学 | N doping multi-stage porous charcoal and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109701493A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109701493B (en) | Preparation method of nitrogen-doped biochar | |
| CN103316632B (en) | A kind of method of giantreed charcoal, preparation method and strengthening ammonia nitrogen absorption | |
| Kyriakou et al. | Enhancing bioproduction and thermotolerance in Saccharomyces cerevisiae via cell immobilization on biochar: Application in a citrus peel waste biorefinery | |
| CN106966392A (en) | A kind of method that utilization municipal sludge prepares nitrogen sulphur codope porous carbon material | |
| CN112194127A (en) | A method for preparing nitrogen-doped carbon material from biomass | |
| CN103408012A (en) | Method for preparing activated carbon from camellia seed waste residues | |
| CN108264045A (en) | Method for preparing porous carbon material with ultra-high specific surface area by pyrolyzing tar from waste biomass | |
| CN106000303A (en) | Biological carbon prepared form grapefruit skin, preparation method and application thereof | |
| CN109847693A (en) | A kind of bentonite modified biochar and its preparation method and application | |
| CN104724703A (en) | Method for preparing adsorptive activated carbon from Musaceae plants | |
| CN107572626A (en) | A black composite material with both hydrophilic and self-floating properties, its preparation method and application | |
| CN105129797B (en) | A kind of preparation method of ammonification-activation plant activated carbon | |
| CN111115629A (en) | A high specific surface area carbon material based on waste tobacco rods and its preparation method and application | |
| CN106904589A (en) | A kind of hydro-thermal method prepares method and the application of bagasse Carbon Materials | |
| CN111318254A (en) | Preparation method of high-efficiency regenerated activated carbon | |
| CN105692587A (en) | Nitrogen-doped carbon aerogel prepared by utilizing natural-structure macromolecular nano-fiber aerogel and preparation method of nitrogen-doped carbon aerogel | |
| CN109574007A (en) | High superficial area porous carbon material and method and application are prepared using fungi pretreatment | |
| CN105344322A (en) | Method for preparing biological activated carbon from waste maidenhair tree leaves and folium ginkgo herb residue | |
| CN106065332A (en) | A kind of method and the application that utilize pomelo peel hydro-thermal carbonization to prepare charcoal | |
| CN107697913A (en) | A kind of preparation method of the classifying porous charcoal of the high capacitance performance based on walnut shell | |
| CN102730681A (en) | Preparation method of high adsorptive activated carbon | |
| CN106672965A (en) | Method for preparing high-surface-area multi-stage porous carbon with cotton straws | |
| CN108144582A (en) | A kind of preparation method of biomass-based magnetic active carbon and the magnetic active carbon of preparation | |
| CN109158083B (en) | Preparation method and application of biomass-based carbon material | |
| CN113120899A (en) | Activated carbon and preparation method and application thereof |
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 | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190521 Address after: 712100 No. 3 Shaocheng Road, Yangling District, Xianyang City, Shaanxi Province Applicant after: Northwest A & F University Applicant after: ANHUI HANSHUIYUN TEA INDUSTRY CO., LTD. Address before: 712000 No. 3 Shaocheng Road, Yangling District, Xianyang City, Shaanxi Province Applicant before: Northwest A & F University |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210827 Address after: 712199 No. 3, Taicheng Road, Yangling Demonstration Zone, Xianyang City, Shaanxi Province Applicant after: NORTHWEST A & F University Applicant after: ANHUI HANSHUIYUN TEA INDUSTRY Co.,Ltd. Applicant after: SHAANXI DONGYU BIOTECHNOLOGY Co.,Ltd. Address before: 712100 No. 3 Shaocheng Road, Yangling District, Xianyang City, Shaanxi Province Applicant before: NORTHWEST A & F University Applicant before: ANHUI HANSHUIYUN TEA INDUSTRY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |