CN114804100A - Porous carbon with ultrahigh specific surface area and preparation method thereof - Google Patents
Porous carbon with ultrahigh specific surface area and preparation method thereof Download PDFInfo
- Publication number
- CN114804100A CN114804100A CN202210516527.4A CN202210516527A CN114804100A CN 114804100 A CN114804100 A CN 114804100A CN 202210516527 A CN202210516527 A CN 202210516527A CN 114804100 A CN114804100 A CN 114804100A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- surface area
- specific surface
- ultra
- high specific
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 36
- 238000001994 activation Methods 0.000 claims description 34
- 230000004913 activation Effects 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 241000208125 Nicotiana Species 0.000 claims description 32
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000011592 zinc chloride Substances 0.000 claims description 18
- 235000005074 zinc chloride Nutrition 0.000 claims description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 17
- 238000003763 carbonization Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 229960003975 potassium Drugs 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000007833 carbon precursor Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000001508 potassium citrate Substances 0.000 claims description 5
- 229960002635 potassium citrate Drugs 0.000 claims description 5
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical group [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 5
- 235000011082 potassium citrates Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000002156 adsorbate Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003463 adsorbent Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 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
- OSPMLGKXWXDPNO-UHFFFAOYSA-M disodium azanide hydroxide Chemical compound [Na+].[OH-].N[Na] OSPMLGKXWXDPNO-UHFFFAOYSA-M 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
Abstract
The invention discloses a porous carbon with ultrahigh specific surface area and a preparation method thereof. The porous carbon has a micropore-mesopore structure, and the specific surface area of the porous carbon is 2775-3608 m 2 The specific surface area is high, and the adsorbent has abundant micropore-mesopore structures, is convenient for mass transfer or reaction of adsorbate molecules, and has great application value.
Description
Technical Field
The invention belongs to the field of environmental protection and new energy material preparation, and particularly relates to a porous carbon with ultrahigh specific surface area and a preparation method thereof.
Background
The porous carbon material has advantages of large specific surface area, developed pore structure, excellent conductivity, stable physicochemical properties and the like, and thus is widely used in the fields of environmental protection, energy sources and the like. Studies have shown that the specific surface area and pore size structure of porous carbon are the main factors determining its properties. Generally, the larger the specific surface area is, the larger the intrinsic space of the porous carbon is, and the more favorable the various physicochemical processes are, so that it is of great significance to increase the specific surface area of the porous carbon. On the other hand, the difference of the porous carbon pore size structure will also significantly affect the application field, for example, when the porous carbon pore size structure is applied to the field of adsorption and separation of volatile organic gases, the number of micropores with the size less than 2nm significantly affects the final adsorption amount, because the micropores provide main adsorption sites; when the mesoporous carbon material is applied to the field of super capacitors as an electrode, mesopores with the size of 2-50 nm are more beneficial to ion transmission.
The porous carbon material has rich sources, and theoretically, any substance containing carbon can be used for preparing the porous carbon. China is a traditional big agricultural country, and the planting amount of tobacco is in the forefront of the world. In the tobacco processing process, a large amount of tobacco waste (tobacco stems) is generated every year, and the direct burying or burning of the waste not only has low comprehensive utilization rate, but also is easy to cause pollution. It is worth noting that tobacco stems contain a large amount of cellulose, hemicellulose and lignin, and also a small amount of pectin, protein and water-soluble substances.
Therefore, the method for converting the tobacco stems into the porous carbon with higher added value and wider application has important practical value. The conversion of biomass feedstock into carbon material is mainly by a high temperature activation process. Generally, the activation method can be further classified into a physical activation method and a chemical activation method. The physical activation method generally uses water vapor and carbon dioxide as activation gas, the activation temperature is generally higher than 900 ℃, the preparation cost is low, but the specific surface area of the obtained porous carbon is generally not high (1500 m) 2 About/g). The chemical activation method generally uses chemical reagents such as zinc chloride, sodium hydroxide sodium amide, potassium hydroxide, potassium carbonate and the like as activators (the activation temperature is generally higher than 500 ℃), pores are formed by etching a carbon sheet through metal or metal compounds generated by chemical reaction with a carbon source, and the prepared porous carbon has a high surface area, but generally does not exceed 2500m 2 (ii) in terms of/g. Meanwhile, the activating agents used by the activating method form a porous structure by etching the carbon skeleton at high temperature, so that the yield of the activated porous carbon is low, and the large-scale production is not facilitated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a porous carbon with ultrahigh specific surface area and a preparation method thereof, wherein the specific surface area of the provided porous carbon is as high as 2775-3608 m 2 The preparation method provided by the invention is simple and controllable, and has high yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention relates to a preparation method of porous carbon with ultrahigh specific surface area, which comprises the steps of soaking tobacco stems in a hydrochloric acid solution, cleaning, drying, crushing to obtain tobacco stem powder, then placing the tobacco stem powder in a solution containing zinc chloride and ethylenediamine, carrying out hydrothermal treatment to obtain a carbon precursor, carrying out carbonization treatment on the carbon precursor to obtain a carbonized product, finally mixing the carbonized product with organic salt containing potassium, carrying out activation treatment, and carrying out acid pickling and drying on the obtained activated product to obtain the porous carbon.
According to the preferable scheme, the tobacco stems are soaked in a hydrochloric acid solution for 24-48 hours after being stirred, the hydrochloric acid solution is replaced every 6-12 hours, and the concentration of the hydrochloric acid solution is 0.5-1.5 mol L -1 。
The inventor finds that the tobacco stems contain a large amount of hemicellulose and lignin and start to crack at a lower temperature (about 200 ℃) to generate a large amount of tar, and the tobacco stems are easy to block after condensation.
Further preferably, the solid-liquid mass volume ratio of the tobacco stems to the hydrochloric acid solution is 50 g: 500 mL-1500 mL.
In a preferred scheme, the mesh number of the tobacco stalk powder is less than 200 meshes.
According to the preferable scheme, tobacco stem powder is placed in a solution containing zinc chloride and ethylenediamine, ultrasonic oscillation is carried out for 1-3 hours, and then the tobacco stem powder is transferred to an autoclave for hydrothermal treatment.
In a preferable scheme, the solution containing zinc chloride and ethylenediamine is obtained by dissolving zinc chloride and ethylenediamine in water, and the solid-liquid mass volume ratio of the zinc chloride to the water is 4 g: 80-160 mL, wherein the volume ratio of the ethylenediamine to the water is 5: 80-160.
According to the invention, the tobacco stem powder treated by hydrochloric acid is placed in the solution containing zinc chloride and ethylenediamine for hydrothermal treatment, on one hand, zinc ions react with oxygen-containing groups in the raw materials, part of C-O bonds are broken, and the content of carbon is improved, on the other hand, nitrogen atoms in the ethylenediamine are introduced into a carbon skeleton, so that defects are caused to the carbon skeleton, a pore structure is generated, the specific surface area is improved, and the performances of the obtained material in the application fields of adsorption, electrochemistry, catalysis and the like can be improved.
In the actual research process, the inventor also tries a large amount of nitrogen-containing materials such as urea and melamine in order to introduce nitrogen atoms into a carbon skeleton, but the final effect is far less than that of the ethylene diamine.
In a preferable scheme, the mass ratio of the tobacco stalk powder to the zinc chloride is 1: 1 to 3.
In a preferable scheme, the temperature of the hydrothermal treatment is 180-200 ℃, and the time of the hydrothermal treatment is 8-12 h.
In the preferable scheme, the carbonization treatment is carried out in a protective atmosphere, the temperature of the carbonization treatment is 400-500 ℃, the time of the carbonization treatment is 1-3h, and the temperature rise rate is 3-10 ℃/min.
The inventor finds that the carbon content can be further improved, the subsequent activation efficiency is improved and the specific surface area is favorably increased by performing the carbonization treatment at 400-500 ℃ and then performing the activation treatment.
Further preferably, the protective atmosphere is selected from nitrogen and/or argon.
In a preferable scheme, in the carbonization treatment process, the flow of introducing the protective atmosphere is 50-100 mL/min.
In a preferred embodiment, the organic salt containing potassium is potassium citrate.
In a preferred scheme, the mass ratio of the carbonized product to the potassium-containing organic salt is 1: 1 to 4.
In the invention, potassium citrate is used as an activating agent and used as an organic salt, so that the potassium element is rich, the potassium element and zinc chloride can generate a synergistic activation effect to generate a rich pore structure, and the organic part is contained to improve the yield of porous carbon.
In a preferred scheme, the activation treatment is carried out in a protective atmosphere, the temperature of the activation treatment is 750-900 ℃, preferably 800-850 ℃, the time of the activation treatment is 1-3h, and the temperature rise rate is 3-10 ℃/min.
Further preferably, the protective atmosphere is selected from nitrogen and/or argon.
According to the preferable scheme, the activated product is placed in a hydrochloric acid solution for acid washing, then is washed to be neutral by deionized water, and then is dried to obtain the porous carbon material, wherein the mass fraction of dissolved HCL in the hydrochloric acid solution is 5-10%.
Further preferably, the drying temperature is 100 ℃, and the drying time is 12 h.
The invention also provides the porous carbon prepared by the preparation method.
The porous carbon has a microporous-mesoporous structure.
The specific surface area of the porous carbon is 2775-3608 m 2 The preferred concentration is 3283-3608 m 2 /g。
The porous carbon prepared by the method has a specific surface area of 2775-3608 m measured by low-temperature nitrogen adsorption (execution standards GB/T21650.2, GB/T19587 and GB/T21650.3) 2 /g。
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1. the technical scheme of the invention adopts the tobacco stems as the carbon source and the renewable waste, has rich tobacco stem sources and low cost, and is suitable for large-scale popularization and application.
2. According to the technical scheme, the novel method of hydrochloric acid soaking and zinc salt hydrothermal is used for treating the biological raw materials, so that impurities can be efficiently removed, the structure and properties of the product can be improved, the generation of tar can be reduced, and the subsequent carbonization and activation are facilitated. Specifically, the method comprises the following steps: firstly, the mineral content of K, Mg, Ca and the like in the raw materials can be effectively reduced and the ash content is reduced by soaking in hydrochloric acid, and on the other hand, a part of cross-linked structures of hemicellulose, lignin and the like can be removed on the basis of keeping the skeleton. Secondly, zinc chloride and ethylenediamine are added simultaneously in the hydrothermal process, zinc ions react with oxygen-containing groups in the raw materials, partial C-O bonds are broken, the carbon content is improved, nitrogen atoms in the ethylenediamine are beneficially introduced into a carbon skeleton, and the porous carbon with the ultrahigh specific surface area is obtained through the synergistic effect of the processes.
3. The technical scheme of the invention adopts organic salt (potassium citrate) containing potassium as a novel activator, the organic salt contains a large amount of potassium element, can generate synergistic activation with zinc chloride to generate rich pore structure, and contains organic part to improve the yield of porous carbon.
4. The porous carbon prepared by the technical scheme of the invention has an ultrahigh specific surface area of 2775-3608 m 2 /g。
5. The porous carbon prepared by the technical scheme of the invention has rich micropore-mesopore structures, and is convenient for mass transfer or reaction of adsorbate molecules. The pore size distribution can be regulated and controlled by changing the activation temperature, and when the activation temperature is increased from 750 ℃ to 900 ℃, the mesopore size is gradually enlarged from 2.7nm to about 4nm, which is beneficial to widening the application scene of the porous carbon prepared by the technical scheme of the invention.
Drawings
FIG. 1 is a graph showing isothermal adsorption of nitrogen in accordance with an embodiment of the present invention.
FIG. 2 is a diagram illustrating an aperture distribution according to an embodiment of the present invention.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The tobacco stem is prepared by selecting agricultural waste tobacco stems of a cigarette factory as raw materials, and carbonizing, activating, acidifying and drying the raw materials.
1) The biological raw material is pretreated. 50g of tobacco stem raw material was added to 500mL of hydrogen chloride solution (0.5mol L) -1 ) After fully stirring, the mixture is soaked for 48 hours, and the fresh solution is replaced every 12 hours. The washed and dried raw material was pulverized (200 mesh) using a pulverizer. Adding 4g of tobacco stalk powder into deionized water (80mL) containing 4g of zinc chloride and 5mL of ethylenediamine, placing the mixture in an ultrasonic environment, fully oscillating for 2 hours, transferring the mixture to a high-pressure reaction kettle, performing hydrothermal treatment for 10 hours at 200 ℃, naturally cooling, cleaning and drying to obtain the pretreated carbon precursor.
2) And (6) carbonizing treatment. Placing a certain mass of carbon precursor in a tubular furnace, heating to a corresponding temperature at a certain heating rate in an inert gas atmosphere, preserving heat for a period of time, and naturally cooling to obtain a carbonized product.
2) And (6) carbonizing treatment. And (3) placing the carbon precursor into a tubular furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere (60mL/min), preserving heat for one hour, and naturally cooling to obtain a carbonized product.
3) And (5) activating treatment. Uniformly mixing the carbonized product with potassium citrate in a certain mass ratio (the mass ratio is 1: 2), placing the mixture in a tubular furnace, heating the mixture to 750 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere (60mL/min), preserving the heat for one hour, and naturally cooling to obtain an activated product.
4) Acid washing and drying. And (3) putting the activated product into sufficient 5% dilute hydrochloric acid for pickling for a certain time, filtering, washing with deionized water until filtrate is neutral, and drying to obtain the porous carbon material with the ultrahigh specific surface area, wherein the porous carbon material is marked as SAC-1.
Example 2
The only difference from example 1 is the activation temperature. The activation temperature used in example 2 was 800 ℃ to produce a porous carbon designated SAC-2.
Example 3
The only difference from example 1 is the activation temperature. The activation temperature used in example 3 was 850 deg.C, producing a porous carbon designated SAC-3.
Example 4
The only difference from example 1 is the activation temperature. The activation temperature used in example 4 was 900 ℃ and a porous carbon was prepared and designated SAC-4.
The porous carbons (SAC-1, SAC-2, SAC-3, SAC-4) in examples 1 to 4 were subjected to vacuum treatment at 150 ℃ for 6 hours, and then subjected to low-temperature nitrogen isothermal adsorption (performance standards GB/T21650.2, GB/T19587, GB/T21650.3) using a JW-BK132Z specific surface area analyzer (manufactured by Beijing Jingwei Gaobaokou Technical Co., Ltd.), the specific surface area was calculated using a multipoint BET calculation method, and the pore size distribution was calculated using an NLDFT model. The results are shown in Table 1.
TABLE 1 pore Structure parameters of porous carbon samples
The results show that the preparation process flow of the porous carbon with the ultrahigh specific surface area is real and effective, and the specific surface areas of the prepared examples SAC-1, SAC-2, SAC-3 and SAC-4 are 2775 m, 3283 m, 3608m and 2550m respectively 2 g –1 Higher than most of the reported porous carbon materials. The reduction in BET surface area at 900 ℃ is mainly due to the collapse of the pore structure at very high activation temperatures. The nitrogen isothermal adsorption curves for all examples are typical type IV, i.e. rise rapidly at lower relative pressures, at p/p0>0.45 has a significant hysteresis loop (see FIG. 1), indicating an abundance of microporous-mesoporous structure. The increase of the activation temperature is beneficial to the formation of mesopores, and also can cause the continued enlargement of part of the mesopores, when the activation temperature is increased from 750 ℃ to 900 ℃, the mesopore diameter is gradually enlarged from 2.7nm to about 4nm (see figure 2), which shows that the pore diameter structure of the embodiment of the invention can be regulated by changing the activation temperature. In particular, SAC-3 exhibits the highest specific surface area and the largest pore volume.
Example 5
The conditions were the same as those in example 3 except thatHydrochloric acid is not used for soaking the tobacco stalk raw material. The experimental result shows that a large amount of tar liquid appears on the pipe wall in the carbonization process, and the nitrogen adsorption test shows that the specific surface area of the tar liquid is 3059m 2 g –1 Smaller than in example 3.
Example 6
The same conditions as in example 3 were used except that the carbonization treatment was not performed. And the specific surface area is 2433m through nitrogen adsorption test 2 g –1 Smaller than in example 3.
Example 7
The same conditions as in example 3 were used except that urea was used instead of ethylenediamine. And the nitrogen adsorption test shows that the specific surface area of the material is 3209m 2 g –1 Smaller than in example 3.
Claims (10)
1. A preparation method of porous carbon with ultrahigh specific surface area is characterized in that: the method comprises the steps of soaking tobacco stems in a hydrochloric acid solution, cleaning, drying, crushing to obtain tobacco stem powder, placing the tobacco stem powder in a solution containing zinc chloride and ethylenediamine, carrying out hydrothermal treatment to obtain a carbon precursor, carrying out carbonization treatment on the carbon precursor to obtain a carbonized product, mixing the carbonized product with organic salt containing potassium, carrying out activation treatment, carrying out acid washing on the obtained activated product, and drying to obtain the porous carbon.
2. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein: soaking tobacco stems in a hydrochloric acid solution, stirring, soaking for 24-48 h, and changing the hydrochloric acid solution every 6-12 h, wherein the concentration of the hydrochloric acid solution is 0.5-1.5 mol L -1 (ii) a The solid-liquid mass volume ratio of the tobacco stems to the hydrochloric acid solution is 50 g: 500 mL-1500 mL.
3. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein: putting the tobacco stalk powder into a solution containing zinc chloride and ethylenediamine, performing ultrasonic oscillation for 1-3h, and then transferring to a high-pressure kettle for hydrothermal treatment.
4. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein: in the solution containing zinc chloride and ethylenediamine, the solution is obtained by dissolving zinc chloride and ethylenediamine in water, and the solid-liquid mass-volume ratio of the zinc chloride to the water is 4 g: 80-160 mL, wherein the volume ratio of the ethylenediamine to the water is 5: 80-160.
5. The method for preparing porous carbon with ultra-high specific surface area according to claim 1 or 4, characterized in that:
the mass ratio of the tobacco stalk powder to the zinc chloride is 1: 1 to 3.
The temperature of the hydrothermal treatment is 180-200 ℃, and the time of the hydrothermal treatment is 8-12 h.
6. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein:
the carbonization treatment is carried out under the protective atmosphere, the temperature of the carbonization treatment is 400-500 ℃, the time of the carbonization treatment is 1-3h, and the temperature rise rate is 3-10 ℃/min; and in the carbonization treatment process, the flow of introducing protective atmosphere is 50-100 mL/min.
7. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein:
the potassium-containing organic salt is potassium citrate;
the mass ratio of the carbonized product to the organic salt containing potassium is 1: 1 to 4.
8. The method for preparing the porous carbon with ultra-high specific surface area according to claim 1, wherein:
the activation treatment is carried out in a protective atmosphere, the temperature of the activation treatment is 750-900 ℃, the time of the activation treatment is 1-3h, and the temperature rise rate is 3-10 ℃/min.
9. Porous carbon having an ultra-high specific surface area prepared by the preparation method as set forth in any one of claims 1 to 8.
10. The porous carbon with ultra-high specific surface area according to claim 9, wherein: the porous carbon has a micropore-mesopore structure, and the specific surface area of the porous carbon is 2775-3608 m 2 /g。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210516527.4A CN114804100B (en) | 2022-05-13 | 2022-05-13 | Porous carbon with ultrahigh specific surface area and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210516527.4A CN114804100B (en) | 2022-05-13 | 2022-05-13 | Porous carbon with ultrahigh specific surface area and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114804100A true CN114804100A (en) | 2022-07-29 |
| CN114804100B CN114804100B (en) | 2023-10-27 |
Family
ID=82513463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210516527.4A Active CN114804100B (en) | 2022-05-13 | 2022-05-13 | Porous carbon with ultrahigh specific surface area and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114804100B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536022A (en) * | 2022-10-26 | 2022-12-30 | 天津科技大学 | Biomass porous carbon material based on mangosteen shells and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407323A (en) * | 2008-09-16 | 2009-04-15 | 上海第二工业大学 | Method for preparing pressed active carbon from tobacco stalk |
| RU2393111C1 (en) * | 2009-03-18 | 2010-06-27 | Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) | Method of producing microporous carbon material from lignocellulose material |
| CN103121682A (en) * | 2013-02-05 | 2013-05-29 | 中南大学 | Method for preparing high-specific-surface-area activated carbon from tobacco stalks |
| WO2014077714A1 (en) * | 2012-11-16 | 2014-05-22 | Politechnika Poznańska | Production of activated carbon from tobacco leaves by simultaneous carbonization and self-activation and the activated carbon thus obtained |
| JP2015013767A (en) * | 2013-07-04 | 2015-01-22 | 国立大学法人九州工業大学 | Method for producing porous carbon material |
| US20160174605A1 (en) * | 2014-12-22 | 2016-06-23 | R.J. Reynolds Tobacco Company | Tobacco-derived carbon material |
| CN108483442A (en) * | 2018-03-27 | 2018-09-04 | 湘潭大学 | A kind of preparation method of high mesoporous rate N doping carbon electrode material |
| CN109012154A (en) * | 2018-08-04 | 2018-12-18 | 安徽科浦环保科技有限公司 | A kind of preparation method of modified tea grounds formaldehyde adsorbent |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN110745824A (en) * | 2019-11-21 | 2020-02-04 | 哈尔滨工业大学 | Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation |
| CN110817844A (en) * | 2019-12-19 | 2020-02-21 | 南昌大学 | Preparation method of nitrogen-sulfur co-doped porous carbon nano-microspheres |
| CN111115629A (en) * | 2019-12-27 | 2020-05-08 | 暨南大学 | High-specific-surface-area carbon material based on waste tobacco stems and preparation method and application thereof |
| CN113603088A (en) * | 2021-07-02 | 2021-11-05 | 四川大学 | High-specific surface area active carbon, super capacitor electrode and preparation method thereof |
| CN114149023A (en) * | 2021-12-02 | 2022-03-08 | 南京工程学院 | High-value conversion and reuse method for tobacco waste |
| CN115497749A (en) * | 2022-09-30 | 2022-12-20 | 华南理工大学 | Tobacco stem-based porous carbon material, preparation method thereof and application thereof in super capacitor |
-
2022
- 2022-05-13 CN CN202210516527.4A patent/CN114804100B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407323A (en) * | 2008-09-16 | 2009-04-15 | 上海第二工业大学 | Method for preparing pressed active carbon from tobacco stalk |
| RU2393111C1 (en) * | 2009-03-18 | 2010-06-27 | Учреждение Российской академии наук Институт химии и химической технологии Сибирского отделения РАН (ИХХТ СО РАН) | Method of producing microporous carbon material from lignocellulose material |
| WO2014077714A1 (en) * | 2012-11-16 | 2014-05-22 | Politechnika Poznańska | Production of activated carbon from tobacco leaves by simultaneous carbonization and self-activation and the activated carbon thus obtained |
| CN103121682A (en) * | 2013-02-05 | 2013-05-29 | 中南大学 | Method for preparing high-specific-surface-area activated carbon from tobacco stalks |
| JP2015013767A (en) * | 2013-07-04 | 2015-01-22 | 国立大学法人九州工業大学 | Method for producing porous carbon material |
| US20160174605A1 (en) * | 2014-12-22 | 2016-06-23 | R.J. Reynolds Tobacco Company | Tobacco-derived carbon material |
| CN108483442A (en) * | 2018-03-27 | 2018-09-04 | 湘潭大学 | A kind of preparation method of high mesoporous rate N doping carbon electrode material |
| CN109012154A (en) * | 2018-08-04 | 2018-12-18 | 安徽科浦环保科技有限公司 | A kind of preparation method of modified tea grounds formaldehyde adsorbent |
| CN109516458A (en) * | 2018-12-05 | 2019-03-26 | 华南师范大学 | A kind of biomass-based graded porous carbon and preparation method thereof |
| CN110745824A (en) * | 2019-11-21 | 2020-02-04 | 哈尔滨工业大学 | Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation |
| CN110817844A (en) * | 2019-12-19 | 2020-02-21 | 南昌大学 | Preparation method of nitrogen-sulfur co-doped porous carbon nano-microspheres |
| CN111115629A (en) * | 2019-12-27 | 2020-05-08 | 暨南大学 | High-specific-surface-area carbon material based on waste tobacco stems and preparation method and application thereof |
| CN113603088A (en) * | 2021-07-02 | 2021-11-05 | 四川大学 | High-specific surface area active carbon, super capacitor electrode and preparation method thereof |
| CN114149023A (en) * | 2021-12-02 | 2022-03-08 | 南京工程学院 | High-value conversion and reuse method for tobacco waste |
| CN115497749A (en) * | 2022-09-30 | 2022-12-20 | 华南理工大学 | Tobacco stem-based porous carbon material, preparation method thereof and application thereof in super capacitor |
Non-Patent Citations (3)
| Title |
|---|
| CHUNHAO WANG ET AL: "Thermal conversion of tobacco stem into gaseous products", 《JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY》, vol. 137, pages 811 - 823, XP036822374, DOI: 10.1007/s10973-019-08010-4 * |
| XIANCHENG MA ET AL: "Heteroatom-doped porous carbons exhibit superior CO2 capture and CO2/ N2 selectivity: Understanding the contribution of functional groups and pore structure", 《SEPARATION AND PURIFICATION TECHNOLOGY》, vol. 259, pages 2 * |
| XIANCHENG MA ET AL: "In-situ activated ultramicroporous carbon materials derived from waste biomass for CO2 capture and benzene adsorption", 《BIOMASS AND BIOENERGY》, vol. 158, pages 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115536022A (en) * | 2022-10-26 | 2022-12-30 | 天津科技大学 | Biomass porous carbon material based on mangosteen shells and preparation method thereof |
| CN115536022B (en) * | 2022-10-26 | 2024-01-16 | 天津科技大学 | Biomass porous carbon material based on mangosteen shells and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114804100B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2023024365A1 (en) | Method for preparing activated carbon by using areca nut and sludge as materials | |
| Khan et al. | Jute-derived microporous/mesoporous carbon with ultra-high surface area using a chemical activation process | |
| CN111115629A (en) | High-specific-surface-area carbon material based on waste tobacco stems and preparation method and application thereof | |
| WO2015106720A1 (en) | Method for producing super activated charcoal from biomass power plant ash | |
| CN111318254B (en) | Preparation method of high-efficiency regenerated activated carbon | |
| CN108455603B (en) | Mesoporous-rich biochar and preparation method thereof | |
| CN108128773B (en) | Method for preparing electrode carbon material for electrochemical capacitor by using peanut shells | |
| CN112973625B (en) | Lignin-based carbon nanotube and preparation method and application thereof | |
| CN110935280A (en) | Nitrogen-doped mesoporous bamboo-based biochar and application thereof | |
| CN112225216A (en) | Medium-micropore lignin-based activated carbon and preparation method thereof | |
| CN114804100B (en) | Porous carbon with ultrahigh specific surface area and preparation method thereof | |
| CN114023980B (en) | Preparation method of nitrogen-doped porous carbon material based on furfural residues and electrocatalytic oxygen reduction performance of nitrogen-doped porous carbon material | |
| CN113213480B (en) | Method for preparing bamboo activated carbon by one-step method | |
| CN111206165A (en) | Preparation method of doped porous carbon-based composite material | |
| CN113908811A (en) | Preparation method of biomass charcoal material for removing phosphorus from sewage | |
| KR20110010491A (en) | Method for producing activated carbons using sewage sludge | |
| CN114538408A (en) | Method for preparing high electrocatalytic activity biochar through micro-aerobic pyrolysis | |
| CN110790256B (en) | Method for simultaneously preparing carbon quantum dots and porous carbon by one-pot method | |
| CN114956040B (en) | Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application | |
| CN112691666A (en) | Amorphous iron oxyhydroxide-biochar composite material and preparation method thereof | |
| CN111908443A (en) | Preparation method of self-doped porous carbon | |
| CN115497749B (en) | Tobacco stem-based porous carbon material, preparation method thereof and application thereof in super capacitor | |
| CN109158083B (en) | Preparation method and application of biomass-based carbon material | |
| CN114426275A (en) | Method for preparing super activated carbon by using traditional Chinese medicine residues, product and application thereof | |
| CN108298535B (en) | Continuous production method of sargassum horneri mesoporous activated carbon |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |