CN114804100B - 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
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- CN114804100B CN114804100B CN202210516527.4A CN202210516527A CN114804100B CN 114804100 B CN114804100 B CN 114804100B CN 202210516527 A CN202210516527 A CN 202210516527A CN 114804100 B CN114804100 B CN 114804100B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 230000004913 activation Effects 0.000 claims description 33
- 241000208125 Nicotiana Species 0.000 claims description 31
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 26
- 238000011282 treatment Methods 0.000 claims description 22
- 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 12
- 239000000843 powder Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229960003975 potassium Drugs 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007833 carbon precursor Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000001508 potassium citrate Substances 0.000 claims description 6
- 229960002635 potassium citrate Drugs 0.000 claims description 6
- 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 6
- 235000011082 potassium citrates Nutrition 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000010355 oscillation Effects 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000002156 adsorbate Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000002131 composite material 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 7
- 230000003213 activating effect Effects 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
- 229920002488 Hemicellulose Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 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
- 239000007789 gas Substances 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005530 etching Methods 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
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- 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 And/g, the specific surface area is high, the porous-mesoporous structure is rich, the mass transfer or reaction of adsorbate molecules is facilitated, and the porous-mesoporous porous-mesoporous composite material has a high application value.
Description
Technical Field
The invention belongs to the field of environmental protection and new energy material preparation, and particularly relates to porous carbon with an ultrahigh specific surface area and a preparation method thereof.
Background
The porous carbon material has the advantages of large specific surface area, developed pore structure, excellent conductivity, stable physicochemical properties and the like, and is widely applied in the fields of environmental protection, energy sources and the like. Research has shown that the specific surface area and pore size structure of porous carbon are the main factors that determine their performance. Generally, the larger the specific surface area is, the larger the internal space of the porous carbon is, and the progress of various physicochemical processes is facilitated, so that the improvement of the specific surface area of the porous carbon is of great significance. On the other hand, the difference of porous carbon pore size structure will also significantly affect its application field, for example, in the adsorption and separation field of volatile organic gases, the number of micropores with a size smaller than 2nm significantly affects the final adsorption amount, since it provides the main adsorption sites; when the electrode is applied to the field of super capacitors, the mesoporous with the size of 2-50 nm is more beneficial to the transmission of ions.
Porous carbon materials are available in a wide variety of sources, and theoretically any carbonaceous material can be used to produce porous carbon. China is a traditional agricultural large country, wherein the planting amount of tobacco is in the first place in the world. In the tobacco processing process, a large amount of tobacco waste (tobacco stems) is generated each year, and the waste is directly buried or incinerated, so that the comprehensive utilization rate is low, and meanwhile, the pollution is easy to cause. Notably, the tobacco stems contain significant amounts of cellulose, hemicellulose, and lignin, while also containing small amounts of pectin, protein, and water-soluble materials.
Therefore, it is of great practical value to provide a method for converting tobacco stems into porous carbon with higher added value and wider application. The method for converting biomass raw materials into carbon materials mainly adopts high-temperature activation. 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 activating gas, the activation temperature is generally higher than 900 ℃, the preparation cost is lower, 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 an activating agent (the activation temperature is generally higher than 500 ℃), and the carbon sheet is etched by metal or metal compound generated by chemical reaction with a carbon source to form pores, so that the prepared porous carbon has higher surface area but also generally does not exceed 2500m 2 And/g. Meanwhile, the activating agents used in the activating method are all porous structures formed by etching the carbon skeleton at high temperature, so that the activated porous carbon has low yield and is not beneficial to large-scale production.
Disclosure of Invention
In order to overcome the defects of the prior art, the inventionAims to provide the porous carbon with the ultrahigh specific surface area and the preparation method thereof, and the specific surface area of the porous carbon reaches 2775-3608 m 2 The preparation method provided by the invention is simple, controllable and high in yield.
In order to achieve the above purpose, the present 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 immersing tobacco stems in hydrochloric acid solution, washing, drying and crushing to obtain tobacco stem powder, then placing the tobacco stem powder in solution containing zinc chloride and ethylenediamine, carrying out hydrothermal treatment to obtain a carbon precursor, carbonizing the carbon precursor to obtain a carbonized product, finally mixing the carbonized product with potassium-containing organic salt, carrying out activation treatment, and carrying out acid washing and drying on the obtained activated product to obtain porous carbon.
In a preferred scheme, the tobacco stems are soaked in hydrochloric acid solution for 24-48 h after being stirred, the hydrochloric acid solution is replaced every 6-12 h, 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 which start to crack at a lower temperature (about 200 ℃) to generate a large amount of tar, and the blockage is easy to form after condensation.
Further preferably, the solid-liquid mass volume ratio of the tobacco stems to the hydrochloric acid solution is 50g:500 mL-1500 mL.
Preferably, the mesh number of the tobacco stalk powder is less than 200 mesh.
In a preferred scheme, tobacco stalk powder is placed in a solution containing zinc chloride and ethylenediamine, and is subjected to ultrasonic vibration for 1-3 hours, and then transferred into an autoclave for hydrothermal treatment.
In a preferred scheme, the solution containing zinc chloride and ethylenediamine is prepared by dissolving zinc chloride and ethylenediamine in water, wherein the solid-liquid mass volume ratio of the zinc chloride to the water is 4g: 80-160 mL, wherein the volume ratio of ethylenediamine to water is 5: 80-160.
According to the invention, the tobacco stem powder treated by hydrochloric acid is placed in a solution containing zinc chloride and ethylenediamine for hydrothermal treatment, on one hand, zinc ions react with oxygen-containing groups in raw materials, partial C-O bonds are broken, the carbon content is improved, and on the other hand, nitrogen atoms in ethylenediamine are introduced into a carbon skeleton, so that defects are caused to the carbon skeleton, the porous structure is facilitated to be generated, the specific surface area is improved, and the performance of the obtained material in the application fields of adsorption, electrochemistry, catalysis and the like can be improved.
In the actual exploration process, the inventor also tries to introduce nitrogen atoms into a carbon skeleton and a large amount of nitrogen-containing materials such as urea, melamine and the like, but the final effect is far smaller than that of adopting ethylenediamine.
In a preferred scheme, the mass ratio of the tobacco stalk powder to the zinc chloride is 1:1 to 3.
In a preferred scheme, the temperature of the hydrothermal treatment is 180-200 ℃, and the time of the hydrothermal treatment is 8-12 h.
In a preferred 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 heating rate is 3-10 ℃/min.
The inventor finds that the carbonization treatment is firstly carried out at 400-500 ℃ and then the activation treatment is carried out, so that the carbon content can be further improved, the subsequent activation efficiency is improved, and the specific surface area is increased.
Further preferably, the protective atmosphere is selected from nitrogen and/or argon.
In a preferred scheme, the flow rate of the protective atmosphere is 50-100 mL/min in the carbonization treatment process.
Preferably, the potassium-containing organic salt 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 activator, and the potassium citrate is used as an organic salt, so that not only can rich potassium elements be provided, but also a synergistic activation effect with zinc chloride can be generated to generate rich pore structures, and the yield of porous carbon can be improved by containing an organic part.
Preferably, the activation treatment is carried out under 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 rising rate is 3-10 ℃/min.
Further preferably, the protective atmosphere is selected from nitrogen and/or argon.
In the preferred scheme, the activated product is placed in hydrochloric acid solution for acid washing, then deionized water is used for washing to neutrality, and then the porous carbon material is obtained after drying, 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 hours.
The invention also provides the porous carbon prepared by the preparation method.
The porous carbon has a micropore-mesopore structure.
The specific surface area of the porous carbon is 2775-3608 m 2 Preferably 3283 to 3608m 2 /g。
The porous carbon prepared by the method of the invention has a specific surface area of 2775-3608 m measured by low-temperature nitrogen adsorption (the implementation 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 carbon sources and as a renewable waste, the tobacco stems are abundant in sources and low in cost, and the method is suitable for large-scale popularization and application.
2. The technical scheme of the invention uses a novel method of hydrochloric acid soaking and zinc salt water heating to treat biological raw materials, can efficiently remove impurities, improve the structure and properties of products, reduce tar generation, and is beneficial to subsequent carbonization and activation. Specific: firstly, the mineral content of K, mg, ca and the like in the raw materials can be effectively reduced by soaking with hydrochloric acid, the ash content is reduced, and on the other hand, part of crosslinking structures of hemicellulose, lignin and the like can be removed on the basis of retaining a framework. And 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 introduced into a carbon skeleton, and the porous carbon with the ultrahigh specific surface area is obtained through the synergistic effect of the process.
3. The technical scheme of the invention adopts potassium-containing organic salt (potassium citrate) as a novel activator, which not only contains a large amount of potassium elements, but also generates synergistic activation with zinc chloride to generate rich pore structures, and contains organic parts to improve the yield of porous carbon.
4. The porous carbon prepared by the technical proposal of the invention has the ultra-high 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 structure, 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 pore size of the mesopores is gradually enlarged from 2.7nm to about 4nm, so that the application scene of the porous carbon prepared by the technical scheme of the invention is widened.
Drawings
FIG. 1 is a graph showing isothermal adsorption of nitrogen in accordance with an embodiment of the present invention.
FIG. 2 is a graph showing pore size distribution according to an embodiment of the present invention.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the scope of the claims.
Example 1
The method is characterized in that agricultural waste tobacco stems in a cigarette factory are selected as raw materials, and the raw materials are carbonized, activated, acidic and dried to obtain the tobacco stem.
1) The biological raw material is pretreated. 50g of tobacco stalk material was added to 500mL of hydrogen chloride solution (0.5 mol L) -1 ) The fresh solution was changed every 12 hours after soaking for 48 hours with sufficient agitation. The washed and dried raw material was pulverized (200 mesh) using a pulverizer. Adding 4g of tobacco stalk powder into deionized water (80 mL) containing 4g of zinc chloride and 5mL of ethylenediamine, placing in an ultrasonic environment, sufficiently oscillating for 2 hours, transferring to a high-pressure reaction kettle, performing hydrothermal treatment at 200 ℃ for 10 hours, naturally cooling, cleaning and drying to obtain a pretreated carbon precursor.
2) And (5) carbonizing treatment. And (3) placing a carbon precursor with a certain mass into a tube furnace, heating to a corresponding temperature at a certain heating rate under an inert gas atmosphere, preserving heat for a period of time, and naturally cooling to obtain a carbonized product.
2) And (5) carbonizing treatment. And (3) placing the carbon precursor in a tube furnace, heating to 450 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere (60 mL/min), preserving heat for one hour, and naturally cooling to obtain a carbonized product.
3) And (5) activating treatment. Uniformly mixing the carbonized product and potassium citrate with a certain mass ratio (the mass ratio is 1:2), placing the mixture in a tube furnace, heating to 750 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere (60 mL/min), preserving heat for one hour, and naturally cooling to obtain an activated product.
4) Acid washing and drying. And (3) placing the activated product in a sufficient amount of 5% dilute hydrochloric acid for pickling for a certain time, filtering, washing with deionized water until the filtrate is neutral, and drying to obtain the porous carbon material with the ultrahigh specific surface area, which is denoted as SAC-1.
Example 2
The only difference from example 1 is the activation temperature. In example 2, the activation temperature was 800℃to give a porous carbon designated SAC-2.
Example 3
The only difference from example 1 is the activation temperature. In example 3, the activation temperature was 850℃and SAC-3 was obtained as a porous carbon.
Example 4
The only difference from example 1 is the activation temperature. In example 4, the activation temperature was 900℃to give a porous carbon designated SAC-4.
The porous carbon (SAC-1, SAC-2, SAC-3, SAC-4) in examples 1 to 4 was vacuum-treated at 150℃for 6 hours, and then subjected to isothermal adsorption of nitrogen at low temperature by using a JW-BK132Z specific surface area analyzer (manufactured by Beijing micro-high Bo science and technology Co., ltd.) (standard GB/T21650.2, GB/T19587, GB/T21650.3) and the specific surface area was calculated by using a multipoint BET calculation method, and the pore size distribution was calculated by 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 process flow of the preparation process of the porous carbon with the ultrahigh specific surface area is truly effective, and the specific surface areas of the prepared examples SAC-1, SAC-2, SAC-3 and SAC-4 are 2775, 3283, 3608 and 2550m respectively 2 g –1 Higher than most reported porous carbon materials. The decrease in BET surface area at 900 ℃ is mainly due to collapse of the pore structure at very high activation temperatures. The isothermal adsorption curves for nitrogen for all examples are typical type IV, i.e., rise rapidly at relatively low pressure, at p/p0>At 0.45, there is a significant hysteresis loop (see FIG. 1), indicating a rich micro-mesoporous structure. The increase in activation temperature favors the formation of mesopores, which also results in a continued expansion of some of the mesopores, as the activation temperature increases from 750 ℃ to 900 ℃, the mesopore size increases gradually from 2.7nm to about 4nm (see fig. 2), which illustrates that the pore size structure of embodiments of the present invention can be tuned by varying the activation temperature. In particular, SAC-3 exhibits the highest specific surface area and the largest pore volume.
Example 5
The other conditions were the same as in example 3 except that no hydrochloric acid was used to soak the tobacco stem raw material. Experimental results show that large areas appear on the pipe wall in the carbonization processThe tar liquid is measured, and the nitrogen adsorption test shows that the specific surface area is 3059m 2 g –1 Less than example 3.
Example 6
The same conditions as in example 3 were used except that no carbonization treatment was performed. And nitrogen adsorption test shows that the specific surface area is 2433m 2 g –1 Less than example 3.
Example 7
The other conditions were the same as in example 3 except that urea was used instead of ethylenediamine. And nitrogen adsorption test shows that the specific surface area is 3209m 2 g –1 Less than example 3.
Claims (9)
1. A preparation method of porous carbon with ultrahigh specific surface area is characterized by comprising the following steps: soaking tobacco stems in hydrochloric acid solution, washing, drying and crushing to obtain tobacco stem powder, then placing the tobacco stem powder in solution containing zinc chloride and ethylenediamine, performing hydrothermal treatment to obtain a carbon precursor, carbonizing the carbon precursor to obtain a carbonized product, mixing the carbonized product with potassium-containing organic salt, performing activation treatment, and pickling and drying the obtained activated product to obtain porous carbon;
the solution containing zinc chloride and ethylenediamine is prepared by dissolving zinc chloride and ethylenediamine in water, wherein the solid-liquid mass volume ratio of the zinc chloride to the water is 4g: 80-160 mL, wherein the volume ratio of ethylenediamine to water is 5: 80-160;
the carbonization temperature is 400-500 ℃;
the temperature of the activation treatment is 750-900 ℃.
2. The method for preparing porous carbon with ultrahigh specific surface area according to claim 1, wherein: soaking tobacco stems in hydrochloric acid solution for 24-48 h after stirring, 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 The method comprises the steps of carrying out a first treatment on the surface of the The solid-liquid mass volume ratio of the tobacco stems to the hydrochloric acid solution is 50g:500 mL-1500 mL.
3. The method for preparing porous carbon with ultrahigh specific surface area according to claim 1, wherein: the tobacco stalk powder is put into a solution containing zinc chloride and ethylenediamine, ultrasonic oscillation is carried out for 1-3h, and then the tobacco stalk powder is transferred into an autoclave for hydrothermal treatment.
4. The method for preparing porous carbon with ultrahigh specific surface area according to claim 1, wherein:
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.
5. The method for preparing porous carbon with ultrahigh specific surface area according to claim 1, wherein:
the carbonization treatment is carried out in a protective atmosphere, the time of the carbonization treatment is 1-3 hours, and the heating rate is 3-10 ℃/min; in the carbonization treatment process, the flow rate of the protective atmosphere is 50-100 mL/min.
6. The method for preparing porous carbon with ultrahigh 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 potassium-containing organic salt is 1:1 to 4.
7. The method for preparing porous carbon with ultrahigh specific surface area according to claim 1, wherein:
the activation treatment is carried out in a protective atmosphere, the time of the activation treatment is 1-3h, and the heating rate is 3-10 ℃/min.
8. The porous carbon having an ultra-high specific surface area produced by the production method according to any one of claims 1 to 7.
9. A porous carbon having an ultra-high specific surface area as set forth in claim 8, wherein: the porous carbon has a micropore-mesopore structure, and the specific surface area of the porous carbon is 2775-3608 m 2 /g。
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Citations (14)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11219244B2 (en) * | 2014-12-22 | 2022-01-11 | R.J. Reynolds Tobacco Company | Tobacco-derived carbon material |
-
2022
- 2022-05-13 CN CN202210516527.4A patent/CN114804100B/en active Active
Patent Citations (14)
| 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 |
| 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 |
|---|
| Heteroatom-doped porous carbons exhibit superior CO2 capture and CO2/ N2 selectivity: Understanding the contribution of functional groups and pore structure;Xiancheng Ma et al;《Separation and Purification Technology》;第259卷;参见第2.1、3.2节 * |
| In-situ activated ultramicroporous carbon materials derived from waste biomass for CO2 capture and benzene adsorption;Xiancheng Ma et al;《Biomass and Bioenergy》;第158卷;第2.1节 * |
| Thermal conversion of tobacco stem into gaseous products;Chunhao Wang et al;《Journal of Thermal Analysis and Calorimetry》;第137卷;第811-823页 * |
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