CN114426275A - Method for preparing super activated carbon by using traditional Chinese medicine residues, product and application thereof - Google Patents
Method for preparing super activated carbon by using traditional Chinese medicine residues, product and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000003814 drug Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 35
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- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B01J35/618—
-
- B01J35/635—
-
- B01J35/638—
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
Abstract
The invention discloses a method for preparing super activated carbon by using traditional Chinese medicine residues, which comprises the following steps: s1, adding the Chinese medicine residues, urea and water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction in the hydrothermal reaction kettle, and filtering and drying a reaction product to obtain a nitrogen-doped hydrothermal carbon precursor; s2, mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, carbonizing in an inert gas atmosphere to realize activation of the nitrogen-doped hydrothermal carbon precursor, sequentially and fully washing the activated product with dilute hydrochloric acid and deionized water to neutrality, and drying to obtain the nitrogen-doped super activated carbon. The invention also discloses a corresponding product and application. The invention fully utilizes the residual waste of the traditional Chinese medicine residue, utilizes KOH activation to obtain the super activated carbon with ultra-large specific surface area and concentrated pores, not only solves the problem of traditional Chinese medicine residue treatment, but also has wide application of the super activated carbon, and can be used as an adsorbent and a capacitor electrode.
Description
Technical Field
The invention belongs to the technical field of harmless treatment of solid waste of traditional Chinese medicines, and particularly relates to a method for preparing super activated carbon by using traditional Chinese medicine residues, and a product and application thereof.
Background
The Chinese medicine culture has a long history of thousands of years, and the Chinese medicine culture is very rich in the background. With the progress of modern medicine, Chinese people and even western medicine pay more and more attention to traditional Chinese medicines. The traditional Chinese medicine residues are solid wastes in the industrialization process of traditional Chinese medicine resources, the annual discharge amount of the traditional Chinese medicine residues in China reaches thousands of tons, along with the prosperity of the traditional Chinese medicine industry, no good solution is always available for the treatment of the traditional Chinese medicine residues, and a great problem is formed.
The traditional Chinese medicine residues are generally wet materials, are not easy to treat after long-term stacking, are easy to rot, have smelly taste, are more serious in summer and cause great pollution to the environment. The existing herb residue treatment mode is extensive, and the herb residue is generally treated by stacking, burying, burning and the like, so that the environment is polluted and land is occupied. However, the Chinese medicine dregs are various in variety and rich in nutrition, contain organic matters such as cellulose and protein and some inorganic matters, are a biological resource which is not fully utilized, and have wide development prospect. Therefore, the resource utilization and the harmless treatment of the Chinese medicine residues are realized, the environment can be protected, and the resource utilization rate can be improved.
With the proposal of the double-carbon target, the carbon dioxide emission reduction is an urgent problem, and the preparation of the activated carbon from the traditional Chinese medicine residues is a good solution. Conventional activated carbon has not been able to meet special requirements in various fields, and thus super activated carbon has been produced. The super activated carbon prepared from the Chinese medicine residues is more and more concerned due to the huge specific surface area and excellent adsorption performance.
In the traditional process, high-temperature carbonization is usually adopted, but the hydrothermal carbonization method adopted in the invention is suitable for carbonization of biomass with high water content, so that additional drying of the Chinese herb residue raw material is not needed, the hydrothermal method mainly adopts medium-low temperature liquid phase control and is simple in process, and a product with complete crystal form, uniform particle size distribution and good dispersibility can be obtained without high-temperature treatment, so that the energy consumption is relatively reduced; the closed condition of the hydrothermal synthesis is beneficial to carrying out toxic reaction systems which are harmful to human health, and the environmental pollution is reduced as much as possible. The reaction and the crystal growth can be effectively controlled in the hydrothermal process by changing factors such as reaction temperature, pressure, reaction time and the like, which is particularly critical, the hydrothermal temperature is a main parameter influencing the physicochemical property of the hydrothermal carbon, and the controllability of the hydrothermal carbonization method provides possibility for finding the optimal reaction conditions of different herb residue materials.
But the specific surface area of the hydrothermal carbon is basically less than 50m2Per g, even less than that of common activated carbon (generally at 300 m)2/g～1000m2In terms of/g, it is not sufficient to stay only in the hydrothermal charcoal as a product, and the original process flow of the hydrothermal charcoal should be improved.
Disclosure of Invention
Aiming at one or more of the defects or the improvement requirements in the prior art, the invention provides a method for preparing super activated carbon by using traditional Chinese medicine residues, which fully utilizes the residual waste materials of the traditional Chinese medicine residues, obtains the super activated carbon with an ultra-large specific surface area and concentrated pores by using KOH activation, not only solves the problem of treatment of the traditional Chinese medicine residues, but also has wide application, can be used as an adsorbent and can be used as a capacitor electrode.
In order to achieve the above objects, according to a first aspect of the present invention, there is provided a method for preparing super activated carbon using herb residues, comprising the steps of:
s1, mixing water and urea serving as a nitrogen source according to a certain proportion to prepare a urea solution, adding the traditional Chinese medicine residues into the urea solution, uniformly mixing, carrying out hydrothermal reaction in an inert gas atmosphere, and filtering and drying a reaction product to obtain a nitrogen-doped hydrothermal carbon precursor;
s2, mixing the nitrogen-doped hydrothermal carbon precursor with KOH according to a proportion, carbonizing the mixture in an inert gas atmosphere to activate the nitrogen-doped hydrothermal carbon precursor, fully washing the activated product with dilute hydrochloric acid and deionized water in sequence, and drying to obtain the nitrogen-doped super activated carbon.
As a further improvement of the invention, the traditional Chinese medicine composition comprises a single traditional Chinese medicine prescription of rhizomes or a traditional Chinese medicine compound taking rhizomes as a main part.
As a further improvement of the invention, the mass ratio of the urea to the traditional Chinese medicine residues to the water is 15: (11-13): (105-110).
As a further improvement of the invention, the traditional Chinese medicine residues are ground into granules in advance and sieved by a sieve of 30-50 meshes.
As a further improvement of the invention, in step S1, the temperature of the hydrothermal reaction is 200-300 ℃, the reaction time is 90-150 min, the reaction pressure is the self-pressure, and the stirring speed is 200-300 rpm.
As a further improvement of the invention, in step S1, the drying temperature is 80-105 ℃, and the drying time is 8-10 h.
As a further improvement of the present invention, in step S2, the mass ratio of the nitrogen-doped hydrothermal carbon precursor to KOH is 1: 2-1: 3.
as a further improvement of the invention, in step S2, the activation temperature is 600-800 ℃, the activation time is 90-150 min, and the inert gas atmosphere is N2And (4) atmosphere.
As a further improvement of the present invention, in step S2, the dilute hydrochloric acid is preferably hydrochloric acid with a mass fraction of 10%.
As a further improvement of the invention, in step S2, the drying temperature is 80-105 ℃, and the drying time is 8-10 h.
According to a second aspect of the invention, the super activated carbon prepared by using the traditional Chinese medicine residues is provided, and is prepared by adopting the method.
According to a third aspect of the invention, the application of the super activated carbon prepared by using the herb residue as an industrial adsorbent, an electrode of a super capacitor or a catalyst is provided.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the method for preparing the super-activated carbon by using the traditional Chinese medicine residues, the doping of the urea is mainly used for providing a nitrogen source, and different nitrogen substances such as pyridine nitrogen, pyrrole nitrogen and the like in the urea can provide alkaline adsorption sites and improve the polarity of the whole carbon skeleton, thereby being beneficial to CO2And the like. In addition, the residual urea decomposes at high temperature to form NH3And gas can promote the further promotion of the porous carbon material pore structure.
(2) According to the method for preparing the super activated carbon by using the traditional Chinese medicine residues, cellulose, hemicellulose and partial lignin can be degraded through hydrothermal carbonization treatment, and lignin-like hydrothermal carbon with a higher heat value is formed through dehydration polymerization, aldol condensation and other complex reactions and aromatization.
(3) The method for preparing the super activated carbon by using the traditional Chinese medicine residues adopts the KOH activation method to prepare the activated carbon with large specific surface area, and avoids ZnCl2In the activation process, ZnCl2Is volatile at high temperature and can pollute the environment.
(4) The method for preparing the super activated carbon by using the traditional Chinese medicine residues has the advantages that the obtained super activated carbon has high nitrogen content and porosity, and can treat CO2Has high selectivity and is suitable for industrial CO2In connection with the examples, the superactive carbon obtained was demonstrated to be CO2The adsorption capacity of the activated carbon is higher than that of the existing industrial activated carbon.
(5) According to the method for preparing the super activated carbon by using the traditional Chinese medicine residues, the obtained super activated carbon has good electrochemical performance and is suitable for being used as a raw material for preparing a super capacitor.
(6) The method for preparing the super activated carbon by using the traditional Chinese medicine residues solves the problem of resource utilization of a large amount of traditional Chinese medicine residue waste, has low cost of raw materials and simple preparation process, can realize large-scale treatment of the solid waste of the traditional Chinese medicine residues, is easy to popularize and apply, and has large industrial demand and better prospect.
Drawings
FIG. 1 is a pore volume and pore diameter distribution diagram of a herb residue-based porous carbon according to example 1 of the present invention;
FIG. 2 is a pore volume and pore diameter distribution diagram of the herb residue-based porous carbon of example 3 of the present invention;
FIG. 3 is an electron microscope scanning image of the herb residue-based porous carbon of example 1 of the present invention;
FIG. 4 is an electron microscope scanning image of the herb residue-based porous carbon of example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for preparing super activated carbon by using traditional Chinese medicine residues, which comprises the following steps:
(1) adding the traditional Chinese medicine residues, urea and water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction in the hydrothermal reaction kettle, and filtering and drying a reaction product to obtain a nitrogen-doped hydrothermal carbon precursor;
(2) and mixing the nitrogen-doped hydrothermal carbon precursor with KOH according to a ratio, carbonizing in an inert gas atmosphere to activate the nitrogen-doped hydrothermal carbon precursor, fully washing an activated product with dilute hydrochloric acid and deionized water in sequence, and drying to obtain the nitrogen-doped super activated carbon.
In the step (1), the traditional Chinese medicine residues are plant traditional Chinese medicines, and comprise single traditional Chinese medicines of rhizomes or traditional Chinese medicine compounds mainly comprising rhizomes, such as radix isatidis, liquorice, sargentgloryvine stem and the like, and the mass ratio of urea to the traditional Chinese medicine residues to water is 15: (11-13): (105-110); the urea is used as a nitrogen source, nitrogen doping is beneficial to improving the specific surface area and further improving the adsorption capacity, and the urea is an organic compound consisting of carbon, nitrogen, oxygen and hydrogen, is easy to obtain, does not contain other impurities and does not generate other adverse effects.
The traditional Chinese medicine residues are ground into particles and sieved by a sieve with 30-50 meshes, so that the traditional Chinese medicine residues are in full contact with the hydrothermal solution to achieve complete reaction.
Further, in the step (1), the hydrothermal reaction is preferably carried out in a high-temperature high-pressure reaction kettle, the temperature of the hydrothermal reaction is 200-300 ℃, the reaction pressure is autogenous pressure, the reaction time is 90-150 min, and the stirring speed is 200-300 rpm. The reaction temperature and the reaction time of the hydrothermal carbonization are determined on the basis of an experiment while reducing energy consumption and ensuring full carbonization of the traditional Chinese medicine residue raw material, and under the reaction conditions, the pore structure of the hydrothermal carbon precursor can be basically formed. Stirring is carried out to ensure that the Chinese medicine residue is fully contacted with the hydrothermal solution to achieve complete reaction, and no special requirement is imposed on the speed as long as the solution can be stirred, and the stirring speed is preferably 200-300 rpm. In addition, in the hydrothermal reaction, the gas atmosphere is not particularly required.
In the step (2), the mass ratio of the nitrogen-doped hydrothermal carbon precursor to KOH is 1: 2-1: 3, activating the hydrothermal carbon precursor in a tubular furnace preferably, wherein the activation temperature is 600-800 ℃, the activation time is 90-150 min, and the activation atmosphere is N2And sequentially washing the activated product with dilute hydrochloric acid and deionized water, fully washing until the product is neutral, and then drying at the temperature of 80-105 ℃ for 8-10 h. The hydrothermal carbon precursor can be further carbonized by adopting the high temperature of 600-800 ℃, certain gas can be released by the decomposition of oxygen-containing functional groups and unstable components along with the increase of the activation temperature, so that the pore structure of the carbon material is developed, but when the activation temperature is too high, a large number of cracks are generated inside the carbon material due to the influence of thermal shrinkage, and then internal micropores collapse is caused, and on the contrary, the hydrothermal carbon precursor has the defect thatA reduction in specific surface area and a reduction in adsorption capacity may be caused. The reaction time is sufficient, the energy consumption is reduced, and the reaction is fully carried out. In addition, the drying temperature is a temperature range in which moisture can be sufficiently evaporated, and the drying time needs to ensure that the drying is sufficiently carried out.
In a preferred embodiment, in the step (2), the temperature is raised to 600-800 ℃ at the speed of 3.4-3.6 ℃/min, the temperature is kept for 90-150 min, and N in the modification and activation process2The flow rate of the atmosphere gas is 200 mL/min-300 mL/min. The temperature rise rate of the invention is not particularly limited, but the temperature rise of the tube furnace is not easy to be too fast, firstly, the reaction is not sufficient, secondly, the load on the tube furnace is large, and the energy waste is caused by too slow temperature rise, therefore, the temperature rise rate is preferably 3.4 ℃/min-3.6 ℃/min. N is a radical of2The flow rate of the atmosphere gas has no special requirement, and a certain gas circulation is ensured, preferably 200 mL/min-300 mL/min.
According to the invention, urea is used as a nitrogen source to carry out nitrogen atom doping, and the nitrogen-containing structure of the carbon material can participate and promote an activation reaction, so that the pore structure is improved, and the adsorption performance is optimized. The required porous carbon obtained by chemical activation has the advantages of high yield, low energy consumption, short time and higher product porosity, and the more mature technology has ZnCl2Activation method, KOH activation method. ZnCl2The activated carbon prepared by the activation method without the KOH activation method has large specific surface area and is due to ZnCl2The catalyst is volatile at high temperature and pollutes the environment, so the reaction tail gas needs to be treated, and the KOH activation method is adopted in the invention.
To better understand the preparation process of the present invention, the following examples are provided:
example 1
(1) Adding 15g of granular Chinese medicine residues (sieved by a 40-mesh sieve), 12g of urea and 108g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the medicinal residue is radix Isatidis single formula medicinal residue, hydrothermal reaction temperature in high temperature high pressure reaction kettle is 270 deg.C, reaction time is 120min, reaction pressure is self pressure, stirring speed is 300rpm, drying temperature is 105 deg.C, and drying time is 8 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2g, the hydrothermal carbon precursor is heated to 600 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 120min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 300 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The super activated carbon prepared in this example had a specific surface area of 1266m as measured by a specific surface area measuring instrument2Per g, total pore volume 0.9702cm3/g。
Example 2
(1) Adding 15g of granular Chinese medicine residues (sieved by a 40-mesh sieve), 11g of urea and 105g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the medicinal residue is radix Isatidis single-material residue, hydrothermal reaction temperature in high temperature high pressure reaction kettle is 200 deg.C, reaction time is 150min, reaction pressure is self pressure, stirring speed is 300rpm, drying temperature is 105 deg.C, and drying time is 8 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 3g, the hydrothermal carbon precursor is heated to 700 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 100min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 300 mL/min. The reaction is finishedAnd cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The super activated carbon prepared in this example had a specific surface area of 1748m as measured by a specific surface area measuring instrument2Per g, total pore volume 1.0284cm3/g。
Example 3
(1) Adding 15g of granular Chinese medicine residues (sieved by a 40-mesh sieve), 13g of urea and 110g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the medicinal residue is radix Isatidis single formula medicinal residue, hydrothermal reaction temperature in high temperature high pressure reaction kettle is 300 deg.C, reaction time is 90min, reaction pressure is self pressure, stirring speed is 300rpm, drying temperature is 105 deg.C, and drying time is 8 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2g, the hydrothermal carbon precursor is heated to 800 ℃ at the speed of 3.6 ℃/min in a horizontal tube furnace and is kept for 90min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 300 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The specific surface area of the super activated carbon prepared in the example measured by a specific surface area tester is 2518m2Per g, total pore volume 1.4004cm3/g。
Example 4
(1) Adding 15g of granular Chinese medicine residues (sieved by a 30-mesh sieve), 12g of urea and 108g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the residue is Glycyrrhrizae radix single-component residue, the hydrothermal reaction temperature in the high temperature high pressure reaction kettle is 250 deg.C, the reaction time is 120min, the reaction pressure is self pressure, the stirring speed is 300rpm, the drying temperature is 105 deg.C, and the drying time is 8 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2.5g, the hydrothermal carbon precursor is heated to 600 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 150min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 300 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The super activated carbon prepared in this example had a specific surface area of 1305m measured by a specific surface area meter2(ii)/g, total pore volume 0.733cm3/g。
Example 5
(1) Adding 15g of granular Chinese medicine residues (sieved by a 50-mesh sieve), 12g of urea and 108g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the residue is Glycyrrhrizae radix single-component residue, hydrothermal reaction temperature in high temperature high pressure reaction kettle is 280 deg.C, reaction time is 120min, reaction pressure is self pressure, stirring speed is 300rpm, drying temperature is 105 deg.C, and drying time is 8 h.
(2) Mixing the nitrogen-doped hydrothermal carbon precursor with KOH in proportion, placing the mixture in a tubular furnace to be carbonized in the nitrogen atmosphere to realize the activation of the hydrothermal carbon precursor, fully washing the activated product with dilute hydrochloric acid and deionized water, and drying to obtain the nitrogen-doped hydrothermal carbon precursorMiscellaneous super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2g, the hydrothermal carbon precursor is heated to 700 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 120min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 300 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The specific surface area of the super activated carbon prepared in the example measured by a specific surface area tester is 1996m2(ii)/g, total pore volume of 1.091cm3/g。
Example 6
(1) Adding 15g of granular Chinese medicine residues (sieved by a 50-mesh sieve), 11g of urea and 106g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the residue is Glycyrrhrizae radix single-component residue, the hydrothermal reaction temperature in the high temperature high pressure reaction kettle is 270 deg.C, the reaction time is 120min, the reaction pressure is self pressure, the stirring rate is 200rpm, the drying temperature is 80 deg.C, and the drying time is 10 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2g, the hydrothermal carbon precursor is heated to 800 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 100min, and N is added in the whole reaction process2Under an atmosphere of N2The gas flow rate was 250 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The super activated carbon prepared in this example was,the specific surface area is 978m measured by a specific surface area determinator2(ii)/g, total pore volume of 0.637cm3/g。
Comparative example
(1) Adding 15g of granular Chinese medicine residues (sieved by a 40-mesh sieve) ground into particles and 120g of water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction, and filtering and drying a reaction product to obtain a hydrothermal carbon precursor; wherein the medicinal residue is radix Isatidis single formula medicinal residue, hydrothermal reaction temperature in high temperature high pressure reaction kettle is 270 deg.C, reaction time is 120min, reaction pressure is self pressure, stirring speed is 300rpm, drying temperature is 105 deg.C, and drying time is 8 h.
(2) And mixing the nitrogen-doped hydrothermal carbon precursor and KOH in proportion, placing the mixture in a tubular furnace to be carbonized in a nitrogen atmosphere to realize activation of the hydrothermal carbon precursor, and fully washing and drying an activated product by using dilute hydrochloric acid and deionized water to obtain the nitrogen-doped super activated carbon. The mass of the nitrogen-doped hydrothermal carbon precursor is 1g, the mass of KOH is 2g, the hydrothermal carbon precursor is heated to 600 ℃ at the speed of 3.5 ℃/min in a horizontal tube furnace and is kept at the temperature for 120min, and N is added in the whole reaction process2Under the atmosphere, N2The gas flow rate was 300 mL/min. And after the reaction is finished, cooling along with the furnace to obtain a product, soaking and cleaning the activated product for multiple times by using hydrochloric acid with the mass fraction of 10%, fully washing the product by using deionized water until the filtrate is neutral, and finally drying the product at 105 ℃ to obtain the super activated carbon.
The specific surface area of the super activated carbon prepared in the comparative example is 1078m measured by a specific surface area determinator2(iv)/g, total pore volume of 0.5952cm3/g。
Fig. 1 is a NLDET differential-integral log pore volume pore size distribution diagram of a super activated carbon in example 1, fig. 2 is a NLDET differential-integral log pore volume pore size distribution diagram of a super activated carbon in example 3, fig. 3 is an electron microscope scan diagram of the super activated carbon in example 1, and fig. 4 is an electron microscope scan diagram of the super activated carbon in example 3. From the experimental results, the sample obtained by the preparation method has large specific surface area and the best effect can reach 2518m2(ii)/g (fruit)Example 3) with a very rich internal porosity, the best results achieved a total pore volume of 1.4004cm3G (example 3), which has a decisive influence on the performance of the superactive carbon, the increase in the specific surface area and the abundance of internal pores leads to a dramatic increase in the adsorption performance. FIG. 2 is a pore volume pore size distribution diagram of the super activated carbon of example 3, wherein dV/dlogD shows the number of pores at that pore size, and it is evident that the peak is visible<1nm, i.e. the concentration of pores appears as<1nm morphology, obtained by integration, having a pore volume of 0.6649cm below 0.7nm3In the case of the example 1 super activated carbon shown in FIG. 1, the pore volume is less than 0.7nm and 66.6% of the total pore volume, which means that the internal pores are mainly concentrated in micropores having a pore volume of less than 0.7nm, which is advantageous for the improvement of the adsorption performance according to the literature. From the electron microscope scanning images of fig. 3 and fig. 4, it can also be seen that the surface of the super activated carbon has a large number of micropores.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing super activated carbon by using traditional Chinese medicine residues is characterized by comprising the following steps:
s1, adding the Chinese medicine residues, urea and water into a hydrothermal reaction kettle, uniformly mixing, carrying out hydrothermal reaction in the hydrothermal reaction kettle, and filtering and drying a reaction product to obtain a nitrogen-doped hydrothermal carbon precursor;
s2, mixing the nitrogen-doped hydrothermal carbon precursor with KOH according to a proportion, carbonizing the mixture in an inert gas atmosphere to activate the nitrogen-doped hydrothermal carbon precursor, washing the activated product to be neutral by using dilute hydrochloric acid and deionized water in sequence, and drying the washed product to obtain the nitrogen-doped super activated carbon.
2. The method for preparing super activated carbon according to claim 1, wherein the herb residue is a plant-based Chinese herb, and comprises a single root-stem-based Chinese herb or a compound Chinese herb mainly comprising root-stem.
3. The method for preparing super activated carbon by using traditional Chinese medicine residues as claimed in claim 1, wherein the mass ratio of the urea to the traditional Chinese medicine residues to the water is 15: (11-13): (105-110).
4. The method for preparing super activated carbon by using the traditional Chinese medicine residues as claimed in claim 1, wherein the traditional Chinese medicine residues are pre-ground into granules and sieved by a 30-50 mesh sieve.
5. The method for preparing super activated carbon using herb residues according to claim 1, wherein the hydrothermal reaction is performed at a temperature of 200 ℃ to 300 ℃, a reaction time of 90min to 150min, a reaction pressure of the hydrothermal reaction is a self pressure, and a stirring rate is 200rpm to 300rpm in step S1.
6. The method for preparing super activated carbon from traditional Chinese medicine residues according to any one of claims 1 to 5, wherein in the step S2, the mass ratio of the nitrogen-doped hydrothermal carbon precursor to KOH is 1: 2-1: 3.
7. the method for preparing super activated carbon using herb residues according to any one of claims 1 to 5, wherein the activation temperature is 600 ℃ to 800 ℃ and the activation time is 90min to 150min in step S2, and the inert gas atmosphere is N2And (4) atmosphere.
8. The method for preparing super activated carbon using herb residues according to claim 7, wherein the activation temperature is 600 ℃ to 800 ℃ and the activation time is 90min to 150min in step S2.
9. A super activated carbon prepared from herb medicine dregs, which is prepared by the method of any one of claims 1 to 8.
10. Use of the super activated carbon prepared from herb residue according to claim 9 as an industrial adsorbent, an electrode of a super capacitor, or a catalyst.
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