CN112551524A - Tobacco stem-based graded porous carbon material and preparation method and application thereof - Google Patents
Tobacco stem-based graded porous carbon material and preparation method and application thereof Download PDFInfo
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- CN112551524A CN112551524A CN202011506897.7A CN202011506897A CN112551524A CN 112551524 A CN112551524 A CN 112551524A CN 202011506897 A CN202011506897 A CN 202011506897A CN 112551524 A CN112551524 A CN 112551524A
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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
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/16—Use of materials for tobacco smoke filters of inorganic materials
- A24D3/163—Carbon
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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
- C01B32/342—Preparation characterised by non-gaseous activating agents
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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
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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Abstract
The invention discloses a tobacco stem-based hierarchical porous carbon material and a preparation method and application thereof. The invention takes the tobacco stems as raw materials, has simple preparation process, low cost and no solvent, and the prepared graded porous carbon has homology with tobacco, large specific surface area, high mesoporous pore channel ratio and large essence adsorption capacity, thereby having application value in the fields of flavoring of cigarette filters and the like.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to a tobacco stem-based graded porous carbon material and a preparation method and application thereof.
Background
China is a large tobacco producing country, and the tobacco production amount per year is about 42 percent of the world. The tobacco stems are byproducts of the tobacco industry, hundreds of thousands of tons of tobacco stem resources are abandoned every year, and the idle and waste of biomass resources are caused. Meanwhile, the improper treatment of the tobacco stems can cause serious environmental pollution. Therefore, how to improve the utilization value of the tobacco raw material and promote the high-value utilization of the tobacco stalk biomass resource is a difficult problem to be solved by the tobacco industry.
The hierarchical porous carbon has special pore size distribution of micropore-mesopore-macropore and developed porosity, can promote the rapid transfer of ions in pore channels, has high desalination capacity and rapid desalination rate, and has potential application in the fields of capacitance desalination and the like. The development of the hierarchical porous carbon material with micropore-mesopore-macropore three-dimensional through can greatly improve the mass transfer of reactants/products and further promote the electrochemical reaction process. However, the existing method for preparing the graded porous carbon by using the tobacco stems as raw materials has the problems that the tobacco stems are difficult to dissolve or disperse in a solvent, and an activating agent cannot be in full contact with the tobacco stems.
In order to solve the problem of difficulty in compounding the tobacco stems and the activating agent, the invention patent CN103121682A discloses a method for preparing the tobacco stem activated carbon with high specific surface area by an impregnation method (5/29/2013). The invention patent CN105175175A discloses (12/23/2015) a method for producing porous carbon by using a tobacco waste hydrothermal method, wherein the method comprises the steps of mixing crushed tobacco waste with water, placing the mixture in a hydrothermal reaction kettle, and reacting to obtain the porous carbon, wherein the specific surface area of a tobacco stem carbon material prepared by the hydrothermal method is small. The invention patent CN105921109A discloses (9/7/2016) porous carbon prepared from tobacco stems, a preparation method and application thereof, wherein the tobacco stems are firstly crushed and then mixed with water for hydrothermal carbon preparationThe chemical reaction, the dried product is activated by an activating agent and then calcined in an inert atmosphere to obtain the tobacco stem-based carbon material, although the specific surface area of the material is improved to a certain extent, the whole process flow is complicated, and the specific surface area of the material is still less than 1000m2(ii) in terms of/g. Therefore, the preparation of graded porous carbon with adjustable pore channels by utilizing tobacco stems still has huge challenges, and a new method for preparing the tobacco stem-based graded porous carbon needs to be provided urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of tobacco stem-based graded porous carbon. The preparation method provided by the invention does not need to use a solvent, and the prepared hierarchical porous carbon has large specific surface area and high mesoporous channel ratio.
The invention further aims to provide the tobacco stem-based graded porous carbon material prepared by the preparation method.
The invention also aims to provide application of the tobacco stem base graded porous carbon material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a tobacco stem-based graded porous carbon material comprises the following steps:
s1, mixing and grinding tobacco stalk powder, carbonate and oxalate to obtain mixed powder; the ratio of the mass of the tobacco stem powder to the mass of the carbonate and the oxalate is 1: (1-6);
s2, placing the mixed powder in an inert atmosphere, and calcining at 400-900 ℃ to obtain the tobacco stem base porous carbon material.
The tobacco stem-based hierarchical porous carbon material is prepared by taking tobacco stems as raw materials, taking carbonate and oxalate as grinding aids and activating agents at the same time and grinding and calcining at high temperature. Under the action of carbonate, oxalate and mechanical force, most of the original structure of the tobacco stems is damaged, and the nano tobacco stem powder can be effectively compounded with a grinding aid and an activating agent. Carbonate and oxalate activators can decompose and produce large amounts of gas at high temperatures compared to conventional activators. Under the heat treatment, the preparation of the graded porous carbon is realized by utilizing the intercalation mechanism and the synergistic action of cracking and cation.
Preferably, in step S1, the tobacco stalk powder has a particle size of 100 to 300 meshes.
More preferably, in step S1, the tobacco stem powder has a particle size of 200 mesh.
Preferably, in step S1, the ratio of the mass of the tobacco stem powder to the mass of the carbonate and oxalate is 1: (1-4). More preferably 1: 2.
preferably, in step S1, the carbonate is one or more of potassium carbonate, calcium carbonate and sodium carbonate.
Preferably, in step S1, the oxalate is one or more of potassium oxalate, calcium oxalate and sodium oxalate.
Preferably, in step S1, the grinding speed is 100 to 500rpm, and the grinding time is 2 to 8 hours.
Preferably, in step S2, the calcination temperature is 600 ℃ to 800 ℃.
A tobacco stem-based graded porous carbon material is obtained by the preparation method.
The specific surface area and the pore volume of the tobacco stem-based graded porous carbon material respectively reach 1800m2G and 1.1cm3The volume per gram (g) and the average pore diameter is 3.5nm, completely meets the performance requirement of the essence adsorption field on the graded porous carbon material, and can be used in the essence adsorption field. Therefore, the application of the tobacco stem-based graded porous carbon material in the field of essence adsorption also should be within the protection scope of the invention.
Preferably, the essence may be one or more of orange oil essence, lily essence, menthol essence or rose essence.
The invention also protects the application of the tobacco stalk-based graded porous carbon material in the field of perfuming cigarette filters.
Compared with the prior art, the invention has the beneficial effects that:
the tobacco stem-based hierarchical porous carbon material is prepared by taking tobacco stems as raw materials, taking carbonate and oxalate as grinding aids and activating agents at the same time and grinding and calcining at high temperature, the preparation process is green and solvent-free, the method is suitable for industrial sustainable production, and the prepared hierarchical porous carbon has large specific surface area and high mesoporous pore ratio and can be used in the fields of essence adsorption and cigarette filter flavoring.
Drawings
Figure 1 is an SEM image of the stem-based graded porous carbon produced in example 1 of the present invention.
Figure 2 is a drawing of nitrogen desorption of the tobacco stem-based graded porous carbon produced in example 1 of the present invention.
FIG. 3 is a pore size distribution diagram of the tobacco stem-based graded porous carbon prepared in example 1 of the present invention.
Detailed Description
In order to more clearly and completely describe the technical scheme of the invention, the invention is further described in detail by the specific embodiments, and it should be understood that the specific embodiments described herein are only used for explaining the invention, and are not used for limiting the invention, and various changes can be made within the scope defined by the claims of the invention.
Example 1
After the tobacco stalk waste is crushed, 200-mesh particles are selected, 5g of tobacco stalk particles, 5g of potassium oxalate and 5g of calcium carbonate are uniformly mixed according to the mass ratio of the tobacco stalk to the mass ratio of carbonate to oxalate of 1:2, and then the mixture is sealed into a ball mill tank. The ball milling time was set to 4 hours and the ball milling speed was set to 200 rpm. After the ball milling is finished, calcining the obtained mixed powder for 2h at 800 ℃ under the protection of nitrogen, and cooling to obtain the tobacco stem-based graded porous carbon material.
Example 2
The preparation method of the cut tobacco stem-based graded porous carbon material described in example 2 is substantially the same as that of example 1 except that the ball milling time is set to 2 hours in example 2.
Example 3
The preparation method of the cut tobacco stem-based graded porous carbon material described in example 3 is substantially the same as that of example 1 except that the ball mill rotation speed is set to 300rpm in example 3.
Example 4
The preparation method of the tobacco stem base graded porous carbon material in the example 4 is basically the same as that in the example 1, except that the carbonate in the example 4 is 1g of sodium carbonate, and the oxalate is 9g of calcium oxalate.
Example 5
The preparation method of the tobacco stem base graded porous carbon material in the example 5 is basically the same as that in the example 1, except that the carbonate in the example 5 is 9g of potassium carbonate, and the oxalate is 1g of sodium oxalate.
Example 6
The preparation method of the tobacco stem-based graded porous carbon material described in example 6 is substantially the same as that of example 1, except that the calcination temperature in example 6 is 700 ℃.
Example 7
After the tobacco stalk waste is crushed, selecting 100-mesh particles, uniformly mixing 5g of tobacco stalk particles, 10g of sodium carbonate and potassium carbonate and 10g of calcium oxalate and sodium oxalate according to the mass ratio of the tobacco stalk to the mass ratio of the carbonate to the mass ratio of the oxalate being 1:4, and sealing the mixture in a ball milling tank. The ball milling time was set to 8h and the ball milling speed was set to 100 rpm. After the ball milling is finished, calcining the obtained mixed powder for 2h at 400 ℃ under the protection of nitrogen, and cooling to obtain the tobacco stem-based graded porous carbon material.
Example 8
After the tobacco stalk waste is crushed, selecting 300-mesh particles, uniformly mixing 5g of tobacco stalk particles, 2.5g of calcium carbonate and 2.5g of potassium oxalate according to the mass ratio of the tobacco stalk to the mass of carbonate and oxalate of 1:1, and sealing the mixture in a ball mill tank. The ball milling time was set to 4 hours and the ball milling speed was set to 500 rpm. After the ball milling is finished, calcining the obtained mixed powder for 2h at 900 ℃ under the protection of nitrogen, and cooling to obtain the tobacco stem-based graded porous carbon material.
Example 9
The preparation method of the tobacco stem-based graded porous carbon material in example 9 is basically the same as that in example 1, except that the ratio of the mass of the tobacco stem to the mass of the carbonate and the oxalate in example 9 is 1:5, the carbonate is 10g of calcium carbonate, and the oxalate is 15g of potassium oxalate.
Example 10
The preparation method of the tobacco stem-based graded porous carbon material in example 10 is basically the same as that in example 1, except that the ratio of the mass of tobacco stems to the mass of carbonate and oxalate in example 10 is 1:6, the carbonate is 15g of calcium carbonate, and the oxalate is 15g of potassium oxalate.
Comparative example 1
Comparative example 1 the carbon material was prepared in substantially the same manner as in example 1 except that potassium oxalate and calcium carbonate were replaced with sodium carbonate, and the mass ratio of tobacco stalks to sodium carbonate was 1: 2.
Comparative example 2
Comparative example 1 the carbon material was prepared in substantially the same manner as in example 1 except that potassium oxalate and calcium carbonate were replaced with potassium oxalate, and the mass ratio of tobacco stems to potassium oxalate was 1: 2.
Characterization and testing
The surface microtopography picture was taken by scanning electron microscope (SEM, Hitachi S-550), as shown in FIG. 1. The nitrogen adsorption and desorption curve and the pore structure data such as the specific surface area, the pore volume and the like are obtained by analysis and test of a full-automatic specific surface area and porosity analyzer (Micromeritics ASAP 2020instrument), a sample is subjected to degassing treatment at 250 ℃ for 12 hours and then is tested, the test results are shown in table 1, and the nitrogen adsorption and desorption curve is shown in fig. 2.
Table 1 shows the performance parameters of the porous carbon materials obtained in examples 1 to 10 and comparative examples 1 to 2.
TABLE 1
As can be seen from Table 1, the tobacco stem-based hierarchical porous carbon material prepared by the method of the invention has a large specific surface area and a high proportion of mesoporous volume, wherein the specific surface area of the tobacco stem-based hierarchical porous carbon material prepared in example 1 is 2100m2The proportion of mesoporous volume is 64.3 percent, which is obviously superior to similar materials.
FIG. 1 is an SEM image of a tobacco stem-based graded porous carbon material prepared in example 1 of the invention. As can be seen from the figure, the prepared tobacco stem-based hierarchical porous carbon material has a remarkable pore channel structure.
Figure 2 is a drawing of nitrogen desorption of the tobacco stem-based graded pore carbon material prepared in example 1 of the present invention. As can be seen from the figure, the tobacco stalk-based hierarchical porous carbon material belongs to type IV desorption and has a developed mesoporous structure.
Fig. 3 is a pore size distribution diagram of the tobacco stem-based hierarchical pore carbon material prepared in example 1 of the present invention, and it can be seen from the diagram that the prepared tobacco stem-based hierarchical pore carbon pore passage has an obvious hierarchical structure.
The flavor adsorption performance of the tobacco stem-based porous carbon material described in example 1 was tested by a static gas phase method. The essence adsorption experiment process is as follows:
weighing 1g of prepared tobacco stem porous carbon sample in a weighing bottle, putting the weighing bottle in a drying oven at 150 ℃ for 12h, removing impurities in an adsorbent, and putting the dried weighing bottle and the adsorbent into a closed container filled with menthol essence. The equilibrium is reached by adsorption for 24h at room temperature. Taking 50mg of sample out of a weighing bottle, putting the sample into a conical flask, adding 50ml of isopropanol serving as an extracting agent into the conical flask, putting the conical flask into a water bath oscillator, controlling the temperature to vibrate at 30 ℃ for 1h, taking 1-2ml of solution out of an injector with a filter, adding the solution into a chromatographic flask, adding the chromatographic flask into an automatic sample injector with a gas chromatograph, detecting, and calculating according to the peak area of essence to obtain the essence content of 473.9mg/g in an adsorption material.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a tobacco stem-based graded porous carbon material is characterized by comprising the following steps:
s1, mixing and grinding tobacco stalk powder, carbonate and oxalate to obtain mixed powder; the ratio of the mass of the tobacco stem powder to the mass of the carbonate and the oxalate is 1: (1-6);
s2, placing the mixed powder in an inert atmosphere, and calcining at 400-900 ℃ to obtain the tobacco stem base porous carbon material.
2. The method for preparing a tobacco stem-based graded porous carbon material according to claim 1, wherein in step S1, the particle size of the tobacco stem powder is 100-300 mesh.
3. The stem-based graded porous carbon material according to claim 1, wherein in step S1, the ratio of the mass of the stem powder to the mass of the carbonate and oxalate is 1: (1-4).
4. The method for preparing a tobacco stem-based graded porous carbon material according to claim 1, wherein in step S1, the carbonate is one or more of potassium carbonate, calcium carbonate and sodium carbonate.
5. The method for preparing a tobacco stem-based graded porous carbon material according to claim 1, wherein in step S1, the oxalate is one or more of potassium oxalate, calcium oxalate and sodium oxalate.
6. The method for preparing a tobacco stem-based graded porous carbon material according to claim 1, wherein in step S1, the grinding speed is 100-500 rpm, and the grinding time is 2-8 h.
7. The method for preparing a tobacco stem-based graded porous carbon material according to claim 1, wherein in step S2, the calcination temperature is 600 ℃ to 800 ℃.
8. A tobacco stem-based graded porous carbon material, which is prepared by the preparation method of any one of claims 1 to 7.
9. The use of the cut stem based graded porous carbon material according to claim 8 in the fields of flavor adsorption and perfuming of cigarette filters.
10. The use of claim 9, wherein the perfume compound is one or more of orange oil perfume, lily essence, menthol perfume or rose perfume.
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| CN116062728A (en) * | 2021-10-30 | 2023-05-05 | 天津师范大学 | Low-temperature, efficient and green preparation method of porous carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111943200A (en) * | 2020-08-21 | 2020-11-17 | 南京林业大学 | Preparation method of tobacco stem porous biochar |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111943200A (en) * | 2020-08-21 | 2020-11-17 | 南京林业大学 | Preparation method of tobacco stem porous biochar |
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| 卢真保 等: ""β-苯乙醇 -活性炭颗粒的制备及其卷烟滤嘴加香效应的研究"", 《山东化工》 * |
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| CN116062728A (en) * | 2021-10-30 | 2023-05-05 | 天津师范大学 | Low-temperature, efficient and green preparation method of porous carbon |
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