CN109735966B - Method for preparing activated carbon fiber with hollow structure from wood fiber - Google Patents
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Abstract
The invention discloses a method for preparing activated carbon fiber by using wood fiber raw material. The wood fiber raw material is made into quantitative paper. Putting the obtained paper into a tube furnace, and heating to 200-300 ℃ under the protection of nitrogenoC, then heating to 400-600 DEG CoAnd C, keeping the temperature for a period of time at the temperature to obtain the carbon fiber. Using phosphoric acid, zinc chloride, ammonium chloride, potassium hydroxide, sodium hydroxide and dipotassium hydrogen phosphate as activating agents to obtain 600-800 parts of carbon fibersoAnd C, carrying out an activation reaction to obtain the activated carbon fiber with a hollow structure. The carbon fiber prepared by the method has the advantages of hollow structure, small aperture and narrow aperture distribution, and can be used as an adsorption material or a catalytic carrier to be applied to the industries of environment, chemical industry, textile industry, military industry and the like.
Description
Technical Field
The invention belongs to the field of activated carbon fiber preparation, and particularly relates to a method for preparing activated carbon fibers with hollow structures by using wood fibers as raw materials.
Background
The active carbon fiber has high specific surface area, good adsorption effect and good microporous structure, so the preparation of the active carbon fiber has become a popular research direction in recent years. An artificial synthetic fiber such as polyacrylonitrile is a precursor for preparing the activated carbon fiber, but the polypropylene fiber is derived from non-renewable fossil resources, and the area of the prepared activated carbon fiber is relatively small. The natural biomass fibers such as cotton fibers, hemp fibers, softwood fibers, hardwood fibers and the like have the advantage of being reproducible, most of the natural fibers have natural hollow structures, and the specific surface area of the activated carbon fibers prepared from the natural biomass fibers is larger than that of the artificially synthesized fibers.
The preparation of the activated carbon fiber mainly comprises carbonization and activation. Wherein the heating rate, the heat preservation time and the flow rate of inert gases (such as nitrogen, argon and the like) have larger influence on the carbonization process. Activation includes physical activation and chemical activation. The chemical activation is generally to fully soak the carbonized fiber in an activating agent (such as potassium hydroxide, zinc chloride and the like) solution with a certain concentration, then to heat to a certain temperature, and then to wash the carbon fiber with a dilute acid solution, and finally the obtained carbon fiber can generate a large amount of pore structures and the specific surface area can be increased.
Various conditions of the carbonization and activation processes, such as temperature rise rate, heat preservation time, inert gas flow rate, the type of the activating agent, the proportion of the activating agent to the ultrapure water and the like, have important influence on properties such as pore distribution, specific surface area, mechanical strength and the like of the prepared activated carbon fiber. Therefore, it is important to explore and optimize each condition.
Disclosure of Invention
The invention aims to prepare the activated carbon fiber with small aperture and narrow aperture distribution and a hollow structure.
The invention is mainly realized by the following technical scheme.
A method for preparing activated carbon fiber with a hollow structure from wood fiber comprises the following steps:
(1) soaking wood fibers in distilled water for 12-48 h, defibering the soaked paper pulp, and making into paper with a quantitative weight of 60-140 g/m2The paper is dried for 48-96 hours at normal temperature;
(2) putting the paper obtained in the step (1) into a tube furnace for carbonization treatment in two stages, wherein in the first stage, the temperature is raised to 200-300 ℃ under the protection of nitrogenoC; in the second stage, continuously introducing nitrogen, and then raising the temperature of the tubular furnace in the first stage to 400-600 ℃ at a temperature rise rate different from that in the first stageoC, and is in the range of 400 to 600oKeeping the temperature at the temperature of C for 30-180 min, and then cooling to 20-30 DEG CoC, obtaining carbon fiber;
(3) the carbon fiber obtained in the step (2) is 600-800%oC performing activationAnd activating for 60-180 min to obtain the activated carbon fiber with the hollow structure.
Preferably, the mass-volume ratio of the wood fiber to the distilled water in the step (1) is 0.7-2.67: 100 g/mL.
Preferably, the temperature rise rate of the first stage in the step (2) is 10-20oC/min。
Preferably, the temperature rise rate of the second stage in the step (2) is 1-10oC/min。
Preferably, the activation in step (3) comprises the steps of:
1) uniformly mixing an activating agent and water in a mass ratio of 0.7-1: 1 to obtain a mixed solution;
2) soaking the carbon fiber in the step (2) in the mixed solution for 6-24 hours, and placing the soaked carbon fiber in a tubular furnace;
3) heating to 600-800 deg.C under nitrogen or argon atmosphereoC, after activating for 60-180 min, cooling to 20-100 DEGoC, soaking in 1-10% hydrochloric acid solution for 0.5-12 h at room temperature, and then soaking with 60-80% hydrochloric acid solutionoWashing the C with distilled water to neutrality at 40-105%oAnd drying under C to obtain the activated carbon fiber.
Preferably, the activating agent in step 1) comprises at least one of phosphoric acid, zinc chloride, ammonium chloride, potassium hydroxide, sodium hydroxide, dipotassium hydrogen phosphate.
Preferably, the wood fibers comprise at least one of softwood pulp, hardwood pulp, hemp pulp, cotton linters.
The preparation method and the obtained product have the following advantages:
1. compared with the existing preparation of the activated carbon fiber, the preparation method has the advantages of wide sources and lower cost, and has wide application prospects in the fields of chemical industry, environmental protection and the like.
2. The process for preparing the activated carbon fiber is simple, does not need complex equipment and is easy for industrial production.
3. The preparation method provided by the invention has the advantages that the carbonization process is divided into two stages, the pore channel of the cellulose is not damaged, the cell cavity of the fibril is kept, and the prepared activated carbon fiber has the characteristics of good hollow structure, small pore diameter, narrow pore diameter distribution and more micropores.
4. The prepared active carbon with a hollow structure can be used as an adsorption material or a catalytic carrier material and has potential application prospects in the industries of environment, chemical industry, textile industry, military industry and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the activated carbon fiber prepared in the example.
Detailed Description
The following structural embodiments describe the present invention in further detail, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Weighing 1.4 g of hemp pulp (the hemp pulp is unbleached sisal hemp pulp), soaking in 200 mL of distilled water for 24h, defibering the soaked pulp board, and making into paper with quantitative volume of 140g/m2The paper is dried for 72 hours at normal temperature;
(2) the paper obtained is placed in a tube furnace under nitrogen protection at 10oHeating to 250 ℃ at a temperature rise rate of C/minoC, then by 5oThe temperature rise rate of C/min is from 250oC heating to 400oC, and is at 400oKeeping the temperature for 120 min under C, and then cooling to 20oAnd C, obtaining the carbon fiber.
(3) Uniformly mixing potassium hydroxide and ultrapure water according to the mass ratio of 0.9:1 to obtain a mixed solution, soaking carbon fibers in the mixed solution for 12 hours, and then soaking the soaked carbon fibers at 750 ℃ in a nitrogen atmosphereoC, activating in a tube furnace for 130 min, cooling to 20oC, soaking in 1 percent hydrochloric acid solution for 0.5 h at room temperature, and then soaking in 65 percent hydrochloric acid solutionoWashing with distilled water of C to neutrality at 40oAnd drying under C to obtain the activated carbon fiber with a hollow structure.
The BET specific surface area of the prepared activated carbon fiber is 1200 m2Per g, wherein the specific surface area of the micropores is 890 m2(ii)/g; the pore size distribution is 1.70-3.50 nm, wherein the micropores account for 75%, and the obtained activated carbon fiber keeps a hollow structure, as shown in figure 1. On the premise that the steps (1) and (3) are not changed, the step (2) is changed into the step of placing the obtained paper into a tube furnace, and the obtained paper is placed in a nitrogen protective atmosphere at a temperature of 10 DEGoC/min heating rate 400oC, preserving the heat for 120 min to obtain the carbon fiber. The BET specific surface area of the finally obtained activated carbon fiber is 900 m2Per g, wherein the specific surface area of the micropores is 300 m2(ii)/g; the pore size distribution is 2.70-5.50 nm, wherein the micropores account for 40%, and the obtained activated carbon fiber can not keep a hollow structure.
Example 2
(1) Weighing 10 g hardwood pulp (the hardwood pulp is bleached eucalyptus pulp), soaking in 500 mL distilled water for 24h, defibering the soaked pulp, and making into paper with a quantitative of 100g/m2The paper is dried for 48 hours at normal temperature;
(2) the obtained paper is put into a tube furnace and is protected by nitrogen gas with the protection of 15oHeating to 200 ℃ at a temperature rise rate of C/minoC, then by 6oThe temperature rise rate of C/min is from 200oC heating to 500oC, and is 500oKeeping the temperature for 30 min under C, and then cooling to 30 DEGoAnd C, obtaining the carbon fiber.
(3) Uniformly mixing potassium hydroxide and ultrapure water according to the mass ratio of 0.7:1 to obtain a mixed solution, soaking carbon fibers in the mixed solution for 6 hours, and then soaking the soaked carbon fibers at 700 ℃ in an argon atmosphereoC, activating in a tube furnace for 120 min, cooling to 30%oC, soaking in 1 percent hydrochloric acid solution for 0.5 h at room temperature, and then soaking with 60 percent hydrochloric acid solutionoWashing with distilled water of C to neutrality at 60oAnd drying under C to obtain the activated carbon fiber with a hollow structure.
The BET specific surface area of the prepared activated carbon fiber is 1125 m2Per g, wherein the specific surface area of the micropores is 862 m2(ii)/g; the pore size distribution is 1.91-3.75 nm, wherein the micropores account for 68%, and the obtained activated carbon fiber keeps a hollow structure, as shown in figure 1.
Example 3
(1) Weighing 1.4 g of hemp pulp (the hemp pulp is unbleached sisal hemp pulp), soaking in 200 mL of distilled water for 12h, defibering the soaked paper pulp, and making into paper with quantitative weight of 140g/m2The paper is dried for 96 hours at normal temperature;
(2) the paper obtained is placed in a tube furnace under nitrogen protection at 10oHeating to 250 ℃ at a temperature rise rate of C/minoC, then with 1oThe temperature rise rate of C/min is from 250oC heating to 400oC, and is at 400oKeeping the temperature for 90 min under C, and then cooling to 25oAnd C, obtaining the carbon fiber.
(3) Uniformly mixing potassium hydroxide and ultrapure water according to the mass ratio of 0.8:1 to obtain a mixed solution, soaking carbon fibers in the mixed solution for 24 hours, and then soaking the soaked carbon fibers in a nitrogen atmosphere at 800 DEGoC, activating in a tube furnace for 180min, cooling to 50%oC, soaking the mixture in 10 percent hydrochloric acid solution for 6 hours at room temperature, and then soaking the mixture in 80 percent hydrochloric acid solutionoWashing with distilled water of C to neutrality at 105oAnd drying under C to obtain the activated carbon fiber with a hollow structure.
The BET specific surface area of the prepared activated carbon fiber is 1256 m2Per g, wherein the specific surface area of the micropores is 918 m2(ii)/g; the pore size distribution is 1.50-3.55 nm, wherein the micropores account for 80%, and the obtained activated carbon fiber keeps a hollow structure, as shown in figure 1.
Example 4
(1) Weighing 8 g of hardwood pulp (the hardwood pulp is bleached eucalyptus pulp), soaking in 300 mL of distilled water for 48h, defibering the soaked pulp, and making into pulp with quantitative of 60 g/m2The paper is dried for 48 hours at normal temperature;
(2) the obtained paper is put into a tube furnace and is protected by nitrogen gas at the temperature of 20 DEGoHeating to 300 ℃ at a temperature rise rate of C/minoC, then at 10oC/min heating rate is from 300oC heating to 600oC, and is at 600oKeeping the temperature for 180min under C, and then cooling to 30 DEGoAnd C, obtaining the carbon fiber.
(3) Uniformly mixing zinc chloride and ultrapure water in a mass ratio of 1:1 to obtain a mixed solution, soaking carbon fibers in the mixed solution for 6 hours, and then soaking the soaked carbon fibers at 600 ℃ in a nitrogen atmosphereoC, activating in a tube furnace for 60 min, cooling to 100%oC, soaking in 5 percent hydrochloric acid solution for 12 hours at room temperature, and then soaking in 70 percent hydrochloric acid solutionoWashing with distilled water of C to neutrality at 105oAnd drying under C to obtain the activated carbon fiber with a hollow structure.
The BET specific surface area of the prepared activated carbon fiber is 1059 m2Per g, wherein the specific surface area of the micropores is 719 m2(ii)/g; the pore size distribution is 1.58-3.92 nm, wherein micropores account for 71%, and the obtained activated carbon fiber keeps a hollow structure, as shown in figure 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A method for preparing an activated carbon fiber having a hollow structure from a wood fiber, comprising the steps of:
(1) soaking wood fibers in distilled water for 12-48 h, defibering the soaked paper pulp, and making into paper with a quantitative weight of 60-140 g/m2The paper is dried for 48-96 hours at normal temperature; the wood fiber comprises at least one of softwood pulp, hardwood pulp, hemp pulp, cotton pulp and cotton linter;
(2) putting the paper obtained in the step (1) into a tube furnace to carry out carbonization treatment in two stages, wherein in the first stage, the temperature is raised to 200-300 ℃ under the protection of nitrogen, and the temperature raising rate in the first stage is 10-20 ℃/min; in the second stage, continuously introducing nitrogen, then increasing the temperature of the tubular furnace in the first stage to 400-600 ℃ at a temperature rise rate different from that in the first stage, preserving the heat at the temperature of 400-600 ℃ for 30-180 min, wherein the temperature rise rate in the second stage is 1-10 ℃/min, and then cooling to 20-30 ℃ to obtain carbon fibers;
(3) and (3) activating the carbon fiber obtained in the step (2) at 600-800 ℃, wherein the activation time is 60-180 min, and thus the activated carbon fiber with a hollow structure is obtained.
2. The method for preparing the activated carbon fiber with the hollow structure from the wood fiber according to claim 1, wherein the mass-to-volume ratio of the wood fiber to the distilled water in the step (1) is 0.7-2.67: 100 g/mL.
3. The method for preparing activated carbon fiber having a hollow structure from wood fiber according to claim 1, wherein the activation in the step (3) comprises the steps of:
1) uniformly mixing an activating agent and water in a mass ratio of 0.7-1: 1 to obtain a mixed solution;
2) soaking the carbon fiber in the step (2) in the mixed solution for 6-24 hours, and placing the soaked carbon fiber in a tubular furnace;
3) heating to 600-800 ℃ in a nitrogen or argon atmosphere, activating for 60-180 min, cooling to 20-100 ℃, soaking in a hydrochloric acid solution with the mass fraction of 1-10% for 0.5-12 h at room temperature, washing with distilled water at 60-80 ℃ to neutrality, and drying at 40-105 ℃ to obtain the activated carbon fiber.
4. The method for preparing activated carbon fiber having a hollow structure from wood fiber according to claim 3, wherein the activating agent in step 1) comprises at least one of phosphoric acid, zinc chloride, ammonium chloride, potassium hydroxide, sodium hydroxide, and dipotassium hydrogen phosphate.
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| JP2012255223A (en) * | 2011-06-07 | 2012-12-27 | National Institute Of Advanced Industrial & Technology | Method for producing carbon fiber |
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