CN109019590B - Lignin-based hierarchical pore carbon material and preparation method thereof - Google Patents
Lignin-based hierarchical pore carbon material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a lignin-based hierarchical porous carbon material and a preparation method thereof, wherein the preparation method comprises the following steps: pretreatment of lignin, preparation of a eutectic solvent, thermal carbonization of the eutectic solvent of the lignin, preparation of a solvothermal carbonization product, activation of the solvothermal carbonization product and preparation of a lignin-based hierarchical porous carbon material. The method selects the eutectic solvent to dissolve the lignin raw material, and has simple preparation, greenness and no toxicity. The lignin-based hierarchical porous carbon material has a rich macroporous-mesoporous-microporous structure, is uniformly and reasonably distributed, and has good adsorption performance. The method can be used in the fields of super capacitor electrode materials, lithium ion battery cathode materials, adsorption materials and the like.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a lignin-based hierarchical pore carbon material and a preparation method thereof.
Background
The activated carbon has a developed porous structure, and the internal specific surface area can reach 500-3000 m2The material is highly thermally and chemically stable and rich in source, and the properties enable the material to be widely applied to the fields of adsorption, catalysis, energy storage and the like. The pore structure of the porous material can be classified according to its size: big hole (>50nm), mesopores or mesopores (2 to 50nm) and micropores (<2nm), generally, the pore structure of the activated carbon is mainly macroporous and microporous, and the mesoporous structure is less. However, in many fields such as energy storage, adsorption, filtration and the like, the mesoporous structure of the hierarchical porous carbon material plays a crucial role, so that the preparation of the hierarchical porous carbon material with reasonable macroporous-mesoporous-microporous distribution has great significance.
The lignin has high carbon content, low oxygen content and a large number of benzene ring structures, and is very suitable to be used as a raw material of a carbon material. The application has low requirements on the consistency of the lignin type and the structure, and is one effective path for realizing high-value and industrial application of the lignin. Porous carbon materials produced from lignin as a raw material can be roughly classified into the following types according to the method.
(1) The lignin-based activated carbon is mainly divided into physical activation and chemical activation. Physical activation refers to activation under high temperature environment by using water vapor or carbon dioxide as an activator; chemical activation refers to mixing an activating agent such as alkali, phosphoric acid, alkali metal salt, etc. with lignin and activating at high temperature. The pore structure of the lignin-based activated carbon mainly comprises micropores and macropores, and a carbon material with rich mesopores is difficult to obtain.
(2) The lignin-based template carbon mainly comprises a hard template method and a soft template method. The hard template comprises nano silica gel particles, zeolite and the like, for example, Chinese patent CN201610362526 discloses a three-dimensional continuous hierarchical porous carbon material prepared by taking monodisperse silica as a template through limited-domain carbonization, template etching and KOH in-situ activation. The soft template includes a surfactant, a colloidal polymer, and the like. In the method, the hard template method needs to use strong acid (such as hydrofluoric acid) to etch and remove the template, so the cost is high and dangerous, and the soft template in the soft template method is not recyclable and has high cost.
(3) The preparation method of the lignin-based carbon fiber uses methods such as melt spinning, electrostatic spinning and the like to prepare the lignin fiber, and prepares the porous carbon fiber by combining heat treatment and activation.
(4) Hydrothermal carbonization, mixing lignin and water, carrying out primary carbonization under the conditions of high temperature and high pressure, and carrying out subsequent activation to obtain the carbon material with a developed pore structure. The hydrothermal carbonization technology has the advantages of capability of adjusting the pore size distribution to a certain degree, green and environment-friendly solvent and high carbon yield. But the defects are mainly that the steam pressure of the system is high, special equipment is needed, the product particles are larger, and the mesoporous structure is less. The room temperature ionic liquid is a substance which is liquid at room temperature or near room temperature and is composed of ions, has the characteristics of small vapor pressure, good solubility and the like, and is widely applied to various fields. In recent years, there has been developed an ionothermal carbonization technique, that is, a solvothermal carbonization technique performed under hydrothermal carbonization-like conditions using an ionic liquid at room temperature instead of water. The method has the advantages that the required steam pressure is low, the solubility of the biomass raw material in a proper ionic liquid system is high, and the obtained carbon material has a rich mesoporous structure. But the disadvantages of the method are that the preparation of the ionic liquid is complex and expensive, and the ionic liquid is difficult to remove from the product.
Eutectic Solvents (DES) are liquids formed by two chemical components cross-linked by hydrogen bonding, have a melting point lower than that of either component, consist of ions only, and are generally considered to be novel ionic liquids. Compared with ionic liquid, DES has some unique advantages, such as better atom economy, good biocompatibility, low toxicity, etc.; most importantly, the DES is simple to prepare, low in cost and high in feasibility of large-scale use. This area of technology is currently still open.
Disclosure of Invention
The invention aims to prepare a hierarchical porous carbon material with reasonable macroporous-mesoporous-microporous distribution by using lignin as a raw material and using a solvothermal carbonization technology based on a eutectic solvent and combining subsequent high-temperature activation. The method can be used in the fields of super capacitor electrode materials, lithium ion battery cathode materials, adsorption materials and the like.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme:
according to the lignin-based hierarchical pore carbon material and the preparation method thereof, the method comprises the following steps:
lignin pretreatment: air-drying and crushing raw material lignin, placing the crushed lignin in an oven, carrying out first drying, and cooling to room temperature after drying to obtain a lignin sample for later use;
preparing a eutectic solvent: uniformly mixing anhydrous choline chloride and formic acid, carrying out a first reaction to obtain a clear transparent liquid, placing the clear transparent liquid in a closed oven, carrying out second drying to remove excessive moisture, sealing and cooling to room temperature to obtain a eutectic solvent for later use;
thermal carbonization of eutectic solvent of lignin: uniformly mixing the eutectic solvent and the lignin sample, placing the mixture in a closed oven, and carrying out a second reaction to obtain a first product;
preparation of a solvothermal carbonization product: and (3) under the stirring state, dripping the first product into deionized water heated to a third reaction temperature to carry out a third reaction. Centrifuging the mixed solution, washing, and carrying out low-temperature vacuum freeze drying to obtain a second product;
activation of solvent thermal carbonization products: and uniformly mixing the second product with potassium hydroxide, adding a small amount of deionized water for dissolving, and carrying out third drying on the mixture. After drying, carrying out first activation on the mixture in a tubular furnace under the nitrogen atmosphere to obtain a third product;
preparing a lignin-based hierarchical porous carbon material: and (3) soaking the third product in hydrochloric acid, fully washing to be neutral, filtering, and performing fourth drying in a closed oven to obtain the lignin-based hierarchical porous carbon material.
The purpose and the technical problem of the invention can be further realized by adopting the following technical measures:
preferably, in the preparation method, a molar ratio of the anhydrous choline chloride to the formic acid is 1:1-5, a solid-to-liquid ratio of the mixture of the lignin and the eutectic solvent is 1:1-15, a volume ratio of the first product to the deionized water is 1:10-50, a mass ratio of the second product to the potassium hydroxide is 1:1-4, and the hydrochloric acid is a hydrochloric acid solution with a mass concentration of 10% -20%.
Preferably, in the preparation method, the drying conditions of the first drying are as follows: the temperature is 80-100 ℃, and the time is 1-3 h; the drying conditions of the second drying are as follows: the temperature is 60-80 ℃, and the time is 4-6 h; the drying conditions of the third drying are as follows: the temperature is 100 ℃ and 120 ℃; the drying conditions of the fourth drying are as follows: the temperature is 80-110 ℃.
Preferably, the preparation method is that the reaction conditions of the first reaction are as follows: the temperature is 50-80 ℃, and the time is 1 h; the reaction conditions of the second reaction are as follows: the temperature is 160-; the reaction conditions of the third reaction are as follows: the temperature is 60-90 ℃; the third reaction temperature is 60-90 ℃; the activation conditions of the first activation are: the temperature is 700 ℃ and 1000 ℃, and the time is 1-4 h.
Preferably, in the preparation method, the lignin is at least one of alkali lignin, lignosulfonate, kraft lignin, prehydrolyzed lignin and organosolv lignin.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means.
According to the lignin-based hierarchical pore carbon material and the preparation method thereof, the lignin-based hierarchical pore carbon material is prepared by any one of the methods.
By the technical scheme, the lignin-based hierarchical porous carbon material at least has the following advantages:
(1) the eutectic solvent (DES) system is adopted to replace ionic liquid as the solvent of the solvothermal method, the preparation is simple and convenient, and the cost is low. DES is easily removed after solvothermal carbonization.
(2) The invention prepares the hierarchical porous carbon material with rich macroporous-mesoporous-microporous structures by a solvothermal carbonization method based on a eutectic system, and increases the specific surface area and the mesoporous volume of the carbon material. The method can be used in the fields of super capacitors, lithium ion batteries, adsorption and the like.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, features and effects of the lignin-based hierarchical porous carbon material and the method for preparing the same according to the present invention will be made with reference to the preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The embodiment of the invention provides a lignin-based hierarchical pore carbon material and a preparation method thereof.
The preparation method comprises the following steps:
lignin pretreatment: air-drying and crushing raw material lignin, placing the crushed lignin in an oven, drying the lignin for 1 to 3 hours at the temperature of between 80 and 100 ℃, and cooling the dried lignin to room temperature to obtain a lignin sample for later use;
preparing a eutectic solvent: uniformly mixing anhydrous choline chloride and formic acid in a molar ratio of 1:1-5, stirring for 1h at 50-80 ℃ to obtain clear and transparent liquid, placing the clear and transparent liquid in a closed oven, drying for 4-6h at 60-80 ℃, removing excessive water, sealing and cooling to room temperature to obtain a eutectic solvent for later use;
thermal carbonization of eutectic solvent of lignin: uniformly mixing the eutectic solvent and the lignin sample, placing the mixture in a closed oven, and reacting for 3-24h at the temperature of 60-190 ℃ to obtain a thermal carbonization mixed solution;
preparation of a solvothermal carbonization product: under the stirring state, the thermal carbonization mixed solution is dripped into deionized water at the temperature of 60-90 ℃ for reaction, and the volume ratio of the thermal carbonization mixed solution to the deionized water is 1: 10-50. Centrifuging the mixed solution, washing, and carrying out low-temperature vacuum freeze drying to obtain a solvent thermal carbonization product;
activation of solvent thermal carbonization products: uniformly mixing the solvent thermal carbonization product with potassium hydroxide in a mass ratio of 1:1-4, adding a small amount of deionized water for dissolving, and drying the mixture at the temperature of 100-120 ℃. After drying, activating the mixture in a tubular furnace in a nitrogen atmosphere at the activation temperature of 700-1000 ℃, and preserving heat for 1-4h to obtain an activated product;
preparing a lignin-based hierarchical porous carbon material: soaking the activated product in a hydrochloric acid solution with the mass concentration of 10% -20%, taking out the activated product, fully washing the activated product with deionized water to be neutral, filtering, placing the product in a closed oven, and drying at 80-110 ℃ to obtain the lignin-based hierarchical porous carbon material.
In this embodiment, lignin includes, but is not limited to: at least one of alkali lignin, lignosulfonate, kraft lignin, prehydrolyzed lignin and organosolv lignin.
The present invention is further illustrated by the following specific examples, which are not to be construed as limiting the invention thereto.
Example 1
(1) And (3) drying the prehydrolyzed lignin in an oven at 90 ℃ for 2 hours, taking out and cooling to room temperature for later use.
(2) Respectively weighing anhydrous choline chloride and formic acid according to a molar ratio of 1:2, stirring for 1h in a water bath at 80 ℃ to mix to obtain a clear transparent liquid, placing in a closed oven at 80 ℃ for 6h, removing excessive water, taking out, sealing and cooling to room temperature to obtain the eutectic solvent.
(3) Weighing 0.5g of prehydrolyzed lignin, placing the prehydrolyzed lignin in a polytetrafluoroethylene lining container, adding 5g of eutectic solvent, placing the prehydrolyzed lignin in a closed container after being completely dissolved, reacting for 6 hours in a drying oven at 160 ℃, taking out, cooling to room temperature, and opening.
(4) And under the stirring state, dripping the mixed solution generated by the reaction in the closed container into deionized water at the temperature of 80 ℃, centrifuging for 5min at the rotating speed of 8000rpm, washing twice with the deionized water, and freeze-drying to obtain the solvent thermal carbonization product.
(5) Respectively weighing the solvent thermal carbonization product and potassium hydroxide according to the mass ratio of 1:3, mixing the two, adding a small amount of deionized water, placing the mixture in a drying oven at 105 ℃ for drying, transferring the mixture into a crucible, heating the mixture to 900 ℃ in a tubular furnace in nitrogen atmosphere, and preserving heat for 2h for activation.
(6) Soaking the activated product in 10% hydrochloric acid solution, taking out the activated product, washing the activated product to be neutral by using deionized water, filtering, placing the activated product in a closed oven, and drying the activated product at 80 ℃ to obtain the lignin-based hierarchical porous carbon material.
And (3) performing scanning electron microscope and nitrogen adsorption tests on the prepared lignin-based hierarchical porous carbon material. The results are shown in the figure.
Table 1 shows pore structure data of the solvent thermal-carbonized product and the activated hierarchical porous carbon material obtained by calculation based on the nitrogen adsorption test data.
Table 1 examples 1 pore structure data for hierarchical porous carbon materials
Example 2
(1) Drying the kraft lignin in an oven at 90 ℃ for 2h, taking out and cooling to room temperature for later use.
(2) Respectively weighing anhydrous choline chloride and formic acid according to a molar ratio of 1:3, stirring for 1h in a water bath at 80 ℃ to mix to obtain a clear transparent liquid, placing in a closed oven at 80 ℃ for 1h, removing excessive water, taking out, sealing and cooling to room temperature to obtain the eutectic solvent.
(3) Weighing 1g of kraft lignin, placing the kraft lignin in a polytetrafluoroethylene lining container, adding 5g of eutectic solvent, placing the container in a closed container after prehydrolysis lignin is completely dissolved, reacting in an oven at 175 ℃ for 12 hours, taking out, cooling to room temperature, and opening.
(4) And under the stirring state, dripping the mixed solution generated by the reaction in the closed container into deionized water at 70 ℃, centrifuging for 5min at the rotating speed of 8000rpm, washing twice with the deionized water, and freeze-drying to obtain the solvent thermal carbonization product.
(5) Respectively weighing the solvent thermal carbonization product and potassium hydroxide according to the mass ratio of 1:4, mixing the two, adding a small amount of deionized water, placing the mixture in a drying oven at 105 ℃ for drying, transferring the mixture into a crucible, heating the mixture to 700 ℃ in a tubular furnace in nitrogen atmosphere, and preserving heat for 4 hours for activation.
(6) And soaking the activated product in 20% hydrochloric acid solution, taking out the activated product, washing the activated product to be neutral by using deionized water, filtering, placing the product in a closed oven, and drying the product at 80 ℃ to obtain the lignin-based hierarchical porous carbon material.
The scanning electron microscope and the nitrogen adsorption test which are the same as those in the example 1 are carried out on the prepared lignin-based hierarchical porous carbon material, and the result is basically the same as that in the example 1.
Example 3
(1) And (3) drying the alkali lignin in an oven at 100 ℃ for 3h, taking out and cooling to room temperature for later use.
(2) Respectively weighing anhydrous choline chloride and formic acid according to a molar ratio of 1:5, stirring for 1h in a water bath at 80 ℃ to mix to obtain a clear transparent liquid, placing in a closed oven at 60 ℃ for 1h, removing excessive water, taking out, sealing and cooling to room temperature to obtain the eutectic solvent.
(3) Weighing 1g of alkali lignin, placing the alkali lignin in a polytetrafluoroethylene lining container, adding 15g of eutectic solvent, placing the container in a closed container after the prehydrolysis lignin is completely dissolved, reacting for 24 hours in a baking oven at 190 ℃, taking out the container, cooling to room temperature, and opening.
(4) And under the stirring state, dripping the mixed solution generated by the reaction in the closed container into deionized water at 60 ℃, centrifuging for 5min at the rotating speed of 8000rpm, washing for three times by using the deionized water, and freeze-drying to obtain the solvent thermal carbonization product.
(5) Respectively weighing the solvent thermal carbonization product and potassium hydroxide according to the mass ratio of 1:2, mixing the two, adding a small amount of deionized water, placing the mixture in a drying oven at 105 ℃ for drying, transferring the mixture into a crucible, heating the mixture to 1000 ℃ in a tubular furnace in nitrogen atmosphere, and preserving heat for 1h for activation.
(6) Soaking the activated product in 10% hydrochloric acid solution, taking out the activated product, washing the activated product to be neutral by using deionized water, filtering, placing the activated product in a closed oven, and drying the activated product at 80 ℃ to obtain the lignin-based hierarchical porous carbon material.
The scanning electron microscope and the nitrogen adsorption test which are the same as those in the example 1 are carried out on the prepared lignin-based hierarchical porous carbon material, and the result is basically the same as that in the example 1.
Drawings
Fig. 1 is SEM images of the solvothermal carbonized product and the activated multi-pore carbon material in example 1, wherein (a), (b) are SEM images of the solvothermal carbonized product, (c), and (d) are SEM images of the activated multi-pore carbon material.
FIG. 2 is a plot of the nitrogen adsorption isotherms of the solvothermal carbonized product and activated multi-stage porous carbon material of example 1.
Fig. 3 is a pore size distribution diagram of the activated multi-level pore carbon material in example 1.
Fig. 1 is SEM images of the solvothermal carbonized product and the activated multi-porous carbon material in example 1, wherein (a), (b) are SEM images of the solvothermal carbonized product showing that the solvothermal carbonized product has a particle size of 70 to 120nm, (c), and (d) are SEM images of the activated multi-porous carbon material showing that the multi-porous carbon is composed of nano-scale carbon microspheres having a particle size of about 10 to 30 nm.
FIG. 2 is a diagram of the nitrogen adsorption isotherms of the solvothermal carbonized product and the activated multi-stage porous carbon material in example 1, in which the nitrogen adsorption isotherms of the solvothermal carbonized product show that the pore structure is small, the pore structure is greatly increased after activation, the curve rapidly rises in the low pressure region to show that the material has micropores, and the appearance of loops in the curve shows that the material has a mesoporous structure which is mutually connected.
Fig. 3 is a pore size distribution diagram of the activated multi-level pore carbon material of example 1, which shows that the multi-level pore carbon material has a large amount of mesoporous material.
Claims (2)
1. A preparation method of a lignin-based hierarchical porous carbon material is characterized by comprising the following steps:
lignin pretreatment: air-drying and crushing raw material lignin, placing the crushed lignin in an oven, carrying out first drying, and cooling to room temperature after drying to obtain a lignin sample for later use;
preparing a eutectic solvent: uniformly mixing anhydrous choline chloride and formic acid, carrying out a first reaction to obtain a clear transparent liquid, placing the clear transparent liquid in a closed oven, carrying out second drying to remove excessive moisture, sealing and cooling to room temperature to obtain a eutectic solvent for later use;
thermal carbonization of eutectic solvent of lignin: uniformly mixing the eutectic solvent and the lignin sample, placing the mixture in a closed oven, and carrying out a second reaction to obtain a first product;
preparation of a solvothermal carbonization product: under the stirring state, dripping the first product into deionized water heated to a third reaction temperature to carry out a third reaction; centrifuging the mixed solution, washing, and carrying out low-temperature vacuum freeze drying to obtain a second product;
activation of solvent thermal carbonization products: uniformly mixing the second product with potassium hydroxide, adding a small amount of deionized water for dissolving, and carrying out third drying on the mixture; after drying, carrying out first activation on the mixture in a tubular furnace under the nitrogen atmosphere to obtain a third product;
preparing a lignin-based hierarchical porous carbon material: soaking the third product in hydrochloric acid, fully washing to neutrality, filtering, and performing fourth drying in a closed oven to obtain a lignin-based hierarchical pore carbon material;
the molar ratio of the anhydrous choline chloride to the formic acid is 1:1-5, the solid-liquid ratio of the mixture of the lignin and the eutectic solvent is 1:1-15, the volume ratio of the first product to the deionized water is 1:10-50, the mass ratio of the second product to the potassium hydroxide is 1:1-4, and the hydrochloric acid is a hydrochloric acid solution with the mass concentration of 10% -20%;
the drying conditions of the first drying are as follows: the temperature is 80-100 ℃, and the time is 1-3 h; the drying conditions of the second drying are as follows: the temperature is 60-80 ℃, and the time is 4-6 h; the drying conditions of the third drying are as follows: the temperature is 100 ℃ and 120 ℃; the drying conditions of the fourth drying are as follows: the temperature is 80-110 ℃;
the reaction conditions of the first reaction are as follows: the temperature is 50-80 ℃, and the time is 1 h; the reaction conditions of the second reaction are as follows: the temperature is 160-; the reaction conditions of the third reaction are as follows: the temperature is 60-90 ℃; the third reaction temperature is 60-90 ℃; the activation conditions of the first activation are: the temperature is 700 ℃ and 1000 ℃, and the time is 1-4 h.
2. The production method according to claim 1,
the lignin is at least one of alkali lignin, lignosulfonate, kraft lignin, prehydrolysis lignin and organic solvent lignin.
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