CN111994907B - Method for preparing boron-doped porous carbon material with high specific surface area from biomass - Google Patents
Method for preparing boron-doped porous carbon material with high specific surface area from biomass Download PDFInfo
- Publication number
- CN111994907B CN111994907B CN202010926183.5A CN202010926183A CN111994907B CN 111994907 B CN111994907 B CN 111994907B CN 202010926183 A CN202010926183 A CN 202010926183A CN 111994907 B CN111994907 B CN 111994907B
- Authority
- CN
- China
- Prior art keywords
- boron
- biomass
- acid
- hydrothermal
- carbon material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
Abstract
The invention relates to a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass, which comprises the following steps of crushing the biomass into tiny particles, uniformly mixing the crushed biomass particles and a boron-containing acidic aqueous solution according to a certain proportion to form a mixture, and putting the mixture into a hydrothermal reaction kettle for hydrothermal reaction; dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction; putting the dried hydrothermal carbon into a pyrolysis furnace, and performing fast pyrolysis under the protection of inert atmosphere to obtain a fast pyrolyzed biomass source boron-doped porous carbon material with high specific surface area; the method has the advantages of wide raw material source, simple process, environmental protection, low equipment requirement, short production process time consumption and high efficiency, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the field of preparation of boron-doped carbon materials, and particularly relates to the field of preparation of boron-doped porous carbon materials with high specific surface area by using biomass.
Background
Biomass is widely distributed in nature and has huge reserves, and is the only carbon neutral energy source which can replace petroleum derived fuels and chemicals. China produces about hundred million tons of waste biomass (crop straws, sawdust, weeds, microalgae, animal waste and the like) every year, the energy sources contained in the waste biomass are equivalent to hundred million tons of standard coal, and the waste biomass is a huge resource treasury. Biomass can be converted into a solid substance containing a large number of aromatic ring structures, namely biochar, through hydrothermal or pyrolysis and other technologies, and the biochar has a very wide application prospect in the fields of environment and chemical industry; in recent years, the use of carbon materials has been increasing, but pure carbon materials are still unsatisfactory in structure and performance. Therefore, heteroatom-modified carbon obtained by heteroatom doping of carbon materials has attracted more and more attention due to its unique physical and chemical properties. The reaction activity of the biochar can be greatly improved by doping the heteroatom, the biochar is an excellent material in the fields of catalysis, adsorption and energy storage, and the common doped heteroatom at present is B, N, P, S and the like; compared with carbon atoms, boron atoms only have one electron less and are very close to carbon atoms in microscopic scale, and after boron is doped with a carbon skeleton structure, the electronic structure of the carbon material is changed, and meanwhile, the graphite lattice distortion of the carbon material is small, so that the graphitization degree and the oxidation resistance of the carbon material can be effectively improved. However, the currently reported preparation method of the boron-doped carbon material has the defects of complex process, difficult boron atom doping, low specific surface area of the obtained carbon material, main pore structure, unfavorable adsorption and mass transfer and the like;
for example, CN201910994262.7 introduces a method for removing heavy metals in water by using boron-doped mesoporous carbon, which uses a template method to prepare boron-doped mesoporous carbon with high specific surface area: mixing boric acid, sucrose, concentrated sulfuric acid and water in proportion to obtain a multi-component solution A, permeating the multi-component solution A into the mesoporous silicon template, and curing to obtain a compound A; mixing boric acid, sucrose, concentrated sulfuric acid and water in proportion to obtain a multi-component solution B, dipping the compound A into the multi-component solution B, and curing to obtain a compound B; finally, carrying out heat treatment on the compound B, and removing the template to obtain boron-doped mesoporous carbon; the carbon material prepared by the method contains boron functional groups, but the template method adopted by the method has the disadvantages of multiple steps, complex process, extremely long time consumption and high energy consumption, and the carbon source is sucrose, so that the cost is high, and the method is not beneficial to industrial large-scale production; for another example, CN201911344836.2 discloses a method for preparing boron-doped carbon nanospheres by using lignin and a product thereof: dissolving lignin and a boron additive in water according to a preset mass ratio to prepare a mixed solution; performing ultrasonic treatment on the mixed solution; drying and grinding the lignin solution to obtain lignin powder; performing pyrolysis treatment on the lignin powder, and cooling to prepare the boron-doped carbon nanospheres; although the method is simple in process, the carbon source is lignin, the requirement on lignin powder is high, the method is not beneficial to popularization, and the prepared boron-doped carbon material has the problems of small specific surface area, low boron atom doping efficiency and the like.
Disclosure of Invention
In order to solve the problems, the invention achieves the purposes through the following technical scheme:
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass into fine particles;
step two, uniformly mixing the crushed biomass particles and the boron-containing acidic aqueous solution according to a certain proportion to form a mixture, and putting the mixture into a hydrothermal reaction kettle for hydrothermal reaction to generate hydrothermal carbon;
step three, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
and step four, putting the dried hydrothermal carbon into a pyrolysis furnace, performing fast pyrolysis under the protection of inert atmosphere, and obtaining a fast pyrolyzed solid product, wherein the solid product is a biomass source high-specific-surface-area boron-doped porous carbon material.
As a further optimization scheme of the invention, the biomass is any one or a combination of more than two of xylitol, xylose, xylan, glucose, cellobiose, cellulose, starch, hemicellulose, chitosan, chitin, sucrose, fructose, wood, bagasse, moso bamboo, corn straw, rapeseed cake, jatropha curcas cake, cake meal, vinasse, waste protein, microalgae, plastic waste, recycled plastic, agricultural and urban organic solid waste, food waste, animal waste, carbohydrate and wood fiber material.
In a further preferred embodiment of the present invention, the boron-containing acidic aqueous solution in the second step is any one of an aqueous solution of boric acid, an aqueous solution of borate and another acid, an aqueous solution of borate and boric acid, an aqueous solution of boride and boric acid, and an aqueous solution of boride and another acid.
As a further preferable aspect of the present invention, the borate includes sodium borate, potassium borate, calcium borate, ammonium borate, sodium metaborate, potassium metaborate, calcium metaborate, and the boride includes boron oxide.
In a further preferred embodiment of the present invention, the other acid is any one of an inorganic acid, an organic acid, and an acidic salt, the inorganic acid includes hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, the organic acid includes formic acid, acetic acid, propionic acid, butyric acid, citric acid, and oxalic acid, and the acidic salt includes ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen sulfate, potassium hydrogen sulfate, and ammonium hydrogen sulfate.
As a further optimization scheme of the invention, the mass ratio of the biomass particles to the boron-containing acidic aqueous solution in the second step is 1:50-1: 1.
As a further optimization scheme of the invention, the hydrothermal reaction temperature in the second step is controlled to be between 80 and 300 ℃,
as a further optimization scheme of the invention, the hydrothermal reaction temperature in the second step is preferably 150-250 ℃.
As a further optimization scheme of the invention, the hydrothermal time is 0.5-24 h.
As a further optimization scheme of the invention, the temperature of the pyrolysis furnace in the fourth step is 350-900 ℃.
The invention has the beneficial effects that:
1) the biomass raw material used by the preparation method is agricultural and forestry waste, and has wide sources and can be regenerated;
2) the method has simple process and less time consumption, and is suitable for industrial large-scale production;
3) the boron-containing acidic aqueous solution used in the invention not only plays a role in doping boron atoms, but also can be used as an activating agent to play a role in pore forming, and the prepared carbon material has the advantages of large specific surface area, high mesoporous rate, high boron atom doping rate and the like.
Drawings
FIG. 1 is an XPS plot of a boron-doped carbon material according to the present invention;
FIG. 2 is a TEM image of a boron-doped carbon material according to the present invention;
FIG. 3 is a graph of isothermal adsorption of boron-doped carbon materials in accordance with the present invention;
FIG. 4 is a report of the nitrogen desorption detection of the boron-doped carbon material in the present invention;
FIG. 5 is a flow chart of the steps of the manufacturing process of the present invention;
Detailed Description
The present application will now be described in further detail with reference to the drawings, it should be noted that the following detailed description is given for illustrative purposes only and is not to be construed as limiting the scope of the present application, as those skilled in the art will be able to make numerous insubstantial modifications and adaptations to the present application based on the above disclosure.
As shown in fig. 1 to 5, a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass into fine particles;
wherein the biomass is any one or a combination of more than two of xylitol, xylose, xylan, glucose, cellobiose, cellulose, starch, hemicellulose, chitosan, chitin, sucrose, fructose, wood, bagasse, bamboo, corn straw, rapeseed cake, jatropha curcas cake, cake meal, vinasse, waste protein, microalgae, plastic waste, recycled plastic, agricultural and urban organic solid waste, food waste, animal waste, carbohydrate and wood fiber material;
step two, mixing the crushed biomass particles with a boron-containing acidic aqueous solution according to the boron/carbon mass ratio of 1:50-1:1, uniformly mixing to form a mixture, and putting the mixture into a hydrothermal reaction kettle for hydrothermal reaction for 0.5-24 hours; controlling the hydrothermal reaction temperature in the hydrothermal reaction kettle at 80-300 ℃, preferably 150-250 ℃;
wherein, the boron-containing acidic aqueous solution refers to any one of a boric acid aqueous solution, an aqueous solution composed of borate and other acids, an aqueous solution composed of borate and boric acid, an aqueous solution composed of boride and boric acid, and an aqueous solution composed of boride and other acids;
the borate comprises sodium borate, potassium borate, calcium borate, ammonium borate, sodium metaborate, potassium metaborate, calcium metaborate, the boride comprises boron oxide;
the other acid is any one of inorganic acid, organic acid and acid salt, wherein the inorganic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, the organic acid comprises formic acid, acetic acid, propionic acid, butyric acid, citric acid and oxalic acid, and the acid salt comprises ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen sulfate, potassium hydrogen sulfate and ammonium hydrogen sulfate;
step three, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
and step four, putting the dried hydrothermal carbon into a pyrolysis furnace, controlling the temperature of the pyrolysis furnace to be 350-900 ℃, and performing fast pyrolysis under the protection of inert atmosphere for 5min-2h to finally obtain a fast pyrolyzed solid product, wherein the solid product is a biomass source high-specific surface area boron-doped porous carbon material.
The technical scheme is a method for converting agricultural and forestry waste biomass with wide sources into a boron-doped porous carbon material by combining boric acid hydrothermal pretreatment with a fast pyrolysis technology; it is important to point out here that the two steps of the hydrothermal reaction and the fast pyrolysis of the boric acid are not simply combined together, and there is a significant synergistic effect among the boric acid solution (or the boron-containing acidic solution), the hydrothermal reaction and the fast pyrolysis;
the hydrothermal reaction process of the mixture of the biomass particles and the boron-containing acidic aqueous solution in the second step in the hydrothermal reaction kettle is a boric acid hydrothermal pretreatment process, and deliming, pore forming, pre-carbonization and acid loading are realized in the hydrothermal pretreatment process;
the step of performing fast pyrolysis on the dried hydrothermal carbon in the pyrolysis furnace in the fourth step is that the hydrothermal carbon is subjected to fast pyrolysis, deep carbonization is performed in the process, a hierarchical pore is formed, and boron is doped into a carbon skeleton;
the principle of the synergistic effect of the two steps of boric acid hydrothermal pretreatment and hydrothermal carbon fast pyrolysis is as follows:
in the hydrothermal process of boric acid, the boric acid can enhance the hydrolysis reaction of biomasses such as hemicellulose, cellulose and the like in the hydrothermal reaction, so that the biomasses are changed into loose and porous three-dimensional network structures, the permeation and dispersion of the boric acid in the biomasses are facilitated, the acid in a solution can be effectively adsorbed, and the efficient and uniform loading of the acid is realized; in addition, alkali metals and alkaline earth metals in the biomass ash can be removed by acid washing in the boric acid hydrothermal process, so that an ideal deashing effect is realized; the hot-pressing shrinkage in the hydrothermal pretreatment is water in a subcritical or supercritical state at the temperature of more than 100 ℃, the dielectric constant is reduced to be between 25 and 35 and is close to that of most organic solvents in a standard state, and the deashing and carbonization reaction of biomass is facilitated;
in addition, a plurality of oxygen-containing functional groups are formed on the organic material through hydrothermal pre-carbonization, and boric acid is used to enable the biomass material to form a loose and porous three-dimensional network structure, so that a large number of oxygen-containing functional groups can be formed on the surface and the loose and internal three-dimensional structure of the material in the hydrothermal pretreatment process of boric acid, and the oxygen-containing functional groups can react with boric acid to enable the boric acid to be successfully loaded on the material, and the loading capacity is very considerable; however, the load does not really dope the boron element into the carbon skeleton, so further carbonization and activation are needed;
because a loose structure is formed by boric acid hydrothermal pre-carbonization, and a large amount of borate is loaded, if long-time high-temperature carbonization and activation operation is carried out, the structure of the material is damaged, so that the carbon skeleton collapses, the final pore structure of the material is influenced, and on the other hand, the loaded boron falls off, and the aim of effectively forming the boron-doped carbon material cannot be achieved; in the prior art, the traditional fast pyrolysis method usually adopts high-temperature gas to rapidly process biomass, but the method has poor treatment effect on blocky or granular materials, and the main product of the fast pyrolysis technology is bio-oil, so that the carbon yield is low;
consequently, with the scheme that boric acid hydrothermal precarbonization and fast pyrolysis combined together in this application for two steps can make a premium and keep away the weak point, can carry out quick carbonization activation to the material inside that forms loose structure, make the oxygen-containing functional group get rid of and form pore structure, and a large amount of load boron can obtain the chance of inserting the carbon skeleton simultaneously, and the fast pyrolysis of short time is handled and is guaranteed the structure again and can not destroyed, thereby reaches ultimate effect.
The invention provides a boric acid hydrothermal pretreatment combined fast pyrolysis method, and the two steps are cooperated with each other, so that the defects of the method are overcome; the boron-doped porous carbon material prepared by the method has the advantages of high boron atom doping rate, large specific surface area, high mesoporous rate and the like.
Example 1
In this example, seven different kinds of biomass were selected and pulverized, and 5g of the above biomass powder was weighed for use, and seven different materials were prepared according to the following preparation methods, respectively;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with boric acid solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven with the temperature of 200 ℃ for hydrothermal reaction for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 700 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are collected and detected respectively, and the specific surface areas of the boron-doped carbon materials prepared from seven different types of biomass are shown in the table 1:
TABLE 1 preparation of boron-doped carbon materials by hydrothermal and fast pyrolysis of different types of biomass boric acid
Example 2
In the embodiment, the influence of different boron sources and acid sources on the properties of the boron-doped biomass carbon material is tested, only the types of the boron sources and the acid sources are changed, and the material is prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles and mixing with boron-containing acidic aqueous solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and putting the reaction kettle into an oven with the temperature of 200 ℃ for hydrothermal treatment for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 700 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under different boron sources and acid sources is shown in table 2:
TABLE 2 specific surface area and composition of boron-doped carbon material prepared by hydrothermal and fast pyrolysis of biomass boric acid under different boron sources and acid sources
Example 3
In this example, the effect of different boron-carbon ratios on the properties of boron-doped biomass carbon materials was tested, only the boron-carbon ratio was changed, and the materials were prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with a boric acid solution according to the boron/carbon mass ratio of 1:1, 1:10, 1:20, 1:30 or 1:50 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and putting the reaction kettle into an oven at 200 ℃ for hydrothermal treatment for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 700 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under the condition of different boron-carbon ratios is shown in the table 3:
TABLE 3 preparation of boron-carbon doped materials by hydrothermal and fast pyrolysis of biomass boric acid at different boron-carbon ratios
Example 4
In this example, the effect of different hydrothermal temperatures on the properties of boron-doped biomass carbon material was tested, only the hydrothermal temperature was changed, and the material was prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with boric acid solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the hydrothermal reaction kettle, and then respectively putting the hydrothermal reaction kettle into an oven with the temperature of 80 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ for hydrothermal treatment for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 700 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under different hydrothermal temperatures is shown in table 4:
TABLE 4 specific surface area and composition of boron-doped carbon material prepared by hydrothermal and fast pyrolysis of biomass boric acid at different hydrothermal temperatures
Example 5
In this example, the effect of different hydrothermal times on the properties of boron-doped biomass carbon material was tested, only the hydrothermal time was changed, and the material was prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with boric acid solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into a 200 ℃ drying oven for hydrothermal reaction for 0.5h, 4h, 8h, 12h, 15h, 20h and 24h respectively;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 700 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under different hydrothermal time conditions is shown in table 5:
TABLE 5 specific surface area and composition of boron-doped carbon material prepared by hydrothermal and fast pyrolysis of biomass boric acid at different hydrothermal times
Example 6
In this example, the effect of different fast pyrolysis temperatures on the properties of boron-doped biomass carbon material was tested, only the fast pyrolysis temperature was changed, and the material was prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with boric acid solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into an oven with the temperature of 200 ℃ for hydrothermal reaction for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 350 ℃, 500 ℃, 700 ℃ and 900 ℃ under the protection of nitrogen atmosphere, and collecting a solid product; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under different fast pyrolysis temperature conditions is shown in table 6:
TABLE 6 preparation of boron-doped carbon materials by hydrothermal and fast pyrolysis of biomass boric acid at different fast pyrolysis temperatures
Example 7
In this example, the effect of different fast pyrolysis times on the properties of boron-doped biomass carbon material was tested, only the fast pyrolysis time was changed, and the material was prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles and mixing with boron-containing acidic aqueous solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and putting the reaction kettle into an oven with the temperature of 200 ℃ for hydrothermal treatment for 12 hours;
step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon;
transferring the dried solid powder into a pyrolysis furnace, rapidly pyrolyzing the solid powder for 5min, 30min, 60min, 90min and 120min at 700 ℃ under the protection of nitrogen atmosphere, and collecting solid products; the solid product is a biomass source boron-doped porous carbon material with high specific surface area.
Different solid products are respectively collected and detected, and the specific surface area of the boron-doped carbon material prepared by the biomass under different fast pyrolysis time conditions is shown in table 7:
TABLE 7 preparation of boron-doped carbon materials by hydrothermal and fast pyrolysis of Biomass boric acid at different fast pyrolysis times
Comparative example 1
In this comparative example, the influence on the properties of the boron-doped biomass carbon material was tested using only the hydrothermal reaction of biomass with a boron-containing acidic solution, i.e., without performing a fast pyrolysis method, and the boron-doped carbon material was prepared according to the following preparation method;
a method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass comprises the following steps:
crushing biomass of phoenix tree into fine particles;
step two, selecting 5g of crushed biomass particles, mixing the crushed biomass particles with boric acid solution according to the boron/carbon mass ratio of 1:1 to form a uniform mixture, putting the uniform mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the hydrothermal reaction kettle, and putting the hydrothermal reaction kettle into a 200 ℃ drying oven for 12 hours respectively;
and step three, taking out the reaction kettle after the hydrothermal reaction, transferring the hydrothermal product into a beaker after the reaction kettle is cooled to room temperature, and drying the hydrothermal product in a 105 ℃ oven for 24 hours, namely dehydrating and drying the obtained hydrothermal carbon.
Collecting the biomass source boron-doped carbon material, detecting, and preparing the boron-doped carbon material with the specific surface area of 608.2m2/g under the condition of not carrying out fast pyrolysis; comparing the data with the data of the example 5, namely under the same conditions, the specific surface area of the boron-doped carbon material subjected to the fast pyrolysis reaction is up to 2068.5m 2/g; thus, it is apparent that the parameters of the boron-doped carbon material produced using the present application are much better than the boron-doped carbon material produced by the comparative example method.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (4)
1. A method for preparing a boron-doped porous carbon material with a high specific surface area by using biomass is characterized by comprising the following steps: the method comprises the following steps:
crushing biomass into tiny particles;
step two, uniformly mixing the crushed biomass particles with the boron-containing acidic aqueous solution in proportion to form a mixture, and carrying out hydrothermal reaction on the mixture to generate hydrothermal carbon;
step three, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
putting the dried hydrothermal carbon into a pyrolysis furnace, and performing fast pyrolysis for 5min under the protection of inert atmosphere to obtain a fast pyrolyzed solid product, wherein the solid product is a biomass source high-specific-surface-area boron-doped porous carbon material;
wherein the mass ratio of boron to carbon of the biomass particles and the boron-containing acidic aqueous solution in the second step is 1:30-1:1, the hydrothermal reaction temperature is 150-250 ℃, and the hydrothermal time is 0.5-20 h;
the temperature of the pyrolysis furnace in the fourth step is 700 ℃.
2. The method for preparing the boron-doped porous carbon material with high specific surface area from biomass according to claim 1, wherein the method comprises the following steps: the biomass is any one or a combination of more than two of cellulose, starch, wood, bagasse, moso bamboo, corn straw, rapeseed cake, jatropha curcas cake, cake meal, vinasse, microalgae, plastic waste, regenerated plastic, food waste and animal waste.
3. The method for preparing the boron-doped porous carbon material with high specific surface area from biomass according to claim 1, wherein the method comprises the following steps: the boric acid-containing aqueous solution in the second step is any one of an aqueous solution of boric acid, an aqueous solution of borate and other acids, an aqueous solution of borate and boric acid, and an aqueous solution of boric oxide and other acids;
wherein, the other acid is any one of inorganic acid, organic acid and acid salt, the inorganic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, the organic acid comprises formic acid, acetic acid, propionic acid, butyric acid, citric acid and oxalic acid, and the acid salt comprises ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen sulfate, potassium hydrogen sulfate and ammonium hydrogen sulfate.
4. The method for preparing the boron-doped porous carbon material with high specific surface area from biomass according to claim 3, wherein the method comprises the following steps: the borate includes sodium borate, potassium borate, calcium borate, ammonium borate, sodium metaborate, potassium metaborate, calcium metaborate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010926183.5A CN111994907B (en) | 2020-09-07 | 2020-09-07 | Method for preparing boron-doped porous carbon material with high specific surface area from biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010926183.5A CN111994907B (en) | 2020-09-07 | 2020-09-07 | Method for preparing boron-doped porous carbon material with high specific surface area from biomass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111994907A CN111994907A (en) | 2020-11-27 |
| CN111994907B true CN111994907B (en) | 2022-03-25 |
Family
ID=73470124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010926183.5A Active CN111994907B (en) | 2020-09-07 | 2020-09-07 | Method for preparing boron-doped porous carbon material with high specific surface area from biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111994907B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112675815B (en) * | 2020-12-15 | 2023-04-21 | 东北农业大学 | Preparation method and application of boron doped porous biochar |
| CN112645325A (en) * | 2020-12-23 | 2021-04-13 | 陇东学院 | Preparation method and application of biomass porous carbon material based on castor seed residues |
| CN113387355A (en) * | 2021-07-30 | 2021-09-14 | 合肥工业大学 | Method for preparing porous carbon spheres from biomass raw material |
| CN114570351B (en) * | 2022-03-02 | 2023-12-29 | 东北林业大学 | Boron-phosphorus co-doped metal-free carbon-based catalytic material and preparation method and application thereof |
| CN115215318A (en) * | 2022-05-30 | 2022-10-21 | 湖北拓扑来微科技有限公司 | High-density ultramicropore carbon electrode material with boron-nitrogen modification and preparation method thereof |
| CN115159496A (en) * | 2022-07-08 | 2022-10-11 | 临涣焦化股份有限公司 | Preparation method of boron atom doped carbon-based new material |
| CN115497749B (en) * | 2022-09-30 | 2023-11-17 | 华南理工大学 | Tobacco stem-based porous carbon material, preparation method thereof and application thereof in super capacitor |
| CN116462193A (en) * | 2023-03-22 | 2023-07-21 | 广西宸宇新材料有限公司 | Modified graphite and preparation and application thereof in battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115652A (en) * | 2016-04-14 | 2016-11-16 | 湘潭大学 | A kind of B (or P), N codope Folium Perillae porous carbon and preparation method thereof |
| CN107346821A (en) * | 2016-05-06 | 2017-11-14 | 苏州汉瀚储能科技有限公司 | A kind of preparation method of boron doping porous carbon ball |
| CN109251031A (en) * | 2018-11-23 | 2019-01-22 | 福建农林大学 | A kind of method of microwave assisted aqueous extraction hot preparation for the nitrogen co-doped porous carbon material of boron of supercapacitor |
| CN110240160A (en) * | 2019-06-26 | 2019-09-17 | 陕西科技大学 | A kind of preparation method of the biomass porous carbon nano-electrode material of sodium-ion battery boron doping |
| CN110422843A (en) * | 2019-08-04 | 2019-11-08 | 大连理工大学 | A kind of environment-friendly preparation method thereof of the biomass-based active carbon material of nitrogen boron codope and its application |
-
2020
- 2020-09-07 CN CN202010926183.5A patent/CN111994907B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115652A (en) * | 2016-04-14 | 2016-11-16 | 湘潭大学 | A kind of B (or P), N codope Folium Perillae porous carbon and preparation method thereof |
| CN107346821A (en) * | 2016-05-06 | 2017-11-14 | 苏州汉瀚储能科技有限公司 | A kind of preparation method of boron doping porous carbon ball |
| CN109251031A (en) * | 2018-11-23 | 2019-01-22 | 福建农林大学 | A kind of method of microwave assisted aqueous extraction hot preparation for the nitrogen co-doped porous carbon material of boron of supercapacitor |
| CN110240160A (en) * | 2019-06-26 | 2019-09-17 | 陕西科技大学 | A kind of preparation method of the biomass porous carbon nano-electrode material of sodium-ion battery boron doping |
| CN110422843A (en) * | 2019-08-04 | 2019-11-08 | 大连理工大学 | A kind of environment-friendly preparation method thereof of the biomass-based active carbon material of nitrogen boron codope and its application |
Non-Patent Citations (1)
| Title |
|---|
| Boron and nitrogen co-doped porous carbon for supercapacitors: A comparison between a microwave-assisted and a conventional hydrothermal process;Yalan Zhou et al.;《Journal of Energy Storage》;20200824;第32卷;第1-9页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111994907A (en) | 2020-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111994907B (en) | Method for preparing boron-doped porous carbon material with high specific surface area from biomass | |
| Senthil et al. | Biomass-derived biochar materials as sustainable energy sources for electrochemical energy storage devices | |
| Wang et al. | Hydrothermal synthesis and applications of advanced carbonaceous materials from biomass: a review | |
| Li et al. | A critical review on the application and recent developments of post-modified biochar in supercapacitors | |
| Manasa et al. | Recent progress on biomass waste derived activated carbon electrode materials for supercapacitors applications—A review | |
| CN108511204B (en) | Preparation method of oxygen-nitrogen co-doped porous hollow carbon microspheres | |
| CN112010302A (en) | Method for preparing hierarchical porous phosphorus-doped carbon material from biomass | |
| CN110589827B (en) | Method for preparing biomass carbon aerogel by double activation method and application thereof | |
| CN112194127A (en) | Method for preparing nitrogen-doped carbon material from biomass | |
| CN108455603B (en) | Mesoporous-rich biochar and preparation method thereof | |
| CN106904589A (en) | A kind of hydro-thermal method prepares method and the application of bagasse Carbon Materials | |
| CN104445186A (en) | Method for preparing mesoporous activated carbon | |
| CN113387355A (en) | Method for preparing porous carbon spheres from biomass raw material | |
| CN106672965B (en) | A method of high-ratio surface multistage mesoporous activated carbon is prepared with cotton stalk | |
| CN111960416A (en) | Method for preparing sulfur-doped carbon material from biomass | |
| CN106365163A (en) | Preparation method of sisal fiber activated carbon, and application of the sisal fiber activated carbon in lithium ion capacitor | |
| Guo et al. | Activation of biomass-derived porous carbon for supercapacitors: A review | |
| CN112811420B (en) | Trichoderma-regulated biomass porous activated carbon and preparation method and application thereof | |
| CN103288080A (en) | Method for preparing high-mesopore-ratio high-adsorptivity ecological carbon | |
| Yin et al. | Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review | |
| CN111646469A (en) | High-activity straw biochar and preparation method thereof | |
| Zhang et al. | Biomass-derived carbon for supercapacitors electrodes-A review of recent advances | |
| Yang et al. | Effects of process parameters on the physicochemical properties of corn stalk hydrochar and the removal of alkali and alkaline earth metals | |
| Liang et al. | Post-modified biomass derived carbon materials for energy storage supercapacitors: a review | |
| CN108821283B (en) | Method for preparing activated carbon by using fir bark microwave-assisted hydrothermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |