CN111960416A - Method for preparing sulfur-doped carbon material from biomass - Google Patents
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Abstract
The invention relates to a method for preparing a sulfur-doped carbon material by biomass, which comprises the following steps of firstly, crushing the biomass into tiny particles, then uniformly mixing the crushed biomass particles with a sulfur-containing acidic solution according to a certain proportion to form a mixture, putting the mixture into a hydrothermal reaction kettle for hydrothermal reaction at a certain temperature, dehydrating and drying hydrothermal carbon obtained after the hydrothermal reaction, putting the dried hydrothermal carbon into a pyrolysis furnace, and carrying out fast pyrolysis under the protection of inert atmosphere at a certain temperature to obtain the sulfur-doped carbon material subjected to fast pyrolysis; the biomass raw material used by the method is agricultural and forestry waste, has wide source and can be regenerated; the method has simple process and less time consumption, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the field of preparation of sulfur-doped carbon materials, and particularly relates to the field of preparation of sulfur-doped carbon materials by using biomass.
Background
The diversification of the carbon material structure and the excellent properties of energy storage, adsorption, load, catalysis and the like attract the attention and research of numerous scientists; biomass-produced carbon materials, particularly high-performance carbon materials, can produce high value-added adsorbing materials or soil improving materials, and are considered to be one of the most effective methods for utilizing biomass. In recent years, research on carbon materials doped with sulfur has increased, and supercapacitors and field emission devices made of carbon materials doped with sulfur have a wide application prospect compared with pure carbon materials. In addition, the surface of the sulfur-doped carbon material has more active sites and good hydrophilicity, so that the sulfur-doped carbon material has remarkable advantages in the aspects of being used as an adsorbing material, a catalytic material and the like.
The methods for preparing sulfur-doped carbon materials from biomass are various, and can be roughly summarized as the following methods:
the direct mixing doping method is characterized in that the method directly carries out high-temperature pyrolysis on the sulfur-containing biomass or the mixture of the biomass and the sulfur-containing material, so that the sulfur element is doped into a carbon skeleton in the process. The method has the advantages of simplicity, directness and low technical requirement. The disadvantages of this are the low doping efficiency and the high temperature requirements, especially for biomass which itself has a low sulfur content, and the very high reaction temperatures and the large amount of sulfur-containing material required for the chemical bonding of the sulfur atoms to the carbon material.
The post-modification doping method comprises the steps of directionally preparing the needed substrate carbon material by utilizing a mature process, and treating the substrate carbon material by utilizing high-temperature sulfur-containing gas to realize surface sulfur doping. The method has the advantages that the prepared sulfur-doped carbon has rich pore structure and large specific surface area, but has very distinct defects, namely only surface sulfur doping can be realized, and the use limitation is large.
A pre-modification doping method, which is to pretreat the raw material by using a special method before biomass pyrolysis so as to improve parameters such as sulfur content, specific surface area, electrochemical performance and the like of sulfur-doped carbon; the pretreatment method can be performed by various methods, including but not limited to hydrothermal method, chemical reagent modification method, and pre-carbonization method. The method has the advantages that the sulfur-doped carbon material with excellent performance can be prepared, and the defects that the modification means is generally complicated to operate, and the preparation time and the cost of the sulfur-doped carbon are improved.
The fast pyrolysis process is a process which accords with the development trend of modern industry, has the characteristics of high production efficiency and suitability for large-scale production; the traditional fast pyrolysis method generally faces the problems of insufficient carbonization, uneven doping and the like, and the invention realizes pre-carbonization and sulfur doping in a hydrothermal kettle by an acid hydrothermal pretreatment method, so that the time required by the subsequent carbonization process is greatly shortened, and the quality of the prepared sulfur-doped active carbon can be ensured; in recent years, some documents disclose methods for preparing sulfur-doped carbon materials, but these methods are significantly different from the present invention.
For example, cn201810985628.x is a preparation method of a sulfur-doped activated carbon-supported noble metal catalyst and an application thereof in hydrogenation of halogenated aromatic nitro compounds. The patent relates to the preparation of sulfur-doped activated carbon, which is carried out according to the following steps: preparing a sulfur-containing compound into an aqueous solution, preparing activated carbon and the aqueous solution into slurry according to a proportion, placing the slurry into a high-pressure hydrothermal kettle, sealing the high-pressure hydrothermal kettle, carrying out hydrothermal reaction at 180-300 ℃ for 10-50 h, cooling to room temperature, filtering, washing with deionized water until filtrate is neutral, and drying the obtained filter cake in vacuum to obtain sulfur-doped activated carbon; the sulfur-containing compound is one or a combination of more of NaS, KS, NaHS and KHS; the mass ratio of the doped sulfur element to the activated carbon is 0.02-0.1: 1, the doping amount of the sulfur element is preferably 4-6 wt%; obviously, the method mentioned in the above patent uses activated carbon with pores, which is different from the biomass material of the present patent. The sulfur-containing solution adopts one or a combination of a plurality of NaS, KS, NaHS and KHS, which is different from sulfuric acid in the patent. And the subsequent non-pyrolysis carbonization is different from the fast pyrolysis of the patent;
CN201610546993.1 a noble metal catalyst loaded by a sulfur-doped carbon material and application thereof. This patent relates to the preparation of a sulfur-doped carbon material, said preparation method being carried out according to the following steps:
(1-a) treating the activated carbon at high temperature by using a sulfur-containing substance in an inert atmosphere, wherein the sulfur-containing substance is elemental sulfur or sulfide to obtain a sulfur-doped carbon material;
(1-b) under an inert atmosphere, taking a sulfur-containing carbon source as a precursor, and carrying out high-temperature carbonization to obtain a sulfur-doped carbon material;
(2) preparing a sulfur-doped carbon material into slurry at the temperature of 20-95 ℃, slowly dropwise adding a solution of a soluble precious metal compound according to the loading amount of the precious metal, and fully and uniformly stirring; after soaking for 0.5-10 h under heat preservation, adding an alkaline solution to adjust the pH value to 7.0-10.0, cooling the temperature to room temperature, filtering, and washing a filter cake to be neutral by deionized water; and preparing the filter cake into slurry at the temperature of 20-95 ℃, dropwise adding a liquid-phase reducing agent, carrying out reduction reaction under stirring, filtering after the reaction is finished, washing the filter cake to be neutral by using deionized water, and carrying out vacuum drying at the temperature of 70-120 ℃ to obtain the sulfur-doped carbon material supported noble metal catalyst.
It is obvious that the method involved in the above patent is a direct mixed doping method, which is different from the pre-modification doping method used in the present patent, and neither pretreatment nor fast pyrolysis is used. The raw materials of the patent are direct, and the biomass raw materials different from the active carbon are used
CN201910814875.8 an in-situ sulfur-doped mesoporous carbon-supported palladium metal catalyst, a preparation method and application thereof. This patent relates to the preparation of a sulfur-doped carbon material, said preparation method being carried out according to the following steps:
dissolving glucose in deionized water, adding a sulfur-containing precursor, carrying out hydrothermal reaction at 180-300 ℃ for 20-50 h, then cooling to room temperature (20-30 ℃), filtering, carrying out vacuum drying on a filter cake at 40-80 ℃ for 8-15 h to obtain a primarily carbonized in-situ doped carbon material, and then heating to 400-800 ℃ in an inert gas (N2, He or Ar) atmosphere to roast for 2-8 h to obtain an in-situ sulfur doped carbon material; the sulfur-containing precursor is one or a mixture of two of KHSO3 and NaHSO3 in any proportion; the mass ratio of the sulfur-containing precursor to glucose in terms of sulfur element is 0.02-0.15: 1, preferably 0.05 to 0.1: 1.
obviously, in the method disclosed in the above patent, the sulfur-containing solution is a mixture of one or two of KHSO3 and NaHSO3 in any proportion, and the bisulfite is used, but the method disclosed in the patent is applicable to sulfuric acid, sulfate and sulfurous acid except the bisulfite, and has wider applicability. Unlike the above-described bisulfite, which provides sulfur atoms only as a sulfur-containing precursor.
Disclosure of Invention
In order to solve the problems, the invention achieves the purposes through the following technical scheme:
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing biomass into tiny particles;
step two, uniformly mixing the crushed biomass particles and a sulfuric acid-containing solution in proportion to form a mixture;
step three, carrying out hydrothermal reaction on the mixture to obtain hydrothermal carbon;
step four, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
and fifthly, putting the dried hydrothermal carbon into a pyrolysis furnace, and carrying out fast pyrolysis under the protection of inert atmosphere at a certain temperature to obtain the fast pyrolyzed sulfur-doped carbon material.
As a further optimized scheme of the invention, in the first step, the biomass is any one or a combination of more than two of lignocellulose biomass, agricultural solid waste and municipal solid waste; the lignocellulose biomass comprises xylitol, xylose, xylan, glucose, cellobiose, cellulose, starch, hemicellulose, chitosan, chitin, sucrose, fructose, wood, bagasse, moso bamboo and corn straws; the agricultural solid waste comprises rapeseed cakes, jatropha curcas cakes, cake pulp, vinasse, waste protein and animal waste, and the urban solid waste comprises waste paper, plastic waste and regenerated plastic.
As a further optimized scheme of the invention, the sulfuric acid-containing solution is any one of sulfuric acid, sulfurous acid and acidic sulfate solution.
As a further optimized scheme of the invention, the acidic sulfate solution comprises NaHSO4, KHSO4, NH4HSO4, (NH4) HSO3, NaHSO3 and KHSO 3.
As a further optimization scheme of the invention, the mixing ratio of the sulfuric acid-containing solution and the biomass in the second step is controlled to be between 0.05:1 and 4:1 according to the mass ratio of sulfur to carbon.
As a further optimization scheme of the invention, the hydrothermal reaction temperature in the third step is 80-300 ℃.
As a further optimization scheme of the invention, the hydrothermal reaction time in the third step is 0.5h to 24 h.
As a further optimization scheme of the invention, the fast pyrolysis temperature in the fifth step is 400-1000 ℃.
As a further optimization scheme of the invention, the time for fast pyrolysis in the fifth step is 1min to 2 h.
The invention has the beneficial effects that:
1) the sulfur-containing acidic solution has multiple functions, and can catalyze the hydrolysis, pore-forming and carbonization processes of biomass besides providing a most basic sulfur source, so that the treatment time of the subsequent pyrolysis step is greatly shortened;
2) the biomass raw material used by the method is agricultural and forestry waste, has wide source and can be regenerated; the method has simple process and less time consumption, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is an XPS spectrum of the S element in a sulfur-doped biomass carbon material according to the present invention;
FIG. 2 is a TEM image of a sulfur-doped biomass carbon material according to the present invention;
FIG. 3 is a BET detection report for a sulfur-doped biochar material according to the present invention;
FIG. 4 is an isothermal adsorption curve for a sulfur-doped biomass carbon material according to 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.
A method for preparing a sulfur-doped carbon material from biomass as shown in fig. 1 to 5 comprises the following steps: the method comprises the following steps:
crushing biomass into tiny particles;
wherein the biomass is any one or the combination of more than two of lignocellulose biomass, agricultural solid waste and municipal solid waste; the lignocellulose biomass comprises xylitol, xylose, xylan, glucose, cellobiose, cellulose, starch, hemicellulose, chitosan, chitin, sucrose, fructose, wood, bagasse, moso bamboo and corn straws; the agricultural solid waste comprises rapeseed cakes, jatropha curcas cakes, cake pulp, vinasse, waste protein and animal waste, and the urban solid waste comprises waste paper, plastic waste and regenerated plastic;
step two, mixing the crushed biomass particles with a sulfuric acid-containing solution according to the mass ratio of sulfur to carbon of 0.05: 1-4: 1, and uniformly forming a mixture;
wherein the sulfuric acid-containing solution is any one of sulfuric acid, sulfurous acid and acidic sulfate solution;
the acidic sulfate solution comprises NaHSO4, KHSO4, NH4HSO4, (NH4) HSO3, NaHSO3 and KHSO 3;
step three, putting the mixture into a hydrothermal reaction kettle to carry out hydrothermal reaction at the hydrothermal temperature of 80-300 ℃, wherein the hydrothermal reaction time is 0.5-24 h;
step four, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
and fifthly, putting the dried hydrothermal carbon into a pyrolysis furnace, performing fast pyrolysis for 1min to 2h at the pyrolysis temperature of 400-1000 ℃, performing fast pyrolysis under the protection of inert atmosphere, and obtaining the sulfur-doped carbon material subjected to fast pyrolysis.
The acid water heating fast pyrolysis method adopted by the invention also belongs to a pre-modification doping method, and the acid water heating means that the acid water solution containing the sulfuric acid solution and the biomass are mixed and then are placed in a hydrothermal kettle containing a polytetrafluoroethylene lining. Carrying out hydrothermal reaction for a certain time at a certain temperature. In the process, the hydrolysis, carbonization and sulfur doping of the biomass are performed cooperatively by acid catalysis. The acid hydrothermal carbonization process usually occurs under the condition that the temperature is lower than 300 ℃, a series of reactions such as dehydration, polymerization, hydrolysis and the like usually occur, and the process of hydrothermal carbonization of the biological hyaluronic acid can complete deep mixing and pre-carbonization of the biomass and the acid in a short time. The acid water thermal carbonization process is a spontaneous adiabatic process, so most of biomass carbon is finally converted into carbon in a carbon material, the extra loss is little, the carbon atom efficiency is high, and the atom economy principle is met. Meanwhile, compared with the common hydrothermal method, the acid hydrothermal method has a good ash removal effect, is particularly suitable for secondary utilization of waste biomass, and realizes ash removal while mixing and pre-carbonization;
in the invention, the acid hydrothermal method and the fast pyrolysis are an organic whole, rather than two steps of cutting, and the acid hydrothermal method and the fast pyrolysis are not suitable for sulfur doping when used alone, and can obtain excellent doping effect only when used together.
Firstly, in the sulfuric acid hydrothermal process, the reaction temperature is low, so that the reaction condition of adding sulfur into a carbon skeleton is difficult to meet, and sulfur doping cannot be realized per se; however, in the process, the hot-pressed water in the reaction kettle is water in a subcritical or supercritical state at the temperature of more than 100 ℃, the dielectric constant is reduced to a level similar to that of a common organic solvent, the condition is favorable for dissolving alkali metals and soluble organic matters in biomass ash in acid to realize deashing of the biomass, and the deashing of the substances provides sites for deep impregnation of sulfuric acid in the biomass to realize uniform impregnation. Meanwhile, in the acid hydrothermal process, a plurality of oxygen-containing functional groups are formed on the organic material by hydrothermal pre-carbonization, and the biomass material can be changed into a loose and porous three-dimensional structure by using sulfuric acid, so that a large number of oxygen-containing functional groups can be formed on the surface and the loose internal three-dimensional structure of the material in the acid hydrothermal pre-treatment process of the sulfuric acid, and the oxygen-containing functional groups can react with the sulfuric acid to successfully load sulfate on the material, and the load capacity is considerable, but the load in the form does not really dope the S element into a carbon skeleton, so that further carbonization and activation are needed;
the fast pyrolysis usually adopts high-temperature gas to rapidly process biomass, has the characteristics of rapid temperature rise, short reaction time and the like, has poor processing effect on blocky or glume-shaped materials, and the main target product of the fast pyrolysis technology is bio-oil, the carbon yield after processing is very low, the sulfur doping reaction is insufficient, and the fast pyrolysis technology is not suitable for preparing sulfur-doped materials; but the pre-carbonization and pre-doping effects in the acid hydrothermal process well make up for the defects, the biomass structure is more stable in the pre-carbonization process, and the transfer of carbon elements to gas-phase and liquid-phase products in the rapid pyrolysis process is reduced. The deep impregnation of sulfuric acid and biomass is completed in the pre-doping process, a good foundation is provided for sulfur doping in the fast pyrolysis process, and a carbon material with high sulfur doping amount can be prepared in a short time.
The acid hydrothermal method and the rapid pyrolysis method are combined for use, so that the sulfur-doped carbon material with large specific surface area can be prepared, and the traditional sulfur-doping method needs to be pyrolyzed at a higher temperature for a long time in order to improve the sulfur-doping effect; in the method, a loose structure is formed due to sulfuric acid hydrothermal pre-carbonization, a large amount of sulfate radicals are loaded, the material structure is damaged by long-time high-temperature carbonization and activation operation, so that a carbon skeleton collapses, the final pore structure of the material is influenced, and loaded S falls off, so that the aim of forming an effective S-doped carbon material cannot be fulfilled;
the acid water thermal combination rapid pyrolysis method used by the invention can make full use of the advantages and avoid the disadvantages by combining the two methods, and can quickly carbonize and activate the interior of the formed material with a loose structure, so that oxygen-containing functional groups are removed to form a pore structure, meanwhile, a large amount of load S can obtain the opportunity of inserting into a carbon skeleton, and the structure is not damaged by short-time rapid treatment, thereby achieving the final effect.
Example 1
In the embodiment, four different types of biomass, namely cellulose, glucose, wood chips and waste gas paper, are respectively selected and crushed, 5g of biomass particles are respectively weighed for standby application, and a sulfur-doped carbon material is prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing with sulfuric acid solution according to the mass ratio of sulfur to carbon of 1:1 to form a uniform mixture,
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing for 30min at 700 ℃ under the protection of nitrogen atmosphere, quickly cooling a product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
Specific surface areas of sulfur-doped carbon materials prepared from four different types of biomass are shown in table 1:
TABLE 1 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid-thermal combined fast pyrolysis of different types of biomass
Example 2
In the embodiment, the influence of different sulfur sources and acid sources on the properties of the boron-doped biomass carbon material is tested, only the types of the sulfur sources and the acid sources are changed, the PH of the solution is controlled to be less than 3 according to the amount of the added acid sources, and the material is prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing with a sulfur-containing acidic solution according to the mass ratio of sulfur to carbon of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing for 30min at 700 ℃ under the protection of nitrogen atmosphere, quickly cooling a product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the sulfur-doped carbon material prepared from the wood chip biomass under the conditions of different sulfur sources and acid sources is shown in table 2:
TABLE 2 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid-water thermal combined fast pyrolysis of different sulfur sources and acid sources
Example 3
In this example, the influence of different sulfur-carbon ratios on the properties of sulfur-doped carbon materials was tested, only the ratio of sulfur to carbon was changed, and the materials were prepared according to the following preparation methods;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, mixing 5g of crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 0.05:1, 0.2:1, 1:1 and 4:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing for 30min at 700 ℃ under the protection of nitrogen atmosphere, quickly cooling a product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the biomass-prepared sulfur-doped carbon material under four different sulfur-to-carbon ratios is shown in table 3:
TABLE 3 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid hydrothermal combined fast pyrolysis at different sulfur-to-carbon ratios
Example 4
In this example, the effect of 5 different hydrothermal temperatures on the properties of sulfur-doped carbon materials was tested, only the hydrothermal temperature was changed, and the materials were prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing the crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and then placing the reaction kettle into an oven with the temperature of 80 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ for hydrothermal treatment for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing for 30min at 700 ℃ under the protection of nitrogen atmosphere, quickly cooling a product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the biomass prepared sulfur-doped carbon material under the conditions of five different hydrothermal temperatures is shown in table 4:
TABLE 4 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid water hot-melt fast pyrolysis at different hydrothermal temperatures
Example 5
In this example, four different hydrothermal times were tested for their effect on the properties of sulfur-doped carbon materials, only the hydrothermal time was varied, and the materials were prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing the crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and then placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 0.5h, 6h, 12h and 24 h;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing for 30min at 700 ℃ under the protection of nitrogen atmosphere, quickly cooling a product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the biomass-prepared sulfur-doped carbon material under four different hydrothermal time conditions is shown in table 5:
TABLE 5 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid hydrothermal combined fast pyrolysis at different hydrothermal times
Example 6
In this example, the effect of different pyrolysis temperatures on the properties of sulfur-doped carbon materials was tested, only the pyrolysis temperature was changed, and the materials were prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing the crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing the solid powder for 30min at 400 ℃, 550 ℃, 700 ℃, 850 ℃ and 1000 ℃ under the protection of nitrogen atmosphere, quickly cooling the product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the biomass-produced sulfur-doped carbon material at different pyrolysis temperatures is shown in table 6:
TABLE 6 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid hydrothermal combined fast pyrolysis at different pyrolysis temperatures
Example 7
In this example, the effect of different pyrolysis times on the properties of sulfur-doped carbon materials was tested, only the pyrolysis time was varied, and the materials were prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing the crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
step four, 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 ℃ drying oven;
and fifthly, transferring the dried solid powder into a pyrolysis furnace, quickly pyrolyzing at 700 ℃ for 1min, 30min, 60min and 120min under the protection of nitrogen atmosphere, quickly cooling the product after pyrolysis, washing and drying to obtain the sulfur-doped carbon material.
The specific surface area of the biomass-produced sulfur-doped carbon material under different pyrolysis times is shown in table 7:
TABLE 7 specific surface area and elemental composition for preparing sulfur-doped carbon materials by acid hydrothermal combined fast pyrolysis at different pyrolysis times
Comparative example 1
In this comparative example, the influence on the properties of the sulfur-doped biomass carbon material was tested using only the hydrothermal reaction process of biomass with a sulfuric acid-containing solution, i.e., without performing the fast pyrolysis method, and the sulfur-doped carbon material was prepared according to the following preparation method;
a method for preparing a sulfur-doped carbon material from biomass comprises the following steps:
crushing sawdust biomass into fine particles;
step two, selecting 5g of crushed biomass particles and mixing the crushed biomass particles with a sulfuric acid solution according to a sulfur/carbon mass ratio of 1:1 to form a uniform mixture;
step three, placing the mixture into a hydrothermal reaction kettle with the volume of 100ml, sealing the reaction kettle, and placing the reaction kettle into a 200 ℃ oven for hydrothermal reaction for 12 hours;
and step four, 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 in an oven at 105 ℃ to obtain the sulfur-doped carbon material.
Collecting the biomass source sulfur-doped carbon material, detecting, and preparing the sulfur-doped carbon material with the specific surface area of 549.9m2/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 sulfur-doped carbon material subjected to the fast pyrolysis reaction is up to 1942.1m 2/g; thus, it is apparent that the parameters of the sulfur-doped carbon materials made using the present application are far superior to those made by the prior art.
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 (9)
1. A method for preparing a sulfur-doped carbon material 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 and a sulfuric acid-containing solution in proportion to form a mixture;
step three, carrying out hydrothermal reaction on the mixture to obtain hydrothermal carbon;
step four, dehydrating and drying the hydrothermal carbon obtained after the hydrothermal reaction;
and fifthly, putting the dried hydrothermal carbon into a pyrolysis furnace, and performing fast pyrolysis under the protection of inert atmosphere to obtain the fast pyrolyzed sulfur-doped carbon material.
2. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: in the step one, the biomass is any one or the combination of more than two of lignocellulose biomass, agricultural solid waste and municipal solid waste; the lignocellulose biomass comprises xylitol, xylose, xylan, glucose, cellobiose, cellulose, starch, hemicellulose, chitosan, chitin, sucrose, fructose, wood, bagasse, moso bamboo and corn straws; the agricultural solid waste comprises rapeseed cakes, jatropha curcas cakes, cake pulp, vinasse, waste protein and animal waste, and the urban solid waste comprises waste paper, plastic waste and regenerated plastic.
3. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: the sulfur-containing acidic solution is any one of sulfuric acid, sulfurous acid and acidic sulfate solution.
4. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 3, wherein the method comprises the following steps: the acidic sulfate solution comprises NaHSO4, KHSO4, NH4HSO4, (NH4) HSO3, NaHSO3 and KHSO 3.
5. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: and in the second step, the mixing ratio of the sulfuric acid-containing solution to the biomass is controlled to be 0.05:1 to 4:1 according to the mass ratio of sulfur to carbon.
6. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: the hydrothermal reaction temperature in the third step is 80-300 ℃.
7. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: the hydrothermal reaction time in the third step is 0.5h to 24 h.
8. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: and in the fifth step, the fast pyrolysis temperature is 400-1000 ℃.
9. The method for preparing the sulfur-doped carbon material by using the biomass as claimed in claim 1, wherein the method comprises the following steps: and the time for fast pyrolysis in the fifth step is 1min to 2 h.
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