CN115414910A - Preparation method of magnetic porous biological carbon material - Google Patents

Preparation method of magnetic porous biological carbon material Download PDF

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CN115414910A
CN115414910A CN202210918762.4A CN202210918762A CN115414910A CN 115414910 A CN115414910 A CN 115414910A CN 202210918762 A CN202210918762 A CN 202210918762A CN 115414910 A CN115414910 A CN 115414910A
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salt
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magnetic porous
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hydrothermal
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CN115414910B (en
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费会
高树民
江海婷
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Wuhan Polytechnic University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton

Abstract

The invention discloses a preparation method of a magnetic porous biological carbon material, which comprises the following steps: cleaning biomass, peeling, airing, shearing into powder, and mixing the powder with a salt solution to obtain a mixed solution; heating the mixed solution to carry out hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon; uniformly mixing hydrothermal carbon, molten salt and ferric salt to obtain a mixture, heating the mixture to be carbonized in an oxygen-isolated environment, cooling, and washing and drying a carbonized product to obtain a carbide; and heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biological carbon material. The magnetic porous biological carbon material prepared by the invention has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and solves the problem of poor adsorption performance caused by difficult control of the morphology structure of the biological carbon due to the internal tissues of the precursor in the conventional biological carbon material.

Description

Preparation method of magnetic porous biological carbon material
Technical Field
The invention relates to the technical field of adsorption material preparation, and particularly relates to a preparation method of a magnetic porous biological carbon material.
Background
At present, the discharge of large amounts of industrial waste water, such as many dyes in dye waste water, is harmful to the environment and human health, and therefore the removal of organic dyes from industrial waste water is very important. The magnetic porous carbon material has the characteristics of high specific surface area, high pore volume, strong adsorption capacity, magnetic separability and the like, and has great application potential in the fields of treatment, purification and the like of dye wastewater.
Lignocellulose such as straw, leaves, sawdust and the like is the most abundant biomass resource on the earth and has a very firm network-shaped organization structure. The firm net structure can be inherited, lignocellulose is used as a carbon source, and the porous carbon material can be conveniently prepared by the processes of pyrolysis, hydrothermal carbonization and the like, and the cost is low. However, the prepared carbon material is limited by the firm network structure of the precursor, the morphology structure is difficult to control, the pore size distribution is wide, and the pores are randomly connected, so that the adsorption performance and the ion transmission performance are poor, and the application of the carbon material in various fields is limited.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a magnetic porous biological carbon material, aiming at improving the adsorption performance of the biological carbon material.
In order to achieve the purpose, the invention provides a preparation method of a magnetic porous biological carbon material, which comprises the following steps:
cleaning, peeling, airing and shearing biomass to prepare powder, and then mixing the powder with a salt solution to obtain a mixed solution;
heating the mixed solution to carry out hydrothermal reaction, then collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
uniformly mixing the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture, heating the mixture to be carbonized under the environment of isolating oxygen, cooling, and then washing and drying a carbonized product to obtain a carbide;
and heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biological carbon material.
Optionally, the steps of cleaning, peeling, airing and cutting the biomass into powder, and then mixing the powder with a salt solution to obtain a mixed solution are as follows:
the biomass comprises at least one of corn stover, soybean stover, and wood chips.
Optionally, the step of cleaning, peeling, air-drying, cutting and crushing the biomass to obtain powder, and then mixing the powder with a salt solution to obtain a mixed solution comprises:
the salt solution comprises at least one of a potassium chloride solution, a sodium sulfate solution and a sodium chloride solution; and/or the presence of a gas in the gas,
the molar concentration of the salt solution is 0.05-0.2 mol/L.
Optionally, the step of cleaning, peeling, air-drying, cutting and crushing the biomass to obtain powder, and then mixing the powder with a salt solution to obtain a mixed solution comprises:
the mass ratio of the biomass to the salt solution is 1: (50-200).
Optionally, the step of heating the mixed solution to perform a hydrothermal reaction, then collecting a solid product generated by the hydrothermal reaction, washing, and drying to obtain hydrothermal carbon:
the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 6-12 h.
Optionally, the hydrothermal carbon, the molten salt, and the iron salt are uniformly mixed to obtain a mixture, the mixture is heated to carbonization and then cooled in an oxygen-isolated environment, and then a carbonized product is washed and dried to obtain a carbide:
the molten salt comprises LiCl/KCl system molten salt, naCl/KCl system molten salt and ZnCl 2 At least one of KCl system molten salts; and/or the presence of a gas in the gas,
the iron salt comprises Fe 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of; and/or the presence of a gas in the gas,
the mass ratio of the hydrothermal carbon to the molten salt to the ferric salt is (0.5-2): (20 to 50): (0.05-0.2).
Optionally, the step of uniformly mixing the hydrothermal carbon, the molten salt, and the iron salt to obtain a mixture, heating the mixture to carbonization in an oxygen-isolated environment, cooling, washing and drying a carbonized product to obtain a carbide, includes:
uniformly ball-milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture;
heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature in the nitrogen atmosphere, washing and drying the carbonized product to obtain the carbide.
Optionally, the step of washing the carbonized product comprises:
adding a hydrochloric acid solution into the carbonized product, then stirring at room temperature for 12-24 h, collecting the precipitate, and washing the precipitate with distilled water.
Alternatively, adding a hydrochloric acid solution to the carbonized product, stirring at room temperature for 12-24 h, collecting the precipitate, and washing the precipitate with distilled water:
the mass concentration of the hydrochloric acid solution is 10-30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
Optionally, the step of heating and activating the carbide in a water vapor environment, and obtaining the magnetic porous biological carbon material after cooling, comprises:
and heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving the heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
According to the technical scheme provided by the invention, biomass is used as a raw material, a hydrothermal reaction is firstly carried out, and internal tissues of the biomass are dispersed into a plurality of small fragments; then, mixing the mixture with molten salt and ferric salt, carbonizing at high temperature, and regulating the morphological structure of the product by taking molten salt ions as a template to obtain iron species embedded carbide with a regular structure; and then activating carbide with steam, and making the embedded iron species exposed and oxidized by the steam into magnetic ferroferric oxide while making pores through a steam-carbon reaction to prepare the magnetic porous biological carbon material. Therefore, the prepared magnetic porous biological carbon material has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and well solves the problem of poor adsorption performance caused by the fact that the morphology and structure of the biological carbon are not easy to control due to the internal tissues of the precursor of the existing biological carbon material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic flow chart of an embodiment of a method for preparing a magnetic porous biochar material according to the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The porous carbon material can be conveniently prepared by using lignocellulose as a carbon source through processes such as pyrolysis, hydrothermal carbonization and the like, and the cost is low, but the prepared carbon material is limited by a firm mesh structure of a precursor, the morphology structure is difficult to control, the pore size distribution is wide, and pores are randomly connected, so that the adsorption performance and the ion transmission performance are poor, and the application of the porous carbon material in various fields is limited.
In order to solve the problem of poor adsorption performance caused by the fact that the morphological structure of the biological carbon material is limited by the organizational structure of the precursor of the biological carbon material and is difficult to regulate, the invention provides a preparation method of a magnetic porous biological carbon material, and fig. 1 shows an embodiment of the preparation method of the magnetic porous biological carbon material provided by the invention. Referring to fig. 1, in the present embodiment, the method for preparing the magnetic porous biocarbon material includes the following steps:
s10, cleaning, peeling, airing and shearing biomass to prepare powder, and mixing the powder with a salt solution to obtain a mixed solution;
s20, heating the mixed solution to perform hydrothermal reaction, collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
s30, uniformly mixing the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture, heating the mixture to carbonization in an oxygen-isolated environment, cooling, and then washing and drying a carbonized product to obtain a carbide;
and S40, heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biological carbon material.
According to the technical scheme provided by the invention, biomass is used as a raw material, is washed, peeled and dried to prepare powder, and is mixed with a salt solution to carry out hydrothermal reaction, so that the internal tissues of the biomass are dispersed into a plurality of small fragments; then, mixing the iron salt with molten salt and ferric salt, carbonizing at high temperature, and regulating the morphological structure of the product by taking molten salt ions as a template to obtain iron species embedded carbide with a regular structure; and then activating carbide with steam, and making the embedded iron species exposed and oxidized by the steam into magnetic ferroferric oxide while making the pores through a water-carbon reaction to prepare the magnetic porous biological carbon material. Therefore, the prepared magnetic porous biological carbon material has the characteristics of large specific surface area and regular structure, has higher adsorption capacity, and well solves the problem that the prior biological carbon material has poor adsorption performance due to the fact that the morphology and structure of the biological carbon are not easy to control due to the internal tissues of the precursor.
The biomass is used for providing a carbon source for the magnetic porous biocarbon material, any lignocellulose biomass containing carbon elements can be selected, in the embodiment of the present invention, at least one of corn straw, soybean straw and wood chips is preferably selected, and any one of the above biomasses or a combination of any two or three of the above biomasses can be selected, which belongs to the protection scope of the present invention. In a preferred embodiment of the present invention, any one of the above biomasses may be selected as the biomass, which is beneficial to simplifying the process.
The salt solution is used for penetrating into an internal tissue structure of the biomass in the hydrothermal reaction process and destroying high-energy ions of the tissue structure of the biomass, the salt solution may be any solution containing salt substances of potassium elements or sodium elements, in the embodiment of the present invention, at least one of a potassium chloride solution, a sodium sulfate solution and a sodium chloride solution is preferably included, either one of the salt solutions or a mixed solution of any two or three of the salt solutions may be selected, and the present invention falls within the protection scope of the present invention. In a preferred embodiment of the present invention, the salt solution is any one of the above salt solutions.
Further, in some embodiments of the invention, the salt solution has a molar concentration of 0.05 to 0.2mol/L.
Still further, in some embodiments of the invention, the mass ratio of the biomass to the salt solution is 1: (50-200), the magnetic porous biological carbon material prepared in the range has better adsorption performance.
Lignocellulose is the most abundant biomass resources on the earth, such as agricultural wastes like straws, stalks and the like, a large amount of agricultural waste biomass like straws, stalks and the like is produced in China every year, the environment is greatly damaged by most of the agricultural waste biomass resources through incineration treatment, and the biomass resources are wasted. The carbon material is prepared from agricultural waste biomass, and is applied to the fields of sewage treatment and energy storage, so that the problem of environmental pollution can be effectively relieved, and considerable economic benefits can be brought. However, lignocellulose has a very strong cellulose-hemicellulose-lignin network structure, which is highly resistant to biological or non-biological attack in the environment. Therefore, lignocellulose-based porous carbon is limited by the firm organization structure of the precursor, and the morphology structure of the lignocellulose-based porous carbon is not easy to control.
In order to obtain desired biochar, the strong structure of the precursor needs to be destroyed, and methods such as pyrolysis and hydrothermal method are used. The hydrothermal method can avoid the defects of volatilization, stress induction defects, phase mutual reaction and the like of reactants at high temperature, and more importantly, the hydrothermal method can control the appearance, size, viscosity distribution and the like of a product by adjusting reaction conditions. In the embodiment of the invention, an inorganic-assisted hydrothermal method is adopted, the reaction temperature of the hydrothermal reaction is controlled to be 80-160 ℃, and the reaction time is controlled to be 6-12 h, so that the lignocellulose tissue structure is decomposed into a plurality of uniform small fragments, and conditions are provided for the formation and activation of a subsequent carbon matrix with a regular structure.
The synthesis method of the magnetic porous carbon material mainly comprises a hydrothermal method, a molten salt synthesis method, a coprecipitation method and a method for directly carbonizing a metal organic framework material. The fused salt synthesis method takes fused salt as a template, can reconstruct the appearance and structure of a product, and is easy to obtain the magnetic porous carbon material with rich pore channels. Specifically, in the embodiment of the invention, the iron-embedded carbide is prepared by using the hydrothermal carbon as a carbon source and using an iron salt as an iron source in an oxygen-isolated environment through a molten salt synthesis method. The oxygen-isolated environment can be realized by filling inert gas such as nitrogen, argon and the like, and the oxygen-isolated environment is realized by filling nitrogen as an example, and the specific steps of the molten salt synthesis method comprise:
s31, uniformly ball-milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture;
and S32, heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature in the nitrogen atmosphere, washing and drying the carbonized product to obtain the carbide.
Firstly, heating the mixture to 200-400 ℃, and preserving heat for 1-3 h to fully melt and effectively dissolve the hydrothermal carbon, the molten salt and the ferric salt, wherein the molten salt and the ferric salt molecules can effectively permeate and diffuse into the internal tissues of the hydrothermal carbon and are fully mixed with the internal structural units of the hydrothermal carbon; further heating the mixture to 500-900 ℃, preserving heat for 1-3 h, further graphitizing the hydrothermal carbon, and enabling the carbon to be in a sp2 hybridization state from a sp3 hybridization state, wherein a carbonized product with a sheet structure is generated in the process, and meanwhile, high-temperature molten salt can continuously permeate and is finally embedded in a carbon material matrix to prevent carbon sheets from being stacked, so that the product keeps the sheet structure; meanwhile, high-energy ions in the molten salt can further etch the carbon sheet to form a large number of micropore pore structures: on the other hand, the iron salt penetrating into the hydrothermal carbon is reduced by carbothermal reduction, further catalyzes the carbon matrix, catalyzes the graphitized carbon coating layer, and finally is uniformly embedded into the carbon matrix. When the temperature of the system is reduced to be lower than the melting point of the salt, the molten salt is recrystallized, a large part of salt particles are embedded in a carbon product matrix and serve as templates, and when the salt particles are separated from the product, abundant macropores or mesopores are left in the carbon product, so that the hierarchical pore structure carbon nano sheet with the uniformly embedded iron species is formed.
And after the carbonization reaction is finished, removing a molten salt template in the carbonized solid product, namely the indicated iron species, so as to obtain the target product. In the embodiment of the present invention, the method is implemented by adding an acidic solution to the carbonized solid product, and specifically includes: adding a hydrochloric acid solution into the carbonized product, stirring at room temperature for 12-24 h to achieve the aim of fully removing the molten salt template and the iron species on the surface, separating and collecting the precipitate in the solution, washing the precipitate with distilled water, and drying to obtain the iron species embedded carbide.
Further, in some embodiments of the present invention, the mass concentration of the hydrochloric acid solution is 10 to 30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
The iron salt is used for providing an iron source for the magnetic porous biological carbon material, and any inorganic salt substance containing iron element can be selected, and in the embodiment of the invention, the iron salt preferably comprises Fe 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of the above iron salts may be any one of the above iron salts, or a mixture of any two or more of them, and all of them fall within the scope of the present invention. In a preferred embodiment of the present invention, the iron salt may be any one of the iron salts.
The molten salt is a short name of a molten inorganic compound and is used as a solvent, a reaction medium and a template in the molten salt synthesis process. In the whole molten salt synthesis process, molten salt undergoes melting, ionization, solidification and other processes; after the molten salt is melted, the liquid environment provided by the molten salt enhances the diffusion and convection mass transfer of reaction components, so that the precursor is highly dispersed; the ionized anions and cations have strong polarization force at high temperature, can be effectively adsorbed or penetrate among generated product particles, and can effectively prevent the agglomeration among the particles; and finally, the molten salt is condensed into crystals, so that the shrinkage and collapse of the porous carbon material can be avoided.
The selection of the molten salt is important, and molten salt synthesis is usually at the melting point (T) of the salt system due to the nature of the molten salt m ) And boiling point (T) b ) At a temperature between. T of most salts m Is a constant value, the melting point of the eutectic mixture complex salt system is usually much lower than the individual components,so that usually multicomponent salts are used as molten salt systems. In addition, salts have different crystal structures, such as LiCl, naCl, and KCl, which are ionic compounds, with similar cubic crystal structures. In the embodiment of the present invention, the molten salt preferably includes LiCl/KCl system molten salt, naCl/KCl system molten salt, and ZnCl 2 At least one of the/KCl system molten salts can be any one of the above molten salts, or a mixture of any two or three of the above molten salts, and all the molten salts belong to the protection scope of the invention. In a preferred embodiment of the present invention, the molten salt may be any one of the above molten salts.
Further, in some embodiments of the present invention, the mass ratio of the hydrothermal carbon, the molten salt, and the iron salt is (0.5-2): (20 to 50): (0.05-0.2).
After the carbide is prepared through a carbonization reaction, the carbide needs to be activated by water vapor, and the magnetic porous biocarbon material is prepared by exposing embedded iron species and oxidizing the iron species into magnetic ferroferric oxide through water vapor during pore forming through a water-carbon reaction. Specifically, in the embodiment of the present invention, the specific steps of performing water vapor activation on the carbide are as follows: heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving the heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
The method provided by the invention takes biomass as a carbon source, firstly carries out hydrothermal treatment, utilizes salt solution to permeate into the internal organization structure of the biomass in the hydrothermal reaction process, destroys high-energy ions of the organization structure of the biomass, and disperses the internal organization of the biomass into a plurality of small carbon blocks; then mixing the small carbon blocks with molten salt and ferric salt, synthesizing by the molten salt, and reconstructing the morphology structures of a plurality of small carbon blocks by taking molten salt ions as templates to obtain iron species embedded carbide with a regular structure; and activating the carbide by steam, and carrying out a water-carbon reaction to expose and oxidize the embedded iron species into magnetic ferroferric oxide while forming the pores, thereby preparing the magnetic porous biochar material. The prepared magnetic porous biochar material has the advantages of large specific surface area, regular structure and higher adsorption performance, and solves the problem that the morphological structure of the biochar is difficult to control due to the internal organization of a precursor. On the other hand, the preparation process comprises the steps of decomposing the biomass into a plurality of small carbon blocks, reconstructing the morphological structure of the small carbon blocks, embedding iron species, and oxidizing the embedded iron species into magnetic ferroferric oxide in a naked way to prepare the magnetic porous biochar material; the process is simple, the equipment used in the preparation process is common equipment and has low price, and the used reagent and solvent are raw materials which have wide sources, low price and small environmental pollution, thereby reducing the production cost of the magnetic porous biochar material.
The magnetic porous biological carbon material prepared by the method provided by the invention is detected by a transmission electron microscope, and the material consists of a large number of nano sheets with regular structures, wherein the nano sheets have a large number of micropores and mesopores; atomic force microscope detection shows that the thickness of the nanosheet is about 15.6nm; the obtained magnetic porous biological carbon material is subjected to element analysis by an atomic emission spectrometry and an element analyzer, and the analysis result shows that the material simultaneously contains 80.46-89.31% of carbon element, 6.85-11.58% of iron element and 1.51-3.21% of oxygen element. N of the material 2 The adsorption and desorption tests show that the specific surface area and the corresponding pore volume of the material are 1325.2m respectively 2 g -1 And 0.852cm 3 g -1 And obvious distribution peaks appear in the micropore range of 0-2 nm or the mesopore range of 2-50 nm. Further, XRD detection revealed that characteristic diffraction peaks of (002) and (100) crystal planes of graphite appeared around 23.6 ° and 45.2 ° in addition to the characteristic diffraction peak of amorphous carbon, indicating that the material was a partially graphitized polycrystalline structure; and the characteristic diffraction peak related to the iron element does not appear, and the characteristic diffraction peak of the iron element or the oxide does not appear probably because the iron species is embedded in the carbon matrix or has too little mass. Magnetic property detection shows that the saturation magnetization of the material is 56.2emu/g, the material has superparamagnetism, and can be rapidly recycled from a water environment under the action of an external magnetic field.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Cleaning, peeling, airing and cutting corn straws, then mechanically milling the corn straws into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.05mol/L according to the weight ratio of 1:50 to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 80 ℃ for hydrothermal reaction for 12 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon prepared in the step (2), liCl/KCl system molten salt and Fe 2 (SO 4 ) 3 According to the weight ratio of 0.5:20: ball-milling and mixing uniformly according to the mass ratio of 0.05 to obtain a mixture; heating the obtained mixture to 200 ℃ at a heating rate of 1 ℃/min, preserving heat for 3h, heating to 600 ℃ and preserving heat for 3h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1: and 100, adding a hydrochloric acid solution with the mass concentration of 10% into the carbonized product, stirring at room temperature for 12 hours, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 600 ℃ at a heating rate of 1 ℃/min in a steam atmosphere, keeping the temperature for 3 hours for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 2
(1) Cleaning, peeling, airing, cutting and crushing corn straws, mechanically milling the corn straws into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.08mol/L according to the weight ratio of 1:100 to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 100 ℃ for hydrothermal reaction for 10 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon prepared in the step (2), liCl/KCl system molten salt and Fe 2 (SO 4 ) 3 According to the following steps of 1:30:0.1 textureBall milling and mixing uniformly in a quantitative ratio to obtain a mixture; heating the obtained mixture to 250 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, heating to 700 ℃ and preserving heat for 2h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1: and 120, adding a hydrochloric acid solution with the mass concentration of 15% into the carbonized product, stirring for 15 hours at room temperature, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 700 ℃ at a heating rate of 2 ℃/min in a water vapor atmosphere, keeping the temperature for 2h for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 3
(1) Cleaning, peeling, airing, cutting and crushing soybean straws, mechanically milling the soybean straws into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.12mol/L according to the weight ratio of 1:150 to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 120 ℃ for hydrothermal reaction for 8 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon prepared in the step (2), naCl/KCl system molten salt and FeCl 3 According to the following steps: 40: ball-milling and uniformly mixing the components according to the mass ratio of 0.15 to obtain a mixture; heating the obtained mixture to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, heating to 800 ℃ and preserving heat for 2h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1:200, adding a hydrochloric acid solution with the mass concentration of 20% into the carbonized product, stirring for 18 hours at room temperature, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 800 ℃ at a heating rate of 3 ℃/min in a water vapor atmosphere, preserving heat for 2h for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 4
(1) Cleaning, peeling, airing, cutting and crushing soybean straws, mechanically milling the soybean straws into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.15mol/L according to the weight ratio of 1:80 to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 140 ℃ for hydrothermal reaction for 6 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) The hydrothermal carbon prepared in the step (2), naCl/KCl system molten salt and FeCl 3 According to the weight ratio of 0.8:50: ball-milling and mixing uniformly according to the mass ratio of 0.18 to obtain a mixture; heating the obtained mixture to 350 ℃ at a heating rate of 4 ℃/min, preserving heat for 3h, heating to 900 ℃ and preserving heat for 1h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1:150, adding a hydrochloric acid solution with the mass concentration of 25% into the carbonized product, stirring for 20 hours at room temperature, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 900 ℃ at a heating rate of 4 ℃/min in a water vapor atmosphere, preserving heat for 2h for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 5
(1) Cleaning, peeling, airing and cutting wood chips, then mechanically milling the wood chips into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.18mol/L according to the weight ratio of 1:120, to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 150 ℃ for hydrothermal reaction for 8 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) Hydrothermal carbon and ZnCl prepared in the step (2) 2 Molten salt of/KCl system, fe 2 (NO 3 ) 3 According to the weight ratio of 1.2:35: ball-milling and mixing uniformly according to the mass ratio of 0.2 to obtain a mixture; heating the obtained mixture to 400 deg.C at a heating rate of 5 deg.C/min, maintaining for 1h, heating to 1000 deg.C, maintaining for 2h, and naturally cooling to room temperature in nitrogen atmosphereTo obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1: and 180, adding a hydrochloric acid solution with the mass concentration of 30% into the carbonized product, stirring at room temperature for 24 hours, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 1000 ℃ at a heating rate of 5 ℃/min in a steam atmosphere, keeping the temperature for 1h for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
Example 6
(1) Cleaning, peeling, airing and cutting wood chips, then mechanically ball-milling the wood chips into powder, and mixing the powder with a potassium chloride solution with the concentration of 0.2mol/L according to the proportion of 1:180 to obtain a mixed solution.
(2) And (2) heating the mixed solution prepared in the step (1) to 160 ℃ for hydrothermal reaction for 6 hours, separating and collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain the hydrothermal carbon.
(3) Hydrothermal carbon and ZnCl prepared in the step (2) 2 Molten salt of/KCl system, fe 2 (NO 3 ) 3 According to the weight ratio of 1.8:45: ball-milling and mixing uniformly according to the mass ratio of 0.12 to obtain a mixture; heating the obtained mixture to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 1h, heating to 1100 ℃, preserving heat for 1h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain a carbonized product; according to the mass ratio of the carbonized product to the hydrochloric acid solution of 1:130, adding a hydrochloric acid solution with the mass concentration of 20% into the carbonized product, stirring for 22 hours at room temperature, washing with distilled water, and drying to obtain the carbide.
(4) And (4) heating the carbide prepared in the step (3) to 1100 ℃ at a heating rate of 3 ℃/min in a water vapor atmosphere, preserving heat for 2h for activation, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
The adsorption performance of the magnetic porous biocarbon materials prepared in examples 1 to 6 was analyzed, and the method and results were as follows:
the method for evaluating the adsorption performance comprises the following steps: the commercially available porous biochar is taken as a comparative example, the magnetic porous biochar materials prepared in the comparative example and the above examples 1 to 6 are respectively placed in an adsorption reaction device under normal temperature and neutral conditions, the purification treatment effect of different materials for 2h on dye wastewater containing malachite green, phenol industrial wastewater and sulfanilamide antibiotic wastewater is examined, and the adsorption performance is evaluated by taking the removal rate of the malachite green as an evaluation index.
The method for evaluating the stability of the adsorption performance comprises the following steps: after the adsorption performance of the material is evaluated, the obtained solid material is washed and dried through centrifugal separation or filtration, and then the adsorption activity stability of the material is inspected according to the adsorption performance evaluation method.
The results of the adsorption performance and stability of the adsorption activity evaluation are shown in table 1 below.
TABLE 1 results of evaluation of adsorption Performance and stability of adsorption Performance in examples and comparative examples
Figure BDA0003773705960000131
The test results in table 1 show that, compared with commercially available porous biochar, the magnetic porous biochar material prepared by the embodiment of the invention has significantly improved adsorption effect and stability, which indicates that the preparation method of the magnetic porous biochar material provided by the invention has the advantages that the prepared magnetic porous biochar material has large specific surface area, regular structure and higher adsorption activity through the processes of decomposition, reconstruction, activation and the like of a biomass precursor tissue structure; in addition, the iron element is distributed in the regular carbon matrix, is not easy to fall off, and can continuously and efficiently exert the adsorption effect.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.

Claims (10)

1. The preparation method of the magnetic porous biological carbon material is characterized by comprising the following steps of:
cleaning biomass, peeling, airing, shearing into powder, and mixing the powder with a salt solution to obtain a mixed solution;
heating the mixed solution to carry out hydrothermal reaction, then collecting a solid product generated by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon;
uniformly mixing the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture, heating the mixture to be carbonized under the environment of isolating oxygen, cooling, and then washing and drying a carbonized product to obtain a carbide;
and heating and activating the carbide in a water vapor environment, and cooling to obtain the magnetic porous biological carbon material.
2. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of cleaning, peeling, air-drying, shearing and crushing biomass to form powder, and then mixing the powder with a salt solution to obtain a mixed solution comprises:
the biomass comprises at least one of corn stover, soybean stover, and wood chips.
3. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of cleaning, peeling, air-drying, shearing and crushing biomass to form powder, and then mixing the powder with a salt solution to obtain a mixed solution comprises:
the salt solution comprises at least one of a potassium chloride solution, a sodium sulfate solution and a sodium chloride solution; and/or the presence of a gas in the gas,
the molar concentration of the salt solution is 0.05-0.2 mol/L.
4. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of cleaning, peeling, air-drying, shearing and crushing biomass to form powder, and then mixing the powder with a salt solution to obtain a mixed solution comprises:
the mass ratio of the biomass to the salt solution is 1: (50-200).
5. The method for preparing a magnetic porous biocarbon material as claimed in claim 1, wherein the step of heating the mixed solution to effect hydrothermal reaction, collecting a solid product formed by the hydrothermal reaction, washing and drying to obtain hydrothermal carbon:
the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 6-12 h.
6. The preparation method of the magnetic porous biochar material according to claim 1, wherein the step of uniformly mixing the hydrothermal carbon, the molten salt and the iron salt to obtain a mixture, heating the mixture to carbonization in an oxygen-isolated environment, cooling, washing and drying a carbonized product to obtain a carbide:
the molten salt comprises LiCl/KCl system molten salt, naCl/KCl system molten salt and ZnCl 2 At least one of KCl system molten salts; and/or the presence of a gas in the gas,
the iron salt comprises Fe 2 (SO 4 ) 3 、FeCl 3 、Fe 2 (NO 3 ) 3 At least one of; and/or the presence of a gas in the gas,
the mass ratio of the hydrothermal carbon to the molten salt to the ferric salt is (0.5-2): (20 to 50): (0.05-0.2).
7. The preparation method of the magnetic porous biological carbon material according to claim 1, wherein the step of uniformly mixing the hydrothermal carbon, the molten salt and the iron salt to obtain a mixture, heating the mixture to carbonization in an oxygen-isolated environment, cooling the mixture, and then washing and drying a carbonized product to obtain a carbide comprises the following steps:
uniformly ball-milling the mixture of the hydrothermal carbon, the molten salt and the ferric salt to obtain a mixture;
heating the mixture to 200-400 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere, preserving heat for 1-3 h, heating to 600-1100 ℃ and preserving heat for 1-3 h, naturally cooling to room temperature in the nitrogen atmosphere, washing and drying the carbonized product to obtain the carbide.
8. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of washing the carbonized product comprises:
adding a hydrochloric acid solution into the carbonized product, then stirring at room temperature for 12-24 h, collecting the precipitate, and washing the precipitate with distilled water.
9. The method for preparing a magnetic porous biocarbon material as claimed in claim 8, wherein the step of adding a hydrochloric acid solution to the carbonized product, then stirring at room temperature for 12-24 hours, collecting the precipitate, and washing the precipitate with distilled water, comprises:
the mass concentration of the hydrochloric acid solution is 10-30%, and the mass ratio of the carbonized product to the hydrochloric acid solution is 1: (100-200).
10. The method for preparing a magnetic porous biochar material according to claim 1, wherein the step of heating and activating the carbide in a water vapor environment and cooling the carbide to obtain the magnetic porous biochar material comprises:
heating the carbide to 600-1100 ℃ at a heating rate of 1-5 ℃/min in a water vapor atmosphere, preserving the heat for 1-3 h, and naturally cooling to room temperature in a nitrogen atmosphere to obtain the magnetic porous biological carbon material.
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