CN110482544B - Activated carbon and preparation method and application thereof - Google Patents
Activated carbon and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides activated carbon and a preparation method and application thereof. The preparation method of the activated carbon comprises the following steps: and (3) dipping: immersing a carbon-containing substrate in a solution containing metal ions; and (3) drying: drying the impregnated product to form a micelle containing metal ions on the surface and/or inside of the carbon-containing matrix; carbonizing and roasting: roasting the dried product to obtain carbide containing a metal cluster structure; a gasification step: and (2) reacting the activated gas with the carbide under the catalysis of the metal cluster structure, so as to form a pore channel structure on the surface and/or in the carbide. The preparation method of the activated carbon provided by the invention can be used for preparing the activated carbon with specific surface area, specific pore volume and mesoporous structure according to needs, and has high yield. And the preparation method is economical, simple and convenient and is easy for large-scale production.
Description
Technical Field
The invention relates to activated carbon and a preparation method and application thereof, belongs to the technical field of porous adsorption materials and preparation thereof, and particularly belongs to the field of porous activated carbon and preparation thereof.
Background
As one of the most important industrial adsorbents, activated carbon is a carbon-containing substance with characteristics of porous structure, high specific surface area, various surface functional groups (such as carboxyl, carbonyl, hydroxyl and the like), high mechanical strength, acid resistance, alkali resistance, heat resistance, easy regeneration after failure and the like, and can be widely applied to the aspects of water purification, air purification, organic solvent recovery, aviation, military, food, catalyst carriers, electrode materials and the like.
In the prior art, coal-based activated carbon, wood activated carbon and the like can be divided according to production raw materials. At present, the most widely used coal-based activated carbon is prepared by the following main processes in sequence: the method comprises the steps of raw material pretreatment, extrusion forming and crushing, a carbonization process and an activation process. The carbonization step is to heat and carbonize the raw materials in a high-temperature furnace, and after carbonization is finished, the carbonized materials react with activated gases such as water vapor, carbon dioxide and the like to produce the activated carbon. However, the method can only obtain the activated carbon with smaller specific surface area or pore structure, and has large use limitation.
Water purification is one of the most important research hotspots in the field of environmental protection at present. Research workers are currently working on the removal of a wide variety of pollutants from bodies of water, including various pollutants such as toxic metal ions, dyes, biodegradable waste, nitrogen and phosphorus containing compounds, sediments, fluorides, hazardous and toxic chemicals, radioactive pollutants, drugs, and the like. The introduction of any small amount of these contaminants into the water body results in a large amount of water body contamination and is difficult to remove, which threatens human health and other biological survival, and thus the treatment of sewage is currently a crucial topic.
In the prior art, various sewage treatment methods have been widely applied to remove pollutants in water bodies so far. Including coagulation-co-precipitation methods, ion exchange methods, physical adsorption methods, oxidation-precipitation methods, reverse osmosis methods, solvent extraction methods, and the like. However, these methods have relative limitations in technical or economic aspects, for example, although the oxidation-precipitation method is convenient in implementation and has the advantage of low cost, the treatment method can generate secondary pollution and bring landfill problems; membrane separation processes have the advantages of relatively energy savings and high separation efficiency, but such processes are not economical and are expensive to maintain. In practical application of production and life, a physical adsorption method is widely favored by people due to low material cost, simple operation and preparation and good adsorption selectivity, but has the defects of low adsorption speed, poor selectivity, difficult regeneration and the like.
The citation document [1] discloses a method for preparing activated carbon by using a coal-made activated carbon furnace, which comprises the steps of briquetting, crushing and drying a mixture of lignite and weakly caking coal, and then carbonizing the mixture by electric heating and natural gas combustion heat supply in a nitrogen atmosphere. After the carbonization reaction, natural gas and oxygen are introduced from a natural gas inlet and an oxygen inlet in proportion, the oxygen is mixed with the natural gas in a mixer after passing through an ion generator, then the mixture enters a combustion chamber for combustion to generate water vapor and carbon dioxide, the generated water vapor, the carbon dioxide and the introduced nitrogen are mixed and then enter a gas distribution chamber through a gas heating chamber, then the mixture enters a reaction unit for activation reaction with raw materials, and finally the temperature is reduced under the nitrogen atmosphere to obtain the activated carbon.
The cited document [2] provides a method for producing activated carbon for coal-based desulfurization, comprising: respectively grinding the Taixi anthracite, 1/3 coking clean coal and non-caking coal into coal powder with the 200-mesh passing rate of more than 80 percent; blending coal by using the Taixi anthracite, 1/3 coking clean coal and non-caking coal as raw materials to obtain mixed raw material coal; respectively taking the mixed raw material coal, the binder and water as raw materials, and uniformly stirring and mixing to obtain coal paste; and (3) extruding and molding the coal paste, curing, and then carrying out oxidation treatment, carbonization treatment and activation treatment to obtain the active carbon. The invention selects the Taixi anthracite, the 1/3 coking clean coal and the non-caking coal, and prepares the active carbon by blending the coal, thereby obtaining the coal-based active carbon for desulfurization which has good strength and high-quality adsorption/desorption performance. The activated carbon is only suitable for desulfurization and is not suitable for other fields, such as: the field of water purification and the like.
Cited document [1 ]: CN108217649A
Cited document [2 ]: CN108014750A
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, the invention firstly provides a preparation method of activated carbon, which can prepare activated carbon with specific surface area, specific pore volume and mesoporous structure according to requirements and has higher yield. Moreover, the method has the characteristics of simple preparation and economy.
The invention further provides the activated carbon which has strong adsorption capacity, and especially has high adsorption capacity in application fields with high requirements on a pore structure, such as industrialized high-efficiency adsorption and desorption water purification.
Means for solving the problems
[1] The preparation method of the activated carbon comprises the following steps:
and (3) dipping: immersing a carbon-containing substrate in a solution containing metal ions;
and (3) drying: drying the impregnated product to form a micelle containing metal ions on the surface and/or inside of the carbon-containing matrix;
carbonizing and roasting: roasting the dried product to obtain carbide containing a metal cluster structure;
a gasification step: and (2) reacting the activated gas with the carbide under the catalysis of the metal cluster structure, so as to form a pore channel structure on the surface and/or in the carbide.
[2] The process according to item [1], wherein the metal forming the metal ion comprises one or a combination of two or more of an alkali metal, an alkaline earth metal, a transition metal and a rare earth metal.
[3]According to [2]]The preparation method of the activated carbon, wherein the metal ions comprise Na+、 K+、Fe3+、Ca2 +、Mg2+、Ni2+、Ru+One or a combination of two or more of them.
[4] The process for producing activated carbon according to any one of [1] to [3], wherein the solution containing a metal ion contains a surfactant, preferably an anionic surfactant; more preferably, the mass concentration of the surfactant is 0.05-8%; more preferably, when the particle size of the carbon-containing matrix is 40 to 200 meshes, preferably 100 to 200 meshes, the mass ratio of the carbon-containing matrix to the solution containing metal ions is 1 to 1000: 100.
[5] The process for producing activated carbon according to [4], wherein the anionic surfactant comprises one or a combination of two or more of an alkyl sulfate, an alkyl sulfate salt, an alkyl carboxylate and an alkyl phosphate salt; wherein the number of carbon atoms in the alkyl group is 5 to 20, preferably 10 to 18.
[6] The process for producing activated carbon according to any one of [1] to [5], wherein the drying comprises natural hot air drying; preferably, the temperature of the natural hot air drying is below 120 ℃.
[7] The preparation method of the activated carbon according to any one of [1] to [6], wherein the carbonization and roasting temperature is 300-800 ℃, and the carbonization and roasting time is 0.5-4 hours.
[8] The process for producing activated carbon according to any one of [1] to [7], wherein the activating gas comprises water vapor and/or carbon dioxide; preferably, the gasification temperature is 800-1000 ℃, the gasification time is 1-5 h, and the introduction amount of the activated gas is calculated by introducing the activated gas with the flow rate of 0.3-1.2 kg/h per kg of reaction materials.
[9] The process for producing activated carbon according to any one of [1] to [8], wherein the process further comprises a post-treatment step comprising removing the metal cluster structure; preferably, the post-treatment step comprises a step of washing with water and/or acid.
[10] The method for preparing activated carbon according to any one of [1] to [9], wherein the carbon-containing matrix comprises one or more of anthracite, blue carbon and microcrystalline graphite.
[11] The activated carbon is prepared by the preparation method of any one of [1] to [10], the methylene blue adsorption value of the activated carbon is more than 150mg/g, and the yield of the activated carbon is more than 40%.
[12] The use of the activated carbon according to [11] in water purification.
ADVANTAGEOUS EFFECTS OF INVENTION
(1) The preparation method of the activated carbon provided by the invention can be used for preparing the activated carbon with specific surface area, specific pore volume and mesoporous structure according to needs, and has high yield. And the preparation method is economical, simple and convenient and is easy for large-scale production.
(2) The active carbon has strong adsorption capacity, and especially has high adsorption capacity in the application fields with high requirement on the structure of the central hole, such as industrialized high-efficiency adsorption and desorption water body purification.
Drawings
FIG. 1 shows a broad field emission spectrum of a metal cluster structure-containing carbide of the present invention;
FIG. 2 shows a local microscopic field emission spectrum of a carbide containing a metal cluster structure according to the present invention;
FIG. 3 is a scanning electron micrograph (5 μm on a scale) of a carbide containing a metal cluster structure according to the present invention;
FIG. 4 is a scanning electron micrograph (1 μm on a scale) of a carbide containing a metal cluster structure according to the present invention;
FIG. 5 is a scanning electron micrograph (500 nm on a scale) of a carbide containing a metal cluster structure according to the present invention;
fig. 6 shows a nitrogen adsorption and desorption curve of the activated carbon of example 1.
Fig. 7 shows the specific surface area and pore volume distribution diagram of the activated carbon of example 1.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
All units used in the present invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include errors allowed in industrial production.
As used herein, "water" includes any feasible water such as tap water, deionized water, distilled water, double distilled water, purified water, ion-exchanged water, and the like.
If "about", "substantially", "approximately" or the like is used herein, the error may be 5%.
If the term "room temperature" is used herein, the term means an ambient temperature of 20 to 30 ℃.
First embodiment
A first embodiment of the present invention provides a method for preparing activated carbon, which includes the steps of:
and (3) dipping: immersing a carbon-containing substrate in a solution containing metal ions;
and (3) drying: drying the impregnated product to form a micelle containing metal ions on the surface and/or inside of the carbon-containing matrix;
carbonizing and roasting: roasting the dried product to obtain carbide containing a metal cluster structure;
a gasification step: and (2) reacting the activated gas with the carbide under the catalysis of the metal cluster structure, so as to form a pore channel structure on the surface and/or in the carbide.
The invention uses the preparation method, can prepare the activated carbon with the required specific surface area, pore volume and mesoporous structure according to the requirement, and has higher yield.
< carbon-containing substrate >
The source of the carbonaceous substrate of the present invention is not particularly limited, and may include various known sources capable of producing activated carbon. For example: the carbon-containing matrix can be coal, blue carbon, graphite, wood material or shells of various fruits and the like.
As the coal, lignite, bituminous coal, anthracite and the like can be mentioned. The lignite comprises a first lignite (PM > 0-30%), a second lignite (PM > 30-50%, Qgr, maf <24MJ/kg) and the like. Bituminous coal includes fat coal, gas fat coal, and the like. The anthracite can be anthracite I (Vdaf is 0-3.5%, H is 0-2.0%), anthracite II (Vdaf is > 3.5-6.5%, H is > 2.0-3.0%), anthracite III (Vdaf is > 6.5-10.0%, H is > 3.0%). In addition, the anthracite coal of the invention is high-metamorphic anthracite coal. For example, the coal sample can be obtained from the ore points of typical high-metamorphic smokeless coal main production areas such as Fujian Longyan, Sanming land, Quanzhou Yongchun and the like.
Blue carbon, also called coke, is a solid fuel formed by a series of complex physicochemical processes such as pyrolysis, polycondensation, solidification, shrinkage and the like under the action of high temperature of coking coal materials. As the graphite, microcrystalline graphite or the like can be used. The wood material can be the trunk or root of various trees. The husk may be any of various lignin fiber-containing husks such as coconut husk.
Preferably, the activated carbon of the invention is coal-based activated carbon, wherein the carbon-containing matrix comprises one or more of anthracite, blue carbon and microcrystalline graphite.
< solution containing Metal ion >
In the present invention, the metal forming the metal ion is not particularly limited as long as it is dried to form a micelle containing the metal ion on the surface and/or inside of the carbon-containing substrate. In the present invention, the metal forming the metal ion includes one or a combination of two or more of alkali metal, alkaline earth metal, transition metal, and rare earth metal. The alkali metal may be, for example: lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs); the alkaline earth metal may be, for example: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba); the transition metal may be, for example: titanium (Ti), vanadium (V), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), etc.; the rare earth metal may be, for example, scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), lutetium (Lu), or the like.
Specifically, the metal ion may be Na+、K+、Fe3+、Ca2+、Mg2+、Ni2+、Ru+One or a combination of two or more of them. The metal ions are used for the purpose of forming metal ion-containing micelles on the surface and/or inside the carbonaceous substrate after drying.
In the present invention, the anion in the solution containing the metal ion is not particularly limited as long as the anion can form a solution containing the metal ion. In the present invention, the mass concentration of the metal ions in the solution containing the metal ions is 0.05% to 8%.
Specifically, the solution containing the metal ions contains a surfactant. In the present invention, the metal ion-containing solution preferably contains an anionic surfactant. The anionic surfactant includes alkyl sulfate, alkyl sulfate ester salt, alkyl carboxylate, alkyl phosphate ester salt, and the like. In general, the number of carbon atoms in the alkyl group is 5 to 20, preferably 10 to 18, and for example, the number of carbon atoms in the alkyl group may be 12, 13, 14, 15, 16, 17, or the like.
Further, for example, the anionic surfactants sodium lauryl sulfate, sodium tridecyl carboxylate, sodium tetradecyl phosphate, sodium pentadecyl sulfate, sodium hexadecyl sulfate, potassium dodecyl carboxylate, potassium dodecyl phosphate, potassium dodecyl sulfate, calcium dodecyl sulfate, and the like. According to the invention, the carbon-containing matrix is soaked in the anionic surfactant, and a micelle containing metal ions can be effectively formed after drying, so that a metal cluster structure can be conveniently formed in the later stage.
In practice, the mass concentration of the surfactant is not particularly limited in the present invention, and an appropriate mass concentration may be used depending on the desired specific surface area, pore volume, mesopore ratio, and the like of the activated carbon. Preferably, in the present invention, the surfactant is contained in the solution containing metal ions at a mass concentration of 0.05% to 8%; preferably, when the particle size of the carbon-containing matrix is 40-200 meshes, preferably 100-200 meshes, the mass ratio of the carbon-containing matrix to the solution containing the metal ions is 1-1000: 100, for example: 1:100, 1:50, 1:10, 1:2, 1:1, 2:1, 10:1, 20:1, 50:1, 100:1, etc.
In addition, the impregnation process can be carried out at normal temperature and normal pressure, and the limitation of other conditions such as temperature and pressure is avoided.
< drying >
In the present invention, the drying step is a more important step. In the invention, the impregnated product is dried, so that the surface and/or the interior of the carbon-containing matrix form a micelle containing metal ions.
Generally, the mass concentration of metal ions in the aqueous solution containing metal ions is continuously increased during the drying process, and micelles containing metal ions are gradually formed. Specifically, when the mass concentration of the anionic surfactant solution exceeds the critical micelle concentration (CMC, mass concentration) at the time of impregnation using an aqueous solution of the anionic surfactant, the anionic surfactant may self-assemble in water to form a micelle structure, the hydrophilic end of which is a concentrated metal ion; the nonpolar groups at the other end are agglomerated in the center of the rubber cluster, and the nonpolar groups of the rubber cluster are adsorbed and aggregated on the surface of the anthracite along with the continuous reduction of the moisture to obtain a metal cluster structure, and the polar end, namely the metal ion end, is parallel to and points to the water body.
Furthermore, the change of the micelle structure is controlled by controlling the drying process, so that the distribution of the metal cluster structure with gasification hole expansion capacity on the surface of the carbon-containing matrix can be controlled. Generally, the rapid drying process can obtain more dispersed micelles containing metal ions, while the longer drying process can obtain more concentrated micelles containing metal ions, and even obtain crystalline micelles containing metal ions.
Specifically, preferably, in the present invention, the drying includes natural hot air drying; preferably, the temperature of the natural hot air drying is below 120 ℃, for example: the natural hot air drying temperature can be 110 deg.C, 100 deg.C, 90 deg.C, 80 deg.C, 70 deg.C, etc.
In the present invention, the drying time is not particularly limited, and a micelle containing a metal ion may be formed. The drying time may be, for example, 20 hours or less, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, and the like.
< calcination >
After the drying treatment, the invention carries out carbonization roasting on the dried product. The apparatus for calcination is not particularly limited, but a pyrolysis tube is preferably used from the viewpoint of the effect of the carbonization calcination and the subsequent gasification step.
The dried product is roasted to carbonize the organic matter and obtain carbide, and the micelle containing metal ion may be converted into metal cluster structure to form carbide containing metal cluster structure. The metal cluster structure may be present in the form of an agglomerate of metal oxides, metal salts, and the like. That is, the surface and/or the interior of the resulting carbide has a metal cluster structure. Specifically, as shown in fig. 5, the particle size of the metal cluster structure of the present invention may be 1 to 500nm, for example: 10 to 450nm, 20 to 400nm, 30 to 350nm, 40 to 300nm, and the like.
Specifically, in the carbonization roasting step, the carbonization roasting temperature is 300-800 ℃, preferably 350-750 ℃, for example: 400-700 ℃, 450-650 ℃, 400-600 ℃ and the like, and the heat preservation is carried out at the temperature for 0.5-4 hours, preferably 1-3.5 hours, such as 1.2 hours, 1.5 hours, 2 hours, 3 hours and the like.
Other conditions for the carbonization and calcination are not particularly limited, and the carbonization and calcination may be performed in a vacuum state, under an inert gas atmosphere, or in air, and the inert gas may be nitrogen gas or the like. In some preferred embodiments of the present invention, the char is subjected to a charring calcination in the presence of an inert gas.
< gasification >
Carbonizing and roasting to obtain carbide, and gasifying. The equipment for the gasification treatment is not particularly limited, and since the gasification is also carried out at a high temperature, it may be carried out in a pyrolysis tube, and preferably, the gasification is carried out directly after the carbonization/baking in order to reduce the shift step and the like.
The gasifying step comprises: and (2) reacting the activated gas with the carbide under the catalysis of the metal cluster structure, so as to form a pore channel structure on the surface and/or in the carbide.
In the invention, the surface and/or the interior of the carbide is provided with the metal cluster structure, which has very important significance for preparing the pore channel structure in the later period. Specifically, the metal cluster structure may act as a catalyst during the gasification step, thereby forming a larger pore structure in the vicinity of the metal cluster structure, since the reaction is endothermic, and the metal cluster structure may be adsorbed and migrated to a lower temperature position in the pore structure as the reaction proceeds, thereby forming a continuous larger pore structure on the surface and/or inside of the carbide as the gasification reaction proceeds.
Specifically, after carbonization and roasting, the temperature is continuously increased to 700-1000 ℃, preferably 750-980 ℃, for example: 800-950 ℃ and the like, then stopping introducing the inert gas, and replacing with introducing the activated gas, wherein the gasification temperature is 700-1000 ℃, preferably 750-980 ℃, for example: 800-950 ℃, and the like, and preserving the heat for 1-10 h, preferably 1.5-8 h, for example: 2-7 h, 3-6 h, 4-5 h and the like. And under the catalysis of the metal cluster structure, reacting the activated gas with the carbide to form a pore structure on the surface and/or inside the carbide, cooling to room temperature (20-30 ℃ C.) in an inert atmosphere, and performing a post-treatment step.
The activated gas is water vapor or carbon dioxide, and the introduction amount of the activated gas is calculated according to the introduction flow rate of 0.3-1.2 kg/h of the activated gas per kilogram of reaction materials.
By controlling the gasification temperature and the flow of the activated gas, the pore volume, the specific surface area, the mesopore ratio and other main factors influencing the adsorption can be controlled. Generally, a relatively concentrated elongated channel structure is obtained by a relatively low flow rate of the activating gas (e.g., a flow rate of 0.3 to 0.5kg/h per kg of reaction material), and/or a relatively low reaction temperature (less than 850 ℃), and/or a relatively long reaction time (e.g., more than 4 hours); and the relatively dispersed pore channel structure with larger pore diameter is obtained by large water vapor flow (for example, the flow rate of introducing each kilogram of reaction materials is 0.8-1.2 kg/h) and/or higher reaction temperature (more than 850 ℃) and/or shorter reaction time (for example, less than 2 hours).
< post-treatment >
In the invention, the product obtained by the gasification step is subjected to post-treatment to obtain the final activated carbon product. The mode of the post-treatment is not particularly limited, and post-treatment methods generally used in the art, including washing, drying, classification, and packaging, may be used.
The washing may be performed using water, an acid and/or an organic solvent such as a low boiling point hydrocarbon, an alcohol, an ether, or a ketone, and preferably, washing may be performed using water and/or an acid to remove the metal cluster structure. The drying may be carried out under conditions of heat and/or reduced pressure to obtain a dried product.
Second embodiment
The second embodiment of the present invention provides an activated carbon prepared by the method of the first embodiment, wherein the activated carbon has a methylene blue adsorption value of 150mg/g or more, and the yield of the activated carbon is 40% or more. The active carbon has high adsorption capacity in the application fields with high requirement on the structure of the central hole, such as industrialized high-efficiency adsorption and desorption water body purification.
Specifically, the activated carbon of the present invention can be prepared to obtain the activated carbon with the desired specific surface area, specific pore volume and mesoporous structure by the method of the present invention according to the needs.
In order to further embody the present invention, the present invention provides an activated carbon having specific parameter ranges. Specifically, the pore diameter range of the mesopores in the activated carbon is 2-50 nm, and the mesopore ratio is more than 40%, can be more than 50%, and can be more than 60%.
In the present invention, the ratio of the activated carbonThe surface area may be greater than 500m2G, preferably 600m2(ii) at least g, more preferably 600m2/g～1200m2/g。
The pore volume of the activated carbon is 0.3-1.1 cm3In which the mesopore volume is greater than 0.5 cm3/g。
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The feed coal in the following examples was Fujian anthracite, and the ash content was less than 4.5 wt%.
Example 1
Crushing coal into 150-200 mesh granular coal, weighing 100Kg of crushed powdered coal and 1.5Kg of sodium dodecyl sulfate, adding 60Kg of water, and uniformly mixing to obtain a reaction material. After drying the reaction mass by hot air at 105 ℃ for 10 hours, the dried reaction mass was placed in a pyrolysis tube. And introducing nitrogen into the pyrolysis tube and heating the pyrolysis tube to ensure that the temperature of the materials in the pyrolysis tube reaches 400 ℃, and keeping the temperature at 400 ℃ for 1h to obtain the carbide containing the metal cluster structure. And continuously heating the pyrolysis tube to ensure that the temperature of the materials in the pyrolysis tube reaches 800 ℃, then stopping introducing nitrogen into the pyrolysis tube, continuously introducing water vapor into the pyrolysis tube according to the flow rate of 0.7kg/h of the introduced water vapor per kg of the reaction materials, keeping the temperature of the reaction materials at 800 ℃ for 3 hours, cooling the reaction materials to room temperature in the nitrogen atmosphere, washing the reaction materials with water or acid, removing the metal cluster structure, and drying the reaction materials to obtain 48.73kg of the coal-based activated carbon.
Example 2
Crushing coal into 150-200 mesh granular coal, weighing 100Kg of crushed powdered coal and 1.5Kg of sodium dodecyl sulfate, adding 60Kg of water, and uniformly mixing to obtain a reaction material. After drying the reaction mass by hot air at 105 ℃ for 10 hours, the dried reaction mass was placed in a pyrolysis tube. And introducing nitrogen into the pyrolysis tube and heating the pyrolysis tube to ensure that the temperature of the materials in the pyrolysis tube reaches 400 ℃, and keeping the temperature at 400 ℃ for 1h to obtain the carbide containing the metal cluster structure. And continuously heating the pyrolysis tube to enable the temperature of the materials in the pyrolysis tube to reach 900 ℃, then stopping introducing nitrogen into the pyrolysis tube, continuously introducing water vapor into the pyrolysis tube according to the flow rate of 0.7kg/h of the introduced water vapor per kg of the reaction materials, keeping the temperature of 900 ℃ for 3 hours, cooling to room temperature in the nitrogen atmosphere, washing with water or acid, removing the metal cluster structure, and drying to obtain 45.52kg of the coal-based activated carbon.
Example 3
Crushing coal into 150-200 mesh granular coal, weighing 100Kg of crushed powdered coal and 1.5Kg of sodium dodecyl sulfate, adding 60Kg of water, and uniformly mixing to obtain a reaction material. After drying the reaction mass by hot air at 105 ℃ for 10 hours, the dried reaction mass was placed in a pyrolysis tube. And introducing nitrogen into the pyrolysis tube and heating the pyrolysis tube to ensure that the temperature of the materials in the pyrolysis tube reaches 400 ℃, and keeping the temperature at 400 ℃ for 1h to obtain the carbide containing the metal cluster structure. And continuously heating the pyrolysis tube to enable the temperature of the materials in the pyrolysis tube to reach 900 ℃, then stopping introducing nitrogen into the pyrolysis tube, continuously introducing carbon dioxide into the pyrolysis tube according to the flow rate of 0.7kg/h of the introduced nitrogen into each kilogram of reaction materials, keeping the temperature of 900 ℃ for 3 hours, cooling to room temperature in the nitrogen atmosphere, washing with water or acid, removing the metal cluster structure, and drying to obtain 50.04kg of coal-based activated carbon.
Example 4
Crushing coal into 150-200 mesh granular coal, weighing 100Kg of crushed powdered coal and 1.5Kg of sodium dodecyl sulfate, adding 60Kg of water, and uniformly mixing to obtain a reaction material. After drying the reaction mass by hot air at 105 ℃ for 10 hours, the dried reaction mass was placed in a pyrolysis tube. And introducing nitrogen into the pyrolysis tube and heating the pyrolysis tube to ensure that the temperature of the materials in the pyrolysis tube reaches 400 ℃, and keeping the temperature at 400 ℃ for 1h to obtain the carbide containing the metal cluster structure. And continuously heating the pyrolysis tube to enable the temperature of the materials in the pyrolysis tube to reach 950 ℃, then stopping introducing nitrogen into the pyrolysis tube, continuously introducing carbon dioxide into the pyrolysis tube according to the flow rate of 0.7kg/h of the introduced nitrogen into each kilogram of reaction materials, keeping the temperature of the reaction materials at 950 ℃ for 3 hours, cooling the reaction materials to room temperature in the nitrogen atmosphere, washing the reaction materials with water or acid, removing the metal cluster structure, and drying the reaction materials to obtain 46.48kg of coal-based activated carbon.
Testing the size and distribution of the metal cluster structure
The sizes and distribution of the carbides containing the metal cluster structures of examples 1-4 of the present invention were obtained by scanning electron microscopy in combination with surface energy spectroscopy, and the results are shown in FIGS. 1-5. Wherein FIG. 1 shows a broad field emission spectrum of a metal cluster structure-containing carbide of the present invention; FIG. 2 shows a local microscopic field emission spectrum of a carbide containing a metal cluster structure according to the present invention; FIG. 3 is a scanning electron micrograph (5 μm on a scale) of a carbide containing a metal cluster structure according to the present invention; FIG. 4 is a scanning electron micrograph (1 μm on a scale) of a carbide containing a metal cluster structure according to the present invention; FIG. 5 is a scanning electron micrograph (500 nm on a scale) of a carbide containing a metal cluster structure according to the present invention. In addition, as can be seen from FIGS. 3 to 5, the particle size of the metal cluster structure of the present invention may be 10 to 500 nm.
Activated carbon pore structure parameter and methylene blue absorption test
The specific surface area and pore volume of the activated carbon were measured using an ASAP2020 physical adsorption apparatus. The specific surface area and the mesopore ratio are calculated by a Brunauer-Emmett-Teller (BET) method; the pore volume and pore diameter are calculated by the non-local density functional theory (NLDFT) method. Wherein, fig. 6 shows a nitrogen adsorption and desorption curve of the activated carbon of example 1; fig. 7 shows the specific surface area and pore volume distribution diagram of the activated carbon of example 1.
The yield of the activated carbon is obtained by a gravimetric method.
The ash contents of examples 1-4 were determined according to the method of national standard GB/T212-2008, and the results are shown in Table 1 below.
The methylene blue adsorption values of examples 1 to 4 were measured according to the method of national standard GB/T7702.6-2008, and the results are shown in Table 1 below.
TABLE 1 structural parameters of activated carbon
As can be seen from Table 1, the activated carbon of the present invention has high yield, high methylene blue adsorption value and low ash content. Also, the activated carbon of the present invention can obtain a desired specific surface area, pore volume, and mesopore ratio as needed.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (17)
1. The preparation method of the activated carbon is characterized by comprising the following steps:
and (3) dipping: soaking a carbon-containing matrix in a solution containing metal ions, wherein the solution containing the metal ions contains a surfactant, the mass concentration of the surfactant is 0.05-8%, and the surfactant is an anionic surfactant;
and (3) drying: drying the impregnated product to form a micelle containing metal ions on the surface and/or inside of the carbon-containing matrix;
carbonizing and roasting: roasting the dried product to obtain carbide containing a metal cluster structure;
a gasification step: and (2) reacting the activated gas with the carbide under the catalysis of the metal cluster structure, so as to form a pore channel structure on the surface and/or in the carbide.
2. The method of producing activated carbon according to claim 1, wherein the metal forming the metal ion comprises one or a combination of two or more of an alkali metal, an alkaline earth metal, a transition metal, and a rare earth metal.
3. The method for producing activated carbon according to claim 2, wherein the metal ion comprises Na+、K+、Fe3+、Ca2+、Mg2+、Ni2+、Ru+One or a combination of two or more of them.
4. The method for producing activated carbon according to any one of claims 1 to 3, wherein the mass ratio of the carbon-containing matrix to the metal ion-containing solution is 1 to 1000:100 when the particle size of the carbon-containing matrix is 40 to 200 mesh.
5. The method for producing activated carbon according to claim 4, wherein the mass ratio of the carbon-containing matrix to the metal ion-containing solution is 1 to 1000:100 when the particle size of the carbon-containing matrix is 100 to 200 mesh.
6. The method for producing an activated carbon according to any one of claims 1 to 3, wherein the anionic surfactant comprises one or a combination of two or more of an alkyl sulfate, an alkyl sulfate salt, an alkyl carboxylate, and an alkyl phosphate salt; wherein the number of carbon atoms in the alkyl group is 5-20.
7. The method for producing activated carbon according to claim 6, wherein the number of carbon atoms in the alkyl group in the anionic surfactant is 10 to 18.
8. The method for producing activated carbon according to any one of claims 1 to 3, wherein the drying includes natural hot air drying.
9. The method for producing activated carbon according to claim 8, wherein the temperature of the natural hot air drying is 120 ℃ or lower.
10. The method for preparing activated carbon according to any one of claims 1 to 3, wherein the temperature of the carbonization roasting is 300 to 800 ℃, and the time of the carbonization roasting is 0.5 to 4 hours.
11. The method for producing activated carbon according to any one of claims 1 to 3, wherein the activating gas includes water vapor and/or carbon dioxide.
12. The method for preparing activated carbon according to any one of claims 1 to 3, wherein the temperature of the gasification is 800 to 1000 ℃, the time of the gasification is 1 to 5 hours, and the amount of the activated gas is measured by introducing the activated gas at a flow rate of 0.3 to 1.2 kg/hour per kg of the reaction material.
13. The method for producing activated carbon according to any one of claims 1 to 3, characterized by further comprising a post-treatment step comprising removal of the metal cluster structure.
14. The method of producing activated carbon according to claim 13, wherein the post-treatment step includes a step of washing with water and/or an acid.
15. The method of any one of claims 1-3, wherein the carbonaceous matrix comprises one or more of anthracite coal, blue carbon, and microcrystalline graphite.
16. An activated carbon produced by the production method according to any one of claims 1 to 15, wherein the activated carbon has a methylene blue adsorption value of 150mg/g or more and a yield of 40% or more.
17. Use of the activated carbon of claim 16 in water purification.
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