CN115304090A - Comprehensive utilization method of coal gasification fine slag - Google Patents
Comprehensive utilization method of coal gasification fine slag Download PDFInfo
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- CN115304090A CN115304090A CN202211136027.4A CN202211136027A CN115304090A CN 115304090 A CN115304090 A CN 115304090A CN 202211136027 A CN202211136027 A CN 202211136027A CN 115304090 A CN115304090 A CN 115304090A
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- 238000002309 gasification Methods 0.000 title claims abstract description 102
- 239000002893 slag Substances 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 132
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 16
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- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 238000001291 vacuum drying Methods 0.000 claims description 16
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- 238000000967 suction filtration Methods 0.000 description 10
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- 238000012512 characterization method Methods 0.000 description 8
- -1 silicon-aluminum compound Chemical class 0.000 description 8
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- 238000001994 activation Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000005354 aluminosilicate glass Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
- C01F7/57—Basic aluminium chlorides, e.g. polyaluminium chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The application discloses a comprehensive utilization method of coal gasification fine slag, and belongs to the technical field of solid waste recycling treatment. The comprehensive utilization method comprises the following steps: providing coal gasification fine slag powder; adding the coal gasification fine slag powder into a protonic acid solution for reaction, and separating after the reaction is finished to obtain a filtrate and a solid I; adding calcium aluminate into the filtrate for reaction, drying the supernatant after the reaction is finished to obtain polyaluminium chloride, washing and drying the solid I, adding the solid I into an alkali solution for reaction, and washing and drying the solid II after the reaction is finished to obtain desiliconized carbon residue; and mixing the desiliconized residual carbon with KOH powder, and then sequentially calcining, washing and drying to obtain the hierarchical porous carbon. According to the method, the polyaluminium chloride and the hierarchical porous carbon are prepared at the same time, so that the additional value of the coal gasification fine slag is obviously improved; on the other hand, the comprehensive utilization of carbon and aluminum components is realized for the first time; in the third aspect, a hierarchical porous carbon material having excellent electrochemical properties is produced.
Description
Technical Field
The application belongs to the technical field of solid waste recycling treatment, and particularly relates to a comprehensive utilization method of coal gasification fine slag.
Background
The gasified slag is solid waste inevitably generated in the coal gasification process, and particularly is a mixed component of unburned carbon, glass-phase aluminosilicate, quartz-phase particles and the like generated by incomplete combustion of coal and oxygen/oxygen-enriched air.
The coal gasification fine slag is formed by taking out slag with smaller particles in the gasification reaction from the top of a furnace along with synthesis gas, has larger carbon content and mainly exists in the form of flocculent porous carbon residue. At present, in the resource utilization of the coal gasification fine slag, the comprehensive utilization of the silicon-aluminum component in the coal gasification fine slag is mainly used, for example, a silicon-aluminum compound in the coal gasification fine slag is converted into an active phase; or the comprehensive utilization of the carbon-silicon component in the coal gasification fine slag is taken as the main part, for example, the coal gasification coarse slag is taken as a carbon and silicon source to prepare the carbon/silicon composite mesoporous material and the like; or mainly utilizes the residual carbon component in the gasified slag, for example, the gasified slag is subjected to acid washing, deashing and carbonization to prepare the porous carbon material.
However, in the resource utilization of the coal gasification fine slag in the prior art, the comprehensive utilization of the carbon-aluminum component is rarely involved, and the composite product is mainly used in the comprehensive utilization of the silicon-aluminum component/carbon-silicon component, so that the additional value of the resource utilization of the coal gasification fine slag is greatly reduced.
Disclosure of Invention
The application aims to provide a comprehensive utilization method of coal gasification fine slag, which is used for solving the technical problems that the existing coal gasification fine slag is low in additional value in resource comprehensive utilization and carbon-aluminum component comprehensive utilization is not involved.
In order to achieve the above purpose, the technical solution of the embodiment of the present application is:
the first aspect of the embodiments of the present application provides a method for comprehensively utilizing coal gasification fine slag, which includes the following steps:
s101: providing coal gasification fine slag powder;
s102: adding the coal gasification fine slag powder into a protonic acid solution for reaction, and separating to obtain a filtrate and a solid I after the reaction is finished;
s103: adding calcium aluminate into the filtrate for reaction, standing and cooling after the reaction is finished, and drying the obtained supernatant to obtain polyaluminium chloride;
s104: washing and drying the solid I, adding the solid I into an alkali solution for reaction, cooling and separating the solid I after the reaction is finished, and washing and drying the solid II to obtain desiliconized carbon residue;
s105: and mixing the desiliconized residual carbon with KOH powder, and then sequentially calcining, washing and drying to obtain the hierarchical porous carbon.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the protonic acid solution in step S102 is a hydrochloric acid solution;
the mass concentration of the hydrochloric acid solution is 6-36%;
the volume of the hydrochloric acid solution is 2-24 times of the mass of the coal gasification fine slag powder.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the temperature of the reaction in step S102 is 60 to 150 ℃, and the time is 30 to 240min.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the volume of the filtrate in step S103 is 4 to 16 times of the mass of the calcium aluminate;
the reaction temperature is 60-140 ℃ and the reaction time is 60-180 min;
the temperature for drying the supernatant is 80-120 ℃.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the alkali solution in step S104 is a sodium hydroxide solution;
the mass concentration of the sodium hydroxide solution is 5-40%;
the volume of the sodium hydroxide solution is 10-35 times of the mass of the solid I.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the temperature of the reaction in step S104 is 60 to 150 ℃, and the time is 60 to 180min.
In a preferred implementation manner of the first aspect of the embodiment of the present application, in step S104, deionized water is used for washing the solid I and the solid II, and the washing is performed until the pH of the filtrate =6.0 to 8.0.
In a preferred implementation manner of the first aspect of the embodiment of the present application, in step S105, the mass of the KOH powder is 2 to 6 times that of the desiliconized residual carbon;
the calcination adopts a rotary furnace, the atmosphere is inert gas, and the gas flow is 60-100 mL/min;
the calcining temperature is 600-900 ℃, the heating rate is 2-5 ℃/min, and the time is 40-100 min.
In a preferred implementation manner of the first aspect of the embodiment of the present application, the drying in step S104 and step S105 is vacuum drying;
the temperature of the vacuum drying is 60-110 ℃, and the time is 10-36 h.
The second aspect of the embodiment of the application provides the application of the porous carbon prepared by the comprehensive utilization method in the preparation of capacitor electrode materials.
Compared with the prior art, the advantages or beneficial effects of the embodiments of the present application at least include:
1) According to the comprehensive utilization method of the coal gasification fine slag provided by the embodiment of the application, protonic acid is utilized to react with coal gasification fine slag powder, so that an aluminum component and a carbon-silicon component in the coal gasification fine slag are separated, wherein the aluminum component is dissolved in a filtrate, and the polyaluminium chloride can be synthesized by utilizing calcium aluminate to react with the filtrate, so that the preparation cost of the polyaluminium chloride is greatly reduced; the carbon-silicon component exists in a solid I form, desiliconized carbon residue can be prepared by reacting the alkali solution with the solid I, and the hierarchical porous carbon can be prepared by activating the desiliconized carbon residue.
2) According to the embodiment of the application, the polyaluminum chloride and the hierarchical porous carbon are prepared simultaneously by taking the coal gasification fine slag as the raw material, so that on one hand, the additional value of the comprehensive utilization of the coal gasification fine slag is obviously improved; on the other hand, the comprehensive utilization of carbon and aluminum components is realized for the first time; and the third aspect prepares the hierarchical porous carbon material with excellent performance, so that the hierarchical porous carbon material has the characteristics of large specific surface area and less impurities, and the electrochemical performance of the capacitor electrode can be more excellent when the hierarchical porous carbon material is used as a capacitor electrode manufacturing raw material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings used in the description of the embodiments will be briefly introduced below. It is obvious that the drawings in the following description are only some of the embodiments described in the present application, and that other drawings can be derived from these drawings by a person skilled in the art without inventive effort.
FIG. 1 is an SEM image of coal gasification fine slag used in the examples of the present application, magnified 20000 times;
FIG. 2 is a SEM photograph at 5000 times magnification of desiliconized carbon residue prepared in example 1 of the present application;
FIG. 3 is a photograph of wastewater before and after the polyaluminum chloride prepared in example 1 of the present application was treated, wherein FIG. 3-a is a photograph of wastewater which was not treated with the polyaluminum chloride; FIG. 3-b is a photograph of the wastewater treated with the polyaluminum chloride;
fig. 4 is an SEM image of the hierarchical porous carbon prepared in example 1 of the present application at magnification of 20000 times;
FIG. 5 is an XRD pattern of the coal gasification fine slag used in the examples of the present application and the hierarchical porous carbon prepared in example 1;
FIG. 6 is an FTIR plot of coal gasification fine slag used in the examples of the present application and the hierarchical porous carbon prepared in example 1;
FIG. 7 is a graph showing the specific surface areas of the coal gasification fine slag used in the examples of the present application and the hierarchical porous carbon prepared in example 1;
FIG. 8 is a pore size diagram of the coal gasification fine slag used in the examples of the present application and the hierarchical porous carbon prepared in example 1;
FIG. 9 is a Raman diagram of the coal gasification fine slag used in the examples of the present application and the hierarchical porous carbon prepared in example 1;
FIG. 10 is a CV curve of the porous carbon electrode material prepared in example 1 of the present application at different scanning speeds;
FIG. 11 is a GCD curve of the porous carbon electrode material prepared in example 1 of the present application under different current densities;
FIG. 12 is a graph showing the rate characteristics of the porous carbon electrode material prepared in example 1 of the present application;
FIG. 13 is a graph showing the change of specific capacitance during 5000 cycles at a current density of 5A/g for the porous carbon electrode material prepared in example 1 of the present application.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In the following description of the present embodiment, the term "and/or" is used to describe an association relationship of associated objects, and indicates that three relationships may exist, for example, a and/or B, and may indicate: a alone, B alone and both A and B. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the following description of the present embodiment, the term "at least one" means one or more, and "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of singular or plural items. For example, "at least one (one) of a, b, or c," or "at least one (one) of a, b, and c," may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood by those skilled in the art that, in the following description of the embodiments of the present application, the sequence of the serial numbers does not mean the sequence of the execution, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In a first aspect, the embodiment of the present application provides a method for comprehensively utilizing coal gasification fine slag, which includes the following steps S101 to S105.
S101: providing coal gasification fine slag powder;
s102: adding the coal gasification fine slag powder into a protonic acid solution for reaction, and separating after the reaction is finished to obtain a filtrate and a solid I;
s103: adding calcium aluminate into the filtrate for reaction, standing and cooling after the reaction is finished, and drying the obtained supernatant to obtain polyaluminium chloride;
s104: washing and drying the solid I, adding the solid I into an alkali solution for reaction, cooling and separating the solid I after the reaction is finished, and washing and drying the solid II to obtain desiliconized carbon residue;
s105: and mixing the desiliconized residual carbon with KOH powder, and then sequentially calcining, washing and drying to obtain the hierarchical porous carbon.
In combination with the first aspect, in an embodiment of the present application, the providing coal gasification fine slag powder includes:
and (3) drying the coal gasification fine slag in an air drying oven, and then sequentially crushing by a crusher and ball milling by a planetary ball mill, wherein the rotation speed of the ball mill is preferably 100-870 r/min, and the ball milling time is preferably 20-360 min.
It should be noted that, in the embodiment of the present application, the rotation speed of the ball mill is controlled to be 100 to 870r/min, so that the crushing efficiency can be better improved, and the particle size of the powder can meet the requirement; meanwhile, the ball milling time is controlled to be 20-360 min, so that the particle size of the powder can meet the requirement, and the aggregation of small-particle-size particles caused by overlong ball milling time can be prevented, and the dispersion performance of the coal gasification fine slag powder is prevented from being influenced.
With reference to the first aspect, in the embodiment of the present application, the protonic acid solution in step S102 is preferably a hydrochloric acid solution, the mass concentration of the hydrochloric acid solution is preferably 6 to 36%, and the volume of the hydrochloric acid solution is preferably 2 to 24 times of the mass of the coal gasification fine slag powder.
It should be noted that, in the embodiment of the present application, a hydrochloric acid solution is selected to perform a hydrothermal reaction with coal gasification fine slag powder, so that not only can a microcrystalline structure of coal gasification fine slag be changed, a carbon skeleton be loosened, a crosslinking degree be reduced, and a reaction activity be improved, but also carbon residue recovered by hydrochloric acid treatment has a good pore structure and a high specific surface area, and thus, the carbon residue has a potential for preparing a porous carbon precursor.
In combination with the first aspect, in the present embodiment, the temperature of the reaction described in step S102 is preferably 60 to 150 ℃, and the time is preferably 30 to 240min.
It should be noted that, in the embodiment of the present application, coal gasification fine slag powder and protonic acid solution react at a temperature of 60 to 150 ℃, so that on one hand, molecular motion can be increased to improve molecular collision, which is more favorable for removing minerals from coal gasification fine slag; on the other hand, the method can avoid the volatilization of the protonic acid solution caused by overhigh temperature, thereby improving the utilization rate of the protonic acid and being beneficial to mineral removal. Meanwhile, the reaction time is controlled to be 30-240 min, so that the minerals and the protonic acid are fully reacted, and the separated minerals can be prevented from being adsorbed mutually.
In combination with the first aspect, in the embodiment of the present application, the volume of the filtrate in step S103 is preferably 4 to 16 times of the mass of the calcium aluminate, so as to ensure that the aluminum ions in the solution and the calcium aluminate can sufficiently react to form polyaluminium chloride; the reaction temperature is preferably 60-140 ℃, and the reaction time is preferably 60-180 min, so that aluminum ions and calcium aluminate are fully reacted, and the purity of the prepared polyaluminium chloride is improved; the temperature for drying the supernatant is preferably 80-120 ℃, so that the combined water in the polyaluminum chloride solution can be evaporated, and the polyaluminum chloride solution can be better dried into powder.
With reference to the first aspect, in the embodiment of the present application, the alkaline solution in step S104 is a sodium hydroxide solution, the mass concentration of the sodium hydroxide solution is preferably 5 to 40%, and the volume of the sodium hydroxide solution is preferably 10 to 35 times of the mass of the solid I.
It should be noted that in the embodiment of the present application, the solid I is reacted with a sodium hydroxide solution, and the sodium hydroxide is a strong base, so that the solid I can react with the active silicon component in the solid I, which is beneficial to improving the removal effect of the active silicon component in the solid I. Meanwhile, the mass concentration of the sodium hydroxide solution and the volume ratio of the sodium hydroxide solution to the solid I are controlled, so that the solid I can be completely immersed in the sodium hydroxide solution, and the silicon in the solid I can be fully reacted with the sodium hydroxide solution.
In combination with the first aspect, in the present embodiment, the temperature of the reaction described in step S104 is preferably 60 to 150 ℃, and the time is preferably 60 to 180min.
It should be noted that, in the embodiment of the present application, the solid I and the alkali solution react at a temperature of 60 to 150 ℃, so that the molecular motion is increased, the molecular collision is improved, and the removal of the active silicon component in the solid I is facilitated. Meanwhile, the reaction time is controlled to be 60-180 min, so that not only is the active silicon component in the solid I fully reacted with the alkali, but also silicic acid colloid generated by the reaction can be prevented from being precipitated in the solid II.
In the embodiment of the present application, deionized water is preferably used for washing the solid I and the solid II in step S104 to prevent the introduction of other mineral ions during the washing process, and the filtrate is preferably washed to have a pH =6.0 to 8.0, so as to sufficiently remove water-soluble impurities and remove an acidic solution or a basic solution attached to the surface of the precipitate.
With reference to the first aspect, in the embodiment of the present application, the mass of the alkali powder in step S105 is preferably 2 to 6 times of the mass of the desiliconized residual carbon;
the calcination adopts a rotary furnace, the atmosphere is inert gas, and the gas flow is 60-100 mL/min;
the calcining temperature is 600-900 ℃, the heating rate is 2-5 ℃/min, and the time is 40-100 min.
It should be noted that in the embodiment of the present application, the desiliconized carbon residue is calcined at a temperature of 600 to 900 ℃, so that potassium hydroxide can be converted into potassium vapor to etch carbon, which is beneficial to forming pores with different sizes; meanwhile, the reaction time is controlled to be 40-100 min, so that the reaction is fully performed, the collapse of desiliconized carbon residue pores in the calcining process is prevented, and the formation of pores with different sizes is facilitated.
In the embodiment of the present application, the drying in step S104 and step S105 is preferably vacuum drying, and the temperature of the vacuum drying is preferably 60 to 110 ℃, and the time is preferably 10 to 36 hours.
In a second aspect, the embodiments of the present application provide an application of the hierarchical porous carbon prepared by the comprehensive utilization method in preparing a capacitor electrode material. The hierarchical porous carbon prepared based on the embodiment of the application has a very high specific surface area, a larger average pore diameter and a more ordered carbon crystal structure, so that the hierarchical porous carbon has a wide application prospect in preparing capacitor electrode materials.
The technical solution of the present application will be further explained with reference to specific embodiments.
Example 1
The embodiment 1 provides a method for comprehensively utilizing coal gasification fine slag, which specifically includes the following steps S101 to S105.
S101: and (3) placing the coal gasification fine slag into a blast drying oven for drying, and then sequentially crushing by a crusher and ball-milling by a planetary ball mill to prepare coal gasification fine slag powder. Wherein the rotating speed of the ball mill is 870r/min, and the ball milling time is 240min.
S102: adding 12g of coal gasification fine slag powder into 72mL of 24% hydrochloric acid, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining and a volume of 100mL, placing into an oven, heating to 90 ℃, keeping the temperature for 150min, cooling to room temperature, and performing suction filtration to obtain filtrate and a solid I.
S103: 40g of calcium aluminate powder is added into 200mL of the filtrate, then oil bath reaction is carried out at the temperature of 80 ℃ for 120min, and after cooling, the upper layer liquid is placed on a heating plate and dried at the temperature of 100 ℃ to obtain the polyaluminum chloride powder.
S104: washing the solid I to be neutral by using deionized water, carrying out vacuum drying at the temperature of 80 ℃ for 12h, then adding the dried powder into a certain amount of sodium oxide solution with the mass concentration of 30%, carrying out oil bath reaction at the temperature of 90 ℃ for 150min, cooling, carrying out suction filtration and washing by using the deionized water to be neutral, and carrying out vacuum drying to obtain the desiliconized carbon residue, wherein the volume of the sodium oxide solution is 30 times of the mass of the solid I.
S105: mixing the desiliconized carbon residue with a certain amount of KOH powder, putting the mixture into a rotary furnace, calcining the mixture for 60min at the temperature of 800 ℃, cooling the mixture to room temperature, washing the mixture by using 1M hydrochloric acid and deionized water in sequence until the mixture is neutral, and drying the mixture in vacuum to obtain hierarchical porous carbon SPL1, wherein the mass of the KOH powder is 4 times that of the desiliconized carbon residue, and the atmosphere is N 2 The gas flow rate is 80mL/min, and the heating rate is 5 ℃/min.
Example 2
The embodiment 2 provides a method for comprehensively utilizing coal gasification fine slag, which specifically includes the following steps S101 to S105.
S101: and (3) placing the coal gasification fine slag into an air-blast drying oven for drying, and then sequentially crushing by a crusher and ball-milling by a planetary ball mill to prepare coal gasification fine slag powder. Wherein the rotating speed of the ball mill is 870r/min, and the ball milling time is 240min.
S102: adding 12g of coal gasification fine slag powder into 72mL of 24% hydrochloric acid, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining and a volume of 100mL, placing into an oven, heating to 90 ℃, keeping the temperature for 150min, cooling to room temperature, and performing suction filtration to obtain filtrate and a solid I.
S103: 40g of calcium aluminate powder is added into 200mL of the filtrate, then oil bath reaction is carried out at the temperature of 80 ℃ for 120min, and after cooling, the upper layer liquid is placed on a heating plate and dried at the temperature of 100 ℃ to obtain the polyaluminum chloride powder.
S104: washing the solid I to be neutral by using deionized water, carrying out vacuum drying at the temperature of 80 ℃ for 12h, then adding the dried powder into a certain amount of sodium oxide solution with the mass concentration of 30%, carrying out oil bath reaction at the temperature of 90 ℃ for 150min, cooling, carrying out suction filtration and washing by using the deionized water to be neutral, and carrying out vacuum drying to obtain the desiliconized residual carbon, wherein the volume of the sodium oxide solution is 30 times of the mass of the solid I.
S105: mixing the desiliconized carbon residue with a certain amount of KOH powder, putting the mixture into a rotary furnace, calcining the mixture for 60min at the temperature of 850 ℃, cooling the mixture to room temperature, washing the mixture by using 1M hydrochloric acid and deionized water in sequence until the mixture is neutral, and drying the mixture in vacuum to obtain hierarchical porous carbon SPL2, wherein the mass of the KOH powder is 4 times that of the desiliconized carbon residue, and the atmosphere is N 2 The gas flow rate is 80mL/min, and the heating rate is 5 ℃/min.
Example 3
The embodiment 3 provides a method for comprehensively utilizing coal gasification fine slag, which specifically includes the following steps S101 to S105.
S101: and (3) placing the coal gasification fine slag into a blast drying oven for drying, and then sequentially crushing by a crusher and ball-milling by a planetary ball mill to prepare coal gasification fine slag powder. Wherein the rotating speed of the ball mill is 870r/min, and the ball milling time is 240min.
S102: adding 12g of coal gasification fine slag powder into 72mL of hydrochloric acid with the mass concentration of 24%, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining and the volume of 100mL, placing into an oven, heating to 90 ℃, keeping the temperature for 150min, cooling to room temperature, and carrying out suction filtration to obtain filtrate and a solid I.
S103: 40g of calcium aluminate powder is added into 200mL of the filtrate, then oil bath reaction is carried out at the temperature of 80 ℃ for 120min, and after cooling, the upper layer liquid is placed on a heating plate and dried at the temperature of 100 ℃ to obtain the polyaluminum chloride powder.
S104: washing the solid I to be neutral by using deionized water, carrying out vacuum drying at the temperature of 80 ℃ for 12h, then adding the dried powder into a certain amount of sodium oxide solution with the mass concentration of 30%, carrying out oil bath reaction at the temperature of 90 ℃ for 150min, cooling, carrying out suction filtration and washing by using the deionized water to be neutral, and carrying out vacuum drying to obtain the desiliconized residual carbon, wherein the volume of the sodium oxide solution is 30 times of the mass of the solid I.
S105: mixing the desiliconized carbon residue with a certain amount of KOH powder, putting the mixture into a rotary furnace, calcining the mixture for 60min at the temperature of 750 ℃, cooling the mixture to room temperature, washing the mixture by using 1M hydrochloric acid and deionized water in sequence until the mixture is neutral, and drying the mixture in vacuum to obtain hierarchical porous carbon SPL3, wherein the mass of the KOH powder is 4 times that of the desiliconized carbon residue, and the atmosphere is N 2 The gas flow rate is 80mL/min, and the heating rate is 5 ℃/min.
Example 4
In embodiment 4, a method for comprehensively utilizing coal gasification fine slag is provided, which specifically includes the following steps S101 to S105.
S101: and (3) placing the coal gasification fine slag into a blast drying oven for drying, and then sequentially crushing by a crusher and ball-milling by a planetary ball mill to prepare coal gasification fine slag powder. Wherein the rotating speed of the ball mill is 870r/min, and the ball milling time is 240min.
S102: adding 12g of coal gasification fine slag powder into 72mL of hydrochloric acid with the mass concentration of 22%, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining and the volume of which is 100mL, putting into an oven, heating to 90 ℃, keeping the temperature for 150min, cooling to room temperature, and performing suction filtration to obtain filtrate and a solid I.
S103: 40g of calcium aluminate powder is added into 200mL of the filtrate, then oil bath reaction is carried out at the temperature of 80 ℃ for 120min, and after cooling, the upper layer liquid is placed on a heating plate and dried at the temperature of 100 ℃ to obtain the polyaluminum chloride powder.
S104: washing the solid I to be neutral by using deionized water, carrying out vacuum drying at the temperature of 80 ℃ for 12h, then adding the dried powder into a certain amount of sodium oxide solution with the mass concentration of 30%, carrying out oil bath reaction at the temperature of 90 ℃ for 150min, cooling, carrying out suction filtration and washing by using the deionized water to be neutral, and carrying out vacuum drying to obtain the desiliconized residual carbon, wherein the volume of the sodium oxide solution is 30 times of the mass of the solid I.
S105: mixing the desiliconized carbon residue with a certain amount of KOH powder, putting the mixture into a rotary furnace, calcining the mixture for 60min at the temperature of 800 ℃, cooling the mixture to room temperature, washing the mixture by using 1M hydrochloric acid and deionized water in sequence until the mixture is neutral, and drying the mixture in vacuum to obtain hierarchical porous carbon SPL4, wherein the mass of the KOH powder is 4 times that of the desiliconized carbon residue, and the atmosphere is N 2 The gas flow rate is 80mL/min, and the heating rate is 5 ℃/min.
Example 5
In embodiment 5, a method for comprehensively utilizing coal gasification fine slag is provided, which specifically includes the following steps S101 to S105.
S101: and (3) placing the coal gasification fine slag into an air-blast drying oven for drying, and then sequentially crushing by a crusher and ball-milling by a planetary ball mill to prepare coal gasification fine slag powder. Wherein the rotating speed of the ball mill is 870r/min, and the ball milling time is 240min.
S102: adding 12g of coal gasification fine slag powder into 72mL of 26% hydrochloric acid, uniformly stirring, transferring into a reaction kettle with a polytetrafluoroethylene lining and a volume of 100mL, placing into an oven, heating to 90 ℃, keeping the temperature for 150min, cooling to room temperature, and performing suction filtration to obtain filtrate and a solid I.
S103: 40g of calcium aluminate powder is added into 200mL of the filtrate, then oil bath reaction is carried out at the temperature of 80 ℃ for 120min, and after cooling, the upper layer liquid is placed on a heating plate and dried at the temperature of 100 ℃ to obtain the polyaluminum chloride powder.
S104: washing the solid I to be neutral by using deionized water, carrying out vacuum drying at the temperature of 80 ℃ for 12h, then adding the dried powder into a certain amount of sodium oxide solution with the mass concentration of 30%, carrying out oil bath reaction at the temperature of 90 ℃ for 150min, cooling, carrying out suction filtration and washing by using the deionized water to be neutral, and carrying out vacuum drying to obtain the desiliconized carbon residue, wherein the volume of the sodium oxide solution is 30 times of the mass of the solid I.
S105: mixing the desiliconized carbon residue with a certain amount of KOH powder, putting the mixture into a rotary furnace, calcining the mixture for 60min at the temperature of 800 ℃, cooling the mixture to room temperature, washing the mixture by using 1M hydrochloric acid and deionized water in sequence until the mixture is neutral, and drying the mixture in vacuum to obtain hierarchical porous carbon SPL5, wherein the mass of the KOH powder is 4 times that of the desiliconized carbon residue, and the atmosphere is N 2 The gas flow rate is 80mL/min, and the heating rate is 5 ℃/min.
In order to verify the technical effect of the comprehensive utilization method of the coal gasification fine slag in the embodiment of the application, the inventor tests and characterizes the raw materials, the intermediates and the products related to the embodiment, and the specific items and results are as follows:
1. the structural representation of the coal gasification fine slag is shown in figure 1. Wherein, figure 1 is SEM picture of coal gasification fine slag magnified 20000 times.
As can be seen from fig. 1: the coal gasification fine slag used in this example is mainly composed of amorphous flocculent carbon, spherical or irregular aluminosilicate glass bodies and mineral quartz. Wherein, flocculent carbon is mainly derived from carbon which is not completely combusted in the coal gasification process, and aluminosilicate glass body is mainly formed by mineral matters in raw material coal in the gasification process.
2. The structural characterization of the desiliconized residual carbon is shown in FIG. 2. Wherein, FIG. 2 is an SEM photograph of the desiliconized residual carbon prepared in example 1, enlarged by 5000 times.
As can be seen from fig. 2: the residual carbon obtained in the comprehensive utilization method of the embodiment only contains flocculent carbon, and most of the melted inorganic particles disappear. Therefore, in the embodiment of the application, the protonic acid solution is used for reacting with the coal gasification fine slag, and the precipitate is further reacted with the alkali solution, so that the mineral substances in the coal gasification fine slag are effectively removed.
3. Appearance characterization of polyaluminum chloride and performance test of treated wastewater: an appropriate amount of the polyaluminum chloride powder prepared in example 1 was added to the wastewater, and the mixture was allowed to stand for 12 hours, wherein the amount of the polyaluminum chloride powder was 600 mg/L, and the results are shown in FIG. 3. Wherein FIG. 3 is a photograph of the sewage before and after the treatment with the polyaluminum chloride of example 1, and specifically, FIG. 3-a is a photograph of the sewage which is not treated with the polyaluminum chloride; FIG. 3-b is a photograph of the wastewater treated with the polyaluminum chloride.
The results show that: the polyaluminum chloride prepared in this example 1 was a yellow powder. Meanwhile, as can be seen from fig. 3: the polyaluminium chloride prepared in the embodiment 1 has a good flocculation effect, and has a remarkable purification effect when being used for sewage treatment.
4. The results of structural and performance characterization of the hierarchical porous carbon are shown in fig. 4 to 11.
4.1 structural characterization of the hierarchical porous carbon, the results are shown in FIG. 4. Fig. 4 is an SEM image magnified 20000 times of the hierarchical porous carbon prepared in example 1.
As can be seen from fig. 4: according to the embodiment of the application, the desiliconized residual carbon is subjected to the release of gas and volatile compounds in the activation process and the etching of potassium vapor to form holes with different hole levels.
4.2 XRD characterization of the graded porous carbon, the results are shown in FIG. 5. Fig. 5 is an XRD chart of the coal gasification fine slag and the hierarchical porous carbon prepared in example 1.
As can be seen from fig. 5: most of the substances in the coal gasification fine slag exist in a glass amorphous state, and only a small amount of quartz (SiO) 2 ) And iron mineral crystals, whereas the XRD spectrum of the hierarchical porous carbon prepared in example 1 shows broad peaks in the vicinity of 23 ° and 43 °, corresponding to the diffraction peaks of (002) and (101) crystal planes of graphite, and the diffraction peak of the (002) crystal plane is shifted toward a lower diffraction angle. In the examples of the present application, the KOH powder and the desiliconized residual carbon are mixed and then calcined and activated in an inert gas atmosphere, so that the distance between graphene layers of the coal gasification fine slag becomes large (0.335 nm → 0.384 nm).
4.3 FTIR characterization of the graded porous carbon, the results are shown in FIG. 6. Fig. 6 is an FTIR chart of the coal gasification fine slag and the hierarchical porous carbon prepared in example 1.
As can be seen from fig. 6: 3448cm -1 The broad peak is the resultant peak of O-H stretching vibration of coal gasification fine slag and hydroxyl in hierarchical porous carbon, and water is adsorbed on the surface; 1635cm -1 C = C stretching vibration at aromatic ringMoving; 1383cm -1 The peak at (a) corresponds to the Si-O or Al-O peak; 997cm -1 The peak is the overlapped peak of the stretching vibration of Si-O-Si and C-O-Si; 466cm -1 The presence of Si is evidenced by the peaks at (a). In addition, compared with the infrared spectrum of the coal gasification fine slag, partial mineral peaks in the infrared spectrum of the hierarchical porous carbon disappear, which indicates that in the embodiment of the application, after the protonic acid reacts with the coal gasification fine slag, the solid I reacts with the alkali solution, and the mineral and active silicon components in the coal gasification fine slag are effectively removed.
4.4 specific surface area and pore size characterization plots of the hierarchical porous carbon, the results of which are shown in FIGS. 7 and 8. Wherein, fig. 7 is a specific surface area diagram of the coal gasification fine slag and the hierarchical porous carbon prepared in example 1; FIG. 8 is a pore size diagram of the coal gasification fine slag used in the examples and the hierarchical porous carbon prepared in example 1.
As can be seen from fig. 7 and 8: the specific surface area of the hierarchical porous carbon is 1255.64m 2 Per g, pore volume 0.8227cm 3 G, average pore diameter of 2.9nm, specific surface area of 412.32m higher than that of commercial porous carbon 2 (iv) g. As shown in fig. 7, the porous carbon residue is embedded by the molten mineral to block the porous channel, so that the adsorption capacity of the coal gasification fine slag is very small; as shown in FIG. 8, the pore size distribution of the hierarchical porous carbon is relatively aggregated between 3.8 and 32nm, indicating the existence of well-developed micropores and a large number of mesopores.
Meanwhile, different from the traditional activated carbon material with high specific surface area and high micropore volume, the hierarchical porous carbon has a hierarchical porous structure, and is beneficial to improving the specific surface area of the material, so that interconnected channels are provided for the transportation and storage of electrolyte ions.
4.5 Raman characterization of the hierarchical porous carbon, the results are shown in FIG. 9. Fig. 9 is a Raman chart of the coal gasification fine slag and the hierarchical porous carbon prepared in example 1.
As can be seen from fig. 9: the coal gasification fine slag and the hierarchical porous carbon contain two main characteristic peaks: d peak (1351 cm) -1 ) And peak G (1596 cm) -1 ) Wherein the coal gasification fine slag and the graded porous carbon have the structure I D /I G Are respectively 1.85 and 1.55,the method shows that a large amount of structural defects exist in a carbon skeleton of the coal gasification fine slag, and relatively more amorphous carbon exists; in the embodiment of the application, the coal gasification fine slag is subjected to deashing treatment and activation, so that the graphite layer can be recombined, the number of defects is reduced, and better structural performance is shown.
4.6 electrochemical Properties of Graded porous carbon
Capacitor electrodes were prepared using the hierarchical porous carbons SPL1-SPL5 prepared in examples 1-5 as raw materials, and the specific preparation method included:
the method comprises the following steps: adding a certain amount of graded porous carbon SPL1-SPL5, conductive carbon black and polyvinylidene fluoride into N, N-dimethylformamide in proportion, and performing ultrasonic dispersion for 1 hour to obtain a slurry mixture. Wherein the mass ratio of the hierarchical porous carbon SPL1-SPL5 to the conductive carbon black to the polyvinylidene fluoride is 8; the volume of the N, N-dimethylformamide is equal to the mass of the hierarchical porous carbon SPL1-SPL 5;
step two: the slurry mixture was adjusted to 1mg/cm 2 Coating the load capacity of the porous carbon electrode material on carbon paper of 1cm multiplied by 1cm, naturally airing, and then drying in vacuum to constant weight to obtain the hierarchical porous carbon electrode material;
step three: a three-electrode system is adopted, a hierarchical porous carbon electrode material is used as a working electrode, hg/HgO is used as a reference electrode, a Pt sheet is used as a counter electrode, and 6mol/L KOH aqueous solution is used as electrolyte, and cyclic voltammetry and constant current charge-discharge tests are performed on an electrochemical workstation.
The test results are shown in tables 1 and 2, wherein the table 1 shows the capacitance performance of the electrodes made of the hierarchical porous carbon SPL1-SPL 5; table 2 shows the capacitance performance of the graded porous carbon SPL1 as an electrode at different current densities.
TABLE 1 capacitive Properties of Graded porous carbon SPL1-SPL5 as electrodes
As can be seen from table 1: the hierarchical porous carbon SPL1-SPL5 used as the electrode in the embodiment of the application has good energy storage capacity; meanwhile, as can be seen from comparison of the respective examples, the hierarchical porous carbon SPL1 prepared in example 1 has a higher specific capacitance.
TABLE 2 capacitive Performance of the Graded porous carbon SPL1 as electrode at different Current Density
| Current Density (A/g) | 0.5 | 1 | 2 | 5 | 10 | 25 |
| Specific capacitance (F/g) | 485.5 | 306.1 | 235.2 | 202.5 | 190.1 | 175.2 |
The results of electrochemical performance tests performed on the hierarchical porous carbon SPL1 electrode prepared in example 1 are shown in fig. 10 to 13. Wherein, fig. 10 is a CV curve of the graded porous carbon electrode prepared in example 1 at different sweep rates; FIG. 11 is a GCD curve for different current densities for the graded porous carbon electrode prepared in example 1; FIG. 12 is a rate characteristic curve for the graded porous carbon electrode prepared in example 1; FIG. 13 is a graph showing the change in specific capacitance of the graded porous carbon electrode prepared in example 1 during 5000 charges and discharges at a current density of 5A/g;
as can be seen from fig. 10: the CV curve is approximately rectangular, and as the scan rate increases, the curve still exhibits an approximate rectangle, indicating that the hierarchical porous carbon electrode has excellent electric double layer storage performance.
As can be seen from fig. 11: the GCD curve is approximately triangular, which indicates that the hierarchical porous carbon electrode is an ideal double-layer capacitor material.
As can be seen from fig. 12: the graded porous carbon electrode prepared in example 1 has a specific capacitance of 306.1F/g at a current density of 1A/g and a specific capacitance of 175.2F/g at a current density of 25A/g, which indicates that the material has better rate characteristics.
As can be seen from fig. 13: after 5000 times of charge and discharge cycles, the capacitor retention rate of the hierarchical porous carbon electrode prepared in example 1 is 94%, and the hierarchical porous carbon electrode has excellent electrochemical performance.
The embodiments in the present specification are described in a progressive manner, and the same or similar parts among the embodiments can be mutually referred to, and each embodiment focuses on the difference from the other embodiments.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the present application; although the present application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications or substitutions do not depart from the spirit and scope of the present disclosure.
Claims (10)
1. A comprehensive utilization method of coal gasification fine slag is characterized by comprising the following steps:
s101: providing coal gasification fine slag powder;
s102: adding the coal gasification fine slag powder into a protonic acid solution for reaction, and separating to obtain a filtrate and a solid I after the reaction is finished;
s103: adding calcium aluminate into the filtrate for reaction, standing and cooling after the reaction is finished, and drying the obtained supernatant to obtain polyaluminium chloride;
s104: washing and drying the solid I, adding the solid I into an alkali solution for reaction, cooling and separating the solid I after the reaction is finished, and washing and drying the solid II to obtain desiliconized carbon residue;
s105: and mixing the desiliconized residual carbon with KOH powder, and then sequentially calcining, washing and drying to obtain the hierarchical porous carbon.
2. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the protonic acid solution in step S102 is a hydrochloric acid solution;
the mass concentration of the hydrochloric acid solution is 6-36%;
the volume of the hydrochloric acid solution is 2-24 times of the mass of the coal gasification fine slag powder.
3. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the reaction temperature in step S102 is 60 to 150 ℃ and the reaction time is 30 to 240min.
4. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the volume of the filtrate in step S103 is 4 to 16 times the mass of the calcium aluminate;
the reaction temperature is 60-140 ℃ and the reaction time is 60-180 min;
the temperature for drying the supernatant is 80-120 ℃.
5. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the alkali solution in step S104 is a sodium hydroxide solution;
the mass concentration of the sodium hydroxide solution is 5-40%;
the volume of the sodium hydroxide solution is 10-35 times of the mass of the solid I.
6. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the reaction temperature in step S104 is 60 to 150 ℃ and the reaction time is 60 to 180min.
7. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein deionized water is used for washing both the solid I and the solid II in step S104, and the washing is performed until the pH of the filtrate =6.0 to 8.0.
8. The method for comprehensively utilizing coal gasification fine slag according to claim 1, wherein the mass of the KOH powder in the step S105 is 2 to 6 times of the mass of the desiliconized residual carbon;
the calcination adopts a rotary furnace, the atmosphere is inert gas, and the gas flow is 60-100 mL/min;
the calcining temperature is 600-900 ℃, the heating rate is 2-5 ℃/min, and the time is 40-100 min.
9. The method for recycling coal gasification fine slag according to claim 1, wherein the drying in step S104 and step S105 is vacuum drying;
the temperature of the vacuum drying is 60-110 ℃, and the time is 10-36 h.
10. Use of hierarchical porous carbon prepared by the comprehensive utilization method of coal gasification fine slag according to any one of claims 1 to 9 in the preparation of capacitor electrode materials.
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