CN114763303A - Coal gangue-based heating material and preparation method thereof - Google Patents
Coal gangue-based heating material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a coal gangue-based heating material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the coal gangue, the carbonaceous material and the binding agent, and ageing the mixture to obtain mixed pug; and pressing and molding the mixed pug, and sintering in a protective atmosphere to obtain the coal gangue-based heating material. The coal gangue and the carbonaceous material are used as raw materials, the characteristics of high thermal resistance and high strength of the coal gangue and high electric conduction and high heat conduction of the carbonaceous material are utilized, the stable combination of the carbonaceous material and the coal gangue is promoted under the action of the binding agent, the strength of the composite heating material is improved, and the electrothermal conversion efficiency is improved; the method has the advantages of wide raw material source, low price, simple process method and environment friendliness, provides a foundation for industrial production of the coal gangue heating material, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of heating materials, and relates to a coal gangue-based heating material and a preparation method thereof.
Background
With the development of science and technology and the improvement of the living standard of people, the heating material is widely applied to the heating of residents in winter, and a heating element is usually additionally arranged between a base plate and a heat insulation material in the heating process. Because of high conductivity and excellent high temperature resistance, heating wires, carbon fibers or electrothermal films are often used as heating elements to realize rapid heating up to a certain extent, but have the disadvantages of low electrothermal conversion efficiency, high cost, complex process, short service life and the like, and thus, development of a novel heating material with high electrothermal conversion efficiency is required.
The coal gangue is associated and symbiotic with coal in the coal forming process, is solid waste generated in the coal production and processing process, occupies a large amount of land along with the increasing stockpiling amount of the coal gangue, and escaped sulfides can pollute farmlands, atmosphere and water bodies.
CN 111763097A discloses a method for preparing porous ceramic by utilizing coal gangue, which comprises the following steps: acid reaction pretreatment of the coal gangue, melting pretreatment of the coal gangue, adding citric acid and a protective agent for mixing, stirring until materials are melted, mixing and drying to obtain coal gangue powder, sieving, adding a proper amount of paraffin oil, ageing, injection molding, degreasing, calcining at low temperature, and sintering at high temperature under pressure to obtain porous ceramic, wherein the protective agent is calcium citrate porous carbon; although the coal gangue, the citric acid, the paraffin oil and the like are jointly treated by the method, the preparation of the porous ceramic still belongs to a simple utilization mode of the coal gangue, and the preparation of functional materials is not involved.
Graphene is a two-dimensional carbon nanomaterial with a single atomic thickness, wherein carbon atoms are connected in an sp2 hybridization manner, and the graphene has excellent electrical conductivity and thermal conductivity and can be used for preparing heating materials. CN 107949081a discloses a preparation method of graphene electrothermal material with controllable electrothermal property, which comprises the following steps: taking the graphene slurry as a conductive filler, taking the aqueous polyurethane emulsion as a binder, and adding an emulsifier with the mass fraction of 3% to prepare the graphene electrothermal carbon slurry; the preparation method comprises the steps of taking a PET film as a carrier, arranging a lead on the PET film, coating the graphene electric heating carbon slurry on the PET film, and drying to obtain the graphene electric heating material with controllable electric heating performance.
In conclusion, for the preparation of the novel heating material, appropriate raw materials and processes need to be selected, and on the basis of meeting the requirements of high electrothermal conversion efficiency and stability, the cost can be reduced, the process is simplified, and the application range of the novel heating material is expanded.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a coal gangue-based heating material and a preparation method thereof, wherein the coal gangue and a carbonaceous material are used as raw materials, and the stable composite heating material with high electrothermal conversion efficiency is prepared under the combination action of a binding agent by utilizing the characteristics of high thermal resistance and high strength of the coal gangue and high electric conductivity and high heat conductivity of the carbonaceous material; the raw materials are wide in source and low in price, and the method is simple to operate and has a good application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing the coal gangue, the carbonaceous material and the binding agent, and then ageing the mixture to obtain mixed pug;
(2) and (2) pressing and forming the mixed pug obtained in the step (1), and sintering in a protective atmosphere to obtain the coal gangue based heating material.
In the invention, the heating material is prepared by taking the coal gangue and the carbonaceous material as main raw materials, thereby not only effectively utilizing the waste of the coal gangue, but also effectively utilizing SiO in the coal gangue2And Al2O3The high thermal resistance of the components is fully utilized, meanwhile, the addition of the high-thermal-conductivity and high-electric-conductivity carbon material generates stable and controllable heat energy by utilizing the mutual friction and collision among the molecules, and the addition of the bonding agent is beneficial to the carbon material in the coal gangueThe composite heating material is fully dispersed and stably combined, and the strength and uniformity of the composite heating material are improved through operations such as ageing, press forming and sintering, so that the electric-heat conversion efficiency is improved; the method has the advantages of simple process and low cost, provides a foundation for the industrial production of the coal gangue heating material, and has good application prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the chemical composition of the coal gangue in the step (1) comprises Al2O3、SiO2、Fe2O3、TiO2、SO2And C.
Preferably, the chemical composition of the coal gangue comprises, in mass fraction: al (Al)2O315 to 50 wt%, for example 15 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%, etc.; SiO 2230 to 45 wt%, for example 30 wt%, 35 wt%, 40 wt% or 45 wt%, etc.; fe2O30.5 to 1.0 wt%, for example 0.5 wt%, 0.6 wt%, 0.8 wt%, or 1.0 wt%, etc.; TiO 222.0 to 2.5 wt%, such as 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.4 wt%, or 2.5 wt%, etc.; SO (SO)20.5 to 1.5 wt%, for example 0.5 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, or 1.5 wt%, etc.; c17-35 wt%, for example 15 wt%, 20 wt%, 30 wt%, 40 wt% or 50 wt%; however, the above-mentioned values are not limited to the recited values, and other values not recited in the respective ranges are also applicable.
In the invention, the loss on ignition of the coal gangue accounts for 20-40 wt% in the subsequent sintering process, the loss after sintering is mainly amorphous C, sulfide and organic matters, and the phases of the remaining components comprise a mullite phase, a quartz phase and a potassium feldspar phase.
Preferably, the coal gangue particles of step (1) have a particle size of not greater than 0.074mm, such as 0.074mm, 0.07mm, 0.065mm, 0.06mm, 0.05mm, 0.04mm or 0.03mm, but not limited to the recited values, and other values not recited in this range are also applicable.
As a preferred technical solution of the present invention, the carbonaceous material in step (1) includes any one or a combination of at least two of graphene, carbon nanotubes or conductive carbon black, and the combination is typically but not limited to: combinations of graphene and carbon nanotubes, carbon nanotubes and conductive carbon black, combinations of graphene, carbon nanotubes and conductive carbon black, and the like.
Preferably, the graphene is in a sheet shape, and the sheet diameter is 1-10 μm, such as 1 μm, 3 μm, 5 μm, 8 μm or 10 μm; a total thickness of 0.2 to 3.0 μm, such as 0.2 μm, 0.5 μm, 1.0 μm, 1.5 μm, 2.0 μm, or 3.0 μm; the number of layers is 1-10, such as 1 layer, 3 layers, 5 layers, 8 layers or 10 layers; however, the above-mentioned values are not limited to the recited values, and other values not recited in the respective ranges are also applicable.
Preferably, the carbon nanotubes have an outer diameter of 10 to 25nm, for example, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm or 25nm, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable; the length is 2 to 50 μm, for example, 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm or 50 μm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the conductive carbon black has a particle size of 100 to 300nm, for example, 100nm, 150nm, 200nm, 250nm, or 300nm, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable; the carbon content is 99.0 wt% or more, for example, 99.0 wt%, 99.1 wt%, 99.2 wt%, 99.3 wt%, 99.4 wt%, 99.5 wt%, or 99.6 wt%, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the binder in step (1) comprises any one of polyvinyl alcohol, aluminum sol or silica sol or a combination of at least two of the following, typical but non-limiting examples being: a combination of polyvinyl alcohol and aluminum sol, a combination of aluminum sol and silica sol, a combination of polyvinyl alcohol, aluminum sol and silica sol, and the like.
In the invention, the binding agent mainly has the function of enabling the mixture of the coal gangue and the carbonaceous material to have plasticity, and is beneficial to compression molding of the mixed material.
In a preferred embodiment of the present invention, the mass ratio of the coal gangue to the carbonaceous material in the step (1) is (1 to 9):1, for example, 1:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1, or 9:1, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In the invention, the mass ratio of the coal gangue to the carbonaceous material in the mixed raw material is one of important factors influencing the performance of the heating material, if the mass ratio of the coal gangue to the carbonaceous material is higher, namely the content of the coal gangue is too high, the carbonaceous material with a high conductive phase is less, the conductivity of the material is poorer, and if the mass ratio of the coal gangue to the carbonaceous material is lower, namely the content of the coal gangue is too low, the thermal resistance of the heating material is lower, and the thermal conversion efficiency is lower.
Preferably, the binding agent of step (1) is added in the form of a solution.
Preferably, the binder solution is added in an amount of 2 to 10 wt% of the total mass of the coal gangue and the carbonaceous material, such as 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt% or 10 wt%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the binder solution has a solid content of 5 to 30 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%, and the like, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a preferred embodiment of the present invention, the temperature of the ageing mixture in step (1) is 25 to 40 ℃, for example, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃ or 40 ℃, but is not limited to the values listed, and other values not listed in the range of the values are also applicable; the humidity is 10 to 40%, for example, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the ageing time in step (1) is 24-36 h, such as 24h, 27h, 30h, 32h, 34h or 36h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the pressure for the press molding in the step (2) is 5 to 50MPa, for example, 5MPa, 10MPa, 20MPa, 30MPa, 40MPa or 50MPa, but the pressure is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the compression molding in step (2) is performed by using a powder tablet press, such as a 769YP-30T powder tablet press.
In a preferred embodiment of the present invention, a drying process is performed before the sintering in step (2).
Preferably, the temperature of the drying treatment is 60 to 120 ℃, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the drying time is 12 to 36 hours, such as 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours or 36 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical scheme of the invention, the protective gas in the step (2) comprises inert gas.
Preferably, the temperature of the sintering treatment in step (2) is 800 to 1100 ℃, for example 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, or 1100 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the time of the sintering treatment in the step (2) is 2 to 12 hours, such as 2 hours, 4 hours, 6 hours, 7 hours, 10 hours or 12 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the gangue-based heat-generating material in step (2) is in the form of a block, and is substantially rectangular parallelepiped, and the cross section thereof is generally square, and the side length thereof is 10 to 50mm, for example, 10mm, 20mm, 30mm, 40mm, or 50mm, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) mixing coal gangue, a carbonaceous material and a binding agent, and ageing, wherein the carbonaceous material comprises graphene, the binding agent comprises any one or combination of at least two of polyvinyl alcohol, alumina sol and silica sol, the mass ratio of the coal gangue to the carbonaceous material is (1-9): 1, the binding agent is added in the form of a solution, the addition amount of the binding agent solution accounts for 2-10 wt% of the total mass of the coal gangue and the carbonaceous material, the solid content of the binding agent solution is 5-30 wt%, the ageing temperature is 25-40 ℃, the humidity is 10-40%, and the time is 24-36 h, so as to obtain a mixed pug;
(2) And (2) pressing and forming the mixed pug obtained in the step (1) under the pressure of 5-50 MPa, drying at 60-120 ℃ for 12-36 h, and sintering at 800-1100 ℃ in a protective atmosphere for 2-12 h to obtain the coal gangue-based heating material.
On the other hand, the invention provides the coal gangue-based heating material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the coal gangue and the carbonaceous material are used as raw materials, the characteristics of high thermal resistance and high strength of the coal gangue and high electric conduction and high heat conduction of the carbonaceous material and the coal gangue are utilized, the stable combination of the carbonaceous material and the coal gangue is promoted under the action of a binding agent, the strength of the composite heating material is improved, the Vickers hardness can reach more than 28.57HV5, the electrothermal conversion efficiency is improved, and the electrothermal conversion temperature is improved to more than 85 ℃;
(2) the method has the advantages of wide raw material source, low price, simple process method and environment friendliness, provides a foundation for industrial production of the coal gangue heating material, and has good application prospect.
Drawings
Fig. 1 is an SEM image of the coal gangue-based heating material provided in example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific implementation mode part of the invention provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing the coal gangue, the carbonaceous material and the binding agent, and ageing the mixture to obtain mixed pug;
(2) and (2) pressing and forming the mixed pug obtained in the step (1), and sintering in a protective atmosphere to obtain the coal gangue based heating material.
The following are typical, but non-limiting, examples of the present invention:
example 1:
the embodiment provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing coal gangue, graphene and polyvinyl alcohol solution, and ageing, wherein the coal gangue comprises Al in chemical composition2O3 30wt％，SiO2 40wt％，Fe2O3 1.0wt％，TiO2 2.0wt％，SO21.0 wt% and 26 wt% of C, wherein the average particle size of the coal gangue is 0.06mm, the graphene is flaky, the diameter of each flake is 5 micrometers, the total thickness is 1.5 micrometers, and the number of layers is 5; the mass ratio of the coal gangue to the graphene is 4:1, the adding amount of the polyvinyl alcohol solution accounts for 5 wt% of the total mass of the coal gangue and the graphene, the solid content of the polyvinyl alcohol solution is 15 wt%, the ageing mixture is at a temperature of 25 ℃, the humidity is 40% and the time is 24 hours, so that mixed pug is obtained;
(2) And (2) pressing and molding the mixed pug obtained in the step (1) under the pressure of 25MPa, then drying at 80 ℃ for 12h, and sintering at 1000 ℃ in an argon atmosphere for 2h to obtain the coal gangue-based heating material.
The coal gangue-based heating material is characterized by a Scanning Electron Microscope (SEM), and an SEM image is shown in figure 1.
In this embodiment, as can be seen from fig. 1, the coal gangue-based heating material is densified, and graphene is uniformly distributed among coal gangue particles;
through testing, the volume density of the coal gangue-based heating material is 1.5g/cm3When the current is 2mA, the electrothermal conversion temperature is 102 ℃ and the Vickers hardness is 32.76HV 5.
Example 2:
the embodiment provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing coal gangue, graphene and polyvinyl alcohol solution, and ageing, wherein the coal gangue comprises Al in chemical composition2O3 50wt％，SiO2 30wt％，Fe2O3 0.5wt％，TiO2 2.0wt％，SO20.5 wt% and 17 wt% of C, wherein the average particle size of the coal gangue is 0.07mm, the graphene is flaky, the sheet diameter is 2 micrometers, the total thickness is 3.0 micrometers, and the number of layers is 9; the mass ratio of the coal gangue to the graphene is 9:1, the adding amount of the polyvinyl alcohol solution accounts for 8 wt% of the total mass of the coal gangue and the graphene, the solid content of the polyvinyl alcohol solution is 5 wt%, the ageing mixture is at the temperature of 30 ℃ and the humidity of 30% for 36 hours, and mixed pug is obtained;
(2) And (2) pressing and molding the mixed pug obtained in the step (1) under the pressure of 40MPa, drying at 100 ℃ for 15h, and sintering at 1100 ℃ for 4h in argon atmosphere to obtain the coal gangue-based heating material.
In the embodiment, through tests, the volume density of the coal gangue-based heating material is 1.6g/cm3When the current is 2mA, the electrothermal conversion temperature is 85 ℃ and the Vickers hardness is 31.35HV 5.
Example 3:
the embodiment provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing the coal gangue, the graphene and the alumina sol solution and then trappingThe chemical composition of the coal gangue comprises Al2O3 15wt％，SiO2 45wt％，Fe2O3 1.0wt％，TiO2 2.5wt％，SO21.5 wt% and 35 wt% of C, wherein the average particle size of the coal gangue is 0.05mm, the graphene is flaky, the flake diameter is 8 microns, the total thickness is 0.5 microns, and the number of layers is 2; the mass ratio of the coal gangue to the graphene is 1:1, the adding amount of the aluminum sol solution accounts for 2 wt% of the total mass of the coal gangue and the graphene, the solid content of the aluminum sol solution is 30 wt%, the ageing material temperature is 40 ℃, the humidity is 10%, and the ageing time is 30 hours, so that mixed pug is obtained;
(2) and (2) pressing and molding the mixed pug obtained in the step (1) under the pressure of 10MPa, then drying at 60 ℃ for 36h, and sintering at 800 ℃ in a neon atmosphere for 12h to obtain the coal gangue-based heating material.
In the embodiment, through tests, the volume density of the coal gangue based heating material is 1.4g/cm3When the current is 2mA, the electrothermal conversion temperature is 103 ℃, and the Vickers hardness is 30.21HV 5.
Example 4:
the embodiment provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing coal gangue, conductive carbon black and silica sol solution, and ageing, wherein the chemical composition of the coal gangue comprises Al2O3 25wt％，SiO2 38wt％，Fe2O3 0.8wt％，TiO2 2.2wt％，SO21.0 wt% and 33 wt% of C, wherein the average grain diameter of the coal gangue is 0.065mm, the average grain diameter of the conductive carbon black is 200nm, and the carbon content is 99.15 wt%; the mass ratio of the coal gangue to the conductive carbon black is 1.5:1, the adding amount of the silica sol accounts for 10 wt% of the total mass of the coal gangue and the conductive carbon black, the solid content of the silica sol solution is 10 wt%, the ageing mixture is at 35 ℃, the humidity is 20%, and the ageing time is 27 hours, so that the mixed pug is obtained;
(2) and (2) pressing and molding the mixed pug obtained in the step (1) under the pressure of 50MPa, then drying at 120 ℃ for 18h, and sintering at 900 ℃ in an argon atmosphere for 6h to obtain the coal gangue-based heating material.
In the embodiment, through tests, the volume density of the coal gangue-based heating material is 1.5g/cm 3When the current is 2mA, the electrothermal conversion temperature is 89.2 ℃ and the Vickers hardness is 28.57HV 5.
Example 5:
the embodiment provides a preparation method of a coal gangue-based heating material, which comprises the following steps:
(1) mixing coal gangue, carbon nano tubes and polyvinyl alcohol solution, and ageing, wherein the chemical composition of the coal gangue comprises Al2O3 40wt％，SiO2 35wt％，Fe2O3 1.0wt％，TiO2 2.0wt％，SO21.0 wt%, C21 wt%, the average grain diameter of coal gangue is 0.055mm, the outer diameter of the carbon nano tube is 20nm, and the length is 30 μm; the mass ratio of the coal gangue to the carbon nano tubes is 3:1, the adding amount of the polyvinyl alcohol solution accounts for 4 wt% of the total mass of the coal gangue and the carbon nano tubes, the solid content of the polyvinyl alcohol solution is 20 wt%, the ageing mixture is at the temperature of 32 ℃, the humidity is 25%, and the time is 32 hours, so that mixed pug is obtained;
(2) and (2) pressing and molding the mixed pug obtained in the step (1) under the pressure of 30MPa, drying at 90 ℃ for 24 hours, and sintering at 950 ℃ in an argon atmosphere for 8 hours to obtain the coal gangue-based heating material.
In the embodiment, through tests, the volume density of the coal gangue-based heating material is 1.56g/cm3When the current is 2mA, the electrothermal conversion temperature is 86 ℃ and the Vickers hardness is 28.86HV 5.
Example 6:
this example provides a preparation method of coal gangue-based heat generating material, which is similar to the method in example 2, except that: the mass ratio of the coal gangue to the graphene in the step (1) is 12: 1.
In the embodiment, because the mass ratio of the coal gangue to the graphene is relatively high, that is, the addition amount of the coal gangue is too much, the content of the high-conductivity phase is low, the conductivity of the material is poor, and when the current is introduced into the finally obtained coal gangue-based heating material to be 2mA, the electrothermal conversion temperature is 76 ℃ and the Vickers hardness is 26.52HV 5.
Example 7:
this example provides a process for the preparation of a coal gangue-based heat generating material, which is comparable to the process of example 3, except that: the mass ratio of the coal gangue to the graphene in the step (1) is 0.8: 1.
In this embodiment, because the mass ratio of the coal gangue to the graphene is relatively low, that is, the added amount of the coal gangue is too small, the resistance of the heating material is relatively low, so that the thermal conversion efficiency is reduced, and when the current is introduced into the finally obtained coal gangue-based heating material to be 2mA, the electrothermal conversion temperature is 72 ℃, and the vickers hardness is 24.47HV 5.
Comparative example 1:
this comparative example provides a method for preparing a coal gangue-based heat generating material, which is comparable to the method in example 1, except that: polyvinyl alcohol is not included in the mixed raw materials in the step (1), namely, no binding agent is added.
In the comparative example, since no binding agent is added in the preparation process of the coal gangue-based heating material, the binding effect of the coal gangue and the graphene is weak, the stability of the composite heating material is weak, the strength is reduced, the Vickers hardness is only 19.23HV5, the uniformity of the material is poor, the heat conduction and the electrical conductivity are weakened, and when the current is introduced to 2mA, the electrothermal conversion temperature is 57 ℃.
It can be seen from the above examples and comparative examples that the method of the present invention uses coal gangue and carbonaceous material as raw materials, and utilizes the characteristics of high electrical conductivity, thermal conductivity and high strength of the coal gangue to promote the stable combination of the carbonaceous material and the coal gangue under the action of the binder, so as to improve the strength of the composite heating material, wherein the vickers hardness can reach above 28.57HV5, and the electrothermal conversion efficiency is improved, and the electrothermal conversion temperature is above 85 ℃; the method has the advantages of wide raw material source, low price, simple process method and environment friendliness, provides a foundation for industrial production of the coal gangue heating material, and has good application prospect.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It will be apparent to those skilled in the art that any modification, equivalent substitution of the process of the invention and addition of ancillary operations, selection of specific means, etc., of the present invention are within the scope and disclosure of the invention.
Claims (10)
1. The preparation method of the coal gangue-based heating material is characterized by comprising the following steps of:
(1) mixing the coal gangue, the carbonaceous material and the binding agent, and ageing the mixture to obtain mixed pug;
(2) and (2) pressing and forming the mixed pug obtained in the step (1), and sintering in a protective atmosphere to obtain the coal gangue based heating material.
2. The method according to claim 1, wherein the coal gangue of step (1) has a chemical composition comprising Al2O3、SiO2、Fe2O3、TiO2、SO2And C;
preferably, the chemical composition of the coal gangue comprises, in mass fraction: al (Al)2O3 15～50wt％，SiO230～45wt％，Fe2O3 0.5～1.0wt％，TiO2 2.0～2.5wt％，SO2 0.5～1.5wt％，C 17～35wt％；
Preferably, the particle size of the coal gangue in the step (1) is not more than 0.074 mm.
3. The production method according to claim 1 or 2, wherein the carbonaceous material of step (1) comprises any one of graphene, carbon nanotubes, or conductive carbon black, or a combination of at least two thereof;
preferably, the graphene is flaky, the sheet diameter is 1-10 mu m, the total thickness is 0.2-3.0 mu m, and the number of layers is 1-10;
preferably, the carbon nano tube has an outer diameter of 10-25 nm and a length of 2-50 μm;
preferably, the particle size of the conductive carbon black is 100-300 nm, and the carbon content is more than 99.0 wt%;
Preferably, the binder in step (1) comprises any one of polyvinyl alcohol, aluminum sol or silica sol or a combination of at least two of the polyvinyl alcohol, the aluminum sol and the silica sol.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the coal gangue to the carbonaceous material in the step (1) is (1-9): 1;
preferably, the binding agent of step (1) is added in the form of a solution;
preferably, the addition amount of the binder solution accounts for 2-10 wt% of the total mass of the coal gangue and the carbonaceous material;
preferably, the solid content of the binder solution is 5-30 wt%.
5. The preparation method according to any one of claims 1 to 4, wherein the temperature of the ageing mixture in the step (1) is 25-40 ℃, and the humidity is 10-40%;
preferably, the ageing time in the step (1) is 24-36 h.
6. The production method according to any one of claims 1 to 5, wherein the pressure for the press-forming in step (2) is 5 to 50 MPa;
preferably, the compression molding in step (2) is performed by using a powder tablet press.
7. The production method according to any one of claims 1 to 6, wherein a drying treatment is performed before the sintering in step (2);
preferably, the temperature of the drying treatment is 60-120 ℃;
Preferably, the drying time is 12-36 h.
8. The production method according to any one of claims 1 to 7, wherein the protective gas of step (2) comprises an inert gas;
preferably, the temperature of the sintering treatment in the step (2) is 800-1100 ℃;
preferably, the time of the sintering treatment in the step (2) is 2-12 h;
preferably, the gangue-based heating material of step (2) is present in a lump form.
9. The method of any one of claims 1 to 8, comprising the steps of:
(1) mixing coal gangue, a carbonaceous material and a binding agent, and ageing, wherein the carbonaceous material comprises graphene, the binding agent comprises any one or combination of at least two of polyvinyl alcohol, alumina sol and silica sol, the mass ratio of the coal gangue to the carbonaceous material is (1-9): 1, the binding agent is added in the form of a solution, the addition amount of the binding agent solution accounts for 2-10 wt% of the total mass of the coal gangue and the carbonaceous material, the solid content of the binding agent solution is 5-30 wt%, the ageing temperature is 25-40 ℃, the humidity is 10-40%, and the time is 24-36 h, so as to obtain a mixed pug;
(2) And (2) pressing and forming the mixed pug obtained in the step (1) under the pressure of 5-50 MPa, drying at 60-120 ℃ for 12-36 h, and sintering at 800-1100 ℃ in a protective atmosphere for 2-12 h to obtain the coal gangue-based heating material.
10. A coal gangue-based heating material obtained by the preparation method according to any one of claims 1 to 9.
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