CN114763303B - Gangue-based heating material and preparation method thereof - Google Patents

Gangue-based heating material and preparation method thereof Download PDF

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CN114763303B
CN114763303B CN202110041407.9A CN202110041407A CN114763303B CN 114763303 B CN114763303 B CN 114763303B CN 202110041407 A CN202110041407 A CN 202110041407A CN 114763303 B CN114763303 B CN 114763303B
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gangue
preparation
heating material
coal gangue
based heating
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CN114763303A (en
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王钰
刘静静
任富强
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Institute of Process Engineering of CAS
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Abstract

The invention provides a gangue-based heating material and a preparation method thereof, wherein the preparation method comprises the following steps: mixing gangue, carbonaceous materials and a binding agent, and then trapping materials to obtain mixed pug; and (3) pressing and forming the mixed pug, and sintering in a protective atmosphere to obtain the gangue-based heating material. According to the method, coal gangue and carbonaceous materials are used as raw materials, the characteristics of high thermal resistance, high strength and high electric conduction and high heat conduction of the coal gangue are utilized, stable combination of the carbonaceous materials and the coal gangue is promoted under the action of a bonding agent, the strength of a composite heating material is improved, and the electric heating conversion efficiency is improved; the method has the advantages of wide raw material sources, low price, simple process method and environmental protection, provides a basis for the industrial production of the gangue heating material, and has good application prospect.

Description

Gangue-based heating material and preparation method thereof
Technical Field
The invention belongs to the technical field of heating materials, and relates to a gangue-based heating material and a preparation method thereof.
Background
With the development of technology and the improvement of living standard of people, heating materials are widely applied to heating of residents in winter, and heating elements are usually arranged between a substrate and a heat insulation material in the heating process. Because of high conductivity and excellent high temperature resistance, the electric heating wire, carbon fiber or electric heating film is often used as a heating element, and rapid heating is realized to a certain extent, but the defects of low electric heat conversion efficiency, high cost, complex process, low service life and the like are also present, so that development of a novel heating material with high electric heat conversion efficiency is required.
The gangue is a rock which accompanies and symbiosis 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 stock of the gangue, and the escaped sulfide can pollute farmlands, atmosphere and water bodies, but the utilization of the gangue is mainly used as a small amount of dopant in the industries of filling, cement and porous ceramics, a large amount of gangue is not effectively utilized, and the application of the gangue for preparing heating materials is not related at present.
CN 111763097a discloses a method for preparing porous ceramics by using coal gangue, which comprises the following steps: acid reaction pretreatment of coal gangue, melting pretreatment of the coal gangue, adding citric acid and a protective agent for mixing, stirring until materials are melted, mixing, 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; the method is characterized in that although gangue is treated together with citric acid, paraffin oil and the like, the preparation of porous ceramics still belongs to a simple utilization mode of the gangue, and the preparation of functional materials is not involved.
Graphene is a two-dimensional carbon nanomaterial with single-atom thickness formed by connecting carbon atoms in an sp2 hybridized mode, and 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 performance, which comprises the following steps: the graphene slurry is used as a conductive filler, the aqueous polyurethane emulsion is used as a binder, and an emulsifier with the mass fraction of 3% is added, so that the graphene electrothermal carbon slurry is prepared; the method comprises the steps of taking a PET film as a carrier, arranging a wire on the PET film, coating the graphene electrothermal carbon paste on the PET film, and then drying to obtain the graphene electrothermal material with controllable electrothermal performance, wherein the preparation process is complex, the raw material cost is high, and the defects of poor interface bonding property and poor high temperature resistance between graphene and the carrier exist.
In summary, for the preparation of the novel heating material, proper raw materials and processes are required to be selected, so that the cost can be reduced, the process is simplified, and the application range is expanded on the basis of meeting the requirements of higher electrothermal conversion efficiency and stability.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a gangue-based heating material and a preparation method thereof, wherein the method takes gangue and carbonaceous materials as raw materials, and utilizes the characteristics of high thermal resistance, high strength and high electric conduction and high heat conduction of the former, and the stable composite heating material with high electrothermal conversion efficiency is prepared under the bonding action of a bonding agent; the raw materials are wide in source and low in price, and the method is simple to operate and has good application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing gangue, carbonaceous materials and a binding agent, and then trapping materials to obtain mixed pug;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, and sintering in a protective atmosphere to obtain the gangue-based heating material.
In the invention, the heating material is prepared by taking the gangue and the carbonaceous material as main raw materials, which not only effectively utilizes the gangue waste, but also is used for SiO in the gangue 2 And Al 2 O 3 The high thermal resistance of the components is fully utilized, meanwhile, the high thermal conductivity and high electric conductivity carbonaceous materials are added, stable and controllable heat energy is generated by utilizing the mutual friction and collision among molecules of the carbonaceous materials, the addition of the binding agent is favorable for fully dispersing and stably combining the carbonaceous materials in the coal gangue, and the strength and uniformity of the composite heating materials are improved through the operations of trapping materials, compression molding, sintering and the like, so that the electrothermal conversion efficiency is improved; the method has simple process and low cost, provides a foundation for the industrial production of the gangue heating material, and has good application prospect.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the chemical composition of the gangue in the step (1) comprises Al 2 O 3 、SiO 2 、Fe 2 O 3 、TiO 2 、SO 2 And C.
Preferably, the saidThe chemical composition of the coal gangue comprises the following components in percentage by mass: al (Al) 2 O 3 15 to 50wt%, for example 15wt%, 20wt%, 30wt%, 40wt% or 50wt%, etc.; siO (SiO) 2 30 to 45wt%, such as 30wt%, 35wt%, 40wt% or 45wt%, etc.; fe (Fe) 2 O 3 0.5 to 1.0wt%, for example, 0.5wt%, 0.6wt%, 0.8wt% or 1.0wt%, etc.; tiO (titanium dioxide) 2 2.0 to 2.5wt%, for example 2.0wt%, 2.1wt%, 2.2wt%, 2.4wt% or 2.5wt%, etc.; SO (SO) 2 0.5 to 1.5wt%, for example 0.5wt%, 0.8wt%, 1.0wt%, 1.2wt% or 1.5wt%, etc.; 17 to 35wt% of C, for example 15wt%, 20wt%, 30wt%, 40wt% or 50wt%, etc.; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the respective ranges are equally applicable.
In the invention, the loss on ignition of the 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 rest components comprise mullite phase, quartz phase and potassium feldspar phase.
Preferably, the particle size of the gangue in step (1) is not greater than 0.074mm, for example, 0.074mm, 0.07mm, 0.065mm, 0.06mm, 0.05mm, 0.04mm or 0.03mm, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the carbonaceous material in step (1) comprises any one or a combination of at least two of graphene, carbon nanotubes or conductive carbon black, and typical, but non-limiting examples of such combinations are: a combination of graphene and carbon nanotubes, a combination of carbon nanotubes and conductive carbon black, a combination of graphene, carbon nanotubes and conductive carbon black, and the like.
Preferably, the graphene is in the form of a sheet, and the sheet diameter is 1 to 10 μm, for example, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, or the like; the total thickness is 0.2 to 3.0 μm, for example 0.2 μm, 0.5 μm, 1.0 μm, 1.5 μm, 2.0 μm or 3.0 μm, etc.; the number of layers is 1 to 10, for example 1 layer, 3 layers, 5 layers, 8 layers or 10 layers, etc.; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the respective ranges are equally applicable.
Preferably, the carbon nanotubes have an outer diameter of 10 to 25nm, for example, 10nm, 12nm, 15nm, 18nm, 20nm, 22nm, 25nm, etc., but are not limited to the recited values, and other non-recited values within the range of values are equally applicable; the length is 2 to 50 μm, for example, 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, or the like, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the particle size of the conductive carbon black is 100 to 300nm, for example, 100nm, 150nm, 200nm, 250nm or 300nm, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable; the carbon content is 99.0wt% or more, for example, 99.0wt%, 99.1wt%, 99.2wt%, 99.3wt%, 99.4wt%, 99.5wt% or 99.6wt%, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the binder of step (1) comprises any one or a combination of at least two of polyvinyl alcohol, aluminum sol or silica sol, typical but non-limiting examples of which are: a combination of polyvinyl alcohol and an aluminum sol, a combination of an aluminum sol and a silica sol, a combination of polyvinyl alcohol, an aluminum sol and a silica sol, and the like.
In the invention, the binder mainly has the function of making the mixture of the gangue and the carbonaceous material have plasticity, and is beneficial to the compression molding of the mixed material.
As a preferred embodiment of the present invention, the mass ratio of the coal gangue to the carbonaceous material in the step (1) is (1-9): 1, for example, 1:1, 1.5:1, 2:1, 3:1, 4:1, 5:1, 6:1 or 9:1, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In the invention, the mass ratio of the coal gangue to the carbonaceous material in the mixed raw materials 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 high electric conductivity is less, 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, so that the heat 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 10wt%, such as 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 8wt%, or 10wt%, etc., based on the total mass of the coal gangue and carbonaceous material, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the binder solution has a solids content of 5 to 30wt%, such as 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
In a preferred embodiment of the present invention, the temperature of the trapped material in the step (1) is 25 to 40 ℃, for example, 25 ℃, 27 ℃, 30 ℃, 32 ℃, 35 ℃, 38 ℃, 40 ℃ or the like, but the trapped material is not limited to the recited values, and other non-recited values within the recited values are equally applicable; the humidity is 10 to 40%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, or the like, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the time of the trapping material in the step (1) is 24-36 h, for example 24h, 27h, 30h, 32h, 34h or 36h, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
In a preferred embodiment of the present invention, the pressure of the press molding in the step (2) is 5 to 50MPa, for example, 5MPa, 10MPa, 20MPa, 30MPa, 40MPa, 50MPa, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are similarly applicable.
Preferably, the compression molding of step (2) is performed using a powder tablet press, for example a 769YP-30T powder tablet press is selected.
As a preferable technical scheme of the invention, before sintering in the step (2), drying treatment is performed.
The temperature of the drying treatment is preferably 60 to 120 ℃, for example 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the drying treatment is performed for a period of time ranging from 12 to 36 hours, for example, from 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours, or 36 hours, etc., but the drying treatment is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the protective gas in step (2) includes an inert gas.
Preferably, the temperature of the sintering treatment in the step (2) is 800 to 1100 ℃, for example 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃ or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the sintering treatment in step (2) is performed for a period of time ranging from 2 to 12 hours, for example, 2 hours, 4 hours, 6 hours, 7 hours, 10 hours, or 12 hours, etc., but the sintering treatment is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the gangue-based heating material in step (2) is in the form of a block, which is substantially rectangular, and has a cross section of generally square shape and a side length of 10-50 mm, for example, 10mm, 20mm, 30mm, 40mm or 50mm, etc., but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing coal gangue, a carbonaceous material and a bonding agent, and then carrying out material trapping, wherein the carbonaceous material comprises graphene, the bonding agent comprises any one or a combination of at least two of polyvinyl alcohol, aluminum sol and silica sol, the mass ratio of the coal gangue to the carbonaceous material is (1-9): 1, the bonding agent is added in a solution form, the addition amount of the bonding agent solution accounts for 2-10 wt% of the total mass of the coal gangue and the carbonaceous material, the solid content of the bonding agent solution is 5-30 wt%, the temperature of the material trapping is 25-40 ℃, the humidity is 10-40%, and the time is 24-36 h, so as to obtain mixed pug;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 5-50 MPa, then drying at 60-120 ℃ for 12-36 h, and sintering at 800-1100 ℃ in protective atmosphere for 2-12 h to obtain the gangue-based heating material.
On the other hand, the invention provides the gangue-based heating material obtained by adopting the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method uses the coal gangue and the carbonaceous material as raw materials, and utilizes the characteristics of high thermal resistance, high strength, high electric conduction and high heat conduction of the former, promotes the stable combination of the carbonaceous material and the coal gangue under the action of a bonding agent, improves the strength of the composite heating material, ensures that the Vickers hardness can reach more than 28.57HV5, improves the electrothermal conversion efficiency, and further improves the electrothermal conversion temperature to reach more than 85 ℃;
(2) The method disclosed by the invention has the advantages of wide raw material sources, low price, simple process method and environmental friendliness, provides a basis for industrial production of the gangue heating material, and has a good application prospect.
Drawings
Fig. 1 is an SEM image of the gangue-based heating material provided in example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The invention provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing gangue, carbonaceous materials and a binding agent, and then trapping materials to obtain mixed pug;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, and sintering in a protective atmosphere to obtain the gangue-based heating material.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing coal gangue, graphene and polyvinyl alcohol solution, and then carrying out material trapping, wherein the chemical composition of the coal gangue comprises Al 2 O 3 30wt％，SiO 2 40wt％，Fe 2 O 3 1.0wt％，TiO 2 2.0wt％，SO 2 1.0wt%, C26 wt%, and coal gangue with average particle size of 0.06mm, wherein the graphene is sheet-shaped, the sheet diameter is 5 μm, the total thickness is 1.5 μm, and the number of layers is 5; the mass ratio of the coal gangue to the graphene is 4:1, the addition amount of the polyvinyl alcohol solution accounts for 5wt% of the total mass of the coal gangue and the graphene, the solid content of the polyvinyl alcohol solution is 15wt%, the temperature of trapped materials is 25 ℃, the humidity is 40%, and the time is 24 hours, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 25MPa, drying at 80 ℃ for 12h, and sintering at 1000 ℃ in an argon atmosphere for 2h to obtain the gangue-based heating material.
The coal gangue-based heating material is characterized by adopting a Scanning Electron Microscope (SEM), and an SEM image of the coal gangue-based heating material is shown in figure 1.
In this embodiment, as can be seen from fig. 1, the gangue-based heating material is densified, and graphene is uniformly distributed among gangue particles;
through test, the volume density of the gangue-based heating material is 1.5g/cm 3 When the current is 2mA, the electrothermal conversion temperature is 102 ℃ and the Vickers hardness is 32.76HV5.
Example 2:
the embodiment provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing coal gangue, graphene and polyvinyl alcohol solution, and then carrying out material trapping, wherein the chemical composition of the coal gangue comprises Al 2 O 3 50wt％，SiO 2 30wt％，Fe 2 O 3 0.5wt％，TiO 2 2.0wt％，SO 2 0.5wt%, C17 wt%, and coal gangue with average particle diameter of 0.07mm, wherein the graphene is in sheet shape, the sheet diameter is 2 μm, the total thickness is 3.0 μm, and the number of layers is 9; the mass ratio of the coal gangue to the graphene is 9:1, the addition amount of the polyvinyl alcohol solution accounts for 8wt% of the total mass of the coal gangue and the graphene, the solid content of the polyvinyl alcohol solution is 5wt%, the temperature of trapped materials is 30 ℃, the humidity is 30%, and the time is 36 hours, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 40MPa, drying at 100 ℃ for 15h, and sintering at 1100 ℃ in an argon atmosphere for 4h to obtain the gangue-based heating material.
In the embodiment, the volume density of the gangue-based heating material is 1.6g/cm 3 When the current is 2mA, the electrothermal conversion temperature is 85 ℃ and the Vickers hardness is 31.35HV5.
Example 3:
the embodiment provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing gangue, graphene and aluminum sol solution, and then trapping, wherein the chemical composition of the gangue comprises Al 2 O 3 15wt％，SiO 2 45wt％，Fe 2 O 3 1.0wt％，TiO 2 2.5wt％，SO 2 1.5wt%, C35 wt%, and coal gangue with average particle diameter of 0.05mm, wherein the graphene is sheet-shaped, the sheet diameter is 8 μm, the total thickness is 0.5 μm, and the number of layers is 2; the mass ratio of the coal gangue to the graphene is 1:1, the addition amount of the aluminum sol solution accounts for 2wt% of the total mass of the coal gangue and the graphene, the solid content of the aluminum sol solution is 30wt%, the temperature of trapped materials is 40 ℃, the humidity is 10%, and the time is 30 hours, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 10MPa, drying at 60 ℃ for 36h, and sintering at 800 ℃ in neon atmosphere for 12h to obtain the gangue-based heating material.
In the embodiment, the volume density of the gangue-based heating material is 1.4g/cm 3 When the current is 2mA, the electrothermal conversion temperature is 103 ℃ and the Vickers hardness is 30.21HV5.
Example 4:
the embodiment provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing gangue, conductive carbon black and silica sol solution, and then trapping, wherein the chemical composition of the gangue comprises Al 2 O 3 25wt％，SiO 2 38wt％，Fe 2 O 3 0.8wt％，TiO 2 2.2wt％，SO 2 1.0wt%, C33 wt%, and coal gangue with average particle diameter of 0.065mm, wherein the average particle diameter of the conductive carbon black is 200nm, and the carbon content is 99.15wt%; the mass ratio of the coal gangue to the conductive carbon black is 1.5:1, the addition amount of the silica sol accounts for 10wt% of the total mass of the coal gangue and the conductive carbon black, the solid content of the silica sol solution is 10wt%, the temperature of trapped materials is 35 ℃, the humidity is 20%, and the time is 27 hours, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 50MPa, drying at 120 ℃ for 18h, and sintering at 900 ℃ in an argon atmosphere for 6h to obtain the gangue-based heating material.
In the embodiment, the volume density of the gangue-based heating material is 1.5g/cm 3 When the current is 2mA, the electrothermal conversion temperature is 89.2 ℃ and the Vickers hardness is 28.57HV5.
Example 5:
the embodiment provides a preparation method of a gangue-based heating material, which comprises the following steps:
(1) Mixing gangue, carbon nano tube and polyvinyl alcohol solution, and then carrying out material trapping, wherein the chemical composition of the gangue comprises Al 2 O 3 40wt％，SiO 2 35wt％，Fe 2 O 3 1.0wt％，TiO 2 2.0wt％，SO 2 1.0wt%, C21 wt%, and coal gangue with average particle diameter of 0.055mm, wherein the carbon nanotube has outer diameter of 20nm and length of 30 μm; the mass ratio of the coal gangue to the carbon nano tubes is 3:1, the addition amount of the polyvinyl alcohol solution accounts for 4wt% of the total mass of the coal gangue and the carbon nano tubes, the solid content of the polyvinyl alcohol solution is 20wt%, the temperature of trapped materials is 32 ℃, the humidity is 25%, and the time is 32 hours, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 30MPa, drying at 90 ℃ for 24 hours, and sintering at 950 ℃ in an argon atmosphere for 8 hours to obtain the gangue-based heating material.
In the embodiment, the volume density of the gangue-based heating material is 1.56g/cm 3 When the current is 2mA, the electrothermal conversion temperature is 86 ℃ and the Vickers hardness is 28.86HV5.
Example 6:
this example provides a method for preparing a gangue-based heating material, which is different from the method in example 2 only in that: and (3) 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 higher, namely the addition amount of the coal gangue is too much, the content of a high conductive phase is low, the conductivity of the material is poor, and when the current of the finally obtained coal gangue-based heating material is 2mA, the electrothermal conversion temperature is 76 ℃ and the Vickers hardness is 26.52HV5.
Example 7:
this example provides a method for preparing a gangue-based heating material, which is different from the method in example 3 only in 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 low, that is, the addition amount of the coal gangue is too small, the resistance of the heating material is low, so that the heat conversion efficiency is reduced, and when the current of the finally obtained coal gangue-based heating material is 2mA, the electric heat conversion temperature is 72 ℃, and the vickers hardness is 24.47HV5.
Comparative example 1:
this comparative example provides a method for producing a coal gangue-based heat generating material, which is different from the method of example 1 only in that: the mixed raw materials in the step (1) do not comprise polyvinyl alcohol, namely no binding agent is added.
In the comparative example, since no binder is added in the preparation process of the gangue-based heating material, the combination effect of the gangue and the graphene is weak, so that 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 electric conductivity are weakened, and when the current is 2mA, the electrothermal conversion temperature is 57 ℃.
It can be seen from the above examples and comparative examples that the method of the invention uses coal gangue and carbonaceous materials as raw materials, and utilizes the characteristics of high electric conductivity, thermal conductivity and high strength to promote the stable combination of the carbonaceous materials and coal gangue under the action of the bonding agent, thereby improving the strength of the composite heating material, ensuring that the Vickers hardness can reach more than 28.57HV5, improving the electrothermal conversion efficiency and the electrothermal conversion temperature of more than 85 ℃; the method has the advantages of wide raw material sources, low price, simple process method and environmental protection, provides a basis for the industrial production of the gangue heating material, and has good application prospect.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modifications, equivalent substitutions and additions to the method of the present invention, selection of particular modes, etc. are intended to fall within the scope of the invention and the disclosure.

Claims (21)

1. The preparation method of the gangue-based heating material is characterized by comprising the following steps of:
(1) Mixing coal gangue, a carbonaceous material and a bonding agent, and then trapping the mixture, wherein the carbonaceous material comprises any one or a combination of at least two of graphene, carbon nano tubes or conductive carbon black, the bonding agent comprises any one or a combination of at least two of polyvinyl alcohol, alumina sol or silica sol, the mass ratio of the coal gangue to the carbonaceous material is (1-9): 1, the temperature of the trapped mixture is 25-40 ℃, and the humidity is 10-40%, so as to obtain a mixed pug;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, and sintering the mixed pug in a protective atmosphere, wherein the sintering temperature is 800-1100 ℃, so as to obtain the gangue-based heating material.
2. The method according to claim 1, wherein the chemical composition of the gangue in step (1) comprises Al 2 O 3 、SiO 2 、Fe 2 O 3 、TiO 2 、SO 2 And C.
3. The preparation method according to claim 2, wherein the chemical composition of the coal gangue comprises, in mass fraction: al (Al) 2 O 3 15~50wt%，SiO 2 30~45wt%，Fe 2 O 3 0.5~1.0wt%，TiO 2 2.0~2.5wt%，SO 2 0.5~1.5wt%，C 17~35wt%。
4. The method of claim 1, wherein the gangue in step (1) has a particle size of no greater than 0.074mm.
5. The preparation method of claim 1, wherein the graphene is in a sheet shape, the sheet diameter is 1-10 μm, the total thickness is 0.2-3.0 μm, and the number of layers is 1-10.
6. The method according to claim 1, wherein the carbon nanotubes have an outer diameter of 10 to 25nm and a length of 2 to 50 μm.
7. The method according to claim 1, wherein the conductive carbon black has a particle diameter of 100 to 300nm and a carbon content of 99.0wt% or more.
8. The method of claim 1, wherein the binding agent of step (1) is added as a solution.
9. The preparation method of claim 8, wherein the addition amount of the binder solution is 2-10wt% of the total mass of the coal gangue and the carbonaceous material.
10. The method of claim 9, wherein the binder solution has a solids content of 5 to 30wt%.
11. The preparation method of claim 1, wherein the time of the trapping material in the step (1) is 24-36 hours.
12. The method according to claim 1, wherein the pressure of the press molding in the step (2) is 5 to 50mpa.
13. The method of claim 1, wherein the compression molding in step (2) is performed using a powder tablet press.
14. The method of claim 1, wherein the step (2) is preceded by a drying process.
15. The method according to claim 14, wherein the temperature of the drying treatment is 60-120 ℃.
16. The method according to claim 14, wherein the drying time is 12 to 36 hours.
17. The method of claim 1, wherein the protective atmosphere of step (2) comprises an inert gas.
18. The method according to claim 1, wherein the sintering treatment in step (2) is performed for 2 to 12 hours.
19. The method of claim 1, wherein the gangue-based heating material of step (2) is present in a lump form.
20. The preparation method according to claim 1, characterized in that the preparation method comprises the steps of:
(1) Mixing coal gangue, a carbonaceous material and a bonding agent, and then trapping the mixture, wherein the carbonaceous material comprises graphene, the bonding agent comprises any one or a combination of at least two of polyvinyl alcohol, aluminum sol and silica sol, the mass ratio of the coal gangue to the carbonaceous material is (1-9): 1, the bonding agent is added in a solution form, the addition amount of the bonding agent solution accounts for 2-10wt% of the total mass of the coal gangue and the carbonaceous material, the solid content of the bonding agent solution is 5-30wt%, the temperature of the trapped mixture is 25-40 ℃, the humidity is 10-40%, and the time is 24-36 h, so that mixed pug is obtained;
(2) And (3) pressing the mixed pug obtained in the step (1) to form, wherein the pressing pressure is 5-50 MPa, then drying at 60-120 ℃ for 12-36 h, and sintering at 800-1100 ℃ in a protective atmosphere for 2-12 h to obtain the gangue-based heating material.
21. A gangue-based heating material obtained by the preparation method of any one of claims 1 to 20.
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