CN110981531A - Foamed ceramic composite board based on shale and copper tailings as main materials and production method thereof - Google Patents
Foamed ceramic composite board based on shale and copper tailings as main materials and production method thereof Download PDFInfo
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Abstract
The invention provides a foamed ceramic composite board based on shale and copper tailings as main materials and a production method thereof, wherein the composite board comprises the following raw materials in parts by mass: 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide; the method comprises the following steps in sequence: s1 preparing raw materials; s2 ball milling and pulping; s3, blank making; s4, drying; and S5 sintering. The invention adopts the copper tailings and the shale which can cause environmental pollution as the main raw materials of the foamed ceramics, thereby reducing the environmental pollution and the production cost; the characteristics of a large amount of silicon contained in the copper tailings and the shale are fully utilized in the production process, the viscosity of a raw material liquid phase in the high-temperature sintering process is improved, the uniformity and the fineness of air holes in a product are ensured, and on the other hand, iron and sulfur in the copper tailings are subjected to a reduction reaction in the high-temperature sintering process, so that the air hole amount of the product is increased, the foaming of the product is promoted, and the product quality is improved.
Description
Technical Field
The invention relates to the technical field of ceramic insulation board production, in particular to a foamed ceramic composite board based on shale and copper tailings as main materials and a production method thereof.
Background
On the marketThe foamed ceramic insulation board mostly uses perlite as a foaming matrix, but the perlite as a scarce functional mineral material is expensive and has scarce resources. At present, the copper ore output in China is rich, and the output of copper tailings is more considerable. Besides a small amount of copper tailings serving as fillers of old mines, most of the copper tailings are stored in a manner of filling hollow lands or building dams for stacking, and the stacked copper tailings not only occupy a large amount of land, but also cover original vegetation, so that an ecological system is damaged. The copper tailings have high heavy metal content due to special physical and chemical properties, and plants are difficult to naturally grow on the tailings. Meanwhile, the tailings fly with the wind and lose rainwater, so that the living environment of residents in the surrounding areas is polluted. Shale is not used efficiently, but SiO in the shale2With Al2O3The content is higher. Therefore, the tailings which have low utilization rate and cause environmental pollution are utilized by the company, and the utilization rate of construction wastes is improved as much as possible under the condition of not influencing the quality of foamed ceramic products, so that the environmental pollution is reduced, and the production cost of factories is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a foamed ceramic composite board based on shale and copper tailings as main materials and a production method thereof.
The invention solves the technical problems through the following technical means:
the foamed ceramic composite board based on shale and copper tailings as main materials comprises the following raw materials in parts by mass: 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide.
Preferably, the foamed ceramic composite board comprises the following raw materials in parts by mass: 65 parts of copper tailing powder, 15 parts of shale, 10 parts of zeolite powder, 5 parts of bentonite, 5 parts of wollastonite and 0.3 part of silicon carbide.
The production method of the foamed ceramic composite board based on the shale and the copper tailings as the main materials sequentially comprises the following steps:
s1 preparing raw materials:
taking 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide by mass parts, and preparing raw materials;
s2 ball milling and pulping:
crushing the prepared raw materials, and mixing the raw materials: ball: water 1: 2: ball milling is carried out according to the mass ratio of 0.6 until the fineness of the mixed slurry obtained by ball milling is 1.2 percent below a 250-mesh sieve;
s3 blank making:
drying the mixed slurry to make powder, and preparing a ceramic blank in a dry pressing mode;
s4 drying:
drying the formed blank in a drying oven at 105 ℃ for 2 hours;
s5 sintering:
feeding the dried blank into a high-temperature electric furnace, raising the temperature for 38 minutes at 0-250 ℃, and preserving the temperature for 8 minutes; heating for 50 minutes at 250-950 ℃ and keeping the temperature for 8 minutes; heating for 40 minutes at 950-1120 ℃ and preserving heat for 8 minutes; the temperature rise time is 22 minutes at 1120-1150 ℃ and the heat preservation time is 8 minutes; heating to 1150-1180 deg.c for 10 min and maintaining for 5 min; heating to 1180-1200 deg.c for 5 min and maintaining for 5 min; sintering to obtain the finished product.
The invention has the advantages that:
compared with the prior art, the invention adopts the copper tailings and the shale which can cause environmental pollution as the main raw materials of the foamed ceramics, thereby reducing the environmental pollution and the production cost; the characteristics of a large amount of silicon contained in the copper tailings and the shale are fully utilized in the production process, the viscosity of a raw material liquid phase in the high-temperature sintering process is improved, the uniformity and the fineness of air holes in a product are ensured, and on the other hand, iron and sulfur in the copper tailings are subjected to a reduction reaction in the high-temperature sintering process, so that the air hole amount of the product is increased, the foaming of the product is promoted, and the product quality is improved.
Drawings
FIG. 1 is a trend chart of thermogravimetric and thermal difference of SiC according to an embodiment of the invention as a function of temperature;
FIG. 2 is a trend chart of thermogravimetry and thermal difference of the iron oxide according to the embodiment of the invention along with temperature change.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the 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 invention.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Example 1
The embodiment provides a foamed ceramic composite board based on shale and copper tailings as main materials, and the foamed ceramic composite board comprises the following raw materials in parts by mass: 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide.
The production method of the foamed ceramic composite board based on the shale and the copper tailings as the main materials sequentially comprises the following steps:
s1 preparing raw materials:
taking 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide by mass parts, and preparing raw materials;
s2 ball milling and pulping:
crushing the prepared raw materials, and mixing the raw materials: ball: water 1: 2: ball milling is carried out according to the mass ratio of 0.6 until the fineness of the mixed slurry obtained by ball milling is 1.3 percent below a 250-mesh sieve;
s3 blank making:
drying the mixed slurry to make powder, and preparing a ceramic blank in a dry pressing mode;
s4 drying:
drying the formed blank in a drying oven at 105 ℃ for 2 hours;
s5 sintering:
feeding the dried blank into a high-temperature electric furnace, raising the temperature for 38 minutes at 0-250 ℃, and preserving the temperature for 8 minutes; heating for 50 minutes at 250-950 ℃ and keeping the temperature for 8 minutes; heating for 40 minutes at 950-1120 ℃ and preserving heat for 8 minutes; the temperature rise time is 22 minutes at 1120-1150 ℃ and the heat preservation time is 8 minutes; heating to 1150-1180 deg.c for 10 min and maintaining for 5 min; heating to 1180-1200 deg.c for 5 min and maintaining for 5 min; sintering to obtain the finished product.
Example 2
The foamed ceramic composite board comprises the following raw materials in parts by mass: 65 parts of copper tailing powder, 15 parts of shale, 10 parts of zeolite powder, 5 parts of bentonite, 5 parts of wollastonite and 0.3 part of silicon carbide.
The output of copper tailings in China is extremely large, the annual output reaches more than 5 hundred million tons, the mineral components of the copper tailings mainly comprise calcite, plagioclase, diopside, amphibole, actinolite, garnet, chalcopyrite, quartz, chlorite, magnetoore, pyrrhotite and the like, the copper tailings belong to aluminosilicate tailings, and meanwhile, the copper tailings contain a large amount of elements such as Fe, S and the like, so that the copper tailings have a good promoting effect on oxidation reaction. The siliceous shale contains much chalcedony, opal and the like, SiO2The content is more than 85 percent.
Copper tailings and shale are used as raw materials, chemical reaction is carried out through catalysis of SiC, a large amount of gas is released, and the gas enables a plurality of silicon-oxygen bonds in silicate melts in the copper tailings and the shale to be broken to form a new inner surface, namely bubbles are generated. SiO formed on SiC surface under high-temperature alkaline condition2The protective layer is easy to react with alkaline melt or alkaline salt to generate silicate liquid phase, so that the protective layer is corroded or damaged, the oxygen diffusion rate is increased, SiC is continuously oxidized with oxygen to generate a large amount of CO or CO2A gas. On the other hand, these basic oxides are the main components of the high-temperature glass phase of the ceramic and have a great influence on the viscosity of the high-temperature melt. Simultaneously, the copper tailings still exist in the copper tailingsIn many Fe and S compounds, oxidation-reduction reaction occurs to generate gas, which promotes foaming of the green body.
The foamed ceramic composite board is prepared according to the composition of the raw materials described in the example 2, in the sintering process, after the temperature is increased to 900 ℃, the contact part of feldspar and quartz, feldspar and high-alumina minerals starts to melt, the liquid phase quantity is continuously increased along with the temperature increase, the interfaces among blank particles are also more and more fuzzy, and when the temperature is higher than 1000 ℃, the feldspar and quartz particles in the blank are obviously eroded until the temperature is almost completely melted at 1200 ℃. At the stage of 900-1200 ℃, the foaming agent undergoes a chemical reaction to generate CO2、O2And the like. CO produced2A part of the gas is dissolved in the high-temperature molten liquid phase and exists in a dissolved state and a free gaseous state, and the other part of the gas exists in a chemically combined state, and the temperature is CO2There are form determinants. With increasing temperature, CO2Continuously generate CO2First in the glass phase in dissolved form, and then the gas in the liquid phase has a decreasing solubility and CO2The concentration rises continuously, so that CO2In the form of bubbles. But CO2The diffusion rate in the high temperature liquid phase is greatly affected by the viscosity of the liquid phase. The chemical reaction of silicon carbide varies depending on the oxidation conditions, and can be classified into active oxidation and inert oxidation, and when inert oxidation occurs, a dense silicon dioxide film is formed on the surface.
The inert oxidation reaction is as follows:
2SiC(s)+3O2(g)→2SiO2(s)+2CO(g)
SiC(s)+2O2(g)→SiO2(s)+CO2(g)
conversion of SiC to SiO2Increase net weight and simultaneously generate CO and CO2The gas expands and diffuses in the silicate liquid phase in a high-temperature molten state, and the gases are not connected in the silicate liquid phase due to poor fluidity and high-temperature viscosity of the silicate liquid phase. The size of the air holes depends on the surface tension and viscosity of the molten liquid phase and the generated gas quantity, and when the gas quantity is large and the high-temperature viscosity is low, the air holes float or fuse to generate large air holes. At the same time as this is done,fe and S contained in the copper tailings also undergo reduction reaction and are decomposed into CO and CO2、SO、SO2And (3) gas:
2Fe2O3+C→4FeO+CO2
2Fe2O3+3C→4Fe+3CO2
in the preparation process of the foamed ceramic with silicon carbide as the foaming agent, the existence of the iron oxide has an adjusting effect on the pore structure of the foamed ceramic, so that the pores are more uniform.
As shown in fig. 1, thermogravimetric analysis and thermal difference analysis were performed on SiC, and SiC was first weight-lost and then weight-increased in the air during the high-temperature calcination. And when the conversion point of weight loss and weight gain is about 900 ℃, and the temperature is before 900 ℃, impurities such as carbon, organic matters and the like in the SiC are subjected to oxidation reaction, and generated gas is volatilized into the air to generate weight loss. After 900 ℃, SiC can generate oxidation reaction to generate SiO2Weight gain occurs. With the continuous progress of SiC oxidation, silica films are continuously generated on the particle surfaces, and the silica films can prevent oxygen from diffusing to the SiC surfaces, so that the weight loss rate tends to be flat, and the slope of a thermogravimetric curve shows that the slope is gradually reduced before 900 ℃. The greater the rate constant for oxidation of SiC and thus the more readily oxidation occurs, resulting in a dramatic increase in the rate of weight gain, which can be seen in the curve as a dramatic increase in the rate of thermogravimetric curves. Therefore, the sintering process after 900 ℃ directly influences the performance of the high-temperature foaming ceramic.
As shown in FIG. 2, thermogravimetric and thermogravimetric analysis of the Fe oxide revealed that after 850 ℃ a thermal decomposition reaction occurred, resulting in a weight loss of about 0.61%, and Fe was produced by the reaction3O4And O2. The influence of the Fe oxide on foaming is mainly reflected in the change of temperature, and the high temperature can promote the decomposition of the oxide and increase the amount of pores.
The copper tailings and the shale contain a large amount of silicon, and the viscosity of a raw material liquid phase can be effectively improved in the high-temperature sintering process, so that uniform and fine pores in a product are ensured, and the product quality is improved; on the other hand, Fe and S in the copper tailings are subjected to reduction reaction in the high-temperature sintering process, so that the pore volume of the product is increased, and the foaming of the product is promoted.
It is noted that, in this document, relational terms such as first and second, and the like, if any, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention 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 technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. The foamed ceramic composite board based on shale and copper tailings as main materials is characterized in that: the foamed ceramic composite board comprises the following raw materials in parts by mass: 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide.
2. The foamed ceramic composite board based on shale and copper tailings as main materials according to claim 1, wherein: the foamed ceramic composite board comprises the following raw materials in parts by mass: 65 parts of copper tailing powder, 15 parts of shale, 10 parts of zeolite powder, 5 parts of bentonite, 5 parts of wollastonite and 0.3 part of silicon carbide.
3. The production method of the foamed ceramic composite board based on the shale and the copper tailings as the main materials according to claim 1, which is characterized in that: the method comprises the following steps in sequence:
s1 preparing raw materials:
taking 60-70 parts of copper tailing powder, 10-20 parts of shale, 8-12 parts of zeolite powder, 3-7 parts of bentonite, 3-7 parts of wollastonite and 0.3-0.5 part of silicon carbide by mass parts, and preparing raw materials;
s2 ball milling and pulping:
crushing the prepared raw materials, and mixing the raw materials: ball: water 1: 2: ball milling is carried out according to the mass ratio of 0.6 until the fineness of the mixed slurry obtained by ball milling is 1.2 percent below a 250-mesh sieve;
s3 blank making:
drying the mixed slurry to make powder, and preparing a ceramic blank in a dry pressing mode;
s4 drying:
drying the formed blank in a drying oven at 105 ℃ for 2 hours;
s5 sintering:
feeding the dried blank into a high-temperature electric furnace, raising the temperature for 38 minutes at 0-250 ℃, and preserving the temperature for 8 minutes; heating for 50 minutes at 250-950 ℃ and keeping the temperature for 8 minutes; heating for 40 minutes at 950-1120 ℃ and preserving heat for 8 minutes; the temperature rise time is 22 minutes at 1120-1150 ℃ and the heat preservation time is 8 minutes; heating to 1150-1180 deg.c for 10 min and maintaining for 5 min; heating to 1180-1200 deg.c for 5 min and maintaining for 5 min; sintering to obtain the finished product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683393A (en) * | 2021-08-12 | 2021-11-23 | 河北工程大学 | Method for preparing high-strength sintered water permeable brick by using copper tailing sand |
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|---|---|---|---|---|
| CN102924113A (en) * | 2012-11-09 | 2013-02-13 | 中南大学 | Copper mine tailing slag porous ceramic material and preparation method thereof |
| CN105399437A (en) * | 2015-11-20 | 2016-03-16 | 信阳科美新型材料有限公司 | Thermal-insulating and decorative porcelain plate quickly fired at ultralow temperature and production method of thermal-insulating and decorative porcelain plate |
| CN106699109A (en) * | 2016-11-22 | 2017-05-24 | 安徽省隆达建材科技有限公司 | Foamed ceramic composite plate based on shale and copper tailings as main materials and production method of foamed ceramic composite plate |
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- 2019-11-12 CN CN201911099816.3A patent/CN110981531A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924113A (en) * | 2012-11-09 | 2013-02-13 | 中南大学 | Copper mine tailing slag porous ceramic material and preparation method thereof |
| CN105399437A (en) * | 2015-11-20 | 2016-03-16 | 信阳科美新型材料有限公司 | Thermal-insulating and decorative porcelain plate quickly fired at ultralow temperature and production method of thermal-insulating and decorative porcelain plate |
| CN106699109A (en) * | 2016-11-22 | 2017-05-24 | 安徽省隆达建材科技有限公司 | Foamed ceramic composite plate based on shale and copper tailings as main materials and production method of foamed ceramic composite plate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113683393A (en) * | 2021-08-12 | 2021-11-23 | 河北工程大学 | Method for preparing high-strength sintered water permeable brick by using copper tailing sand |
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