CN111320489A - Solid waste based high-strength foamed ceramic and preparation method thereof - Google Patents
Solid waste based high-strength foamed ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a solid waste based high-strength foamed ceramic and a preparation method thereof. Carrying out wet ball milling on raw materials including silicate tailings, manganese slag, steel slag, potassium feldspar, bentonite and a foaming agent to obtain slurry; the obtained slurry is dried, screened and pressed to form a ceramic blank, and the ceramic blank is sintered to obtain the high-strength foamed ceramic.
Description
Technical Field
The invention relates to solid waste based foamed ceramic, in particular to high-strength foamed ceramic prepared from solid waste such as silicate tailings, metallurgical slag and the like, and a preparation method of the high-strength foamed ceramic, belonging to the technical field of secondary resource utilization.
Background
Resources and environment are two major problems facing the present society. The mining amount of mines and the yield of nonferrous metallurgy in China are continuously increased, and huge material wealth is brought to human society; meanwhile, a large amount of tailings are produced in mining and selecting of the mine, and a large amount of metallurgical slag is discharged in the metallurgical process. The tailings and the metallurgical slag not only seriously affect the quality of the living environment of human beings, but also cause huge waste of resources. Therefore, the reasonable and effective utilization of tailings and metallurgical slag has become one of the solid waste treatment problems which need to be solved urgently today.
Most tailings and metallurgical slags contain large amounts of active silicon (aluminum) oxygen tetrahedrons, abundant oxide-like useful components, and useful properties, resource and material properties that have not been recognized and yet to be exploited are evident. The porous ceramic material has the advantages of stable chemical property, high temperature resistance, corrosion resistance and the like, is widely applied to wastewater treatment, building materials and biomedicine, and is widely concerned by people. So far, the main raw materials for preparing porous ceramics at home and abroad are mostly pure Al2O3、SiO2、ZrO2Mainly, clay, kaolin, CaO, MgO and the like are added as fluxing agents. The manufacturing process of the raw materials is complex, and the raw materials are relatively high in cost. The existing process for preparing porous ceramic by utilizing smelting slag and tailings has the defects of high sintering temperature, high energy consumption, long process flow, low strength of the prepared porous ceramic and the like, for example, in a patent (CN 109053217A), the porous ceramic prepared by utilizing nickel smelting slag has low strength which is only 3.01MPa although the utilization of solid waste is realized; in the patent (CN 107903033A), the iron tailings are used for preparing the foamed ceramic, the addition amount of the pore-forming agent in the preparation process is high, and the preparation process needs to be carried out by granulating firstly and then sintering, so that the operation is complex and the large-scale production is difficult to realize; in the patent (CN 109608167A), the coal gangue, the iron tailings and the fly ash are used for preparing the foamed ceramic insulation board, the preparation temperature is relatively high and is at least 1200 ℃, and the energy consumption is large.
Disclosure of Invention
Aiming at the defects of the prior art for preparing foamed ceramic products by utilizing tailings, metallurgical slag and the like, the invention aims to provide the high-strength porous foamed ceramic which takes solid wastes such as the tailings, the metallurgical slag and the like as main components, can solve the problems of environmental pollution and land occupation of mining water, atmosphere, soil and the like caused by stacking industrial solid wastes, can change wastes into valuables, and can realize the massive, high-value, efficient and safe utilization of solid wastes by utilizing the solid wastes to obtain the porous ceramic with high performance and high added value.
The second purpose of the invention is to provide a method for preparing high-strength foamed ceramics by using solid wastes such as tailings, metallurgical slag and the like as main components and matching a small amount of potassium feldspar, bentonite and the like, the method has the advantages of low cost and simple preparation process, is mainly prepared from industrial wastes, does not need to add high-purity fluxing agent, has low sintering temperature, and solves the inherent defects of complex operation, high sintering temperature and the like caused by the need of adding high-purity fluxing agent in the existing process for preparing foamed ceramics by using solid wastes.
In order to realize the technical purpose, the invention provides a preparation method of solid waste based high-strength foamed ceramic, which comprises the steps of carrying out wet ball milling on raw materials including silicate tailings, manganese slag, steel slag, potassium feldspar, bentonite and a foaming agent to obtain slurry; drying and sieving the obtained slurry, pressing and forming to obtain a ceramic blank, and sintering the ceramic blank to obtain the ceramic product.
The foamed ceramic provided by the invention adopts tailings taking aluminosilicate as a main component to provide frame elements such as silicon and aluminum for the foamed ceramic, and reasonably compounds metallurgical slag, and utilizes the metal elements in the metallurgical slag to be co-dissolved with basic elements or elements in auxiliary materials, wherein calcium ions in steel slag and manganese slag can promote the formation of a silicon-calcium system crystal phase, and transition metal elements such as manganese element and iron element play roles in promoting densification and enhancing the crystal phase; in the secondary crystallization process, more ions containing iron, manganese and the like can be dissolved in the primary crystal phase in a solid solution manner to form a new crystal phase. The strength of these crystal phases is higher than that of conventional silica-alumina ceramics. The temperature required for sintering is also relatively low through the interaction between the ore phases.
In a preferred scheme, the raw materials comprise the following components in percentage by mass: 30-60% of silicate tailings, 8-40% of manganese slag, 5-35% of steel slag, 5-8% of potassium feldspar, 2-5% of bentonite and 0.1-0.5% of silicon carbide foaming agent.
Preferably, the wet ball milling conditions are as follows: the ball milling method is characterized in that water is used as a ball milling medium, the mass ratio of balls to materials to water is 5-3: 3-2: 1-1, the ball milling rotating speed is 300-380 rpm, and the ball milling time is 5-12 hours.
In a preferable scheme, the drying temperature is 50-70 ℃, and the drying time is 8-12 h.
In a preferable scheme, the sieving adopts a sieve with 200-300 meshes.
In the preferable scheme, the forming pressure adopted by the compression forming is 15-30 MPa.
In the preferred scheme, two-stage sintering is adopted in the sintering, and the first-stage sintering is carried out at the temperature of 1000-1050 ℃ for 20-30 min; sintering the second-stage sintering at 1120-1150 ℃ for 20-40 min; the first stage sintering mainly utilizes the decomposition of SiC at the temperature to realize pore-forming and form a porous structure, and the second stage sintering mainly carries out complex solid-phase reaction to form a ceramic phase with better mechanical strength.
The silicon carbide adopted in the preparation process of the foamed ceramic is used as a foaming agent.
The invention also provides solid waste based high-strength foamed ceramic which is prepared by the preparation method.
In the preferable scheme, the porosity of the solid waste base high-strength foamed ceramic is 0.5-4%, and the compressive strength is 8-18 MPa. The higher the porosity of the solid waste base high-strength foamed ceramic is, the lower the corresponding mechanical strength is. The porosity of the solid waste base high-strength foamed ceramic with excellent mechanical property and high porosity is preferably 3.12-3.97%, and the compressive strength is 10.7-12.3 MPa.
The invention relates to a preparation method of solid waste based high-strength foamed ceramic, which comprises the following steps:
step 1) weighing a certain amount of silicate tailings, metallurgical slag (manganese slag and steel slag), potassium feldspar, bentonite and a foaming agent (30-60% of silicate tailings, 8-40% of manganese slag, 5-35% of steel slag, 5-8% of potassium feldspar, 2-5% of bentonite and 0.1-0.5% of silicon carbide), adding the silicate tailings, the metallurgical slag, the potassium feldspar and the bentonite into a ball milling tank according to a ball ratio of 5:3:1, and carrying out ball milling for 5-12 hours at 300-380 rpm to obtain uniformly mixed slurry;
step 2) drying the slurry obtained in the step 1), and sieving to ensure that the particle size of the powder meets a 200-300-mesh screen;
and 3) putting the undersize powder obtained in the step 2) into a mold, and molding under 15-30 MPa to obtain a ceramic blank.
And 4) sintering the blank obtained in the step 3) in a muffle furnace at the sintering temperature: the first section is sintered for 20-30 min at 1000-1050 ℃, and the second section is sintered for 20-40 min at 1120-1150 ℃.
The solid waste-based porous ceramic has the compressive strength of 11.2MPa, the apparent porosity of 1.84 percent and the water absorption of 3.63 percent; leaching tests show that the leaching rate of manganese is 0.004mg/L, and the leaching rate of iron is 0.006 mg/L. The foamed ceramic prepared by the method has high strength and small heavy metal harm.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1) the solid waste based foamed ceramic is prepared from two solid wastes of solid waste tailings and metallurgical slag, the raw materials are cheap and easy to obtain, the massive consumption of the solid wastes can be realized, the tailings and the metallurgical slag are comprehensively recycled and utilized, the method is a main means for reducing hazardous wastes from the source and controlling the environmental quality, is also a main direction for reducing the consumption of native resources in China, and is beneficial to promoting the realization of the unification of economic benefits and ecological environmental benefits in China.
2) The solid waste base foamed ceramic has the characteristic of high strength.
3) The preparation process of the solid waste base foamed ceramic has low energy consumption, simple steps and operation and good industrial application prospect.
Drawings
FIG. 1 is a schematic representation of a porous ceramic foam prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Table 1 shows the main element composition (%)
Table 2 shows the formulations containing the different raw materials (%)
Preparing solid waste base porous ceramic: the elemental composition of each raw material was analyzed by X-ray fluorescence spectroscopy (table 1), and then 4 formulations were prepared in different mass percentages (table 2). Wet grinding the raw materials in a ball milling tank according to different formulas according to the ratio of ball to material to water of 5:3:1 for 8h, drying the obtained slurry at 60 ℃ for 8h, sieving the dried powder with a 350-mesh sieve, filling the sieved powder into a mould, and forming under 20 MPa; and (3) sintering at 1000 ℃ for 30min, sintering at 1130 ℃ for 30min, cooling along with the furnace, and taking out samples which are respectively marked as #1, #2, #3 and # 4.
According to the Archimedes principle, the water absorption rate and the porosity of each sample are measured by a pycnometer method; and (3) measuring the compressive strength of each sample by using an electro-hydraulic servo dynamic and static testing machine. The experiment shows that: the porosities of #1 to #4 are: 3.84%, 3.63%, 4.26% and 0.42%; the apparent porosity is respectively as follows: 3.21%, 1.84%, 2.45% and 0.56%; the compressive strength is respectively as follows: 8.3MPa, 11.2MPa, 10.5MPa and 17.1 MPa.
Example 2
Table 3 shows the raw material recipe for preparing the porous ceramic foam
Preparing solid waste base porous ceramic: weighing different raw materials according to a formula #5, putting the raw materials into a ball milling tank, wet-milling for 10h, drying the obtained slurry at 60 ℃ for 8h, sieving the dried powder with a 325-mesh sieve, putting the sieved powder into a mould, and molding under 30 MPa; sintering at 1000 deg.C for 30min in the first stage, sintering at 1120 deg.C, 1130 deg.C, 1140 deg.C for 30min in the second stage, cooling with furnace, and taking out samples marked as #1, #2, and # 3. The experiment shows that: the porosities of #1 to #3 are: 3.97%, 3.63% and 3.12%; the apparent porosity is respectively as follows: 2.27%, 1.84% and 1.44%; the compressive strength is respectively as follows: 10.7MPa, 11.2MPa and 12.3 MPa.
Example 3
Table 4 shows the raw material recipe for preparing the porous ceramic foam
Preparing solid waste base porous ceramic: weighing different raw materials according to formulas #5 and #6, wet-grinding for 10h according to the proportion of ball, material and water of 3: 2:1, drying the obtained slurry at 60 ℃ for 8h, sieving the dried powder with a 300-mesh sieve, filling the sieved powder into a mould, and forming under 25 MPa; sintering at 1000 deg.C for 20min in the first stage, sintering at 1130 deg.C for 40min in the second stage, cooling with the furnace, and taking out samples marked as #1 and # 2. The experiment shows that: the porosities of #1 and #2 are: 8.1% and 6.9%; the compressive strength is respectively as follows: 2.7MPa and 5.1 MPa.
Claims (9)
1. A preparation method of solid waste based high-strength foamed ceramic is characterized by comprising the following steps: carrying out wet ball milling on raw materials including silicate tailings, manganese slag, steel slag, potassium feldspar, bentonite and a foaming agent to obtain slurry; and drying and sieving the obtained slurry, and then pressing and forming to obtain a ceramic blank, and sintering the ceramic blank to obtain the ceramic material.
2. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the raw materials comprise the following components in percentage by mass:
30 to 60 percent of silicate tailings,
8 to 40 percent of manganese slag,
5 to 35 percent of steel slag,
5 to 8 percent of potassium feldspar,
2 to 5 percent of bentonite,
0.1 to 0.5 percent of silicon carbide foaming agent.
3. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the wet ball milling conditions are as follows: taking water as a ball milling medium, wherein the mass ratio of balls to materials to water is (5-3): 3-2): 1-1, the ball milling speed is 300-380 rpm, and the ball milling time is 5-12 h.
4. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the drying temperature is 50-70 ℃, and the drying time is 8-12 h.
5. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the screen mesh is 200-300 meshes.
6. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the forming pressure adopted by the compression forming is 15-30 MPa.
7. The method for preparing the solid waste based high-strength foamed ceramic according to claim 1, wherein the method comprises the following steps: the sintering adopts two-stage sintering, the first stage sintering is carried out for 20-30 min at the temperature of 1000-1050 ℃, and the second stage sintering is carried out for 20-40 min at the temperature of 1120-1150 ℃.
8. The solid waste base high-strength foamed ceramic is characterized in that: the preparation method of any one of claims 1 to 7.
9. The solid waste based high strength foamed ceramic according to claim 8, wherein: the porosity is 0.5-4%, and the compressive strength is 8-18 MPa.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960847A (en) * | 2020-08-13 | 2020-11-20 | 景德镇陶瓷大学 | Preparation method of foamed ceramic with diopside as main crystal phase and product prepared by preparation method |
| CN113480324A (en) * | 2021-07-27 | 2021-10-08 | 辽宁工业大学 | Foamed ceramic prepared from fly ash and metallurgical waste residues and preparation method thereof |
| CN115611611A (en) * | 2022-10-12 | 2023-01-17 | 北京科技大学 | Method for preparing foamed ceramic by using iron tailings in cooperation with metallurgical solid waste |
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Application publication date: 20200623 |