CN114804771A - Concrete prepared from high-activity superfine copper tailing cement mineral admixture - Google Patents
Concrete prepared from high-activity superfine copper tailing cement mineral admixture Download PDFInfo
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- CN114804771A CN114804771A CN202210492082.0A CN202210492082A CN114804771A CN 114804771 A CN114804771 A CN 114804771A CN 202210492082 A CN202210492082 A CN 202210492082A CN 114804771 A CN114804771 A CN 114804771A
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- superfine copper
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/144—Slags from the production of specific metals other than iron or of specific alloys, e.g. ferrochrome slags
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses concrete prepared by using a high-activity superfine copper tailing cement mineral admixture, which comprises the following raw materials: superfine copper tailings and cement. According to the invention, the superfine copper tailings are calcined at high temperature, and then are mechanically ground to replace cement materials to prepare concrete, a large amount of calcium carbonate in the superfine copper tailings is decomposed into calcium oxide by utilizing the high-temperature calcination, and the reaction product, namely ettringite, of the calcium oxide in the concrete has a large volume, so that the concrete is expanded, and the shrinkage of the concrete can be effectively compensated. In addition, the calcined superfine copper tailings are mechanically activated through mechanical grinding to generate nanoparticles with a composite function, the mechanically activated superfine copper tailings are mixed with 10% of cement in advance to effectively disperse the nanoparticles, the crystal nucleus effect of the nanoparticles is fully exerted, and the overall strength of the concrete is improved. The feasibility of the superfine copper tailings as concrete materials is greatly improved in the aspects, and the superfine copper tailings can be applied to the technical field of concrete production.
Description
Technical Field
The invention relates to the field of metal beneficiation waste resource utilization, in particular to concrete prepared from a high-activity superfine copper tailing cement mineral admixture.
Background
In the process of mining and smelting copper ores, a large amount of copper tailing solid waste is often generated, the solid waste is accumulated, the conditions that the land is occupied, resources are wasted and the like are caused, and the problem of polluting the local ecological environment is caused, so that a tailing pond becomes an important hazard source and the life and property safety are harmed.
The problem of how to treat the copper tailing solid waste is always difficult. The copper tailing solid waste can be broken during treatment to generate a plurality of superfine copper tailings, the superfine copper tailings can be lifted in strong wind, sand storm can be caused, the atmospheric environment is seriously polluted, and the tailing collapse and landslide accident can be easily caused in heavy rain. Due to the low utilization rate of the copper tailings, the waste of mineral resources is serious, and the utilization rate of enterprises with higher levels internationally to the copper tailings is over 80 percent. Based on the analysis, the invention adopts the superfine copper tailings to replace part of cement, can reduce the consumption of the cement in the construction industry, thereby reducing the carbon emission, and can also help the copper tailings to eliminate the reservoir and improve the utilization rate of mineral resources.
In order to overcome the defects of the prior art, the invention provides the method for preparing the concrete by using the superfine copper tailings to replace part of cement, and the method is efficient, green and wide in application prospect. The superfine copper tailings are treated by a high-temperature calcination method, and calcium oxide and other substances contained in the treated superfine copper tailings are utilized to form a product which is the same as cement hydration in the hydration process, so that the superfine copper tailings have great potential in the aspect of replacing cement. Theoretically and practically, it is feasible to make concrete using ultrafine copper tailings calcined at high temperature instead of part of the cement, because: 1) the superfine copper tailings after high-temperature calcination can generate rich calcium oxide, and in the process of concrete reaction, the calcium oxide reacts to generate ettringite and generates a volume expansion phenomenon, so that the shrinkage of concrete can be compensated by using the phenomenon; 2) the superfine copper tailings treated at high temperature are mechanically ground, and through the mechanical force effects of impact, friction, extrusion and the like during grinding, nanoparticles with composite functions are generated to promote hydration, so that the development of the compressive strength and the improvement of the durability of concrete are facilitated, solid wastes are fully utilized, and the using amount of cement is reduced.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and the concrete is prepared by using the superfine tailings as one of the sources of the mixing cementing materials of the concrete. A large amount of calcium carbonate in the superfine copper tailings is decomposed into calcium oxide by high-temperature calcination, and the reaction product, namely ettringite, of the calcium oxide in the concrete is large in size, so that the concrete can expand, and the shrinkage of the concrete can be effectively compensated. In addition, the calcined superfine copper tailings are mechanically activated through mechanical grinding to generate nanoparticles with a composite function, the mechanically activated superfine copper tailings are mixed with 10% of cement in advance to effectively disperse the nanoparticles, the crystal nucleus effect of the nanoparticles is fully exerted, and the overall strength of the concrete is improved. In these aspects, the feasibility of the superfine copper tailings as concrete materials is greatly improved, and the superfine copper tailings can be applied to the technical field of concrete production.
The technical scheme adopted by the invention is as follows: the concrete prepared by using the high-activity superfine copper tailing cement mineral admixture comprises the following raw materials: ultra-fine copper tailings of Langya mountain of Chuzhou city, Anhui province, common 42.5 portland cement of conch brand, and common tap water of city.
As a further improvement of the invention, the fly ash-free concrete also comprises sand, pebbles, a water reducing agent, metakaolin and fly ash.
As a further improvement of the invention, the composition in parts by weight is as follows: 0-100 parts of superfine copper tailings after calcination and grinding, 0-450 parts of 42.5 cement, 0-350 parts of urban common tap water, 13-246 parts of fly ash, 0-244 parts of stones, 13-246 parts of metakaolin and 0-255 parts of sand.
As a further improvement of the invention, the superfine copper tailings are superfine mineral particles obtained after metal copper is subjected to mineral separation, preferably, the tailings are copper tailing warehouse stacking waste materials, and in the radioactive nuclide limit detection of building materials, the internal irradiation index is 0.3, the external irradiation index is 0.2, and the internal irradiation index and the external irradiation index are both less than 1.0, so that the requirement of the building main body materials is met.
As a further improvement of the invention, the fly ash is commercial fly ash, preferably, the fly ash is more than two-grade fly ash, and the fineness of the fly ash is 200 meshes and accounts for more than 90%.
As a further improvement of the invention, the metakaolin is a commercially available calcined metakaolin powder, preferably with a fineness of 400 mesh accounting for more than 90%.
A method for treating superfine copper tailings comprises the following steps:
the method comprises the following steps: and placing the superfine copper tailings into a muffle furnace for calcination treatment. Preferably, the calcination temperature of the ultra-fine copper tailings is determined to be 800 ℃. Preferably, the superfine copper tailings after calcination are subjected to a grinding treatment.
A method for preparing concrete by using a high-activity superfine copper tailings cement mineral admixture comprises the following steps:
the method comprises the following steps: mixing the superfine copper tailings with cement, fly ash, sand and stones. Preferably, the superfine copper tailings are obtained by calcining and grinding. Water was then added and stirred well. And then, standard curing.
The improved preparation method comprises the following steps:
the method comprises the following steps: the superfine copper tailings and ten percent of cement are mixed uniformly. Preferably, the superfine copper tailings are obtained by calcining and grinding. Then adding the rest cement, sand, pebble and metakaolin into the mixture and stirring the mixture. Finally water was added and stirred well. And then, standard curing.
The invention has the beneficial effects that:
(1) changing waste into valuable: the superfine copper tailings have complex components and contain heavy metals, the collapse and landslide accidents of tailings are easily caused when raining, and the soil fertility can be damaged after heavy metal elements migrate into a farmland, so that the growth of crops is influenced, and serious environmental pollution and safety problems are caused. The concrete prepared by the high-activity superfine copper tailing cement mineral admixture greatly simplifies the disposal and utilization process of the superfine copper tailing, reduces the economic, safety and environmental burden of non-ferrous metal mine enterprises, and meets the requirements of national environmental protection policies.
(2) Compensation of concrete shrinkage: for concrete without the use of ultra-fine copper tailings, shrinkage occurs during curing. The calcined superfine copper tailings are rich in calcium oxide, the calcium oxide can react in concrete to generate expansive products such as ettringite and the like, so that the volume of the concrete expands, and the calcined superfine copper tailings are used for replacing part of cement to effectively compensate the shrinkage of the concrete.
(3) The mechanical property of the concrete is improved: the superfine copper tailings after calcination and grinding are used for replacing part of cement, and through the solid-solid chemical reaction of the superfine copper tailings after calcination and mechanical grinding, nano particles with composite functions can be generated, and the nano particles can be used as nucleation sites of concrete hydration products, so that the hydration is further promoted, and the compressive strength of the concrete is improved.
(4) Changing the harm into treasure: the superfine copper tailings not only contain heavy metals, but also contain a large amount of precious silicon, calcium, aluminum and other ions. According to the concrete prepared by using the high-activity superfine copper tailing cement mineral admixture, the superfine copper tailing is used for replacing cement to prepare the concrete, so that the silicate meshes in the superfine copper tailing can be depolymerized by using cement clinker to participate in hydration reaction; and active silicon-aluminum plasma in the superfine copper tailings can react with calcium hydroxide, calcium silicate hydrate, aluminate hydrate and the like generated by hydrating cement clinker minerals, so that more cementite is formed, and the method has outstanding economic, social and environmental benefits and a huge application prospect.
Description of the drawings:
in order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a graph of laser particle size of treated and untreated ultra-fine copper tailings of example 1 of the present invention;
FIG. 2 is a graph showing the compression strength of each benchmark group at different ages in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern for each baseline group of 28 days for example 1 of the present invention;
FIG. 4 is a plot of the percent porosity of the 28 day test pieces from each baseline group as measured by low field NMR spectroscopy in example 1 of the invention;
FIG. 5 is a mass content plot for each baseline group of 28-day coupons determined by thermogravimetric analysis of example 1 of the present invention.
FIG. 6 shows the compression strength of each baseline group at different ages in example 2 of the present invention.
FIG. 7 is a 28-day SEM micrographic image of the reference group 6 specimens and the reference group 8 specimens of example 2 of the present invention.
The specific implementation mode is as follows:
in order to make the present invention more comprehensible and to make technical solutions and advantages thereof more apparent, the present invention is described in further detail below with reference to embodiments and accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The specific experimental methods not mentioned in the following examples are generally carried out according to conventional experimental methods.
Example 1:
the concrete prepared by the high-activity superfine copper tailing cement mineral admixture comprises superfine copper tailing, common 42.5 Portland cement, sand, pebbles, fly ash and urban common tap water. The specific weight parts (kg) ratio is shown in Table 1,
TABLE 1
Wherein: the common 42.5 portland cement is Anhui Huainan conchCement, manufactured by cement limited; the water is urban common tap water; the fly ash is commercial fly ash, the fly ash is more than two-grade fly ash, and the fineness of the fly ash is more than 90 percent of 200 meshes; the sand is common river sand, and the fineness modulus is 2.5; the stones are 10-20 mm continuous graded limestone stones; the superfine copper tailings are from a tailing pond of Langyan mountain of Chuzhou city of Anhui province, subjected to calcination at 800 ℃ and grinding treatment, and have apparent density of 2756kg/m 3 The particle size of copper tailings is concentrated between 10 and 150 mu m, the copper tailings are typical 100-mesh materials, harmful element radioactivity evaluation is carried out on the tailings, and the detection method and the judgment standard are GB6566 building material radionuclide limitation. The detection results show that the internal irradiation index is 0.3, the external irradiation index is 0.2, both are less than 1.0, the requirements of main building materials are met, the chemical components of the tailings are shown in the table 2 (unit:%),
TABLE 2
| SiO 2 | CaO | Fe 2 O 3 | Al 2 O 3 | MgO | K 2 O | TiO 2 |
| 28.64 | 29.73 | 12.11 | 6.11 | 0.17 | 0.90 | 0.27 |
The slurry is prepared according to the mixture ratio shown in the table 1, poured into a cubic steel mold with the side length of 150mm, and placed into a standard curing room with the temperature of 20 +/-2 ℃ and the relative humidity of more than 95% for curing for 1 day. After that, the test block is demoulded and maintained for 3 days, 7 days and 28 days. And (5) testing the compressive strength of test blocks in different ages by using a press machine. Furthermore, 3-day mineral components of the neat slurry (containing no sand) shown in Table 1 were analyzed by TTR-III θ/θ X-ray diffractometer, the pore structure of the 28-day mortar block was analyzed by MesoMR23-060V-1 low-field NMR spectrometer, and the hydration level of the 28-day mortar block was analyzed by thermogravimetric analyzer. Table 3 shows the compressive strengths (unit: MPa) of the reference groups 1 to 5 at the ages of 3 days, 7 days and 28 days
TABLE 3
From fig. 1, it can be seen that the particle size of the superfine copper tailings after calcination and grinding is reduced compared with that of the untreated whole, which indicates that the treated superfine copper tailings have higher activity, and are beneficial to promoting the whole hydration of concrete and improving the whole strength. As can be seen from table 3 and fig. 1, it is feasible to replace part of the cement with the superfine copper tailings subjected to calcination and grinding treatment, and the compressive strength of the concrete is not reduced within a certain replacement range. For example, when superfine copper tailings subjected to calcination and grinding are used for replacing two portions of portland cement, the compressive strength of the concrete at each age shows a reinforcing phenomenon. Fig. 2 is an X-ray diffraction pattern of 28d age of each reference group, and it can be seen that the use of ultrafine copper tailings subjected to calcination and grinding instead of cement can accelerate the hydration process of concrete as a whole, increase the generation of hydration products, and improve the hydration degree of concrete. Fig. 3 is a graph of the pore volume percentage of each reference group 28d of test blocks measured by nuclear magnetic resonance, and it can be seen that the ultrafine copper tailings with different substitution degrees refine the pore structure of the concrete, and reduce the porosity of the concrete as a whole, so that the concrete is more compact. FIG. 4 is a thermogravimetric analysis chart of each of the reference group 28d test blocks, and it can be seen that, when the superfine copper tailings subjected to calcination and grinding are not used to replace cement, reference group 1 obviously shows that the contents of calcium carbonate and calcium bicarbonate are high, more ettringite and calcium sulphoaluminate monosulfide exist, and the yield of calcium silico (aluminate) hydrate is relatively low; when the superfine copper tailings after calcination and grinding are used for replacing cement, the yield of the calcium silicate hydrate colloid is remarkably improved. The results fully prove that the superfine copper tailings subjected to calcination and grinding are feasible to replace cement, and have positive promotion effect on the strength of concrete, so that the application prospect is wide.
Example 2:
the concrete prepared by using the high-activity superfine copper tailing cement mineral admixture comprises superfine copper tailing, 42.5 cement, metakaolin, sand, stones and urban common tap water. The specific weight parts (kg) formulation is shown in table 4,
TABLE 4
Wherein: wherein: the common 42.5 portland cement is produced by Anhui Huainan conch cement Co., Ltd; the water is urban common tap water; metakaolin is calcined kaolin powder sold in the market, and the fineness is preferably 400 meshes and accounts for more than 90%; the sand is common river sand, and the fineness modulus is 2.5; the stones are 10-20 mm continuous graded limestone stones; the superfine copper tailings are from a tailing pond of Langyan mountain of Chuzhou city of Anhui province, subjected to calcination at 800 ℃ and grinding treatment, and have apparent density of 2756kg/m 3 The particle size of copper tailings is concentrated between 10 and 150 mu m, the copper tailings are typical 100-mesh materials, harmful element radioactivity evaluation is carried out on the tailings, and the detection method and the judgment standard are GB6566 building material radionuclide limitation. Detection knotThe internal irradiation index of the fruit is 0.3, the external irradiation index is 0.2, both are less than 1.0, the requirements of main building materials are met, and the chemical components of the tailings are as shown in the table 2
Concrete was prepared according to the formulation shown in table 4, poured into a cubic steel mold with side length of 150mm, and placed in a standard curing room with a temperature of 20 ± 2 ℃ and a relative humidity of more than 95% for curing for 1 day. Thereafter, the test block was demolded and maintained for 3, 7 and 28 days of age, respectively. And (3) testing the compressive strength of test blocks in different ages by using a press, wherein 3 test blocks form a group, and the test results are averaged. Table 5 shows the compressive strengths (in MPa) of the 3 reference groups.
TABLE 5
It can be seen that baseline group 7 was stronger than baseline group 6 at each age, and that baseline group 8 was stronger than baseline group 6 at ages 7d and 28d, with increases of 12.5% and 13.4%, respectively. The intensity of the other groups slightly decreased, but the decrease in each age was not large. As can be seen from the 28-day test block scanning electron microscope micro-topography images of the reference group 6 and the reference group 8 in fig. 6, compared with the reference group 6, the number of hydration products and the degree of compaction of the whole structure of the reference group 8 are higher. This is a good demonstration of the feasibility of using ultrafine copper tailings treated by calcination and grinding instead of cement. According to the regulation of GB50010 'concrete structure design specification' on concrete strength grade, the concrete strength grades of the reference group 6, the reference group 7 and the reference group 8 are respectively C40, C45 and C45, and the use requirements of related projects are met.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (6)
1. The concrete prepared by using the high-activity superfine copper tailing cement mineral admixture is characterized by comprising the following raw materials: superfine copper tailings, cement and urban common tap water.
2. The concrete prepared by using the high-activity ultrafine copper tailing cement mineral admixture as claimed in claim 1, which is characterized by further comprising sand, pebbles, metakaolin and fly ash.
3. The concrete prepared by using the high-activity superfine copper tailing cement mineral admixture as claimed in claim 2, which is characterized by comprising the following components in parts by weight: 0-100 parts of superfine copper tailings, 0-450 parts of 42.5 cement, 0-350 parts of urban common tap water, 13-246 parts of fly ash, 0-244 parts of stones, 13-246 parts of metakaolin and 0-255 parts of sand.
4. The concrete prepared by using the high-activity superfine copper tailing cement mineral admixture according to claim 1, wherein the superfine copper tailing is superfine mineral particles obtained after metal copper is beneficiated, preferably, the tailing is copper tailing warehouse stacking waste, and in the radionuclide limit detection of building materials, the internal irradiation index is 0.3, the external irradiation index is 0.2, and the internal irradiation index and the external irradiation index are both less than 1.0, so that the concrete meets the requirements of building main materials. Further preferably, the superfine copper tailings are subjected to calcination and grinding treatment.
5. The concrete prepared by using the high-activity superfine copper tailing cement mineral admixture as claimed in claim 2, wherein the fly ash is commercial fly ash, preferably, the fly ash is more than two-grade fly ash, and the fineness is more than 200 meshes and accounts for 90%.
6. The concrete prepared by using the high-activity superfine copper tailing cement mineral admixture as claimed in claim 2, wherein the metakaolin is commercial calcined kaolin powder, and the fineness is preferably 400 meshes and accounts for more than 90%.
A method for treating superfine copper tailings comprises the following steps:
the method comprises the following steps: and placing the superfine copper tailings into a muffle furnace for calcining treatment. Preferably, the calcination temperature of the ultra-fine copper tailings is determined to be 800 ℃. Further preferably, the calcined superfine copper tailings are subjected to grinding treatment.
A method for preparing concrete by using a high-activity superfine copper tailings cement mineral admixture comprises the following steps:
the method comprises the following steps: mixing the superfine copper tailings with cement, fly ash, sand and stones. Preferably, the superfine copper tailings are superfine copper tailings which are subjected to calcination and grinding treatment. Water was then added and stirred well. And then, standard curing.
The improved preparation method comprises the following steps:
the method comprises the following steps: the superfine copper tailings and ten percent of cement are mixed uniformly. Preferably, the superfine copper tailings are obtained by calcining and grinding. Then ninety percent of cement, sand, gravel and metakaolin are added for stirring. Water was then added and stirred well. And then, standard curing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115611568A (en) * | 2022-12-20 | 2023-01-17 | 矿冶科技集团有限公司 | Copper tailing based high-performance concrete and preparation method thereof |
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| CN108558304A (en) * | 2018-01-18 | 2018-09-21 | 江西省建筑材料工业科学研究设计院 | A kind of high antiskid long-life ultra-high performance concrete road surface road |
| CN114230258A (en) * | 2022-01-17 | 2022-03-25 | 安徽理工大学 | Autoclaved sand-lime brick prepared from superfine copper tailings |
| CN114560660A (en) * | 2022-03-15 | 2022-05-31 | 安徽理工大学 | Pervious concrete prepared from copper tailings |
| CN114956722A (en) * | 2022-05-06 | 2022-08-30 | 安徽理工大学 | Ultra-high-strength concrete prepared from superfine copper tailings |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108558304A (en) * | 2018-01-18 | 2018-09-21 | 江西省建筑材料工业科学研究设计院 | A kind of high antiskid long-life ultra-high performance concrete road surface road |
| CN114230258A (en) * | 2022-01-17 | 2022-03-25 | 安徽理工大学 | Autoclaved sand-lime brick prepared from superfine copper tailings |
| CN114560660A (en) * | 2022-03-15 | 2022-05-31 | 安徽理工大学 | Pervious concrete prepared from copper tailings |
| CN114956722A (en) * | 2022-05-06 | 2022-08-30 | 安徽理工大学 | Ultra-high-strength concrete prepared from superfine copper tailings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115611568A (en) * | 2022-12-20 | 2023-01-17 | 矿冶科技集团有限公司 | Copper tailing based high-performance concrete and preparation method thereof |
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