CN111715178A - Copper smelting waste residue based adsorption material and preparation method thereof - Google Patents
Copper smelting waste residue based adsorption material and preparation method thereof Download PDFInfo
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- CN111715178A CN111715178A CN202010641226.5A CN202010641226A CN111715178A CN 111715178 A CN111715178 A CN 111715178A CN 202010641226 A CN202010641226 A CN 202010641226A CN 111715178 A CN111715178 A CN 111715178A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical field of smelting slag resource utilization and harmless treatment, and discloses a copper smelting waste slag-based adsorption material and a preparation method thereof, wherein raw materials for preparing the adsorption material consist of copper smelting waste slag, clay and a pore-forming agent; the preparation method of the adsorbing material comprises the following steps: drying and grinding copper smelting waste residues and clay into dry powder, and drying and crushing the pore-forming agent; weighing copper smelting waste residue powder, clay powder and crushed pore-forming agent according to the proportion, uniformly mixing and stirring, sending into a balling granulator for granulation and molding, and finally drying and calcining to obtain the finished adsorbing material. The adsorbing material disclosed by the invention is rough in surface and porous in the interior, and can be used as a heavy metal adsorbing material; the preparation method of the invention recycles the copper smelting waste residue, and has good economic benefit and social benefit. The invention adopts the solid waste of copper smelting enterprises as the raw material to prepare the heavy metal adsorption material, and the heavy metal wastewater is adsorbed and treated, thereby having the advantage of saving natural resources and achieving the purpose of treating wastes with processes of wastes.
Description
Technical Field
The invention belongs to the technical field of smelting slag resource utilization and harmless treatment, and particularly relates to a copper smelting slag-based adsorption material and a preparation method thereof.
Background
At present, the existing copper smelting enterprises mostly adopt a pyrometallurgical process to treat copper sulfide concentrate, and the process can generate a large amount of copper smelting waste residues. The copper smelting waste slag mainly comprises iron silicon oxide, copper iron silicon oxide, aluminum oxide, calcium oxide and the like. At present, the produced copper smelting waste slag is mainly buried or stockpiled, and the stockpiled landfill occupies a large area on one hand, and on the other hand, the copper smelting waste slag contains active heavy metal components, so that the copper smelting waste slag is easy to cause environmental pollution if the management is poor; and also enterprises deliver the copper smelting waste residues to third-party solid waste treatment enterprises for recycling valuable metals.
The methods for removing heavy metals from wastewater can be broadly divided into two categories: firstly, heavy metals in a dissolved state in the wastewater are converted into insoluble heavy metal compounds or elements, and the insoluble heavy metal compounds or elements are removed from the wastewater through precipitation or floating, and can be removed by adopting a neutralization precipitation method, a sulfide precipitation method, a floating separation method, an ion flotation method, an electrolytic precipitation or electrolytic floating method, a diaphragm electrolysis method and other methods; and secondly, the heavy metals in the wastewater are concentrated and separated under the condition of not changing the chemical form of the heavy metals, and the heavy metals can be concentrated and separated by adopting methods such as an evaporation method, an adsorption method, a reverse osmosis method, an electrodialysis method, an ion exchange method and the like. The first type of process is the most widely used neutralization precipitation, sulfide precipitation and electrolytic precipitation. From the perspective of heavy metal recycling, the second method is more advantageous than the first method because when the second method is used for treatment, the heavy metal is concentrated in an original state, no chemical agent is required to be added, and the heavy metal can be directly recycled after treatment. In the first method, heavy metals are recycled only after multiple chemical form transformations by means of multiple use of chemical agents. After some heavy metal waste water such as electroplating rinsing water is used for recovering heavy metal in the waste water by the second method, the waste water can be easily circulated in a closed loop.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) the prior art has low harmless treatment and resource utilization rate of copper smelting waste residue.
(2) In the formula of the adsorbing material in the prior art, natural resources such as minerals and the like or industrial raw materials are mainly used, and the raw material cost of the wastewater heavy metal adsorbing material is high.
(3) In the prior art, organic pore-forming agents such as rural waste straws and the like are not adopted, so that the energy consumption in the preparation and firing process of the adsorbing material is higher.
The difficulty in solving the above problems and defects is: in a smelting enterprise, the smelting waste slag is adopted to prepare a water treatment material, and the water treatment material is applied to the heavy metal wastewater treatment of the enterprise.
The significance of solving the problems and the defects is as follows: the water treatment adsorbing material is prepared by utilizing the solid waste of the smelting enterprise, and is applied to the heavy metal wastewater treatment of the enterprise, so that the waste treatment by waste can be realized particularly in the enterprise.
The invention adopts the solid waste of copper smelting enterprises as the raw material to prepare the heavy metal adsorption material, and the heavy metal wastewater is adsorbed and treated, thereby having the advantage of saving natural resources and achieving the purpose of treating waste by waste.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a copper smelting waste residue-based adsorption material and a preparation method thereof.
The invention is realized in such a way that the copper smelting waste residue-based adsorption material is prepared from the following raw materials in percentage by mass: 60-85 wt.% of copper smelting waste slag, 10-30 wt.% of clay and 5-10 wt.% of pore-forming agent; the copper smelting waste slag is waste slag formed in the process of treating copper sulfide concentrate to produce anode copper products by a pyrometallurgical process, and the components of the waste slag comprise SiO225-35wt.％、Fe 27-45wt.％、CaO 1-6wt.％、Al2O33-10 wt.%; the clay is a viscous soil containing little sand, and is prepared from various hydrated silicic acidsSalt and a certain amount of alumina, alkali metal oxide and alkaline earth metal oxide, and contains quartz, feldspar, mica, sulfate, sulfide, carbonate and other components, and has better viscoplasticity; the pore-forming agent is an organic pore-forming agent with pore-forming effect, and preferably rural waste straws.
The invention also aims to provide a method for preparing the copper smelting waste residue-based adsorption material, which comprises the following steps:
(1) respectively drying copper smelting waste residues and clay and then grinding into dry powder;
(2) drying and crushing the pore-forming agent, wherein the water content of the treated pore-forming agent is less than 20 wt%, and the granularity requirement is less than 0.5 mm;
(3) weighing the powder materials according to the raw material proportion, and uniformly mixing and stirring to prepare the adsorbing material powder material;
(4) sending the adsorbing material powder into a pelletizing granulator for pelletizing and forming to prepare an adsorbing material blank;
(5) drying the adsorbing material blank at 105 ℃ for 3-5 hours;
(6) and putting the dried adsorbing material blank into a sintering furnace, heating to 1000-1100 ℃, preserving the heat for 1.5-3 hours, cooling along with the furnace, and discharging to obtain the finished adsorbing material.
(7) The method specifically comprises the following steps: soaking the fired copper slag-based adsorption material finished product into 0.5-1.5mol/L NaOH solution for 10-25 h; after soaking, washing the mixture with distilled water until the solution is neutral; and (4) drying in an oven at 105 ℃ to obtain the modified copper slag-based adsorption material.
The invention also aims to provide a filter material for removing heavy metal ions in wastewater.
By combining all the technical schemes, the invention has the advantages and positive effects that:
the raw materials used for preparing the adsorbing material consist of copper smelting waste residues, clay and a pore-forming agent; the preparation method of the adsorbing material comprises the following steps: drying and grinding copper smelting waste residues and clay into dry powder, and drying and crushing the pore-forming agent; weighing copper smelting waste residue powder, clay powder and crushed pore-forming agent according to the proportion, uniformly mixing and stirring, sending into a balling granulator for granulation and molding, and finally drying and calcining to obtain the finished adsorbing material. The adsorbing material disclosed by the invention is rough in surface and porous in the interior, and can be used as a heavy metal adsorbing material; the preparation method of the invention recycles the copper smelting waste residue, and has good economic benefit and social benefit.
The invention is characterized in that more than 60 wt.% of raw materials in the formula of the adsorption material are copper smelting waste residues, the prepared wastewater heavy metal adsorption material has low cost, and the purpose of treating wastes with wastes can be realized.
The invention is also characterized in that the pore-forming agent is organic pore-forming agent such as rural waste straw, and the like, so that energy can be saved and production cost can be reduced in the process of firing the adsorption material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a copper smelting slag-based adsorption material according to an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a copper smelting waste residue-based adsorption material and a preparation method thereof, and the invention is described in detail with reference to the accompanying drawings.
The adsorbing material provided by the invention is prepared from the following raw materials in percentage by mass: 60-85 wt.% of copper smelting waste slag, 10-30 wt.% of clay and 5-10 wt.% of pore-forming agent.
The copper smelting waste residue treated by the invention is waste residue formed in the process of producing anode copper products by treating copper concentrate by adopting a pyrogenic process, and mainly comprises the following components:
the iron and calcium oxides in the copper smelting slag in the formula of the adsorption material have a combustion assisting effect in the sintering process of the adsorption material, so that the sintering temperature can be reduced, and the reduction of the sintering energy consumption of the adsorption material is facilitated.
The pore-forming agent in the formula of the adsorption material is an organic pore-forming agent, and waste straws in rural areas are preferably selected.
The invention modifies the prepared adsorbing material: soaking the fired copper slag-based adsorption material finished product into 0.5-1.5mol/L NaOH solution for 10-25 h; after soaking, washing the mixture with distilled water until the solution is neutral; and (5) drying in an oven at 105 ℃ to obtain a finished product of the modified copper slag-based adsorption material.
As shown in figure 1, the method for preparing the copper smelting waste residue-based adsorption material specifically comprises the following steps:
s101, respectively drying the copper smelting waste residue and the clay, and grinding the copper smelting waste residue and the clay into dry powder, wherein the granularity requirement is less than 75 microns.
And S102, drying and crushing the pore-forming agent, wherein the water content of the processed pore-forming agent is less than 20 wt.%, and the granularity requirement is less than 0.5 mm.
S103, respectively weighing the powder according to the raw material proportion of 60-85 wt.% of copper smelting waste residues, 10-30 wt.% of clay and 5-10 wt.% of pore-forming agent, and uniformly mixing and stirring to obtain the adsorbing material powder.
And S104, conveying the adsorbing material powder into a pelletizing granulator for pelletizing and forming to obtain an adsorbing material blank.
S105, drying the adsorbing material blank at 105 ℃ for 3-5 hours.
S106, putting the dried adsorbing material blank into a sintering furnace, heating to 1000-1100 ℃, preserving the heat for 1.5-3 hours, cooling along with the furnace, and discharging to obtain the adsorbing material finished product.
S107, soaking the fired copper slag-based adsorption material finished product into 0.5-1.5mol/L NaOH solution for 10-25 h; after soaking, washing the mixture with distilled water until the solution is neutral; and (4) drying in an oven at 105 ℃ to obtain the modified copper slag-based adsorption material.
The preparation method is simple and easy to implement and low in cost, and the prepared adsorbing material is rough in surface and porous in interior, can be applied to adsorption removal treatment of heavy metal ions in industrial wastewater, can realize harmless treatment and resource utilization of copper smelting waste residues, and has good economic benefit and social benefit.
The copper smelting slag-based adsorption material and the preparation method thereof provided by the invention can be implemented by other steps by persons skilled in the art, and the invention shown in fig. 1 is only one specific example.
The invention is further described with reference to specific examples.
Example one
The copper smelting waste residue of a certain company comprises the following main components:
drying and grinding the copper smelting waste slag into dry powder with the granularity less than 75 microns.
Drying and grinding the clay into dry powder with the particle size of less than 75 microns.
The dry and crushed rural waste straw is used as a pore-forming agent, the water content is less than 20 wt.%, and the particle size is less than 0.5 mm.
And respectively weighing the powder according to the raw material proportion of 80 wt.% of copper smelting waste residues, 15 wt.% of clay and 5 wt.% of pore-forming agent, and uniformly mixing and stirring to obtain the adsorbing material powder.
And (4) conveying the adsorbing material powder into a pelletizing granulator for pelletizing and forming to obtain an adsorbing material blank.
The adsorbing material blank was dried at 105 ℃ for 4 hours.
And (3) putting the dried adsorbing material blank into a sintering furnace, raising the temperature at a speed of 15 ℃/min, keeping the temperature at 1050 ℃ for 2 hours, cooling along with the furnace, and discharging to obtain a finished adsorbing material.
Soaking the fired copper slag-based adsorption material finished product into 0.5mol/L NaOH solution for 15 h; after soaking, washing the mixture with distilled water until the solution is neutral; drying in an oven at 105 deg.C, and taking out for use.
Experimental preparation of simulated Cu-containing material with initial concentration of 20mg/L2+And transferring 50mL of the solution into a plurality of 100mL PET bottles, and adding 1g of the alkali modified copper slag-based adsorbing material. Adsorbing at 35 deg.C under oscillation speed of 200r/min, taking out after 240min, filtering, and measuring Cu in supernatant by atomic absorption instrument2+Concentration is 3mg/L, and the modified copper slag-based adsorption material is used for simulating Cu in wastewater2+The removal rate of (2) is up to 85%.
Example two
The copper smelting waste residue of a certain company comprises the following main components:
drying and grinding the copper smelting waste slag into dry powder with the granularity less than 75 microns.
Drying and grinding the clay into dry powder with the particle size of less than 75 microns.
The dry and crushed rural waste straw is used as a pore-forming agent, the water content is less than 20 wt.%, and the particle size is less than 0.5 mm.
And respectively weighing the powder according to the raw material proportion of 70 wt.% of copper smelting waste residues, 23 wt.% of clay and 7 wt.% of pore-forming agent, and uniformly mixing and stirring to obtain the adsorbing material powder.
And (4) conveying the adsorbing material powder into a pelletizing granulator for pelletizing and forming to obtain an adsorbing material blank.
The adsorbing material blank was dried at 105 ℃ for 4 hours.
And (3) putting the dried adsorbing material blank into a sintering furnace, raising the temperature at a speed of 15 ℃/min, keeping the temperature at 1050 ℃ for 2 hours, cooling along with the furnace, and discharging to obtain a finished adsorbing material.
Soaking the fired copper slag-based adsorption material finished product into 1mol/L NaOH solution for 15 h; after soaking, washing the mixture with distilled water until the solution is neutral; drying in an oven at 105 deg.C, and taking out for use.
Experimental preparation of simulated Cu-containing material with initial concentration of 50mg/L2+And transferring 50mL of the solution into a plurality of 100mL PET bottles, and adding 1g of the alkali modified copper slag-based adsorbing material. Adsorbing at 35 deg.C under oscillation speed of 200r/min, taking out after 120min, filtering, and measuring Cu in supernatant by atomic absorption instrument2+The concentration is 5.8mg/L, and the modified copper slag-based adsorption material is used for simulating Cu in wastewater2+The removal rate of (2) is up to 88%.
In the description of the present invention, "a plurality" means two or more unless otherwise specified; the terms "upper", "lower", "left", "right", "inner", "outer", "front", "rear", "head", "tail", and the like, indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, are only for convenience in describing and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus, should not be construed as limiting the invention. Furthermore, the terms "first," "second," "third," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The copper smelting waste residue based adsorption material is characterized by being prepared from the following raw materials in percentage by mass: 60-85 wt.% of copper smelting waste slag, 10-30 wt.% of clay and 5-10 wt.% of pore-forming agent.
2. The method of claim 1The copper smelting waste residue-based adsorption material is characterized in that the copper smelting waste residue is waste residue formed in the process of treating copper sulfide concentrate to produce anode copper products by adopting a pyrometallurgical process, and comprises SiO225-35 wt.%, Fe27-45 wt.%, CaO 1-6 wt.%, and Al2O33-10wt.％。
3. The copper smelting slag-based adsorption material according to claim 1, wherein the clay is a low sand-containing, cohesive soil, is composed of a plurality of hydrated silicates and alumina, alkali metal oxides and alkaline earth metal oxides, and contains quartz, feldspar, mica, sulfate, sulfide and carbonate components.
4. The copper smelting slag-based adsorption material of claim 1, wherein the pore-forming agent is an organic pore-forming agent with a pore-forming effect, and comprises rural waste straw.
5. A method for preparing the copper smelting waste residue based adsorption material according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) respectively drying copper smelting waste residues and clay and then grinding into dry powder;
(2) drying and crushing the pore-forming agent, wherein the water content of the treated pore-forming agent is less than 20 wt%, and the granularity requirement is less than 0.5 mm;
(3) weighing the powder materials according to the raw material proportion, and uniformly mixing and stirring to prepare the adsorbing material powder material;
(4) sending the adsorbing material powder into a pelletizing granulator for pelletizing and forming to prepare an adsorbing material blank;
(5) drying the adsorbing material blank;
(6) sintering and cooling the dried adsorbing material to obtain a finished adsorbing material;
(7) soaking the fired copper slag-based adsorption material finished product in a modification solution, and washing until the solution is neutral after soaking; and drying to obtain the modified copper slag-based adsorption material.
6. The method for producing a copper smelting slag-based adsorption material according to claim 5, wherein the step (5) dries the adsorption material ingot at 105 ℃ for 3 to 5 hours.
7. The method for preparing the copper smelting slag-based adsorption material as claimed in claim 5, wherein the step (6) comprises the steps of placing the dried adsorption material blank into a sintering furnace, heating to 1000-1100 ℃, keeping the temperature for 1.5-3 hours, cooling along with the furnace, and discharging to obtain the finished adsorption material.
8. The method for preparing the copper smelting slag-based adsorption material according to claim 5, wherein the step (7) specifically comprises: soaking the fired copper slag-based adsorption material finished product into 0.5-1.5mol/L NaOH solution for 10-25 h; after soaking, washing the mixture with distilled water until the solution is neutral; and (4) drying in an oven at 105 ℃ to obtain the modified copper slag-based adsorption material.
9. A filter material prepared from the copper smelting waste residue-based adsorption material of claims 1-4 and used for removing heavy metal ions in wastewater.
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| CN112661231A (en) * | 2020-12-16 | 2021-04-16 | 重庆大学 | Multifunctional long-acting composite filler and preparation method thereof |
| CN112851169A (en) * | 2021-02-18 | 2021-05-28 | 北京建筑材料科学研究总院有限公司 | Method for solidifying heavy metal elements in copper slag |
| CN116332436A (en) * | 2023-05-19 | 2023-06-27 | 赛恩斯环保股份有限公司 | Manganese-containing wastewater treatment method |
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