CN110451680B - Method for treating non-ferrous smelting waste acid - Google Patents
Method for treating non-ferrous smelting waste acid Download PDFInfo
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- CN110451680B CN110451680B CN201910685534.5A CN201910685534A CN110451680B CN 110451680 B CN110451680 B CN 110451680B CN 201910685534 A CN201910685534 A CN 201910685534A CN 110451680 B CN110451680 B CN 110451680B
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- 239000002699 waste material Substances 0.000 title abstract 5
- 238000003723 Smelting Methods 0.000 title abstract 4
- 239000002253 acid Substances 0.000 title abstract 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title abstract 3
- 239000000706 filtrate Substances 0.000 abstract 5
- PIJPYDMVFNTHIP-UHFFFAOYSA-L Lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- 239000010949 copper Substances 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 2
- 229910052602 gypsum Inorganic materials 0.000 abstract 2
- 239000010440 gypsum Substances 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 2
- BWFPGXWASODCHM-UHFFFAOYSA-N Copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract 1
- 238000010306 acid treatment Methods 0.000 abstract 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 abstract 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000002893 slag Substances 0.000 abstract 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/20—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention discloses a method for treating waste acid from non-ferrous smelting. Firstly, filtering colored smelting waste acid by adopting a membrane filter to obtain lead sulfate filter residue, and recovering lead sulfate; adding a vulcanizing agent into the obtained filtrate to enable copper in the filtrate to be vulcanized to generate copper sulfide precipitate, and recovering copper resources after filtering; then adding a vulcanizing agent into the obtained filtrate again to vulcanize heavy metals such as arsenic and the like to generate precipitates for removal; adding carbide slag into the obtained filtrate to adjust the pH value of the filtrate to prepare gypsum, and dehydrating by adopting a centrifugal machine to obtain dehydrated gypsum; finally, the obtained sewage is subjected to advanced treatment and is discharged or recycled after reaching the standard. The treatment method can effectively solve the technical problem that a large amount of dangerous waste residues are generated in the existing non-ferrous smelting waste acid treatment technology.
Description
The technical field is as follows:
the invention belongs to the technical field of non-ferrous smelting pollution treatment, and particularly relates to a non-ferrous smelting waste acid treatment method.
Secondly, the background technology:
the waste acid is mainly washed by dynamic wave flue gas in a sulfuric acid workshop, and the waste acid wastewater contains various heavy metal ions which are high in concentration, complex in form and high in toxicity. With the gradual depletion of mineral resources, the lead-zinc smelting industry faces the situation of no stable and single mineral source, and the components in the waste acid are more complex. Northwest lead-zinc smelters have been used for treating hundred kinds of ores, the waste acid of the smelters has the characteristics of high acid, high Hg, high COD and high F, and the original method for treating Hg, COD and F by neutralization with sulfide-lime is difficult to achieve the stable standard of Hg, COD and F; before 2010, the environmental protection pressure is small, and the environmental protection is not beneficial. Therefore, most lead-zinc smelting enterprises pay little attention to the research work in this aspect, which not only causes serious pollution to the environment, but also even causes the loss of metals such as mercury.
The waste acid generated in the acid making process by using the non-ferrous smelting flue gas contains a large amount of heavy metals such as arsenic, lead, copper and the like, and the commonly used waste acid treatment process is to firstly vulcanize the waste acid to remove most of the heavy metals and then adjust the pH value of the waste acid to be neutral. With the increasing environmental protection situation, the conventional treatment process of waste acid is difficult to meet the emission requirement. The conventional treatment process of the contaminated acid precipitates and filters copper, lead, arsenic and other heavy metals together through vulcanization, thereby causing the waste of copper and lead resources; meanwhile, heavy metals are difficult to completely remove through one-step vulcanization, part of the heavy metals enter a neutralization process and react with carbide slag to enter gypsum, the quality of the gypsum is influenced, and the produced gypsum is dangerous and waste and is difficult to recycle.
The treatment mode of the waste acid is always a difficult problem in the copper smelting industry, and in recent years, enterprises are also researching and exploring more efficient, convenient and environment-friendly waste acid purification processes.
Thirdly, the invention content:
the technical problem to be solved by the invention is as follows: according to the technical problems in the existing colored smelting waste acid treatment method, the invention provides a novel colored smelting waste acid treatment method. The treatment method can effectively solve the technical problem that a large amount of hazardous waste residues are generated in the existing waste acid treatment technology.
In order to solve the problems, the invention adopts the technical scheme that:
the invention provides a method for treating nonferrous smelting waste acid, which comprises the following steps:
a. firstly, filtering non-ferrous smelting waste acid by using a membrane filter to obtain lead sulfate filter residue, and recovering lead sulfate in the lead sulfate filter residue;
b. b, adding a vulcanizing agent into the filtrate obtained after filtration in the step a, controlling an ORP value to be 10-50 mv, so that copper in the filtrate is vulcanized to generate copper sulfide precipitate, and recovering copper resources after filtration;
c. b, adding a vulcanizing agent into the filtrate obtained after filtration in the step b again, and controlling the ORP value to be-20-0 mv to vulcanize heavy metals such as arsenic and the like to generate precipitates for removal;
d. adding carbide slag into the filtrate obtained in the step c to adjust the pH value of the filtrate to 7-8 to prepare gypsum, and dehydrating the prepared gypsum by adopting a centrifugal machine to obtain dehydrated gypsum;
e. and d, carrying out advanced treatment on the sewage obtained in the step d, and discharging or recycling the sewage up to the standard.
According to the method for treating the non-ferrous smelting waste acid, the non-ferrous smelting waste acid in the step a is at least one of heavy metal-containing acidic wastewater obtained by washing and purifying flue gas in the acid making process by smelting flue gas, treatment wastewater mixed with flue gas and electrolysis system discharge water.
According to the method for treating the nonferrous smelting waste acid, the mesh number of the filtering membrane of the membrane filter in the step a is 100-500 meshes.
According to the method for treating the nonferrous smelting waste acid, the mass percent of lead in the lead sulfate filter residue in the step a is 50-70% on a dry basis.
According to the method for treating the nonferrous smelting waste acid, in the step b, the vulcanizing agent is sodium sulfide, sodium hydrosulfide or hydrogen sulfide; and the mass percentage of copper contained in the obtained copper sulfide precipitate is 20-28% on a dry basis.
According to the method for treating the nonferrous smelting waste acid, the vulcanizing agent in the step c is sodium sulfide, sodium hydrosulfide or hydrogen sulfide.
According to the method for treating the nonferrous smelting waste acid, the water content of the dehydrated gypsum obtained in the step d is reduced to be less than or equal to 15 percent; on a dry basis, the obtained dehydrated gypsum contains 40-60% by mass of calcium sulfate.
According to the method for treating the nonferrous smelting waste acid, the specific process of the advanced treatment in the step e is as follows: and d, adding nano iron into the sewage obtained after the centrifugal separation in the step d, wherein the adding amount of the nano iron is 200-500 ppm, filtering after adding the nano iron, and discharging or recycling the obtained supernatant after reaching the standard.
The invention has the following positive beneficial effects:
1. and filtering the waste acid by using a membrane filter to obtain lead sulfate filter residues, wherein at least 98% of lead in the colored smelting waste acid can be recovered.
2. By vulcanizing the waste acid in two stages, at least 80% of copper in the nonferrous smelting waste acid can be recovered, and at least 95% of arsenic and other heavy metals can be removed.
3. After the contaminated acid is vulcanized in two stages, the heavy metal ions in the vulcanized liquid are reduced to be extremely low. The vulcanized liquid is neutralized, the obtained gypsum has high purity, a large amount of gypsum slag containing heavy metal generated by the traditional process is avoided, sulfate radicals in the waste liquid are effectively recycled, and the addition of a neutralizing agent in the neutralization treatment process of a back-end system is greatly reduced.
4. By utilizing the technical scheme of the invention, the non-ferrous smelting waste acid can be stably discharged after reaching the standard after being treated.
Fourthly, the specific implementation mode:
the invention is further illustrated by the following examples, which do not limit the scope of the invention.
Example 1:
the waste acid of a certain copper smelting plant is taken as a treatment object, and the concentration of each main component is as follows: 15.3 percent (mass percentage concentration) of sulfuric acid, 2133.8mg/L of copper ions, 13420.5mg/L of arsenic ions, 374.2mg/L of cadmium ions and 15.9mg/L of lead ions.
The method for treating the waste acid from the nonferrous smelting by using the technical scheme of the invention comprises the following detailed steps:
a. firstly, pumping the waste acid into a membrane filter by a pump for filtering (the mesh number of a filtering membrane of the membrane filter is 300 meshes), obtaining lead sulfate filter residue after filtering, obtaining a filter cake containing 62.3 percent (calculated by a dry basis) of lead sulfate after filtering the lead sulfate filter residue by a plate-and-frame filter press, and smelting the lead sulfate filter cake in a lead smelting system;
b. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtration by the membrane filter in the step a, controlling the ORP value of the solution to be 30mv, so that copper in the filtrate is sulfurized to generate copper sulfide precipitate, then, filtering the solution in a filter press to obtain a filter cake containing 25.7% of copper sulfide (calculated by dry basis), and smelting the filter cake in a copper smelting system;
c. c, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after the filtration of the filter press in the step b, and controlling the ORP value to be minus 10mv to enable heavy metals such as arsenic and the like to be vulcanized to generate precipitates; filtering the adjusted solution in a filter press to obtain a filter cake, and performing centralized treatment;
d. adding carbide slag into the filtrate obtained after filtering by the filter press in the step c to adjust the pH value of the filtrate to 7.3, feeding the obtained mixed solution into a thickener, feeding the supernatant of the thickener into a next process, feeding the underflow of the thickener into a centrifugal machine for separation to obtain gypsum powder with the water content of 14.2%, and returning the filtrate of the centrifugal machine to the thickener for recycling;
e. d, adding 300ppm of nano iron into the supernatant obtained in the step d, completing mud-water separation of the obtained mixed solution in an inclined plate sedimentation tank, and performing centralized treatment after filter pressing of bottom mud; the clear liquid comprises the following main components: the pH value is 7.2, the copper ions are 0.05mg/L, the arsenic ions are 0.03mg/L, the cadmium ions are 0.011mg/L and the lead ions are 0.02mg/L, the special emission requirements of the emission standard of industrial pollutants of lead and zinc are met, and the emission reaches the standard.
Example 2:
the waste acid of a certain copper smelting plant is taken as a treatment object, and the concentration of each main component is as follows: 14.1 percent (mass percentage concentration) of sulfuric acid, 3765.7mg/L of copper ions, 15028.6mg/L of arsenic ions, 325.1mg/L of cadmium ions and 18.1mg/L of lead ions.
The method for treating the waste acid from the nonferrous smelting by using the technical scheme of the invention comprises the following detailed steps:
a. firstly pumping the waste acid into a membrane filter by a pump for filtering (the mesh number of a filtering membrane of the membrane filter is 350 meshes), filtering to obtain lead sulfate filter residue, filtering the lead sulfate filter residue by a plate-and-frame filter press to obtain a filter cake containing 60.8 percent (calculated by dry basis) of lead sulfate, and smelting the lead sulfate filter cake in a lead smelting system;
b. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtration by the membrane filter in the step a, controlling the ORP value of the solution to be 35mv, so that copper in the filtrate is sulfurized to generate copper sulfide precipitate, then, filtering the solution in a filter press to obtain a filter cake containing 27.3% of copper sulfide (calculated by dry basis), and smelting the filter cake in a copper smelting system;
c. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtering by the filter press in the step b, and controlling the ORP value to be-12 mv to enable heavy metals such as arsenic and the like to be vulcanized to generate precipitates; filtering the adjusted solution in a filter press to obtain a filter cake, and performing centralized treatment;
d. adding carbide slag into the filtrate obtained after filtering by the filter press in the step c to adjust the pH value of the filtrate to 7.5, feeding the obtained mixed solution into a thickener, feeding the supernatant of the thickener into a next process, feeding the underflow of the thickener into a centrifugal machine for separation to obtain gypsum powder with the water content of 14.3%, and returning the filtrate of the centrifugal machine to the thickener for recycling;
e. d, adding 350ppm of nano iron into the supernatant obtained in the step d, completing mud-water separation of the obtained mixed solution in an inclined plate sedimentation tank, and performing centralized treatment after filter pressing of bottom mud; the clear liquid comprises the following main components: the pH value is 7.3, the copper ions are 0.03mg/L, the arsenic ions are 0.05mg/L, the cadmium ions are 0.009mg/L, and the lead ions are 0.017mg/L, so that the special emission requirements of the emission standard of industrial pollutants of lead and zinc are met, and the emission reaches the standard.
Example 3:
the waste acid of a certain copper smelting plant is taken as a treatment object, and the concentration of each main component is as follows: 18.9 percent (mass percentage concentration) of sulfuric acid, 4568.4mg/L of copper ions, 9021.6mg/L of arsenic ions, 355.3mg/L of cadmium ions and 24.8mg/L of lead ions.
The method for treating the waste acid from the nonferrous smelting by using the technical scheme of the invention comprises the following detailed steps:
a. firstly, pumping the waste acid into a membrane filter by a pump for filtering (the mesh number of a filtering membrane of the membrane filter is 300 meshes), obtaining lead sulfate filter residue after filtering, obtaining a filter cake containing 66.1 percent (calculated by a dry basis) of lead sulfate after filtering the lead sulfate filter residue by a plate-and-frame filter press, and smelting the lead sulfate filter cake in a lead smelting system;
b. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtration by the membrane filter in the step a, controlling the ORP value of the solution to be 29mv, so that copper in the filtrate is sulfurized to generate copper sulfide precipitate, then, filtering the solution in a filter press to obtain a filter cake containing 24.6% of copper sulfide (calculated by dry basis), and smelting the filter cake in a copper smelting system;
c. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtering by the filter press in the step b, and controlling the ORP value to be-14 mv to enable heavy metals such as arsenic and the like to be vulcanized to generate precipitates; filtering the adjusted solution in a filter press to obtain a filter cake, and performing centralized treatment;
d. adding carbide slag into the filtrate obtained after filtering by the filter press in the step c to adjust the pH value of the filtrate to 7.4, feeding the obtained mixed solution into a thickener, feeding the supernatant of the thickener into a next process, feeding the underflow of the thickener into a centrifugal machine for separation to obtain gypsum powder with the water content of 14.0%, and returning the filtrate of the centrifugal machine to the thickener for recycling;
e. d, adding 400ppm of nano iron into the supernatant obtained in the step d, completing mud-water separation of the obtained mixed solution in an inclined plate sedimentation tank, and performing centralized treatment after filter pressing of bottom mud; the clear liquid comprises the following main components: the pH value is 7.0, the copper ions are 0.05mg/L, the arsenic ions are 0.06mg/L, the cadmium ions are 0.008mg/L, and the lead ions are 0.016mg/L, so that the special discharge requirement of the discharge standard of industrial pollutants of lead and zinc is met, and the discharge reaches the standard.
Example 4:
the waste acid of a certain copper smelting plant is taken as a treatment object, and the concentration of each main component is as follows: 22.7 percent (mass percentage concentration) of sulfuric acid, 5711.6mg/L of copper ions, 18232.4mg/L of arsenic ions, 301.8mg/L of cadmium ions and 10.9mg/L of lead ions.
The method for processing the waste acid from the nonferrous smelting by using the technical scheme of the invention comprises the following detailed steps:
a. firstly, pumping the waste acid into a membrane filter by a pump for filtering (the mesh number of a filtering membrane of the membrane filter is 400 meshes), obtaining lead sulfate filter residue after filtering, obtaining a filter cake containing 64.2 percent (calculated by a dry basis) of lead sulfate after filtering the lead sulfate filter residue by a plate-and-frame filter press, and smelting the lead sulfate filter cake in a lead smelting system;
b. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtration by the membrane filter in the step a, controlling the ORP value of the solution to be 27mv, so that copper in the filtrate is sulfurized to generate copper sulfide precipitate, then, filtering the solution in a filter press to obtain a filter cake containing 26.9% of copper sulfide (calculated by dry basis), and smelting the filter cake in a copper smelting system;
c. b, adding a sodium sulfide solution with the mass percentage concentration of 10% into the filtrate obtained after filtering by the filter press in the step b, and controlling the ORP value to be-15 mv to enable heavy metals such as arsenic and the like to be vulcanized to generate precipitates; the adjusted solution enters a filter press for filtration, and the obtained filter cake is treated in a centralized way;
d. adding carbide slag into the filtrate obtained after filtering by the filter press in the step c to adjust the pH value of the filtrate to 7.1, feeding the obtained mixed solution into a thickener, feeding the supernatant of the thickener into a next process, feeding the underflow of the thickener into a centrifugal machine for separation to obtain gypsum powder with the water content of 13.7%, and returning the filtrate of the centrifugal machine to the thickener for recycling;
e. d, adding 250ppm of nano iron into the supernatant obtained in the step d, completing mud-water separation of the obtained mixed solution in an inclined plate sedimentation tank, and performing centralized treatment after filter pressing of the bottom mud; the clear liquid comprises the following main components: the pH value is 7.0, copper ions are 0.04mg/L, arsenic ions are 0.07mg/L, cadmium ions are 0.001mg/L, and lead ions are 0.015mg/L, so that the special emission requirements of the emission standard of industrial pollutants of lead and zinc are met, and the emission reaches the standard.
Claims (2)
1. The method for treating the nonferrous smelting waste acid is characterized by comprising the following steps:
a. firstly, filtering non-ferrous smelting waste acid by using a membrane filter to obtain lead sulfate filter residue, and recovering lead sulfate in the lead sulfate filter residue;
the filtering membrane mesh number of the membrane filter is 100-500 meshes; the mass percentage of lead in the lead sulfate filter residue is 50-70%;
b. b, adding a vulcanizing agent into the filtrate obtained after filtration in the step a, controlling an ORP value to be 10-50 mv, so that copper in the filtrate is vulcanized to generate copper sulfide precipitate, and recovering copper resources after filtration;
the vulcanizing agent is sodium sulfide, sodium hydrosulfide or hydrogen sulfide; the mass percentage of copper contained in the obtained copper sulfide precipitate is 20-28% on a dry basis;
c. b, adding a vulcanizing agent into the filtrate obtained after filtration in the step b again, and controlling the ORP value to be-20-0 mv to vulcanize heavy metals such as arsenic and the like to generate precipitates for removal;
the vulcanizing agent is sodium sulfide, sodium hydrosulfide or hydrogen sulfide;
d. adding carbide slag into the filtrate obtained in the step c to adjust the pH value of the filtrate to 7-8 to prepare gypsum, and dehydrating the prepared gypsum by adopting a centrifugal machine to obtain dehydrated gypsum;
the water content in the obtained dehydrated gypsum is reduced to be less than or equal to 15 percent; on a dry basis, the obtained dehydrated gypsum contains 40-60% of calcium sulfate by mass;
e. d, carrying out advanced treatment on the sewage obtained in the step d, and discharging or recycling the sewage up to the standard;
the specific process of the advanced treatment comprises the following steps: adding nano iron into the obtained sewage, wherein the adding amount of the nano iron is 200-500 ppm, filtering after adding the nano iron, and discharging or recycling the obtained supernatant after reaching the standard.
2. The method for treating the nonferrous smelting waste acid according to claim 1, wherein: the non-ferrous smelting waste acid in the step a is at least one of heavy metal-containing acidic wastewater obtained by washing and purifying flue gas in the acid making process by smelting flue gas, treatment wastewater mixed with flue gas and discharge water of an electrolysis system.
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| CN112062250A (en) * | 2020-08-14 | 2020-12-11 | 昆明铂锐金属材料有限公司 | Method for treating non-ferrous smelting wastewater by using phosphogypsum reduction product |
| CN113233646A (en) * | 2021-05-17 | 2021-08-10 | 紫金铜业有限公司 | Treatment process of high-concentration arsenic-containing waste acid |
| CN115259441A (en) * | 2022-07-05 | 2022-11-01 | 铜陵有色金属集团股份有限公司 | Process for removing arsenic from waste acid |
| CN114956390A (en) * | 2022-07-06 | 2022-08-30 | 河南省冶金研究所有限责任公司 | Method for removing heavy metal waste acid and reducing red mud solid waste grade by comprehensively utilizing lead smelting |
| CN115849641B (en) * | 2023-02-20 | 2023-05-02 | 山东恒邦冶炼股份有限公司 | Equipment and method for vulcanizing waste acid |
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| CN105567984A (en) * | 2016-01-18 | 2016-05-11 | 中南大学 | Method for potential controlled selection separation of copper refinery ash |
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