CN108754148B - Treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel - Google Patents
Treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel Download PDFInfo
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Abstract
The invention discloses a treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel, which adopts sulfuric acid reduction leaching, extraction-electrowinning copper extraction, neutralization impurity removal, vulcanization cobalt precipitation and carbonization manganese precipitation, and solution evaporation crystallization, can maximally extract and recycle valuable metals in the solid waste residues, has simple process flow, convenient operation and low disposal cost, is an economic, low-consumption, high-recovery rate, and cyclic utilization treatment process for smelting heavy metal solid waste residues containing copper, manganese, cobalt and the like, achieves the aims of maximally saving resources and reducing production and operation costs, realizes the national principle of 'reduction, reutilization and resource' in waste disposal, maximally comprehensively utilizes the heavy metal solid waste residues containing copper, manganese, cobalt and the like, and basically achieves 'dry complete squeezing'; the reduction of waste is realized, the zero emission of the waste is greatly promoted, and the final disposal quantity of the waste is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of treatment of waste residues containing heavy metals, and particularly relates to a treatment method for recycling copper, manganese, cobalt, zinc and nickel containing heavy metal waste residues.
Background
At present, industrial production in China is rapidly developed in the early stage, so that industrial solid wastes generated are rapidly increased, if the wastes cannot be effectively treated, the environment is polluted, a large-area storage yard is needed, and resources are wasted. Therefore, from the viewpoint of slowing down resource exhaustion and resource reuse, hazardous industrial solid wastes containing multiple metals such as copper, manganese, cobalt, zinc and the like belong to metal resources that can be developed and utilized. In recent 10 years, the non-ferrous metal smelting industry in China is rapidly developed, the yield of 10 non-ferrous metals is continuously 11 years and is the first in the world, wherein the yield of heavy metals such as copper, lead, zinc and the like is ten million tons; the production and discharge amount of the heavy metal smelting waste slag is increased year by year, and the current annual production amount is over ten million tons and the annual stock quantity is hundreds of millions of tons. The stockpiled heavy metal smelting solid waste not only occupies land, but also contains heavy metals and toxic elements with high mobility, such As As, Cd, Cr, Cu, Ni, Pb, Zn and the like, thereby causing great pollution and potential threat to the environment and being one of the main forms of heavy metal polluted environment.
Aiming at the characteristics of more, more and more heavy metal waste residues and impurities, the method selects a plurality of typical heavy metal solid wastes generated in the non-ferrous smelting process as treatment objects, develops the heavy metal smelting solid waste stabilization treatment research, develops the lead-zinc smelting waste water neutralization residue and zinc dipping residue hydrothermal vulcanization stabilization treatment technology, the arsenic-containing ash and zinc smelting volatile kiln residue mechanical chemical stabilization treatment technology, the waste acid system residue sulfur fixation treatment technology and the high arsenic ash hot pressing melting solidification treatment technology, and provides new ideas and references for the further research of the heavy metal smelting solid waste harmless safety treatment technology. Waste water neutralization slag and zinc dipping slag generated by lead-zinc smelting are subjected to hydrothermal vulcanization stabilization treatment, the stabilization transformation of heavy metal forms is realized in the hydrothermal process, the leaching concentration of heavy metals in the waste slag after treatment is greatly reduced, and the national control standard is met; the arsenic-containing soot and zinc smelting volatilizing kiln slag are subjected to mechanical chemical stabilization treatment, and a self-propagating reaction induced by mechanical force is carried out, so that the stable transformation of the form of heavy metal in the waste slag is realized; the waste acid system slag is fixed by sulfur, so that the physical wrapping and chemical form stabilization transformation of heavy metal are realized, a solidified body has long-term stability, the compressive strength reaches 21.9MPa, and the solidified body can be used as a sulfur building material for resource utilization; the high-arsenic soot is subjected to hot-pressing melting solidification treatment, so that the high-efficiency immobilization of arsenic in the soot can be realized at a lower solidification temperature, and a solidified body is compact and glossy and can be prepared into a crystal product. The research results provide a new approach for the stable and safe treatment and disposal of the heavy metal smelting waste residues, provide reference for the safe treatment and disposal of dangerous wastes generated in the nonferrous smelting industry, and ensure the sustainable development of the nonferrous smelting industry.
The waste slag containing heavy metals such as copper, manganese, cobalt and the like is generated from waste slag after purification and impurity removal in the nonferrous smelting industry, and the sludge containing the heavy metals has the characteristics of easy accumulation, instability, easy loss and the like, and can cause serious environmental pollution if not properly treated. Although the waste residues containing copper, manganese and cobalt belong to dangerous industrial solid wastes, the copper-containing grade of the waste residues after drying treatment is generally between 8 and 13 percent, and the waste residues also contain rare and non-ferrous metals such as copper, manganese, cobalt, zinc and the like.
At present, in the treatment process of hazardous industrial solid waste containing heavy metals, the common treatment methods mainly comprise three treatment processes of safe landfill, pyrogenic treatment, wet treatment and the like, wherein: 1. the safe landfill method not only occupies the land to cause the waste of resources, but also leaves huge hidden troubles of environmental pollution for the offspring; 2. although the existing pyrogenic process treatment process has the advantages of concentrated large-scale treatment of different dangerous solid waste varieties to generate harmless slag and short flow, the following 3 problems exist: the flue gas pollution is large, the energy consumption is high, the recovery rate of valuable metals is low, and the resource is not favorably utilized to the maximum extent; the wet treatment process needs to adopt different wet treatment processes according to different dangerous solid waste varieties, so that the centralized cooperative treatment of large batch and multiple varieties is difficult to achieve, and the waste water and waste residues generated in the production process still belong to dangerous wastes, so that the harmless effects of pollution control without waste production and waste utilization without waste production cannot be achieved.
The patent application with the publication number of CN102230086A discloses a method for simultaneously leaching cobalt and nickel from heavy metal sulfide slag removed by a manganese ore leaching process, belonging to the technical field of cobalt and nickel recovery. The method comprises the following basic steps: adding sulfide slag into a reactor, then adding a mixed acid solution of nitric acid and sulfuric acid, and regulating the liquid-solid ratio of ore pulp to be 2: 1-7: 1 by using water; the reaction leaching solution is obtained after the stirring reaction is carried out for 20-120 minutes at the temperature of 45-100 ℃, the leaching rate of cobalt and nickel exceeds 90%, but the method only aims at recovering cobalt and nickel, the recycling rate is low, and no related technology can simultaneously recover rare and non-ferrous metals such as copper, manganese, cobalt, zinc and the like from heavy metal waste residues at present.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel, which is economical, low in consumption and high in recovery rate, aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel is completed according to the following working procedures: acid leaching → extraction-electrodeposition → neutralization → cobalt sulfide precipitation → manganese precipitation-evaporation.
Preferably, the acid leaching step is as follows:
firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to the liquid-solid ratio of 2-4:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.0-1.2 times, and then mixing the heavy metal-containing raw material residue with the sulfuric acid according to the molar ratio of oxidized metal element content in the heavy metal residue being 1: 1 adding a reducing agent, controlling the pH value of the solution to be constant at 1.5-2.0, namely a reaction end point, performing pressure filtration separation on leached slurry by using a plate-and-frame filter press, washing filter cake slag by using water for additional use, returning the washing water to a leaching burdening section for recycling, blending and diluting filtrate after copper extraction by using raffinate until the concentration of copper ions is 10-12g/L, and sending the filtrate to an extraction-electrodeposition process.
Further preferably, the reducing agent in the acid leaching process is one or a mixture of ammonium sulfite, ammonium bisulfite, ammonium metabisulfite and oxalic acid.
More preferably, the reaction temperature in the acid leaching process is controlled to be 70-80 ℃, and the reaction time is 1.5-2.5 h.
Preferably, the extraction-electrodeposition step is as follows:
after the acid leaching process, sending the qualified filtrate prepared by raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, the extractant is a hydroximic extractant, raffinate returns to leaching ingredients and is prepared with an extraction stock solution, the extraction cycle is 2-5 times, and when the copper sulfate content is more than or equal to 45g/L, the raffinate is sent to an electrodeposition working section for producing an electrodeposition copper plate.
Further preferably, in the copper extraction process: the content of Cu extracted from the stock solution is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of washing water is 4-6g/L, the acidity of back extraction acid is 190g/L,
more preferably, the extractant is Lix 984N.
Preferably, the neutralization step is as follows:
removing impurities from the extraction residual liquid after the extraction-electrodeposition process to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 25-35 minutes, slowly and uniformly adding lime under stirring to adjust the pH value to 3.5-4.0, controlling the temperature to be 55-65 ℃, reacting for 1.5-2.5 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cake slag with water, and using the filter cake slag for later use.
Preferably, the cobalt sulfide precipitation step is as follows:
and (3) delivering the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding a sodium sulfide solution with the mass concentration of 18-22% in advance in a spraying manner according to 1.2-1.4 times of the molar weight ratio under the stirring state, controlling the temperature at 70-80 ℃, the pH at 4.4-5.4, reacting for 0.5-2 hours, performing solid-liquid separation by using a plate and frame filter press, washing filter cake slag by using fresh water, metering and packaging, and delivering the filtrate to a manganese precipitation-evaporation process for recycling manganese.
Preferably, the manganese precipitation-evaporation process comprises the following steps:
recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight 0.8-1.5 times of that of the manganese ion content according to the manganese ion content in the solution under the stirring state, controlling the temperature at 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the manganese content in the solution is less than or equal to 2mg/L, conveying the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning evaporation condensate water to the system for recycling.
The invention has the beneficial effects that:
the treatment method for recycling heavy metal waste residues adopts sulfuric acid reduction leaching, extraction-electrodeposition copper extraction, neutralization impurity removal, vulcanization cobalt precipitation and carbonization manganese precipitation, and the solution is evaporated and crystallized, so that valuable metals in the solid waste residues can be maximally extracted, recycled and utilized, the method has the advantages of simple process flow, convenient operation, low disposal cost, economy, low consumption and high recovery rate, can recycle the process of the heavy metal solid waste residues containing copper, manganese, cobalt and the like, achieves the purposes of maximally saving resources and reducing the production operation cost, realizes the national principle of waste disposal reduction, reutilization and recycling, maximally comprehensively utilizes the heavy metal solid waste residues containing copper, manganese, cobalt and the like, and basically achieves 'dry extraction to the greatest extent'; the reduction of waste is realized, the zero emission of the waste is greatly promoted, and the final disposal quantity of the waste is greatly reduced.
According to the treatment method for recycling the heavy metal waste residues, the cobalt and manganese are separated by precipitation, the amount of water introduced into the system is small, and the water is returned to the leaching process for recycling, so that zero discharge of water can be realized, the cost is reduced, the resources are saved, the resources are really recycled, the energy is saved, the emission is reduced, and the environment is protected.
Drawings
FIG. 1 shows a process flow for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel.
Detailed Description
The following are specific examples of the present disclosure, which are used to illustrate technical solutions to be solved in the present disclosure and help those skilled in the art understand the present disclosure, but the present disclosure is not limited to these examples.
Example 1 treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel
The method comprises the following steps of (1) processing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel according to the following procedures: acid leaching → extraction-electrodeposition → neutralization → cobalt sulfide precipitation → manganese precipitation-evaporation.
Example 2 method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel
The method comprises the following steps of (1) processing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel according to the following procedures:
⑴ pickling step
Firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to the liquid-solid ratio of 2:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.0 time, and then adding the heavy metal residue with the oxidized metal element content being 1: 1, adding ammonium sulfite, controlling the reaction temperature at 70-80 ℃, reacting for 1.5h, controlling the pH value of the solution to be 1.5-2.0 to be constant to be a reaction end point, pressurizing, filtering and separating the leached slurry by a plate-and-frame filter press, washing filter cake slag by water for use, returning washing water to a leaching batching section for recycling, blending and diluting the filtrate by raffinate after copper extraction until the concentration of copper ions is 10-12g/L, and sending to an extraction-electrodeposition process.
⑵ extraction-electrodeposition step
After the acid leaching process, sending filtrate qualified by blending extraction raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, each tail end is provided with a clarifying tank, an extractant adopts Lix984N, raffinate returns to leach ingredients and blend extraction stock solution, and in the copper extraction process: the content of Cu extracted from the stock solution is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of washing water is 6g/L, the acidity of back extraction acid is 170g/L, the extraction cycle is 2 times, and when the content of copper sulfate is more than or equal to 45g/L, the copper plate is sent to an electrodeposition working section to produce an electrodeposition copper plate.
⑶ neutralization step
And (3) removing impurities from the extraction residual liquid after the extraction-electrodeposition process is finished to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 25 minutes, slowly and uniformly adding lime under a stirring state to adjust the pH value to 3.5-4.0, controlling the temperature at 55 ℃, reacting for 1.5 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cake slag with water, and using the filter cake slag for later use, wherein the filtrate is reserved.
⑷ sulfurizing and cobalt-precipitating process
And (3) delivering the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding a sodium sulfide solution with the mass concentration of 18% in advance in a spraying manner according to 1.2 times of the molar weight under the stirring state, controlling the temperature at 70-80 ℃, controlling the pH within the range of 4.4-5.4, reacting for 0.5 hour, performing solid-liquid separation by a plate-and-frame filter press, washing filter cake slag with fresh water, metering and packaging, and delivering the filtrate to a manganese precipitation-evaporation process for recycling manganese.
⑸ precipitation of manganese
Recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight 0.8 time of that of manganese ions in the solution under the stirring state, controlling the temperature at 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the manganese content in the solution is less than or equal to 2mg/L, delivering the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning the evaporation condensate water to the system for recycling.
Example 3 treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel
The method comprises the following steps of (1) processing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel according to the following procedures:
⑴ pickling step
Firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to a liquid-solid ratio of 4:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.2 times, and then adding the heavy metal residue with the molar ratio of oxidized metal element content being 1: 1, adding ammonium bisulfite, controlling the reaction temperature at 70-80 ℃, reacting for 2.5h, controlling the pH value of the solution to be 1.5-2.0 to be constant to be a reaction end point, performing pressure filtration and separation on the leached slurry by a plate-and-frame filter press, washing filter cake slag by water for use, returning the washing water to a leaching batching section for recycling, and blending and diluting the filtrate by raffinate after copper extraction until the concentration of copper ions is 10-12g/L, and sending to an extraction-electrodeposition process.
⑵ extraction-electrodeposition step
After the acid leaching process, sending filtrate qualified by blending raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, each tail end is provided with a clarifying tank, an extractant adopts Lix984N, the raffinate returns to leach ingredients and is blended with an extraction stock solution, and in the copper extraction process: the content of Cu extracted from the stock solution is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of washing water is 4g/L, the acidity of back extraction acid is 190g/L, the extraction cycle is 5 times, and when the content of copper sulfate is more than or equal to 45g/L, the copper plate is sent to an electrodeposition working section to produce an electrodeposition copper plate.
⑶ neutralization step
And (3) removing impurities from the extraction residual liquid after the extraction-electrodeposition process is finished to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 35 minutes, slowly and uniformly adding lime under a stirring state to adjust the pH value to 3.5-4.0, controlling the temperature at 65 ℃, reacting for 2.5 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cake slag with water, and using the filter cake slag for later use, wherein the filtrate is reserved.
⑷ sulfurizing and cobalt-precipitating process
And (3) delivering the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding a sodium sulfide solution with the mass concentration of 22% in advance in a spraying manner according to 1.4 times of the molar weight under the stirring state, controlling the temperature at 70-80 ℃, controlling the pH within the range of 4.4-5.4, reacting for 2 hours, performing solid-liquid separation by using a plate-and-frame filter press, washing filter cake slag with fresh water, metering and packaging, and delivering the filtrate to a manganese precipitation-evaporation process for recycling manganese.
⑸ precipitation of manganese
Recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight being 1.5 times of that of manganese ions in the solution under the stirring state, controlling the temperature to be 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the manganese content in the solution is less than or equal to 2mg/L, delivering the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning evaporation condensate water to the system for recycling.
Example 4 method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel
The method comprises the following steps of (1) processing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel according to the following procedures:
⑴ pickling step
Firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to the liquid-solid ratio of 3:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.1 times, and then adding the heavy metal residue with the oxidized metal element content being 1: 1, adding ammonium sulfite, controlling the reaction temperature at 70-80 ℃, reacting for 2 hours, controlling the pH value of the solution to be 1.5-2.0 to be constant to be a reaction end point, performing pressure filtration and separation on the leached slurry by a plate-and-frame filter press, washing filter cake slag by water for use, returning the washing water to a leaching batching section for recycling, and blending and diluting the filtrate after copper extraction by raffinate until the concentration of copper ions is 10-12g/L, and sending to an extraction-electrodeposition process.
⑵ extraction-electrodeposition step
After the acid leaching process, sending filtrate qualified by blending extraction raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, each tail end is provided with a clarifying tank, an extractant adopts Lix984N, raffinate returns to leach ingredients and blend extraction stock solution, and in the copper extraction process: the content of Cu extracted from the stock solution is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of washing water is 5g/L, the acidity of back extraction acid is 180g/L, the extraction cycle is carried out for 3 times, and when the content of copper sulfate is more than or equal to 45g/L, the copper plate is sent to an electrodeposition working section to produce an electrodeposition copper plate.
⑶ neutralization step
And (3) after the extraction-electrodeposition process is finished, removing impurities from the raffinate to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 30 minutes, slowly and uniformly adding lime under a stirring state to adjust the pH value to 3.5-4.0, controlling the temperature at 60 ℃, reacting for 2 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cakes with water, and using the filter cakes for later use, wherein the filtrate is used for later use.
⑷ sulfurizing and cobalt-precipitating process
And (3) delivering the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding a sodium sulfide solution with the mass concentration of 20% in advance in a spraying manner according to 1.3 times of the molar weight under the stirring state, controlling the temperature at 70-80 ℃, controlling the pH within the range of 4.4-5.4, reacting for 1 hour, performing solid-liquid separation by using a plate-and-frame filter press, washing filter cake slag with fresh water, metering and packaging, and delivering the filtrate to a manganese precipitation-evaporation process for recycling manganese.
⑸ precipitation of manganese
Recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight being 1.1 times of that of manganese ions in the solution under the stirring state, controlling the temperature to be 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the manganese content in the solution is less than or equal to 2mg/L, delivering the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning evaporation condensate water to the system for recycling.
Example 5 Recycling test of heavy metal waste residue containing copper, manganese, cobalt, zinc and nickel
The method comprises the following steps of (1) processing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel according to the following procedures:
⑴ pickling step
The working procedure is mainly to add acid to leach valuable heavy metals in the waste residue to the maximum, and because cobalt and manganese in the waste residue exist in a high-price form, a proper amount of reducing agent is added in the leaching process to greatly improve the leaching rate of each metal.
Raw material analysis: the main chemical element composition of the heavy metal-containing waste residue (see table 1 below).
TABLE 1 copper manganese slag analysis data
Firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to the liquid-solid ratio of 3:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.1 times, and then adding the heavy metal residue with the oxidized metal element content being 1: 1, adding ammonium sulfite, controlling the reaction temperature at 70-80 ℃, reacting for 2 hours, controlling the pH value of the solution to be 1.5-2.0 to be constant to be a reaction end point, performing pressure filtration and separation on the leached slurry by a plate-and-frame filter press, washing filter cake slag by water for use, returning the washing water to a leaching batching section for recycling, and blending and diluting the filtrate after copper extraction by raffinate until the concentration of copper ions is 10-12g/L, and sending to an extraction-electrodeposition process.
Leaching analysis data (see tables 2 and 3 below)
Table 2 leach filtrate analysis data
TABLE 3 analysis of filter cake slag
The process adopts sulfuric acid reduction leaching, adopts ammonium sulfite as a reducing agent, can greatly reduce high-valence metal ions in waste residues, improves the leaching rate, and can directly evaporate, crystallize and recover the ammonium sulfite in the form of ammonium sulfate after the ammonium sulfite reacts, thereby avoiding secondary pollution to the whole system; the leaching rate of copper in the leaching process can reach more than 98 percent, the leaching rate of manganese can reach 98 percent, the recovery rate of cobalt can reach more than 96 percent, the slag amount is 10-15 percent, metal ions in the waste slag can be greatly leached, and the content of heavy metal in the leached slag can be reduced to be less than 0.5.
⑵ extraction-electrodeposition step
After the acid leaching process, sending filtrate qualified by blending extraction raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, each tail end is provided with a clarifying tank, an extractant adopts Lix984N, raffinate returns to leach ingredients and blend extraction stock solution, and in the copper extraction process: the content of Cu extracted from the stock solution is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of washing water is 5g/L, the acidity of back extraction acid is 180g/L, the extraction cycle is carried out for 3 times, and when the content of copper sulfate is more than or equal to 45g/L, the copper plate is sent to an electrodeposition working section to produce an electrodeposition copper plate.
The extraction system in the process adopts three extractions, two back extractions, two washes and a clarifying tank arranged at each tail end, so that a better phase splitting effect can be achieved, and the extraction process is controlled as follows: the Cu content of the stock solution is as follows: 10-12g/L, the temperature is controlled to be 25-40 ℃, the acidity of washing water is 5g/L, the acidity of back extraction acid is 180g/L, and raffinate returns to leaching ingredients and blending extraction stock solution, and the cycle is carried out for 3 times, so that the consumption of new water in the whole process can be reduced, the enrichment of manganese and cobalt can be achieved, the cost for next cobalt-manganese separation, recovery and disposal can be reduced, and the overall economic benefit can be improved. After the raffinate is circularly enriched in the leaching section, the manganese can reach 80-120 g/L and the cobalt can reach 9-15 g/L, and the copper sulfate content is more than or equal to 45g/L, and the raffinate is sent to an electrodeposition working section to produce an electrodeposition copper plate.
⑶ neutralization step
And (3) removing impurities from the extraction residual liquid after the extraction-electrodeposition process is finished to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 30 minutes, slowly and uniformly adding lime under a stirring state to adjust the pH value to 3.5-4.0, controlling the temperature at 60 ℃, reacting for 2 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cake slag with water, and using the filter cake slag for later use, wherein the filtrate is used for later use.
When manganese in the raffinate is enriched to more than 80g/L after the raffinate is recycled for three times, the raffinate is sent to a neutralization section for impurity removal before cobalt and manganese separation. The ferrous iron in the waste water is oxidized to the trivalent iron by aeration oxidation for 30 minutes (compressed air is directly blown). The detection shows that the loss of manganese is about 5 percent in the neutralization process, and the loss of cobalt is less than 1 percent. The neutralization slag analysis data are shown in table 4.
TABLE 4 neutralization slag analysis data
⑷ sulfurizing and cobalt-precipitating process
And (3) delivering the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding a sodium sulfide solution with the mass concentration of 20% in advance in a spraying manner according to 1.3 times of the molar weight under the stirring state, controlling the temperature at 70-80 ℃, controlling the pH within the range of 4.4-5.4, reacting for 1 hour, performing solid-liquid separation by using a plate-and-frame filter press, washing filter cake slag with fresh water, metering and packaging, and delivering the filtrate to a manganese precipitation-evaporation process for recycling manganese. The analysis data of the sulphided slag are shown in Table 5.
TABLE 5 analysis of the sulfidizing slags
The method for separating cobalt and manganese ions by a sulfide precipitation method is based on the fact that the solubility products of heavy metal sulfides are different, metal ions are separated by a vulcanizing agent under certain conditions, and the characteristic of the material that manganese is high and cobalt is low is considered. The loss of manganese is about 4-6% in the process of cobalt deposition by sulfuration, and the recovery of cobalt can reach more than 95%.
⑸ precipitation of manganese
Recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight of 1.1 times according to the content of manganese ions in the solution under the stirring state, controlling the temperature to be 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the content of manganese in the solution is less than or equal to 2mg/L, sending the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning evaporation condensate water to the system for recycling. The manganese carbonate analytical data are shown in Table 6.
TABLE 6 manganese carbonate analytical data
Claims (4)
1. A treatment method for recycling heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel is completed according to the following working procedures: acid leaching → extraction-electrodeposition → neutralization → cobalt sulfide precipitation → manganese precipitation-evaporation;
the acid leaching process comprises the following steps: firstly slurrying and washing heavy metal waste residue materials containing copper, manganese, cobalt, zinc and nickel by using water, metering the pretreated heavy metal-containing raw material residue, adding water according to the liquid-solid ratio of 2-4:1, starting stirring and slurrying, slowly adding 98% sulfuric acid with the molar ratio of metal element content in the heavy metal residue being 1.0-1.2 times, and then according to experimental data, according to the molar ratio of oxidized metal element content in the heavy metal residue being 1: 1 adding a reducing agent, controlling the pH value of the solution to be constant at 1.5-2.0, namely a reaction end point, performing pressure filtration separation on leached slurry through a plate-and-frame filter press, washing filter cake slag with water for use, returning the washing water to a leaching burdening section for recycling, blending and diluting filtrate after copper extraction with raffinate until the concentration of copper ions is 10-12g/L, and sending the filtrate to an extraction-electrodeposition process;
wherein, the reducing agent in the acid leaching process is one or a mixture of ammonium sulfite, ammonium bisulfite, ammonium metabisulfite and oxalic acid;
the extraction-electrodeposition process is as follows: after the acid leaching process, sending the qualified filtrate prepared by raffinate to an extraction system for copper extraction separation, wherein the extraction system adopts three extractions, two back extractions and two washes, the extractant is a hydroximic extractant, raffinate returns to leaching ingredients and is prepared with an extraction stock solution, the extraction cycle is 2-5 times, and the raffinate is sent to an electrodeposition working section for producing an electrodeposition copper plate when the copper sulfate content is more than or equal to 45 g/L;
the neutralization process comprises the following steps: removing impurities from the extraction residual liquid after the extraction-electrodeposition process is carried out to a neutralization section before cobalt and manganese separation, carrying out aeration oxidation for 25-35 minutes, slowly and uniformly adding lime under stirring to adjust the pH value to 3.5-4.0, controlling the temperature to 55-65 ℃, reacting for 1.5-2.5 hours, carrying out solid-liquid separation after the pH value is not changed, washing filter cake slag with water for use, and reserving filtrate;
the cobalt sulfide precipitation process comprises the following steps: sending the filtrate obtained by the neutralization process to a vulcanization process for cobalt separation and extraction, slowly and uniformly adding sodium sulfide solution with the mass concentration of 18-22% in advance in a spraying mode according to 1.2-1.4 times of the molar weight under the stirring state, controlling the temperature at 70-80 ℃, controlling the pH within the range of 4.4-5.4, reacting for 0.5-2 hours, then carrying out solid-liquid separation by a plate and frame filter press, washing filter cake slag by fresh water, metering and packaging, and sending the filtrate to a manganese precipitation-evaporation process for recycling manganese;
the manganese precipitation-evaporation process comprises the following steps: recovering manganese from the filtrate after the cobalt sulfide precipitation process, slowly and uniformly adding ammonium bicarbonate with the molar weight 0.8-1.5 times of that of manganese ions in the solution under the stirring state, controlling the temperature at 45-55 ℃, performing solid-liquid separation by a plate-and-frame filter press when the manganese content in the solution is less than or equal to 2mg/L, sending the filtrate to an evaporation system, performing evaporation crystallization to recover ammonium sulfate, and returning evaporation condensate water to the system for recycling.
2. The method for recycling the waste residues of heavy metals containing copper, manganese, cobalt, zinc and nickel according to claim 1, characterized in that the reaction temperature in the acid leaching process is controlled at 70-80 ℃ and the reaction time is 1.5-2.5 h.
3. The method for recycling and treating the heavy metal waste residues containing copper, manganese, cobalt, zinc and nickel according to claim 1, wherein in the copper extraction process: the Cu content of the raw solution extraction is 10-12g/L, the temperature is controlled between 25-40 ℃, the acidity of the washing water is 4-6g/L, and the acidity of the back extraction acid is 190 g/L.
4. The method for recycling the waste residues of heavy metals containing copper, manganese, cobalt, zinc and nickel according to claim 1, wherein the extractant is Lix 984N.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| CN105256141A (en) * | 2015-10-26 | 2016-01-20 | 广西银亿再生资源有限公司 | Electroplating-sludge resourceful treatment and comprehensive recycling method |
-
2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021331A (en) * | 2010-12-11 | 2011-04-20 | 付春平 | Processing method for comprehensively recovering high manganese asbolite |
| CN105256141A (en) * | 2015-10-26 | 2016-01-20 | 广西银亿再生资源有限公司 | Electroplating-sludge resourceful treatment and comprehensive recycling method |
| CN105256141B (en) * | 2015-10-26 | 2017-12-19 | 广西银亿再生资源有限公司 | A kind of electric plating sludge resource processing and the method for comprehensive reutilization |
Non-Patent Citations (1)
| Title |
|---|
| 巴甲矿业公司埃尔波利奥项目铜、钻、锌、锰回收的湿法冶金处理;李卫民;《国外工程技术》;20091031(第5期);第1-10、22页 * |
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