CN111004921A - Method for recovering copper in scrap copper smelting slag - Google Patents
Method for recovering copper in scrap copper smelting slag Download PDFInfo
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- CN111004921A CN111004921A CN201911368649.8A CN201911368649A CN111004921A CN 111004921 A CN111004921 A CN 111004921A CN 201911368649 A CN201911368649 A CN 201911368649A CN 111004921 A CN111004921 A CN 111004921A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/18—Extraction of metal compounds from ores or concentrates by wet processes with the aid of microorganisms or enzymes, e.g. bacteria or algae
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- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
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Abstract
The invention provides a method for recovering copper in scrap copper smelting slag. The method comprises the steps of pretreating the scrap copper smelting slag to obtain fine grinding smelting slag with the material with the particle size of less than 0.074mm accounting for 70-90 wt%, inoculating specific mixed strains into specific inorganic solution for culturing to obtain a special bacterial culture solution, performing biological leaching treatment on the pretreated fine grinding smelting slag by using the bacterial culture solution, sequentially performing solvent extraction and back extraction, performing electro-deposited copper treatment, and recovering to obtain copper. The method can effectively improve the recovery rate of copper, and has the advantages of simple treatment process, mild conditions and environmental friendliness.
Description
Technical Field
The invention relates to the technical field of metal materials, in particular to a method for recovering copper in scrap copper smelting slag.
Background
Copper is a strategic resource, has excellent electrical conductivity, good thermal conductivity and corrosion resistance, and is widely used in the industries of electric power, traffic, buildings and the like. China is the largest copper consuming country in the world and accounts for about 50% of the copper consumption in the world. In 2018, the consumption of copper in China is up to 1305 ten thousand tons, and contradictory to the consumption, the metal amount and refined copper of copper concentrate in China in the same year are only 151 ten thousand tons and 904 ten thousand tons, and gaps are huge. Therefore, the situation of copper recycling is particularly urgent in China.
The smelting regeneration scale of the scrap copper is more than 300 million tons every year in China, and more than 30 million tons of scrap copper smelting slag can be generated in the smelting process. The scrap copper smelting slag comprises a copper-containing material (10-20%), a zinc-containing material (15-35%), a metallic ferrotitanium material, other ash components and the like. At present, the smelting slag is usually treated by a gravity separation process, and coarse-grained copper-containing metal materials in the slag are separated and recovered for returning to a furnace for use. The copper content in the reselected smelting slag is still as high as about 10 percent, which is far higher than the industrial grade of natural ore, and the method has high recovery value.
At present, the recovery processing method of scrap copper smelting slag comprises a pyrogenic dilution method, a mineral separation method and a leaching method. The pyrogenic process depletion method has the advantages of reduction and high metal recovery rate, but has high energy consumption and serious environmental pollution; the beneficiation method has the advantages of low cost and simple process flow, but has high requirements on physical property difference and low recovery rate; the leaching method has the advantages of low energy consumption, strong selectivity and no waste gas discharge, but has multiple working procedures, high acid and alkali consumption and high waste water treatment pressure. Therefore, the comprehensive utilization of scrap copper smelting slag is still an industrial problem.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for recovering copper from scrap copper smelting slag. The recovery method provided by the invention can improve the recovery rate of copper, and has the advantages of mild reaction, simple recovery process and environmental friendliness.
The invention provides a method for recovering copper in scrap copper smelting slag, which comprises the following steps:
a) screening scrap copper smelting slag by 2mm, and carrying out table treatment on the screened smelting slag with the particle size of less than 2mm to separate out metallic materials with the particle size of less than 2 mm; finely grinding the separated residual smelting slag tailings to obtain pretreated smelting slag;
the material with the grain diameter less than 0.074mm in the pretreated smelting slag accounts for 70-90 wt%;
b) inoculating mixed strains in an inorganic solution, and performing aerated culture to obtain a bacterial culture solution;
the inorganic solution is as follows: dissolving ammonium sulfate, potassium chloride, dipotassium hydrogen phosphate, calcium nitrate and ferrous sulfate in sulfuric acid solution to obtain mixed solution;
the mixed strain comprises: thiobacillus ferrooxidans, Thiobacillus thiooxidans and Microspirillum ferrooxidans;
c) mixing, leaching and filtering the pretreated smelting slag and the bacterial culture solution to obtain a copper-containing solution and smelting slag after copper removal;
d) extracting the copper-containing solution by using an extractant solution, and separating a water phase from an organic phase; carrying out back extraction on the organic phase by using a sulfuric acid aqueous solution to obtain a copper-containing aqueous phase;
the extractant is one or more of Lix984, Lix973, M5640 and N902;
e) carrying out electrodeposition copper treatment on the copper-containing water phase to obtain copper;
the step a) and the step b) are not limited in order.
Preferably, in the step b), the concentration of ammonium sulfate is 2-6 g/L, the concentration of potassium chloride is 0.1-0.2 g/L, the concentration of dipotassium hydrogen phosphate is 0.1-1 g/L, the concentration of calcium nitrate is 0.01-0.03 g/L, and the concentration of ferrous sulfate is 20-50 g/L; the concentration of the adopted sulfuric acid solution is 2-4 g/L, and the pH value is 1.5-2.0.
Preferably, in the step b), the ratio of the thiobacillus ferrooxidans to the thiobacillus thiooxidans to the microspirillum ferrooxidans in the mixed strains is 1 to (0-5), and the content of the thiobacillus thiooxidans to the microspirillum ferrooxidans is not 0.
Preferably, in the step b), the mass ratio of the mixed strain to the inorganic solution is 1 to (0-1000), and the using amount of the inorganic solution is not 0;
in the aeration culture process, the pH value is kept between 1.5 and 2.0, the air flow is 0.06 to 0.1L/L.h, the dissolved oxygen is 6 to 8mg/L, and the aeration culture time is 24 to 48 h.
Preferably, in the step c), the liquid-solid ratio of the bacteria culture solution to the pretreated smelting slag is (3-10) mL: 1 g.
Preferably, in the step c), the leaching conditions are as follows: the temperature is 25-35 ℃, and the mixture is leached for 6-72 hours at the stirring speed of 150-350 rpm.
Preferably, in the step d), the solvent of the extractant solution is one or more of kerosene and benzene;
the mass ratio of the extracting agent to the solvent is 1: 3-5.
Preferably, in the step d), the volume ratio of the extractant solution to the copper-containing solution is 1 to (1-2);
the concentration of the aqueous solution of sulfuric acid is 160-180 g/L;
the volume ratio of the organic phase to the aqueous solution of sulfuric acid is (3-5) to 1.
Preferably, in the step e), the current density of the electrodeposited copper is 180-220A/m3The temperature is 60-100 ℃.
Preferably, in the step a), before screening, washing treatment is further performed;
the washing treatment comprises: and mixing the scrap copper smelting slag with water until the mass concentration of the scrap copper smelting slag is 30-75%, and placing the mixture in an ore washer for washing for 5-20 min.
The invention provides a method for recovering copper in scrap copper smelting slag, which comprises the steps of pretreating the scrap copper smelting slag to obtain fine grinding smelting slag with the material particle size of less than 0.074mm accounting for 70-90 wt%, inoculating a specific mixed strain into a specific inorganic solution for culturing to obtain a special bacterial culture solution, performing biological leaching treatment on the pretreated fine grinding smelting slag by using the bacterial culture solution, then sequentially performing solvent extraction and back extraction, and finally performing electrodeposition copper treatment and recovering to obtain copper. The method can effectively improve the recovery rate of copper, and has the advantages of simple treatment process, mild conditions and environmental friendliness.
Detailed Description
The invention provides a method for recovering copper in scrap copper smelting slag, which comprises the following steps:
a) screening scrap copper smelting slag by 2mm, and carrying out table treatment on the screened smelting slag with the particle size of less than 2mm to separate out metallic materials with the particle size of less than 2 mm; finely grinding the separated residual smelting slag tailings to obtain pretreated smelting slag;
the material with the grain diameter less than 0.074mm in the pretreated smelting slag accounts for 70-90 wt%;
b) inoculating mixed strains in an inorganic solution, and performing aerated culture to obtain a bacterial culture solution;
the inorganic solution is as follows: dissolving ammonium sulfate, potassium chloride, dipotassium hydrogen phosphate, calcium nitrate and ferrous sulfate in sulfuric acid solution to obtain mixed solution;
the mixed strain comprises: thiobacillus ferrooxidans, Thiobacillus thiooxidans and Microspirillum ferrooxidans;
c) mixing, leaching and filtering the pretreated smelting slag and the bacterial culture solution to obtain a copper-containing solution and smelting slag after copper removal;
d) extracting the copper-containing solution by using an extractant solution, and separating a water phase from an organic phase; carrying out back extraction on the organic phase by using a sulfuric acid aqueous solution to obtain a copper-containing aqueous phase;
the extractant is one or more of Lix984, Lix973, M5640 and N902;
e) carrying out electrodeposition copper treatment on the copper-containing water phase to obtain copper;
the step a) and the step b) are not limited in order.
The method comprises the steps of pretreating the scrap copper smelting slag to obtain fine grinding smelting slag with the material with the particle size of less than 0.074mm accounting for 70-90 wt%, inoculating specific mixed strains into specific inorganic solution for culturing to obtain a special bacterial culture solution, performing biological leaching treatment on the pretreated fine grinding smelting slag by using the bacterial culture solution, sequentially performing solvent extraction and back extraction, performing electro-deposited copper treatment, and recovering to obtain copper. The method can effectively improve the recovery rate of copper, and has the advantages of simple treatment process, mild conditions and environmental friendliness.
According to the invention, the scrap copper smelting slag is screened by 2mm, the screened smelting slag with the particle size of less than 2mm is subjected to table shaking treatment, and the metallic material with the particle size of less than 2mm is separated; and finely grinding the separated residual smelting slag tailings to obtain finely ground smelting slag.
In the present invention, it is preferable to perform a washing treatment before the sieving. In the present invention, the washing treatment preferably includes: and mixing the scrap copper smelting slag with water until the mass concentration of the scrap copper smelting slag is 30-75%, and placing the mixture in an ore washer for washing for 5-20 min. Discharging the washed smelting slag, and performing subsequent treatment.
In the present invention, after the washing treatment, the resultant was subjected to 2mm sieving. In the invention, the material is preferably washed after being screened, and the screened materials with different particle sizes are separately treated after being washed. Wherein, materials (copper-zinc alloy, stainless steel, metallic iron and the like) with the grain diameter of more than 2mm are recycled; and carrying out table treatment on the smelting slag with the particle size of less than 2mm, and separating out the metallic material with the particle size of less than 2 mm. After metallic materials with the particle size of less than 2mm are separated, fine grinding is carried out on the residual smelting slag tailings until the materials with the particle size of less than 0.074mm account for 70-90 wt%, and the pretreatment is finished. When the fineness of the grinding material is less than 0.074mm and accounts for 70-90%, the micro-fine particle copper-zinc alloy material wrapped by the ash residue component can be fully dissociated, in addition, the surface area of other copper-zinc oxide particles after fine grinding is also sharply increased, the leaching rate of copper and zinc in the slag is improved, the reaction speed is accelerated, and therefore the copper recovery efficiency is improved. In some embodiments of the invention, 80 wt% of the material finely ground to less than 0.074 mm; in some embodiments of the invention, 85 wt% of the material finely ground to less than 0.074 mm.
According to the invention, mixed strains are inoculated in an inorganic solution and aerated for culture to obtain a bacterial culture solution.
In the invention, the inorganic solution is: dissolving ammonium sulfate, potassium chloride, dipotassium hydrogen phosphate, calcium nitrate and ferrous sulfate in sulfuric acid solution to obtain mixed solution; namely, sulfuric acid solution is used as a dissolving solution, and the specific inorganic salt is dissolved in the dissolving solution.
In the invention, the concentration of the adopted sulfuric acid solution is preferably 2-4 g/L, and the pH value is 1.5-2.0. In some embodiments of the invention, the pH of the sulfuric acid liquor is 1.8.
In the present invention, in the inorganic solution: the concentration of the ammonium sulfate is preferably 2-6 g/L; in some embodiments of the invention, the concentration is 5 g/L. The concentration of the potassium chloride is preferably 0.1-0.2 g/L; in some embodiments of the invention, the concentration is 0.2 g/L. The concentration of the dipotassium phosphate is preferably 0.1-1 g/L; in some embodiments of the invention, the concentration is 0.5 g/L. The concentration of the calcium nitrate is preferably 0.01-0.03 g/L; in some embodiments of the invention, the concentration is 0.02 g/L. The concentration of the ferrous sulfate is 20-50 g/L; in some embodiments of the invention, the concentration is 45 g/L.
In the invention, the mixed strain comprises: thiobacillus ferrooxidans, Thiobacillus thiooxidans and Microspirillum ferrooxidans. In the invention, the mixed strains comprise thiobacillus ferrooxidans, thiobacillus thiooxidans and microspirillum ferrooxidans in the ratio of 1 to (0-5), and the content of thiobacillus thiooxidans and microspirillum ferrooxidans is not 0; in some embodiments of the invention, the seed ratio is 1: 3: 5. In some embodiments of the present invention, the preservation unit of the mixed strain is the China center for type culture Collection, and the preservation number is CCTCC M2017267. In the invention, the strain ratio refers to the mass ratio of three strains.
In the invention, the mass ratio of the mixed strain to the inorganic solution is preferably 1 to (0-1000), and the using amount of the inorganic solution is not 0. After mixing the two, aerated culture was performed. In the culture process, the pH value of the system is preferably kept between 1.5 and 2.0. The aeration gas amount is preferably 0.06-0.1L/L.h, and the dissolved oxygen is preferably controlled at 6-8 mg/L. The time of aeration culture is preferably 24-48 h; in some embodiments of the invention, the aerated culture is for 36 h. After the culture, a bacteria culture solution is obtained.
The invention has no restriction on the sequence of obtaining the fine grinding smelting slag and the bacteria culture solution, and can obtain the fine grinding smelting slag and the bacteria culture solution sequentially or simultaneously.
According to the invention, after the fine grinding smelting slag and the bacterial culture solution are obtained, the fine grinding smelting slag and the bacterial culture solution are mixed, leached and filtered to obtain the copper-containing solution and the smelting slag after copper removal.
In the invention, the liquid-solid ratio of the bacteria culture solution to the finely ground smelting slag is preferably (3-10) mL: 1 g; in some embodiments of the invention, the liquid-to-solid ratio is 10 mL: 1 g.
In the invention, the leaching temperature condition is preferably 25-35 ℃; in some embodiments of the invention, the temperature is 30 ℃. The leaching is preferably carried out under the condition of stirring, and the stirring speed is preferably 150-350 rpm; in some embodiments of the invention, the rate of agitation is 300 rpm. In the invention, the leaching time is preferably 6-72 h; in some embodiments of the invention, the time for leaching is 24 hours or 36 hours. And after leaching, filtering to obtain a copper-containing solution and smelting slag after copper removal. Wherein the copper material in the copper-containing solution is mainly copper-zinc alloy; after leaching treatment, under the action of the biological copper leaching agent (namely the obtained bacterial culture solution), copper is leached from the smelting slag, so that the copper-zinc alloy is obtained.
In the prior art, copper sulfide, copper oxide minerals or smelting slag of the copper minerals are usually leached when copper is recovered, and in the invention, the leached copper materials are mainly copper-zinc alloy through the leaching treatment; 60-70% of copper in the scrap copper smelting slag exists in the copper-zinc alloy, so that the leaching and subsequent treatment materials of the invention are different from the prior art, and the copper recovery rate can be effectively improved.
According to the invention, after the copper-containing solution is obtained, the copper-containing solution is extracted by adopting an extractant solution, and a water phase and an organic phase are separated; and carrying out back extraction on the organic phase by using an aqueous solution of sulfuric acid to obtain a copper-containing aqueous phase.
In the invention, the extractant in the extractant solution is one or more of Lix984, Lix973, M5640 and N902; in some embodiments of the invention, the extractant is Lix 984. In the invention, the solvent in the extractant solution is preferably one or more of kerosene and benzene; more preferably kerosene. The kerosene is preferably 260# kerosene. In the invention, in the extractant solution, the mass ratio of the extractant to the solvent is preferably 1 to (3-5); in some embodiments of the invention, the mass ratio is 1: 4.
In the invention, the volume ratio of the extractant solution to the copper-containing solution is preferably 1 to (1-2); in some embodiments of the invention, the volume ratio is 1: 1. The extraction temperature is not limited, and the extraction can be carried out at normal temperature. The extraction time is preferably 1-8 min; in some embodiments of the invention, the time of the extraction is 4min or 5 min. In the extraction, an aqueous phase and an organic phase are formed, and the aqueous phase is separated from the organic phase. And adding sulfuric acid into the water phase to adjust the pH value to 1.5-2.0, and returning to be used as a biological copper leaching agent for leaching treatment in the leaching step after aeration.
In the invention, the organic phase is back extracted by using the aqueous solution of sulfuric acid to obtain the copper-containing aqueous phase. The concentration of the aqueous solution of the sulfuric acid is preferably 160-180 g/L; if the concentration of sulfuric acid is too low, the effect of back extraction of copper is not ideal, and if the concentration of sulfuric acid is too high, the structure of the extractant in the organic phase is damaged, and the recycling of the extractant is influenced. In some embodiments of the invention, the concentration is 170g/L or 175 g/L. The volume ratio of the organic phase to the aqueous solution of sulfuric acid is preferably (3-5) to 1; in some embodiments of the invention, the volume ratio is 2: 1. The back extraction temperature is not limited, and the back extraction can be carried out at normal temperature. The back extraction time is preferably 1-8 min; in some embodiments of the invention, the time for the back-extraction is 4min or 5 min. And (4) carrying out back extraction to obtain a copper-containing water phase.
According to the invention, after the copper-containing aqueous phase is obtained, the copper-containing aqueous phase is subjected to an electrodeposition copper treatment to obtain copper.
In the present invention, the electrode system used for the electrodeposition copper treatment is not particularly limitedConventional electrode systems for the electrodeposition of copper, which are well known to the person skilled in the art, are sufficient. In some embodiments of the invention, the anode is a lead-silver alloy plate and the cathode is a stainless steel plate. In the invention, the current density of the electrodeposited copper treatment is preferably 180-220A/m3(ii) a The electrodeposition temperature is preferably 60-100 ℃; in some embodiments, the temperature is 60 ℃. In the process of the electrodeposition copper treatment, copper ions in the solution are reduced, so that a copper simple substance product is obtained.
The recovery method provided by the invention is simple and feasible, mild in condition and environment-friendly, and can effectively improve the recovery rate of copper.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, the preservation number of the mixed strain is CCTCC M2017267, and the preservation unit is China center for type culture Collection. In the procedure of electrodepositing copper, a lead-silver alloy plate is used as an anode, and a stainless steel plate is used as a cathode.
Example 1
S1 pretreatment of smelting slag
Mixing scrap copper smelting slag (the copper content is 8.45 wt%) with water until the concentration of the smelting slag is 65%, and adding the mixture into a rotary ore washer to wash for 15 min; discharging the washed smelting slag, screening by 2mm, and washing, wherein the copper-zinc alloy, the stainless steel and the metallic iron with the granularity larger than 2mm are recovered; and treating the smelting slag with the granularity of less than 2mm by adopting a shaking table, separating and recovering the metallic material with the granularity of less than 2mm, and ball-milling the residual smelting slag tailings with the granularity of less than 2mm until the granularity of less than 0.074mm accounts for 85% to obtain the pretreated smelting slag.
S2 preparation of biological copper leaching agent
Mixing strains: thiobacillus ferrooxidans, thiobacillus thiooxidans and microspirillum ferrooxidans, wherein the strain ratio of the thiobacillus ferrooxidans to the thiobacillus thiooxidans to the microspirillum ferrooxidans is 1: 3: 5.
Ammonium sulfate (5 g/L in the system), potassium chloride (0.2 g/L in the system), dipotassium hydrogen phosphate (0.5 g/L in the system), calcium nitrate (0.02 g/L in the system) and ferrous sulfate (45 g/L in the system) were added to a sulfuric acid solution having a pH of 1.8, and mixed to obtain an inorganic solution. Inoculating the mixed strain into the inorganic solution, wherein the mass ratio of the mixed strain to the inorganic solution is 1: 200. Keeping the pH value at 1.8, performing aerated culture for 36h, keeping the air volume at 0.1L/L.h, and controlling the dissolved oxygen at 8 mg/L. Obtaining the bacteria culture solution.
S3 bioleaching
Uniformly mixing the pretreated smelting slag and the bacterial culture solution according to the mass ratio of the bacterial culture solution to the pretreated smelting slag of 10: 1, leaching for 24 hours at the temperature of 30 ℃ and the stirring speed of 300rpm, and filtering to obtain a copper-containing solution and the smelting slag after copper removal. The concentration of copper ions in the obtained copper-containing solution is 8.06g/L, and the leaching rate of copper in the smelting slag is 95.38 percent, namely 95.38 percent of copper in the pretreated smelting slag is leached.
S4, extraction-stripping
Evenly mixing Lix984:260# kerosene according to the mass ratio of 1: 4 to obtain an extractant solution; extracting for 4min according to the volume ratio of the extractant solution to the copper-containing solution of 1: 1, and separating a water phase from an organic phase.
And (3) adopting a sulfuric acid aqueous solution of 175g/L as a stripping agent, and carrying out back extraction for 5min according to the volume ratio of the loaded organic phase to the stripping agent of 2: 1 to obtain a copper-containing aqueous phase. The extraction rate of copper was 98.45% and the back-extraction rate was 99.16%.
S5 recovery of copper by electrodeposition
And carrying out electrodeposition copper treatment on the copper-containing water phase.
Electrodeposition conditions: the current density is 180A/m3The temperature is 60 ℃ and the time is 2 h. The copper is obtained by deposition on the cathode plate, the purity is more than 99.95 percent, and the copper recovery rate of the copper-containing material in the copper-containing water phase is 96 percent.
Example 2
S1 pretreatment of smelting slag
Mixing scrap copper smelting slag (the copper content is 11.24 wt%) with water until the concentration of the smelting slag is 55%, and adding the mixture into a rotary ore washer to wash for 10 min; discharging the washed smelting slag, screening by 2mm, and washing, wherein the copper-zinc alloy, the stainless steel and the metallic iron with the granularity larger than 2mm are recovered; and treating the smelting slag with the granularity of less than 2mm by adopting a shaking table, separating and recovering the metallic material with the granularity of less than 2mm, and ball-milling the residual smelting slag tailings with the granularity of less than 2mm until the granularity of less than 0.074mm accounts for 80% to obtain the pretreated smelting slag.
S2 preparation of biological copper leaching agent
Mixing strains: thiobacillus ferrooxidans, thiobacillus thiooxidans and microspirillum ferrooxidans, wherein the strain ratio of the thiobacillus ferrooxidans to the thiobacillus thiooxidans to the microspirillum ferrooxidans is 1: 3: 5.
Ammonium sulfate (5 g/L in the system), potassium chloride (0.2 g/L in the system), dipotassium hydrogen phosphate (0.5 g/L in the system), calcium nitrate (0.02 g/L in the system) and ferrous sulfate (45 g/L in the system) were added to a sulfuric acid solution having a pH of 1.8, and mixed to obtain an inorganic solution. Inoculating the mixed strain into the inorganic solution, wherein the mass ratio of the mixed strain to the inorganic solution is 1: 200. Keeping the pH value at 1.8, performing aerated culture for 36h, keeping the air volume at 0.06L/L.h, and controlling the dissolved oxygen at 6 mg/L. Obtaining the bacteria culture solution.
S3 bioleaching
Uniformly mixing the pretreated smelting slag and the bacterial culture solution according to the mass ratio of the bacterial culture solution to the pretreated smelting slag of 10: 1, leaching for 36 hours at the temperature of 30 ℃ and the stirring speed of 300rpm, and filtering to obtain a copper-containing solution and the smelting slag after copper removal. The concentration of copper ions in the obtained copper-containing solution is 10.51g/L, and the leaching rate of copper in the smelting slag is 93.51 percent.
S4, extraction-stripping
Evenly mixing Lix984:260# kerosene according to the mass ratio of 1: 4 to obtain an extractant solution; extracting for 5min according to the volume ratio of the extractant solution to the copper-containing solution of 1: 1, and separating a water phase from an organic phase.
And back-extracting for 4min by using 170g/L sulfuric acid aqueous solution as a back-extracting agent according to the volume ratio of the loaded organic phase to the back-extracting agent of 2: 1 to obtain the copper-containing aqueous phase. The extraction rate of copper was 98.21% and the back-extraction rate was 99.24%.
S5 recovery of copper by electrodeposition
And carrying out electrodeposition copper treatment on the copper-containing water phase.
Electrodeposition conditions: current density 220A/m3The temperature is 60 ℃ and the time is 2 h. The copper is obtained by deposition on the cathode plate, the purity is more than 99.95 percent, and the copper recovery rate of the copper-containing material in the copper-containing water phase is 96 percent.
Example 3
S1 pretreatment of smelting slag
Mixing scrap copper smelting slag (the copper content is 8.45 wt%) with water until the concentration of the smelting slag is 60%, and adding the mixture into a rotary ore washer to wash for 15 min; discharging the washed smelting slag, screening by 2mm, and washing, wherein the copper-zinc alloy, the stainless steel and the metallic iron with the granularity larger than 2mm are recovered; and treating the smelting slag with the granularity of less than 2mm by adopting a shaking table, separating and recovering the metallic material with the granularity of less than 2mm, and ball-milling the residual smelting slag tailings with the granularity of less than 2mm until the granularity of less than 0.074mm accounts for 82%, so as to obtain the pretreated smelting slag.
S2 preparation of biological copper leaching agent
Mixing strains: thiobacillus ferrooxidans, thiobacillus thiooxidans and microspirillum ferrooxidans, wherein the strain ratio of the thiobacillus ferrooxidans to the thiobacillus thiooxidans to the microspirillum ferrooxidans is 1: 3: 5.
Ammonium sulfate (5 g/L in the system), potassium chloride (0.2 g/L in the system), dipotassium hydrogen phosphate (0.5 g/L in the system), calcium nitrate (0.02 g/L in the system) and ferrous sulfate (45 g/L in the system) were added to a sulfuric acid solution having a pH of 1.8, and mixed to obtain an inorganic solution. Inoculating the mixed strain into the inorganic solution, wherein the mass ratio of the mixed strain to the inorganic solution is 1: 200. Keeping the pH value at 1.8, performing aerated culture for 36h, keeping the air volume at 0.1L/L.h, and controlling the dissolved oxygen at 8 mg/L. Obtaining the bacteria culture solution.
S3 bioleaching
Uniformly mixing the pretreated smelting slag and the bacterial culture solution according to the mass ratio of the bacterial culture solution to the pretreated smelting slag of 10: 1, leaching for 24 hours at the temperature of 30 ℃ and the stirring speed of 300rpm, and filtering to obtain a copper-containing solution and the smelting slag after copper removal. The concentration of copper ions in the obtained copper-containing solution is 8.06g/L, and the leaching rate of copper in the smelting slag is 95.44%.
S4, extraction-stripping
Evenly mixing Lix984:260# kerosene according to the mass ratio of 1: 4 to obtain an extractant solution; extracting for 4min according to the volume ratio of the extractant solution to the copper-containing solution of 1: 1, and separating a water phase from an organic phase.
And (3) adopting a sulfuric acid aqueous solution of 175g/L as a stripping agent, and carrying out back extraction for 5min according to the volume ratio of the loaded organic phase to the stripping agent of 2: 1 to obtain a copper-containing aqueous phase. The extraction rate of copper was 97.89%, and the back-extraction rate was 99.33%.
S5 recovery of copper by electrodeposition
And carrying out electrodeposition copper treatment on the copper-containing water phase.
Electrodeposition conditions: the current density is 180A/m3The temperature is 60 ℃ and the time is 2 h. The copper is obtained by deposition on the cathode plate, the purity is more than 99.95 percent, and the copper recovery rate of the copper-containing material in the copper-containing water phase is 96 percent.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for recovering copper in scrap copper smelting slag is characterized by comprising the following steps:
a) screening scrap copper smelting slag by 2mm, and carrying out table treatment on the screened smelting slag with the particle size of less than 2mm to separate out metallic materials with the particle size of less than 2 mm; finely grinding the separated residual smelting slag tailings to obtain pretreated smelting slag;
the material with the grain diameter less than 0.074mm in the pretreated smelting slag accounts for 70-90 wt%;
b) inoculating mixed strains in an inorganic solution, and performing aerated culture to obtain a bacterial culture solution;
the inorganic solution is as follows: dissolving ammonium sulfate, potassium chloride, dipotassium hydrogen phosphate, calcium nitrate and ferrous sulfate in sulfuric acid solution to obtain mixed solution;
the mixed strain comprises: thiobacillus ferrooxidans, Thiobacillus thiooxidans and Microspirillum ferrooxidans;
c) mixing, leaching and filtering the pretreated smelting slag and the bacterial culture solution to obtain a copper-containing solution and smelting slag after copper removal;
d) extracting the copper-containing solution by using an extractant solution, and separating a water phase from an organic phase; carrying out back extraction on the organic phase by using a sulfuric acid aqueous solution to obtain a copper-containing aqueous phase;
the extractant is one or more of Lix984, Lix973, M5640 and N902;
e) carrying out electrodeposition copper treatment on the copper-containing water phase to obtain copper;
the step a) and the step b) are not limited in order.
2. The recovery method according to claim 1, wherein in the step b), the concentration of ammonium sulfate is 2 to 6g/L, the concentration of potassium chloride is 0.1 to 0.2g/L, the concentration of dipotassium hydrogen phosphate is 0.1 to 1g/L, the concentration of calcium nitrate is 0.01 to 0.03g/L, and the concentration of ferrous sulfate is 20 to 50 g/L; the concentration of the adopted sulfuric acid solution is 2-4 g/L, and the pH value is 1.5-2.0.
3. The recovery method according to claim 1, wherein in the step b), the ratio of the thiobacillus ferrooxidans to the thiobacillus thiooxidans to the microspiromyces ferrooxidans is 1: 0-5, and the content of the thiobacillus thiooxidans to the microspiromyces ferrooxidans is not 0.
4. The recovery method according to claim 1, wherein in the step b), the mass ratio of the mixed strain to the inorganic solution is 1: 0-1000, and the use amount of the inorganic solution is not 0;
in the aeration culture process, the pH value is kept between 1.5 and 2.0, the air flow is 0.06 to 0.1L/L.h, the dissolved oxygen is 6 to 8mg/L, and the aeration culture time is 24 to 48 h.
5. The recycling method according to claim 1, wherein in step c), the liquid-solid ratio of the bacteria culture solution to the pretreated smelting slag is (3-10) mL: 1 g.
6. A recovery method according to claim 1, characterized in that in step c), the leaching conditions are: the temperature is 25-35 ℃, and the mixture is leached for 6-72 hours at the stirring speed of 150-350 rpm.
7. The recovery method according to claim 1, wherein in the step d), the solvent of the extractant solution is one or more of kerosene and benzene;
the mass ratio of the extracting agent to the solvent is 1: 3-5.
8. The recovery method of claim 1, wherein in the step d), the volume ratio of the extractant solution to the copper-containing solution is 1: 1-2;
the concentration of the aqueous solution of sulfuric acid is 160-180 g/L;
the volume ratio of the organic phase to the aqueous solution of sulfuric acid is (3-5) to 1.
9. The recycling method according to claim 1, wherein in the step e), the current density of the electrodeposited copper is 180 to 220A/m3The temperature is 60-100 ℃.
10. The recycling method according to claim 1, wherein in the step a), before screening, washing treatment is further performed;
the washing treatment comprises: and mixing the scrap copper smelting slag with water until the mass concentration of the scrap copper smelting slag is 30-75%, and placing the mixture in an ore washer for washing for 5-20 min.
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| CN113499860A (en) * | 2021-07-08 | 2021-10-15 | 江西新金叶实业有限公司 | Efficient flotation method for smelting slag recycled by copper regeneration |
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