CN113025811A - Deep elution method for chlorine in copper sulfide precipitation slag - Google Patents
Deep elution method for chlorine in copper sulfide precipitation slag Download PDFInfo
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- CN113025811A CN113025811A CN202110247407.4A CN202110247407A CN113025811A CN 113025811 A CN113025811 A CN 113025811A CN 202110247407 A CN202110247407 A CN 202110247407A CN 113025811 A CN113025811 A CN 113025811A
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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
- C22B1/00—Preliminary treatment of ores or scrap
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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
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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
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Abstract
The invention discloses a deep elution method for chlorine in copper sulfide precipitation slag. Aiming at the problem of overhigh chlorine content in the copper sulfide precipitation slag obtained from the high-chlorine copper solution, the invention adopts the following technical scheme: 1) preparing soluble sulfide into sulfide solution by using water; 2) adding a sulfide solution into the copper sulfide precipitation slag, heating, stirring, washing, performing vacuum filtration after washing, and returning the obtained filtrate to the copper sulfide precipitation working section as a chlorine washing solution; 3) adding tap water into the filter residue obtained in the step 2) for leaching, wherein the obtained filter residue is low-chlorine copper sulfide concentrate, and returning the obtained chlorine washing water to a sulfide dissolving working section. The method can realize the high-efficiency removal of chlorine in the copper sulfide precipitation slag, meet the requirements of a pressure oxidation leaching process on chloride ions, and simultaneously generate no extra chlorine-containing wastewater.
Description
Technical Field
The invention belongs to the field of wet metallurgy, relates to an elution method of chlorine in high-chlorine system copper sulfide precipitation slag, and particularly relates to a deep elution method of chlorine in copper sulfide precipitation slag.
Background
In the cobalt metallurgy industry, in order to obtain high-quality cobalt solution, an extraction process is mostly adopted to remove impurity ions such as copper, manganese, zinc and the like to purify the solution, an organic phase loaded with the impurity ions is subjected to hydrochloric acid back extraction to obtain a high-chlorine solution containing copper, manganese and zinc, a vulcanization process is generally adopted to precipitate copper in order to recover valuable metal copper in the high-chlorine solution, and the main components of copper precipitation slag are CuS and Cu2S, the copper content in the slag is about 20 percent.
At present, the copper content in the copper deposition slag obtained by adopting the potential control vulcanization technology can reach about 60 percent, the copper grade is far higher than that of common copper concentrate, the impurity content is low, and the recovery value and the significance are higher. In order to further recover the copper in the copper sulfide precipitation slag, a pressure oxidation process (or a pressure oxidation leaching system) is adopted to leach and recover the copper, although the leaching of the chloride ions to the copper is beneficial when the copper sulfide is leached by a wet method, the content of the chloride in the copper sulfide precipitation slag reaches about 6 percent, the corrosion of the chloride ions to a high-pressure autoclave body and a pipeline is serious in the reaction process, the shutdown and maintenance frequency of a pressure oxidation leaching working section is increased, and further huge economic loss is caused.
Disclosure of Invention
In order to return the copper sulfide precipitation slag to a pressure oxidation leaching system, the invention provides a deep elution method of chlorine in the copper sulfide precipitation slag, which is based on the fact that cuprous ions and sulfur ions have strong binding capacity, so that the high-efficiency removal of the chlorine in the copper sulfide precipitation slag is realized, the requirement of a pressure oxidation leaching process on the chlorine ions is met, and meanwhile, no extra chlorine-containing wastewater is generated.
The invention is realized by the following modes: a deep elution method of chlorine in copper sulfide precipitation slag comprises the following steps:
1) preparing soluble sulfide into sulfide solution by using water;
2) adding sulfide solution into the copper sulfide precipitation slag, heating to 25-80 ℃ under stirring, carrying out slurry washing, carrying out vacuum filtration after 30-120min of slurry washing, and returning the obtained filtrate, namely chlorine washing liquid, to the copper sulfide precipitation working section;
3) adding tap water into the filter residue obtained in the step 2) for leaching, wherein the obtained filter residue is low-chlorine copper sulfide concentrate used for recovering copper, and the obtained chlorine washing water is returned to a sulfide dissolving working section.
The principle of the invention is as follows: since Cu in the high-chlorine copper solution system exists mainly in the form of copper chloride complex ions, particularly when the potential is reduced to about 520mV, the Cu (II) -Cl complex ions are converted into Cu (I) -Cl complex ions, and the reaction formula is shown as follows:
in addition, the stability constant of Cu (I) -Cl complex ion is large (
Stability constant beta of2＝105.50，
Stability constant beta of3＝105.70) Indicating that the compound can exist stably in the solution. Therefore, Cu (I) -Cl brought into fine precipitation unit cells in the copper sulfide precipitation slag by entrainment and entrainment is not easy to be removed by water washing, acid washing and alkali washing. While using Na2The S solution is used for carrying out slurry washing on the copper sulfide precipitation slag, and Cu (I) and S are utilized2-Has strong binding capacity, promotes the destabilization and the release of Cu (I) -Cl complex ionsEvolution of Cl-The purpose of elution is achieved, and the reaction formula is as follows:
further, in the step 1), the soluble sulfide is one or two of sodium sulfide and sodium hydrosulfide, the purity is analytically pure or industrial grade, the mass percent of the industrial grade sodium sulfide is not less than 60%, and the mass percent of the industrial grade sodium hydrosulfide is not less than 70%.
Further, in the step 1), the concentration of the sulfide solution is 140-200 g/L.
Further, in the step 2), the liquid-solid ratio of slurry washing is 5:1-20:1, and the stirring speed is 300-; more preferably: the stirring speed is 300-450r/min, the slurry washing temperature is 60-80 ℃, and the slurry washing time is 90-120 min.
Furthermore, in the step 2), the liquid-solid ratio of the slurry washing is 15:1-20: 1.
Further, in the step 3), the leaching liquid-solid ratio is 1:5-5: 1.
Furthermore, in the step 3), the liquid-solid ratio of the leaching is 1:2-3: 1.
The invention has the beneficial effects that: 1) the method can realize deep elution of chlorine in the copper sulfide slag, so that the low-chlorine copper slag meets the requirement of a pressure oxidation process on chlorine, the precipitation rate of the chlorine can reach more than 99.90 percent, and the chlorine content in the copper sulfide slag after chlorine washing is less than 0.005 percent; 2) the sulfide chlorine washing liquid returns to the copper sulfide precipitation working section, and the leaching water returns to the preparation of the sulfide solution, so that extra chlorine-containing wastewater is not generated; 3) the method has the advantages of simple process and high chlorine elution rate, and is easy for industrial popularization.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
The method adopts a potential-controlled vulcanization technology to treat the high-chlorine copper-containing solution to obtain the vulcanized copper-deposited slag, and comprises the following main components: cu55.38%, S34.63% and Cl5.4%. Taking 150g of the copper sulfide precipitation slag in a beaker, adding 140g/L NaHS solution according to the liquid-solid ratio of 20:1, stirring at the speed of 450r/min, heating the copper sulfide precipitation slag to 80 ℃, continuing stirring for 120min, carrying out vacuum filtration, and returning the filtrate to the copper sulfide precipitation process; and leaching the filter residue once by adding tap water according to the liquid-solid ratio of 1:2, and drying the filter residue to obtain the low-chlorine copper concentrate, wherein the low-chlorine copper concentrate comprises 54.73% of Cu54%, 33.51% of S, 0.0047% of Cl0.0047% of the filter residue, and the Cl elution rate in the copper sulfide precipitation slag reaches 99.92%.
Example 2
The method adopts a potential-controlled vulcanization technology to treat the high-chlorine copper-containing solution to obtain the vulcanized copper-deposited slag, and comprises the following main components: cu61.11%, S24.78%, Cl4.1%. Taking 600g of the copper sulfide precipitated slag to be put into a 10L glass reaction kettle, and adding 200g/L of Na according to the liquid-solid ratio of 15:12Stirring the solution S at the stirring speed of 300r/min, heating the solution in a water bath to 70 ℃, continuing stirring for 90min, carrying out vacuum filtration, and returning the filtrate to the copper sulfide precipitation; and leaching the filter residue once by adding tap water according to the liquid-solid ratio of 3:1, and drying the filter residue to obtain the low-chlorine copper concentrate, wherein the low-chlorine copper concentrate comprises 62.32% of CuS, 25.51% of S, 0.0042% of Cl0, and the Cl elution rate in the copper sulfide precipitation slag reaches 99.90%.
Example 3
The method adopts a direct vulcanization method to treat the high-chlorine copper-containing solution to obtain the vulcanized copper-precipitation slag, and comprises the following main components: cu25.24%, Zn19.76%, Mn6.44%, S21.36% and Cl6.7%. Taking 150g of the copper sulfide precipitation slag in a beaker, and adding 180g/L of Na according to the liquid-solid ratio of 20:12Stirring the solution S at the speed of 450r/min, heating the solution in a water bath to 60 ℃, continuing stirring for 120min, carrying out vacuum filtration, and returning the filtrate to the copper sulfide precipitation; and leaching the filter residue once by adding tap water according to the liquid-solid ratio of 2:1, and drying the filter residue to obtain the low-chlorine copper concentrate, wherein the low-chlorine copper concentrate comprises 24.67% of Cu24%, 22.42% of S, 0.0045% of Cl0.0045%, and the Cl elution rate in the copper sulfide precipitation slag reaches 99.93%.
Example 4
Treating high chlorine by direct sulfurizationThe copper-containing solution is prepared from the following main components of the copper sulfide precipitation slag: cu25.24%, Zn19.76%, Mn6.44%, S21.36% and Cl6.7%. Taking 600g of the copper sulfide precipitated slag to be put into a 10L glass reaction kettle, and adding 200g/L of Na according to the liquid-solid ratio of 15:12Stirring the solution S at the stirring speed of 300r/min, heating the solution in a water bath to 80 ℃, continuing stirring for 120min, carrying out vacuum filtration, and returning the filtrate to the copper sulfide precipitation; and leaching the filter residue once by adding tap water according to the liquid-solid ratio of 1:1, and drying the filter residue to obtain the low-chlorine copper concentrate, wherein the low-chlorine copper concentrate comprises 25.46 percent of Cu25%, 23.15 percent of S, 0.0037 percent of Cl0.0037 percent of Cl and the elution rate of Cl in the copper sulfide precipitation slag reaches 99.94 percent.
Claims (10)
1. A deep elution method of chlorine in copper sulfide precipitation slag is characterized by comprising the following steps:
1) preparing soluble sulfide into sulfide solution with the concentration of 40-200g/L by using water;
2) adding sulfide solution into the copper sulfide precipitation slag, heating to 25-80 ℃ under stirring, carrying out slurry washing, carrying out vacuum filtration after 30-120min of slurry washing, and returning the obtained filtrate, namely chlorine washing liquid, to the copper sulfide precipitation working section;
3) adding tap water into the filter residue obtained in the step 2) for leaching, wherein the obtained filter residue is low-chlorine copper sulfide concentrate, and returning the obtained chlorine washing water to a sulfide dissolving working section.
2. The method for deeply eluting chlorine in copper sulfide precipitated slag according to claim 1, wherein in the step 1), the soluble sulfide is one or two of sodium sulfide and sodium hydrosulfide, the purity is analytically pure or industrial grade, the mass percent of the industrial grade sodium sulfide is not less than 60%, and the mass percent of the industrial grade sodium hydrosulfide is not less than 70%.
3. The method as claimed in claim 1, wherein in the step 1), the concentration of the sulfide solution is 140-200 g/L.
4. The deep elution method of chlorine in the copper sulfide precipitated slag according to any one of claims 1 to 3, wherein in the step 2), the liquid-solid ratio of slurry washing is 5:1 to 20: 1.
5. The method for deeply eluting chlorine in the copper sulfide precipitated slag according to claim 4, wherein in the step 2), the liquid-solid ratio of slurry washing is 15:1-20: 1.
6. The method as claimed in any one of claims 1 to 3, wherein the stirring speed in step 2) is 300-500 r/min.
7. The method for deep elution of chlorine in the copper sulfide precipitated slag according to any one of claims 1 to 3, wherein the slurry washing temperature in the step 2) is 60 to 80 ℃.
8. The method for deeply eluting chlorine in the copper sulfide precipitated slag according to any one of claims 1 to 3, wherein the slurry washing time in the step 2) is 90 to 120 min.
9. The deep elution method for chlorine in copper sulfide precipitated slag according to any one of claims 1 to 3, wherein in the step 3), the leaching liquid-solid ratio is 1:5-5: 1.
10. The method for deeply eluting chlorine in the copper sulfide precipitated slag according to claim 9, wherein in the step 3), the leaching liquid-solid ratio is 1:2-3: 1.
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