阅读说明：本技术 白合金中综合提取有价金属的提取方法 (method for comprehensively extracting valuable metals from white alloy ) 是由 许开华 李琴香 李玉华 朱少文 彭亚光 哈维生 谭逢强 于 2018-05-28 设计创作，主要内容包括：本发明公开了白合金中综合提取有价金属的提取方法,该方法通过向白合金中加入氧化剂进行氧化浸出,获得浸出浆料；向浸出浆料中定量氧化二价铁后水解沉铁锗,获得锗精矿,固液分离后获得滤液；向滤液中加入除铁剂再次进行深度除铁,获得钴铜滤液；对钴铜滤液依次进行铜萃取、P204萃取除杂和P507萃取富集,获得电池级CoSO<Sub>4</Sub>溶液；这样,本发明在常压下对白合金进行氧化浸出,生产工艺安全高效,并且采用分步除铁,在第一次除铁时沉锗,利用溶液中铁作为沉锗剂,成本低,具有较好的经济效益。(The invention discloses an extraction method for comprehensively extracting valuable metals from white alloy, which comprises the steps of adding an oxidant into the white alloy for oxidation leaching to obtain leaching slurry; quantitatively oxidizing ferrous iron in the leached slurry, then hydrolyzing and precipitating iron and germanium to obtain germanium concentrate, and carrying out solid-liquid separation to obtain filtrate; adding an iron removing agent into the filtrate for deep iron removal again to obtain cobalt-copper filtrate; sequentially carrying out copper extraction, P204 extraction impurity removal and P507 extraction enrichment on the cobalt-copper filtrate to obtain a battery-grade CoSO4 solution; therefore, the method carries out oxidation leaching on the white alloy under normal pressure, the production process is safe and efficient, step-by-step iron removal is adopted, germanium is precipitated during the first iron removal, and iron in the solution is used as a germanium precipitation agent, so that the method is low in cost and has better economic benefit.)

1. The method for comprehensively extracting valuable metals from white alloys is characterized by comprising the following steps:

step 1, putting white alloy into a reaction tank, adding a first oxidant into the white alloy for oxidation leaching to obtain leached slurry;

step 2, adding a second oxidant into the leaching slurry obtained in the step 1 to quantitatively oxidize ferrous iron in the solution, adjusting the pH value of the solution, realizing germanium coprecipitation through hydrolysis of ferric iron, and performing solid-liquid separation to obtain a filtrate;

step 3, adding an iron removing agent into the filtrate obtained in the step 2 for deep iron removal to obtain cobalt-copper filtrate;

Step 4, carrying out copper extraction on the cobalt-copper filtrate obtained in the step 3 to obtain an extract, and carrying out back extraction on the extract to obtain a CuSO4 solution; and removing impurities from the extraction liquid by adopting P204 extraction, and performing cobalt enrichment on the extraction liquid after impurity removal by adopting P507 extraction to obtain a battery-grade CoSO4 solution.

2. The method for comprehensively extracting valuable metals from white alloys according to claim 1, characterized in that the reaction temperature of the oxidation leaching in the step 1 is 0-100 ℃, the reaction time is 2-8 h, and the pH value is less than 4.

3. the method for comprehensively extracting valuable metals from white alloys according to claim 2, wherein the first oxidant in step 1 is at least one of manganese dioxide, sodium chlorate, hydrogen peroxide, potassium permanganate or sodium thiosulfate, and the mass of the oxidant added is 0.1-5 times of the mass of the white alloys.

4. The method for comprehensively extracting valuable metals from white alloy according to claim 3, wherein the second oxidant in the step 2 is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate, and the reagent for adjusting the pH value is sodium hydroxide or ammonia water.

5. The method for comprehensively extracting valuable metals from white alloy according to claim 4, wherein the reaction temperature in the step 2 is 70-100 ℃, the pH value is 1.8-2.5, and the reaction time is 0.5-6 h.

6. the method for comprehensively extracting valuable metals from white alloy according to claim 4, characterized in that the content of ferric iron in the solution in the step 2 is controlled to be 5-40 times of the content of germanium.

7. The method for comprehensively extracting valuable metals from white alloy according to claim 6, wherein the oxidant in the iron remover in the step 3 is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate.

8. the method for comprehensively extracting valuable metals from white alloy according to claim 7, wherein the deep iron removal in the step 3 is to control the content of iron in the filtrate to be not more than 500mg/L at the reaction temperature of 70-100 ℃ and the pH value of 2.5-4.5.

9. The method for comprehensively extracting valuable metals from white alloys according to any one of claims 1 to 8, characterized in that an oxidant is added into the leaching slurry obtained in the step 1 in the step 2 to quantitatively oxidize ferrous iron in the solution, the pH value of the solution is adjusted, germanium coprecipitation is realized through hydrolysis of ferric iron, germanium concentrate is obtained after solid-liquid separation, and the method further comprises the following steps after the step 2: and performing chlorination distillation, rectification and hydrolysis on the germanium concentrate in sequence to obtain high-purity germanium dioxide.

10. The method for comprehensively extracting valuable metals from white alloy according to claim 9, wherein the step 4 comprises the steps of performing copper extraction on the cobalt-copper filtrate obtained in the step 3 to obtain an extract, performing back extraction on the extract to obtain a CuSO4 solution, and then: the CuSO4 solution was electrodeposited using an insoluble anode and a permanent cathode to obtain cathode copper.

Technical Field

the invention belongs to the technical field of white alloy leaching, and particularly relates to an extraction method for comprehensively extracting valuable metals from white alloys.

Background

the white alloy is an alloy material containing multiple elements such as cobalt, iron, copper, germanium and the like, and is widely applied to various parts, elastic elements, daily necessities and the like in precision instruments, medical instruments, communication industry and sanitary engineering, so that a large amount of waste is generated every year; meanwhile, with the increasing global cobalt consumption and the relative scarcity of Chinese cobalt resources, some domestic enterprises are disputed to import cobalt ore resources from African countries such as democratic Congo, Zanbia and the like; the recent democratic Congo government has issued a policy of restricting export of the cobalt ore of the country and encouraging the export of the cobalt ore after being deeply processed into a cobalt product; each enterprise can only adopt an electric furnace to smelt the cobalt-containing concentrate into cobalt-copper-germanium-iron alloy (namely white alloy) and then transport the cobalt-copper-germanium-iron alloy back to China, so that considerable white alloy materials are left to be treated every year in China.

however, the cobalt white alloy has strong corrosion resistance and difficult treatment, and the leaching rate of metals is low because sulfuric acid pressure leaching or electro-dissolution treatment processes are mostly adopted abroad.

disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide an extraction method for comprehensively extracting valuable metals from white alloys.

The invention provides an extraction method for comprehensively extracting valuable metals from white alloys, which is implemented by the following steps:

step 1, putting white alloy into a reaction tank, adding a first oxidant into the white alloy for oxidation leaching to obtain leached slurry;

step 2, adding a second oxidant into the leaching slurry obtained in the step 1 to quantitatively oxidize ferrous iron in the solution, adjusting the pH value of the solution, realizing germanium coprecipitation through hydrolysis of ferric iron, and performing solid-liquid separation to obtain a filtrate;

Step 3, adding an iron removing agent into the filtrate obtained in the step 2 for deep iron removal to obtain cobalt-copper filtrate;

step 4, carrying out copper extraction on the cobalt-copper filtrate obtained in the step 3 to obtain an extract, and carrying out back extraction on the extract to obtain a CuSO4 solution; and removing impurities from the extraction liquid by adopting P204 extraction, and performing cobalt enrichment on the extraction liquid after impurity removal by adopting P507 extraction to obtain a battery-grade CoSO4 solution.

In the scheme, the reaction temperature of the oxidation leaching in the step 1 is 0-100 ℃, the reaction time is 2-8 hours, and the pH value is less than 4.

in the scheme, the first oxidant in the step 1 is at least one of manganese dioxide, sodium chlorate, hydrogen peroxide, potassium permanganate or sodium thiosulfate, and the mass of the oxidant added is 0.1-5 times of that of the white alloy.

In the scheme, the second oxidant in the step 2 is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate, and the reagent for adjusting the pH value is sodium hydroxide or ammonia water.

In the scheme, the reaction temperature in the step 2 is 70-100 ℃, the pH value is 1.8-2.5, and the reaction time is 0.5-6 h.

In the scheme, the content of the ferric iron in the solution in the step 2 is controlled to be 5-40 times of the content of the germanium.

In the above scheme, the oxidant in the iron remover in step 3 is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate.

In the scheme, the deep iron removal in the step 3 is to control the content of iron in the filtrate to be not more than 500mg/L at the reaction temperature of 70-100 ℃ and the pH value of 2.5-4.5.

in the above scheme, in the step 2, an oxidant is added to the leached slurry obtained in the step 1 to quantitatively oxidize ferrous iron in the solution, the pH value of the solution is adjusted, germanium coprecipitation is realized by hydrolysis of ferric iron, a germanium concentrate is obtained after solid-liquid separation, and the step 2 further includes: and performing chlorination distillation, rectification and hydrolysis on the germanium concentrate in sequence to obtain high-purity germanium dioxide.

In the foregoing scheme, the step 4 includes performing copper extraction on the cobalt-copper filtrate obtained in the step 3 to obtain an extract, performing back extraction on the extract to obtain a CuSO4 solution, and then: the CuSO4 solution was electrodeposited using an insoluble anode and a permanent cathode to obtain cathode copper.

compared with the prior art, the invention provides the extraction method for comprehensively extracting valuable metals from the white alloy, and the method comprises the steps of adding an oxidant into the white alloy for oxidation leaching to obtain leaching slurry; quantitatively oxidizing ferrous iron in the leached slurry, then hydrolyzing and precipitating iron and germanium to obtain germanium concentrate, and carrying out solid-liquid separation to obtain filtrate; adding an iron removing agent into the filtrate for deep iron removal again to obtain cobalt-copper filtrate; sequentially carrying out copper extraction, P204 extraction impurity removal and P507 extraction enrichment on the cobalt-copper filtrate to obtain a battery-grade CoSO4 solution; therefore, the method carries out oxidation leaching on the white alloy under normal pressure, the production process is safe and efficient, step-by-step iron removal is adopted, germanium is precipitated during the first iron removal, and iron in the solution is used as a germanium precipitation agent, so that the method is low in cost and has better economic benefit; in addition, the method can further process the germanium concentrate while recovering the byproducts of the divalent cobalt and the divalent copper, can directly obtain high-purity GeO2, has large processing capacity and high output, can effectively improve the productivity, and has the advantages of low cost, high recovery rate of the germanium, the cobalt and the copper, high added value of the product and industrial application value.

Drawings

fig. 1 is a process flow chart of an extraction method for comprehensively extracting valuable metals from white alloys according to an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The embodiment of the invention provides an extraction method for comprehensively extracting valuable metals from white alloys, which is implemented by the following steps:

Step 1, after ball milling of white alloy, weighing 80-mesh screen underflow, and putting the weighed white alloy into a reaction tank; preparing a first oxidant solution, wherein the mass of the first oxidant solution is 0.1-5 times of that of the white alloy, putting the prepared first oxidant solution into a reaction tank, adjusting the reaction temperature to be 0-100 ℃, adjusting the pH value to be less than 4, and reacting for 2-8 hours under normal pressure to obtain leaching slurry;

Wherein, the first oxidant is at least one of manganese dioxide, sodium chlorate, hydrogen peroxide, potassium permanganate or sodium thiosulfate;

Step 2, adding a second oxidant into the leached slurry, adding sodium hydroxide or ammonia water to adjust the pH value of the solution, reacting for 0.5-6 h at the reaction temperature of 70-100 ℃ and the pH value of 1.8-2.5 to control the content of ferric iron in the solution to be 5-40 times of the content of germanium, thus realizing germanium coprecipitation through hydrolysis of ferric iron, and finally performing solid-liquid separation to obtain a filtrate;

wherein the second oxidant is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate;

step 3, adding an iron remover into the filtrate to perform deep iron removal again, controlling the iron content in the filtrate to be not more than 500mg/L at the reaction temperature of 70-100 ℃ and the pH value of 2.5-4.5, namely completing the deep iron removal to obtain cobalt-copper filtrate, wherein the oxidant in the iron remover is at least one of air, pure oxygen, hydrogen peroxide, sodium chlorate or sodium persulfate;

step 4, weighing the cobalt-copper filtrate after iron removal, and performing copper extraction on the cobalt-copper filtrate after iron removal to obtain an extraction liquid, wherein the selected extraction agent is a copper extraction agent, the ratio is 1: 1-5: 1, and the pH value is 2-4;

weighing an extraction liquid after copper extraction, and removing impurities from the extraction liquid after copper extraction by adopting P204 extraction, wherein when the P204 extraction is adopted, an organic phase composition is P204+260# solvent oil, the ratio is 1: 1-5: 1, countercurrent extraction is carried out, and the balanced pH value is 2-5; weighing raffinate after P204 extraction impurity removal, and performing cobalt enrichment on the raffinate after P204 extraction impurity removal by adopting P507 extraction, wherein when the P507 extraction is adopted, an organic phase is P507+260# solvent oil, the ratio is 1: 1-5: 1, countercurrent extraction is performed, the balanced pH value is 2-5, and finally, a battery-grade CoSO4 solution is obtained; wherein the extraction rate of cobalt is 99.5%.

wherein, in the step 2, an oxidant is added into the leached slurry obtained in the step 1 to quantitatively oxidize ferrous iron in the solution, the pH value of the solution is adjusted, germanium coprecipitation is realized through hydrolysis of ferric iron, germanium concentrate is obtained after solid-liquid separation, and the step 2 further comprises the following steps: and (3) performing chlorination distillation, rectification and hydrolysis on the germanium concentrate in sequence to obtain high-purity germanium dioxide.

Wherein, in the step 4, the cobalt-copper filtrate obtained in the step 3 is subjected to copper extraction to obtain an extract, and then the method further comprises the following steps: carrying out back extraction on the extract liquor to obtain a CuSO4 solution, and carrying out electrodeposition on the CuSO4 solution by adopting an insoluble anode and a permanent cathode to obtain cathode copper;

specifically, a Pb-Ag anode electrode and a titanium alloy cathode electrode are adopted, and the CuSO4 solution is electrodeposited at a low current density to obtain electrodeposited copper; the method comprises the following steps of washing electrodeposited copper for 2min by adopting clean water at 80 ℃, washing the electrodeposited copper for 2min by adopting dilute acid at 80 ℃ and under the condition that the pH is less than 1, and finally manually stripping the electrodeposited copper after washing for two times to obtain cathode copper, wherein the leaching rate of the copper reaches 99.5%, and the recovery rate of the copper reaches 99.5%.

the invention provides an extraction method for comprehensively extracting valuable metals from white alloy, which comprises the steps of adding an oxidant into the white alloy for oxidation leaching to obtain leaching slurry; quantitatively oxidizing ferrous iron in the leached slurry, then hydrolyzing and precipitating iron and germanium to obtain germanium concentrate, and carrying out solid-liquid separation to obtain filtrate; adding an iron removing agent into the filtrate for deep iron removal again to obtain cobalt-copper filtrate; sequentially carrying out copper extraction, P204 extraction impurity removal and P507 extraction enrichment on the cobalt-copper filtrate to obtain a battery-grade CoSO4 solution; therefore, the method carries out oxidation leaching on the white alloy under normal pressure, the production process is safe and efficient, step-by-step iron removal is adopted, germanium is precipitated during the first iron removal, and iron in the solution is used as a germanium precipitation agent, so that the method is low in cost and has better economic benefit; in addition, the method can further process the germanium concentrate while recovering the byproducts of the divalent cobalt and the divalent copper, can directly obtain high-purity GeO2, has large processing capacity and high output, can effectively improve the productivity, and has the advantages of low cost, high recovery rate of the germanium, the cobalt and the copper, high added value of the product and industrial application value.