CN113088698B - Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore - Google Patents
Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore Download PDFInfo
- Publication number
- CN113088698B CN113088698B CN202110331679.2A CN202110331679A CN113088698B CN 113088698 B CN113088698 B CN 113088698B CN 202110331679 A CN202110331679 A CN 202110331679A CN 113088698 B CN113088698 B CN 113088698B
- Authority
- CN
- China
- Prior art keywords
- copper
- leaching
- germanium
- roasted ore
- recovery rate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
-
- 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
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- 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
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
- C22B41/00—Obtaining germanium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore, belonging to the technical field of wet-process zinc smelting 3+ The ratio of Ge to/is and the pH value, so that germanium is precipitated into slag, a supernatant containing germanium and meeting the purification requirement is produced, copper is replaced by iron powder in acid leaching liquid after copper is leached again in the acid leaching process, the copper and the germanium are respectively recovered, the recovery rate of copper in roasted ore is improved to 75-80% from less than 40%, and a supernatant containing Ge of less than or equal to 0.30mg/L is produced; the method solves the problem that the germanium slag entering and the copper hydrolysis cannot be considered simultaneously when the high-copper high-germanium roasted ore is leached by the conventional method, and effectively realizes the respective recovery of germanium and copper.
Description
Technical Field
The invention belongs to the technical field of wet-process zinc smelting, and particularly relates to a method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore.
Background
The conventional zinc wet smelting process includes first stage middle leaching of roasted ore to produce middle and bottom liquid, purifying the middle liquid to eliminate impurity for electrolytic zinc deposition, leaching the middle liquid with weak acid, returning the filtrate of the middle liquid and the bottom liquid to middle leaching, acid leaching residue, and recovering valuable metals such as zinc, germanium, etc. from the acid leaching residue in fuming furnace or rotary kiln.
When high germanium (Ge0.02-0.05 wt%) roasted ore is leached conventionally, the purification operation is facilitated by ensuring that Ge in the middle supernatant is less than or equal to 0.30mg/L, and the method can be realized only by increasing the pH value of ore pulp and precipitating germanium into slag as much as possible.
Copper in the roasted ore is easy to dissolve into the solution during leaching by a conventional method, but the copper has poor stability and is easy to hydrolyze in the solution (the copper hydrolysis pH value is 4.604 at 25 ℃), the copper leaching rate is only 30-40% when the copper is leached at the middle temperature and the pH value is 5.2-5.4, and the rest of the copper entering the acid leaching slag is finally lost in fuming furnace water quenching slag or kiln slag (zinc hydrometallurgy, Meiguang and the like, published by the university of China and south, published in 2001, P112-113). In recent years, in order to improve economic benefits, enterprises control the pH value of ore pulp at the middle leaching end of high copper (Cu0.5-0.8 wt%) roasted ore with extremely low germanium content to be reduced to 4.5 or even lower, ensure that copper is not hydrolyzed into slag to enter the middle supernatant as much as possible, and recover copper to copper slag through purification and cadmium processes, wherein the copper recovery rate is 80%.
Due to Cu 2+ And Ge 4+ The hydrolysis pH value of the method is close, when the high-copper high-germanium roasted ore is leached by a conventional method, the germanium is difficult to enter the slag and the copper is difficult to enter the solution, because the germanium enters the slag and needs a higher pH value, and the copper enters the solution and needs a lower pH value, so that the method is a pair of spears and is difficult to realize simultaneous consideration. Meanwhile, germanium in the supernatant fluid is the element which is most difficult to remove in purification and has the greatest influence on zinc electrolysis, and in order to ensure normal operation of production, production enterprises intentionally increase the pH value of ore pulp to reduce the content of germanium in the supernatant fluid, but a large amount of copper is hydrolyzed and enters acid leaching residue to be lost, and the copper recovery rate is less than 40%.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for improving the copper recovery rate in the conventional leaching process of high-copper high-germanium roasted ore, wherein manganese powder and ferrous sulfate are supplemented in the middle leaching process, the roasted ore is added in two steps, and Fe is controlled 3+ /Ge 4+ 200-300, and hydrolyzing a great amount of leached germanium and copper into slag at the leaching end point pH of 5.2-5.4, wherein Ge in the upper supernatant is less than or equal to 0.30mg/L, and Cu is less than or equal to 300 mg/L; controlling the end point acidity (H) during acid leaching 2 SO 4 ) 1-5 g/L, leaching the copper in the hydrolyzed slag again, and replacing and separating out the copper in the acidic solution by using iron powder after liquid-solid separation.
In order to realize the purpose, the invention is realized by the following technical scheme:
the method for improving the copper recovery rate in the conventional leaching process of the high-copper high-germanium roasted ore comprises the following steps:
(1) two-step neutral leaching: respectively adding manganese powder and ferrous sulfate into the zinc electrodeposition waste liquid, adding high-copper and high-germanium roasted ore for 2 times, adding the roasted ore for 1 time according to the end point acidity of 5-10 g/L, adding the roasted ore for 2 times according to the end point pH of 5.2-5.4, leaching again, and adding a flocculating agent into the middle leaching ore pulp for clarification;
(2) acid leaching: adding zinc electrodeposition waste liquid into the middle leaching bottom flow, controlling the end point acidity of the slurry to be 1-3 g/L, carrying out acid leaching, and filtering acid leaching pulp after the acid leaching to obtain acid leaching liquid and acid leaching slag;
(3) replacing copper with iron powder in pickle liquor: according to Cu in pickle liquor 2+ Adding iron powder to replace copper by 1.5-2.0 times of the mass of the copper powder, and performing liquid-solid separation to obtain replaced copper slag and replaced acid liquid.
Furthermore, in the high-copper high-germanium roasting ore, the ratio of Cu: 0.3-0.6% wt, Ge: 0.02 to 0.04 wt%.
Furthermore, the supernatant produced in the step (1) has Ge content less than or equal to 0.30mg/L and Cu content less than or equal to 300 mg/L.
Further, in the pickle liquor in the step (2), the Cu content is 400-1400 mg/L.
Further, the supernatant clarified in the step (1) is sent to a purification process for impurity removal.
And (3) further, conveying the acid leaching residue in the step (2) into a fuming furnace or a rotary kiln, and volatilizing according to a traditional method to recover germanium.
The invention has the beneficial effects that:
according to the invention, when the high-copper high-germanium roasted ore is leached, neutral leaching is carried out step by step under different acidity respectively, so that the hydrolysis rate of germanium is effectively improved, and decomposed germanium can be precipitated into slag along with ferric iron by controlling the proportion of iron to germanium, and can be leached again only in a small amount in the subsequent acid leaching process with lower pH value, so that the efficient slag feeding of germanium is ensured; and adding acid liquor to perform acid leaching after the two-step neutral leaching, leaching the copper hydrolyzed into the slag into the solution again during the neutral leaching, and replacing the copper hydrolyzed into the slag by iron powder to effectively recover the copper hydrolyzed into the slag during the neutral leaching. The technical scheme of the invention not only ensures that germanium enters the slag, but also reduces the copper entering the acid leaching slag, improves the copper recovery rate, solves the contradiction that the germanium enters the slag and the supernatant in the copper enters the high-copper high-germanium roasted ore in the conventional leaching process, and effectively realizes the respective recovery of the germanium and the copper. In addition, according to the technical scheme of the invention, the Ge content in the produced middle supernatant is less than or equal to 0.30mg/L, and the quality requirement of a purification process on the front liquid can be met.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
The method for improving the copper recovery rate in the conventional leaching process of the high-copper high-germanium roasted ore comprises the following steps:
(1) two-step neutral leaching: 1) and (4) oxidizing ferrous iron. Preparing zinc electrodeposition waste liquid and the displaced acidic liquid according to volume percentage, respectively adding manganese powder and ferrous sulfate, and adding Cu for 2 times: 0.3-0.6% wt, Ge: 0.02-0.04 wt% of high-copper high-germanium roasted ore, adding the roasted ore for the first step according to the final acidity of 5-10 g/L to perform neutral leaching, wherein in the neutral leaching process, bivalent iron added to and leached from the roasted ore is oxidized into trivalent iron by manganese powder, and part of germanium and most of copper in the roasted ore are leached. The reaction formula which occurs is:
2FeSO 4 +MnO 2 +2H 2 SO 4 =Fe 2 (SO 4 ) 3 +MnSO 4 +2H 2 O （1）
CuO+H 2 SO 4 =CuSO 4 +H 2 O （2）
GeO 2 +2H 2 SO 4 =Ge(SO 4 ) 2 +2H 2 O （3）
adding roasted ore according to the end point pH value of 5.2-5.4 for the 2 nd time, and leaching for 1.0 h. At higher pH, ferric iron is hydrolyzed completely to precipitate ferric hydroxide colloid, germanium is hydrolyzed to germanium hydroxide, and the germanium is absorbed by the ferric hydroxide colloidThe germanium iron is co-precipitated into the slag, and the degree of adsorption of the germanium hydroxide is determined by Fe in the slurry before the 2 nd roasting of the ore 3+ /Ge 4+ Ratio, Fe 3+ /Ge 4+ The larger the ratio, the better the adsorption effect on germanium.
After neutral leaching, adding a flocculating agent into the middle leaching ore pulp for clarification, and then conveying the middle clear to a purification process for impurity removal; the obtained supernatant has Ge content not more than 0.30mg/L and Cu content not more than 300 mg/L.
(2) Acid leaching: adding zinc electrodeposition waste liquid into the middle leaching bottom flow, controlling the end point acidity of the slurry to be 1-3 g/L, leaching for 4.0h, and filtering acid pulp to obtain acid leaching liquid and acid leaching slag. In the acidic leaching, the copper precipitated by hydrolysis in the step (1) is leached again, while the germanium precipitated by adsorption of the iron hydroxide colloid is leached only in a small amount, because the iron germanium will form a stable structure as long as the iron hydroxide colloid is not largely damaged, which requires controlling the acidity of the acidic leaching to prevent the iron hydroxide colloid from being largely damaged. The Cu content in the pickle liquor is 400-1400 mg/L. And (4) conveying the acid leaching residues into a fuming furnace or a rotary kiln to volatilize and recover zinc and germanium according to a traditional method.
(3) Replacing copper with iron powder in pickle liquor: according to Cu in pickle liquor 2+ Adding iron powder to replace copper by 1.5-2.0 times of the mass of the copper powder, and performing liquid-solid separation to obtain replaced copper slag and replaced acid liquid.
Example 1
The high-copper high-germanium roasted ore used in the embodiment mainly comprises the following components: zn58.39% wt, Fe8.91% wt, Cu0.32% wt, Ge0.035% wt.
(1) Two-step neutral leaching: 2500mL of the electrodeposition waste liquid is mixed with 1500mL of the replaced acidic solution, 10g of manganese powder and 30g of ferrous sulfate are added, and neutral leaching is carried out. 480g of roasted ore is added in the 1 st time, and the end point acidity is controlled as follows: 6g/L, leaching for 1.0h, taking ore pulp, filtering and analyzing to obtain Fe 3+ /Ge 4+ =290，H 2 SO 4 7.96g/L, adding 80g of roasted ore in the 2 nd time, leaching for 1.0h, controlling the pH value of ore pulp to be 5.4, adding a flocculating agent, clarifying for 0.5h, and obtaining 2700mL of supernatant, wherein the supernatant contains 0.22mg/L of Ge0.22mg/L and 278mg/L of Cu.
(2) Acid leaching: adding 180mL of waste electrolyte into the middle leaching bottom flow, leaching for 4.0h, and filtering to obtain acid1460mL of immersion liquid containing Cu420mg/L, H 2 SO 4 1.51 g/L. And (4) conveying the acid leaching residue into a fuming furnace to volatilize and recover germanium.
(3) Replacing copper by iron powder in pickle liquor: according to Cu 2+ Adding 1.2g of iron powder into the pickle liquor with the mass 2.0 times of that of the pickle liquor to obtain 2.8g of displaced copper slag, wherein the mass ratio of Cu: 21.27% wt, Fe: 21.63% wt, Ge: 0.58% wt. And returning the acid solution after replacement to the lower wheel for neutral leaching. Finally, copper brought by the roasted ore is produced in two forms of replacing copper slag with acid liquid, copper slag after zinc and cadmium are leached in a cadmium working procedure and the like.
The roasted ore contains 1.79g of Cu0.75g of the supernatant, 0.60g of the replaced copper slag, and the recovery rate of the copper of the supernatant and the replaced copper slag is 75.42 percent.
Comparative example 1 (completion of the intermediate immersion in one step, otherwise same as in example 1)
(1) Neutral leaching: 2500mL of the electrodeposition waste liquid is mixed with 1500mL of the replaced acidic solution, 10g of manganese powder and 30g of ferrous sulfate are added, and neutral leaching is carried out. 560g of roasted ore is added to leach for 2.0h, the pH value of ore pulp is 5.4, flocculating agent is added to clarify for 0.5h, 2700mL of middle supernatant is obtained, and the middle supernatant contains 1.82mg/L of Ge1 and 286mg/L of Cu.
(2) Acid leaching: adding 180mL of waste electrolyte into the middle leaching bottom flow, leaching for 4.0H, and filtering to obtain 1440mL of acid leaching solution containing 430mg/L of Cu and H 2 SO 4 1.65 g/L. And (4) conveying the acid leaching residue into a fuming furnace to volatilize and recover germanium.
(3) Replacing copper with iron powder in pickle liquor: according to Cu 2+ Adding 1.2g of iron powder into the pickle liquor with the mass 2.0 times of that of the pickle liquor to obtain 2.7g of displaced copper slag, wherein the mass ratio of Cu: 22.96% wt, Fe: 20.03% wt, Ge: 0.53% wt. And returning the acid solution after replacement to the lower wheel for neutral leaching.
The roasted ore contains 1.79g of Cu0.77g of the supernatant, 0.62g of the replaced copper slag, and the recovery rate of the copper of the supernatant and the replaced copper slag is 77.65%.
Compared with the example 1, when the middle leaching is completed in one step, the influence on the copper recovery rate is not obvious, but the middle supernatant contains 1.82mg/L of Gem, the germanium is not effectively precipitated, and the quality requirement of the solution before the purification process can not be met (the middle supernatant Ge is less than or equal to 0.30 mg/L).
Example 2
The high-copper high-germanium roasted ore used in the embodiment mainly comprises the following components: zn57.62% wt, Fe9.87% wt, Cu0.47% wt, Ge0.028% wt.
(1) Two-step neutral leaching: 2500mL of the electrodeposition waste liquid and 1400mL of the replaced acidic solution are fully mixed, and 10g of manganese powder and 15g of ferrous sulfate are added. Two-step neutral leaching is started, 510g of roasted ore is added for the 1 st time, and the end-point acidity is controlled as follows: 10g/L, leaching for 1.0h, taking ore pulp, filtering and analyzing to obtain Fe 3+ /Ge 4+ =240，H 2 SO 4 5.66g/L, adding 50g of roasted ore for the 2 nd time, leaching for 1.0h, adding a flocculating agent to stop leaching and clarifying for 0.5h, and obtaining 2650mL of supernatant, wherein the supernatant contains 0.16mg/L of Ge0.16mg/L and 290mg/L of Cu.
(2) Acid leaching: adding 200mL of accumulated waste liquid into the middle leaching bottom flow, leaching for 4.0H, and filtering to obtain 1450mL of acid leaching liquid containing Cu910mg/L and H 2 SO 4 2.66 g/L. And (4) conveying the acid leaching residue into a fuming furnace to volatilize and recover germanium.
(3) Replacing copper with iron powder in pickle liquor: according to Cu 2+ 2.2g of iron powder is added into the pickle liquor with the amount of 1.7 times of the amount of the iron powder to obtain 3.7g of displaced copper slag containing 35.28 percent by weight of Cu0, 24.58 percent by weight of FeC and 0.39 percent by weight of GeC. And returning the acid solution after replacement to the next round for immersion.
The roasted ore contains Cu2.63g, the supernatant contains Cu0.77g, the replaced copper slag Cu1.30g, and the recovery rate of the copper in the supernatant and the replaced copper slag is 78.71%.
Comparative example 2 (same as example 2 except that manganese powder and ferrous sulfate were not added)
The high-copper high-germanium roasted ore used in the embodiment mainly comprises the following components: zn57.62% wt, Fe9.87% wt, Cu0.47% wt, Ge0.028% wt.
(1) Two-step neutral leaching: collecting 2500mL of electrodeposition waste liquid, fully mixing 1400mL of the acid liquid after replacement in example 1, performing neutral leaching, adding 510g of roasted ore in the 1 st time, and after leaching for 1.0h, controlling the end-point acidity to be: 10g/L, taking ore pulp, filtering and analyzing to obtain Fe 3+ /Ge 4+ =20，H 2 SO 4 5.74g/L, adding 50g of roasted ore in the 2 nd time, leaching for 1.0h, adding a flocculating agent, stopping leaching and clarifying for 0.5h, wherein the pH value of ore pulp is 5.4. 2850mL of middle supernatant containing Ge4.22mg/L and Cu290mg/L is obtained.
(2) Acid leaching: is immersed inAdding 200mL of waste electrolysis solution into the underflow, leaching for 4.0H, and filtering to obtain 1400mL of pickle liquor containing 892/L Cu and 892mg/L H 2 SO 4 2.52 g/L. And (4) conveying the acid leaching residue into a fuming furnace to volatilize and recover germanium.
(3) Replacing copper with iron powder in pickle liquor: according to Cu 2+ 2.2g of iron powder is added into the pickle liquor with the amount of 1.7 times of the amount of the iron powder to obtain 3.8g of displaced copper slag containing 34.21 wt% of Cu0, 22.31 wt% of FeC and 0.59 wt% of GeC. And returning the acid solution after replacement to the next round for immersion.
The roasted ore contains Cu2.63g, the supernatant contains Cu0.81g, the replaced copper slag Cu1.25g, and the recovery rate of the copper of the supernatant and the replaced copper slag is 78.33%.
In comparison with example 2, Fe in the slurry was not added with manganese powder and ferrous sulfate 3+ /Ge 4+ And =30, the influence on the copper recovery rate is not obvious, but the supernatant contains Ge4.22mg/L, germanium is not effectively precipitated, and the quality requirement of the solution before the purification process cannot be met (the supernatant Ge is less than or equal to 0.30 mg/L).
Example 3
The high-copper high-germanium roasted ore used in the embodiment mainly comprises the following components: zn56.39% wt, Fe10.91% wt, Cu0.58% wt, Ge0.022% wt.
(1) Two-step neutral leaching: taking 2500mL of electrodeposition waste liquid and 1400mL of replaced acid liquid, fully mixing, adding 10g of manganese powder and 20g of ferrous sulfate, then starting two-step neutral leaching, adding 490g of roasted ore in the 1 st time, and controlling the end-point acidity as follows: 8g/L, leaching for 1.0h, taking ore pulp, filtering and analyzing to obtain Fe 3+ /Ge=210，H 2 SO 4 9.28g/L, 90g of roasted ore is added in the 2 nd time, after leaching for 1.0h, the pH of ore pulp is 5.2, after a flocculating agent is added, leaching clarification is stopped for 0.5h, and supernatant 2750mL containing 0.24mg/L of Ge0.and 298mg/L of Cu is obtained.
(2) Acid leaching: adding 200mL of waste electrolyte into the middle leaching bottom flow, leaching for 4.0H, and filtering to obtain 1400mL of acid leaching solution containing Cu1360mg/L and H 2 SO 4 2.13g/L。
(3) Replacing copper with iron powder in pickle liquor: according to Cu 2+ 2.9g of iron powder is added into the pickle liquor with the amount of 1.5 times of the amount of the iron powder to obtain 4.9g of displaced copper slag containing 38.68 wt% of Cu0.96 wt% of Fe20.96 wt% of Ge0.21 wt%. And returning the acid immersion liquid to the next round for immersion after replacement.
The roasted ore contains Cu3.36g, the supernatant contains Cu0.82g, the replaced copper slag Cu1.90g, and the recovery rate of the supernatant and the replaced copper slag copper is 80.95%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. A method for improving the recovery rate of copper during conventional leaching of high-copper high-germanium roasted ore is characterized by comprising the following steps: the method for improving the copper recovery rate in the conventional leaching process of the high-copper high-germanium roasted ore comprises the following steps:
(1) two-step neutral leaching: adding manganese powder and ferrous sulfate into zinc electrodeposition waste liquid, adding high-copper and high-germanium roasted ore for 2 times, controlling the end point acidity to be 5-10 g/L after adding the roasted ore for 1 time, and controlling the leaching of Fe in end point slurry after adding the roasted ore for 1 time 3+ /Ge 4+ = 200-300, adding roasted ore for leaching again according to the end point pH5.2-5.4 for the 2 nd time, and adding a flocculating agent into the middle leaching ore pulp for clarification;
(2) acid leaching: adding zinc electrodeposition waste liquid into the middle leaching bottom flow, controlling the end point acidity of the slurry to be 1-3 g/L, carrying out acid leaching, and filtering acid leaching pulp after the acid leaching to obtain acid leaching liquid and acid leaching slag;
(3) replacing copper with iron powder in pickle liquor: according to Cu in pickle liquor 2+ Adding iron powder to replace copper by 1.5-2.0 times of the mass of the copper powder, and performing liquid-solid separation to obtain replaced copper slag and replaced acid liquid.
2. The method for improving the copper recovery rate during the conventional leaching of the high-copper high-germanium roasted ore according to claim 1, characterized by comprising the following steps: in the high-copper high-germanium roasted ore, Cu: 0.3-0.6% wt, Ge: 0.02 to 0.04 wt%.
3. The method for improving the copper recovery rate during the conventional leaching of the high-copper high-germanium roasted ore according to claim 1, characterized by comprising the following steps: and (2) in the supernatant produced in the step (1), Ge is less than or equal to 0.30mg/L, and Cu is less than or equal to 300 mg/L.
4. The method for improving the copper recovery rate during the conventional leaching of the high-copper high-germanium roasted ore according to claim 1, characterized by comprising the following steps: in the pickle liquor in the step (2), the Cu content is 400-1400 mg/L.
5. The method for improving the copper recovery rate during the conventional leaching of the high-copper high-germanium roasted ore according to claim 1, characterized by comprising the following steps: and (2) delivering the clarified middle supernatant obtained in the step (1) to a purification process for impurity removal.
6. The method for improving the copper recovery rate during the conventional leaching of the high-copper high-germanium roasted ore according to claim 1, characterized by comprising the following steps: and (3) conveying the acid leaching residue in the step (2) into a fuming furnace or a rotary kiln to volatilize and recover germanium according to a traditional method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331679.2A CN113088698B (en) | 2021-03-29 | 2021-03-29 | Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110331679.2A CN113088698B (en) | 2021-03-29 | 2021-03-29 | Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113088698A CN113088698A (en) | 2021-07-09 |
| CN113088698B true CN113088698B (en) | 2022-08-05 |
Family
ID=76670623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110331679.2A Active CN113088698B (en) | 2021-03-29 | 2021-03-29 | Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113088698B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113652558A (en) * | 2021-07-30 | 2021-11-16 | 葫芦岛锌业股份有限公司 | Method for recovering germanium from germanium-containing waste liquid |
| CN115029562B (en) * | 2022-01-05 | 2023-09-15 | 昆明理工大学 | Method for separating copper and germanium in zinc hydrometallurgy process |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2624658C3 (en) * | 1976-06-02 | 1980-04-17 | Ruhr - Zink Gmbh, 4354 Datteln | Process for the processing of residues left by the leaching of roasted zinc blende |
| SU1084324A1 (en) * | 1982-08-09 | 1984-04-07 | Лениногорский Ордена Трудового Красного Знамени Полиметаллический Комбинат | Method for processing zinc cinders |
| CN110541070B (en) * | 2018-05-28 | 2021-06-08 | 荆门市格林美新材料有限公司 | Method for comprehensively extracting valuable metals from white alloy |
| CN110093506B (en) * | 2019-04-09 | 2021-03-26 | 云南驰宏锌锗股份有限公司 | Method for efficiently extracting valuable metals from germanium-containing zinc leaching residues and reducing valuable metals |
| CN111363917B (en) * | 2020-03-25 | 2021-11-09 | 云南云铜锌业股份有限公司 | Treatment method of high silicon zinc roasted ore |
| CN112442606A (en) * | 2020-11-24 | 2021-03-05 | 荆门市格林美新材料有限公司 | Method for recovering germanium from germanium-containing copper-cobalt alloy |
-
2021
- 2021-03-29 CN CN202110331679.2A patent/CN113088698B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113088698A (en) | 2021-07-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3756687B2 (en) | Method for removing and fixing arsenic from arsenic-containing solutions | |
| CA1223126A (en) | Process for recovering zinc from ferrites | |
| CN113088698B (en) | Method for improving copper recovery rate during conventional leaching of high-copper high-germanium roasted ore | |
| CN102517455A (en) | Method for recovering cadmium from copper cadmium residues | |
| US4162294A (en) | Process for working up nonferrous metal hydroxide sludge waste | |
| CN113549766A (en) | Method for removing arsenic from lead smelting smoke dust and recovering valuable metals | |
| CN113151689A (en) | Method for enriching cobalt in zinc hydrometallurgy zinc powder and antimonate purification slag | |
| CN105274352B (en) | A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate | |
| CN113088710A (en) | Method for separating copper and germanium from copper and germanium replacement slag | |
| CN114517258B (en) | Wet zinc smelting two-stage leaching method for improving copper recovery rate | |
| CN112410555A (en) | Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue | |
| CN115029562B (en) | Method for separating copper and germanium in zinc hydrometallurgy process | |
| CN110172583B (en) | Method for efficiently treating arsenic-containing soot in reduction mode | |
| CA1097507A (en) | Process of treating residues from the leaching of roasted zinc blende | |
| CN111235404A (en) | Impurity removal method for producing cobalt hydroxide from copper raffinate | |
| US4778520A (en) | Process for leaching zinc from partially desulfurized zinc concentrates by sulfuric acid | |
| CN112458277B (en) | Method for recovering valuable metals from deep-sea polymetallic sulphide ores | |
| JP3411320B2 (en) | Zinc smelting method | |
| CN109913647B (en) | Wet processing method for recovering copper and zinc in bismuth middling | |
| CN113881857A (en) | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process | |
| CN115011810A (en) | Leaching process for improving copper recovery rate in zinc roasted ore | |
| CN109796049B (en) | Method for preparing iron oxide red by using iron slag precipitated by zinc hydrometallurgy goethite method | |
| CN112458306A (en) | Method for reducing zinc content of flotation silver concentrate in zinc hydrometallurgy process | |
| CS201026B2 (en) | Method for the isolation of copper from metallic materials | |
| US1496004A (en) | Process of preparing pure zinc-sulphate solutions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |