CN110760680A - Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue - Google Patents

Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue Download PDF

Info

Publication number
CN110760680A
CN110760680A CN201911057934.8A CN201911057934A CN110760680A CN 110760680 A CN110760680 A CN 110760680A CN 201911057934 A CN201911057934 A CN 201911057934A CN 110760680 A CN110760680 A CN 110760680A
Authority
CN
China
Prior art keywords
manganese
cobalt
leaching
solution
waste residue
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.)
Granted
Application number
CN201911057934.8A
Other languages
Chinese (zh)
Other versions
CN110760680B (en
Inventor
叶有明
谢雪珍
覃荣
谢雨寻
农永萍
廖政达
蒋才云
蓝峻峰
郑文仪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangxi Xiatian Manganese Mine Co ltd
Original Assignee
Guangxi Science and Technology Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangxi Science and Technology Normal University filed Critical Guangxi Science and Technology Normal University
Priority to CN201911057934.8A priority Critical patent/CN110760680B/en
Publication of CN110760680A publication Critical patent/CN110760680A/en
Application granted granted Critical
Publication of CN110760680B publication Critical patent/CN110760680B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by 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
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • 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
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
    • 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
    • C22B47/00—Obtaining manganese
    • 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)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residues, which comprises the following steps: (1) crushing and sieving: crushing the manganese-sulfur purification waste residue and sieving; (2) leaching: sequentially adding MnO into the screened manganese-sulfur purification waste residue2Heating, stirring and dissolving iron powder and a dilute sulfuric acid solution, leaching and filtering to obtain a sulfur-containing filter cake and a manganese-cobalt-nickel solution; (3) removing impurities of Fe: adding limestone into manganese cobalt nickel filtrate to adjust pH to obtain Fe (OH)3Precipitating, filtering, and collecting filtrate; (4) concentration: concentrating the filtrate after impurity removal to obtain a concentrated solution; (5) and (3) manganese separation: extracting and separating a cobalt-nickel solution and a manganese-loaded organic phase from the concentrated solution by using a P204 extractant;(6) separating and recovering cobalt: and (3) extracting and separating the cobalt-loaded organic phase and the nickel sulfate solution from the cobalt-nickel solution by adopting a P507 extraction agent, and performing back extraction on the cobalt-loaded organic phase by adopting a sulfuric acid solution to obtain a cobalt sulfate solution. The process is simple and easy to implement, can realize the rapid leaching of manganese and cobalt and can control the generation of hydrogen sulfide.

Description

Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue
Technical Field
The invention belongs to the field of comprehensive recovery of electrolytic manganese sulfur-containing waste residues, and particularly relates to a method for leaching, recovering and separating cobalt from manganese sulfur purification waste residues.
Background
Cobalt and nickel are associated metals of manganese ore in south China, most of raw materials used by electrolytic manganese production enterprises in Guangxi at present are low-grade manganese oxide ore, the impurity content of ore is high, and electrolytic waste residues are manganese and sulfur purification waste residues and mainly contain Ba, Mn, Ni, Co, S and the like. Although the contents of cobalt and nickel are not high, the contents are higher than those of natural cobalt-nickel minerals. The Guangxi electrolytic manganese production enterprise produces about 1 ten thousand tons of manganese-sulfur purification waste residues every year, the manganese content in the residues is about 15%, the cobalt content is about 1.0%, and the nickel content is about 0.8%, so that the research on leaching and recovering cobalt and nickel from the manganese-sulfur purification waste residues is of great significance.
The sulfuric acid leaching method is one of the most used methods for recovering valuable metals in slag in the current industrial production, has the characteristics of low cost and low energy consumption, and is one of the most easily-realized industrialized manganese-cobalt-nickel leaching methods, but the leaching process has the problems of long leaching time, low efficiency, difficult leaching of cobalt-nickel sulfide, easy transformation of sulfur into hydrogen sulfide, environmental pollution and the like.
Chinese patent CN103898327B proposes a method for extracting nickel from manganese-cobalt-nickel waste residue, which comprises the steps of obtaining a cobalt-nickel solution after aging and leaching by adopting concentrated sulfuric acid, removing impurities from the cobalt-nickel solution, removing impurities such as copper, iron, calcium, magnesium, manganese and zinc, adding NaF to remove calcium or/and magnesium, adding a P204 extractant to further remove impurities, and extracting and separating a nickel sulfate solution and cobalt by using a P507 extractant to obtain a nickel sulfate product. The process has relatively simple production conditions and high nickel recovery rate. But the use amount of concentrated sulfuric acid is large, and the leaching time is long.
Chinese patent CN103555959B discloses a process for comprehensively utilizing leaching residues in the production of electrolytic manganese metal and manganese dioxide, which comprises the following parts: the recovery of manganese, ammonium sulfate, calcium sulfate and ammonia gas, the recovery of manganese ore, dihydrate gypsum, iron and sulfur-cobalt-nickel-copper concentrate, the crystallization separation of ammonium sulfate and the preparation of compound fertilizer base stock. But there is no specific process for recovering and separating the cobalt nickel valuable metals.
Chinese patent CN105152153B proposes a comprehensive recycling method of leaching slag in electrolytic manganese metal production, which relates to the recovery of copper-cobalt-nickel precious metal mineral powder, the patent adjusts pH to precipitate MnS, and then sodium fermat S.D.D is used as a precipitator to precipitate heavy metal Me, thereby achieving the purpose of recovering copper-cobalt-nickel precious metal. However, the sodium ferbamate reagent is used in a large amount, the metal recovery rate is low, and no specific metal separation is performed.
At present, no feasible treatment scheme capable of fixing sulfur and efficiently and simply leaching and recycling exists for sulfur and manganese purification waste residues. .
Disclosure of Invention
The invention aims to solve the technical problems and provides a method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residues, which is simple and feasible in process, can realize rapid leaching of manganese and cobalt and can control the generation of hydrogen sulfide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residues comprises the following steps:
(1) crushing and sieving: crushing the manganese-sulfur purification waste residue and sieving;
(2) leaching: adding the filtered manganese-sulfur purification waste residue in sequenceInto MnO2Heating, stirring and dissolving iron powder and a dilute sulfuric acid solution, leaching and filtering to obtain a sulfur-containing filter cake and a manganese-cobalt-nickel solution;
(3) removing impurities of Fe: adding limestone into manganese cobalt nickel filtrate to adjust pH to obtain Fe (OH)3Precipitating, filtering, and collecting filtrate;
(4) concentration: concentrating the filtrate after impurity removal to obtain a concentrated solution;
(5) and (3) manganese separation: extracting and separating a cobalt-nickel solution and a manganese-loaded organic phase from the concentrated solution by using a P204 extractant;
(6) separating and recovering cobalt: and (3) extracting and separating the cobalt-loaded organic phase and the nickel sulfate solution from the cobalt-nickel solution by adopting a P507 extraction agent, and performing back extraction on the cobalt-loaded organic phase by adopting a sulfuric acid solution to obtain a cobalt sulfate solution.
As a further technical scheme, the content of cobalt ions in the leached manganese-cobalt-nickel solution is more than 3g/L, and the leached acidity is maintained at 0.5-2.0 mol/L.
As a further technical solution, the MnO mentioned above2The dosage of the manganese-sulfur purification waste residue is 0.5-1.0 time of the weight of the manganese-sulfur purification waste residue; the dosage of the iron powder is 0.7-1.0 time of that of the manganese-sulfur purification waste residue; the concentration of the dilute sulfuric acid solution is 0.5-2.0 mol/L, and the dilute sulfuric acid solution is added according to the proportion that 1g of manganese sulfur purification waste residue is added into 2-8 ml of dilute sulfuric acid solution; the heating temperature is 40-100 ℃, and the leaching time is 30-120 min.
As a further technical scheme, when the content of cobalt ions in the manganese-cobalt-nickel solution does not reach 3g/L, adding water and concentrated sulfuric acid into the leached manganese-cobalt-nickel solution according to the proportion of (2-8) ml of circulating liquid to adjust the acidity to 0.5-2.0 mol/L according to 1g of manganese-sulfur purification waste residue, and circulating the solution as the circulating liquid into the original screened manganese-sulfur purification waste residue to continue leaching, wherein the circulating frequency is not higher than 4 times.
As a further technical scheme, the screening is carried out, and the mesh number is 40-80 meshes.
As a further technical scheme, in the impurity removal of Fe, the pH value is adjusted to 2-4.
As a further technical scheme, in the concentration, the concentration end point is that the concentration of cobalt reaches 8-12 g/L.
As a further technical scheme, the P204 extracting agent is prepared by mixing sulfonated kerosene and P204 in a volume ratio of 1 (1-3) before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%; and carrying out back extraction on the manganese-loaded organic phase by adopting a 1mol/L sulfuric acid solution to obtain a manganese sulfate solution.
As a further technical scheme, the P507 extracting agent is prepared by mixing sulfonated kerosene and P507 according to the volume ratio of 1 (1-3) in advance before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%.
As a further technical means, the above-mentioned Fe (OH)3And (3) acidifying the precipitate by using a dilute sulfuric acid solution, and returning the precipitate to the step (2).
As a further technical scheme, the stirring and dissolving are carried out at the speed of 50-150 r/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the method is simple and easy to implement, and realizes the rapid leaching of manganese and cobalt. The reaction principle of leaching of the invention is as follows: (1)2H++Fe＝Fe2++H2↑，(2)MnO2+4H++2Fe2+＝Mn2++2Fe3++2H2O，(3)S2-+2Fe3+＝2Fe2++ S ↓, in this step, the invention adds the sulfuric acid solution of low concentration, has improved the safety of industrialization, secondly, in MnO2Under the action of redox catalysis of iron powder, the leaching temperature is reduced to 40-100 ℃ from 150-180 ℃ disclosed in patent CN103898327B, and the leaching time is shortened to 30-120 min from 2-3.5 hours, so that the aims of saving energy, reducing consumption and improving the leaching efficiency are fulfilled.
2. The invention can control the generation of hydrogen sulfide. As the reaction principle of leaching mentioned in point 1, the present invention purifies S in a waste residue from manganese sulfide2-By MnO2And iron powder is oxidized and reduced into S, so that sulfur is fixed, and the pollution of the overflow of hydrogen sulfide to the environment is avoided. About 20 percent of manganese and sulfur purification waste residueThe sulfur left in the filter cake can be further recycled according to the conventional recycling operation in the field, so that the comprehensive utilization of the sulfur is realized.
3. Due to MnO added in the invention2Is 0.5 to 1.0 time of the weight of the manganese sulfur purification waste residue, belongs to excessive addition, thereby finally obtaining S2-+2Fe3+＝2Fe2+Fe in + S ↓reaction2+Will be oxidized into Fe3+Therefore, in the step (3), limestone is added into the manganese-cobalt-nickel filtrate to adjust the pH of the reaction system to 2-4, so that Fe (OH) is ensured3Precipitate is generated, and iron impurities are removed after filtration. And (3) after the iron in the precipitate can be acidified by dilute sulfuric acid, the iron can be returned to the leaching step in the step (2) to be used as a sulfur fixation effect, so that the consumption of iron powder in the leaching step is reduced, and the cost of raw materials is reduced.
4. The invention adopts MnO2The manganese-sulfur purification waste residue is treated without introducing new impurities, and MnO can be adopted2The manganese ore (such as brown manganese ore and pyrolusite) is used as substitute, and the usage amount is pure MnO23 times of the raw material, and the raw material source is wide.
5. According to the invention, when the cobalt ion content of the leaching solution is below 3g/L, water and concentrated sulfuric acid are added into the manganese-cobalt-nickel solution, the manganese-cobalt-nickel solution is circulated to the screened manganese-sulfur purification waste residue for multiple times, and the manganese-cobalt-nickel solution is repeatedly leached under the acidity of 0.5-2.0 mol/L until the cobalt ion concentration reaches 3g/L, so that the consumption of iron powder and sulfuric acid during leaching can be obviously reduced through repeated leaching, and the concentrated sulfuric acid is used for acidity adjustment.
6. The method adopts the conventional method in the field, realizes the recovery and separation of manganese by taking sulfonated kerosene as a diluent and P204 as an extracting agent, and can return to an electrolytic manganese or manganese sulfate production line for use; by using sulfonated kerosene as a diluent and P507 as an extracting agent, the separation of cobalt and nickel is realized, and the method can be used for generating high-purity cobalt sulfate.
Drawings
FIG. 1 is a process flow diagram for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
As shown in figure 1, the method for leaching, recovering and separating cobalt from the manganese-sulfur purification waste residue comprises the following steps:
(1) crushing and sieving: crushing the manganese-sulfur purification waste residue and sieving;
(2) leaching: sequentially adding MnO into the screened manganese-sulfur purification waste residue2Heating, stirring and dissolving iron powder and a dilute sulfuric acid solution, leaching and filtering to obtain a sulfur-containing filter cake and a manganese-cobalt-nickel solution;
(3) removing impurities of Fe: adding limestone into manganese cobalt nickel filtrate to adjust pH to obtain Fe (OH)3Precipitating, filtering, and collecting filtrate;
(4) concentration: concentrating the filtrate after impurity removal to obtain a concentrated solution;
(5) and (3) manganese separation: extracting and separating a cobalt-nickel solution and a manganese-loaded organic phase from the concentrated solution by using a P204 extractant;
(6) separating and recovering cobalt: and (3) extracting and separating the cobalt-loaded organic phase and the nickel sulfate solution from the cobalt-nickel solution by adopting a P507 extraction agent, and performing back extraction on the cobalt-loaded organic phase by adopting a sulfuric acid solution to obtain a cobalt sulfate solution.
The content of cobalt ions in the leached manganese-cobalt-nickel solution is more than 3g/L, and the acidity of the leaching is maintained at 0.5-2.0 mol/L.
The MnO as described above2The dosage of the manganese-sulfur purification waste residue is 0.5-1.0 time of the weight of the manganese-sulfur purification waste residue; the dosage of the iron powder is 0.7-1.0 time of that of the manganese-sulfur purification waste residue; the concentration of the dilute sulfuric acid solution is 0.5-2.0 mol/L, and the dilute sulfuric acid solution is added according to the proportion that 1g of manganese sulfur purification waste residue is added into 2-8 ml of dilute sulfuric acid solution; the heating temperature is 40-100 ℃, and the leaching time is 30-120 min.
And when the content of cobalt ions in the manganese-cobalt-nickel solution does not reach 3g/L, adding water and concentrated sulfuric acid into the leached manganese-cobalt-nickel solution according to the proportion of (2-8) ml of circulating liquid to adjust the acidity to 0.5-2.0 mol/L, and circulating the solution serving as the circulating liquid into the original screened manganese-sulfur purification waste residue to continue leaching, wherein the circulating frequency is not higher than 4 times.
And sieving the materials to obtain the sieve with 40-80 meshes.
And in the impurity removal of Fe, adjusting the pH value to 2-4.
In the concentration, the concentration end point is that the concentration of cobalt reaches 8-12 g/L.
The P204 extracting agent is prepared by mixing sulfonated kerosene and P204 according to the volume ratio of 1 (1-3) before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%; and carrying out back extraction on the manganese-loaded organic phase by adopting a 1mol/L sulfuric acid solution to obtain a manganese sulfate solution.
The P507 extracting agent is prepared by mixing sulfonated kerosene and P507 according to the volume ratio of 1 (1-3) before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%.
To the above-mentioned Fe (OH)3And (3) acidifying the precipitate by using a dilute sulfuric acid solution, and returning the precipitate to the step (2).
The stirring and dissolving are carried out at the speed of 50-150 r/min.
Following the above procedure, the following example was carried out.
Example 1:
crushing 10g of manganese-sulfur purification waste residue, sieving with a 40-mesh sieve, and sequentially adding 5g of MnO into the manganese-sulfur purification waste residue2And 7g of iron powder, adding 80mL of 0.5mol/L sulfuric acid solution, heating to 80 ℃, stirring on a 100r/min stirrer, leaching for 30min, filtering the leachate to obtain leachate, adjusting the pH of the leachate to 4 with limestone to remove iron, filtering the solution, and concentrating the solution to 20 mL. Diluting 20mLP204 with 20mL of sulfonated kerosene to prepare an extractant, then saponifying with sodium hydroxide with the saponification rate of 10%, then adding the extractant into the concentrated solution, stirring for 10min on a 100r/min magnetic stirrer, then transferring the extract into a separating funnel for phase separation, and carrying out back extraction on the obtained organic phase with 1mol/L of sulfuric acid to recover and separate manganese sulfate, wherein the recovery rate of the manganese is 84.3%. Adding 15mL of sulfonated kerosene and 15mLP507 mixed extractant after saponification of sodium hydroxide into raffinate phase, wherein the saponification rate is 40%, stirring for 10 minutes on a magnetic stirrer at 100r/min, transferring extract liquid into a separating funnel for phase separation, and recovering and separating sulfuric acid from obtained organic phase by back extraction of 1mol/L sulfuric acidCobalt recovery was found to be 90.31%. The nickel sulfate is in the residual phase, and the recovery rate of the nickel is 89.2%.
Example 2:
crushing 10g of manganese-sulfur purification waste residue, sieving with a 40-mesh sieve, and sequentially adding 7g of MnO into the manganese-sulfur purification waste residue2And 7g of iron powder, adding 80mL of 0.5mol/L sulfuric acid solution, heating to 85 ℃, stirring on a 100r/min stirrer, leaching for 30min, filtering the leachate to obtain leachate, adjusting the pH of the leachate to 4 with limestone to remove iron, filtering the solution, and concentrating the solution to 20 mL. Diluting 30mLP204 with 15mL of sulfonated kerosene to prepare an extractant, then saponifying with sodium hydroxide, wherein the saponification rate is 60%, then adding the extractant into the concentrated solution, stirring for 10min on a 100r/min magnetic stirrer, then transferring the extract into a separating funnel for phase separation, and performing back extraction on the obtained organic phase with 1mol/L of sulfuric acid to recover and separate manganese sulfate, wherein the recovery rate of the manganese is 90.25%. 10mL of sulfonated kerosene and 30mLP507 mixed extractant after saponification of sodium hydroxide are added into the raffinate phase, the saponification rate is 60%, the mixture is stirred for 10 minutes on a magnetic stirrer at 100r/min, then the extract liquid is transferred to a separating funnel for phase separation, the obtained organic phase is subjected to back extraction by using 1mol/L sulfuric acid to recover and separate cobalt sulfate, and the measured recovery rate of the cobalt is 91.15%. The nickel sulfate is in the residual phase, and the recovery rate of the nickel is 92.62%.
Example 3:
crushing 10g of manganese-sulfur purification waste residue, sieving with a 40-mesh sieve, and sequentially adding 9g of MnO into the manganese-sulfur purification waste residue2And 7g of iron powder, adding 80mL of 0.5mol/L sulfuric acid solution, heating to 90 ℃, stirring on a 100r/min stirrer, leaching for 30min, filtering the leachate to obtain leachate, adjusting the pH of the leachate to 4 with limestone to remove iron, filtering the solution, and concentrating the solution to 20 mL. Diluting 45mLP204 with 15mL of sulfonated kerosene to prepare an extractant, then saponifying with sodium hydroxide with the saponification rate of 40%, then adding the extractant into the concentrated solution, stirring for 10min on a 100r/min magnetic stirrer, transferring the extract into a separating funnel for phase separation, and carrying out back extraction on the obtained organic phase with 1mol/L of sulfuric acid to recover and separate manganese sulfate, wherein the recovery rate of the manganese is 92.36%. 10mL of sulfonated kerosene and 30mLP507 mixed extracting agent after the extraction raffinate phase is added with sodium hydroxide for saponification, the saponification rate is 80 percent, and the magnetic field is generated at 100r/minStirring for 10 minutes by a force stirrer, transferring the extract into a separating funnel for phase separation, and performing back extraction on the obtained organic phase by using 1mol/L sulfuric acid to recover and separate cobalt sulfate, wherein the recovery rate of the cobalt is measured to be 87.45%. The nickel sulfate is in the residual phase, and the recovery rate of the nickel is 88.52%.
Example 4:
crushing 10g of manganese-sulfur purification waste residue, sieving the crushed residue with a 80-mesh sieve, and sequentially adding 10g of MnO into the manganese-sulfur purification waste residue2And 7g of iron powder, adding 80mL of 0.5mol/L sulfuric acid solution, heating to 90 ℃, stirring on a 100r/min stirrer, leaching for 45min, filtering the leachate to obtain leachate, adjusting the pH of the leachate to 3 with limestone to remove iron, filtering the solution, and concentrating the solution to 20 mL. Diluting 25mLP204 with 10mL of sulfonated kerosene to prepare an extractant, then saponifying with sodium hydroxide, wherein the saponification rate is 80%, then adding the extractant into the concentrated solution, stirring for 10min on a 100r/min magnetic stirrer, then transferring the extract into a separating funnel for phase separation, and performing back extraction on the obtained organic phase with 1mol/L of sulfuric acid to recover and separate manganese sulfate, wherein the recovery rate of the manganese is 93.32%. Adding 10mL of sulfonated kerosene and 20mLP507 mixed extractant after saponification of sodium hydroxide into the raffinate phase, wherein the saponification rate is 20%, stirring the mixture on a magnetic stirrer at 100r/min for 10 minutes, transferring the extract into a separating funnel for phase separation, recovering and separating cobalt sulfate from the obtained organic phase by back extraction of 1mol/L sulfuric acid, and determining that the recovery rate of cobalt is 92.85%. The nickel sulfate in the residual phase, and the recovery rate of nickel is 93.72%.
Example 5:
crushing 10g of manganese and sulfur purification waste residue, sieving the crushed waste residue with a 100-mesh sieve, sequentially adding 21g of manganese ore and 7g of iron powder into the manganese and sulfur purification waste residue, adding 80mL of 0.5mol/L sulfuric acid solution, heating the mixture to 95 ℃, stirring the mixture on a 100r/min stirrer, leaching the mixture for 60min, filtering the leachate to obtain leachate, adjusting the pH of the leachate to 4.0 by limestone, removing iron, filtering the solution, and concentrating the solution to 20 mL. Diluting 30mLP204 with 15mL of sulfonated kerosene to prepare an extractant, then saponifying with sodium hydroxide with the saponification rate of 30%, then adding the extractant into the concentrated solution, stirring for 10min on a 100r/min magnetic stirrer, transferring the extract into a separating funnel for phase separation, and carrying out back extraction on the obtained organic phase with 1mol/L of sulfuric acid to recover and separate manganese sulfate, wherein the recovery rate of the manganese is 93.67%. 15mL of sulfonated kerosene and 25mLP507 mixed extractant after saponification of sodium hydroxide are added into the raffinate phase, the saponification rate is 40%, the mixture is stirred for 10 minutes on a magnetic stirrer at 100r/min, then the extract liquid is transferred to a separating funnel for phase separation, the obtained organic phase is subjected to back extraction by using 1mol/L sulfuric acid to recover and separate cobalt sulfate, and the measured recovery rate of the cobalt is 91.96%. The nickel sulfate is in the residual phase, and the recovery rate of the nickel is 92.37%.
In addition to the examples given in this example, the dilute sulfuric acid solution of the present invention can be used at concentrations of 1mol/L and 2 mol/L; the leaching temperature and the leaching time in the invention can also be 40 ℃ and 120min, 50 ℃ and 120min, 60 ℃ and 90min, 70 ℃ and 90min and 100 ℃ and 30 min; the pH range of the limestone iron removal can also be 2, when the pH is lower than 2, iron hydroxide precipitation is not easy to form, when the pH is higher than 4, much calcium carbonate is consumed, more carbon dioxide is generated, and the pH range is convenient for later extraction and separation.
The extraction of manganese sulfate with the P204 extractant and cobalt sulfate with the P507 extractant are conventional in the art, and therefore, the implementation data are not given in excess.
The invention uses examples for comparative experiments:
the present invention adopts the conditions of example 4 to perform a leachate circulation experiment, and the raw materials, steps and parameters of the following comparative examples are the same as those of example 4, and each time the leaching solution is supplemented with water to 80 mL.
The comparison after the experiment is shown in the table one:
watch 1
From the table i, it can be seen that the method of leaching repeatedly using the leachate is really feasible, but because of the high manganese concentration, the number of times of leaching repeatedly is too large to be supersaturated, and therefore, it is preferable to repeat four times. The iron and sulfuric acid investment can be saved by circulating leaching.
The above-described embodiments are only specific examples for further explaining the object, technical solution and advantageous effects of the present invention in detail, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement and the like made within the scope of the present disclosure are included in the protection scope of the present invention.

Claims (10)

1. A method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue is characterized by comprising the following steps:
(1) crushing and sieving: crushing the manganese-sulfur purification waste residue and sieving;
(2) leaching: sequentially adding MnO into the screened manganese-sulfur purification waste residue2Heating, stirring and dissolving iron powder and a dilute sulfuric acid solution, leaching and filtering to obtain a sulfur-containing filter cake and a manganese-cobalt-nickel solution;
(3) removing impurities of Fe: adding limestone into manganese cobalt nickel filtrate to adjust pH to obtain Fe (OH)3Precipitating, filtering, and collecting filtrate;
(4) concentration: concentrating the filtrate after impurity removal to obtain a concentrated solution;
(5) and (3) manganese separation: extracting and separating a cobalt-nickel solution and a manganese-loaded organic phase from the concentrated solution by using a P204 extractant;
(6) separating and recovering cobalt: and (3) extracting and separating the cobalt-loaded organic phase and the nickel sulfate solution from the cobalt-nickel solution by adopting a P507 extraction agent, and performing back extraction on the cobalt-loaded organic phase by adopting a sulfuric acid solution to obtain a cobalt sulfate solution.
2. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: the content of cobalt ions in the leached manganese-cobalt-nickel solution is more than 3g/L, and the leached acidity is maintained at 0.5-2.0 mol/L.
3. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 2, is characterized in that: the MnO2The dosage of the manganese-sulfur purification waste residue is 0.5-1.0 time of the weight of the manganese-sulfur purification waste residue; the dosage of the iron powder is 0.7-1.0 time of that of the manganese-sulfur purification waste residue; the concentration of the dilute sulfuric acid solution is 0.5-2.0 mol/L, and the dilute sulfuric acid solution contains 1g of manganeseAdding 2-8 ml of dilute sulfuric acid solution into the sulfur purification waste residue in a ratio; the heating temperature is 40-100 ℃, and the leaching time is 30-120 min.
4. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 3, is characterized in that: and when the content of cobalt ions in the manganese-cobalt-nickel solution does not reach 3g/L, adding water and concentrated sulfuric acid into the leached manganese-cobalt-nickel solution according to the proportion of (2-8) ml of circulating liquid to adjust the acidity to 0.5-2.0 mol/L, and circulating the solution serving as the circulating liquid into the original screened manganese-sulfur purification waste residue to continue leaching, wherein the circulating frequency is not higher than 4 times.
5. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: the method is characterized in that: and sieving the materials to obtain 40-80 meshes.
6. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: and in the impurity removal of Fe, adjusting the pH value to 2-4.
7. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: in the concentration, the concentration end point is that the concentration of cobalt reaches 8-12 g/L.
8. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: the P204 extracting agent is prepared by mixing sulfonated kerosene and P204 according to the volume ratio of 1 (1-3) before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%; and carrying out back extraction on the manganese-loaded organic phase by adopting a 1mol/L sulfuric acid solution to obtain a manganese sulfate solution.
9. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: the P507 extracting agent is prepared by mixing sulfonated kerosene and P507 according to the volume ratio of 1 (1-3) before extraction, and then adding NaOH solution for saponification, wherein the saponification rate is 10-80%.
10. The method for leaching, recovering and separating cobalt from manganese sulfur purification waste residue according to claim 1, is characterized in that: to the Fe (OH)3And (3) acidifying the precipitate by using a dilute sulfuric acid solution, and returning the precipitate to the step (2).
CN201911057934.8A 2019-11-01 2019-11-01 Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue Active CN110760680B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911057934.8A CN110760680B (en) 2019-11-01 2019-11-01 Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911057934.8A CN110760680B (en) 2019-11-01 2019-11-01 Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue

Publications (2)

Publication Number Publication Date
CN110760680A true CN110760680A (en) 2020-02-07
CN110760680B CN110760680B (en) 2021-05-11

Family

ID=69335621

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911057934.8A Active CN110760680B (en) 2019-11-01 2019-11-01 Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue

Country Status (1)

Country Link
CN (1) CN110760680B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111304439A (en) * 2020-03-31 2020-06-19 北京矿冶科技集团有限公司 Method for recovering valuable metals from submarine manganese ore resources
CN112575208A (en) * 2020-12-02 2021-03-30 桂林理工大学 Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag
CN112662877A (en) * 2020-12-02 2021-04-16 广西科技师范学院 Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag
CN113735179A (en) * 2021-08-24 2021-12-03 广西锰华新能源科技发展有限公司 Method for preparing high-purity ferric sulfate by using ferro-manganese
CN114293036A (en) * 2021-12-24 2022-04-08 南方锰业集团有限责任公司大新锰矿分公司 Method for inhibiting generation of hydrogen sulfide in leaching process of high-sulfur manganese carbonate ore

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724697A (en) * 2004-07-19 2006-01-25 中南大学 Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore
CN103773961A (en) * 2014-01-23 2014-05-07 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue
CN103898328A (en) * 2014-01-23 2014-07-02 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt from manganese-cobalt-nickel waste residues
CN103898327A (en) * 2014-01-23 2014-07-02 广西有色金属集团汇元锰业有限公司 Method for extracting nickel from manganese cobalt nickel waste slag
WO2017151882A1 (en) * 2016-03-02 2017-09-08 Kasaaian Arash Sulfide recycling in manganese production
CN110157911A (en) * 2019-04-03 2019-08-23 张响 A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1724697A (en) * 2004-07-19 2006-01-25 中南大学 Method of manufacturing electrolytic metal manganese using titanium white waste acid and manganese dioxide ore
CN103773961A (en) * 2014-01-23 2014-05-07 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt and nickel from manganese, cobalt and nickel waste residue
CN103898328A (en) * 2014-01-23 2014-07-02 广西有色金属集团汇元锰业有限公司 Method for extracting cobalt from manganese-cobalt-nickel waste residues
CN103898327A (en) * 2014-01-23 2014-07-02 广西有色金属集团汇元锰业有限公司 Method for extracting nickel from manganese cobalt nickel waste slag
WO2017151882A1 (en) * 2016-03-02 2017-09-08 Kasaaian Arash Sulfide recycling in manganese production
CN110157911A (en) * 2019-04-03 2019-08-23 张响 A kind of technique of comprehensive reutilization electrolytic manganese residues and manganese tailing

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111304439A (en) * 2020-03-31 2020-06-19 北京矿冶科技集团有限公司 Method for recovering valuable metals from submarine manganese ore resources
CN112575208A (en) * 2020-12-02 2021-03-30 桂林理工大学 Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag
CN112662877A (en) * 2020-12-02 2021-04-16 广西科技师范学院 Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag
CN112575208B (en) * 2020-12-02 2021-08-24 桂林理工大学 Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag
CN112662877B (en) * 2020-12-02 2023-12-12 广西科技师范学院 Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag
CN113735179A (en) * 2021-08-24 2021-12-03 广西锰华新能源科技发展有限公司 Method for preparing high-purity ferric sulfate by using ferro-manganese
CN114293036A (en) * 2021-12-24 2022-04-08 南方锰业集团有限责任公司大新锰矿分公司 Method for inhibiting generation of hydrogen sulfide in leaching process of high-sulfur manganese carbonate ore

Also Published As

Publication number Publication date
CN110760680B (en) 2021-05-11

Similar Documents

Publication Publication Date Title
CN110760680B (en) Method for leaching, recovering and separating cobalt from manganese-sulfur purification waste residue
CN110938743B (en) Method for extracting lithium and nickel and cobalt from waste lithium ion battery step by step
CN110885090A (en) Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method
CN112662877B (en) Method for preparing high-purity nickel sulfate from electrolytic manganese sulfide slag
CN102094119A (en) Method for preparing electrolytic manganese metal with low-grade pyrolusite wet leaching
CN108570557B (en) Method for separating iron, chromium, nickel, copper and zinc from high-iron high-chromium electroplating sludge leachate
CN111471864B (en) Method for recovering copper, aluminum and iron from waste lithium ion battery leachate
CN110835683B (en) Method for selectively extracting lithium from waste lithium ion battery material
CN103276196B (en) Method for extracting vanadium from vanadium-titanium magnetite concentrates
CN110066920B (en) Method for selectively leaching and separating vanadium and iron from stone coal vanadium ore
CN112939046A (en) Comprehensive recycling method of coal-based solid waste
CN112079371A (en) Recovery method for removing fluorine in nickel-cobalt-manganese solution
CN113292057B (en) Recovery method of waste lithium iron phosphate battery
CN112110466B (en) Method for removing iron impurities in fly ash and intermediate product thereof
CN112375910A (en) Recovery processing method of waste power battery powder
CN112410555A (en) Comprehensive recovery method for flotation silver concentrate from zinc hydrometallurgy acidic leaching residue
CN111254276A (en) Method for selectively extracting valuable metals from waste lithium ion battery powder based on phase conversion of sodium reduction roasting
CN113512652B (en) Method for extracting gallium metal from coal-series solid waste
CN110699553B (en) Method for leaching, recovering and separating nickel from manganese-sulfur purification waste residue
CN114621080A (en) Method for preparing iron manganese oxalate by using high-iron manganese oxide ore
CN110331284A (en) A method of electrolytic manganese is prepared using pyrolusite
CN111500860B (en) Process method for recovering copper from low-grade copper oxide ore
CN101693554A (en) Method for extracting vanadium pentoxide from stone coal ores
CN113293307A (en) Method for extracting iron and cobalt from neodymium iron boron waste iron tailings obtained by hydrochloric acid optimum dissolution method
CN110735032B (en) Vanadium-titanium-iron paragenetic ore treatment process

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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221212

Address after: 545800 Xiatian Tangkou, gucai villager committee, Xiangzhou Town, Xiangzhou County, Laibin City, Guangxi Zhuang Autonomous Region

Patentee after: Guangxi Xiatian Manganese Mine Co.,Ltd.

Address before: No. 966, Tiebei Avenue, Xingbin District, Laibin City, Guangxi Zhuang Autonomous Region

Patentee before: GUANGXI SCIENCE & TECHNOLOGY NORMAL University