CN113528823A - Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag - Google Patents

Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag Download PDF

Info

Publication number
CN113528823A
CN113528823A CN202110520238.7A CN202110520238A CN113528823A CN 113528823 A CN113528823 A CN 113528823A CN 202110520238 A CN202110520238 A CN 202110520238A CN 113528823 A CN113528823 A CN 113528823A
Authority
CN
China
Prior art keywords
leaching
stage
extraction
zinc
copper
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.)
Pending
Application number
CN202110520238.7A
Other languages
Chinese (zh)
Inventor
邵传兵
汪友元
鲁兴武
李琦
李俞良
余江鸿
程亮
李玉
张恩玉
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.)
Northwest Research Institute of Mining and Metallurgy
Original Assignee
Northwest Research Institute of Mining and Metallurgy
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 Northwest Research Institute of Mining and Metallurgy filed Critical Northwest Research Institute of Mining and Metallurgy
Priority to CN202110520238.7A priority Critical patent/CN113528823A/en
Publication of CN113528823A publication Critical patent/CN113528823A/en
Pending legal-status Critical Current

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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/06—Carbonates
    • 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
    • C22B15/0086—Treating solutions by physical 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/20—Obtaining zinc otherwise than by distilling
    • C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
    • 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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • 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)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention relates to the technical field of non-ferrous metal recovery, and discloses a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag, which comprises the following steps of (1) primary leaching: adding the leachate C obtained in the step (2) and a leaching agent into a first-stage weak acid leaching tank, putting the neutralized slag into the first-stage weak acid leaching tank, leaching for 2 hours at 85 +/-5 ℃, performing liquid-solid separation by using a filter press at the end of leaching to obtain a first-stage leaching slag A and a first-stage leaching solution B, taking the first-stage leaching slag A as a raw material in the step (2), and performing the operation in the step (3) on the first-stage leaching solution B; step (2) secondary leaching: adding calculated production water and a leaching agent sulfuric acid into a two-stage acidic leaching tank; the invention realizes that the copper, the cobalt and the zinc in the slag respectively reach the total leaching rate indexes of more than 95 percent, 90 percent and 90 percent through two-stage leaching, and the leaching rate of harmful elements such as calcium, arsenic and the like is lower than 1.6 percent, thereby creating good conditions for the high-efficiency recovery of valuable elements.

Description

Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag
Technical Field
The invention relates to the technical field of non-ferrous metal recovery, in particular to a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag.
Background
The arsenic-cobalt-zinc-containing neutralization slag is waste residue obtained by carrying out oxidation neutralization treatment on smelting wastewater in the non-ferrous metal smelting process, has low content of valuable elements and complex components, and is easy to cause serious pollution to the surrounding water environment.
Along with the sustainable development of social economy, the demand of cobalt resources for war is increased day by day, but the cobalt ores capable of being exploited and smelted are gradually reduced, the contradiction between supply and demand is increasingly revealed, and the arsenic-containing neutralized slag is safely and comprehensively recovered, so that the pollution degree of the dangerous solid waste to the environment can be greatly digested and alleviated, the valuable element cobalt contained in the arsenic-containing neutralized slag can be effectively recovered, the comprehensive utilization of resources is realized, and the sustainable development and operation concept of the colored industry is met.
At present, the dangerous materials with recovery value are mainly recovered and treated by the following three ways: 1. slag yard stockpiling: because the content of valuable elements is low, the recovery technology is strict, the recovery cost is high, and a plurality of smelting enterprises adopt stockpiling treatment; 2. a small amount of private enterprises can see the materials from production enterprises at low cost, simple acidic leaching and neutralization precipitation are adopted, and dual-purpose sodium carbonate precipitation is adopted to obtain copper-containing crude basic zinc carbonate; 3. according to the processing cost of 2000 yuan/ton, a company with processing qualification is entrusted to properly process, but the prior art has the problem of low recovery efficiency.
Disclosure of Invention
The invention provides a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag, which realizes the purposes that the total recovery rate of valuable elements cobalt and zinc in the slag is more than 90 percent, the total recovery rate of copper is more than 95 percent, the production environment is friendly, the control index is simple, the operability is strong, the metal recovery rate is high, and the industrial application is easy to realize.
In order to achieve the purpose, the invention provides the following technical scheme: a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag comprises the following steps:
leaching in the first stage of the step (1): adding the leachate C obtained in the step (2) and a leaching agent into a first-stage weak acid leaching tank, putting the neutralized slag into the first-stage weak acid leaching tank, leaching for 2 hours at 85 +/-5 ℃, performing liquid-solid separation by using a filter press at the end of leaching to obtain a first-stage leaching slag A and a first-stage leaching solution B, taking the first-stage leaching slag A as a raw material in the step (2), and performing the operation in the step (3) on the first-stage leaching solution B;
step (2) secondary leaching: adding calculated production water and sulfuric acid serving as a leaching agent into a second-stage acidic leaching tank, adding the first-stage leaching residue A obtained in the step (1) under the condition of starting stirring, heating and maintaining the reaction temperature to be more than 80 ℃, leaching for 2 hours, and performing filter pressing and washing to obtain a second-stage leaching solution C and a second-stage leaching residue D;
step (3), first-stage leaching solution extraction decoppering and back extraction solution electrodeposition: carrying out copper extraction on the leachate B obtained in the step (1) and a copper extraction organic phase according to a phase ratio (oil phase/water phase) O/A =1/3, wherein the extraction time is 3min, the system temperature is 20 ℃, the extraction stage number is 3, extraction raffinate E and a copper-loaded organic phase F are obtained by extraction, the extraction raffinate E enters a step (4), after the copper-loaded organic phase F is subjected to primary washing by pure water, 200G/L sulfuric acid solution is used for carrying out 3-stage back extraction according to a phase ratio O/A =2/1, copper-rich back extraction liquid G and a regenerated organic phase H are obtained, the regenerated organic phase H is subjected to cyclic extraction of copper, and the copper-rich back extraction liquid G is subjected to deep oil removal by activated carbon and then is electrodeposited according to a conventional copper electrodeposition process to obtain a product cathode copper;
and (4) purifying and calcium removing the copper extraction raffinate: pumping the raffinate E obtained in the step (3) into an indirect heating reaction kettle, heating to 85 +/-5 ℃, adding ammonium fluoride (NH 4F) and a regulator, and reacting for 60-90 min; after the reaction is finished, transferring the solution into a sedimentation tank, naturally cooling and standing for more than 12 hours, and respectively obtaining calcium-magnesium slag and calcium-removed solution I after liquid-solid separation;
after calcium removal, liquid extraction of zinc and impurity metals: pumping the calcium-removed liquid I obtained in the step (4) into a mixing and clarifying extraction box by a pump, mixing the calcium-removed liquid I with an organic phase mainly comprising a P204 extractant according to a ratio (oil phase/water phase) O/A =1/2, extracting for 5min at a system temperature of 20 ℃, extracting for 6 grades to obtain a loaded organic phase J and an extraction raffinate K, wherein the raffinate K enters the step (6), and after the loaded organic phase J is subjected to two-stage countercurrent washing by a dilute sulfuric acid solution with the pH value of 1, carrying out 3-level back extraction by using 130-160g/L sulfuric acid solution according to the ratio of O/A =2/1 to obtain an impurity-containing zinc-rich back extraction solution M and a regenerated organic phase L, returning the regenerated organic phase to the liquid zinc and impurity cycle extraction after calcium removal, the zinc-rich strip liquor M is deeply degreased by active carbon and then precipitated by ammonium bicarbonate to obtain mixed inorganic salt mainly comprising basic zinc carbonate;
and (6) precipitating cobalt carbonate by using a zinc extraction raffinate: and (3) adding precipitator ammonium bicarbonate into the solution until the pH value of the solution is 8-8.5, precipitating cobalt in a cobalt carbonate precipitation mode, and washing the cobalt with hot water to be neutral to obtain a first-grade cobalt carbonate product, wherein the main component of the raffinate K obtained in the step (5) is estimated to be 2.6-3g/L, the content ratio of other heavy metal ions is not more than 0.1mg/L, and the content ratio of cobalt to impurities is more than 26000.
Further, in the step (1), the leaching agent comprises two substances of sulfuric acid (in terms of 93%) and hydrogen peroxide (in terms of 30%), the dosage of the sulfuric acid is 60-90ml/kg of neutralized slag, the dosage of the hydrogen peroxide is 30-50ml/kg of neutralized slag, and the liquid-solid mass ratio L/S =2.5-3 during leaching.
As a further scheme of the invention, the dosage of the sulfuric acid used as the leaching agent in the step (2) is 70-100ml/kg of neutralization slag (based on the consumption of the initial neutralization slag, 40% -50% of the total dosage of the sulfuric acid is added in the first stage, and 50% -60% of the sulfuric acid is added in the second stage), and the liquid-solid mass ratio L/S =2 is controlled during leaching.
Preferably, in the step (3), the copper extraction oil phase composition is as follows: 40% LIX984+60% 200% mineral spirits.
Further, in the step (4), ammonium fluoride (NH)4F) The dosage is 100 percent of the total mass of calcium in the solution, the regulator is 40g/L sodium hydroxide solution, and the final pH value of the solution at the later stage of calcium precipitation is controlled to be 5.2-5.5.
As a further embodiment of the present invention, in the step (5), the composition of the zinc and impurity extraction oil phase is: 40% P204+60%200 solvent oil, the extraction oil phase is subjected to 3-stage saponification treatment with 40g/L sodium hydroxide solution before being extracted, and the saponification phase ratio is O/A = 3/2.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention realizes the comprehensive recovery of valuable elements copper, zinc and cobalt in the neutralized slag in a proper product form.
2. The recovery process of the invention is a full wet process, no waste gas is discharged, only a small amount of waste liquid and waste residue are generated, and the recycling economy and green industrial waste utilization and decrement indexes are realized.
3. The invention realizes that the copper, the cobalt and the zinc in the slag respectively reach the total leaching rate indexes of more than 95 percent, 90 percent and 90 percent through two-stage leaching, and the leaching rate of harmful elements such as calcium, arsenic and the like is lower than 1.6 percent, thereby creating good conditions for the high-efficiency recovery of valuable elements.
4. The invention adopts the prior advanced solvent extraction process to purify and separate and recover valuable metals of copper, zinc and cobalt from the solution, and has the advantages of high metal recovery rate, thorough impurity purification and low operation cost.
Drawings
FIG. 1 is a schematic flow structure diagram of a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag provided by the invention.
The drawings are for illustrative purposes only and are not to be construed as limiting the patent; for the purpose of better illustrating the embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the invention provides a production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag, which comprises the following steps:
leaching in the first stage of the step (1): putting 10kg of neutralization slag into an enamel reaction kettle filled with 28L of water in advance, starting a stirring and electric heating device, slowly adding 300mL of hydrogen peroxide, slowly adding 700mL of 93% sulfuric acid, controlling the temperature to be 80 ℃ and reacting for 2 hours, and filtering;
step (2) secondary leaching: carrying out second-stage leaching on the first-stage leaching residue, pre-filling 15L of water into an enamel reaction kettle, starting a stirring and electric heating device, slowly adding 1000mL of 93% sulfuric acid, and controlling the temperature to be 80 ℃ to react for 2 hours;
table 1 two-section leaching analysis data table
Figure 458859DEST_PATH_IMAGE001
Step (3), first-stage leaching solution extraction decoppering and back extraction solution electrodeposition: mixing the primary leachate obtained in the step (1) with a copper extraction organic phase (40% LIX984+60%200 solvent oil) according to a phase ratio (oil phase/water phase) O/A =1/3 to extract copper, wherein the extraction time is 3min, the mixing temperature is 20 ℃, the extraction level is 3 levels, the copper-loaded organic phase F is subjected to primary washing by pure water (the mixing time is 3min, the mixing temperature is 20 ℃, the phase ratio O/A = 3/1), and then is subjected to 3 levels of back extraction by 200g/L sulfuric acid solution according to a phase ratio O/A =2/1 (the mixing time is 3min, and the mixing temperature is 20 ℃);
the results of this procedure are shown in table 2 below:
TABLE 2 copper extraction analysis data sheet
Figure 579261DEST_PATH_IMAGE003
And (4) purifying and calcium removing the copper extraction raffinate: adding the raffinate obtained in the step (3) into a reaction kettle, heating to 85 +/-5 ℃, and adding ammonium fluoride (NH)4F) And a regulator, and reacting for 60 min; after the reaction is finished, stopping stirring, naturally cooling and standing for 12 hours, and carrying out liquid-solid separation;
the results of this procedure are shown in table 3 below:
TABLE 3 chemical decalcification analysis data sheet
Figure DEST_PATH_IMAGE004
After calcium removal, liquid extraction of zinc and impurity metals: mixing the calcium-removed solution obtained in the step (4) with an organic phase (which is saponified by 40g/L sodium hydroxide in advance and has the grade 3 and the grade 6 compared with O/A = 3/2) mainly containing a P204 extracting agent according to the ratio (oil phase/water phase) O/A =1/2, wherein the extraction time is 5min, the system temperature is 20 ℃, the grade 6 of extraction is performed, two-stage countercurrent washing is performed on the loaded organic phase by a dilute sulfuric acid solution with the pH value of 1 (the mixing time is 3min, the mixing temperature is 20 ℃, the grade O/A =3/1 compared with the mixing temperature), 3-stage back extraction is performed by a 150g/L sulfuric acid solution according to the ratio O/A =2/1, and the zinc-rich back extraction solution is deoiled by activated carbon and then is precipitated by ammonium bicarbonate to obtain a mixed salt;
the results of this procedure are shown in table 4 below:
TABLE 4 extraction and precipitation recovery analysis data sheet
Figure 358999DEST_PATH_IMAGE005
And (6) precipitating cobalt carbonate by using a zinc extraction raffinate: heating 1L of the extraction residual liquid obtained in the step (5) to 80 ℃, slowly adding a saturated ammonium bicarbonate solution to the pH value of 8, stirring for 30min, and carrying out hot filtration; and (5) washing the filter cake with the produced water to be neutral to obtain the cobalt carbonate product.
The results of this procedure are shown in Table 5 below.
TABLE 5 analytical data sheet for precipitated cobalt carbonate
Figure DEST_PATH_IMAGE006
The total metal recovery (%) of this example, zinc 93.46, copper 95.52, cobalt 91.74, and cadmium 93.36 were obtained by calculation.
The standard parts used in the invention can be purchased from the market, the special-shaped parts can be customized according to the description of the specification and the accompanying drawings, the specific connection mode of each part adopts conventional means such as bolts, rivets, welding and the like mature in the prior art, the machines, the parts and equipment adopt conventional models in the prior art, and the circuit connection adopts the conventional connection mode in the prior art, so that the detailed description is omitted.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (6)

1. A production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag is characterized by comprising the following steps: the method comprises the following steps:
leaching in the first stage of the step (1): adding the leachate C obtained in the step (2) and a leaching agent into a first-stage weak acid leaching tank, putting the neutralized slag into the first-stage weak acid leaching tank, leaching for 2 hours at 85 +/-5 ℃, performing liquid-solid separation by using a filter press at the end of leaching to obtain a first-stage leaching slag A and a first-stage leaching solution B, taking the first-stage leaching slag A as a raw material in the step (2), and performing the operation in the step (3) on the first-stage leaching solution B;
step (2) secondary leaching: adding calculated production water and sulfuric acid serving as a leaching agent into a second-stage acidic leaching tank, adding the first-stage leaching residue A obtained in the step (1) under the condition of starting stirring, heating and maintaining the reaction temperature to be more than 80 ℃, leaching for 2 hours, and performing filter pressing and washing to obtain a second-stage leaching solution C and a second-stage leaching residue D;
step (3), first-stage leaching solution extraction decoppering and back extraction solution electrodeposition: carrying out copper extraction on the leachate B obtained in the step (1) and a copper extraction organic phase according to a phase ratio (oil phase/water phase) O/A =1/3, wherein the extraction time is 3min, the system temperature is 20 ℃, the extraction stage number is 3, extraction raffinate E and a copper-loaded organic phase F are obtained by extraction, the extraction raffinate E enters a step (4), after the copper-loaded organic phase F is subjected to primary washing by pure water, 200G/L sulfuric acid solution is used for carrying out 3-stage back extraction according to a phase ratio O/A =2/1, copper-rich back extraction liquid G and a regenerated organic phase H are obtained, the regenerated organic phase H is subjected to cyclic extraction of copper, and the copper-rich back extraction liquid G is subjected to deep oil removal by activated carbon and then is electrodeposited according to a conventional copper electrodeposition process to obtain a product cathode copper;
and (4) purifying and calcium removing the copper extraction raffinate: pumping the raffinate E obtained in the step (3) into an indirect heating reaction kettle, heating to 85 +/-5 ℃, adding ammonium fluoride (NH 4F) and a regulator, and reacting for 60-90 min; after the reaction is finished, transferring the solution into a sedimentation tank, naturally cooling and standing for more than 12 hours, and respectively obtaining calcium-magnesium slag and calcium-removed solution I after liquid-solid separation;
after calcium removal, liquid extraction of zinc and impurity metals: pumping the calcium-removed liquid I obtained in the step (4) into a mixing and clarifying extraction box by a pump, mixing the calcium-removed liquid I with an organic phase mainly comprising a P204 extractant according to a ratio (oil phase/water phase) O/A =1/2, extracting for 5min at a system temperature of 20 ℃, extracting for 6 grades to obtain a loaded organic phase J and an extraction raffinate K, wherein the raffinate K enters the step (6), and after the loaded organic phase J is subjected to two-stage countercurrent washing by a dilute sulfuric acid solution with the pH value of 1, carrying out 3-level back extraction by using 130-160g/L sulfuric acid solution according to the ratio of O/A =2/1 to obtain an impurity-containing zinc-rich back extraction solution M and a regenerated organic phase L, returning the regenerated organic phase to the liquid zinc and impurity cycle extraction after calcium removal, the zinc-rich strip liquor M is deeply degreased by active carbon and then precipitated by ammonium bicarbonate to obtain mixed inorganic salt mainly comprising basic zinc carbonate;
and (6) precipitating cobalt carbonate by using a zinc extraction raffinate: and (3) adding precipitator ammonium bicarbonate into the solution until the pH value of the solution is 8-8.5, precipitating cobalt in a cobalt carbonate precipitation mode, and washing the cobalt with hot water to be neutral to obtain a first-grade cobalt carbonate product, wherein the main component of the raffinate K obtained in the step (5) is estimated to be 2.6-3g/L, the content ratio of other heavy metal ions is not more than 0.1mg/L, and the content ratio of cobalt to impurities is more than 26000.
2. The production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag according to claim 1, which is characterized by comprising the following steps: in the step (1), the leaching agent comprises sulfuric acid (in terms of 93%) and hydrogen peroxide (in terms of 30%), the amount of the sulfuric acid is 60-90ml/kg of neutralized slag, the amount of the hydrogen peroxide is 30-50ml/kg of neutralized slag, and the liquid-solid mass ratio L/S =2.5-3 during leaching.
3. The production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag according to claim 2, which is characterized by comprising the following steps: the dosage of the leaching agent sulfuric acid in the step (2) is 70-100ml/kg of neutralization slag (based on the consumption of the initial neutralization slag, 40% -50% of the total dosage of the sulfuric acid is added in the first section, and 50% -60% of the sulfuric acid is added in the second section), and the liquid-solid mass ratio L/S =2 is controlled during leaching.
4. The production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag according to claim 1, which is characterized by comprising the following steps: in the step (3), the copper extraction oil phase composition is as follows: 40% LIX984+60% 200% mineral spirits.
5. The production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag according to claim 1, which is characterized by comprising the following steps: in the step (4), ammonium fluoride (NH)4F) The dosage is 100 percent of the total mass of calcium in the solution, the regulator is 40g/L sodium hydroxide solution, and the final pH value of the solution at the later stage of calcium precipitation is controlled to be 5.2-5.5.
6. The production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag according to claim 1, which is characterized by comprising the following steps: in the step (5), the zinc and impurity extraction oil phase composition is as follows: 40% P204+60%200 solvent oil, the extraction oil phase is subjected to 3-stage saponification treatment with 40g/L sodium hydroxide solution before being extracted, and the saponification phase ratio is O/A = 3/2.
CN202110520238.7A 2021-05-13 2021-05-13 Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag Pending CN113528823A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110520238.7A CN113528823A (en) 2021-05-13 2021-05-13 Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110520238.7A CN113528823A (en) 2021-05-13 2021-05-13 Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag

Publications (1)

Publication Number Publication Date
CN113528823A true CN113528823A (en) 2021-10-22

Family

ID=78095349

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110520238.7A Pending CN113528823A (en) 2021-05-13 2021-05-13 Production method for comprehensively recovering copper, zinc and cobalt in arsenic-containing neutralized slag

Country Status (1)

Country Link
CN (1) CN113528823A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008076A (en) * 1975-01-15 1977-02-15 Duisburger Kupferhutte Method for processing manganese nodules and recovering the values contained therein
WO1998014623A1 (en) * 1996-10-02 1998-04-09 International Curator Resources Limited Hydrometallurgical extraction of copper, zinc and cobalt from ores containing manganese dioxide
CN104846202A (en) * 2015-05-15 2015-08-19 西北矿冶研究院 Method for producing electrodeposited copper from multi-metal copper slag
CN109913658A (en) * 2019-04-04 2019-06-21 昆明理工大学 A method of the pickle liquor of smelting smoke dust containing arsenical copper arsenic, copper, Zn-Ca series separation and recycling
CN113046574A (en) * 2021-03-17 2021-06-29 沈阳有色金属研究院有限公司 Method for preparing high-purity nickel and cobalt products by treating crude cobalt hydroxide with copper electrolysis decoppering post-treatment solution

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4008076A (en) * 1975-01-15 1977-02-15 Duisburger Kupferhutte Method for processing manganese nodules and recovering the values contained therein
WO1998014623A1 (en) * 1996-10-02 1998-04-09 International Curator Resources Limited Hydrometallurgical extraction of copper, zinc and cobalt from ores containing manganese dioxide
CN104846202A (en) * 2015-05-15 2015-08-19 西北矿冶研究院 Method for producing electrodeposited copper from multi-metal copper slag
CN109913658A (en) * 2019-04-04 2019-06-21 昆明理工大学 A method of the pickle liquor of smelting smoke dust containing arsenical copper arsenic, copper, Zn-Ca series separation and recycling
CN113046574A (en) * 2021-03-17 2021-06-29 沈阳有色金属研究院有限公司 Method for preparing high-purity nickel and cobalt products by treating crude cobalt hydroxide with copper electrolysis decoppering post-treatment solution

Similar Documents

Publication Publication Date Title
CN108002408B (en) Method for preparing nickel sulfate, manganese, lithium, cobalt and cobaltosic oxide from battery waste
CN109706319B (en) Method for low-cost recovery of metal and production of refined nickel sulfate from electroplating sludge
CN101838736B (en) Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
CN105200235B (en) The method that valuable metal prepares tough cathode and LITHIUM BATTERY nickel sulfate is reclaimed from electroplating sludge
CN109234526B (en) Treatment method of laterite-nickel ore
CN103643044B (en) The direct extracting copper of a kind of Bellamya aeruginosa wet method, zinc technology
CN106048217B (en) The comprehensive reutilization method of oxide powder and zinc
CN103224259A (en) Method for refining crude nickel sulphate and recycling valuable metals
CN103060562B (en) Purification method of inorganic highly-acidic nickel salt solution
CN102260795A (en) Method for directly producing electrolytic nickel by using copper nickel renewable resources
CN1786225A (en) Wet treatment method of iron containing nickel sulfide material
KR101021180B1 (en) Method for producing high purity cobalt surfate
CN101974685A (en) Process for extracting nickel-cobalt from laterite by using resin-in-pulp adsorption technology
WO2015146329A1 (en) Copper removal method for aqueous nickel chloride solution
CN104480325A (en) Method for extracting cobalt from cobalt-containing raw material
CN102912133A (en) Method for classifying and purifying heavy metals in electroplating sludge
CN107354484A (en) Method for removing chlorine in zinc electrolysis waste liquid
CN106435213A (en) Method for comprehensively recovering zinc nickel cadmium from copper cadmium residues
CN102021336A (en) Method for separating zinc, fluorine and chlorine from fluorine- and chlorine-containing zinc sulfate solution
CN103771526A (en) Method for preparing high-purity manganese sulfate with industrial manganese sulfate as raw material
CN105800819A (en) Method for high-efficiency separation of valuable metal ions in complex solution containing heavy metals
CN106630313A (en) Reduction circulation process method for recycling zinc elements in iron-containing waste acid
CN102515389A (en) Harmless treatment process for acidic copper-containing wastewater
CN102443700B (en) Method for recovering nickel from nickel-laterite leaching solution and device
CN116377243A (en) Method for separating nickel, cobalt and manganese from nickel-cobalt hydroxide raw material

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20211022

RJ01 Rejection of invention patent application after publication