CN113174493B - Method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag - Google Patents
Method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag Download PDFInfo
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Abstract
The invention discloses a method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag, which comprises the steps of heating and soaking selenium steaming slag by using sulfuric acid, filtering to obtain copper separating liquid of the selenium steaming slag, then adding the alkaline cobalt slag for soaking to obtain a copper-cobalt-containing solution, extracting copper and cobalt in the copper-cobalt-containing solution by using an extracting agent P204, returning an extracting agent obtained by back extraction of kerosene for extracting the copper-cobalt-containing solution, electrodepositing the copper-cobalt-containing solution after extraction of copper and cobalt to recover metal copper, extracting cobalt in the cobalt-containing solution after removal of metal copper by using P507, returning the extracting agent obtained by back extraction for extracting the cobalt-containing solution, electrodepositing the cobalt-containing solution after extraction of cobalt to recover the metal cobalt, returning a sulfuric acid solution generated in the electrodepositing process for soaking the selenium steaming slag, and discharging no waste liquid in the whole process; the method realizes comprehensive treatment of wastes, is scientific and environment-friendly, does not discharge waste liquid, has high metal recovery rate, and obtains products with high purity and remarkable economic benefit.
Description
Technical Field
The invention relates to the technical field of recovery of valuable metals in selenium steaming slag and alkaline cobalt slag, in particular to a method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag.
Background
In the copper electrolysis process, anode sludge containing valuable metals is produced in large quantities. The common smelter needs to recover the valuable metals in the anode mud. In the treatment of the anode mud, selenium steaming is firstly carried out, selenium steaming slag contains a large amount of valuable metals, and then sulfuric acid is used for leaching. The copper ion content in the leaching solution is generally 5-10 g/L, the sulfuric acid concentration is 20-60 g/L, the chloride ion content is 10-15 g/L, and other impurity ions are also contained.
The alkaline cobalt slag is generated in the non-ferrous smelting process, contains 20-30% of cobalt and has the pH value of 7-10, and valuable metal cobalt in the alkaline cobalt slag is generally recovered by adopting a sulfuric acid soaking and chemical purification method.
At present, copper separating liquid of selenium steaming slag is generally treated by concentrating to produce copper sulfate and then adding soda ash to produce basic copper carbonate. The process has the advantages of low recovery efficiency, high production cost and no production of high-benefit metal copper. The basic cobalt slag is typically soaked with sulfuric acid and then chemically purified to recover cobalt. When the two kinds of waste residues are treated, a large amount of sulfuric acid and chemical reagents are consumed, the metal recovery rate is low, the product purity is not high, and the economic benefit is low.
Disclosure of Invention
The invention aims to provide a method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag, aiming at the problems that a large amount of sulfuric acid and chemical reagents for purification are required to be consumed when valuable metals are recovered from the selenium steaming slag and the alkaline cobalt slag at present, the metal recovery rate is low, and the economic benefit is low.
The invention discloses a method for recovering copper and cobalt by jointly treating steamed selenium slag and alkaline cobalt slag, which comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 15-20 g/L to 40-60 ℃, adding selenium steaming slag with the mass concentration of 30-50% of that of the sulfuric acid solution, stirring at the stirring speed of 1-3R/S for reaction for 70-100 h, and filtering a leaching solution to obtain a copper separating solution of the selenium steaming slag, wherein the mass concentration of copper in the copper separating solution of the selenium steaming slag is 5-10 g/L, and the mass concentration of sulfuric acid is 20-60 g/L;
(2) adding alkaline cobalt slag with the mass of 20-50% of that of the solution into the copper separating liquid of the selenium steaming slag, stirring and reacting for 20-50 h at the stirring speed of 1-3R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 1-5 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9-10 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 1-1: 5 of ratio of O/A, extracting copper and cobalt in the copper-cobalt pre-extraction solution, wherein the mixing time of each stage of extraction is 3-15 min, the clarification time is 3-15 min, and obtaining a copper-cobalt-containing organic phase and a copper-cobalt-extraction solution after the extraction is finished; the extraction agent A is obtained by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 70-90% until the saponification rate is 65-75%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 20-30%, wherein the saponifying agent is any one of sodium hydroxide, ammonia water and calcium hydroxide;
(4) performing back extraction on the copper and cobalt-containing organic phase by adopting kerosene, taking the organic phase obtained by extracting the kerosene as an extracting agent A, returning to the step (3) for extracting the solution before copper and cobalt extraction, taking the obtained aqueous phase as the solution after copper and cobalt extraction, recovering copper by electrodeposition, and controlling the current density to be 150-200A/m 2 After the copper and cobalt containing solution is subjected to electrodeposition to recover copper, the cobalt containing solution remains;
(5) adjusting the pH value of the cobalt-containing solution to 8-9 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 1-1: 5 of ratio of O/A to cobalt in the cobalt-containing solution, extracting cobalt in the cobalt-containing solution, wherein the mixing time of each stage of extraction is 3-15 min, the clarification time is 3-15 min, and obtaining a cobalt-containing organic phase and a cobalt extraction liquid after the extraction is finished; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 70-90% until the saponification rate is 60-70%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 20-30%, wherein the saponifying agent is any one of sodium hydroxide, ammonia water and calcium hydroxide;
(6) performing back extraction on the cobalt-containing organic phase by adopting kerosene, taking the organic phase obtained by extracting the kerosene as an extracting agent B, returning to the step (5) for circularly extracting the cobalt-containing solution, taking the obtained aqueous phase as the cobalt-containing solution after extraction, recovering cobalt by electrodeposition, and controlling the current density to be 120-180A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming slag.
And (4) returning the liquid obtained after copper and cobalt extraction in the step (3) to the step (1) for circularly soaking the selenium steaming slag.
And (4) when the organic phase containing copper and cobalt is subjected to kerosene back extraction in the step (4), performing 2-stage back extraction with the ratio of O/A being 1: 1-1: 6, wherein the mixing time and the clarification time in each stage of extraction are 10-20 min and 10-20 min respectively.
And (4) returning the liquid obtained after cobalt extraction in the step (5) to the step (1) for circularly soaking the selenium steaming slag.
And (4) when the cobalt-containing organic phase is subjected to kerosene back extraction in the step (6), performing 2-stage back extraction with the ratio of O/A being 1: 1-1: 6, wherein the mixing time of each stage of extraction is 10-20 min, and the clarification time is 10-20 min.
Heating and soaking selenium steaming slag by using sulfuric acid, filtering to obtain copper-separated liquid of the selenium steaming slag, adding alkaline cobalt slag for soaking to obtain a copper-cobalt-containing pre-extraction solution, extracting copper and cobalt in the copper-cobalt-containing pre-extraction solution by using an extracting agent P204, returning an extracting agent obtained by back-extraction of kerosene to extract the copper-cobalt-containing pre-extraction solution, electrodepositing the copper-cobalt-containing post-extraction solution to recover metal copper, extracting cobalt in the cobalt-containing solution by using P507 after removing the metal copper, returning the extracting agent obtained by back-extraction of the kerosene to extract the cobalt-containing solution, electrodepositing the cobalt-containing post-extraction solution to recover the metal cobalt, returning a sulfuric acid solution generated in the electrodepositing process to soak the selenium steaming slag, and discharging no waste liquid in the whole process; the method realizes comprehensive treatment of wastes, is scientific and environment-friendly, does not discharge waste liquid, has high metal recovery rate, and obtains products with high purity and remarkable economic benefit.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, 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 from the embodiments of the present invention by a person skilled in the art, are within the scope of the present invention.
Example 1
Referring to fig. 1, a method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 18g/L to 50 ℃, adding 40% of steamed selenium slag by mass of the sulfuric acid solution, stirring at the stirring speed of 2R/S for reaction for 80 hours, and filtering a leaching solution to obtain a copper separating solution of the steamed selenium slag, wherein the mass concentration of copper in the copper separating solution of the steamed selenium slag is 8g/L, and the mass concentration of sulfuric acid is 40 g/L; filter residues generated by filtering can be circularly put into a sulfuric acid solution to leach out copper;
(2) adding alkaline cobalt slag with the mass of 40% of the solution into the copper separating liquid of the selenium steaming slag, stirring and reacting for 35 hours at the stirring speed of 2R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 3 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9.5 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A is 1: 3, extracting copper and cobalt in the copper-cobalt pre-extraction solution, mixing the copper and cobalt in each stage of extraction for 10min, clarifying the mixture for 10min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt-extraction rear liquid after the extraction is finished, and returning the copper-cobalt-extraction rear liquid to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is obtained by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 80% until the saponification rate is 70%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 25%, and using ammonia water as the saponifying agent;
(4) carrying out back extraction on the copper-cobalt-containing organic phase by adopting kerosene, carrying out 2-stage back extraction under the conditions of normal temperature and 1: 3 of phase ratio O/A, wherein the mixing time and the settling time are 15min and 15min respectively during each stage of extraction, the organic phase obtained by extracting the kerosene is an extracting agent A, the organic phase is returned to the step (3) to be circularly used for extracting a copper-cobalt pre-extraction solution, the obtained water phase is a copper-cobalt-containing post-extraction solution, copper is recovered by electrodeposition, and the current density is 180A/m 2 After the copper and cobalt-containing solution is subjected to electrodeposition to recover copper, the cobalt-containing solution is remained;
(5) adjusting the pH value of the cobalt-containing solution to 8.5 by using sulfuric acid, adding an extracting agent B after adjustment, carrying out 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 3, extracting cobalt in the cobalt-containing solution, mixing for 10min during each stage of extraction, clarifying for 10min, obtaining a cobalt-containing organic phase and a cobalt-extracted liquid after extraction, and returning the cobalt-extracted liquid to the step (1) for circularly soaking selenium-evaporated slag; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 80% until the saponification rate is 65%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 25%, wherein the saponifying agent is ammonia water;
(6) performing 2-stage back extraction on the cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 3 of phase ratio O/A, mixing time of 15min and clarification time of 15min during each-stage extraction, returning the organic phase obtained by the kerosene extraction as an extracting agent B to the step (5) for circularly extracting the cobalt-containing solution, obtaining a water phase which is the cobalt-containing solution after extraction, recovering cobalt by electrodeposition, and obtaining a current density of 150A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming slag.
Example 2
A method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 15g/L to 60 ℃, adding 50% of the mass of the sulfuric acid solution into the selenium steaming slag, stirring and reacting for 100 hours at the stirring speed of 3R/S, filtering a leaching solution to obtain a copper separating solution of the selenium steaming slag, wherein the mass concentration of copper in the copper separating solution of the selenium steaming slag is 10g/L, and the mass concentration of sulfuric acid is 50 g/L;
(2) adding alkaline cobalt slag with the mass of 50% of the solution into the copper separating liquid of the selenium steaming slag, stirring and reacting for 50 hours at the stirring speed of 3R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the copper-cobalt pre-extraction solution contains 5g/L of cobalt;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 10 by using ammonia water, adding an extracting agent A after adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 2, extracting copper and cobalt in the copper-cobalt pre-extraction solution, mixing the copper and cobalt in each stage of extraction for 6min, clarifying for 6min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt-extraction rear liquid after the extraction is finished, and returning the copper-cobalt-extraction rear liquid to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is prepared by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 90% until the saponification rate is 75%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 20%, wherein the saponifying agent is sodium hydroxide;
(4) performing kerosene back extraction on the copper-cobalt-containing organic phase, performing 2-stage back extraction at normal temperature under the condition that the ratio of O/A is 1: 2, mixing time is 10min and clarification time is 10min during each stage of extraction, taking the organic phase obtained by the kerosene extraction as an extracting agent A, returning to the step (3) for extracting a copper-cobalt pre-extraction solution circularly, obtaining a water phase which is a copper-cobalt-containing post-extraction solution, recovering copper by electrodeposition, and obtaining a current density of 200A/m 2 After the copper and cobalt-containing solution is subjected to electrodeposition to recover copper, the cobalt-containing solution is remained;
(5) adjusting the pH value of the cobalt-containing solution to 8 by using sulfuric acid, adding an extracting agent B after adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 2 of ratio of O/A to O/A, extracting cobalt in the cobalt-containing solution, wherein the mixing time and the clarification time are respectively 15min and 15min during each stage of extraction, obtaining a cobalt-containing organic phase and a cobalt-extracted liquid after extraction, and returning the cobalt-extracted liquid to the step (1) for circularly soaking selenium-evaporated slag; the extraction agent B is obtained by saponifying the P507 extraction agent by a saponifying agent with the mass fraction of 90% until the saponification rate is 60%, diluting the saponified P507 by sulfonated kerosene until the volume fraction is 20%, and the saponifying agent is sodium hydroxide;
(6) performing kerosene back extraction on the cobalt-containing organic phase, performing 2-stage back extraction at normal temperature under the condition that the ratio of O/A is 1: 2, mixing time is 20min and settling time is 20min during each stage of extraction, taking the organic phase obtained by the kerosene extraction as an extracting agent B, returning to the step (5) for circularly extracting the cobalt-containing solution, obtaining a water phase which is the solution after cobalt extraction, recovering cobalt by electrodeposition, and obtaining the current density of 180A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming residue.
Example 3
A method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 20g/L to 40 ℃, adding 30% of the selenium steaming slag by mass of the sulfuric acid solution, stirring and reacting for 70 hours at the stirring speed of 1R/S, and filtering a leaching solution to obtain a copper separating solution of the selenium steaming slag, wherein the mass concentration of copper in the copper separating solution of the selenium steaming slag is 5g/L, and the mass concentration of sulfuric acid is 30 g/L;
(2) adding alkaline cobalt slag with the solution mass of 20% into the copper separating liquid of the selenium steaming slag, stirring and reacting for 20 hours at the stirring speed of 1R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 1 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 5, extracting copper and cobalt in the copper-cobalt pre-extraction solution, mixing the copper and cobalt in each stage of extraction for 15min, settling for 15min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt post-extraction solution after the extraction is finished, and returning the copper-cobalt post-extraction solution to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is prepared by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 70% until the saponification rate is 65%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 30%, wherein the saponifying agent is calcium hydroxide;
(4) performing kerosene back extraction on the copper-cobalt-containing organic phase, performing 2-stage back extraction at normal temperature under the condition that the ratio of O/A is 1: 6, mixing time is 20min and clarification time is 20min during each stage of extraction, the organic phase obtained by the kerosene extraction is an extracting agent A, returning to the step (3) for extracting a copper-cobalt pre-extraction solution circularly, the obtained water phase is a copper-cobalt-containing post-extraction solution, recovering copper by electrodeposition, and obtaining the current density of 150A/m 2 After the copper and cobalt-containing solution is subjected to electrodeposition to recover copper, the cobalt-containing solution is remained;
(5) adjusting the pH value of the cobalt-containing solution to 9 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 5 of ratio of O/A to O/A, extracting cobalt in the cobalt-containing solution, wherein the mixing time and the clarification time are 12min and 12min respectively during each stage of extraction, obtaining a cobalt-containing organic phase and a cobalt-extracted liquid after the extraction is finished, and returning the cobalt-extracted liquid to the step (1) for circularly soaking the selenium-evaporated residue; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 70% until the saponification rate is 70%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 30%, wherein the saponifying agent is calcium hydroxide;
(6) performing 2-stage back extraction on the cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 6 of ratio O/A, wherein the mixing time and the clarification time in each stage of extraction are 18min and 18min respectively, the organic phase obtained by the kerosene extraction is used as an extracting agent B, and returning to the step (a)5) Circularly extracting cobalt-containing solution to obtain water phase, recovering cobalt by electrodeposition, and obtaining current density of 120A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming slag.
Example 4
A method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 17g/L to 45 ℃, adding steamed selenium slag with the mass percent of 35% of that of the sulfuric acid solution, stirring and reacting for 90 hours at the stirring speed of 1.5R/S, and filtering a leaching solution to obtain a copper separating solution of the steamed selenium slag, wherein the mass concentration of copper in the copper separating solution of the steamed selenium slag is 6g/L, and the mass concentration of sulfuric acid is 20 g/L;
(2) adding alkaline cobalt slag with the mass of 30% of the solution into the copper separating liquid of the selenium steaming slag, stirring and reacting for 40 hours at the stirring speed of 1.5R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 2 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9.2 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 1, extracting copper and cobalt in the copper-cobalt pre-extraction solution, mixing the copper and cobalt in each stage of extraction for 3min, settling for 3min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt post-extraction solution after the extraction is finished, and returning the copper-cobalt post-extraction solution to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is prepared by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 75% until the saponification rate is 68%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 28%, and using sodium hydroxide as the saponifying agent;
(4) performing kerosene back extraction on the copper-cobalt-containing organic phase, performing 2-stage back extraction at normal temperature under the condition that the ratio of O/A is 1: 1, mixing time is 13min and clarification time is 13min during each stage of extraction, the organic phase obtained by the kerosene extraction is an extracting agent A, returning to the step (3) for extracting a copper-cobalt pre-extraction solution circularly, the obtained water phase is a copper-cobalt-containing post-extraction solution, recovering copper by electrodeposition, and obtaining the current density of 160A/m 2 After the copper and cobalt-containing solution is subjected to electrodeposition to recover copper, the cobalt-containing solution is remained;
(5) adjusting the pH value of the cobalt-containing solution to 8.7 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 1 of ratio of O/A to O/A, extracting cobalt in the cobalt-containing solution, wherein the mixing time and the clarification time are 3min and 3min respectively during each stage of extraction, obtaining a cobalt-containing organic phase and a cobalt-extracted liquid after the extraction is finished, and returning the cobalt-extracted liquid to the step (1) for circularly soaking selenium-evaporated slag; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 75% until the saponification rate is 68%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 28%, and using sodium hydroxide as the saponifying agent;
(6) performing 2-stage back extraction on the cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 1 of phase ratio O/A, mixing time of 10min and settling time of 10min during each stage of extraction, returning the organic phase obtained by the kerosene extraction as an extracting agent B to the step (5) for circularly extracting the cobalt-containing solution, obtaining a water phase which is the cobalt-containing solution after extraction, recovering cobalt by electrodeposition, and obtaining a current density of 140A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming residue.
Example 5
A method for recovering copper and cobalt by combined treatment of selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 19g/L to 55 ℃, adding 45% of the selenium steaming slag of the sulfuric acid solution, stirring and reacting for 75 hours at the stirring speed of 2.5R/S, and filtering the leaching solution to obtain copper separating liquid of the selenium steaming slag, wherein the mass concentration of copper in the copper separating liquid of the selenium steaming slag is 9g/L, and the mass concentration of sulfuric acid is 55 g/L;
(2) adding alkaline cobalt slag with the solution mass of 45% into the copper separating liquid of the selenium steaming slag, stirring and reacting for 45 hours at the stirring speed of 2.5R/S, and obtaining a copper-cobalt extraction front solution after the alkaline cobalt slag is completely dissolved, wherein the copper-cobalt extraction front solution contains 4g/L of cobalt;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9.7 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 4, extracting copper and cobalt in the copper-cobalt pre-extraction solution, mixing the copper and cobalt in each stage of extraction for 12min, clarifying for 12min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt-extraction rear liquid after the extraction is finished, and returning the copper-cobalt-extraction rear liquid to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is obtained by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 85% until the saponification rate is 72%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 22%, wherein the saponifying agent is ammonia water;
(4) carrying out 2-stage back extraction on the organic phase containing copper and cobalt by adopting kerosene under the conditions of normal temperature and 1: 4 of phase ratio O/A, wherein the mixing time and the clarification time of each stage of extraction are 18min and 18min respectively, the organic phase obtained by the kerosene extraction is an extractant A, the organic phase is returned to the step (3) to be circularly used for extracting a solution before copper and cobalt extraction, the obtained water phase is a solution after copper and cobalt extraction, copper is recovered by electrodeposition, and the current density is 170A/m 2 After the copper and cobalt containing solution is subjected to electrodeposition to recover copper, the cobalt containing solution remains;
(5) adjusting the pH value of the cobalt-containing solution to 8.2 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 4 of ratio of O/A to O/A, extracting cobalt in the cobalt-containing solution, wherein the mixing time of each stage of extraction is 6min, the clarification time is 6min, obtaining a cobalt-containing organic phase and a cobalt-extracted liquid after the extraction is finished, and returning the cobalt-extracted liquid to the step (1) for circularly soaking selenium-evaporated slag; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 85% until the saponification rate is 62%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 22%, wherein the saponifying agent is ammonia water;
(6) performing 2-stage back extraction on the cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 4 of phase ratio O/A, mixing time of 12min and settling time of 12min during each-stage extraction, returning the organic phase obtained by the kerosene extraction as an extracting agent B to the step (5) for circularly extracting the cobalt-containing solution, obtaining a water phase which is the cobalt-containing solution after extraction, recovering cobalt by electrodeposition, and obtaining a current density of 160A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming slag.
Example 6
A method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag comprises the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 16g/L to 48 ℃, adding steamed selenium slag with the mass percent of 42% of that of the sulfuric acid solution, stirring and reacting for 82 hours at the stirring speed of 1R/S, filtering a leaching solution to obtain a copper separating solution of the steamed selenium slag, wherein the mass concentration of copper in the copper separating solution of the steamed selenium slag is 7.8g/L, and the mass concentration of sulfuric acid is 45 g/L;
(2) adding alkaline cobalt slag with the solution mass of 38% into the copper separating liquid of the selenium steaming slag, stirring and reacting for 42 hours at the stirring speed of 1-3R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 3.7 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9.4 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of O/A to O/A is 1: 2.5, extracting copper and cobalt in the copper-cobalt pre-extraction solution, wherein the mixing time of each stage of extraction is 8min, the clarification time is 8min, obtaining a copper-cobalt-containing organic phase and a copper-cobalt post-extraction solution after the extraction is finished, and returning the copper-cobalt post-extraction solution to the step (1) for circularly soaking and steaming selenium slag; the extraction agent A is prepared by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 84% until the saponification rate is 73%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 26%, wherein the saponifying agent is sodium hydroxide;
(4) carrying out 2-stage back extraction on the copper-cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 2.5 of phase ratio O/A, wherein the mixing time and the clarification time of each stage of extraction are 14min and 14min respectively, the organic phase obtained by extracting the kerosene is an extracting agent A, the organic phase is returned to the step (3) to be circularly used for extracting the copper-cobalt pre-extraction solution, the obtained water phase is the copper-cobalt-containing post-extraction solution, copper is recovered by electrodeposition, and the current density is 190A/m 2 After the copper and cobalt containing solution is subjected to electrodeposition to recover copper, the cobalt containing solution remains;
(5) adjusting the pH value of the cobalt-containing solution to 8.4 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction at normal temperature under the condition that the ratio of the pH value to the oxygen concentration (O/A) is 1: 1-3.5, extracting cobalt in the cobalt-containing solution, wherein the mixing time of each stage of extraction is 13min, the clarification time is 13min, obtaining a cobalt-containing organic phase and a cobalt-extraction liquid after the extraction is finished, and returning the cobalt-extraction liquid to the step (1) for circularly soaking selenium-steaming slag; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 88% until the saponification rate is 67%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 24%, wherein the saponifying agent is sodium hydroxide;
（6）performing 2-stage back extraction on the cobalt-containing organic phase by adopting kerosene under the conditions of normal temperature and 1: 3.5 of phase ratio O/A, wherein the mixing time and the clarification time of each stage of extraction are 14min and 14min, the organic phase obtained by extracting the kerosene is an extracting agent B, the organic phase is returned to the step (5) to be circularly used for extracting the cobalt-containing solution, the obtained water phase is the cobalt-containing solution after extraction, cobalt is recovered by electrodeposition, and the current density is 170A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming residue.
Claims (5)
1. A method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag is characterized by comprising the following steps:
(1) heating a sulfuric acid solution with the mass concentration of 15-20 g/L to 40-60 ℃, adding steamed selenium slag with the mass of 30-50% of that of the sulfuric acid solution, stirring at the stirring speed of 1-3R/S for reaction for 70-100 h, filtering a leaching solution to obtain a steamed selenium slag copper separating solution, wherein the mass concentration of copper in the steamed selenium slag copper separating solution is 5-10 g/L, and the mass concentration of sulfuric acid is 20-60 g/L;
(2) adding alkaline cobalt slag with the mass of 20-50% of that of the solution into the copper separating liquid of the selenium steaming slag, stirring and reacting for 20-50 h at the stirring speed of 1-3R/S, and obtaining a copper-cobalt pre-extraction solution after the alkaline cobalt slag is completely dissolved, wherein the cobalt content in the copper-cobalt pre-extraction solution is 1-5 g/L;
(3) adjusting the pH value of the copper-cobalt pre-extraction solution to 9-10 by using ammonia water, adding an extracting agent A after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 1-1: 5 of ratio of O/A, extracting copper and cobalt in the copper-cobalt pre-extraction solution, wherein the mixing time of each stage of extraction is 3-15 min, the clarification time is 3-15 min, and obtaining a copper-cobalt-containing organic phase and a copper-cobalt-extraction solution after the extraction is finished; the extraction agent A is obtained by saponifying a P204 extraction agent by using a saponifying agent with the mass fraction of 70-90% until the saponification rate is 65-75%, diluting the saponified P204 by using sulfonated kerosene until the volume fraction is 20-30%, wherein the saponifying agent is any one of sodium hydroxide, ammonia water and calcium hydroxide;
(4) performing back extraction on the copper and cobalt-containing organic phase by adopting kerosene, taking the organic phase obtained by extracting the kerosene as an extracting agent A, returning to the step (3) for extracting the solution before copper and cobalt extraction, taking the obtained aqueous phase as the solution after copper and cobalt extraction, and recovering copper by electrodepositionThe current density is 150 to 200A/m 2 After the copper and cobalt containing solution is subjected to electrodeposition to recover copper, the cobalt containing solution remains;
(5) adjusting the pH value of the cobalt-containing solution to 8-9 by using sulfuric acid, adding an extracting agent B after the adjustment, performing 2-stage extraction under the conditions of normal temperature and 1: 1-1: 5 of ratio of O/A to cobalt in the cobalt-containing solution, extracting cobalt in the cobalt-containing solution, wherein the mixing time of each stage of extraction is 3-15 min, the clarification time is 3-15 min, and obtaining a cobalt-containing organic phase and a cobalt extraction liquid after the extraction is finished; the extraction agent B is obtained by saponifying the P507 extraction agent by using a saponifying agent with the mass fraction of 70-90% until the saponification rate is 60-70%, diluting the saponified P507 by using sulfonated kerosene until the volume fraction is 20-30%, wherein the saponifying agent is any one of sodium hydroxide, ammonia water and calcium hydroxide;
(6) performing back extraction on the cobalt-containing organic phase by adopting kerosene, taking the organic phase obtained by extracting the kerosene as an extracting agent B, returning to the step (5) for circularly extracting the cobalt-containing solution, taking the obtained aqueous phase as the cobalt-containing solution after extraction, recovering cobalt by electrodeposition, and controlling the current density to be 120-180A/m 2 And sulfuric acid generated in the electrodeposition process is used for soaking the selenium steaming residue.
2. The method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag according to claim 1, characterized by comprising the following steps: and (4) when the organic phase containing copper and cobalt is subjected to kerosene back extraction in the step (4), performing 2-stage back extraction with the ratio of O/A being 1: 1-1: 6, wherein the mixing time and the clarification time in each stage of extraction are 10-20 min and 10-20 min respectively.
3. The method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag according to claim 1, characterized by comprising the following steps: and (6) when the cobalt-containing organic phase is subjected to kerosene back extraction, performing 2-stage back extraction with the ratio of O/A being 1: 1-1: 6, wherein the mixing time of each stage of extraction is 10-20 min, and the clarification time is 10-20 min.
4. The method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag according to claim 1, characterized by comprising the following steps: and (4) returning the copper and cobalt extracted liquid in the step (3) to the step (1) for circularly soaking the selenium steaming slag.
5. The method for recovering copper and cobalt by jointly treating selenium steaming slag and alkaline cobalt slag according to claim 1, characterized by comprising the following steps: and (5) returning the liquid after cobalt extraction in the step (5) to the step (1) for circularly soaking the selenium steaming slag.
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