CN115216643A - Purification and recovery process of nickel in high-ammonium-salt wastewater - Google Patents
Purification and recovery process of nickel in high-ammonium-salt wastewater Download PDFInfo
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- 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
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- 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
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0492—Separation of nickel from cobalt in ammoniacal type solutions
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- 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
- C22B3/30—Oximes
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- 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
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- 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
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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Abstract
The invention relates to a process for purifying and recovering nickel in high-ammonium-salt wastewater. Adding a sodium carbonate solution into a mixed solution A after organic phase separation, controlling different pH values to obtain nickel carbonate and cobalt carbonate mixed precipitate, cobalt carbonate precipitate and magnesium carbonate precipitate, adding a sodium hydroxide solution into a filtrate C after magnesium carbonate filtration, heating to obtain ammonia gas and a filtrate D, wherein the ammonia gas is used for forming ammonia water and is mixed with the nickel carbonate and the cobalt carbonate to form a complex solution, and separating Ni in the complex solution by using a Lix84i extraction agent 2+ And Co 2+ The filtrate D is used for carrying out back extraction on the extracted organic phase to obtain a nickel chloride and nickel sulfate mixed solution, and the nickel chloride and nickel sulfate mixed solution and the raffinate are respectively obtained by an electrodeposition methodTo the cathode nickel and the cathode cobalt. According to the invention, high-concentration ammonium ions in the wastewater are fully utilized to separate and purify nickel and cobalt, and sodium chloride and sodium sulfate generated in the wastewater are utilized to back-extract the Lix84i extractant, so that the whole process is efficient and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to a process for purifying and recovering nickel in high-ammonium salt wastewater.
Background
Nickel is a silver white metal, has good mechanical strength, ductility and high chemical stability, is widely applied to the production of stainless steel and various alloys, and becomes an indispensable metal for developing the modern aerospace industry, the military industry, the medical instrument industry and the modern civilization of developing human beings. China belongs to one of countries with abundant nickel resources in the world, accounts for about 9 percent of the total reserves and is the fourth in the world. Along with the rapid development of the world economy, the demand of related industries on nickel is also increased sharply, and the nickel ore resources available for mining in the world are gradually reduced at present, so that the recovery of nickel resources from waste materials is more and more important. At present, the nickel-containing wastewater treatment method mainly comprises an adsorption method, a liquid membrane extraction method, a chemical precipitation method, an ion exchange method and an electrolysis method. Besides the electrolytic method, other methods only change the existing form of nickel ions, so that the nickel ions are migrated, but the pollution is not completely eliminated, and the economic benefit is not obtained. High ammonium salt wastewater is the main wastewater generated in the cobalt smelting process, and the wastewater contains magnesium ions, nickel ions, cobalt ions, chloride ions and sulfate ions besides high-concentration ammonium ions, once the wastewater is discharged into a water body, particularly lakes and gulfs which flow slowly, a large amount of propagation of algae and other microorganisms is easily caused, and the wastewater is one of the main reasons for eutrophication of the water body, so the wastewater needs to be treated before being discharged.
Patent CN108996752A discloses a method for recovering low-concentration nickel from nickel extraction waste water, ozone is introduced into the waste water for reaction, an alkaline substance is added in the reaction process to maintain the pH value of the waste water between 10 and 11, and after the reaction is finished, nickel oxyhydroxide with the purity of more than 98 percent can be obtained. The method for recovering nickel is to prepare nickel oxyhydroxide by ozone oxidation under alkaline conditions.
Patent publication No. CN108658320A discloses a method for recovering heavy metal nickel from chemical nickel plating wastewater, which comprises adsorbing and enriching heavy metal nickel in chemical nickel plating cleaning wastewater by ion exchange resin to obtain wastewater containing hypophosphorous acid; eluting and regenerating the ion exchange resin to obtain a regenerated liquid containing nickel ions; and carrying out electrochemical catalytic oxidation on the wastewater containing the hypophosphorous acid, and carrying out electro-reduction on the regenerated liquid containing the nickel ions so as to recover the metallic nickel. The method for recovering and purifying the nickel is an ion exchange method and an electroreduction method.
The patent publication No. CN113620471A discloses a method for deeply removing nickel and cobalt from cobalt raffinate, which belongs to the technical field of wastewater treatment, wherein Su Qing DA201-C resin and D402 large-aperture chelating resin which are saturated in adsorption are subjected to steam blowing by using a steam blowing machine, then dilute alkali is added to obtain the initial DA201-A resin and the D402 large-aperture chelating resin, the adsorption capacity is regenerated, oil in the wastewater is adsorbed by recycling, and a modified chelating agent is added to the wastewater after adsorption, so that nickel and cobalt ions can be flocculated to obtain flocculates, and then the wastewater is filtered to obtain qualified discharged wastewater. The invention adopts the modified chelating agent to flocculate nickel ions and cobalt ions in the wastewater, but does not disclose how to separate the nickel ions and the cobalt ions and purify and recover metallic nickel.
Patent CN109022823A discloses a method for homogeneous precipitation separation of nickel, cobalt and manganese from laterite-nickel ore pickle liquor, belonging to the technical field of comprehensive utilization of complex multi-metal resources. The method comprises the following steps: preparing a sodium hydroxide solution or finely ground calcium oxide or magnesium oxide into a whey to be used as a precipitator; the precipitator is conveyed to the homogeneous reactor through a pipeline with a speed control device, and a refiner is arranged at the outlet end to refine the precipitator; the nickel-cobalt-manganese-containing solution is conveyed to a homogeneous reactor through a pipeline with a speed control device, and an atomizer is arranged at the outlet end to atomize the acid solution: carrying out a homogeneous reaction on the nickel-cobalt-manganic acid solution atomized at a controlled speed and the precipitator refined at a controlled speed in a homogeneous reactor to obtain slurry after the reaction; filtering the reacted slurry to obtain the solution after the nickel and cobalt precipitation and the sandy nickel and cobalt manganese slag. The technical scheme disclosed by the invention is a method for recovering nickel ions, cobalt ions and manganese ions by taking sodium hydroxide or calcium oxide or magnesium oxide as a precipitator to perform precipitation reaction on the nickel ions, cobalt ions and manganese ions in the wastewater.
Patent CN111304466a discloses a method for extracting and separating cobalt and nickel from nickel-cobalt peracid leaching solution, which specifically comprises the following steps: extracting the nickel-cobalt high-acid leaching solution by using a first extracting agent to obtain a first loaded organic phase and a first raffinate; carrying out back extraction on the first loaded organic phase to obtain a sulfuric acid solution and a blank organic phase; extracting the first raffinate by a second extracting agent to obtain a second loaded organic phase and a second raffinate; carrying out back extraction on the second loaded organic phase by using a sulfuric acid solution to obtain a cobalt sulfate solution; concentrating the second raffinate to obtain a nickel sulfate solution; the method adopts an extraction process to recover the residual acid in the pickle liquor, does not need to add a large amount of alkali for neutralization, avoids cobalt and nickel loss and difficult solid-liquid separation caused by the alkali-added neutralization, reduces the cost of the medicament, and effectively recovers the residual acid; after cobalt and nickel are extracted, sulfuric acid recovered from the acid leaching solution is used as a stripping agent, so that the sulfuric acid is not required to be consumed additionally, and the production cost is far lower than that of other processes. However, since the high-acid leachate of the present invention does not contain high-concentration ammonium ions, there is no disclosure of a technique for separating nickel ions and cobalt ions in the presence of high-concentration ammonium ions in the present invention.
Disclosure of Invention
The invention aims to provide a process for purifying and recovering nickel in high-ammonium-salt wastewater. Adding a sodium carbonate solution into a mixed solution A after organic phase separation, controlling different pH values to obtain nickel carbonate and cobalt carbonate mixed precipitate, cobalt carbonate precipitate and magnesium carbonate precipitate, adding a sodium hydroxide solution into a filtrate C after magnesium carbonate filtration, heating to obtain ammonia gas and a filtrate D, wherein the ammonia gas is used for forming ammonia water and is mixed with the nickel carbonate and the cobalt carbonate to form a complex solution, and separating Ni in the complex solution by using a Lix84i extraction agent 2+ And Co 2+ And (3) carrying out back extraction on the extracted organic phase by using the filtrate D to obtain a nickel chloride and nickel sulfate mixed solution, and respectively carrying out an electrodeposition method on the nickel chloride and nickel sulfate mixed solution and the raffinate to obtain cathode nickel and cathode cobalt. According to the invention, high-concentration ammonium ions in the wastewater are fully utilized to separate and purify nickel and cobalt, and sodium chloride and sodium sulfate generated in the wastewater are utilized to back-extract the Lix84i extractant, so that the whole process is efficient and environment-friendly.
The purpose of the invention can be realized by the following technical scheme:
a purification and recovery process of nickel in high ammonium salt wastewater comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and a filtrate B;
(4) Adding sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until the filtrate B contains Mg 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C;
(5) Adding sodium hydroxide aqueous solution into the filtrate C continuously until the pH value is 10.8-11.2, heating to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving ammonia gas generated in the step (5) in deionized water to obtain ammonia water, and dissolving the mixture of nickel carbonate and cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using a Lix841i extracting agent and a diluent as organic phases to obtain an extracted organic phase and raffinate;
(8) And (3) back-extracting the organic phase extracted in the step (7) by using the filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7), the nickel sulfate and nickel chloride solution are subjected to an electrodeposition method to obtain cathode nickel, and the raffinate in the step (7) is subjected to an electrodeposition method to obtain cathode cobalt.
As a preferable technical scheme of the invention, the high ammonium salt wastewater contains NH 4 + 、Ni 2+ 、 Co 2+ 、Mg 2+ 、Cl - And SO 4 2- 。
As a preferable technical scheme of the invention, the mass concentration of the ammonia water in the step (6) is controlled to be 13-15%.
As a preferable technical scheme of the invention, the concentration of the sodium carbonate aqueous solution in the step (2), the step (3) and the step (4) is 0.5-1.0 mol/L.
As a preferable embodiment of the present invention, the concentration of the aqueous sodium hydroxide solution in the step (5) is 0.2 to 0.6mol/L.
In a preferred embodiment of the present invention, the heating temperature in the step (5) is 60 to 90 ℃.
As a preferred technical scheme of the invention, the raffinate in the step (7) is extracted by using the organic phase after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 × 10 -5 mol/L。
As a preferable technical scheme of the invention, the volume content of the diluent in the organic phase in the step (7) is 80-85%.
As a preferable technical scheme of the invention, the volume ratio of the organic phase to the mixed solution B in the extraction process in the step (7) is controlled to be 1.
As a preferred technical scheme of the invention, the volume ratio of the organic phase after extraction and the filtrate D in the back extraction process in the step (8) is controlled to be 3-8:1, the back extraction temperature is 20-30 ℃, and the back extraction equilibrium time is controlled to be 3-6 min.
The invention has the beneficial effects that:
(1) The invention adds sodium carbonate aqueous solution into high ammonium salt wastewater, respectively obtains nickel carbonate and cobalt carbonate mixed precipitate, cobalt carbonate precipitate and magnesium carbonate precipitate by controlling the pH value in the wastewater, and can prevent Co (NH) from forming by controlling the range of the pH value 3 ) 6 2+ And Ni (NH) 3 ) 6 2+ The complex influences the precipitation of nickel ions and cobalt ions, can separate magnesium ions in the wastewater, and primarily separates the cobalt ions and the nickel ions;
(2) In the process of forming the mixed liquid B, the quality of the ammonia water is controlledThe concentration is 13-15%, co (NH) is formed in the mixed liquid B 3 ) 6 3+ And Ni (NH) 3 ) 6 2+ The two complexes can be completely separated from nickel ions and cobalt ions by taking Lix841i as an organic phase, and high-purity nickel and cobalt can be prepared finally;
(3) Adding a sodium hydroxide solution into filtrate C after filtering magnesium carbonate, and heating to obtain ammonia gas and filtrate D, wherein the ammonia gas is used for forming ammonia water and is mixed with nickel carbonate and cobalt carbonate for precipitation to form a complex solution and is used for separating nickel ions and cobalt ions; carrying out back extraction on the extracted organic phase by using the filtrate D to obtain a mixed solution of nickel chloride and nickel sulfate so as to further obtain elemental nickel and elemental cobalt; the high-concentration ammonium ions in the wastewater are fully utilized to separate and purify nickel and cobalt, and the sodium chloride and sodium sulfate generated in the wastewater are utilized to back extract the Lix84i extractant, so that the whole process is efficient and environment-friendly.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description of the embodiments, structures, characteristics and effects according to the present invention will be given with reference to the preferred embodiments.
Example 1
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ 、Cl - And SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 0.8mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding the sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A is 2+ The concentration is less than 1X 10 -5 Filtering to obtain cobalt carbonate and a filtrate B;
(4) Adding the sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until the filtrate B contains Mg 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C;
(5) Adding 0.5mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 60 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 mol/L to obtain filtrate D;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 15%, and dissolving the mixture of the nickel carbonate and the cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using an Lix841i extracting agent and a diluent as an organic phase, controlling the volume ratio of the diluent in the organic phase to be 80% to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using a filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process is controlled to be 5:1, the back-extraction temperature is 30 ℃, the back-extraction equilibrium time is 6min, the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7) in sequence, the nickel sulfate and nickel chloride solution obtain cathode nickel by an electrodeposition method, and the raffinate in the step (7) obtains cathode cobalt by the electrodeposition method; extracting the raffinate obtained in the step (7) by using the organic phase obtained after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 x 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of the embodiment can reach 99.8%.
Example 2
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ Cl-and SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 0.6mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding the sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A is 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate B at mol/L;
(4) Adding the sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until Mg in the filtrate B 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C;
(5) Adding 0.4mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 80 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 14%, and dissolving the mixture of nickel carbonate and cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using Lix841i as an organic phase extracting agent and a diluent, controlling the volume ratio of the diluent in the organic phase to be 82% to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B in the extraction process to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using the filtrate D to obtain a nickel sulfate solution, a nickel chloride solution and a back-extracted organic phase, controlling the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process to be 6:1, controlling the back-extraction temperature to be 30 ℃, keeping the back-extraction equilibrium time to be 5min, and successively using the back-extracted organic phase for extracting the mixed solution B in the step (7), namely nickel sulfate and nickel chlorideObtaining cathode nickel from the nickel chloride solution by an electrodeposition method, and obtaining cathode cobalt from the raffinate in the step (7) by the electrodeposition method; extracting the raffinate obtained in the step (7) by using the organic phase obtained after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 x 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of the embodiment can reach 99.5%.
Example 3
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ 、Cl - And SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 1.0mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding the sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A is 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and a filtrate B;
(4) Adding the sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until the filtrate B contains Mg 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C;
(5) Adding 0.3mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 90 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 13%, and dissolving the mixture of nickel carbonate and cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using Lix841i as an organic phase extracting agent and a diluent, controlling the volume ratio of the diluent in the organic phase to be 85 percent to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B in the extraction process to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using a filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process is controlled to be 7:1, the back-extraction temperature is 30 ℃, the back-extraction equilibrium time is 6min, the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7) in sequence, the nickel sulfate and nickel chloride solution obtain cathode nickel by an electrodeposition method, and the raffinate in the step (7) obtains cathode cobalt by the electrodeposition method; the raffinate in the step (7) is extracted by using the organic phase after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 x 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of the embodiment can reach 99.7%.
Comparative example 1
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ Cl-and SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 0.8mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Continuously adding the sodium carbonate aqueous solution into the filtrate A until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate B at mol/L;
(4) Adding the sodium carbonate into the filtrate BThe solution is adjusted to pH value of 9.2-10.5, magnesium carbonate precipitation is separated out until Mg in the filtrate B 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C;
(5) Adding 0.5mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 60 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 8%, and dissolving the mixture of the nickel carbonate and the cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using an Lix841i extracting agent and a diluent as an organic phase, controlling the volume ratio of the diluent in the organic phase to be 80% to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using a filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process is controlled to be 5:1, the back-extraction temperature is 30 ℃, the back-extraction equilibrium time is 6min, the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7) in sequence, the nickel sulfate and nickel chloride solution obtain cathode nickel by an electrodeposition method, and the raffinate in the step (7) obtains cathode cobalt by the electrodeposition method; the raffinate in the step (7) is extracted by using the organic phase after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 × 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of this comparative example was 89.8%.
Comparative example 2
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ 、Cl - And SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 0.6mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Continuously adding the sodium carbonate aqueous solution into the filtrate A until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate B at mol/L;
(4) Adding the sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until the filtrate B contains Mg 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C at mol/L;
(5) Adding 0.4mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 80 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 20%, and dissolving the mixture of nickel carbonate and cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using Lix841i as an organic phase extracting agent and a diluent, controlling the volume ratio of the diluent in the organic phase to be 82% to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B in the extraction process to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using a filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process is controlled to be 6:1, the back-extraction temperature is 30 ℃, the back-extraction equilibrium time is 5min, the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7) in sequence, the nickel sulfate and nickel chloride solution obtain cathode nickel by an electrodeposition method, and the raffinate in the step (7) obtains cathode cobalt by the electrodeposition method; extracting the extract in the step (7)Extracting the raffinate with the organic phase obtained after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 x 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of this comparative example was 88.5%
Comparative example 3
Purification and recovery process of nickel in high-ammonium-salt wastewater, wherein the high-ammonium-salt wastewater contains NH 4 + 、 Ni 2+ 、Co 2+ 、Mg 2+ 、Cl - And SO 4 2- The process comprises the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding 1.0mol/L sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, and separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding the sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A is 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and a filtrate B;
(4) Adding the sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until Mg in the filtrate B 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C at mol/L;
(5) Adding 0.3mol/L sodium hydroxide aqueous solution into the filtrate C to a pH value of 10.8-11.2, heating to 90 ℃ to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving the ammonia gas generated in the step (5) in deionized water to obtain ammonia water with the mass concentration of 10%, and dissolving the mixture of the nickel carbonate and the cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting a mixed solution B by using an Lix841i extracting agent and a diluent as an organic phase, controlling the volume ratio of the diluent in the organic phase to be 85% to obtain an extracted organic phase and a raffinate, controlling the volume ratio of the organic phase to the mixed solution B to be 1;
(8) Back-extracting the organic phase extracted in the step (7) by using a filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the volume ratio of the extracted organic phase to the filtrate D in the back-extraction process is controlled to be 7:1, the back-extraction temperature is 30 ℃, the back-extraction equilibrium time is 6min, the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7) in sequence, the nickel sulfate and nickel chloride solution obtain cathode nickel by an electrodeposition method, and the raffinate in the step (7) obtains cathode cobalt by the electrodeposition method; the raffinate in the step (7) is extracted by using the organic phase after the back extraction in the step (8) until Ni in the raffinate 2+ Less than 1 x 10 -5 mol/L。
The purity of the nickel obtained by the electrodeposition method of this comparative example was 87.9%.
From the nickel purity data of examples 1 to 3 and comparative examples 1 to 3 it can be seen that:
comparative example 1 the mass concentration of ammonia water in step (6) was adjusted to 8% based on example 1, and the mixed solution B prepared therefrom was such that cobalt ions were present as Co (NH) 3 ) 6 3+ And Co (NH) 3 ) 6 2+ The Lix84i extractant is used for extracting Ni 2+ While Co is extracted 2+ Resulting in cobalt in the final electrodeposited nickel, which is significantly less pure.
Comparative example 2 the mass concentration of ammonia water in the step (6) was adjusted to 8% based on the example 2, and the mixed solution B prepared therefrom was such that cobalt ions were present as Co (NH) 3 ) 6 3+ And Co (NH) 3 ) 6 2+ The Lix84i extractant is used for extracting Ni 2+ While Co is extracted 2+ The nickel obtained by the final electrodeposition method contains cobalt, and the purity of the nickel is obviously reduced.
Comparative example 3 the mass concentration of ammonia water in the step (6) was adjusted to 8% based on the example 3, and the mixed solution B prepared therefrom was such that cobalt ions were present as Co (NH) 3 ) 6 3+ And Co (NH) 3 ) 6 2+ The Lix84i extractant is used for extracting Ni 2+ While Co is extracted 2+ The nickel obtained by the final electrodeposition method contains cobalt, and the purity of the nickel is obviously reduced.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (10)
1. A purification and recovery process of nickel in high ammonium salt wastewater is characterized by comprising the following steps:
(1) Removing an organic phase from the high ammonium salt wastewater by an oil-water separator to obtain a mixed solution A;
(2) Adding sodium carbonate aqueous solution into the mixed solution A, controlling the pH value to be 7.2-8.2, separating out nickel carbonate and cobalt carbonate mixed precipitate until Ni in the mixed solution A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain a mixture of nickel carbonate and cobalt carbonate and a filtrate A;
(3) Adding sodium carbonate aqueous solution into the filtrate A continuously until the pH value is 8.5-9.15, and separating out cobalt carbonate precipitate until Co in the filtrate A 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and a filtrate B;
(4) Adding sodium carbonate aqueous solution into the filtrate B continuously until the pH value is 9.2-10.5, and separating out magnesium carbonate precipitate until the filtrate B contains Mg 2+ The concentration is less than 1 × 10 -5 Filtering to obtain cobalt carbonate and filtrate C at mol/L;
(5) Adding sodium hydroxide aqueous solution into the filtrate C continuously until the pH value is 10.8-11.2, heating to generate ammonia gas, and controlling NH in the solution 4+ The concentration is less than 1 × 10 -5 Obtaining filtrate D by mol/L;
(6) Dissolving ammonia gas generated in the step (5) in deionized water to obtain ammonia water, and dissolving the mixture of nickel carbonate and cobalt carbonate obtained in the step (1) in the ammonia water to obtain a mixed solution B;
(7) Extracting the mixed solution B by using a Lix841i extracting agent and a diluent as an organic phase to obtain an extracted organic phase and raffinate;
(8) And (4) back-extracting the organic phase extracted in the step (7) by using the filtrate D to obtain a nickel sulfate and nickel chloride solution and a back-extracted organic phase, wherein the back-extracted organic phase is continuously used for extracting the mixed solution B in the step (7), the nickel sulfate and nickel chloride solution are used for obtaining cathode nickel by an electrodeposition method, and the raffinate in the step (7) is used for obtaining cathode cobalt by the electrodeposition method.
2. The process of claim 1, wherein the high ammonium salt wastewater contains NH 4 + 、Ni 2+ 、Co 2+ 、Mg 2+ 、Cl - And SO 4 2- 。
3. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the mass concentration of the ammonia water in the step (6) is controlled to be 13-15%.
4. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the concentration of the sodium carbonate aqueous solution in the step (2), the step (3) and the step (4) is 0.5-1.0 mol/L.
5. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the concentration of the sodium hydroxide aqueous solution in the step (5) is 0.2-0.6 mol/L.
6. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the heating temperature in the step (5) is 60-90 ℃.
7. The process of claim 1, wherein the raffinate in step (7) is extracted with the stripped organic phase in step (8) until Ni in the raffinate is removed 2+ Less than 1 x 10 -5 mol/L。
8. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the volume content of the diluent in the organic phase in the step (7) is 80-85%.
9. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the volume ratio of the organic phase to the mixed solution B in the extraction process in the step (7) is controlled to be 1.
10. The process for purifying and recovering nickel in high ammonium salt wastewater according to claim 1, wherein the volume ratio of the organic phase extracted in the back extraction process in the step (8) to the filtrate D is controlled to be 3-8:1, the back extraction temperature is 20-30 ℃, and the back extraction equilibrium time is controlled to be 3-6 min.
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| CN114604910A (en) * | 2022-03-15 | 2022-06-10 | 重庆大学 | Magnesium and nickel solution mineralized CO2Method for simultaneously obtaining nickel carbonate |
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| US3981968A (en) * | 1973-10-19 | 1976-09-21 | Freeport Minerals Company | Solvent extraction of nickel from ammoniacal solutions |
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