WO2016024470A1 - ニッケルの回収方法 - Google Patents
ニッケルの回収方法 Download PDFInfo
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- WO2016024470A1 WO2016024470A1 PCT/JP2015/071032 JP2015071032W WO2016024470A1 WO 2016024470 A1 WO2016024470 A1 WO 2016024470A1 JP 2015071032 W JP2015071032 W JP 2015071032W WO 2016024470 A1 WO2016024470 A1 WO 2016024470A1
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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
- C22B23/0407—Leaching processes
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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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B23/0453—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
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
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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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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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
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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
-
- 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
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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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- 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
Definitions
- the present invention relates to a method for recovering nickel from a byproduct of an electric nickel production process by a chlorine leaching method.
- nickel sulfide and nickel sulfide produced by sulfuric acid leaching from nickel matte and low-grade laterite ore produced from dry smelting are used as raw materials. Chlorine leaching of most of the metals such as nickel, cobalt, copper, etc. And in the said hydrometallurgical method, after removing a metal impurity etc. from the solution obtained by chlorine leaching, electronickel is manufactured by electrowinning.
- the electro-nickel manufacturing process includes a chlorine leaching step S11 for leaching a metal such as nickel with nickel sulfide as a raw material to produce a copper-containing nickel chloride solution as a chlorine leaching solution, and a chlorine leaching step S11.
- the copper contained in the nickel sulfide is fed from the chlorine leaching solution (copper-containing nickel chloride solution) obtained through the chlorine leaching step S11 to the cementation step S21. And fixed and removed.
- the cementation residue containing the immobilized copper is returned again to the chlorine leaching step S11, and in the chlorine leaching step S11, the monovalent copper ions in the solution become divalent copper ions by reaction with chlorine gas, and the divalent Nickel is leached by the oxidizing power of copper ions.
- the copper contained in the nickel mat is also fixed and removed in the same manner as the copper contained in the nickel sulfide.
- the divalent copper ions contained in the copper-containing nickel chloride solution are reduced to monovalent copper ions by the nickel mat added as a raw material, and the sulfur in the chlorine leaching residue Fixed.
- nickel metal and nickel sulfide which are the main forms of nickel matte, preferentially reduce divalent copper ions to monovalent copper ions, and the monovalent copper ions generated by the remaining nickel metal and the like are sulfided. It becomes fixed as copper. Therefore, when the amount of copper circulating in the electric nickel production process system is increased, the amount of nickel mat for fixing as sulfide after being reduced from divalent copper ions to monovalent copper ions is relatively In some cases, the copper in the copper-containing nickel chloride solution cannot be fixed and removed reliably and efficiently.
- the amount of copper circulating in the system increases due to the increase of nickel sulfide as a raw material, the copper in the copper-containing nickel chloride solution is removed in the same way as before.
- the amount of nickel mat is insufficient to remove copper, so the amount of nickel mat must be increased, and copper cannot be removed efficiently and effectively.
- Patent Document 1 cannot cope with an increase in the amount of copper circulated in the system, and can effectively and effectively remove copper contained in the copper-containing nickel chloride solution. It is hoped that
- the cementation process needs to be at least two stages. For example, as shown in FIG. 8, first in the first cementation step S22, nickel sulfide is added to a nickel chloride solution containing copper (copper-containing nickel chloride solution) to reduce copper, and then In the second cementation step S23, it is necessary to add and immobilize nickel matte and chlorine leaching residue.
- the above-mentioned two-stage process is a main continuous path through which most of the treated water in the process passes, and therefore, each process needs to be operated properly at the same time. This is disadvantageous when compared with a simple one-step process.
- nickel in the nickel electrolysis process using the chlorine leaching method, nickel can be recovered from the by-product, and the nickel remaining in the by-product can be reduced, while at the same time simplifying the cementation process. It has been requested.
- the present invention has been proposed in view of such circumstances, and by recovering nickel from the by-product of the electrical nickel production process by the chlorine leaching method, it is possible to reduce nickel remaining in the by-product. It is an object of the present invention to provide a nickel recovery method that simultaneously simplifies the cementation process.
- the present inventors mixed nickel by-product with a predetermined aqueous solution when recovering nickel from the by-product of the electrolytic nickel production process.
- the present inventors have found that the remaining nickel can be reduced and completed the present invention.
- the nickel recovery method according to the present invention for achieving the above object is a nickel recovery method for recovering nickel from a by-product of an electric nickel production process by a chlorine leaching method, wherein nickel sulfide is oxidized and leached.
- by-product containing 5 wt% to 20 wt% nickel the dissolved amount of chlorine is 80 g / L to 390 g / L and the concentration of copper is 30 g / L to 70 g / L.
- the slurry concentration is preferably 130 g / L to 350 g / L in terms of solid content.
- the solid phase can be returned to the cementation step.
- the slurry when the by-product is a slurry obtained by repulping the residue, the slurry can be returned to the cementation step without solid-liquid separation.
- the solid phase can be discharged out of the electric nickel production process when the by-product is an adhering substance adhering to the inner wall of the melting tank.
- the solid phase can be returned to the sulfur recovery process if the by-product is part of the chlorine leaching residue.
- FIG. 1 is a process diagram of an electric nickel production process by a chlorine leaching method to which a nickel recovery method according to the present invention is applied.
- FIG. 2 is a graph showing the transition of the reaction time and the oxidation / reduction potential based on Ag / AgCl in Example 1 and Examples 4 to 7.
- FIG. 3 is a graph showing the transition of the reaction time and the oxidation / reduction potential based on Ag / AgCl in Example 2, Example 8 and Example 9.
- FIG. 4 is a graph showing the transition of the reaction time and oxidation / reduction potential based on Ag / AgCl in Examples 1 to 3.
- FIG. 5 is a graph showing the transition of the reaction time and the redox potential on the basis of Ag / AgCl in Example 1, Comparative Example 1 and Comparative Example 4.
- FIG. 6 is a graph showing transition of reaction time and oxidation / reduction potential on the basis of Ag / AgCl in Example 2, Comparative Example 2, Comparative Example 3 and Comparative Example 5.
- FIG. 7 is a process diagram of an electric nickel production process by a conventional chlorine leaching method.
- FIG. 8 is a process diagram of an electric nickel production process by a conventional chlorine leaching method (Patent Document 3).
- present embodiments Specific embodiments to which the present invention is applied (hereinafter referred to as “present embodiments”) will be described in detail along the following items. Note that the present invention is not limited to the following embodiments, and various modifications can be made without departing from the scope of the present invention.
- the nickel recovery method according to the present embodiment is an S ° slurry that is a by-product of the electro-nickel manufacturing process by the chlorine leaching method in the nickel recovery step S60, the nickel recovery step S70, and the nickel recovery step S80.
- nickel is recovered from residue flakes and chlorine leaching residues.
- the electro-nickel manufacturing process includes chlorine leaching step S10 for leaching a metal such as nickel using nickel sulfide as a raw material to produce a copper-containing nickel chloride solution as a chlorine leaching solution, and a chlorine leaching step S10. And a cementation step S20 for immobilizing monovalent copper ions by adding a nickel matte and chlorine leaching residue to the copper-containing nickel chloride solution obtained in the above.
- the electronickel production process includes, as a subsequent step of the cementation step S20, a purification step S30 for removing impurities other than nickel from the final cementation solution, and an electrowinning method from the nickel chloride solution obtained in the purification step S30. And an electrolysis step S40 for obtaining electric nickel.
- the electrolytic nickel production process includes a sulfur recovery step S50 for recovering product sulfur from the chlorine leaching residue obtained in the chlorine leaching step S10 and a S ° obtained in the sulfur recovery step S50 as a subsequent step of the chlorine leaching step S10.
- the nickel recovery step S60 in which the predetermined solution is added to the slurry and mixed by stirring, and the residual solution obtained in the sulfur recovery step S50, the predetermined solution is added and mixed by stirring.
- a nickel recovery step S80 for obtaining a liquid phase and a solid phase by adding a predetermined solution to a part of the chlorine leaching residue obtained in the chlorine leaching step S10 and mixing with stirring, followed by solid-liquid separation. And have.
- nickel remaining in each by-product can be reduced by recovering nickel through the above-described steps, and at the same time, simplification of the cementation step S20 in the electrolytic nickel manufacturing process is realized. Can do.
- the chlorine leaching step S10 for example, nickel sulfide produced by wet smelting from nickel oxide ore is used as a raw material, and metal components such as nickel and copper are oxidized and leached with chlorine gas, and a copper-containing nickel chloride solution as a chlorine leaching solution is obtained. Generate.
- the chlorine leaching solution (copper-containing nickel chloride solution) containing copper generated from the chlorine leaching step S10 is sent to the cementation step S20.
- impurities mainly composed of sulfur remaining in the solid phase in the chlorine leaching step S10 are regarded as chlorine leaching residues, and product sulfur is recovered through a sulfur recovery step S50 described later.
- the nickel in the chlorine leaching residue is recovered from the chlorine leaching residue obtained by extracting a part of the chlorine leaching residue in the nickel recovery step S80 described later.
- the copper leaching solution (copper-containing nickel chloride solution) was transferred to the cementation step S20 described later from the chlorine leaching step S10, and a copper removal electrolysis step (not shown) was provided, resulting in excess. Copper may be removed by electrolytic deposition.
- cementation step S20 the copper-containing nickel chloride solution generated in the chlorine leaching step S10 is fed, and the copper in the copper-containing nickel chloride solution is fixed and removed.
- a nickel mat produced from dry smelting is used as a raw material for the copper-containing nickel chloride solution, and the slurry is repulped with the nickel chloride solution generated in the subsequent electrolysis step S40. Add.
- a chlorine leaching residue mainly containing sulfur generated as a by-product in the chlorine leaching step S10 is added.
- the S ° slurry generated as a by-product in the sulfur recovery step S50 may be added.
- the cementation step S20 nickel in the solution from which copper is fixed and removed becomes divalent nickel ions, and the solution is sent to the liquid purification step S30 as a cementation final solution.
- the copper sulfide and the unreacted nickel remaining in the solid phase after being immobilized are sent again to the chlorine leaching step S10 as cementation residues.
- the reaction temperature in the cementation step S20 is preferably 70 ° C. to 100 ° C., more preferably 80 ° C. to 90 ° C. If the temperature condition is less than 70 ° C., it is difficult to reduce the divalent copper ions remaining in the copper-containing nickel chloride solution to monovalent copper ions, and the progress of the reaction for fixing the monovalent copper ions with sulfur stagnate. End up.
- the cementation step S20 by setting the temperature condition to 70 ° C. or higher, the reaction of reducing the remaining divalent copper ions to monovalent copper ions and efficiently fixing the monovalent copper ions with sulfur proceeds. Can be made.
- the cementation final solution is fed from the cementation step S20.
- impurities other than nickel, such as iron, cobalt, and copper contained in the final cementation liquid by a liquid purification process such as an oxidation neutralization method. Remove.
- the liquid purification process S30 includes a deironing process, a decobalting process, a deleading process, a dezincing process, and the like as main processes not shown.
- Electrolysis process In the electrolysis step S40, electronickel is produced by the electrowinning method using the nickel chloride solution obtained through the liquid purification step S30.
- nickel ions in the nickel chloride solution are deposited as metal on the cathode side, and electric nickel is generated.
- chlorine ions in the nickel chloride solution are generated as chlorine gas and used in the chlorine leaching step S10 and the like.
- the sulfur recovery step S50 the chlorine leaching residue obtained in the chlorine leaching step S10 is heated in a melting tank, the contained sulfur content is melted, and the chlorine leaching residue is made into a slurry, which is used as a solid-liquid separator. Charge and obtain product sulfur as liquid phase. Moreover, the residue obtained as a solid phase is pulverized and repulped to obtain an S ° slurry. In the obtained S ° slurry, nickel in the S ° slurry is recovered in a nickel recovery step S60 described later.
- Nickel recovery process using S ° slurry In the nickel recovery step S60, the S ° slurry obtained in the sulfur recovery step S50 and a predetermined solution are mixed and stirred to obtain a slurry, and then solid-liquid separation is performed to obtain a liquid phase and a solid phase.
- the obtained liquid phase is returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 and merged with the chlorine leaching solution.
- the obtained solid phase is charged into the cementation step S20.
- the obtained slurry may be charged into the cementation step S20 without performing solid-liquid separation.
- the nickel recovery step S60 it is preferable to adjust the slurry concentration of the obtained slurry so that the solid content is 130 g / L to 350 g / L.
- the solid content is less than 130 g / L, there is a problem that it becomes difficult to restore the water balance of the plant because the liquid amount becomes too large, and the quality of nickel in the S ° slurry, which is a by-product of the electrolytic nickel production process, If it is low, there will be a problem that the driving force for reduction of divalent copper ions to monovalent copper ions is reduced and it takes time.
- the stirring of the S ° slurry and the predetermined solution applies a known technique for these effective contacts. That is, in the nickel recovery step S60, an agitation unit capable of agitation within the range of the solid content at the slurry concentration described above may be selected.
- the predetermined solution contains at least 80 g / L to 390 g / L of the dissolved chlorine, and the copper concentration is 30 g / L to 70 g.
- An aqueous solution containing / L is used.
- 15 wt% to 20 wt% of nickel remaining in the S ° slurry is leached by chlorine dissolved in the predetermined solution, and the nickel remaining in the finally obtained solid phase can be reduced.
- the nickel in the solid phase can be reduced to about 11 wt% to 16 wt%.
- the leached nickel is taken into the finally obtained liquid phase and returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 to join the chlorine leaching solution, so that the amount of nickel contained in the chlorine leaching solution And the nickel leaching rate in the chlorine leaching step S10 increases apparently. Even when the slurry is charged into the cementation step S20 without solid-liquid separation, the nickel leaching rate in the chlorine leaching step S10 is apparently increased in the same manner as when the liquid phase is returned to the transfer path. To do.
- the water balance in the system is lost due to the addition of the predetermined solution, but the amount of water in the system that hardly contains nickel, for example, a poor solution (not shown), is commensurate with the added water. It is sufficient to take measures such as discharging only water or heating and evaporating water in the system.
- an aqueous solution containing chloride ions such as a chlorine leaching solution (copper-containing nickel chloride solution) containing copper generated from the chlorine leaching step S10 and a nickel chloride solution discharged in the electrolysis step S40 is used during the mixing process.
- An aqueous solution containing cupric chloride is more preferable because it does not lower the cupric chloride concentration.
- a chlorine leaching solution copper-containing nickel chloride solution
- a recovery measure due to the disruption of the water balance in the system is unnecessary, and more efficient operation is possible.
- the residue flaker obtained in the sulfur recovery step S50 and a predetermined solution are mixed and stirred to obtain a slurry, and then solid-liquid separation is performed to obtain a liquid phase and a solid phase.
- the slurry concentration, the stirring means, and the predetermined solution are the same as in the nickel recovery step S60, and thus the description thereof is omitted here.
- the obtained liquid phase is returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 and merged with the chlorine leaching solution. Further, the obtained solid phase is discharged out of the system.
- an aqueous solution similar to the predetermined solution in the nickel recovery step S60 is used as the predetermined solution.
- 5 wt% to 7 wt% of nickel remaining in the residual flake is leached by chlorine dissolved in the predetermined solution, and the nickel remaining in the finally obtained solid phase is reduced to about 2 wt%. Not only can nickel loss in the entire process be reduced.
- the leached nickel is taken into the finally obtained liquid phase and returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 to join the chlorine leaching solution, so that the amount of nickel contained in the chlorine leaching solution And the nickel leaching rate in the chlorine leaching step S10 increases apparently.
- the water balance in the system is lost because the predetermined solution is added, but the amount of water in the system that does not substantially contain nickel, for example, a poor solution (not shown), is commensurate with the added water. It is sufficient to take measures such as discharging only water or heating and evaporating water in the system.
- the liquid volume of the liquid phase obtained by solid-liquid separation of the slurry is equal to the liquid volume of the predetermined solution. For this reason, since the weight of the obtained solid phase is equal to the weight of the residue flaker obtained in the sulfur recovery step S51 in the prior art shown in FIG. 7 and discharged out of the system, the solid phase is discharged out of the system. Will not adversely affect the entire process.
- Nickel recovery process using chlorine leach residue In the nickel recovery step S80, a chlorine leaching residue obtained by extracting a part of the chlorine leaching residue charged in the sulfur recovery step S50 and a predetermined solution are mixed and stirred to obtain a slurry, and then solid-liquid separated to obtain a liquid phase. To obtain a solid phase. Note that the slurry concentration, the stirring means, and the predetermined solution are the same as in the nickel recovery step S60, and thus the description thereof is omitted here.
- the obtained liquid phase is returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 to join the chlorine leaching solution. Moreover, the obtained solid phase is charged into the sulfur recovery step S50 of the next step.
- the predetermined solution when joining the liquid phase to the chlorine leaching solution, an aqueous solution similar to the predetermined solution in the nickel recovery step S60 is used as the predetermined solution.
- the nickel 5 wt% to 7 wt% remaining in the chlorine leaching residue is leached by chlorine dissolved in the predetermined solution, and the nickel remaining in the finally obtained solid phase can be reduced.
- the amount of nickel in the solid phase can be reduced to about 3 wt% to 5 wt%.
- the leached nickel is taken into the finally obtained liquid phase and returned to the transfer path from the chlorine leaching step S10 to the cementation step S20 to join the chlorine leaching solution, so that the amount of nickel contained in the chlorine leaching solution And the nickel leaching rate in the chlorine leaching step S10 increases apparently.
- the water balance in the system is lost because the predetermined solution is added, but the amount of water in the system that hardly contains nickel, for example, a poor liquid (not shown), is commensurate with the added water. It is sufficient to take measures such as discharging only water or heating and evaporating water in the system.
- nickel can be recovered by performing at least one of the nickel recovery step S60, nickel recovery step S70 and nickel recovery step S80, and nickel remaining in each byproduct can be reduced. Become. In each nickel recovery process, nickel (nickel loss) discharged outside the system is reduced, and therefore it is preferable to perform the nickel recovery process S70.
- nickel recovery step S60 or nickel recovery step S70 is performed in addition to nickel recovery step S80, or if all nickel recovery steps are performed, the chlorine leaching residue after nickel is recovered by nickel recovery step S80 The sulfur recovery step S50 is charged. Thereafter, nickel is further recovered, which is preferable because the nickel recovery rate is higher than when it is performed individually.
- the nickel recovery method is, for example, a method in which the nickel recovery method is applied to the conventional electric nickel manufacturing process shown in FIG. 7, that is, a nickel recovery step S60, a nickel recovery step S70, and a nickel recovery step S80 are added. is there.
- Nickel sulfide and nickel matte circulates in the system in the same manner as in the conventional electric nickel production process. Therefore, for example, if the amount of nickel sulfide produced from hydrometallurgy is increased for the purpose of increasing the production of electric nickel, the amount of copper circulated in the electric nickel production process system inevitably increases. It will be.
- the chlorine leaching solution obtained from the chlorine leaching step S11 is about 550 mV in terms of the oxidation / reduction potential based on Ag / AgCl.
- the coexisting copper ions are in an excess state of divalent copper ions, and are first reduced to monovalent copper ions, so that the reducing power of nickel metal in the cementation step S21 is insufficient.
- a liquid phase obtained by mixing and stirring various by-products and a predetermined solution and solid-liquid separation is a leaching of nickel remaining in various by-products, and dissolved chlorine is consumed as nickel chloride.
- the coexisting copper ions also decrease to an oxidation / reduction potential of about 350 mV on the basis of Ag / AgCl where the abundance ratio of monovalent copper ions and divalent copper ions is balanced.
- the first cementation step (first cementation step S22) with nickel sulfide required in the nickel manufacturing process is not necessary.
- various by-products of the electrolytic nickel production process include chlorine having a dissolved chlorine amount of 80 g / L to 390 g / L and a copper concentration of 30 g / L to 70 g / L. And an aqueous copper-containing solution. Further, the solid content in the concentration of the slurry obtained by adding chlorine and copper-containing aqueous solution to various by-products is adjusted to 130 g / L to 350 g / L.
- nickel recovery method is applied to an electrical nickel production process, nickel can be efficiently recovered from the by-product of the electrical nickel production process by the chlorine leaching method, and the remaining nickel in the by-product can be reduced. Simplification of the cementation process can be realized at the same time.
- Tables 1 and 2 show the raw materials and starting liquids used.
- Example 1 In Example 1, 140 g of S 0 slurry was added to the initial liquid 1 heated by the above-described adjustment method, and the temperature was adjusted so that the reaction temperature became a liquid temperature of 100 ° C. to 110 ° C. for 4 hours.
- Example 1 solid-liquid separation was performed by suction filtration to obtain a leaching residue 1 (solid phase) and a leaching solution 1 (liquid phase).
- Example 2 In Example 2, a leaching residue 2 (solid phase) and a leaching liquid 2 (liquid phase) were obtained in the same manner as in Example 1 except that 140 g of the residue flavor was added to the initial liquid 1.
- Example 3 In Example 3, a leaching residue 3 (solid phase) and a leaching liquid 3 (liquid phase) were obtained in the same manner as in Example 1 except that 140 g of chlorine leaching residue was added to the initial liquid 1.
- Example 4 In Example 4, a leaching residue 4 (solid phase) and a leaching liquid 4 (liquid phase) were obtained in the same manner as in Example 1 except that 116 g of S 0 slurry was added to the initial liquid 1.
- Example 5 In Example 5, a leaching residue 5 (solid phase) and a leaching liquid 5 (liquid phase) were obtained in the same manner as in Example 1 except that 72 g of S 0 slurry was added to the initial liquid 1.
- Example 6 In Example 6, a leaching residue 6 (solid phase) and a leaching liquid 6 (liquid phase) were obtained in the same manner as in Example 1 except that 52 g of S 0 slurry was added to the initial liquid 1.
- Example 7 In Example 7, a leaching residue 7 (solid phase) and a leaching liquid 7 (liquid phase) were obtained in the same manner as in Example 1 except that 30 g of S 0 slurry was added to the initial liquid 1.
- Example 8 In Example 8, a leaching residue 8 (solid phase) and a leaching liquid 8 (liquid phase) were obtained in the same manner as in Example 1 except that 72 g of the residue flavor was added to the starting liquid 1.
- Example 9 In Example 9, a leaching residue 9 (solid phase) and a leaching solution 9 (liquid phase) were obtained in the same manner as in Example 1 except that 30 g of the residue flavor was added to the starting liquid 1.
- Comparative Example 1 In Comparative Example 1, the leaching residue 10 (solid phase) and the leaching liquid 10 (liquid phase) were the same as in Example 1 except that 140 g of S 0 slurry was added to 400 mL of the initial liquid 2 heated by the adjustment method described above. )
- Comparative Example 2 In Comparative Example 2, the leaching residue 11 (solid phase) and the leaching solution 11 (liquid phase) were added in the same manner as in Example 1 except that 140 g of chlorine leaching residue was added to the starting liquid 2 heated by the above-described adjustment method. Obtained.
- Comparative Example 3 In Comparative Example 3, the leaching residue 12 (solid phase) and the leaching solution 12 (liquid phase) were the same as in Example 1 except that 140 g of chlorine leaching residue was added to 400 mL of the initial liquid 3 heated by the above adjustment method. )
- Comparative Example 4 ⁇ Preparation of starting liquid 4>
- a cupric chloride reagent was dissolved in pure water and adjusted to pH 0.00 (25 ° C.) with hydrochloric acid to obtain an initial solution 4.
- the obtained starting liquid 4 had a copper concentration of 52 g / L and a dissolved chlorine concentration of 80 g / L.
- Comparative Example 5 Comparative Example 5
- the leaching residue 14 (solid phase) and the leaching solution 14 (liquid phase) were added in the same manner as in Example 1 except that 140 g of chlorine leaching residue was added to the starting liquid 4 heated by the above-described adjustment method. Obtained.
- Example 1 to 9 as shown in Tables 3 and 4, when the addition amount of each raw material is increased, the leaching of nickel is promoted to increase the nickel concentration of the leaching solution, and conversely the chlorine concentration is decreased. It was. In Examples 1 to 9, the copper concentration also decreased with the decrease in the chlorine concentration. This is because consumption of dissolved chlorine and reduction of divalent copper ions to monovalent copper ions proceeded, and the copper sulfide was fixed and removed on the solid phase (leaching residue) side.
- the redox potential based on Ag / AgCl is constant (reaction equilibrium) at about 330 mV to 350 mV, and it was found that no further addition of each raw material or extension of the reaction time is necessary.
- the reactivity of the raw materials is S 0 slurry earliest, then chlorine leach residue, the residue Fureka was found to be the slowest.
- Comparative Example 1 to Comparative Example 5 “Change in reaction time and oxidation / reduction potential on the basis of Ag / AgCl” was measured when starting materials 2 to 4 were used to leach the raw materials, and the results were graphed. As shown in FIG. 5 and FIG. In FIGS. 5 and 6, the results of Example 1 and Example 2 used with the starting liquid 1 are also shown as comparison targets.
- the residue produced in the chlorine leaching process (for example, the chlorine leaching process S10 in FIG. 1) (for example, the chlorine leaching residue in FIG. 1) is obtained.
- nickel can be recovered by slurrying again with an aqueous solution and mixing with a liquid containing cupric chloride. Further, since the amount of nickel recovered is considered to be proportional to the amount of excess chloride ions in the liquid phase, it was found that the higher the copper ion concentration, the more efficiently nickel can be recovered.
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Abstract
Description
2.塩素浸出工程
3.セメンテーション工程
4.浄液工程
5.電解工程
6.硫黄回収工程
7.S°スラリーを用いたニッケル回収工程
8.残渣フレーカを用いたニッケル回収工程
9.塩素浸出残渣を用いたニッケル回収工程
本実施の形態に係るニッケルの回収方法は、図1に示すように、ニッケル回収工程S60、ニッケル回収工程S70及びニッケル回収工程S80において、塩素浸出法による電気ニッケル製造プロセスの副産物であるS°スラリー、残渣フレーカ及び塩素浸出残渣からニッケルを回収する方法である。
塩素浸出工程S10では、例えばニッケル酸化鉱から湿式製錬して製造したニッケル硫化物を原料とし、塩素ガスによってニッケルや銅等の金属成分を酸化浸出し、塩素浸出液としての含銅塩化ニッケル溶液を生成する。塩素浸出工程S10から生成された銅を含有する塩素浸出液(含銅塩化ニッケル溶液)は、セメンテーション工程S20に送液される。
セメンテーション工程S20では、塩素浸出工程S10にて生成した含銅塩化ニッケル溶液が送液され、含銅塩化ニッケル溶液中の銅を固定化し除去する。セメンテーション工程S20では、含銅塩化ニッケル溶液に対して、例えば乾式製錬から産出されたニッケルマットを原料とし、粉砕処理して後工程の電解工程S40にて生成した塩化ニッケル溶液によってレパルプしたスラリーを添加する。
Ni0+S0+2CuCl⇒NiCl2+Cu2S…(反応式2)
浄液工程S30では、セメンテーション工程S20からセメンテーション終液が送液され、例えば酸化中和法等の浄液処理によってセメンテーション終液中に含まれる鉄、コバルト、銅等のニッケル以外の不純物を除去する。具体的に、浄液工程S30には、図示しない主な工程として、脱鉄工程、脱コバルト工程、脱鉛工程、脱亜鉛工程等がある。
電解工程S40では、浄液工程S30を経て得られた塩化ニッケル溶液を用いて、電解採取法によって電気ニッケルを製造する。電解工程S40においては、カソード側では、塩化ニッケル溶液中のニッケルイオンがメタルとして析出し、電気ニッケルが生成される。また、アノード側では、塩化ニッケル溶液中の塩素イオンが塩素ガスとして発生し、塩素浸出工程S10等において用いられる。
硫黄回収工程S50では、塩素浸出工程S10で得られた塩素浸出残渣を融解槽中で加熱し、含有される硫黄分を溶融させ、塩素浸出残渣をスラリー状にして、これを固液分離装置に装入し、液相として製品硫黄を得る。また、固相として得られた残渣を粉砕し、レパルプしてS°スラリーを得る。得られたS°スラリーは、後述するニッケル回収工程S60で、S°スラリー中のニッケルが回収される。
ニッケル回収工程S60では、硫黄回収工程S50で得られたS°スラリーと所定溶液とを混合撹拌してスラリーを得た後に、固液分離して液相と固相とを得る。
ニッケル回収工程S70では、硫黄回収工程S50で得られた残渣フレーカと所定溶液とを混合撹拌してスラリーを得た後に、固液分離して液相と固相とを得る。なお、スラリー濃度、撹拌手段、所定溶液については、ニッケル回収工程S60と同様であるので、ここでの説明は省略する。
ニッケル回収工程S80では、硫黄回収工程S50に装入される塩素浸出残渣の一部を抜き出した塩素浸出残渣と所定溶液とを混合撹拌してスラリーを得た後に、固液分離して液相と固相とを得る。なお、スラリー濃度、撹拌手段、所定溶液については、ニッケル回収工程S60と同様であるので、ここでの説明は省略する。
500mLの邪魔板付きセパラブルフラスコに、表2に示す始液1を400mL入れ、回転速度300rpmにて撹拌しながらオイルバスにて100℃~105℃となるように加温した。また、表2に示す始液2~始液4についても、始液1と同様にして調整を行った。
実施例1では、前記の調整方法にて加温した始液1にS0スラリーを140g投入し、反応温度が100℃~110℃の液温となるよう温度調整して4hr反応させた。
実施例2では、始液1に残渣フレーカを140g投入した以外は実施例1と同様にして、浸出残渣2(固相)と浸出液2(液相)を得た。
実施例3では、始液1に塩素浸出残渣を140g投入した以外は実施例1と同様にして、浸出残渣3(固相)と浸出液3(液相)を得た。
実施例4では、始液1にS0スラリーを116g投入した以外は実施例1と同様にして、浸出残渣4(固相)と浸出液4(液相)を得た。
実施例5では、始液1にS0スラリーを72g投入した以外は実施例1と同様にして、浸出残渣5(固相)と浸出液5(液相)を得た。
実施例6では、始液1にS0スラリーを52g投入した以外は実施例1と同様にして、浸出残渣6(固相)と浸出液6(液相)を得た。
実施例7では、始液1にS0スラリーを30g投入した以外は実施例1と同様にして、浸出残渣7(固相)と浸出液7(液相)を得た。
実施例8では、始液1に残渣フレーカを72g投入した以外は実施例1と同様にして、浸出残渣8(固相)と浸出液8(液相)を得た。
実施例9では、始液1に残渣フレーカを30g投入した以外は実施例1と同様にして、浸出残渣9(固相)と浸出液9(液相)を得た。
比較例1では、前記の調整方法にて加温した400mLの始液2にS0スラリーを140g投入した以外は実施例1と同様にして、浸出残渣10(固相)と浸出液10(液相)を得た。
比較例2では、前記の調整方法にて加温した始液2に塩素浸出残渣を140g投入した以外は実施例1と同様にして、浸出残渣11(固相)と浸出液11(液相)を得た。
比較例3では、前記の調整方法にて加温した400mLの始液3に塩素浸出残渣を140g投入した以外は実施例1と同様にして、浸出残渣12(固相)と浸出液12(液相)を得た。
<始液4の作製>
比較例4では、塩化第2銅の試薬を純水に溶解し、塩酸にてpH0.00(25℃)に調整して始液4を得た。得られた始液4の銅濃度は52g/L、溶存塩素濃度は80g/Lであった。
比較例5では、前記の調整方法にて加温した始液4に塩素浸出残渣を140g投入した以外は実施例1と同様にして、浸出残渣14(固相)と浸出液14(液相)を得た。
Ni0+S0+2CuCl⇒NiCl2+Cu2S…(反応式2)
Claims (7)
- 塩素浸出法による電気ニッケル製造プロセスの副産物からニッケルを回収するニッケルの回収方法であって、
ニッケル硫化物を酸化浸出して塩素浸出液と塩素浸出残渣とを得る塩素浸出工程と、
前記塩素浸出液中の銅を固定化して除去するセメンテーション工程と、
融解槽中で前記塩素浸出残渣をスラリーにした後に固液分離して硫黄含有溶液と残渣とを得る硫黄回収工程と、
5wt%~20wt%のニッケルを含有する前記副産物に、塩素の溶存量が80g/L~390g/Lであり且つ銅の濃度が30g/L~70g/Lである水溶液を添加してスラリーを得て、該スラリーを固相と液相とに固液分離するニッケル回収工程と
を有し、前記塩素浸出工程から前記セメンテーション工程への移送経路に前記液相を戻し入れることを特徴とするニッケルの回収方法。 - 前記スラリーのスラリー濃度は、固形分が130g/L~350g/Lであることを特徴とする請求項1に記載のニッケルの回収方法。
- 前記副産物が前記残渣をレパルプしたスラリーである場合には、前記固相を前記セメンテーション工程に戻し入れることを特徴とする請求項1に記載のニッケルの回収方法。
- 前記副産物が前記残渣をレパルプしたスラリーである場合には、前記固液分離せずに該スラリーを前記セメンテーション工程に戻し入れることを特徴とする請求項1に記載のニッケルの回収方法。
- 前記副産物が前記融解槽の内壁に付着した付着物である場合には、前記固相を前記電気ニッケル製造プロセスの系外に排出することを特徴とする請求項1に記載のニッケルの回収方法。
- 前記副産物が前記塩素浸出残渣の一部である場合には、前記固相を前記硫黄回収工程に戻し入れることを特徴とする請求項1に記載のニッケルの回収方法。
- 前記水溶液の代替として前記塩素浸出液を用いることを特徴とする請求項1に記載のニッケルの回収方法。
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