JP5565339B2 - Effective chlorine removal method and cobalt recovery method - Google Patents

Description

  The present invention eliminates effective chlorine by removing effective chlorine contained in a cobalt chloride solution by using a column and using this effective chlorine removing method when removing impurities. The present invention relates to a cobalt recovery method for recovering cobalt.

  Cobalt is a metal widely used in industrial applications as a special alloy or magnetic material. Cobalt is usually produced in the form of oxides and sulfides, but most of it is produced as a by-product of nickel smelting and copper smelting. For this reason, in order to collect cobalt, it is indispensable to separate and remove impurities such as nickel and copper from by-products.

  In general, in order to remove impurities, first, a raw material containing cobalt is dissolved with a mineral acid such as hydrochloric acid or sulfuric acid to obtain a cobalt solution. Since the obtained cobalt solution contains various elements contained in the raw material, it contains various impurities. Next, it is a general method to remove impurities in the cobalt solution and then collect cobalt as a metal by electrowinning.

  Thus, the purity of the metal cobalt obtained by electrowinning is determined by the composition of the electrolytic solution used. Therefore, in order to obtain high-purity metal cobalt, it is necessary to remove impurities in the cobalt solution. .

  For example, when removing nickel as an impurity from a cobalt solution, cobalt and nickel are separated and nickel is removed. Currently, a solvent extraction method has been implemented as a method for efficiently separating nickel and cobalt. In the solvent extraction method in a chloride bath, cobalt that forms a stable chloro complex is extracted into an organic phase and separated from nickel, and then cobalt is back-extracted from the organic phase with an aqueous solution having a low chloride ion concentration such as water. . The cobalt chloride solution used as the back extract contains manganese and zinc that are very similar in extraction behavior to cobalt. Therefore, it is necessary to remove impurities such as manganese and zinc from the cobalt chloride solution of the back extract.

  First, manganese is removed as follows. In order to remove manganese, there is a method of removing manganese as an impurity from a cobalt chloride solution by an oxidation neutralization method using chlorine as an oxidizing agent and cobalt carbonate as a neutralizing agent (see, for example, Patent Document 1). .

  Next, zinc is removed from the cobalt chloride solution from which manganese has been removed. In order to remove zinc, there is a method of removing zinc which is an impurity from a cobalt chloride solution with a strongly basic anion exchange resin.

  However, this cobalt chloride solution contains chlorine used as an oxidizing agent in the demanganese process as effective chlorine. When chlorine gas dissolves in water, it reacts with water to generate hypochlorous acid and hydrochloric acid, and a part of hypochlorous acid dissociates into hypochlorite ions and hydrogen ions. Chlorine gas, hypochlorous acid and hypochlorous acid ions are called effective chlorine and have strong oxidizing power. For this reason, when removing zinc from the cobalt chloride solution, effective chlorine oxidizes the strongly basic anion exchange resin, weakening the exchange group, dropping off the exchange group, and chlorinating the resin substrate, deteriorating the resin. Resulting in. This reduces the total ion exchange capacity of the strongly basic anion exchange resin. Therefore, it is necessary to remove effective chlorine from the cobalt chloride solution before the dezincing step.

  As a method of removing effective chlorine from a cobalt chloride solution, there is a method of removing effective chlorine using a reducing agent. However, when a reducing agent is added to the cobalt chloride solution, there arises a problem that the composition of the cobalt chloride solution changes. Examples of the reducing agent include ascorbic acid, divalent tin ion, divalent iron ion, and hydrazine. For example, when ascorbic acid is used, the total organic carbon concentration in the cobalt chloride solution becomes high, and wastewater treatment becomes difficult. When divalent tin ions and divalent iron ions are used, these metal ions remain, so that a tin removal and iron removal step is further required to obtain a high purity cobalt chloride solution. Toxicity is a problem when hydrazine is used. In addition, since these reducing agents decompose quickly in an aqueous solution, they cannot be stored for a long time in an aqueous solution and are difficult to manage at a constant concentration. In addition, when activated carbon is used, the purchase and regeneration of activated carbon is costly.

  Therefore, in removing effective chlorine from a cobalt chloride solution, it is required to remove effective chlorine without causing problems when using the above reducing agent under conditions that do not affect the composition of the cobalt chloride solution. Yes.

JP 2004-123469 A

  Therefore, the present invention has been proposed in view of such circumstances, and an effective chlorine removal method capable of removing effective chlorine from a cobalt chloride solution under conditions that do not affect the composition of the cobalt chloride solution, In addition, an object of the present invention is to provide a cobalt recovery method for recovering cobalt by removing effective chlorine by using this effective chlorine removal method when removing impurities.

  The method for removing effective chlorine according to the present invention that achieves the above-described object is to adsorb effective chlorine on cobalt by passing a cobalt chloride solution containing effective chlorine and having a pH of 3.0 or less through a column packed with cobalt. Remove effective chlorine from the cobalt chloride solution.

  In addition, the cobalt recovery method according to the present invention that achieves the above-described object includes removing chlorine by adding chlorine to a cobalt chloride solution containing impurities generated by a nickel or copper hydrometallurgical process, This is a method for recovering cobalt to be recovered, in which chlorine is contained as effective chlorine, and a cobalt chloride solution having a pH of 3.0 or less is passed through a column packed with cobalt to remove effective chlorine.

  According to the present invention, effective chlorine is adsorbed by cobalt by passing a cobalt chloride solution containing effective chlorine through a column packed with cobalt, so that effective chlorine is removed from the cobalt chloride solution without using a reducing agent or the like. can do. Therefore, in the present invention, effective chlorine can be removed under conditions that do not affect the composition without changing the composition of the cobalt chloride solution.

  In addition, according to the present invention, when adding cobalt or chlorine to a cobalt chloride solution containing impurities generated by a hydrometallurgical process to remove impurities and recovering cobalt, the added chlorine is removed. Effective chlorine can be removed by passing a cobalt chloride solution containing as effective chlorine and having a pH of 3.0 or less through a column packed with cobalt. Thereby, in this invention, when collect | recovering cobalt from a by-product, it can prevent that an effective chlorine influences the other process of removing an impurity.

  Hereinafter, the method for removing effective chlorine and the method for recovering cobalt according to the present invention will be described in detail. In addition, the effective chlorine removal method according to the present embodiment can be appropriately changed as long as the gist of the present invention is not changed.

  The method for removing effective chlorine is a method for removing effective chlorine from a cobalt chloride solution. This effective chlorine removal method is effective, for example, from the cobalt chloride solution produced when removing nickel and copper impurities in the pretreatment when electrolytically collecting cobalt, a by-product produced in nickel smelting and copper smelting. Can be used to remove chlorine.

  When electrolytically collecting cobalt, impurity nickel is removed from a solution containing cobalt before electrolysis. The nickel is removed from the solution by separating nickel and cobalt by solvent extraction in a chloride bath and extracting cobalt by back extraction. The cobalt chloride solution of the back extract contains manganese and other impurities that are very similar in extraction behavior to cobalt. For this reason, manganese must be removed from the cobalt chloride solution. Manganese is removed by adding chlorination as an oxidizing agent to the cobalt chloride solution and performing oxidation neutralization. For this reason, due to the chlorine added as an oxidizing agent, the cobalt chloride solution contains chlorine gas of effective chlorine, hypochlorous acid, and hypochlorite ions. Since this effective chlorine adversely affects the strongly basic anion exchange resin in the next step of removing zinc, it is necessary to remove it from the cobalt chloride solution.

  Therefore, effective chlorine can be removed from the cobalt chloride solution by using the method for removing effective chlorine of the present invention. The method for removing effective chlorine is not limited to the cobalt chloride solution produced in the pretreatment for electrolytically collecting cobalt, which is a by-product such as nickel smelting, as described above, but effective chlorine is removed from other cobalt chloride solutions containing effective chlorine. Even if it is removed, it can be applied.

  Specifically, the effective chlorine is removed by passing a cobalt chloride solution through a column packed with cobalt and adsorbing the effective chlorine to the cobalt, so that the effluent flowing through the column is removed from the effective chlorine. It can be obtained as a solution.

  The packing material packed in the column is cobalt. Examples of the cobalt include metallic cobalt, electrolytic cobalt obtained by electrolytic purification and electrolytic collection, and poor-sized electrolytic cobalt that is repeated in the process. In the case of using poor-sized electrocobalt that is repeated in the process, the cost can be reduced as compared with the case of using activated carbon that has been conventionally used for removing effective chlorine. In this method of removing effective chlorine, since cobalt is used even if the filler is mixed in the cobalt chloride solution that has passed through the column by using cobalt as the filler, there is no influence on the cobalt chloride solution.

  The filling rate of the filler is appropriately determined in consideration of the adsorption capacity of cobalt to be filled for effective chlorine, and is, for example, about 20% to 80%, and preferably about 50%. Further, the shape of the filler may be any of granular (granular), pellet (small block), block, plate, etc. By making it spherical, the surface area can be increased, and the adsorption capacity can be increased. Can be improved.

  The cobalt chloride solution passed through the column has a pH of 3.0 or less. When the pH of the cobalt chloride solution is greater than 3.0, chlorine gas is not generated, and effective chlorine is present in the form of hypochlorous acid and hypochlorite ions. Reacts with cobalt to produce cobalt oxide, and at pH 7.0 and above, produces cobalt hydroxide. Cobalt oxide and cobalt hydroxide are insoluble in the cobalt chloride solution. For this reason, the production of cobalt oxide and cobalt hydroxide causes column clogging or ineffective removal of available chlorine. Since the effective chlorine form of the cobalt chloride solution having a pH of 1.8 is about 80% hypochlorous acid and about 20% chlorine gas, the effective chlorine concentration decreases with time. For these reasons, the pH of the cobalt chloride solution is 3.0 or less, preferably 1.7 or more and 2.4 or less, and more preferably 1.8.

The liquid passing rate of the cobalt chloride solution through the column is about SV = ¹ to 12h ⁻¹ , and SV = 6h ⁻¹ is preferable. The flow rate (Space Velocity: SV) is a unit indicating how much solution is passed per hour with respect to the capacity of the packing material packed in the column. Volume / filler volume / hour). When the liquid flow rate is higher than 12h ⁻¹ and fast, effective chlorine can be removed, but there is a possibility that the removal may be incomplete, and an excessive capacity pump will be used. The cost for operating this pump is increased. On the other hand, when the liquid passing speed is smaller than 1 h ⁻¹ and slow, removal of effective chlorine takes time, so that the removal efficiency is lowered. Therefore, it is preferable that the liquid passing rate is about ¹ to 12 h ⁻¹ .

  Here, the result of having performed using sodium hypochlorite solution how much effective chlorine can be removed using the column filled with cobalt is shown.

Since the sodium hypochlorite solution is alkaline, the pH was adjusted to 1.8 using 6N hydrochloric acid. The sodium hypochlorite solution used has a pH of 1.8, and an effective chlorine concentration of 7 to 9 mg / L and a concentration of 34 to 53 mg / L in a range of 200 mL each. Several were prepared. A 1 mm-thick electrocobalt was cut into 5 mm squares and packed into a glass column with a diameter of 15 mm so that the packing rate was about 50%. Then, the prepared sodium hypochlorite solution was passed through the column at a feed rate SV = 6 h ⁻¹ . The effective chlorine concentration in the effluent obtained by passing the liquid was confirmed every 30 minutes.

  As a result, 2.8 L of sodium hypochlorite solution having an effective chlorine concentration of 7 to 9 mg / L and 1.6 L of sodium hypochlorite solution having an effective chlorine concentration of 34 to 53 mg / L were passed at any concentration. In addition, no effective chlorine was detected in the effluent by passing through a column packed with cobalt. That is, the effective chlorine concentration in the effluent was <0.5 mg / L.

  The obtained effluent contained cobalt. This is considered that the filler cobalt oxidized by available chlorine and the filler cobalt dissolved by dilute hydrochloric acid were eluted. As a result of measuring the cobalt concentration in the effluent, when 0.2 L of a hydrochloric acid solution having a pH of 1.8 was passed, about 40 mg / L and 2.8 L of a sodium hypochlorite solution having an effective chlorine concentration of 7 to 9 mg / L were passed. Then, it was found that about 120 mg / L of cobalt was eluted when 1.6 L of sodium hypochlorite solution having about 60 mg / L and effective chlorine concentration of 34 to 53 mg / L was passed. The pH of the effluent was 1.8, there was no change in pH due to passing through a column packed with cobalt, and there was no effect on the composition of the sodium hypochlorite solution.

  As described above, in the method for removing effective chlorine, effective chlorine is adsorbed on cobalt as a filler by passing a sodium hypochlorite solution containing effective chlorine through a column packed with cobalt. Therefore, a sodium hypochlorite solution from which effective chlorine has been removed is obtained as an effluent.

  Therefore, even when the sodium hypochlorite solution is changed to a cobalt chloride solution, effective chlorine is adsorbed on the packing cobalt by passing the cobalt chloride solution through a column filled with cobalt. And effective chlorine can be removed from the cobalt chloride solution. In this way, by using the effective chlorine removal method, the conventionally used reducing agent is not added to the cobalt chloride solution, so that a cobalt chloride solution from which effective chlorine has been removed is obtained without changing the composition of the cobalt chloride solution. be able to.

  Further, in this effective chlorine removal method, by setting the pH of the cobalt chloride solution to 3.0 or less, cobalt oxide and cobalt hydroxide are not generated, the column is not clogged, and effective chlorine is removed. Effective chlorine can be removed without becoming incomplete.

In this method of removing effective chlorine, the effective chlorine can be removed without incomplete removal of effective chlorine by setting the liquid flow rate (SV) of the cobalt chloride solution to 6 to 12 h ^−1. it can.

  From the above, this effective chlorine removal method is, for example, from the cobalt chloride solution produced in the pretreatment step of removing impurities when electrolytically collecting cobalt of a secondary acid produced from nickel smelting or copper smelting. Effective for removing effective chlorine.

  For example, byproducts of nickel smelting and copper smelting contain impurities such as nickel in addition to cobalt. In order to electrolytically collect cobalt from this byproduct, a solution pretreated through a plurality of steps for removing impurities is used as an electrolytic solution. Below, the process of removing impurities, such as nickel, from the by-product of nickel smelting and copper smelting is demonstrated easily.

  First, impurity nickel is removed from the by-product. As a method for removing nickel, cobalt and nickel are separated from a cobalt solution obtained by dissolving impurities such as cobalt and nickel with a mineral acid such as hydrochloric acid and sulfuric acid by a solvent extraction method using a chloride bath, and cobalt is back-extracted. Remove the nickel. At this time, the cobalt chloride solution of the back extract contains manganese and zinc that are very similar in extraction behavior to cobalt in addition to cobalt. Therefore, manganese is removed from the cobalt chloride solution in the next step.

  As a method for removing manganese, manganese as an impurity is removed from a cobalt chloride solution by an oxidation neutralization method using chlorine as an oxidizing agent and cobalt carbonate as a neutralizing agent. The cobalt chloride solution from which manganese has been removed contains effective chlorine gas, hypochlorous acid, and hypochlorite ions due to chlorine added as an oxidizing agent. This available chlorine adversely affects the strongly basic anion exchange resin in the next removal of zinc. The pH of the cobalt chloride solution from which manganese has been removed is about 1.8.

  Therefore, by using the above-described effective chlorine removal method, by passing a cobalt chloride solution through a column filled with cobalt, the effective chlorine is adsorbed on the cobalt of the filler, and the effective chlorine can be removed.

  And next, when removing the zinc from the cobalt chloride solution from which the effective chlorine has been removed by the strong basic anion exchange resin, the effective chlorine has been removed from the cobalt chloride solution. Oxidation, weak basification of exchange groups, removal of exchange groups, and chlorination of resin substrates can be prevented. Thereby, since strong basic anion exchange resin does not deteriorate, zinc can be removed from a cobalt chloride solution. In addition, impurities other than nickel, manganese, and zinc are appropriately removed by an appropriate method.

  Next, by using a cobalt chloride solution from which impurities such as nickel, manganese, zinc and the like are removed as an electrolytic solution and electrolytically collecting, high-purity cobalt can be collected.

  From the above, when electrolytically collecting cobalt from byproducts of nickel smelting and copper smelting, the effective chlorine removal method described above is used to remove effective chlorine from the cobalt chloride solution generated in the pretreatment for removing impurities. Thus, effective chlorine can be removed without adding a reducing agent to the cobalt chloride solution. Therefore, effective chlorine can be removed from the cobalt chloride solution without changing the composition of the cobalt chloride solution depending on the reducing agent when removing impurities, and without causing trouble in the ion exchange resin when removing zinc. .

  EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to these Examples.

(Sample 1)
In sample 1, first, a cobalt chloride solution having an effective chlorine concentration of 1.0 mg / L and a pH of 1.8 was prepared. Moreover, 1 mm thick electrocobalt was cut into 5 mm squares and packed into a glass column with a diameter of 15 mm so that the packing rate was about 50%. The prepared cobalt chloride solution was passed through the column at a fluidization speed SV = 6 h ⁻¹ . Then, the effective chlorine concentration in the effluent is measured by the iodine titration method (method of measuring the effective chlorine concentration by adding potassium iodide and titrating the liberated iodine with a sodium thiosulfate solution), and the pH is measured with a pH meter ( (Manufactured by Nisshin Rika Co., Ltd., digital pH controller, NPH-690D).

  As a result, in Sample 1, as shown in Table 1, no effective chlorine was detected in the effluent by passing through a column filled with electrocobalt (effective chlorine concentration in the effluent: <0.5 mg / L). Further, the pH of the effluent was 1.8, and there was no pH change due to the flow through the column filled with electrocobalt.

(Sample 2)
In sample 2, as in sample 1, first, a cobalt chloride solution having an effective chlorine concentration of 1.0 mg / L and a pH of 1.8 was passed through the column at a feed rate SV = 6 h ⁻¹ . From 300 minutes, the sodium hypochlorite solution was standardly added to the cobalt chloride solution to an effective chlorine concentration of 7.4 mg / L, and the solution adjusted to pH 1.8 using 6N hydrochloric acid was added to the column. The liquid was passed through. Then, as in Sample 1, the effective chlorine concentration and pH in the effluent were measured.

  As a result, in Sample 2, as shown in Table 1, no effective chlorine was detected from the effluent by passing through a column packed with cobalt (effective chlorine concentration in the effluent: <0.5 mg / L ). Further, the pH of the effluent was 1.8, and there was no pH change due to the flow through the column filled with electrocobalt.

(Sample 3 to Sample 41)
In Sample 3 to Sample 41, a sodium hypochlorite solution was standardly added to a cobalt chloride solution so as to have an effective chlorine concentration as shown in Table 1 from a passing time of 300 minutes, and shown in Table 1 using 6N hydrochloric acid. The test was performed in the same manner as Sample 2 except that the pH was adjusted and the solution was passed through the column at the flow rate shown in Table 1.

  Table 1 below shows the results of Sample 1 to Sample 41.

  From the results shown in Table 1, in Sample 1 to Sample 39, the effective chlorine concentration of the effluent is much lower than the effective chlorine concentration of the cobalt chloride solution before passing through the column. It can be seen that effective chlorine has been removed from the cobalt chloride solution.

  Moreover, from the results of Sample 1 to Sample 33, it can be seen that by setting the pH of the cobalt chloride solution to 1.8, the effective chlorine can be appropriately removed regardless of the effective chlorine concentration and the flow rate of the cobalt chloride solution.

  From the results of Sample 34 to Sample 39, it is understood that effective chlorine can be appropriately removed if the pH of the cobalt chloride solution is 3.0 or less.

  On the other hand, it can be seen from the results of samples 40 and 41 that when the pH of the cobalt chloride solution becomes 4.0, effective chlorine cannot be removed sufficiently.

  In addition, in the process of removing manganese from the by-product produced by the hydrometallurgical method of nickel or copper and recovering cobalt, in the process of removing manganese, there is a possibility that the effective chlorine concentration may vary depending on the operation status, As shown in Sample 1 to Sample 39, it can be seen that effective chlorine can be appropriately removed even if the effective chlorine concentration varies.

Claims (3)

  A method for removing effective chlorine from a cobalt chloride solution, wherein a cobalt chloride solution containing effective chlorine and having a pH of 3.0 or less is passed through a column packed with cobalt. The method for removing effective chlorine according to claim ¹ , wherein a flow rate of the cobalt chloride solution is ¹ to 12 h ⁻¹ . In the cobalt recovery method of removing chlorine by adding chlorine to a cobalt chloride solution containing impurities generated by a nickel or copper hydrometallurgical process, and recovering cobalt,
A method for recovering cobalt, which comprises removing the effective chlorine by passing the cobalt chloride solution containing the chlorine as effective chlorine and having a pH of 3.0 or less through a column packed with cobalt.