JPS6023176B2 - Copper removal from nickel and/or cobalt containing solutions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and removing copper from a nickel and/or cobalt-containing solution in a nickel and/or cobalt smelting process using a specific chelate resin.

In general, cobalt rarely exists alone as an ore, and is mostly accompanied by steel ore or nickel ore, and is often produced as a by-product along with nickel in the smelting process of the ore.

The nickel- and/or cobalt-containing solution produced in this way generally contains some copper, and in order to electrolytically recover nickel and/or cobalt from it, copper in the nickel- and/or cobalt-containing solution must be prepared in advance. It is necessary to separate and remove the copper and keep the copper concentration below 1 female. Conventionally, methods for removing copper from nickel and/or cobalt-containing solutions include adding a sulfurizing agent such as hydrogen sulfide or sodium hydrogen sulfide to precipitate and remove copper as sulfide, or using slaked lime, caustic soda, etc. A method has been used in which copper is precipitated and removed as a hydroxide by adding a neutralizing agent. However, in any of the above methods, the separation of copper from nickel and/or cobalt is poor, and a considerable amount of nickel and/or cobalt coexists with copper. Further processing had to be done to recover the nickel and cobalt.

In addition, since both methods handle precipitates,
The process is complicated, resulting in handling loss and dirt around the equipment.Furthermore, in the case of the sulfurization method, toxic hydrogen sulfide gas is generated, so extreme care and gas absorption equipment are required to preserve the environment. It was necessary.

On the other hand, recently, methods of removing copper using ion exchange resins or chelate resins have been studied.

However, this ion exchange resin or chelate resin has low selectivity, does not remove copper sufficiently, and has poor heat resistance, making it impractical. ' In view of the serious drawbacks inherent in the sulfurization and neutralization methods described above, the present inventors have proposed that a method of treating a nickel and/or cobalt-containing solution with a chelate resin in a nickel and/or cobalt smelting process is an effective method for removing copper. I was convinced that it was also the most effective.

Therefore, we have further improved the chelate resin treatment method that has been tried so far to produce nickel and/or cobalt that is a simple process, has good separation of copper from nickel and cobalt, and does not pose any environmental protection problems. As a result of intensive research aimed at providing a method for removing steel from containing solutions, we found that all of the above objectives can be achieved by using a specific chelate resin for the contact reaction with the solution, and we have developed the present invention. completed. That is, the present invention provides a method for removing copper from a nickel and/or cobalt-containing solution in a nickel and/or cobalt smelting process, by converting the solution into a compound of the general formula (1) [where M is an alkali metal or hydrogen, R, R2 represents hydrogen or an alkyl group.

The method is characterized in that the phenol compound represented by the above is brought into contact with a phenol-based chelate resin obtained by three-dimensionally crosslinking phenols and aldehydes. The phenolic chelate resin used in the present invention is
678y, for example, a resin obtained by three-dimensionally crosslinking (1-oxyphenylene-2,6)-pismethyliminodiacetic acid, phenol, and formalin (trade name, Uniseletsk UR-50,
(manufactured by Unitika).

The nickel- and/or cobalt-containing solution to be treated in the present invention is a sulfate solution, nitrate solution, ammonium salt solution, etc. containing a certain amount of copper in addition to nickel and/or cobalt. The pH value of the solution in the case of contact is preferably 1 to 10.

If the pH value is 10 or more, the alkali resistance of the resin decreases, which is not preferable. In addition, in the case of a solution with a higher content of nickel and/or cobalt than copper, p
The adsorption amount of copper is saturated when H is 4.5, and when it becomes higher than that,
The adsorption amount of nickel and/or cobalt increases. Furthermore, if the pH is 2 or less, the amount of copper adsorbed decreases, so it is necessary to keep the pH to a minimum of 1. Therefore, the adsorption efficiency,
Considering the number of steps, etc., it is optimal to carry out the reaction at a pH of 1.5 to 4.5 when the solution comes into contact with the phenolic chelate resin. The method of the present invention may be carried out either continuously or batchwise, but it is more advantageous to carry out the method continuously.
In the case of continuous operation, granular phenolic chelate resin is packed into a packed tower or perforated plate tower, and the nickel and/or cobalt-containing solution is passed through at a rate (per resin (referred to as R)). The amount of solution passing in 1 hour (evening) is 1 to 5 hours - R, Hr and the temperature is steady to 80o.
The liquid may be passed under the condition of o. The direction of flow of the nickel and/or cobalt-containing solution may be either upward flow or downward flow. In addition, a combination of a mixing tank and a standing tank is arranged in multiple stages, and the granular or powdered phenolic chelate resin and the nickel and/or cobalt-containing solution are brought into contact with each other in a suspended state in the mixing tank. This can also be carried out by repeating the operation of separating solid and liquid in a static tank, or by using a mixing tank or a combination of a static tank and a packed tower.

In the above operation, the phenolic chelate resin that has adsorbed copper adsorbs a certain amount of nickel and/or cobalt in addition to copper. It is preferable to pass an aqueous copper salt solution.

(Hereinafter, this operation will be referred to as high purification). In the high purification operation, nickel and/or
Alternatively, cobalt is replaced with copper in the copper salt aqueous solution, increasing the concentration of copper in the resin and thus increasing the separability of copper from nickel and/or cobalt. For this copper salt aqueous solution, use the post-desorption solution after desorption (described later).
Well, there's no need to refill it. As the steel salt aqueous solution, a sulfuric acid steel aqueous solution or a nitric acid saving solution is used. Further, this high purification operation is preferably carried out at a pH value of 0.5 to 5, particularly 0.5 to 1.5.

When the pH is around 1, the concentration ratios of nickel to copper and cobalt to copper in the resin are at a minimum. Further, if it is less than 1, the adsorption amount of copper decreases, while if it is more than 1, the above concentration ratio increases and the separability of copper from nickel and cobalt decreases. For the above reasons, in the high purification operation, p
It is best to carry out the test when H is around 1, that is, from 0.5 to 1.5. After the high purification operation, the phenolic chelate resin is then subjected to a well-known desorption operation to desorb the steel.

For example, copper adsorbed on the resin is removed by treatment with sulfuric acid, hydrochloric acid, or nitric acid of 1 to 100 g, and the resin is regenerated. The recycled resin can be used repeatedly. Further, as described above, part or all of the desorption solution may be repeatedly used in the high purification step, or high purity copper may be recovered by electrolysis. When each of the operations detailed above is performed at a high temperature of, for example, 50 oo or higher, the performance of the phenolic chelate resin deteriorates, resulting in problems such as a decrease in adsorption capacity and a decrease in adsorption rate.

In order to concretely demonstrate this fact, the change in adsorption capacity retention rate with the number of days when a phenolic chelate resin is immersed in a solution (temperature 65 qo) containing nickel and cobalt for 40 min and 15 min is plotted. Furthermore, the adsorption capacity retention rates at the breakthrough point are shown in FIG. 12. Here, the adsorption capacity retention rate is expressed as a percentage, with the adsorption capacity of the resin at room temperature as the denominator and the adsorption capacity of the resin at high temperature as the numerator. In addition, the breakthrough point adsorption capacity refers to the adsorption capacity at which more than 1 female/Z of copper leaks into the solution after adsorption when a nickel and/or cobalt-containing solution is passed through the resin. It corresponds to speed. As is clear from the figure, the adsorption capacity decreased to about 50% after 20 days, and the breakthrough adsorption capacity, that is, the reaction rate, decreased to 50%.
After a few days, it decreased to about 50%.

In order to prevent the above drawbacks when processing high-temperature solutions, the phenolic chelate resin is brought into contact with an aqueous ammonium salt solution in advance to convert some or all of the H type into the ammonia form (hereinafter referred to as ammonification). ), it is also preferable to convert some or all of the H type into a nickel type (hereinafter referred to as nickelization) or cobalt type (hereinafter referred to as cobaltization) by contacting with an aqueous nickel salt solution or a cobalt salt aqueous solution. . While the resin is repeatedly used, it shrinks and the adsorption rate decreases, but by carrying out the above-mentioned ammonification operation, it swells and the adsorption rate is restored. Furthermore, by nickelizing and/or cobaltizing the resin, the adsorption capacity does not decrease even at high temperatures, and the heat resistance of the resin improves. The above-mentioned ammonification, nickelation and/or cobaltation operations are carried out either by ammonification followed by nickelization and/or cobaltation, or by simultaneous ammonification and nickelation and/or cobaltation, depending on the solution to be treated. Either one or the other can be selected as appropriate.

As explained above, according to the present invention, there is no problem with precipitation of nickel and cobalt, which was a problem with the conventional method, and the solution after desorption can be purified to high purity by repeated use or electrolysis. of copper can be recovered and there can be no loss of nickel and cobalt.

Furthermore, since no precipitate is generated during the operation, the furnace filtration step of the conventional method is not necessary, and problems such as the complexity of the process and the staining around the device are eliminated. Furthermore, since there is no generation of harmful hydrogen sulfide gas that occurs in the case of the sulfurization method, there is no need for gas absorption equipment, which is very advantageous in terms of environmental protection. Furthermore, the use of a specific chelate resin improves selectivity and solves the problem of heat resistance, thereby completing the practical application of a copper removal method using a chelate resin. The present invention will be explained in more detail below based on Examples.

Example 1 A column was filled with 60% of phenolic chelate resin (manufactured by Unitika, trade name: UNISEREC UR-50), and this was filled with 18% of nickel, 14.8% of cobalt, and 0.53% of copper. A sulfuric acid solution containing acetic acid at a pH of 2 and a temperature of 30
The steel concentration in the treatment liquid was examined by contacting the steel under the following conditions: 00, liquid flow rate 2 so/even, and hr.

As a result, the copper concentration after 5 hours of contact was less than 0.59', and the copper concentration after 1 hour of contact was also less than 0.59', making it possible to completely remove copper. This was confirmed.

The removal rate at this time was 99.90% or more. Example
2 The phenolic chelate resin used in Example 1
．． 8th evening/Nickel sulfate solution containing nickel and pH
By contacting the resin for 3.5 hours at a flow rate of 2.2 hours and a flow rate of 5 hours, 0.3 hours/hour of nickel was adsorbed and the resin was nickelized.

The resin was then treated with nickel 18/day, cobalt 14.8/day.
A sulfuric acid solution containing 0.53 t of copper and 0.53 t of copper;
H2.0, temperature 30℃, and liquid flow rate 2 nights/so-R, H
Copper was adsorbed by contacting for 29 hours under conditions of r. After washing the resin after adsorbing copper with water,
The copper-containing sulfuric acid steel solution and the pHI. 0, liquid passing rate 0.
High purification treatment was carried out by contacting for 6 hours with 5 so/min-R and Hr. Then, the resin obtained above is
Copper was desorbed from the resin by contacting the resin with a sulfuric acid solution for 2 hours at a flow rate of 1-R, Hr. The results obtained above are summarized in Table-1.

As is clear from the table, the copper concentration in the solution after copper adsorption was less than 0.001 min/min, and a de-enbrossing rate of 99.8% was obtained.

In addition, due to the high purification operation, N in the liquid after desorption was
i/Cu ratio is 0.037 and Co/Cu ratio is 0.004
Therefore, the separability of copper from nickel and cobalt was very high. Example 3 The purpose of the present invention was to investigate the heat resistance of resin at high temperatures.

The phenolic chelate resin used in Example 1 was soaked in a solution containing nickel and cobalt for 20 days at a temperature of 60 qo, and the resin was soaked for 40 days in a solution containing nickel and cobalt. /The Nickel, 15th evening/
For the treatment solution containing cobalt and copper, the adsorption of copper, removal of copper, and nickelization were repeated every 5 days for 20 days to investigate changes over time in the adsorption capacity of the resin at high temperatures. It was measured.

The conditions for adsorption, desorption, and nickelization were as follows. Adsorption: pH 4. Fluid flow rate 2〆'〆-
R, Hr desorption: 4N-sulfuric acid, liquid flow rate 1/2-
R, Hb nickelization: 4 days/pass the sulfuric acid solution containing nickel at pH 2 and pH 4, 0.3mo/day - adsorb R nickel on the resin and perform the above operations at room temperature. Table 2 shows a comparison of the adsorption capacity of the H-type resin when the above was carried out.

Table-2 The numbers in parentheses indicate the adsorption capacity retention rate (unit effort).

It was confirmed that the adsorption capacity of the nickelized resin at high temperatures decreased by only 10% or less over time compared to that of the H-type resin at room temperature, and was effective in improving heat resistance. Example 4 The purpose of this example was to investigate changes in the reaction rate of resin at high temperatures.

The phenolic chelate resin used in Example 1 was heated to a temperature of 80
At the same time, the immersion resin was soaked in 0.00 water for 30 days, and the immersion resin was used to adsorb copper, desorb it, and ammonia to a treatment solution containing nickel, cobalt, and copper. The operations of nickelization and nickelization
The test was repeated every day for 30 days to measure the change over time in the breakthrough exchange capacity of the resin (copper 1:9/leakage) at high temperatures.

The conditions for copper adsorption, desorption, and nickelization are as in Example 2.
(However, nickelization was carried out only at pH 4), and ammonification was carried out by passing ammonium hydroxide from the resin through the resin. The results are shown in Table-3. Public-3 The breakthrough exchange capacity, ie, the reaction rate, hardly decreased even after 30 days.

Comparative Example 1 In the same manner as in Example 1, except that a phenolic chelate resin in which one iminodiacetic acid group was introduced into the conventional fer/fer nucleus (manufactured by Unitika, trade name: UNICEREC UR-30) was used. The copper concentration was investigated.

As a result, the copper concentration after 5 hours of contact was 10:9, and the copper concentration after 1 hour of contact was 30:9.The copper leakage concentration was so high that it could not be used for nickel electrolysis.

The removal rate at this time was 95%.

[Brief explanation of the drawing]

Figure 11 shows the change in adsorption capacity retention rate depending on the number of days that have passed when the resin was immersed in a treatment solution at a temperature of 65 qo, and Figure 12 shows the change in adsorption capacity retention rate when the resin was immersed in a treatment solution at a temperature of 65 qo. This figure shows the change in the adsorption capacity retention rate at the breakthrough point depending on the number of days. Figure 1 Figure 2

Claims (1)

[Scope of Claims] 1. When removing copper from a nickel and/or cobalt-containing solution in a nickel and/or cobalt smelting process, the solution is converted to the general formula (I)▲mathematical formula, chemical formula,
There are tables, etc. ▼ [However, M is an alkali metal or hydrogen, R_1, R
_2 represents hydrogen or an alkyl group. A method for removing copper from a nickel- and/or cobalt-containing solution, which comprises contacting a phenolic compound represented by the above with a phenolic chelate resin obtained by three-dimensionally crosslinking phenols and aldehydes. 2 Claim 1 in which the resin after contact is brought into contact with a copper salt aqueous solution
Copper removal method described in section. 3. The copper removal method according to claim 1 or 2, wherein the phenolic chelate resin is ammoniated, nickelized and/or cobaltized.