WO2020211757A1

WO2020211757A1 - Method for recovering copper from phosphoric acid extractant-containing solution

Info

Publication number: WO2020211757A1
Application number: PCT/CN2020/084745
Authority: WO
Inventors: 王恒利; 郑明臻; 戴江洪; 崔宏志; 张阳; 王瑞梅
Original assignee: 中国恩菲工程技术有限公司
Priority date: 2019-04-16
Filing date: 2020-04-14
Publication date: 2020-10-22
Also published as: CN109897958A; CN109897958B; EA202192091A1

Abstract

A method for recovering copper from a phosphoric acid extractant-containing solution. The method comprises: mixing a phosphoric acid extractant-containing solution with solvent oil to obtain an oil-water mixture; performing oil-water separation on the oil-water mixture to obtain a water phase and an oil phase; and performing oxime extraction on the water phase to obtain metallic copper. A phosphoric acid extractant-containing solution is mixed with solvent oil, and oil-water separation is then performed, so as to reduce the content of a phosphoric acid extractant in a water-phase solution; an oxime extraction process is then performed, so that the oxime extraction process can be normally operated, an organic phase can be recycled, and the quality of product copper can also be improved. According to the method, existing operations such as air flotation, ultrasound, resin or fiber agglomeration, and activated carbon adsorption are replaced with simple mixing and oil-water separation means, thereby simplifying the operation, device and process, and significantly saving recovery and investment operation costs.

Description

Method for recovering copper in solution containing phosphoric acid extractant

Technical field

The invention relates to the technical field of hydrometallurgy, and in particular to a method for recovering copper in a phosphoric acid-containing extractant solution.

Background technique

In the extraction process of zinc, nickel and cobalt, phosphoric acid extractants such as P204, P507 or C272 are generally used to separate and purify metal ions. If the copper in the extraction solution has recovery value, people usually use oxime extractant to extract copper-copper electrowinning to recover copper. However, the solution containing phosphoric acid extractant (zinc raffinate, reverse copper manganese liquid, etc.) needs to undergo a deep degreasing operation before entering the copper extraction system, otherwise the phosphoric acid extractant will be enriched in the copper extraction system. When the phosphoric acid extractant is enriched to a certain level, it will not only accelerate the decomposition of the oxime extractant and cause the breakdown of the copper extraction system, but also cause the impurity ions such as iron, zinc, calcium, and manganese to be extracted into the organic phase along with the copper. , Affect the quality of copper products.

At present, the domestic treatment of this type of solution can be divided into the following two types: 1. When the amount of solution is relatively large, the degreasing method of clarification + air flotation + resin (or fiber coalescence) is adopted to reduce the total content of organic matter in the solution. To 2-10ppm; 2. When the solution volume is relatively small, use the degreasing method of clarification + activated carbon adsorption to reduce the total organic content in the solution to 2-10ppm. Both resin and fiber coalescence and degreasing can realize the recycling of organic matter, and the operating cost is low. However, the one-time investment of this degreasing method is relatively large, and if the solution is saturated with calcium, the effect is not good when the resin and fiber are used to coalesce the degreasing. Although the equipment investment of the activated carbon adsorption degreasing method is not high, the operating cost is high because the activated carbon is expensive and cannot be reused.

Summary of the invention

The main purpose of the present invention is to provide a method for recovering copper in a solution containing a phosphoric acid extractant to solve the problem of high recovery cost in the prior art.

In order to achieve the above objective, the present invention provides a method for recovering copper in a phosphoric acid-containing extractant solution, the method comprising: mixing the phosphoric acid-containing extractant solution with solvent oil to obtain an oil-water mixture; and performing oil-water separation on the oil-water mixture, Obtain a water phase and an oil phase; perform oxime extraction on the water phase to obtain metallic copper.

Further, the phosphoric acid-containing extractant solution and the solvent oil are mixed in a volume ratio of 20-100:1.

Further, the phosphoric acid extractant in the phosphoric acid extractant solution is one or more of P204, P507 and C272.

Further, the mineral spirit is the same as the mineral spirit of the extraction agent used in the steps of phosphoric acid extraction and oxime extraction; preferably, the mineral spirit is sulfonated kerosene, 260# solvent oil or Escaid 110.

Further, the step of separating oil and water is carried out by standing and clarifying. Preferably, the step of separating oil and water is carried out in an extraction tank, a mixing tank or a clarification tank.

Further, the mixing time of the phosphoric acid-containing extractant solution and the mineral spirits is 1-10 min.

Further, the oil-water separation rate is 1.5-5m ³ /h/m ² .

Further, the content of the phosphoric acid extractant in the phosphoric acid extractant solution is 5 to 80 ppm.

Furthermore, the volume concentration of the phosphoric acid extractant in the oil phase is 0.5% to 1.5%, and preferably the content of the phosphoric acid extractant in the water phase is less than 1 ppm.

Further, the extractant in the oxime extraction process is M5640 or LIX984.

Applying the technical solution of the present invention, by mixing the phosphoric acid extractant solution with solvent oil, and then separating the oil and water, the content of the phosphoric acid extractant in the aqueous solution is reduced, and then the oxime extraction process can not only make the oxime The similar extraction process runs normally, and the organic phase can be recycled and the quality of the product copper can be improved. The method replaces existing operations such as air flotation, ultrasound, resin, fiber coalescence, and activated carbon adsorption by simple mixing and oil-water separation, simplifies operation, equipment and process flow, and saves investment and operating costs.

detailed description

It should be noted that the embodiments in this application and the features in the embodiments can be combined with each other if there is no conflict. Hereinafter, the present invention will be described in detail in conjunction with embodiments.

The purpose of the present invention is to overcome the shortcomings of the prior art and provide a pretreatment method for the phosphoric acid-containing extractant solution before entering the oxime extraction system, which is easy to operate, low cost, short process flow and simple equipment to replace the existing Some solution degreasing process.

As mentioned in the background art, in the prior art, when the copper in the phosphoric acid-containing extractant solution is recovered, the presence of the phosphoric acid extractant will affect the normal production of the copper extraction process and the copper quality of the product. The removal method of phosphoric acid extractant has the problem of high investment or operating cost. In order to improve this situation, the applicant summarized and analyzed the existing method of removing phosphoric acid extractant, and found the treatment idea of the existing method Both are carried out for all the oil phases in the solution, whether it is the extractant or the solvent oil that dissolves the extractant, are removed at the same time, so the input cost is high. However, it is only the phosphoric acid extractant in the oil phase that actually affects copper recovery. Therefore, the inventor realized that, according to the principle of similar compatibility, by increasing the content of solvent oil in the solution containing phosphoric acid extractant, the phosphoric acid extractant It is more soluble in the oil phase, thereby reducing its content in the water phase. When it is reduced to the extent that it does not affect the oxime extraction process, the copper recovery process can be carried out normally without affecting the copper recovery quality. And such a processing idea has been verified by experiments, not only the processing cost is greatly reduced, but also the processing process is simple and convenient, and has industrial application value.

Therefore, on the basis of the above-mentioned ideas, the applicant proposed the scheme of this application. In a typical implementation of the present application, a method for recovering copper in a solution containing a phosphoric acid extractant is provided. The method includes: mixing a phosphoric acid extractant solution with a solvent oil to obtain an oil-water mixture; The mixture is separated from oil and water to obtain a water phase and an oil phase; the water phase is subjected to oxime extraction to obtain metallic copper.

In the above-mentioned method of this application, the phosphoric acid extractant solution is mixed with mineral spirits, and then oil-water separation is used to reduce the content of the phosphoric acid extractant in the aqueous solution, and then the oxime extraction process can not only make the oxime The extraction process runs normally, and the organic phase can be recycled and the quality of the product copper can be improved. The method replaces existing operations such as air flotation, ultrasound, resin, fiber coalescence, and activated carbon adsorption by simple mixing and oil-water separation, simplifies operation, equipment and process flow, and saves investment and operating costs.

In the above step of oxime extraction of the aqueous phase, the copper ion and the extractant for extracting copper (such as M5640 or LIX984, during extraction, the metal chelate with copper ion is dissolved in the organic solvent, so that the copper is extracted, and Hydrogen ions precipitated) combine to form metal organic compounds. The extractant is usually prepared by dissolving in an organic solvent. The specific extraction uses a countercurrent extraction process commonly used in the industry, that is, the water phase and the organic phase flow in opposite directions, and the extraction efficiency is ensured by setting an appropriate number of extraction stages. In order to further improve the purity of the recovered metal copper, the impurity metal ions with the subsequent extraction sequence are usually washed into the water phase to improve the purity of copper.

In the above recovery method, the specific type of the phosphoric acid extractant in the phosphoric acid extractant solution is various existing phosphoric acid extractants, which can be 204, P507 and/or C272. The specific type and amount of mineral spirits may vary slightly according to the amount of phosphoric acid extractant in the phosphoric acid extractant solution. In a preferred embodiment, the phosphoric acid-containing extractant solution and the solvent oil are mixed in a volume ratio of 20-100:1. In another preferred embodiment, the phosphoric acid extractant in the phosphoric acid extractant solution is P204, P507 and/or C272. In some preferred embodiments, the mineral spirit is the same as the extractant used in the oxime extraction step; more preferably, the mineral spirit is sulfonated kerosene, 260# solvent oil or Escaid 110.

Mixing according to the volume ratio of 20-100:1 can dissolve the phosphoric acid extractant in the solution into the solvent oil phase as much as possible, thereby reducing the content of the phosphoric acid extractant in the water phase to not affect the subsequent value The extraction and recovery of metals by oxime not only reduces the degradation of the extractant during the oxime extraction process caused by the accumulation of phosphoric acid extractant content, but also reduces the possibility of extracting other impurity metals at the same time, thus ensuring the normality of the copper extraction system. Operation and product copper quality.

In the above preferred embodiment, selecting the same solvent oil as the oxime extraction process and the phosphoric acid extraction process is equivalent to pretreating the phosphoric acid extractant before the oxime extraction of the valuable metals, so as to remove the phosphoric acid The extractant is separated from the solution, thereby reducing the adverse effect of the phosphoric acid extractant on the subsequent oxime extraction.

In the above recovery method, the oil-water separation step of the oil-water mixture can be carried out in any manner, which can be selected according to actual application scenarios. In this application, the oil-water separation step is carried out by mixing and standing still. The specific standing equipment used includes but is not limited to being carried out in an extraction tank, a mixing tank or a clarification tank.

In the above recovery method, there is no special requirement for the mixing time of the phosphoric acid-containing extractant solution and the solvent oil, as long as the mixing is uniform to achieve the maximum oil-water separation. In a preferred embodiment of the present application, the time for mixing the phosphoric acid-containing extractant solution with the solvent oil is 1-10 min.

In the above oil-water separation step, the specific separation rate can also be reasonably controlled according to actual conditions. In this application, the oil-water separation rate is preferably 1.5-5m ³ /h/m ² , and the oil-water separation rate is controlled within this range, which has the advantages of economical oil-water separation operation, good separation effect, and less residual oil.

The recovery method of this application is applicable to any solution containing phosphoric acid extractant. For the content of phosphoric acid extractant, when the content of phosphoric acid extractant is high, the ratio of mixed oil and water can be increased. From the viewpoint of industrial production efficiency, it is preferable that the total content of the phosphoric acid extractant in the phosphoric acid extractant solution is 5 to 80 ppm.

The lower the oil content in the water phase obtained in the above oil-water separation step, the better, and the higher the content of the phosphoric acid extractant in the oil phase, the better. Of course, the content of the phosphoric acid extractant in the oil phase also varies with the content of the phosphoric acid extractant in the solution. In this application, the volume concentration of the phosphoric acid extractant in the oil phase is preferably 0.5% to 1.5%, and the content of the phosphoric acid extractant in the water phase is preferably less than 1 ppm. When the content of the phosphoric acid extractant in the water phase is controlled below 1 ppm, the normal operation of the copper extraction system and the quality of the product copper can be guaranteed. The higher the content of the phosphoric acid extractant in the oil phase, the more beneficial the recycling of the extractant.

The following will further illustrate the beneficial effects of the present application in conjunction with specific embodiments.

Example 1:

Mix the solution containing P204～5ppm, 260#solvent oil～45ppm and 260#solvent oil at a ratio of 100:1 in the extraction box for 2min, the clarification rate is 4m ³ /h/m ² , the solution after clarification contains 0.5ppm P204 extractant , The solution is sent to the oxime extraction system to recover the copper in the solution, the solvent oil part is returned to the extraction tank of this level, and the part is open to the organic preparation of the phosphoric acid extraction process.

Example 2:

Mix the solution containing P507～25ppm, 260#solvent oil～75ppm and 260#solvent oil at a ratio of 50:1 in the mixing tank for 3min, clarify in the clarification tank with a clarification rate of 4m ³ /h/m ² , after clarification The solution contains 0.7 ppm of P507 extractant. The solution is sent to the oxime extraction system to recover the copper in the solution. The solvent oil is partly returned to the treatment process, and partly opened to the organic preparation of the phosphoric acid extraction process.

Example 3:

Mix the solution containing P204～38ppm, sulfonated kerosene～112ppm and sulfonated kerosene in the extraction tank at a ratio of 20:1 for 2min, and the clarification rate is 3m ³ /h/m ^2. After clarification, the solution contains 0.9 ppm of P204 extractant. The oxime extraction system is sent to recover the copper in the solution, and the sulfonated kerosene is partly returned to the extraction tank of this level, and partly opened to the organic preparation of the phosphoric acid extraction process.

Example 4:

Mix the solution containing P204～72ppm and Escaid 110～108ppm with Escaid 110 in the extraction box at a ratio of 50:1 for 3 minutes, with a clarification rate of 4.5m ³ /h/m ^2. After clarification, the solution contains 0.9 ppm of P204 extractant. The oxime extraction system recovers the copper in the solution, and the Escaid 110 partly returns to the extraction tank of this level, and partly opens to the organic preparation of the phosphoric acid extraction process.

Example 5:

Mix the solution containing P204～20ppm, 260#solvent oil～80ppm and 260#solvent oil at a ratio of 50:1 in the extraction box for 1min, the clarification rate is 2m ³ /h/m ² , and the clarified solution contains 0.8ppm P204 extractant , The solution is sent to the oxime extraction system to recover the copper in the solution. The 260# solvent oil is partly returned to the extraction tank of this level, and partly opened to the organic preparation of the phosphoric acid extraction process.

Example 6:

Mix the solution containing C272-9ppm, 260#solvent oil～80ppm and 260#solvent oil at a ratio of 30:1 in the extraction box for 10min, the clarification rate is 5m ³ /h/m ² , the clarified solution contains 0.7ppm C272 extractant , The solution is sent to the oxime extraction system to recover the copper in the solution. The 260# solvent oil is partly returned to the extraction tank of this level, and partly opened to the organic preparation of the phosphoric acid extraction process.

Example 7:

Mix the solution containing P204～92ppm, 260#solvent oil～108ppm and 260#solvent oil at a ratio of 215:1 in the extraction box for 13min, the clarification rate is 5.5m ³ /h/m ² , the clarified solution contains P204 extractant 0.9 ppm, the solution is sent to the oxime extraction system to recover the copper in the solution, and the 260# solvent oil is partly returned to the extraction tank of this level, and partly opened to the organic preparation of the phosphoric acid extraction process.

Comparative example 1

The solution containing P204～38ppm and sulfonated kerosene～112ppm adopts the existing clarification + air flotation + resin degreasing method. The degreasing solution contains P204 extractant at 0.9 ppm, and the solution is sent to the oxime extraction system to recover the solution. Part of the copper and sulfonated kerosene are returned to the extraction tank of this level, and part of the circuit is opened to the organic preparation of the phosphoric acid extraction process.

Comparative example 2

The solution containing P204～38ppm and sulfonated kerosene～112ppm adopts the existing activated carbon degreasing method. The degreasing solution contains P204 extractant at 0.5ppm. The solution is sent to an oxime extraction system to recover copper and sulfonate in the solution. Part of the chemical kerosene is returned to the extraction tank of this level, and part of it is opened to the organic preparation of the phosphoric acid extraction process.

Detection:

The molybdenum blue method was used to detect the content of the phosphoric acid extractant in the solution after the treatment of the above examples. The test results are shown in Table 1. The copper concentration in the solution was 5g/L as the basis for the extraction of phosphoric acid in each example. The cost of the agent solution treatment process is estimated, and the results are shown in Table 1.

Table 1:

It can be seen from the comparison between Comparative Example 1 and Example 3 that for the solution with the same high content of phosphoric acid extractant, the existing method and the method of this application are used for copper recovery, respectively. When the same extractant content effect is achieved, Next, the processing cost of this application is lower than 1/4 of the existing cost. Comparing Comparative Example 2 with Example 3, it can be seen that when activated carbon is used to treat the extractant with the same content, the cost required is more than 6 times the cost of the method of the present application. It can be seen that the method of the present application not only greatly reduces the cost, but also can maintain the stable operation of the copper recovery system simply, quickly and conveniently, thereby reducing the cost of the enterprise.

From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the present invention uses solvent oil and phosphoric acid-containing extractant solution for mixing and oil-water separation, effectively diluting the phosphoric acid extractant in the solution The concentration in the oxime extraction system reduces the concentration of phosphoric acid extractant in the oxime extraction system, saves investment and operating costs, and simplifies operation, equipment and process flow.

The foregoing descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc., made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

A method for recovering copper in a phosphoric acid-containing extractant solution, characterized in that the method comprises:

Mixing the phosphoric acid-containing extractant solution with solvent oil to obtain an oil-water mixture;

Performing oil-water separation on the oil-water mixture to obtain a water phase and an oil phase;

The aqueous phase is subjected to oxime extraction to obtain metallic copper.
The recovery method according to claim 1, wherein the phosphoric acid-containing extractant solution and the solvent oil are mixed in a volume ratio of 20-100:1.
The recovery method according to claim 1, wherein the phosphoric acid extractant in the phosphoric acid extractant solution is one or more of P204, P507 and C272.
The recovery method according to claim 1, wherein the solvent oil is the same as the solvent oil of the extractant used in the phosphoric acid extraction and the oxime extraction step; preferably the solvent oil is sulfonated kerosene , 260# Solvent oil or Escaid 110.
The recovery method according to claim 1, characterized in that the step of separating oil and water is carried out by standing and clarifying, preferably the step of separating oil and water is carried out in an extraction tank, a mixing tank or a clarification tank.
The recovery method according to claim 1, wherein the time for mixing the phosphoric acid-containing extractant solution with the solvent oil is 1-10 min.
The recovery method according to any one of claims 1 to 6, wherein the oil-water separation rate is 1.5-5m 3 /h/m 2 .
The recovery method according to claim 3, wherein the content of the phosphoric acid extractant in the phosphoric acid extractant solution is 5 to 80 ppm.
The recovery method according to claim 1, wherein the volume concentration of the phosphoric acid extractant in the oil phase is 0.5% to 1.5%, preferably the phosphoric acid extractant in the water phase Content <1ppm.
The recovery method according to claim 1, wherein the extractant in the oxime extraction process is M5640 or LIX984.