Deep purification and impurity removal method for nickel mixed solution

Abstract

The invention relates to a deep purification and impurity removal method for a nickel mixed solution, which comprises the following steps: adsorbing an impurity element A in the nickel mixed solution through Lewait chelate resin, and adsorbing arsenic through [WO4] 2-and / or [MoO4] 2-modified anion exchange resin to obtain an exchanged solution, the impurity element A comprises copper, iron, cobalt, lead and zinc. According to the method, the raw materials can be recycled in the whole process, the loss of nickel in the whole process is smaller than 0.5%, and the loss of tungstate is smaller than 0.2%. The content of copper in the finally obtained exchanged liquid is below 1ppm, the content of iron, cobalt, lead and zinc is below 0.3 ppm, the content of arsenic is below 0.5 ppm, and the industrial production requirements are completely met. The two serially connected stirring pools containing different anion exchange resins are used for stirring adsorption, so that the mass transfer rate is higher, the operation is simpler, and the cost is lower.

Description

Technical Field

[0001] The invention belongs to the technical field of industrial metallurgy, and relates to a method for deep purification and impurity removal of a nickel mixed solution, and specifically to a method for removing elements such as copper, iron, cobalt, lead, zinc, and arsenic from a nickel mixed solution. Background Art

[0002] In the process of nickel smelting and non-ferrous metal production, copper, iron, cobalt, lead, zinc and arsenic are the most common impurity elements, which not only affect the extraction and recycling of valuable metals, but also cause harm to product quality, the environment and society. Therefore, the removal of copper, iron, cobalt, lead, zinc, arsenic and other elements from waste acid and wastewater generated in the process of non-ferrous metal smelting and other production processes is a hot topic in current research.

[0003] At present, the common methods for removing impurities from nickel solutions at home and abroad mainly include chemical precipitation, adsorption, biological method, ion exchange, extraction, etc. Chemical precipitation methods include neutralization precipitation, sulfide precipitation and ferrite method, but this method is prone to nickel loss. The biological method is very sensitive to changes in experimental conditions and is only suitable for laboratory experiments, making it difficult to achieve industrialization. The application scope of adsorption methods is also relatively limited due to restrictions on site, cost, operability, etc. The extraction method and ion exchange method have large processing capacity, simple operation, good separation effect, and are conducive to the recycling of various valuable components. However, the dissolution of the extractant in the solution is likely to cause certain harm to the product quality. According to specific needs, some companies are more optimistic about the ion exchange method.

[0004] For example, in the prior art, a fixed bed ion exchange adsorption reactor is used to load an alkaline anion exchange resin to treat arsenic-containing wastewater. The form and removal effect of arsenic are experimentally studied, and it is found that the resin has good adsorption of As(III) anions, but poor adsorption of As(V) anions. Multi-stage adsorption is required to achieve the effect. If As(V) is reduced to As(III), the industrial production environment will be deteriorated, because As(III) in the solution is easy to volatilize and arsine is highly toxic. There is an ion exchange fiber (IEF) to remove As(V), but the adsorption process is a molecular diffusion process. Although this method can reduce the concentration of As in the solution to a very low level, the adsorption process is slow, takes a long time, and is difficult to apply industrially. There is a scheme of using a selective chelating resin containing a thiol group to selectively adsorb As(III) ions, but this scheme is for the removal of As in wastewater and can only be used to treat wastewater with a low metal concentration, because it uses a thiol chelating resin. If the metal ion concentration in the solution is slightly higher, it will cause resin poisoning or loss of the main metal. For example, nickel ions can easily combine with sulfur on the integrated resin, leading to resin poisoning and loss of the main metal nickel.

[0005] Patent document CN106966445B discloses a method for removing arsenic from an arsenic-containing nickel sulfate solution. The method obtains an arsenic tungstate heteropoly acid solution by adding tungstate to the nickel sulfate solution, and then flows into an exchange column equipped with a large-pore anion resin for adsorption to achieve the purpose of arsenic removal. However, this method is easily affected by other metal impurities in the nickel sulfate solution. The tungstate added to the solution will also react with iron, cobalt, lead, zinc and other ions, affecting the coordination process and thus resulting in a reduction in the arsenic removal rate. The adsorption reaction takes a long time, and adsorption through an ion exchange column will prevent the process from being fully carried out, making it difficult to achieve the purpose of deep arsenic removal. Patent document CN107090546A discloses a method for removing arsenic from nickel sulfate. The method prepares [WO 4 ] 2- Type or [MoO 4 ] 2- type anion exchange resin, through the functional groups on the resin ([WO 4 ] 2- or [MoO 4 ] 2- ) to react with arsenic (pentavalent) in the solution to generate heteropolyacid, thereby adsorbing and removing arsenic. However, this method is only applicable to the adsorption of arsenic in nickel sulfate solution, and does not take into account the difficulty in removing other metal impurities in the solution. In addition, the large-pore resin solution cannot effectively adsorb these metal ions. Summary of the invention

[0006] In view of the deficiencies of the prior art, the object of the present invention is to provide a method for deep purification and impurity removal of a nickel mixed solution. For an industrial nickel mixed solution containing multiple impurity elements such as copper, iron, cobalt, lead, zinc, arsenic, etc., a method for deep purification and impurity removal of a nickel mixed solution suitable for industrialization is provided, which has low cost, simple operation, environmental safety, small nickel loss, and does not introduce impurity ions.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] The present invention discloses a method for deep purification and impurity removal of a nickel mixed solution. The nickel mixed solution is firstly subjected to Lewatit chelate resin to adsorb the impurity element A, and then subjected to [WO 4 ] 2- and / or [MoO 4 ] 2- Modified anion exchange resin, preferably [WO 4 ] 2- The modified anion exchange resin adsorbs arsenic to obtain the exchange liquid.

[0009] The impurity elements A include copper, iron, cobalt, lead and zinc.

[0010] The invention provides a method for deep purification and impurity removal of a nickel mixed solution. The method comprises the following steps: firstly passing the nickel mixed solution through a Lewatit chelating resin to adsorb copper, iron, cobalt, lead and zinc in the nickel mixed solution to remove these impurity metal elements; and then passing the adsorbed solution through a [WO 4 ] 2- and / or [MoO 4 ] 2- Modified anionic resin, in which the [WO 4 ] 2- Functional groups or [MoO 4 ] 2- The functional groups will form large-sized heteropolyacids with the arsenic-containing groups in the solution and be adsorbed by the anion resin, thereby achieving the purpose of arsenic removal.

[0011] The inventors found through research that the nickel mixed solution produced in the metallurgical industry is mostly Cl - / [SO 4 ] 2- The invention discloses an acidic solution of the system, in which impurity elements such as copper, iron, cobalt, lead, zinc and the like are present in the form of anions, and arsenic is present in the form of arsenate. Therefore, the invention firstly passes the nickel mixed solution through Lewatit chelating resin to adsorb the anions containing copper, iron, cobalt, lead and zinc in the nickel mixed solution. In the process, most of the impurity metal elements in the nickel mixed solution are removed, and the influence of the elements on the subsequent heteropoly acid coordination process is avoided while purifying and removing impurities, and the adsorption efficiency of arsenic is also improved.

[0012] However, since there are many kinds of impurity elements in the nickel mixed solution, it is not easy to adsorb copper, iron, cobalt, lead and zinc at the same time. The inventors tried a large number of ion exchange resins and found that only Lewatit chelate resin can adsorb copper, iron, cobalt, lead and zinc at the same time and achieve excellent adsorption effect. At the same time, the adsorption conditions (pH, temperature) of Lewatit chelate resin are similar to [WO 4 ] 2- / [MoO 4 ] 2- The modified anion resin is the same, and the nickel mixed solution can be sequentially passed through Lewatit chelating resin, [WO 4 ] 2- / [MoO 4 ] 2- Modified anion exchange resins make the process more continuous and simpler.

[0013] In a preferred embodiment, the nickel mixed solution contains copper, iron, cobalt, lead, zinc and arsenic, and the arsenic is trivalent arsenic or pentavalent arsenic.

[0014] In the actual operation process, if trivalent arsenic is contained, an oxidant is first added to oxidize the trivalent arsenic into pentavalent arsenic. The oxidant is hydrogen peroxide or ozone.

[0015] Preferably, the nickel mixed solution is Cl - and / or [SO 4 ] 2- system.

[0016] In a preferred embodiment, when the nickel mixed solution contains trivalent arsenic, an oxidant is first used to oxidize the trivalent arsenic into pentavalent arsenic.

[0017] More preferably, the oxidant is hydrogen peroxide.

[0018] In a preferred embodiment, the nickel mixed solution is first adjusted to a pH of ≤ 2, preferably 1 to 2, using dilute sulfuric acid or sodium hydroxide solution.

[0019] In a preferred embodiment, the temperature of the nickel mixed solution is 25-60°C.

[0020] A preferred embodiment, the [WO 4 ] 2- or [MoO 4 ] 2- The process of obtaining modified anion exchange resin is as follows: first, Cl - The anion exchange resin is passed through a sodium hydroxide solution to form OH - Type resin, then OH - The resin is passed through a tungstate or molybdate solution, and then the WO remaining on the resin surface is washed off with distilled water. 4 2- or MoO 4 2- You can get it.

[0021] Further preferably, the Cl - The anion exchange resin is one of the models D201, D301 and D314, preferably D301 anion resin.

[0022] A preferred solution is to add the nickel mixed solution to a stirred tank A containing Lewatit chelate resin, and stir for 1-4 hours, preferably 2-3 hours, at a stirring speed of 300-600 rpm, preferably 350-450 rpm, to allow the Lewatit chelate resin to adsorb the impurity element A, and then add the adsorbed solution to a stirred tank A containing [WO 4 ] 2- and / or [MoO 4 ] 2- Type, preferably [WO 4 ] 2-The modified anion exchange resin is placed in a stirring tank B and stirred at a stirring speed of 300-600 rpm for 4-8 hours, preferably 5-7 hours, to adsorb arsenic to obtain an exchange liquid.

[0023] The inventors found that compared with Lewatit chelating resin, [WO 4 ] 2- and / or [MoO 4 ] 2- The anion exchange resin is placed in the ion exchange column and adsorbed under stirring. The adsorption effect is high. The use of a stirrer can enhance the mass transfer between the resin and the solution and accelerate the diffusion rate of the particles, which improves the adsorption efficiency of the impurity elements and saves adsorption time. However, the stirring speed is a key factor of the equipment. If the stirring speed is too slow, the mass transfer will be too slow, thereby affecting the adsorption efficiency. If the stirring speed is too fast, it will easily cause the solution to splash and cause physical damage to the resin. And the use of two large stirring tanks in series makes it easier to achieve continuous operation and large-scale industrial production.

[0024] The preferred solution is to combine the adsorbed Lewatit chelating resin with [WO 4 ] 2- The anion exchange resin is first washed with acid and water until it is neutral, then desorbed with an alkaline solution, and then the resin is washed with water until it is neutral to complete the regeneration of the resin.

[0025] In actual operation, acid washing, water washing and alkaline solution desorption are also carried out in a stirring tank under stirring, which can achieve better regeneration effect.

[0026] Further preferably, the acid is dilute sulfuric acid or dilute hydrochloric acid, and the concentration is 0.1-1 mol / L, preferably 0.5 mol / L. After the adsorbed resin is pickled, the nickel enters the pickling solution.

[0027] Further preferably, the alkaline solution is a sodium hydroxide solution, and the concentration of sodium hydroxide in the sodium hydroxide solution is 0.1-2 mol / L, preferably 1 mol / L. After the alkaline washing, the metal elements enter the desorption solution.

[0028] Preferably, the water washing is distilled water washing. The resin can be mixed evenly by water washing.

[0029] In a preferred embodiment, in the exchanged liquid, the copper content is below 1 ppm, the iron, cobalt, lead and zinc contents are below 0.3 ppm, and the arsenic content is below 0.5 ppm, which fully meets the requirements of industrial production.

[0030] Principles and advantages of the present invention:

[0031] At present, the impurity removal of nickel solution is generally carried out in steps. Copper removal, simultaneous iron and cobalt removal and arsenic removal are carried out in three different stages, and the impurity removal efficiency is low. The inventors found through research that most of the nickel mixed solution produced in the metallurgical industry is Cl - / [SO 4 ] 2- system, in which copper, iron, cobalt, lead, zinc and other impurity elements exist in the form of anions, and arsenic exists in the form of arsenate or arsenic acid molecules. Under this condition, Lewatit chelating resin can be used to adsorb and remove copper, iron, cobalt, lead, zinc and other impurities in the nickel mixed solution, and then [WO 4 ] 2- and / or [MoO 4 ] 2- The modified anion resin adsorbs and removes arsenic from the solution. The adsorption efficiency of Lewatit chelating resin is not affected by the presence of a large amount of Ni in the solution. 2+ The influence of arsenic on the nickel sulfate solution can be reduced, and the loss of nickel can be minimized during the impurity removal and purification process. Although there is a process for removing arsenic from nickel sulfate solution using modified anion exchange resin in the existing literature (Patent Publication No.: CN107090546A), this method can only be used for the adsorption of arsenic in nickel sulfate solution, without considering the removal of other impurity elements in the solution. To obtain high-quality nickel sulfate solution, other impurity ions in the solution must also be considered, and the process is relatively laborious and complicated.

[0032] In view of this situation, the present invention uses two different anion exchange resin columns to adsorb copper, iron, cobalt, lead, zinc and arsenic in the nickel mixed solution. The nickel mixed solution is passed through the first stirring tank filled with Lewatit chelating resin to adsorb copper, iron, cobalt, lead and zinc in the nickel mixed solution to remove these impurity metal elements; then the nickel mixed solution after the first adsorption is passed through the second stirring tank filled with [WO 4 ] 2- The stirred cell of modified macroporous anion resin, in which the [WO 4 ] 2- The functional groups will form large-sized arsenic tungsten heteropolyacids with the arsenic-containing groups in the solution and be adsorbed by the large-pore anion resin to achieve the purpose of arsenic removal. In this process, the first stage of adsorption removes most of the impurity metal elements in the nickel mixed solution, and while purifying and removing impurities, it also avoids the influence of these elements on the subsequent arsenic tungsten coordination process, and also improves the adsorption efficiency of arsenic. After adsorption and impurity removal, the resin is first washed with acid to remove the nickel adsorbed on the surface, then washed with distilled water to neutrality, and then desorbed with low-concentration sodium hydroxide, and then washed with distilled water to neutrality. The resin can be regenerated and recycled, and the desorption liquid removes the adsorbed impurity element arsenic by precipitation.

[0033] In actual operation, Lewatit chelating resin, [WO 4 ] 2- The modified anion exchange resins are respectively loaded into two stirring tanks and connected to a microcomputer system, which can realize real-time monitoring of the stirring speed, pH and element concentration in the solution.

[0034] The present invention can deeply remove impurities such as copper, iron, cobalt, lead, zinc, arsenic, etc. in a nickel mixed solution. After being processed by the scheme of the present invention, the content of copper in the nickel mixed solution is below 1ppm, the content of iron, cobalt, lead, and zinc is below 0.3ppm, and the content of arsenic is below 0.5ppm, which fully meets the requirements of industrial production, and no impurities are introduced during the entire treatment process, and no harm is caused to the environment. In addition, the outstanding technical effect of the present invention is also reflected in that the impurity elements in the nickel mixed solution can be deeply removed at one time, and the liquid after impurity removal does not need to be purified twice. The loss rate of nickel in the impurity removal process is small (<0.5%), and the resin after impurity removal can be reused. The present invention is suitable for large-scale industrial applications and has the advantages of being simple and efficient, low cost, and recyclable raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 Schematic diagram of the equipment for deep purification and impurity removal of nickel mixed solution in the present invention. DETAILED DESCRIPTION

[0036] To explain the technical content, objectives and effects of the present invention in detail, the following is a detailed description in conjunction with the implementation modes, but the present invention is not limited to the following embodiments.

[0037] In the present invention, the WO used in all the embodiments and comparative examples is 4 2 Type resin or MoO 4 2- The type resins are obtained by the following method: D201 or D301 anion resin is passed through a 2 mol / L sodium hydroxide solution to obtain OH - Type resin, then OH - The resin was passed through a 0.5 mol / L tungstate solution or molybdate solution, and then the residual WO on the surface of the resin was washed off with distilled water. 4 2- or MoO 4 2- , that is, to obtain the transformed WO 4 2 Type resin or MoO 4 2- Type resin.

[0038] The WO used in all the examples and comparative examples 42- The type resins are obtained by the following method: D201, D301 or D314 anion resin is passed through a 2 mol / L sodium hydroxide solution to obtain OH - Type resin, then OH - The resin was passed through a 0.5 mol / L tungstate solution, and then the WO remaining on the resin surface was washed with distilled water. 4 2- , that is, to obtain the transformed WO 4 2- Type resin.

[0039] Example 1

[0040] Prepare a nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); use dilute sulfuric acid to adjust the solution pH to 1, add the nickel mixed solution (25° C.) into a stirring tank A containing Lewatit VPOC 1026 chelate, stir at a stirring speed of 400 rpm for 2 hours, so that the Lewatit chelate resin adsorbs the impurity element A, and then add the adsorbed solution containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0041] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.82, 0.24, 0.29, 0.22 and 0.27 mg / L respectively, the concentration of arsenic was 0.29 mg / L, the loss rate of tungsten was 0.11%, and the loss rate of nickel was 0.3%.

[0042] Example 2

[0043] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) was prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid were AR grade, and distilled water was used); the pH value of the solution was adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) was added to a stirring tank A containing Lewatit chelating resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelating resin to adsorb the impurity element A, and the adsorbed solution was then added to a stirring tank containing [MoO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0044] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.94, 0.22, 0.29, 0.28 and 0.25 mg / L respectively, the concentration of arsenic was 5.97 mg / L, the loss rate of tungsten was 0.12%, and the loss rate of nickel was 0.5%.

[0045] Example 3

[0046] A nickel sulfate solution containing 100 g / L nickel, 70 g / L chlorine, 1 g / L copper, iron, cobalt, lead, zinc, and 150 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2-The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0047] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the water were 0.88, 0.27, 0.28, 0.26 and 0.27 mg / L respectively, the concentration of arsenic was 0.31 mg / L, the loss rate of tungsten was 0.07%, and the loss rate of nickel was 0.4%.

[0048] Example 4

[0049] A nickel sulfate solution containing 20 g / L nickel, 70 g / L chlorine, 200 mg / L copper, iron, cobalt, lead, zinc, and 50 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0050] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.77, 0.21, 0.23, 0.25 and 0.21 mg / L respectively, the concentration of arsenic was 0.28 mg / L, the loss rate of tungsten was 0.13%, and the loss rate of nickel was 0.4%.

[0051] Example 5

[0052] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (60° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0053] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.57, 0.15, 0.19, 0.17 and 0.2 mg / L respectively, the concentration of arsenic was 0.17 mg / L, the loss rate of tungsten was 0.15%, and the loss rate of nickel was 0.5%.

[0054] Example 6

[0055] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2-The modified D201 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0056] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.85, 0.24, 0.29, 0.24 and 0.23 mg / L respectively, the concentration of arsenic was 19.4 mg / L, the loss rate of tungsten was 0.17%, and the loss rate of nickel was 0.4%.

[0057] Example 7

[0058] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D314 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then eluted with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0059] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.91, 0.27, 0.22, 0.21 and 0.26 mg / L respectively, the concentration of arsenic was 24.8 mg / L, the loss rate of tungsten was 0.09%, and the loss rate of nickel was 0.4%.

[0060] Example 8

[0061] Take industrial nickel mixed solution ([SO 4 ]2- , Cl - The concentrations of the system, nickel, copper, iron, cobalt, lead, zinc, and arsenic [As(III)+As(V)] are 62 g / L, 517.5 mg / L, 697.4 g / L, 409.3 mg / L, 227.3 mg / L, 355 mg / L, and 55.7 mg / L, respectively. An appropriate amount of hydrogen peroxide is added to oxidize the solution, and the pH value of the solution is adjusted to 1 with dilute sulfuric acid. The nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A. The adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0062] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.79, 0.25, 0.28, 0.27 and 0.24 mg / L respectively, the concentration of arsenic was 0.28 mg / L, the loss rate of tungsten was 0.13%, and the loss rate of nickel was 0.4%.

[0063] Comparative Example 1

[0064] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 4 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2-The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0065] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.57, 0.2, 0.18, 0.21 and 0.23 mg / L respectively, the concentration of arsenic was 41.9 mg / L, the loss rate of tungsten was 0.12%, and the loss rate of nickel was 0.8%.

[0066] Comparative Example 2

[0067] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) was prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid were AR grade, and distilled water was used); the pH value of the solution was adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) was added to a stirring tank A containing D301 anion exchange resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the D301 anion exchange resin to adsorb the impurity element A, and the adsorbed solution was then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0068] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 53.4, 68.3, 57.8, 75.9 and 81.7 mg / L respectively, the concentration of arsenic was 0.27 mg / L, the loss rate of tungsten was 0.15%, and the loss rate of nickel was 0.3%.

[0069] Comparative Example 3

[0070] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (III) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 400 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 400 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0071] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 0.89, 0.25, 0.27, 24 and 0.26 mg / L respectively, the concentration of arsenic was 92.4 mg / L, the loss rate of tungsten was 0.12%, and the loss rate of nickel was 0.5%.

[0072] Comparative Example 4

[0073] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) was prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid were AR grade, and distilled water was used); the pH value of the solution was adjusted to 1 with dilute sulfuric acid, and the nickel mixed solution (25° C.) was passed through Lewatit chelating resin and [WO 4 ] 2- The ion exchange column of modified D301 anion exchange resin was used to obtain the adsorbed liquid, and the copper, iron, cobalt, lead, zinc and arsenic in the ion exchange liquid were detected. The exchanged resin was then eluted with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc and arsenic separate from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc and arsenic in the desorption liquid were detected.

[0074] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 9.4, 6.7, 6.1, 5.2 and 3.9 mg / L respectively, the concentration of arsenic was 19.7 mg / L, the loss rate of tungsten was 0.17%, and the loss rate of nickel was 0.4%.

[0075] Comparative Example 5

[0076] A nickel sulfate solution containing 60 g / L nickel, 70 g / L chlorine, 500 mg / L copper, iron, cobalt, lead, zinc, and 100 mg / L arsenic (V) is prepared (nickel sulfate, copper sulfate, iron sulfate, cobalt sulfate, lead sulfate, zinc sulfate, and arsenic acid are AR grade, and distilled water is used); the pH value of the solution is adjusted to 1 using dilute sulfuric acid, and the nickel mixed solution (25° C.) is added to a stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 200 rpm for 2 hours to allow the Lewatit chelate resin to adsorb the impurity element A, and the adsorbed solution is then added to a stirring tank containing [WO 4 ] 2- The modified D301 anion exchange resin was stirred in stirring tank B at a stirring speed of 200 rpm for 6 hours to adsorb arsenic to obtain an exchange liquid, and copper, iron, cobalt, lead, zinc, and arsenic in the ion exchange liquid were detected. The exchanged resin was then rinsed with 0.5 mol / L dilute sulfuric acid to wash away the nickel remaining on the resin surface, and then the resin was washed with distilled water to neutrality, and then the washed resin was desorbed with 0.5 mol / L sodium hydroxide solution to make copper, iron, cobalt, lead, zinc, and arsenic detach from the resin and enter the desorption liquid, and the copper, iron, cobalt, lead, zinc, and arsenic in the desorption liquid were detected.

[0077] After the exchange, the concentrations of copper, iron, cobalt, lead and zinc in the liquid were 15.7, 21.5, 27.1, 24.9 and 28.6 mg / L respectively, the concentration of arsenic was 7.94 mg / L, the loss rate of tungsten was 0.16%, and the loss rate of nickel was 0.4%.

Claims

1. A method for deep purification and impurity removal of a nickel mixed solution, characterized in that: The nickel mixed solution is first passed through Lewatit chelating resin to adsorb the impurity element A, and then passed through [WO4] 2- and / or [MoO4] 2- The modified anion exchange resin adsorbs arsenic to obtain the exchange liquid; The impurity elements A include copper, iron, cobalt, lead and zinc.

2. A method for deep purification and impurity removal of a nickel mixed solution according to claim 1, characterized in that: The nickel mixed solution contains copper, iron, cobalt, lead, zinc and arsenic, and the arsenic is trivalent or pentavalent arsenic. The nickel mixed solution is Cl - and / or [SO4] 2- system.

3. A method for deep purification and impurity removal of a nickel mixed solution according to claim 2, characterized in that: When the nickel mixed solution contains trivalent arsenic, an oxidant is first used to oxidize the trivalent arsenic into pentavalent arsenic.

4. A method for deep purification and impurity removal of a nickel mixed solution according to claim 1, characterized in that: First, adjust the nickel mixed solution to pH ≤ 2 with dilute sulfuric acid or sodium hydroxide; The temperature of the nickel mixed solution is 10-80°C.

5. The method for deep purification and impurity removal of a nickel mixed solution according to claim 1, characterized in that: Said [WO4] 2- or [MoO4] 2- The process of obtaining modified anion exchange resin is as follows: first, Cl - The anion exchange resin is passed through a sodium hydroxide solution to form OH - Type resin, then OH - The resin is passed through a tungstate or molybdate solution, and then the WO4 remaining on the resin surface is washed off with distilled water. 2- or MoO4 2- You can get it.

6. A method for deep purification and impurity removal of a nickel mixed solution according to claim 5, characterized in that: The Cl - The anion exchange resin is one of the models D201, D301 and D314.

7. A method for deep purification and impurity removal of a nickel mixed solution according to any one of claims 1 to 6, characterized in that: The nickel mixed solution is added to the stirring tank A containing Lewatit chelate resin, and stirred at a stirring speed of 300-600rpm for 1-4h to allow the Lewatit chelate resin to adsorb the impurity element A. The adsorbed liquid is then added to the stirring tank A containing [WO4] 2- and / or [MoO4] 2- The modified anion exchange resin is stirred in stirring tank B at a stirring speed of 300-600 rpm for 4-8 hours to adsorb arsenic to obtain an exchange liquid.

8. The method for deep purification and impurity removal of a nickel mixed solution according to claim 1, characterized in that: The adsorbed Lewatit chelating resin was mixed with [WO4] 2- or [MoO4] 2- The modified anion exchange resin is firstly acid-washed, washed with water until neutral, and then desorbed with an alkaline solution. The resin is then washed with water until neutral to complete the regeneration of the resin.

9. The method for deep purification and impurity removal of a nickel mixed solution according to claim 8, characterized in that: The acid is dilute sulfuric acid or dilute hydrochloric acid, with a concentration of 0.1 to 1 mol / L. The alkaline solution is a sodium hydroxide solution, and the concentration of sodium hydroxide in the sodium hydroxide solution is 0.1-2 mol / L. The water washing is distilled water washing.

10. The method for deep purification and impurity removal of a nickel mixed solution according to claim 1, characterized in that: In the exchanged liquid, the copper content is ≤1ppm, the iron, cobalt, lead and zinc content is ≤0.3ppm, and the arsenic content is ≤0.5ppm.

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