Processing method of laterite nickel ore

Abstract

The present invention provides a method for treating laterite nickel ore. The method comprises step S1, wherein the laterite nickel ore is subjected to acid leaching, neutralization and iron and aluminum removal treatments in sequence to obtain a pretreated pulp; step S2, wherein the pretreated pulp is subjected to adsorption treatment using IDA resin to obtain a lean pulp and an adsorbed resin; step S3, wherein the adsorbed resin is washed using a nickel-containing solution to obtain a washed resin and a washed liquid; step S4, wherein the washed resin is subjected to desorption treatment using a strong acid solution to obtain a nickel-cobalt solution and a desorbed resin; step S5, wherein the washed liquid is subjected to nickel-cobalt precipitation, manganese precipitation and concentration in sequence to obtain a magnesium-containing resin regeneration liquid; and step S6, wherein the desorbed resin is subjected to transformation and regeneration using the magnesium-containing resin regeneration liquid to obtain a regenerated resin. The present application greatly reduces the amount of purchased process raw materials, thereby saving costs and reducing the amount of final waste liquid.

Description

Technical Field

[0001] The present invention relates to the field of resin regeneration, and in particular to a method for processing laterite nickel ore. Background Art

[0002] The resin adsorption method can be used to recover nickel and cobalt ions from multi-component sulfate liquid phases or solid-containing slurries. A more economical approach is to use mature commercial IDA chelating resins, column or stirred mixing to selectively adsorb nickel and cobalt, followed by acid desorption, and then lime milk transformation to improve performance and ensure the adsorption of nickel and cobalt during re-adsorption. The above treatment process can avoid the problems of large footprint and high investment in solid-liquid separation equipment in traditional chemical precipitation processes. However, in actual applications, existing technologies only consider the recycling of resins, without considering the utilization and cost of other chemical raw materials. Moreover, directly reusing the resin after acid desorption may result in lower resin adsorption performance. Although the adsorption performance can be improved after regeneration with sodium hydroxide solution, sodium hydroxide cannot be recycled, which will greatly increase the cost of purchased raw materials for the process. Summary of the Invention

[0003] The main purpose of the present invention is to provide a method for treating laterite nickel ore to solve the problem in the prior art that the transformation and regeneration of IDA resin after acid desorption requires the purchase of raw materials, resulting in high costs.

[0004] To achieve the above-mentioned object, according to one aspect of the present invention, a method for treating laterite nickel ore is provided, which comprises: step S1, sequentially subjecting the laterite nickel ore to acid leaching and neutralization and iron and aluminum removal treatment to obtain a pretreated slurry; step S2, subjecting the pretreated slurry to adsorption treatment with IDA resin to obtain a lean slurry and an adsorbed resin; step S3, washing the adsorbed resin with a nickel-containing solution to obtain a washed resin and a washed liquid; step S4, desorbing the washed resin with a strong acid solution to obtain a nickel-cobalt solution and a desorbed resin; step S5, sequentially subjecting the washed liquid to nickel-cobalt precipitation, manganese precipitation, and concentration to obtain a magnesium-containing resin regeneration liquid; and step S6, subjecting the desorbed resin to transformation regeneration with the magnesium-containing resin regeneration liquid to obtain a regenerated resin; wherein the pH value of the magnesium-containing resin regeneration liquid is ≥9, and the concentration of magnesium ions in the magnesium-containing resin regeneration liquid is ≥10 g / L.

[0005] Furthermore, the volume ratio of the nickel-containing solution to the adsorbed resin is 2-10:1, the nickel ion concentration of the nickel-containing solution is preferably 3-5 g / L, and the pH value of the nickel-containing solution is preferably 3-4.

[0006] Furthermore, the above-mentioned treatment method also includes: adjusting the pH value and nickel ion concentration of a portion of the nickel-cobalt solution, and returning it to step S3 as a nickel-containing solution to wash the adsorbed resin; precipitating the remaining nickel-cobalt solution with an alkaline reagent to obtain a nickel-cobalt precipitation intermediate; preferably, the partial nickel-cobalt solution accounts for 10 to 30% of the total nickel-cobalt solution; preferably, the pH value of the partial nickel-cobalt solution is adjusted to 3 to 3.7, and the nickel ion concentration of the partial nickel-cobalt solution is preferably 3 to 5 g / L, and the alkaline reagent is preferably sodium hydroxide and / or potassium hydroxide.

[0007] Furthermore, the above treatment method further comprises: returning the regenerated resin to the adsorption treatment step as new IDA resin to perform adsorption treatment on the pretreated slurry.

[0008] Furthermore, the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 2 to 10:1, and the concentration of magnesium ions in the magnesium-containing resin regeneration liquid is preferably 10 to 30 g / L.

[0009] Furthermore, the above-mentioned step S1 includes: acid leaching the laterite nickel ore to obtain an acid leaching solution; circulating leaching the acid leaching solution to obtain a leached solution; using a neutralizing agent to neutralize the leached solution to remove iron and aluminum to obtain a pretreated ore pulp; the endpoint pH value of the pretreated ore pulp is 3 to 3.7, and the solid content of the pretreated ore pulp is preferably ≤28%; the neutralizing agent is preferably residual ore and / or lime milk.

[0010] Furthermore, the above-mentioned step S5 includes: step S51, under the condition of a pH value of 6.5 to 7, performing nickel-cobalt precipitation on the washed liquid and then performing solid-liquid separation to obtain a nickel-cobalt precipitate and a precipitated primary liquid; step S52, under the condition of a pH value of 8 to 8.5, performing manganese precipitation on the precipitated primary liquid and then performing solid-liquid separation to obtain a manganese slag and a precipitated secondary liquid; and step S53, concentrating the precipitated secondary liquid and adjusting the pH value to obtain a magnesium-containing resin regeneration liquid.

[0011] Furthermore, the nickel-cobalt precipitate is returned to step S1 for cyclic leaching.

[0012] Furthermore, in the above step S4, the pH value of the strong acid solution is ≤2, and the strong acid solution is preferably selected from any one or more of sulfuric acid, hydrochloric acid, and nitric acid.

[0013] Furthermore, in the above step S2, the volume ratio of the pretreated pulp to the IDA resin is 2 to 10:1, and the brand of the IDA resin is preferably selected from any one or more of S390, M4195, IRC748, SR-5, and TP207.

[0014] Applying the technical solution of the present application, the above-mentioned treatment method involves acid leaching of the laterite nickel ore, neutralization and iron and aluminum removal pretreatment steps, and adsorption of the pretreated ore pulp by IDA resin, so that high-value ions such as nickel are basically adsorbed on the adsorbed resin. Washing the adsorbed resin with a nickel-containing solution is beneficial for removing impurity ions such as manganese and magnesium that are co-adsorbed thereon, thereby improving the purity of the ions in the adsorbed resin and, at the same time, helping to improve the purity of the nickel-cobalt solution. The order of adsorption affinity of IDA resin for various cations is as follows: H + >Ni 2+ >Co 2+ >Mn 2+ >>Ca 2+ >Mg 2+ >>Na + The adsorption, desorption, and regeneration of ions from the treatment solution (pretreatment slurry or the intermediate solution generated during laterite nickel treatment) by IDA resins is determined by their contact with the treatment solution in a specific chemical state. The selective adsorption of ions by IDA resins is determined by the order of adsorption affinity and the concentration difference between the solution and resin phases. The cations on the desorbed resin are H ions. During regeneration, a magnesium-containing resin regeneration solution with a high magnesium ion concentration and high pH value can be used to displace the H ions on the desorbed resin, converting the cations on the desorbed resin to Mg ions, resulting in a regenerated resin with a high magnesium ion concentration. When this regenerated resin is used as a new IDA resin for adsorption treatment of pretreatment slurry, the Mg ion concentration in the adsorption solution (pretreatment slurry) is lower than that on the regenerated resin. Furthermore, the adsorption affinity of Mg ions is much lower than that of Ni ions. Therefore, Ni ions can displace the Mg ions on the regenerated resin (Mg ions are transferred to the lean slurry), leaving a large amount of Ni ions adsorbed on the adsorbed resin, ensuring the high adsorption capacity of the regenerated resin for nickel and cobalt ions. It can be seen that the present application solves the problem of high cost caused by the need to purchase raw materials for the transformation and regeneration of IDA resin after acid desorption by converting the intermediate product produced during the laterite nickel ore resin adsorption process into a regeneration agent for the resin transformation and regeneration process. This can greatly reduce the amount of purchased process raw materials, not only saving costs (reducing the cost by about 10% compared to purchasing magnesium-containing agents or sodium-containing agents), but also reducing the amount of final waste liquid. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0016] Figure 1 A schematic diagram of a processing flow of laterite nickel ore provided according to Example 1 of the present invention is shown. DETAILED DESCRIPTION

[0017] It should be noted that, in the absence of conflict, the embodiments and features of the embodiments in this application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0018] As analyzed in the background technology of this application, the prior art has the problem that the transformation and regeneration of IDA resin after acid desorption requires the purchase of raw materials, resulting in high costs. In order to solve this problem, this application provides a method for processing laterite nickel ore.

[0019] In one embodiment of the present application, a method for treating laterite nickel ore is provided, which includes: step S1, sequentially subjecting the laterite nickel ore to acid leaching, neutralization and iron and aluminum removal treatment to obtain a pretreated slurry; step S2, subjecting the pretreated slurry to adsorption treatment with IDA resin to obtain a lean slurry and an adsorbed resin; step S3, washing the adsorbed resin with a nickel-containing solution to obtain a washed resin and a washed liquid; step S4, desorbing the washed resin with a strong acid solution to obtain a nickel-cobalt solution and a desorbed resin; step S5, sequentially subjecting the washed liquid to nickel-cobalt precipitation, manganese precipitation and concentration to obtain a magnesium-containing resin regeneration liquid; and step S6, subjecting the desorbed resin to transformation regeneration with the magnesium-containing resin regeneration liquid to obtain a regenerated resin; wherein the pH value of the magnesium-containing resin regeneration liquid is ≥9, and the concentration of magnesium ions in the magnesium-containing resin regeneration liquid is ≥10 g / L.

[0020] The above treatment method involves acid leaching of the laterite nickel ore, neutralization and iron and aluminum removal pretreatment, and adsorption of the pretreated ore pulp by IDA resin, which essentially adsorbs high-value ions such as nickel onto the adsorbed resin. Washing the adsorbed resin with a nickel-containing solution helps remove co-adsorbed impurity ions such as manganese and magnesium, thereby improving the purity of the ions in the adsorbed resin and, at the same time, helping to improve the purity of the nickel-cobalt solution. The order of adsorption affinity of IDA resin for various cations is as follows: H + >Ni 2+ >Co 2+ >Mn 2+ >>Ca 2+ >Mg 2+ >>Na +The adsorption, desorption, and regeneration of ions from the treatment solution (pretreatment slurry or the intermediate solution generated during laterite nickel treatment) by IDA resins is determined by their contact with the treatment solution in a specific chemical state. The selective adsorption of ions by IDA resins is determined by the order of adsorption affinity and the concentration difference between the solution and resin phases. The cations on the desorbed resin are H ions. During regeneration, a magnesium-containing resin regeneration solution with a high magnesium ion concentration and high pH value can be used to displace the H ions on the desorbed resin, converting the cations on the desorbed resin to Mg ions, resulting in a regenerated resin with a high magnesium ion concentration. When this regenerated resin is used as a new IDA resin for adsorption treatment of pretreatment slurry, the Mg ion concentration in the adsorption solution (pretreatment slurry) is lower than that on the regenerated resin. Furthermore, the adsorption affinity of Mg ions is much lower than that of Ni ions. Therefore, Ni ions can displace the Mg ions on the regenerated resin (Mg ions are transferred to the lean slurry), leaving a large amount of Ni ions adsorbed on the adsorbed resin, ensuring the high adsorption capacity of the regenerated resin for nickel and cobalt ions. It can be seen that the present application solves the problem of high cost caused by the need to purchase raw materials for the transformation and regeneration of IDA resin after acid desorption by converting the intermediate product produced during the laterite nickel ore resin adsorption process into a regeneration agent for the resin transformation and regeneration process. This can greatly reduce the amount of purchased process raw materials, not only saving costs (reducing the cost by about 10% compared to purchasing magnesium-containing agents or sodium-containing agents), but also reducing the amount of final waste liquid.

[0021] The selective adsorption of ions by IDA resin is determined by the order of adsorption affinity and the concentration difference between the ions in the solution and resin phases. The volume ratio of the nickel-containing solution to the adsorbed resin is preferably 2 to 10:1 (10:1, 5:1, or 2:1), the nickel ion concentration of the nickel-containing solution is 3 to 5 g / L, and the pH of the nickel-containing solution is preferably 3 to 4. This facilitates more thorough removal of impurity ions from the adsorbed resin, thereby improving the purity of the ions in the adsorbed resin.

[0022] In one embodiment of the present application, the above-mentioned treatment method further includes: adjusting the pH value and nickel ion concentration of a portion of the nickel-cobalt solution, and returning it to step S3 as a nickel-containing solution to wash the adsorbed resin; precipitating the remaining nickel-cobalt solution with an alkaline reagent to obtain a nickel-cobalt precipitation intermediate; preferably, the portion of the nickel-cobalt solution accounts for 10 to 30% of the total amount of the nickel-cobalt solution; preferably, the pH value of the portion of the nickel-cobalt solution is adjusted to 3 to 3.7 (such as 3, 3.2, 3.5, or 3.7), and preferably, the nickel ion concentration of the portion of the nickel-cobalt solution is 3 to 5 g / L (such as 3 g / L, 4 g / L, or 5 g / L), and preferably, the alkaline reagent is sodium hydroxide and / or potassium hydroxide.

[0023] A large amount of nickel-cobalt ions are enriched in the above-mentioned nickel-cobalt solution. As the core treatment solution in the above-mentioned treatment process, the inventor of this application has carried out the above-mentioned treatment respectively to the nickel-cobalt solution. On the one hand, 10~30% (such as 10%, 15%, 20%, 25%, or 30%) of the nickel-cobalt solution total amount is regulated and then returned to step S3 as a new nickel-containing solution to wash the resin after adsorption, thereby greatly reducing cost and improving the enrichment degree of nickel-cobalt ions, and giving the nickel-cobalt solution more valuable additional effects. On the other hand, the remaining most of the nickel-cobalt solution is precipitated to obtain the nickel-cobalt precipitation intermediate with high application value. In addition, the kind of preferred alkaline reagent helps to reduce the introduction probability of alkaline reagent to the foreign ions in the nickel-cobalt precipitation intermediate.

[0024] In one embodiment of the present application, the above-mentioned treatment method further comprises: returning the regenerated resin to the adsorption treatment step as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0025] When the regenerated resin is used as a new IDA resin to adsorb the pretreated slurry, the Mg ion concentration in the adsorption solution (pretreated slurry) is lower than the Mg ion concentration on the regenerated resin, and the adsorption affinity of Mg ions is much lower than that of Ni ions. Therefore, Ni ions can replace the Mg ions on the regenerated resin (Mg ions to the lean slurry), and Ni ions are adsorbed on the adsorbed resin in large quantities, thereby avoiding the purchase of alkaline regeneration solution and greatly reducing costs.

[0026] Preferably, the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 2 to 10:1, such as 10:1, 5:1, or 2:1. Preferably, the concentration of magnesium ions in the magnesium-containing resin regeneration liquid is 10 to 30 g / L, such as 10 g / L, 15 g / L, 20 g / L, 25 g / L, or 30 g / L, thereby helping to further improve the efficiency and effect of the transformation regeneration.

[0027] In one embodiment of the present application, the above-mentioned step S1 includes: acid leaching laterite nickel ore to obtain an acid leaching solution; circulating leaching the acid leaching solution to obtain a leached liquid; using a neutralizing agent to neutralize and remove iron and aluminum from the leached liquid to obtain a pretreated slurry; the endpoint pH value of the pretreated slurry is 3 to 3.7, such as a pH value of 3, 3.2, 3.5, or 3.7, and the solid content of the pretreated slurry is preferably ≤28%, such as 28%, 25%, 22%, or 20%; the neutralizing agent is preferably residual ore and / or lime milk.

[0028] The above steps reduce the content of impurities in the obtained pre-treated pulp as much as possible, and the control of the endpoint pH value helps to remove the iron and aluminum in the leached liquid as much as possible, thereby laying the foundation for the extraction of high-value ions such as nickel and cobalt. The solid content of the pre-treated pulp determines the dispersion concentration of each metal ion in the pre-treated pulp. The preferred solid content of the pre-treated pulp will not cause the efficiency of the adsorption treatment in step S2 to be too low, the water consumption to be too large, and a large amount of waste liquid to be caused by its too low concentration, nor will it cause the effect of the adsorption treatment in step S2 to be too poor due to its too high concentration. Therefore, the preferred solid content of the pre-treated pulp helps to balance the efficiency, effect and low cost of the adsorption treatment. Further, in order to improve the effect of the neutralization and iron and aluminum removal treatment, it is preferred to carry out two or more iron and aluminum removal treatments, and the temperature of each iron and aluminum removal treatment is preferably independently 75 to 85°C, such as 75°C, 80°C, or 85°C, and the time of each iron and aluminum removal treatment is preferably independently 4 to 6h, such as 4h, 5h, or 6h. Of course, the above processes of acid leaching of laterite nickel ore, circulating leaching of the acid leaching solution, and neutralization and iron and aluminum removal of the leached solution can all adopt the current conventional corresponding methods, which will not be described in detail here.

[0029] In one embodiment of the present application, the above-mentioned step S5 includes: step S51, under the condition of a pH value of 6.5 to 7, nickel-cobalt precipitation is performed on the washed liquid, and then solid-liquid separation is performed to obtain a nickel-cobalt precipitate and a precipitated primary liquid; step S52, under the condition of a pH value of 8 to 8.5, manganese precipitation is performed on the precipitated primary liquid, and then solid-liquid separation is performed to obtain a manganese slag and a precipitated secondary liquid; and step S53, concentrating the precipitated secondary liquid and adjusting the pH to obtain a magnesium-containing resin regeneration liquid.

[0030] The above steps are directed to different conditions for nickel-cobalt precipitation and manganese precipitation, and sequential precipitation of nickel-cobalt and manganese is achieved under the conditions of pH values ​​of 6.5-7 and pH values ​​of 8-8.5 (for example, sequential precipitation of nickel-cobalt and manganese is achieved under the conditions of pH values ​​of 7 and pH value of 8.5, sequential precipitation of nickel-cobalt and manganese is achieved under the conditions of pH values ​​of 6.5 and pH value of 8, or sequential precipitation of nickel-cobalt and manganese is achieved under the conditions of pH values ​​of 6.8 and pH value of 8.2). The secondary precipitated liquid except nickel-cobalt and manganese is concentrated and the pH value is adjusted to obtain a magnesium-containing resin regeneration liquid having a magnesium ion concentration and a pH value that meet certain requirements, thereby achieving the purpose of converting the intermediate product generated in the laterite nickel ore resin adsorption process into a raw material for the resin transformation and regeneration process.

[0031] Preferably, the nickel-cobalt precipitate is returned to step S1 for cyclic leaching, which helps to further purify the nickel-cobalt precipitate, thereby recovering high-value ions such as nickel and cobalt therein as much as possible, reducing solid waste, and further improving the economy and environmental protection of the entire laterite nickel ore treatment method.

[0032] In one embodiment of the present application, in the above step S4, the pH value of the strong acid solution is ≤2, such as the pH value of the strong acid solution is 2, 1.5, or 1. Preferably, the strong acid solution is selected from any one or more of sulfuric acid, hydrochloric acid, and nitric acid.

[0033] In order to further promote the adequacy of acid desorption, the pH value and type of the above strong acid solution are preferred, and the type of strong acid solution used determines the type of anions in the nickel-containing solution. The preferred type of the above strong acid solution helps to reduce the probability of introducing new impurity ions during the washing process.

[0034] Preferably, the volume ratio of the pretreated ore pulp to the IDA resin is 2 to 10:1, such as the volume ratio of the pretreated ore pulp to the IDA resin is 2:1, 5:1, 8:1, or 10:1. Preferably, the brand of the IDA resin is selected from any one or more of S390, M4195, IRC748, SR-5, and TP207. There is no specific limitation on the specific type of the IDA resin, and any sodium-based IDA chelating resin containing an IDA functional group capable of adsorbing nickel ions and / or cobalt ions can be used.

[0035] The beneficial effects of the present application are further illustrated below with reference to the embodiments and comparative examples.

[0036] Example 1

[0037] Table 1 Initial metal ion concentrations in the treated laterite nickel ore (mg / L)

[0038]

[0039] according to Figure 1 The processing flow chart of the laterite nickel ore shown in the figure is used to process the laterite nickel ore to be processed shown in Table 1 above:

[0040] Step S1, pressurized acid leaching of laterite nickel ore with sulfuric acid to obtain an acid leaching solution (wherein the sulfuric acid concentration is about 20g / L); circulating leaching of the acid leaching solution to obtain a circulating leaching slurry; filtering the circulating leaching slurry to obtain a post-leaching liquid; neutralizing the post-leaching liquid with residual ore to remove iron and aluminum to obtain a pretreated slurry (end point pH value is 3.7); adding water to dilute the pretreated slurry to obtain a pretreated slurry with a solid content of 28%.

[0041] In step S2, the pretreated pulp is subjected to adsorption treatment using fresh IDA chelating resin (brand S390) and then screened to obtain lean pulp and adsorbed resin, wherein the volume ratio of the pretreated pulp to the IDA resin is 10:1; the lean pulp is sent to the tailings treatment system and discharged into the tailings pond after treatment.

[0042] In step S3, a nickel-containing solution having a pH of about 3 and a nickel concentration of about 5 g / L is added to wash the adsorbed resin to remove metal ions such as manganese and magnesium on the adsorbed resin, and then sieved to obtain a washed resin and a washed liquid, wherein the volume ratio of the nickel-containing solution to the adsorbed resin is 10:1.

[0043] Step S4: Desorbing the washed resin with sulfuric acid having a pH of 2 to obtain a nickel-cobalt solution and a desorbed resin; the nickel-cobalt solution is divided into two parts, 10% of the nickel-cobalt solution is adjusted to a pH of approximately 3 and a nickel ion concentration of approximately 5 g / L and then returned to the washing process as a nickel-containing solution, and the 90% nickel-cobalt solution is subjected to nickel-cobalt precipitation with sodium hydroxide to obtain a nickel-cobalt intermediate product.

[0044] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain a nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain a manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 30 g / L and a pH of 9.5 to serve as a magnesium-containing resin regeneration liquid.

[0045] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin, wherein the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 10:1.

[0046] The regenerated resin is returned to step 2 of the adsorption process as new IDA resin to perform adsorption treatment on the pretreated slurry.

[0047] Example 2

[0048] The difference from Example 1 is that, in step S3, a nickel-containing solution with a pH of about 3.7 and a nickel concentration of about 3 g / L is added to wash the adsorbed resin to remove metal ions such as manganese and magnesium on the adsorbed resin, and then the washed resin and the washed liquid are obtained by sieving through a sieve. Finally, in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0049] Example 3

[0050] The difference from Example 1 is that in step S3, the volume ratio of the nickel-containing solution to the adsorbed resin is 5:1, and finally in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0051] Example 4

[0052] The difference from Example 1 is that in step S3, the volume ratio of the nickel-containing solution to the adsorbed resin is 2:1, and finally in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0053] Example 5

[0054] The difference from Example 1 is that in step S3, the volume ratio of the nickel-containing solution to the adsorbed resin is 1:1, and finally in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0055] Example 6

[0056] The difference from Example 1 is that in step S2, the volume ratio of the pretreated pulp to the IDA resin is 4:1, and finally in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as new IDA resin to perform adsorption treatment on the pretreated pulp.

[0057] Example 7

[0058] The difference from Example 1 is that, in step S1, the laterite nickel ore is pressure-acid-leached with sulfuric acid to obtain an acid leaching solution (containing a sulfuric acid concentration of approximately 20 g / L); the acid leaching solution is circulated to obtain a circulating leached pulp; the circulating leached pulp is filtered to obtain a post-leaching solution; the post-leaching solution is neutralized and iron and aluminum are removed with lime milk to obtain a pretreated pulp (endpoint pH 3); the pretreated pulp is diluted with water to obtain a pretreated pulp with a solid content of 20%. Finally, in step S6, the regenerated resin is returned to step 2 of the adsorption treatment as new IDA resin to perform adsorption treatment on the pretreated pulp.

[0059] Example 8

[0060] The difference from Example 1 is that, in step S2, the regenerated resin obtained in step S6 is used to perform adsorption treatment on the pretreated slurry.

[0061] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain a nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain a manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 15 g / L and a pH of 9.5 to serve as a magnesium-containing resin regeneration liquid.

[0062] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin.

[0063] Example 9

[0064] The difference from Example 1 is that, in step S2, the regenerated resin obtained in step S6 is used to perform adsorption treatment on the pretreated slurry.

[0065] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 5 g / L and a pH of 9.5 to serve as a magnesium-containing resin regeneration liquid.

[0066] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin.

[0067] Example 10

[0068] The difference from Example 1 is that, in step S2, the regenerated resin obtained in step S6 is used to perform adsorption treatment on the pretreated slurry.

[0069] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain a nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain a manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 30 g / L as a magnesium-containing resin regeneration liquid.

[0070] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin, wherein the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 5:1.

[0071] Example 11

[0072] The difference from Example 1 is that, in step S2, the regenerated resin obtained in step S6 is used to perform adsorption treatment on the pretreated slurry.

[0073] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain a nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain a manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 30 g / L as a magnesium-containing resin regeneration liquid.

[0074] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin, wherein the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 2:1.

[0075] Example 12

[0076] The difference from Example 1 is that, in step S2, the regenerated resin obtained in step S6 is used to perform adsorption treatment on the pretreated slurry.

[0077] Step S5: adding sodium hydroxide solution to adjust the pH of the washed liquid to 7 for nickel-cobalt precipitation, filtering to obtain a nickel-cobalt precipitate and a primary precipitation liquid, and returning the nickel-cobalt precipitate to the circulating leaching process; adding sodium hydroxide solution to adjust the pH of the primary precipitation liquid to 8.5 for manganese precipitation, filtering to obtain a manganese slag and a secondary precipitation liquid; concentrating the secondary precipitation liquid to a magnesium concentration of 30 g / L and a pH of 9.5 to serve as a magnesium-containing resin regeneration liquid.

[0078] Step S6, contacting the magnesium-containing resin regeneration liquid with the desorbed resin to perform transformation regeneration to obtain the regenerated resin, wherein the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 1:1.

[0079] Comparative Example 1

[0080] The difference from Example 1 is that, in step S5, sodium hydroxide solution is added to adjust the pH of the washed liquid to 7 to perform nickel-cobalt precipitation, and nickel-cobalt precipitate and primary precipitation liquid are obtained after filtration. The nickel-cobalt precipitate is returned to the circulating leaching process, and the primary precipitation liquid is incorporated into the waste liquid treatment system.

[0081] In step S6, the purchased magnesium hydroxide is added with water to prepare a magnesium-containing liquid with a pH of 9, which is contacted with the desorbed resin for transformation and regeneration to obtain a regenerated resin, wherein the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 10:1; the regenerated resin is returned to step 2 of the adsorption treatment as a new IDA resin to perform adsorption treatment on the pretreated slurry.

[0082] Comparative Example 2

[0083] The difference from Example 1 is that in step S6, the pH of the washed solution obtained in step S4 is adjusted to 9, which will result in the generation of various precipitates and cannot be used as a regeneration solution for the magnesium-containing resin.

[0084] The purity of the nickel-cobalt intermediate products in Examples 1 to 12, Comparative Examples 1 and 2, and the adsorption capacity (mg / mL resin) of the resin for cobalt ions and nickel ions after adsorption were measured, and the results are shown in Table 2 below.

[0085] Table 2

[0086]

[0087] It can be seen from the data in Table 2 that Example 5 is outside the range of the volume ratio of the nickel-containing solution to the resin after adsorption. Since the volume reduction of the nickel-containing solution will lead to a decrease in the nickel adsorbed on the resin after washing, the nickel adsorption capacity is low, which will also partially affect the impurity washing effect, so the purity of the nickel-cobalt intermediate product is slightly reduced.

[0088] In Example 6, the volume ratio of the ore pulp to the IDA resin after pretreatment is reduced, and the volume ratio during adsorption is reduced, that is, the amount of IDA resin used is relatively increased, and the average utilization rate is reduced, resulting in a slight decrease in the equilibrium concentration on the IDA resin. More IDA resin functional groups will also be provided to impurities, thereby causing the nickel-cobalt selectivity advantage to be slightly reduced.

[0089] Excessive dilution in Example 7 resulted in a decrease in the initial concentration of nickel and cobalt in the pretreated slurry, a decrease in the concentration driving force during the adsorption process, and a greater effect on nickel and cobalt with lower concentrations than on impurity elements with higher concentrations, thereby slightly reducing the nickel and cobalt adsorption capacity and the purity of the intermediate product.

[0090] In Example 9, the magnesium concentration of the regeneration liquid is reduced, and in Example 12, the amount of regeneration liquid used is reduced. Both will lead to a decrease in the transformation regeneration effect, that is, the counterions on some functional groups of the obtained regenerated resin are not converted from hydrogen to magnesium. When it is used for adsorption again, the adsorption capacity and selectivity of the regenerated resin for nickel and cobalt will be slightly reduced, thereby resulting in a slight decrease in its adsorption capacity for cobalt ions and nickel ions, and a slight decrease in the purity of the nickel-cobalt intermediate product.

[0091] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0092] The above treatment method involves acid leaching of the laterite nickel ore, neutralization and iron and aluminum removal pretreatment, and adsorption of the pretreated ore pulp by IDA resin, which essentially adsorbs high-value ions such as nickel onto the adsorbed resin. Washing the adsorbed resin with a nickel-containing solution helps remove co-adsorbed impurity ions such as manganese and magnesium, thereby improving the purity of the ions in the adsorbed resin and, at the same time, helping to improve the purity of the nickel-cobalt solution. The order of adsorption affinity of IDA resin for various cations is as follows: H + >Ni 2+ >Co 2+ >Mn 2+ >>Ca 2+ >Mg 2+ >>Na +The adsorption, desorption, and regeneration of ions from the treatment solution (pretreatment slurry or the intermediate solution generated during laterite nickel treatment) by IDA resins is determined by their contact with the treatment solution in a specific chemical state. The selective adsorption of ions by IDA resins is determined by the order of adsorption affinity and the concentration difference between the solution and resin phases. The cations on the desorbed resin are H ions. During regeneration, a magnesium-containing resin regeneration solution with a high magnesium ion concentration and high pH value can be used to displace the H ions on the desorbed resin, converting the cations on the desorbed resin to Mg ions, resulting in a regenerated resin with a high magnesium ion concentration. When this regenerated resin is used as a new IDA resin for adsorption treatment of pretreatment slurry, the Mg ion concentration in the adsorption solution (pretreatment slurry) is lower than that on the regenerated resin. Furthermore, the adsorption affinity of Mg ions is much lower than that of Ni ions. Therefore, Ni ions can displace the Mg ions on the regenerated resin (Mg ions are transferred to the lean slurry), leaving a large amount of Ni ions adsorbed on the adsorbed resin, ensuring the high adsorption capacity of the regenerated resin for nickel and cobalt ions. It can be seen that the present application solves the problem of high cost caused by the need to purchase raw materials for the transformation and regeneration of IDA resin after acid desorption by converting the intermediate product produced during the laterite nickel ore resin adsorption process into a regeneration agent for the resin transformation and regeneration process. This can greatly reduce the amount of purchased process raw materials, not only saving costs (reducing the cost by about 10% compared to purchasing magnesium-containing agents or sodium-containing agents), but also reducing the amount of final waste liquid.

[0093] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for processing laterite nickel ore, characterized in that: The processing method comprises: Step S1, performing acid leaching, neutralization and iron and aluminum removal treatments on the laterite nickel ore in sequence to obtain a pretreated ore pulp; Step S2, performing adsorption treatment on the pretreated pulp using IDA resin to obtain lean pulp and adsorbed resin; Step S3, washing the adsorbed resin with a nickel-containing solution to obtain a washed resin and a washed liquid; Step S4, desorbing the washed resin using a strong acid solution to obtain a nickel-cobalt solution and a desorbed resin; Step S5, sequentially performing nickel-cobalt precipitation, manganese precipitation, and concentration on the washed liquid to obtain a magnesium-containing resin regeneration liquid; specifically, step S5 includes: Step S51, performing nickel-cobalt precipitation on the washed liquid and then performing solid-liquid separation under the condition of a pH value of 6.5-7 to obtain a nickel-cobalt precipitate and a primary precipitation liquid; Step S52, performing the manganese precipitation on the primary precipitate liquid and then performing solid-liquid separation under the condition of a pH value of 8 to 8.5 to obtain manganese slag and a secondary precipitate liquid; Step S53, concentrating the precipitated secondary liquid and adjusting the pH value to obtain the magnesium-containing resin regeneration liquid; and Step S6, using the magnesium-containing resin regeneration liquid to transform and regenerate the desorbed resin to obtain a regenerated resin; The pH value of the magnesium-containing resin regeneration liquid is ≥9, the concentration of magnesium ions in the magnesium-containing resin regeneration liquid is ≥10 g / L, and the volume ratio of the magnesium-containing resin regeneration liquid to the desorbed resin is 2-10:

1.

2. The processing method according to claim 1, characterized in that The volume ratio of the nickel-containing solution to the adsorbed resin is 2-10:

1.

3. The processing method according to claim 2, characterized in that The nickel ion concentration of the nickel-containing solution is 3-5 g / L, The pH value of the nickel-containing solution is 3-4.

4. The processing method according to claim 1 or 2, characterized in that: The processing method further comprises: After adjusting the pH value and nickel ion concentration of a portion of the nickel-cobalt solution, the solution is returned to step S3 as the nickel-containing solution to wash the adsorbed resin; The remaining nickel-cobalt solution is precipitated with an alkaline reagent to obtain a nickel-cobalt precipitation intermediate.

5. The processing method according to claim 4, characterized in that: Part of the nickel-cobalt solution accounts for 10-30% of the total amount of the nickel-cobalt solution; The pH value of the nickel-cobalt solution is adjusted to 3-3.

7. The nickel ion concentration of some of the nickel-cobalt solutions is 3-5 g / L. The alkaline reagent is sodium hydroxide and / or potassium hydroxide.

6. The processing method according to claim 1 or 2, characterized in that: The processing method further comprises: The regenerated resin is returned to the adsorption treatment step as new IDA resin to perform adsorption treatment on the pretreated slurry.

7. The processing method according to claim 1 or 2, characterized in that: The concentration of magnesium ions in the magnesium-containing resin regeneration solution is 10-30 g / L.

8. The processing method according to claim 1 or 2, characterized in that: The step S1 comprises: acid leaching the laterite nickel ore to obtain an acid leaching solution; Circulating the acid leaching solution to obtain a leached solution; Using a neutralizing agent to neutralize and remove iron and aluminum from the leached liquid to obtain the pretreated ore pulp; The endpoint pH value of the slurry after the pretreatment is 3-3.

7.

9. The processing method according to claim 8, characterized in that: The solid content of the slurry after the pretreatment is ≤28%; The neutralizing agent is residual ore and / or lime milk.

10. The processing method according to claim 8, characterized in that: The nickel-cobalt precipitate is returned to step S1 for the cyclic leaching.

11. The processing method according to claim 1 or 2, characterized in that: In step S4, the pH value of the strong acid solution is ≤2.

12. The processing method according to claim 11, characterized in that: The strong acid solution is selected from any one or more of sulfuric acid, hydrochloric acid, and nitric acid.

13. The processing method according to claim 1 or 2, characterized in that: In step S2, the volume ratio of the pretreated slurry to the IDA resin is 2-10:

1.

14. The processing method according to claim 13, characterized in that: The brand of the IDA resin is selected from any one or more of S390, M4195, IRC748, SR-5, and TP207.

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