Application of magnesium hydroxide emulsion and regeneration method of nickel-cobalt adsorbed IDA resin

Abstract

The present invention provides an application of a magnesium hydroxide emulsion and a regeneration method for a nickel-cobalt adsorbed IDA resin. The present application provides an application of a magnesium hydroxide emulsion in the saponification transformation of a hydrogen-based IDA resin. The magnesium hydroxide emulsion provided in the present application is used as a saponifier in the saponification transformation of a hydrogen-based IDA resin to transform the hydrogen-based IDA resin into a magnesium-based IDA resin, which is used for the adsorption of a nickel-cobalt-containing feed liquid. While ensuring a high adsorption capacity for nickel ions and cobalt ions, it can also avoid precipitation in the system, and can be used in a stirring process or a column process at the same time, and is easy to perform resin screening, which can effectively extend the service life of the resin.

Description

Technical Field

[0001] The invention relates to the field of resin regeneration, and in particular to an application of a magnesium hydroxide emulsion and a regeneration method for nickel-cobalt adsorbed IDA resin. Background Art

[0002] The resin adsorption method can be used to recover nickel and cobalt ions from multi-component sulfate liquid phase or solid-containing slurry. A more economical approach is to use mature commercial IDA chelating resin, column or stirring mixture to selectively adsorb nickel and cobalt, then desorb with acid, and then transform into lime milk to improve performance and ensure the amount of nickel and cobalt adsorbed when adsorbed again. However, in actual applications, there are great problems with lime milk transformation. During the transformation process, lime milk replaces hydrogen with calcium. In the sulfate system, a large amount of calcium sulfate precipitation will be produced during re-adsorption, which cannot be used for column process. The stirring process will also cause the amount of slag to increase, the solid content of the system will increase, the difficulty of resin screening will increase, and the resin wear will be aggravated.

[0003] In view of this, the present invention is proposed. Summary of the invention

[0004] The main purpose of the present invention is to provide an application of magnesium hydroxide emulsion and a regeneration method of nickel-cobalt adsorbed IDA resin, so as to solve the problem in the prior art that a large amount of calcium sulfate precipitation will be generated when the IDA resin after acid desorption using lime milk is adsorbed again containing sulfuric acid solution, and it cannot be used for column process. If it is used for stirring process, it will lead to an increase in slag amount, an increase in system solid content, an increase in resin screening difficulty and an increase in resin wear.

[0005] In order to achieve the above object, according to one aspect of the present invention, there is provided an application of a magnesium hydroxide emulsion in the saponification transformation of a hydrogen-based IDA resin.

[0006] Furthermore, the mass concentration of the magnesium hydroxide is 0.5-10%, preferably 1-10%.

[0007] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a regeneration method of nickel-cobalt adsorbed IDA resin is also provided, and the regeneration method comprises: step S1, acid desorption of nickel-cobalt adsorbed IDA resin to obtain hydrogen-based IDA resin and nickel-cobalt desorption liquid; step S2, mixing hydrogen-based IDA resin with saponifier, performing magnesium soap transformation and then screening to obtain magnesium-based IDA resin, wherein the saponifier is magnesium hydroxide emulsion.

[0008] Furthermore, the mass concentration of the magnesium hydroxide emulsion is 0.5 to 10%, preferably 1 to 10%.

[0009] Further, in step S2, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:(4-20), more preferably 1:(4-10);

[0010] Furthermore, during the magnesium soap transformation process, the magnesium excess coefficient is 1.25-30, preferably 1.5-20.

[0011] Further, step S1 includes: step S11, washing the nickel-cobalt adsorbed IDA resin with a weak acid solution to obtain a washed IDA resin, preferably the pH of the weak acid solution is 0.5 to 2.5, and more preferably the weak acid solution is a dilute sulfuric acid solution with a pH of 1.5 to 2.5; step S12, acid desorption of the washed IDA resin with a strong acid solution to obtain a hydrogen-based IDA resin, preferably the strong acid solution is an acid solution with a concentration of 50 to 300 g / L, and the acid solution is selected from at least one of sulfuric acid, hydrochloric acid or nitric acid.

[0012] Furthermore, in step S1, the preparation method of nickel-cobalt adsorbed IDA resin comprises: passing a nickel-cobalt-containing sulfuric acid solution into a sodium-based IDA resin for adsorbing nickel ions and cobalt ions to obtain a nickel-cobalt adsorbed IDA resin.

[0013] Furthermore, the sodium-based IDA resin is a resin containing an IDA functional group, and the brand is preferably S390, M4195, IRC748, SR-5 or TP207.

[0014] Furthermore, the nickel-cobalt-containing sulfuric acid solution is a pretreated laterite slurry.

[0015] Furthermore, the pretreated laterite slurry is obtained by sequentially subjecting the laterite nickel ore to acid leaching, neutralization to remove iron and aluminum, and solid-liquid separation.

[0016] Furthermore, the magnesium-based IDA resin is used for the adsorption of nickel-cobalt-containing sulfuric acid solution.

[0017] By applying the technical solution of the present application, the magnesium hydroxide emulsion provided by the present application is used as a saponifier in the saponification transformation of a hydrogen-based IDA resin, and the hydrogen-based IDA resin is transformed into a magnesium-based IDA resin. The magnesium-based IDA resin is used for the adsorption of a nickel-cobalt-containing liquid. While ensuring a high adsorption capacity for nickel ions and cobalt ions, precipitation in the system can be avoided. At the same time, it can be used in a stirring process or a column process, and is easy to perform resin screening, which can effectively extend the service life of the resin. DETAILED DESCRIPTION

[0018] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0019] As analyzed in the background technology of this application, the prior art uses lime milk to transform the IDA resin into acid desorption, and when it adsorbs the solution containing sulfuric acid, a large amount of calcium sulfate precipitation will be produced, which makes it impossible to use it in the column process. If it is used in the stirring process, it will cause the amount of slag to increase, the solid content of the system to increase, and the difficulty of resin screening and aggravate the resin wear. In order to solve this problem, this application provides an application of magnesium hydroxide emulsion and a regeneration method of nickel-cobalt adsorbed IDA resin.

[0020] In one aspect of the present application, a magnesium hydroxide emulsion is provided for use in the saponification transformation of a hydrogen-based IDA resin.

[0021] By applying the technical solution of the present application, the magnesium hydroxide emulsion provided by the present application is used as a saponifier in the saponification transformation of a hydrogen-based IDA resin, and the hydrogen-based IDA resin is transformed into a magnesium-based IDA resin. The magnesium-based IDA resin is used for the adsorption of a nickel-cobalt-containing liquid. While ensuring a high adsorption capacity for nickel ions and cobalt ions, precipitation in the system can be avoided. At the same time, it can be used in a stirring process or a column process, and is easy to perform resin screening, which can effectively extend the service life of the resin.

[0022] In order to further improve the transformation efficiency of hydrogen-based IDA resin, the mass concentration of magnesium hydroxide emulsion is preferably 0.5-10%, especially when the mass concentration of magnesium hydroxide emulsion is 1-10%, it is more conducive to the transformation of hydrogen-based IDA resin into magnesium-based IDA resin.

[0023] Typically but not limiting, the mass concentration of the magnesium hydroxide emulsion is 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 8%, 10% or a range consisting of any two values.

[0024] In a second typical embodiment of the present application, a regeneration method for a nickel-cobalt adsorbed IDA resin is also provided, and the regeneration method comprises: step S1, acid desorbing the nickel-cobalt adsorbed IDA resin to obtain a hydrogen-based IDA resin and a nickel-cobalt desorption solution; step S2, mixing the hydrogen-based IDA resin with a saponifier, performing a magnesium soap transformation, and then screening to obtain a magnesium-based IDA resin; wherein the saponifier is a magnesium hydroxide emulsion, and the magnesium hydroxide emulsion has the same meaning as in the above-mentioned first typical embodiment, and will not be repeated here.

[0025] The present application provides a regeneration method for nickel-cobalt adsorption IDA resin, which sequentially subjects the nickel-cobalt adsorption IDA resin to acid desorption and magnesium soap transformation to obtain a magnesium-based IDA resin. The magnesium-based IDA resin is used for the adsorption of nickel-cobalt-containing sulfuric acid solution. While ensuring a high adsorption capacity for nickel ions and cobalt ions, precipitation in the system can be avoided. The magnesium-based IDA resin can also be used in a stirring process or a column process, and is easy to perform resin screening, which can effectively extend the service life of the resin.

[0026] In order to further improve the sufficiency of the saponification transformation of the hydrogen-based IDA resin, in step S2, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is preferably 1: (4 to 20), especially when the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1: (4 to 10), it is more conducive to improving the saponification transformation efficiency of the hydrogen-based IDA resin.

[0027] Typically, but not limiting, the volume ratio of hydrogen-based IDA resin to magnesium hydroxide emulsion is 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:15, 1:18, 1:20 or a range consisting of any two values.

[0028] In order to further promote the saponification transformation of the hydrogen-based IDA resin, the preferred step S2, in the magnesium soap transformation, the magnesium excess coefficient is 1.25 to 30, especially when the magnesium excess coefficient is 1.5 to 20, which is more conducive to improving the adsorption capacity of nickel ions and cobalt ions of the magnesium-based IDA resin.

[0029] The above magnesium excess coefficient is the ratio of the molar amount of magnesium in the magnesium hydroxide emulsion to the molar amount of magnesium that can be theoretically bound to the functional groups of the resin to be transformed.

[0030] In order to further promote the adequacy of acid desorption, the preferred step S1 includes: step S11, washing the nickel-cobalt adsorbed IDA resin with a weak acid solution, and washing the IDA resin; step S12, acid desorbing the adsorbed IDA resin with a strong acid solution to obtain a hydrogen-based IDA resin. In the above step S11, the pH of the weak acid solution is preferably 0.5-2.5, so as to improve the efficiency of washing, and the preferred weak acid solution is a dilute sulfuric acid solution with a pH of 1.5-2.5; the strong acid solution is an acid solution with a concentration of 50-300 g / L, and the strong acid solution is preferably a mixed strong acid solution formed by any one or more acids of sulfuric acid, hydrochloric acid or nitric acid.

[0031] In the above step S1, the preparation method of nickel-cobalt adsorption IDA resin includes: passing a nickel-cobalt-containing sulfuric acid solution into a sodium-based IDA resin for adsorption of nickel ions and themselves to obtain a nickel-cobalt adsorption resin.

[0032] The above-mentioned cobalt-nickel-containing sulfuric acid solution refers to a sulfuric acid solution containing cobalt ions and / or nickel ions, which is derived from the ore pulp of laterite nickel ore or other sulfuric acid solutions containing cobalt ions and / or nickel ions.

[0033] In some embodiments of the present application, the above-mentioned nickel-cobalt-containing sulfuric acid liquid is a pretreated laterite slurry, which is obtained by sequentially subjecting laterite nickel ore to acid leaching, neutralization to remove iron and aluminum, and solid-liquid separation.

[0034] Preferably, the above-mentioned pretreated laterite slurry is prepared according to the following steps: acid leaching the laterite nickel ore with sulfuric acid to obtain an acid leached slurry; adjusting the pH of the acid leached slurry to 3.8-5 to perform a neutralization and iron and aluminum removal process to obtain a neutralized slurry; and subjecting the neutralized slurry to a solid-liquid separation process to filter out solid particles with a particle size ≥180 μm to obtain a pretreated laterite slurry.

[0035] The specific type of the above-mentioned sodium-based IDA resin is not specifically limited. Any sodium-based IDA chelating resin containing an IDA functional group capable of adsorbing nickel ions and / or cobalt ions can be used, and its brands include but are not limited to S390, M4195, IRC748, SR-5, and TP207.

[0036] In order to further reduce the cost of removing nickel and cobalt from the nickel-cobalt-containing sulfuric acid solution, the magnesium-based IDA resin obtained in the above step 2 is preferably used for adsorption treatment of nickel ions and / or cobalt ions in the nickel-cobalt-containing sulfuric acid solution.

[0037] The affinity of IDA resin to various cations is in the following order: + >Ni 2+ >Co 2+ >Mn 2+ >>Ca 2+ >Mg 2+ >>Na +

[0038] Therefore, the magnesium-based IDA resin is more conducive to the adsorption of nickel ions and / or cobalt ions than the calcium-based IDA resin.

[0039] In some embodiments of the present application, an adsorption method for pretreating laterite slurry is provided, comprising the following steps:

[0040] Step S0, passing the pretreated laterite slurry into a sodium-based IDA resin, stirring it to perform adsorption treatment of nickel ions and cobalt ions, and then screening it to obtain a nickel-cobalt adsorption IDA resin;

[0041] Step S11, washing the nickel-cobalt adsorbed IDA resin with a weak acid solution to obtain a washed IDA resin, wherein the pH of the weak acid solution is 0.5 to 2.5;

[0042] Step S12, acid desorption of the washed IDA resin using a concentrated sulfuric acid solution with a mass concentration of 50 to 300 g / L to obtain a hydrogen-based IDA resin;

[0043] Step S2, mixing hydrogen-based IDA resin and magnesium hydroxide emulsion, performing magnesium soap transformation, and then screening to obtain magnesium-based IDA resin; wherein the mass concentration of the magnesium hydroxide emulsion is 0.5-10%;

[0044] Step S3, returning the magnesium-based IDA resin to step S0 to replace the sodium-based IDA resin to pre-treat the laterite slurry for adsorption of nickel ions and cobalt ions.

[0045] The beneficial effects of the present application are further illustrated below in combination with embodiments and comparative examples.

[0046] Example 1

[0047] This embodiment provides an adsorption method for pre-treating laterite slurry. The concentrations of main metal ions in the pre-treated laterite slurry are shown in Table 1 below.

[0048] Table 1 Concentration of main metal ions in pretreated laterite slurry (mg / L)

[0049]

[0050] The specific steps of the adsorption method are as follows:

[0051] (1) passing the pretreated laterite slurry into a sodium-based IDA resin and stirring to perform adsorption treatment of nickel ions and cobalt ions, and then screening to obtain a nickel-cobalt adsorbed IDA resin and a laterite slurry after adsorption;

[0052] (2) washing the nickel-cobalt adsorbed IDA resin with a dilute sulfuric acid solution to obtain a washed IDA resin, wherein the pH of the dilute sulfuric acid solution is 2;

[0053] (3) acid desorption of the washed IDA resin using a concentrated sulfuric acid solution with a mass concentration of 50 g / L to obtain a hydrogen-based IDA resin;

[0054] (4) mixing hydrogen-based IDA resin and magnesium hydroxide emulsion, performing magnesium soap transformation, and then screening to obtain magnesium-based IDA resin; wherein the mass concentration of the magnesium hydroxide emulsion is 10%, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:10, and the magnesium excess coefficient is 17;

[0055] (5) Returning the magnesium-based IDA resin to step (1) to replace the sodium-based IDA resin to continue the adsorption treatment of nickel ions and cobalt ions in the pre-treated laterite slurry.

[0056] Example 2

[0057] The difference between this embodiment and embodiment 1 is that in step (4), the mass concentration of the magnesium hydroxide emulsion is 0.5%, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:20, and the magnesium excess coefficient is 1.7.

[0058] Example 3

[0059] The difference between this embodiment and embodiment 1 is that in step (4), the mass concentration of the magnesium hydroxide emulsion is 5%, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:5, and the magnesium excess coefficient is 4.25.

[0060] Example 4

[0061] The difference between this embodiment and embodiment 1 is that in step (4), the mass concentration of the magnesium hydroxide emulsion is 1%, and the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:8, and the magnesium excess coefficient is 1.36.

[0062] Example 5

[0063] The difference between this embodiment and embodiment 2 is that in step (4), the mass concentration of the magnesium hydroxide emulsion is 0.2% and the magnesium excess coefficient is 0.68.

[0064] Example 6

[0065] The difference between this embodiment and embodiment 1 is that in step (4), the volume ratio of hydrogen-based IDA resin to magnesium hydroxide emulsion is 1:0.5, and the magnesium excess coefficient is 0.85.

[0066] Example 7

[0067] The difference between this embodiment and embodiment 1 is that the pH value of the dilute sulfuric acid solution in step (2) is 2.5.

[0068] Example 8

[0069] The difference between this embodiment and embodiment 1 is that step (2) is not performed, and the nickel-cobalt adsorbed IDA resin is directly subjected to acid desorption using a concentrated sulfuric acid solution with a mass concentration of 300 g / L.

[0070] Comparative Example 1

[0071] The difference between this comparative example and Example 1 is that steps (4) to (5) are not performed, and the hydrogen-based IDA resin is directly returned to step (1) to replace the sodium-based IDA resin to continue the adsorption treatment of nickel ions and cobalt ions in the pretreated laterite slurry.

[0072] Comparative Example 2

[0073] The difference between this comparative example and Example 1 is that in step (4), calcium hydroxide emulsion with a mass concentration of 10% is used to replace magnesium hydroxide emulsion, and the calcium excess coefficient is 13.5.

[0074] Test Example 1

[0075] The adsorption capacities (mg / mL resin) of the magnesium-based IDA resins provided in Examples 1 to 8, the hydrogen-based IDA resins or the calcium-based IDA resins provided in Comparative Examples 1 to 2 for cobalt ions and nickel ions were measured respectively. The results are shown in Table 2 below.

[0076] In addition, the concentrations (mg / L) of nickel ions and cobalt ions in the adsorbed laterite slurry obtained after adsorption treatment of the pretreated laterite slurry by the magnesium-based IDA resin provided in Examples 1 to 8, the hydrogen-based IDA resin provided in Comparative Examples 1 to 2, or the calcium-based IDA resin were also measured, and the results are shown in Table 2 below.

[0077] Table 2

[0078]

[0079] Example 9

[0080] This embodiment provides an adsorption method for a slurry in a pretreatment process of laterite ore. The concentrations of main metal ions in the pretreatment laterite ore slurry are shown in Table 3 below.

[0081] Table 3 Concentration of main metal ions in the feed solution during pretreatment of laterite ore (mg / L)

[0082]

[0083] The specific steps of the adsorption method are as follows:

[0084] (1) passing the pre-treated laterite ore process liquid through a sodium-based IDA resin column to adsorb nickel ions and cobalt ions and then sieving to obtain a nickel-cobalt adsorbed IDA resin and a laterite ore slurry after adsorption;

[0085] (2) washing the nickel-cobalt adsorbed IDA resin with a dilute sulfuric acid solution to obtain a washed IDA resin, wherein the pH of the dilute sulfuric acid solution is 2;

[0086] (3) acid desorption of the washed IDA resin using a concentrated sulfuric acid solution with a mass concentration of 50 g / L to obtain a hydrogen-based IDA resin;

[0087] (4) mixing hydrogen-based IDA resin and magnesium hydroxide emulsion, performing magnesium soap transformation, and then screening to obtain magnesium-based IDA resin; wherein the mass concentration of magnesium hydroxide emulsion is 1%, and the volume ratio of hydrogen-based IDA resin to magnesium hydroxide emulsion is 1:10, and the magnesium excess coefficient is 1.7;

[0088] (5) The magnesium-based IDA resin is returned to step (1) to replace the sodium-based IDA resin to continue the adsorption treatment of nickel ions and cobalt ions in the pretreatment process of the laterite ore feed liquid.

[0089] Comparative Example 3

[0090] The difference between this comparative example and Example 9 is that steps (4) to (5) are not performed, and the hydrogen-based IDA resin is directly returned to step (1) to replace the sodium-based IDA resin to continue the adsorption treatment of nickel ions and cobalt ions in the pretreated laterite slurry.

[0091] Comparative Example 4

[0092] The difference between this comparative example and Example 9 is that in step (4), calcium hydroxide emulsion with a mass concentration of 10% is used to replace magnesium hydroxide emulsion.

[0093] Test Example 2

[0094] As in the previous Experimental Example 1, the concentrations (mg / L) of nickel ions and cobalt ions in the adsorbed laterite slurry obtained after pre-treatment with the magnesium-based IDA resin provided in Example 9, the hydrogen-based IDA resin provided in Comparative Examples 4 to 6, the calcium-based IDA resin or the sodium-based IDA resin were respectively determined, and the results are shown in Table 4 below.

[0095] Table 4

[0096]

[0097] From the above description, it can be seen that the above-mentioned embodiments of the present invention achieve the following technical effects: the magnesium hydroxide emulsion provided in the present application is used as a saponifier in the saponification transformation of the hydrogen-based IDA resin, and the hydrogen-based IDA resin is transformed into a magnesium-based IDA resin. The magnesium-based IDA resin is used for the adsorption of nickel-cobalt-containing liquid. While ensuring a high adsorption capacity of nickel ions and cobalt ions, it can also avoid precipitation in the system, and can also be used in a stirring process or a column process at the same time, and is easy to perform resin screening, which can effectively extend the service life of the resin.

[0098] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for regenerating nickel-cobalt adsorbed IDA resin, characterized in that: The regeneration method comprises: Step S1, subjecting the nickel-cobalt adsorbed IDA resin to acid desorption to obtain hydrogen-based IDA resin and nickel-cobalt desorption solution; Step S2, mixing the hydrogen-based IDA resin with a saponifier, performing magnesium soap transformation, and then screening to obtain a magnesium-based IDA resin, wherein the saponifier is magnesium hydroxide emulsion; The step S1 comprises: Step S11, washing the nickel-cobalt adsorbed IDA resin with a weak acid solution to obtain a washed IDA resin; the weak acid solution is a dilute sulfuric acid solution with a pH of 0.5 to 2.5; Step S12, using a strong acid solution to perform acid desorption on the washed IDA resin to obtain the hydrogen-based IDA resin; the strong acid solution is an acid solution with a concentration of 50-300 g / L; The mass concentration of the magnesium hydroxide emulsion is 0.5-10%; During the transformation of the magnesium soap, the magnesium excess coefficient is 1.25-30.

2. The regeneration method according to claim 1, characterized in that: The mass concentration of the magnesium hydroxide emulsion is 1-10%.

3. The regeneration method according to claim 1, characterized in that: In the step S2, the volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:(4-20).

4. The regeneration method according to claim 3, characterized in that: The volume ratio of the hydrogen-based IDA resin to the magnesium hydroxide emulsion is 1:(4-10).

5. The regeneration method according to claim 1, characterized in that: During the transformation of the magnesium soap, the magnesium excess coefficient is 1.5-20.

6. The regeneration method according to claim 1, characterized in that: The strong acid solution is selected from at least one of sulfuric acid, hydrochloric acid or nitric acid.

7. The regeneration method according to any one of claims 1 to 5, characterized in that: The step S1, the preparation method of the nickel-cobalt adsorbing IDA resin comprises: passing a nickel-cobalt-containing sulfuric acid solution into a sodium-based IDA resin for adsorbing nickel ions and cobalt ions to obtain the nickel-cobalt adsorbing IDA resin.

8. The regeneration method according to claim 7, characterized in that: The sodium-based IDA resin is a resin containing an IDA functional group.

9. The regeneration method according to claim 8, characterized in that: The grades of the sodium-based IDA resin are S390, M4195, IRC748, SR-5 or TP207.

10. The regeneration method according to claim 7, characterized in that: The nickel-cobalt-containing sulfuric acid solution is a pretreated laterite slurry.

11. The regeneration method according to claim 10, characterized in that: The pretreated laterite slurry is obtained by sequentially subjecting laterite nickel ore to acid leaching, neutralization to remove iron and aluminum, and solid-liquid separation.

12. The regeneration method according to claim 7, characterized in that: The magnesium-based IDA resin is used for adsorption of nickel-cobalt-containing sulfuric acid solution.

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