WO2024036914A1

WO2024036914A1 - Washing technological process for increasing nickel-cobalt separation rate of nickel adsorption resin

Info

Publication number: WO2024036914A1
Application number: PCT/CN2023/078841
Authority: WO
Inventors: 马永刚; 黄善富
Original assignee: 上海锦源晟新能源材料有限公司
Priority date: 2022-08-19
Filing date: 2023-02-28
Publication date: 2024-02-22
Also published as: CN115341105A

Abstract

A washing technological process for increasing the nickel-cobalt separation rate of a nickel adsorption resin. The washing technological process comprises the following steps: (1) introducing a nickel-cobalt sulfate solution containing impurities into a resin column for adsorption treatment until the resin column reaches adsorption saturation, and then obtaining a saturated resin column and an adsorption tail liquid; (2) after a nickel sulfate solution is used and the pH value is adjusted, washing the saturated resin column in step (1) to obtain a liquid after washing, the liquid after washing being combined with the nickel-cobalt sulfate solution containing impurities in step (1); and (3) resolving the washed resin column by using sulfuric acid to obtain a finished nickel sulfate solution, and returning the finished nickel sulfate solution in step (3) to step (2) to replace the nickel sulfate solution to wash the saturated resin column in step (1). The technological process increases the nickel-cobalt separation rate of the nickel adsorption resin, reduces cobalt adsorption entrainment, and does not introduce new impurity elements into the system.

Description

A washing process method to improve the nickel and cobalt separation rate of nickel adsorption resin

Technical field

The embodiments of the present application relate to the field of hydrometallurgy, such as a method for separating nickel and cobalt, and in particular, to a washing process method for improving the separation rate of nickel and cobalt from a nickel adsorption resin.

Background technique

In nature, nickel and cobalt often coexist in raw ores. The raw materials for the production of battery-grade cobalt sulfate products are mostly intermediate products in the nickel smelting process. Therefore, in the cobalt salt production process, how to effectively separate nickel and cobalt at low cost has always been a problem. Industry research hot spots.

In recent years, in the smelting process of producing cobalt salt products using crude cobalt hydroxide and nickel cobalt hydroxide as raw materials, the raw materials are reduced and acid leached with sulfuric acid to obtain a highly miscellaneous cobalt sulfate solution. Among them, the main impact on the production of battery-grade products is Impurity elements are nickel, copper, calcium, magnesium, zinc, manganese, and iron. The content of impurity elements varies depending on the raw materials. For this highly impurity cobalt sulfate solution, most manufacturing companies choose extraction or resin adsorption processes for solution purification, impurity removal and product production.

The extraction method is a relatively mature traditional process. Its general process is: raw material leaching and dissolving → leach liquid extraction, purification and impurity removal → impurity removal liquid extraction to extract cobalt → cobalt extraction liquid to recover nickel. The extraction method has a long production process and high solution purification costs, so some manufacturers have conducted extensive research on resin adsorption methods. In recent years, with the mature grafting application of polymerized amine carboxyl technology in ion exchange resins, the chelating ability of heavy metal ions and the relative selectivity of Cu/Ni/Co/Zn/Fe separation systems have been greatly improved, and many Mixed solutions of metal elements can be easily separated through a single process. Based on breakthroughs in resin technology and combined with the content characteristics of impurity elements in the raw materials, an adsorption resin with large adsorption saturation capacity and high selectivity can be used to separate and enrich nickel and cobalt directly from the raw material leachate using the resin method, thus saving a lot of impurity removal time. Process costs.

The general process flow for separating and enriching nickel and cobalt from solution by resin method is: raw material leaching and dissolving→resin separation and enrichment of nickel→resin separation and enrichment of cobalt. Compared with the traditional extraction process, the resin method does not require the purification of iron, calcium, magnesium, manganese, and zinc impurity elements in the solution, and does not require a lengthy oil removal process due to the introduction of oil. Therefore, the resin method is a very competitive development direction in the future nickel and cobalt wet smelting process.

At present, one of the main technical problems in the application of resin method in the treatment of nickel and cobalt solutions is that the adsorption resin has low selectivity for nickel and cobalt. Especially in the nickel adsorption stage, the cobalt content entering the nickel adsorption resin is relatively low. High, which results in a low cobalt direct recovery rate in the whole process and has a certain impact on the quality of the product nickel sulfate solution.

Contents of the invention

The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.

The embodiments of the present application provide a washing process method for improving the nickel and cobalt separation rate of the nickel adsorption resin. The process method improves the nickel and cobalt separation rate of the nickel adsorption resin and reduces the cobalt adsorption entrainment without introducing new impurity elements into the system.

The embodiment of the present application provides a washing process method for improving the nickel and cobalt separation rate of nickel adsorption resin. The process method includes the following steps:

(1) Pass the nickel cobalt sulfate solution containing impurities into a resin column for adsorption treatment until the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) After using the nickel sulfate solution and adjusting the pH, wash the saturated resin column described in step (1) to obtain a washed liquid, which is mixed with the impurity-containing nickel cobalt sulfate solution described in step (1) merge;

(3) Use sulfuric acid to analyze the washed resin column to obtain a finished nickel sulfate solution;

The finished nickel sulfate solution in step (3) is returned to step (2) to replace the nickel sulfate solution to wash the saturated resin column in step (1).

In this application, in view of the characteristics of the adsorption resin selected for the separation and enrichment of nickel and cobalt in high-impurity nickel and cobalt sulfate solutions, it is proposed that the nickel adsorption resin's analytical solution, nickel sulfate finished product, is used as a wash for the nickel adsorption resin after adding alkali to adjust the pH. , washing can replace the raw material residue in the gaps of the nickel adsorption resin, and at the same time, it can replace the cobalt adsorbed by the nickel adsorption resin, thereby improving the nickel-cobalt separation rate and greatly reducing the cobalt content in the nickel finished liquid.

As the preferred technical solution of this application, the flow rate of the nickel cobalt sulfate solution containing impurities in step (1) is 15-25BV/h, such as 16BV/h, 17BV/h, 18BV/h, 19BV/h, 20BV/h , 21BV/h, 22BV/h, 23BV/h or 24BV/h, etc., but are not limited to the listed values, other unlisted values within this range are also applicable.

As a preferred technical solution of the present application, when the Ni content in the effluent of the resin column in step (1) is lower than 0.01g/L, the resin column is adsorbed saturated.

As the preferred technical solution of this application, the dosage of the nickel sulfate solution in step (2) is 1.5~2.5BV, such as 1.6BV/h, 1.7BV/h, 1.8BV/h, 1.9BV/h, 2.0BV/h , 2.1BV/h, 2.2BV/h, 2.3BV/h or 2.4BV/h, etc., but are not limited to the listed values, other unlisted values within this range are also applicable.

As the preferred technical solution of this application, the pH is adjusted to 3.5 to 4.0 in step (2), such as 3.6, 3.7, 3.8 or 3.9, etc., but it is not limited to the listed values. Other unlisted values within this range are the same. Be applicable.

In this application, the pH of the washing liquid in step (2) is controlled to be 3.5 to 4.0. At this time, the nickel adsorption resin has the greatest separation rate of nickel and cobalt. At the same time, through washing, the residual raw material solution in the resin gaps will be replaced with the finished nickel sulfate solution. , Therefore, it will not cause impurity pollution to the system, and the wash water will be returned to merge with the raw materials, without causing cobalt efflux loss.

As the preferred technical solution of this application, the flow rate of the nickel sulfate solution in step (2) is 1 to 3BV/h, such as 1.2BV/h, 1.5BV/h, 1.8BV/h, 2BV/h, 2.2BV/h , 2.5BV/h or 2.8BV/h, etc., but it is not limited to the listed values. Other unlisted values within this range are also applicable.

As a preferred technical solution of the present application, the concentration of sulfuric acid in step (3) is 10 to 20wt%, such as 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt% or 19wt% etc., but are not limited to the listed values, and other unlisted values within this range are also applicable.

As the preferred technical solution of this application, the flow rate of sulfuric acid in step (3) is 1 to 3BV/h, such as 1.2BV/h, 1.5BV/h, 1.8BV/h, 2BV/h, 2.2BV/h, 2.5 BV/h or 2.8BV/h, etc., but are not limited to the listed values, other unlisted values within this range are also applicable.

As the preferred technical solution of this application, the pH of the finished nickel sulfate solution in step (3) is 1.5 to 2.0, such as 1.6, 1.7, 1.8 or 1.9, etc., but is not limited to the listed values. There are other values within this range. The same applies to the listed values.

As the preferred technical solution of this application, the above-mentioned washing process method for improving the nickel and cobalt separation rate of nickel adsorption resin includes the following steps:

(1) Pass the nickel cobalt sulfate solution containing impurities into the resin column at a flow rate of 15 to 25 BV/h for adsorption treatment. When the Ni content in the effluent of the resin column is less than 0.01g/L, the resin column The adsorption is saturated to obtain a saturated resin column and adsorption tail liquid;

(2) Use 1.5~2.5BV nickel sulfate solution and adjust the pH to 3.5~4.0, then wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 1~3BV/h to obtain washing. back liquid, the washed liquid is combined with the impurity-containing nickel cobalt sulfate solution described in step (1);

(3) Use sulfuric acid with a concentration of 10 to 20 wt% to analyze the resin column after washing. The flow rate of the sulfuric acid is 1 to 3 BV/h to obtain a finished nickel sulfate solution. The pH of the finished nickel sulfate solution is is 1.5~2.0;

Compared with related technologies, the embodiments of the present application at least have the following beneficial effects:

Other aspects will be apparent after reading and understanding the drawings and detailed description.

Description of drawings

The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solutions herein, and do not constitute a limitation of the technical solutions herein.

Figure 1 is a schematic flow chart of a washing process method for improving the nickel and cobalt separation rate of nickel adsorption resin provided by the specific embodiment of the present application.

This application is described in further detail below. However, the following examples are only simple examples of this application and do not represent or limit the scope of protection of this application. The scope of protection of this application shall be determined by the claims.

Detailed ways

In order to better explain the present application and facilitate understanding of the technical solution of the present application, the process is shown in Figure 1. Typical but non-limiting embodiments of the present application are as follows:

Example 1

This embodiment provides a washing process method for improving the nickel and cobalt separation rate of nickel adsorption resin. The process method includes the following steps:

Table 1

(1) Pass 1000 mL of nickel cobalt sulfate solution containing impurities (the element content is shown in Table 1) into the resin column at a flow rate of 15 BV/h for adsorption treatment until the Ni content in the effluent from the resin column is less than 0.01g. /L, the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) Use 2.0BV nickel sulfate solution and adjust the pH to 3.5, then wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 2BV/h to obtain a washed liquid. The back liquid is combined with the impurity-containing nickel cobalt sulfate solution described in step (1);

(3) Use 15wt% sulfuric acid to analyze the resin column after washing. The flow rate of the sulfuric acid is 2BV/h to obtain a finished nickel sulfate solution. The pH of the finished nickel sulfate solution is 1.5 to 2.0. ;

Example 2

(1) Pass 1000 mL of nickel cobalt sulfate solution containing impurities (element content is shown in Table 1) into the resin column at a flow rate of 20 BV/h for adsorption treatment until the Ni content in the effluent from the resin column is less than 0.01g. /L, the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) After using 2.5BV nickel sulfate solution and adjusting the pH to 4.0, wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 3BV/h to obtain a washed liquid. The back liquid is combined with the impurity-containing nickel cobalt sulfate solution described in step (1);

(3) Use 20wt% sulfuric acid to analyze the resin column after washing. The flow rate of the sulfuric acid is 3BV/h to obtain a finished nickel sulfate solution. The pH of the finished nickel sulfate solution is 1.5 to 2.0. ;

Example 3

(1) Add 1000 mL of nickel cobalt sulfate solution containing impurities (element content is shown in Table 1) at a flow rate of 15BV/h is passed into the resin column for adsorption treatment. When the Ni content in the effluent of the resin column is lower than 0.01g/L, the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) Use 1.5BV nickel sulfate solution and adjust the pH to 3.5, then wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 1BV/h to obtain a washed liquid. The back liquid is combined with the impurity-containing nickel cobalt sulfate solution described in step (1);

(3) Use 10wt% sulfuric acid to analyze the resin column after washing. The flow rate of the sulfuric acid is 1BV/h to obtain a finished nickel sulfate solution. The pH of the finished nickel sulfate solution is 1.5 to 2.0. ;

Example 4

Table 2

(1) Pass 1000 mL of nickel cobalt sulfate solution containing impurities (element content is shown in Table 2) into the resin column at a flow rate of 25BV/h for adsorption treatment until the Ni content in the effluent from the resin column is less than 0.01g. /L, the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) After using 2.0BV nickel sulfate solution and adjusting the pH to 4.0, wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 2BV/h to obtain a washed liquid. The back liquid is combined with the impurity-containing nickel cobalt sulfate solution described in step (1);

Example 5

In this example, except for the nickel cobalt sulfate solution containing impurities (the element content is shown in Table 2), the remaining conditions are the same as Example 2.

Example 6

In this example, except for the nickel cobalt sulfate solution containing impurities (element content is shown in Table 2), the remaining conditions are the same as Example 3.

Comparative example 1

In this comparative example, except for the use of deionized water in the washing process in step (2), the remaining conditions are the same as in Example 1.

Comparative example 2

In this comparative example, the other conditions are the same as those in Example 1 except that the washing treatment in step (2) is not carried out and the analysis treatment is directly carried out.

Comparative example 3

In this comparative example, except for the use of deionized water in the washing process in step (2), the remaining conditions are the same as in Example 4.

Comparative example 4

In this comparative example, the other conditions are the same as those in Example 4 except that the washing treatment in step (2) is not carried out and the analysis treatment is carried out directly.

The elemental composition of the analyzed nickel sulfate solution obtained from step (2) of Examples 1-6 and Comparative Examples 1-4 by washing the finished nickel sulfate solution obtained in step (3) and the nickel adsorption liquid was tested. And the results are shown in Table 3 and Table 4 respectively.

Analysis results of nickel sulfate solutions obtained in Table 3 Examples and Comparative Examples

Table 4 Analysis results of post-adsorption liquid obtained in Examples and Comparative Examples

It can be seen from the test results in Table 3 and Table 4 that the washing process method for improving the nickel and cobalt separation rate of the nickel adsorption resin provided in Examples 1-6 can improve the nickel and cobalt separation rate of the nickel adsorption resin and reduce the cobalt adsorption entrainment. Compared with Example 1, Comparative Examples 1 and 2 use deionized water for washing or do not perform the washing treatment of step (2), resulting in a higher cobalt content in the analytical nickel sulfate solution and a lower nickel-cobalt separation rate; Comparative Examples 1 and 3 and The results of 4 compared to Example 4 are the same as the conclusions of Comparative Examples 1 and 2 above.

The applicant declares that this application illustrates the detailed structural features of the present application through the above embodiments, but the present application is not limited to the above detailed structural features, that is, it does not mean that the present application must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvements to the present application, equivalent replacements of the components selected in the present application, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present application.

The preferred embodiments of the present application have been described in detail above. However, the present application is not limited to the specific details in the above-mentioned embodiments. Within the scope of the technical concept of the present application, a variety of simple modifications can be made to the technical solutions of the present application. These simple modifications All fall within the protection scope of this application.

In addition, it should be noted that each specific technical feature described in the above specific embodiments, As long as there is no conflict, they can be combined in any suitable way. In order to avoid unnecessary repetition, various possible combinations will not be further described in this application.

In addition, any combination of various embodiments of the present application can also be carried out. As long as they do not violate the idea of the present application, they should also be regarded as the contents disclosed in the present application.

Claims

A washing process method for improving the nickel and cobalt separation rate of nickel adsorption resin, which includes the following steps:

(1) Pass the nickel cobalt sulfate solution containing impurities into a resin column for adsorption treatment until the resin column is adsorbed saturated to obtain a saturated resin column and adsorption tail liquid;

(2) After using the nickel sulfate solution and adjusting the pH, wash the saturated resin column described in step (1) to obtain a washed liquid, which is mixed with the impurity-containing nickel cobalt sulfate solution described in step (1) merge;

(3) Use sulfuric acid to analyze the washed resin column to obtain a finished nickel sulfate solution;

The finished nickel sulfate solution in step (3) is returned to step (2) to replace the nickel sulfate solution to wash the saturated resin column in step (1).
The process method according to claim 1, wherein the flow rate of the nickel cobalt sulfate solution containing impurities in step (1) is 15-25 BV/h.
The process method according to claim 1 or 2, wherein when the Ni content in the effluent of the resin column in step (1) is lower than 0.01g/L, the resin column is adsorbed saturated.
The process method according to any one of claims 1 to 3, wherein the dosage of the nickel sulfate solution in step (2) is 1.5 to 2.5 BV.
The process according to any one of claims 1 to 4, wherein the pH in step (2) is adjusted to 3.5-4.0.
The process method according to any one of claims 1 to 5, wherein the flow rate of the nickel sulfate solution in step (2) is 1 to 3 BV/h.
The process according to any one of claims 1 to 6, wherein the concentration of sulfuric acid in step (3) is 10 to 20 wt%.
The process method according to any one of claims 1 to 7, wherein the flow rate of sulfuric acid in step (3) is 1 to 3 BV/h.
The process method according to any one of claims 1 to 8, wherein the pH of the finished nickel sulfate solution in step (3) is 1.5 to 2.0.
The process according to any one of claims 1-9, which includes the following steps:

(1) Pass the nickel cobalt sulfate solution containing impurities into the resin column at a flow rate of 15 to 25 BV/h for adsorption treatment. When the Ni content in the effluent of the resin column is less than 0.01g/L, the resin column The adsorption is saturated to obtain a saturated resin column and adsorption tail liquid;

(2) Use 1.5~2.5BV nickel sulfate solution and adjust the pH to 3.5~4.0, then wash the saturated resin column described in step (1). The flow rate of the nickel sulfate solution is 1~3BV/h to obtain washing. The back liquid is combined with the nickel cobalt sulfate solution containing impurities described in step (1);

(3) Use sulfuric acid with a concentration of 10 to 20 wt% to analyze the resin column after washing. The flow rate of the sulfuric acid is 1 to 3 BV/h to obtain a finished nickel sulfate solution. The pH of the finished nickel sulfate solution is is 1.5~2.0;

The finished nickel sulfate solution in step (3) is returned to step (2) to replace the nickel sulfate solution to wash the saturated resin column in step (1).