Preparation method of battery-grade nickel raw material

Abstract

The invention provides a preparation method of a battery-grade nickel raw material, and the preparation method comprises the following steps: (1) carrying out impurity removal leaching treatment on a nickel-containing material, carrying out neutralization iron and aluminum removal treatment to obtain an impurity-removed leaching solution, and carrying out first resin adsorption treatment on the impurity-removed leaching solution to obtain a nickel solution without copper, iron and chromium; (2) carrying out second resin adsorption treatment on the nickel solution without copper, iron and chromium, and carrying out desorption treatment on the obtained resin to obtain a nickel-rich salt solution; and (3) performing extraction and purification treatment on the nickel-rich salt solution to obtain a nickel-loaded organic phase, performing acid pickling on the nickel-loaded organic phase, and performing reverse extraction treatment to obtain the battery-grade nickel raw material. The preparation method for preparing the battery-grade nickel raw material from the laterite-nickel ore is simple in process, high in production efficiency, low in cost and environmentally friendly, and the obtained battery-grade nickel raw material is high in purity; the method solves the problems of high production cost, low efficiency and serious pollution caused by a complicated laterite-nickel ore recovery industrialization process and a large amount of water when the leachate is directly subjected to nickel-cobalt co-extraction.

Description

Technical Field

[0001] This invention belongs to the field of battery materials technology and relates to a method for preparing battery-grade nickel raw materials. Background Technology

[0002] Driven by the demand for long-range driving in new energy vehicles, ternary NCM / NCA lithium batteries (nickel-cobalt-manganese lithium batteries / nickel-cobalt-aluminum lithium batteries) are expected to gradually surpass lithium iron phosphate batteries in market share. To ensure the supply of nickel and cobalt resources for the new energy industry, laterite nickel ore has become a key area of ​​mining worldwide.

[0003] Currently, the general process for producing laterite nickel ore both domestically and internationally involves high-pressure leaching followed by multi-stage neutralization to remove iron and aluminum, resulting in a leaching solution after iron and aluminum removal. This solution is then subjected to multi-stage precipitation of metallurgical impurities (MHP) to obtain the intermediate nickel-cobalt product, MHP. The MHP undergoes pulping, acid dissolution, and further iron and aluminum removal to obtain a purified nickel-cobalt leaching solution. This leaching solution is then subjected to a P204 impurity extraction, P507 cobalt and magnesium extraction, C272 deep impurity removal, and crystallization back-dissolution process to finally obtain high-purity battery-grade nickel raw materials. Clearly, this process is not only cumbersome, environmentally unfriendly, and energy-intensive, but also consumes large quantities of various auxiliary materials, such as large amounts of liquid alkali during MHP precipitation, lime slurry for impurity removal in the MHP leaching solution, flocculants for solid-liquid separation, large amounts of acids and alkalis consumed in each extraction stage, and large amounts of activated carbon for TOC treatment.

[0004] To simplify the process of extracting battery-grade nickel-cobalt raw materials from laterite nickel ore and further reduce costs and increase efficiency, existing technologies directly perform nickel-cobalt co-extraction from the iron-aluminum removal solution of laterite nickel ore. The resulting mixed solution is then purified to obtain a battery-grade nickel-cobalt solution. Regarding laterite nickel ore, existing technologies have proposed several validated nickel-cobalt co-extraction techniques and corresponding processes, which have also solved the problem of manganese third-phase formation during co-extraction. However, when co-extraction technology is industrialized, the nickel concentration in the leachate after iron-aluminum removal from laterite nickel ore is low (3g / L-4.5g / L). Direct co-extraction results in a large water volume in the extraction tank, leading to significant extractant loss and high oil processing pressure. These issues not only affect the production efficiency, cost, and environmental friendliness of the co-extraction technology but also impose higher requirements on the production plant area and investment costs. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing battery-grade nickel raw materials. The method for preparing battery-grade nickel raw materials from laterite nickel ore described in this invention solves various problems in the current industry, such as the cumbersome industrial process for recovering battery-grade nickel from laterite nickel ore, and the high production costs, low efficiency, and high pollution caused by the large amount of water required for direct nickel-cobalt co-extraction using laterite nickel ore leaching and impurity removal solutions.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing battery-grade nickel raw materials, the method comprising the following steps:

[0008] (1) After the nickel-containing material is subjected to impurity removal leaching treatment, the impurity removal leaching solution is obtained by neutralization and iron and aluminum removal treatment. The impurity removal leaching solution is subjected to first resin adsorption treatment to obtain a nickel solution with copper, iron and chromium removed.

[0009] (2) The nickel solution after removing copper, iron and chromium is subjected to a second resin adsorption treatment, and the obtained resin is subjected to desorption treatment to obtain a nickel-rich salt solution.

[0010] (3) Extract and purify the nickel-rich salt solution to obtain a nickel-loaded organic phase. After acid washing, the nickel-loaded organic phase is back-extracted to obtain battery-grade nickel raw material.

[0011] The battery-grade nickel raw material prepared according to this invention does not require the use of sodium hydroxide, significantly reducing the preparation cost of nickel raw materials. High-purity battery-grade nickel raw materials can be prepared from nickel-containing leachates containing various and numerous impurities in a short time using a simple method.

[0012] Preferably, the nickel-containing material in step (1) includes laterite nickel ore.

[0013] Preferably, the impurity removal leaching agent in step (1) includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, or nitric acid.

[0014] Preferably, the neutralizing agent used in the neutralization and removal of iron and aluminum includes any one or a combination of at least two of limestone, lime milk, or magnesium oxide.

[0015] Preferably, the pH of the impurity removal leachate in step (1) is 5 to 5.5, for example: 5, 5.1, 5.2, 5.3, 5.4 or 5.5, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0016] Preferably, the first resin adsorption treatment in step (1) includes column adsorption.

[0017] Preferably, the resin used in the first resin adsorption treatment in step (1) includes any one or a combination of at least two of LSC-930, D854, D851, CH-90Na, CXO-18, HP606 or HP4080.

[0018] The first resin adsorption treatment of the present invention can adsorb impurity ions such as copper, iron and chromium in the leachate to obtain a nickel-rich solution with low impurity content.

[0019] Preferably, the column flow rate of the first resin adsorption treatment in step (1) is 0.5 BV / h to 10 BV / h, for example: 0.5 BV / h, 1 BV / h, 2 BV / h, 5 BV / h, 8 BV / h or 10 BV / h, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0020] Preferably, in step (1), the number of resin series stages in the first resin adsorption treatment is 1 to 20, for example: 1 stage, 2 stages, 5 stages, 10 stages, 15 stages or 20 stages, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0021] Preferably, during the first resin adsorption process in step (1), adsorption is stopped when the total mass concentration of Cu, Fe and Cr elements in the adsorption tail liquid is >0.2 mg / L.

[0022] Preferably, in step (1), the resin is desorbed and recycled after the first adsorption treatment.

[0023] Preferably, the desorbent used in the desorption and recovery treatment includes hydrochloric acid with a mass concentration of 5% to 40%.

[0024] Preferably, after the desorption and recovery treatment, the obtained desorption resin is rinsed until the pH of the effluent is greater than 0.5.

[0025] Preferably, the second resin adsorption treatment in step (2) includes column adsorption.

[0026] Preferably, the resin used in step (2) the second resin adsorption treatment includes LSC-495 and / or DZ851.

[0027] This invention uses specific LSC-495 and / or DZ851 to adsorb nickel salts onto resin, and then desorbs the resin to obtain a nickel salt solution with high purity.

[0028] Preferably, the column flow rate of the second resin adsorption treatment in step (2) is 0.5 BV / h to 30 BV / h, for example: 0.5 BV / h, 1 BV / h, 5 BV / h, 10 BV / h, 20 BV / h or 30 BV / h, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0029] Preferably, in step (2), the number of resin series stages in the second resin adsorption treatment is 1 to 20, for example: 1 stage, 2 stages, 5 stages, 10 stages, 15 stages or 20 stages, etc., not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0030] Preferably, in step (2), during the second resin adsorption process, adsorption is stopped when the mass concentration of Ni in the adsorption tail liquid is >1 mg / L.

[0031] Preferably, the resin is washed before the desorption process in step (2).

[0032] Preferably, the flow rate of the washing process is 0.5 BV / h to 40 BV / h, for example: 0.5 BV / h, 5 BV / h, 10 BV / h, 20 BV / h, 30 BV / h or 40 BV / h, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0033] Preferably, the detergent used in the washing process includes distilled water, industrial water, and H2O. + Acidic solutions with a concentration of 0.0001 mol / L to 0.01 mol / L or containing Ni 2+ Any one or a combination of at least two of the following aqueous solutions with a mass concentration of <1 mg / L.

[0034] Preferably, the desorbent used in step (2) includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, or nitric acid. Typical but non-limiting combinations include combinations of sulfuric acid and hydrochloric acid, combinations of sulfuric acid and nitric acid, or combinations of hydrochloric acid and nitric acid.

[0035] Preferably, the mass concentration of the desorbent used in step (2) is 5% to 25%, for example: 5%, 10%, 15%, 20% or 25%, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0036] Preferably, during the desorption process described in step (2), desorption is stopped when the pH of the desorbed solution is greater than 1.5.

[0037] The extraction and purification process in step (3) uses any one or a combination of at least two of the following extractants: UC811, HQ811, DY319, HBL110, or HBL116.

[0038] Preferably, the dilution rate of the extractant used in the extraction and purification process is 10% to 50%, for example: 10%, 20%, 30%, 40% or 50%, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0039] Preferably, the saponification rate of the extractant used in the extraction and purification process is 5% to 60%, for example: 5%, 10%, 32%, 40% or 60%, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0040] Preferably, the diluent used in the extraction and purification process includes kerosene and / or light white oil.

[0041] Preferably, the extraction and purification process has 1 to 9 extraction stages, such as 1, 2, 3, 5 or 9 stages, and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0042] Preferably, the washing stage of the extraction and purification process is 1 to 8 stages, such as 1, 2, 4, 6 or 8 stages, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0043] The acid solution used for pickling in step (3) includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, or nitric acid.

[0044] Preferably, the amount of acid solution added is 2 mol / L to 6 mol / L, for example: 2 mol / L, 3 mol / L, 4 mol / L, 5 mol / L or 6 mol / L, etc., and is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0045] Preferably, the number of stages of the back-extraction process in step (3) is 5 to 8, for example: 5, 6, 7 or 8 stages.

[0046] Preferably, the organic phase obtained from the back-extraction process is washed with water, clarified, and then saponified and recycled to the extraction section.

[0047] Preferably, the water washing process has 1 to 2 stages, for example, stage 1 or stage 2.

[0048] Preferably, the clarification level is 1 to 2 levels, for example, level 1 or level 2.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The preparation method described in this invention is low-cost and environmentally friendly, and can prepare high-purity battery-grade nickel raw materials from nickel-containing leachates containing a variety of impurities without the need for any extraction of organic matter. Detailed Implementation

[0051] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0052] The "range" disclosed in this invention can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of the specific range. This type of range definition can include or exclude endpoints; any endpoint can be independently included or excluded, and they can be arbitrarily combined, meaning any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for specific parameters, it is understood that ranges of 60~110 and 80~120 are also expected. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this invention, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0" and "5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is described as an integer ≥2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc. For instance, when a parameter is described as an integer selected from "2~10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0053] In this invention, "a combination of at least two" refers to a quantity greater than or equal to two, unless otherwise specified. For example, "any combination of one or at least two" means one or more or more items. It can be understood that when referring to "a combination of at least two," it refers to any suitable combination of multiple items, that is, a combination of "at least two" items carried out in a manner that does not conflict with and enables the implementation of this invention.

[0054] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions.

[0055] The term "embodiment" as used in this invention means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of the invention. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a mutually exclusive, independent, or alternative embodiment. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this invention can be combined with other embodiments.

[0056] Those skilled in the art will understand that the order in which the steps are written in the methods of the various embodiments does not imply a strict execution order. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps of the present invention may be performed sequentially or randomly, but are preferably performed sequentially. For example, if the method includes steps (a) and (b), it means that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the method may also include step (c), meaning that step (c) can be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0057] In this invention, open-ended technical features or solutions described using terms such as "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, A includes a1, a2, and a3. Unless otherwise specified, it may also include other members or exclude additional members. This can be considered as providing both technical features or solutions where "A is composed of a1, a2, and a3" or "A is selected from a1, a2, and a3," and technical features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0058] In this invention, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0059] In this invention, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on the quantity.

[0060] In this invention, "optional" means that something is optional, that is, it refers to any one of the two parallel solutions of "having" or "not having". If there are multiple "optional" options in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, then each "optional" option is independent.

[0061] In this invention, "room temperature" generally refers to 4℃~35℃, and can refer to 20℃±5℃. In some embodiments of this invention, room temperature refers to 20℃~30℃.

[0062] The composition of laterite nickel ore used in the embodiments and comparative examples of this invention is shown in Table 1.

[0063] Table 1

[0064]

[0065] Example 1

[0066] This embodiment provides a method for preparing battery-grade nickel raw materials, the preparation method comprising the following steps:

[0067] (1) After leaching lateritic nickel ore with sulfuric acid to remove impurities, limestone was used to remove iron and aluminum, resulting in a leaching solution with a pH of 5.2. The composition of the leaching solution is shown in Table 2.

[0068] Table 2

[0069]

[0070] The leaching solution was subjected to column adsorption treatment using a 5-stage LSC-930 resin. Adsorption was stopped when the Cu / Fe / Cr concentration in the adsorption tail solution was >0.2 mg / L, resulting in a nickel solution with copper, iron, and chromium removed. The composition of the nickel solution with copper, iron, and chromium removed is shown in Table 3.

[0071] Table 3

[0072]

[0073] The flow rate of the impurity-removing leachate through the column is 20 BV / h;

[0074] (2) The nickel solution for removing copper, iron, and chromium was subjected to column adsorption using an 8-stage LSC-495 resin. The flow rate of the nickel solution for removing copper, iron, and chromium was 3 BV / h. Adsorption was stopped when the mass concentration of Ni in the adsorption tail liquid was >1 mg / L. After adsorption, the resin was washed at a flow rate of 6 BV / h with distilled water as the washing agent. After washing, the resin was desorbed using a 15% sulfuric acid solution to obtain a nickel-rich salt solution. The composition is shown in Table 4.

[0075] Table 4

[0076]

[0077] (3) The nickel-rich salt solution obtained in step (2) was extracted with a UC811 extractant system containing a dilution rate of 50%, a saponification rate of 45%, and light white oil as the diluent. The extraction stage was 6 stages and the O / A ratio was 1.4. Then, H was used as the extractant. + A 0.05 mol / L sulfuric acid solution was used to elute Ca, Mg impurities, Co, and Mn from the nickel-loaded organic phase. The washing process consisted of five stages with an O / A ratio of 20:1. The wash water was then transferred to the extraction section for nickel recovery. Finally, H₂O was used... + The washed organic phase was back-extracted using a 6 mol / L sulfuric acid solution. The back-extraction stage was 7 stages with an O / A ratio of 8.5:1, yielding battery-grade nickel feedstock. The composition is shown in Table 5.

[0078] Table 5

[0079]

[0080] After back-extraction, the organic material is washed with water for one stage (O / A ratio of 25), clarified for one stage, and then saponified and recycled to the extraction section.

[0081] Example 2

[0082] This embodiment provides a method for preparing battery-grade nickel raw materials, the preparation method comprising the following steps:

[0083] (1) After leaching laterite nickel ore with sulfuric acid, limestone was used to remove iron and aluminum, resulting in a leaching solution with a pH of 4.8. The composition of the leaching solution is shown in Table 6.

[0084] Table 6

[0085]

[0086] The leaching solution was subjected to column adsorption treatment using D851 resin with a series of 5 stages. Adsorption was stopped when the Cu / Fe / Cr concentration in the adsorption tail liquid was >0.2 mg / L, resulting in a nickel solution with copper, iron, and chromium removed. The composition of the nickel solution with copper, iron, and chromium removed is shown in Table 7. Since the concentrations of Fe, Cr, and Cu in the leaching solution increased, the column flow rate of the leaching solution was reduced to 15 BV / h.

[0087] Table 7

[0088]

[0089] (2) A nickel solution for removing copper, iron, and chromium was subjected to column adsorption using D854 resin with a series stage of 8. The flow rate of the nickel solution for removing copper, iron, and chromium was 2.6 BV / h. Adsorption was stopped when the mass concentration of Ni in the adsorption tail liquid was >1 mg / L. After adsorption, the resin was washed at a flow rate of 6 BV / h with distilled water as the washing agent. After washing, the resin was desorbed using 15% sulfuric acid solution to obtain a nickel-rich salt solution. The composition is shown in Table 8.

[0090] Table 8

[0091]

[0092] (3) From the composition of the nickel-rich salt solution in Table 8, it can be inferred that if the extractant has a stronger selectivity for Al and Zn than for Ni during nickel extraction, then the Al and Zn content in the extracted nickel raw material will significantly exceed the standard, failing to meet the requirements for the preparation of battery cathode materials. Therefore, the HBL110 extractant, which has a stronger selectivity for Ni, was selected. The nickel-rich salt solution obtained in step (2) was extracted using an HBL110 extractant system with a dilution rate of 45%, a saponification rate of 50%, and light white oil as the diluent. The extraction stages were 8, the O / A ratio was 3.2:1, and then H... + A 0.1 mol / L sulfuric acid solution was used to elute Al, Zn, Ca, Mg impurities, as well as Co and Mn, from the nickel-loaded organic phase. The washing process consisted of six stages with an O / A ratio of 20:1. The wash water was then transferred to the extraction section for nickel recovery. Finally, H₂O was used... + The washed organic phase was subjected to segmented back-extraction using a 2.5 mol / L sulfuric acid solution. The back-extraction stage consisted of 3+4 stages, meaning that the back-extraction solution from the last 4 stages was added with 2.5 mol / L sulfuric acid to serve as the back-acid for the first three stages. The O / A ratio for the back-extraction was 14:1, yielding battery-grade nickel raw material with the composition shown in Table 9.

[0093] Table 9

[0094]

[0095] After back-extraction, the organic material is washed with water for one stage (O / A ratio of 25), clarified for one stage, and then saponified and recycled to the extraction section.

[0096] Example 3

[0097] The only difference between this embodiment and Example 1 is that, after leaching the lateritic nickel ore with sulfuric acid, calcium carbonate is used for impurity removal, resulting in a leaching solution with a pH of 5.5, the composition of which is shown in Table 10 below:

[0098] Table 10

[0099]

[0100] All other conditions and parameters were exactly the same as in Example 1, and the final composition of the battery-grade nickel raw material obtained is shown in Table 11 below:

[0101] Table 11

[0102]

[0103] Comparing Examples 1-3, it can be seen that by increasing the endpoint pH during the impurity removal process of laterite nickel ore leaching solution and adding more calcium carbonate, impurities such as Fe, Al, Cr, Zn, Cu and Si in the leaching solution can be reduced to a lower concentration. Therefore, when other conditions of this process remain unchanged, the battery-grade nickel raw material obtained has a lower impurity concentration and higher purity.

[0104] Example 4

[0105] The only difference between this embodiment and Embodiment 1 is that the flow rate of the impurity removal leaching solution through the column is 1 BV / h. All other conditions and parameters are exactly the same as in Embodiment 1. The final composition of the battery-grade nickel raw material is shown in Table 12 below.

[0106] Table 12

[0107]

[0108] If the flow rate of the leaching solution through the column is too slow, the purity of the nickel raw material will not be significantly improved, but the production efficiency for removing copper, iron and chromium will be greatly reduced.

[0109] Example 5

[0110] The only difference between this embodiment and Embodiment 1 is that the flow rate of the impurity removal leaching solution through the column is 80 BV / h. All other conditions and parameters are exactly the same as in Embodiment 1. The final composition of the battery-grade nickel raw material is shown in Table 13 below.

[0111] Table 13

[0112]

[0113] If the flow rate of the leaching solution through the column is too fast, Fe, Cr and Cu will not be completely removed, resulting in a decrease in the purity of the nickel raw material.

[0114] Example 6

[0115] The only difference between this embodiment and Embodiment 1 is that H is used. + A 0.1 mol / L sulfuric acid solution was used to elute Ca, Mg impurities, Co, and Mn from the nickel-loaded organic phase. Other conditions and parameters were exactly the same as in Example 1. The final composition of the battery-grade nickel raw material is shown in Table 14 below.

[0116] Table 14

[0117]

[0118] Increasing the concentration of washing acid can improve the elution rate of Ca and Mg impurities, resulting in higher purity battery-grade nickel raw materials. However, if the washing acid concentration is too high, nickel will also be eluted, and returning the nickel in the washing solution to the extraction section requires additional alkali, thus increasing production costs. Increasing the O / A ratio and the number of washing stages in the washing section can also help to elute impurities.

[0119] Comparative Example 1

[0120] The only difference between this comparative example and Example 1 is that the column adsorption treatment in step (1) is not performed; all other conditions and parameters are exactly the same as in Example 1.

[0121] If the binding force between certain nickel resins and Fe, Cr and Cu is too strong, the Fe, Cr and Cu enriched on the resin will be difficult to desorb, and the cyclic adsorption performance of the resin will be severely damaged. This is the core reason for adding copper, iron and chromium adsorption to the process of this invention.

[0122] Comparative Example 2

[0123] The only difference between this comparative example and Example 1 is that the column adsorption treatment in step (2) is not performed. All other conditions and parameters are exactly the same as in Example 1. The composition of the battery-grade nickel raw material obtained is shown in Table 15 below.

[0124] Table 15

[0125]

[0126] The column adsorption process in step (2) can remove most of the Al, Ca, Mg, and Zn impurities during the purification and enrichment of nickel. If step (2) is not performed and nickel extraction is carried out directly, these impurities in the obtained battery-grade nickel raw material are likely to exceed the standards, and the concentrations of Co and Mn are also not up to standard. If HBL110, an extractant with higher selectivity for Ni than Fe, Al, and Zn, is used for nickel extraction, the concentration of washing acid needs to be increased to strongly wash the impurities in the organic matter. However, the nickel lost in the washing solution during strong washing is returned to the extraction section, which requires the consumption of alkali, thus reducing production efficiency and production costs. Similarly, since Ca is difficult to elute, the removal of Ca also requires increasing the washing intensity.

[0127] Furthermore, if step (2) is not performed, the nickel solution that has undergone iron, chromium and copper removal by resin will directly enter the extraction section, resulting in a huge amount of water in the extraction tank. This will lead to problems such as high loss of extractant and high pressure in oil treatment. These issues not only affect the production efficiency, cost and environmental friendliness of co-extraction technology, but also place higher demands on the production plant area and investment costs.

[0128] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A method for preparing battery-grade nickel raw materials, characterized in that, The preparation method includes the following steps: (1) After the nickel-containing material is subjected to impurity removal leaching treatment, the impurity removal leaching solution is obtained by neutralization and iron and aluminum removal treatment. The impurity removal leaching solution is subjected to first resin adsorption treatment to obtain a nickel solution with copper, iron and chromium removed. (2) The nickel solution after removing copper, iron and chromium is subjected to a second resin adsorption treatment, and the obtained resin is subjected to desorption treatment to obtain a nickel-rich salt solution. (3) Extract and purify the nickel-rich salt solution to obtain a nickel-loaded organic phase. After acid washing, the nickel-loaded organic phase is back-extracted to obtain battery-grade nickel raw material.

2. The preparation method according to claim 1, characterized in that, The nickel-containing material mentioned in step (1) includes laterite nickel ore.

3. The preparation method according to claim 1 or 2, characterized in that, The impurity removal leaching agent in step (1) includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, or nitric acid; Preferably, the neutralizing agent used in the neutralization and iron-aluminum removal process in step (1) includes any one or a combination of at least two of limestone, lime milk, or magnesium oxide; Preferably, the pH of the impurity removal leachate in step (1) is 4.5 to 5.

5.

4. The preparation method according to any one of claims 1-3, characterized in that, Step (1) The first resin adsorption treatment includes column adsorption; Preferably, the resin used in the first resin adsorption treatment in step (1) includes any one or a combination of at least two of LSC-930, D854, D851, CH-90Na, CXO-18, HP606 or HP4080. Preferably, in step (1), the column flow rate of the first resin adsorption treatment is 5 BV / h to 50 BV / h; Preferably, in step (1), the number of resin cascade stages in the first resin adsorption treatment is 1 to 20. Preferably, during the first resin adsorption process in step (1), adsorption is stopped when the total mass concentration of Cu, Fe and Cr elements in the adsorption tail liquid is >0.2 mg / L.

5. The preparation method according to any one of claims 1-4, characterized in that, Step (2) The second resin adsorption treatment includes column adsorption; Preferably, the resin used in step (2) for the second resin adsorption treatment includes LSC-495 and / or DZ851; Preferably, in step (2), the column flow rate for the second resin adsorption treatment is 0.5 BV / h to 30 BV / h; Preferably, in step (2), the number of resin cascade stages in the second resin adsorption treatment is 1 to 20. Preferably, in step (2), during the second resin adsorption process, adsorption is stopped when the mass concentration of Ni in the adsorption tail liquid is >1 mg / L.

6. The preparation method according to any one of claims 1-5, characterized in that, Before the desorption process described in step (2), the resin is washed. Preferably, the flow rate of the washing process is 0.5 BV / h to 40 BV / h; Preferably, the detergent used in the washing process includes distilled water, industrial water, and H2O. + Acidic solutions with a concentration of 0.0001 mol / L to 0.01 mol / L or containing Ni 2+ Any one or a combination of at least two of the following aqueous solutions with a mass concentration of <1 mg / L.

7. The preparation method according to any one of claims 1-6, characterized in that, The desorption agent used in step (2) includes any one of sulfuric acid, hydrochloric acid, or nitric acid; Preferably, the mass concentration of the desorbent used in step (2) is 5% to 25%; Preferably, during the desorption process described in step (2), desorption is stopped when the pH of the desorbed solution is greater than 1.

5.

8. The preparation method according to any one of claims 1-7, characterized in that, The extraction and purification process in step (3) uses any one or a combination of at least two of the following extractants: UC811, HQ811, DY319, HBL110, or HBL116. Preferably, the dilution rate of the extractant used in the extraction and purification process is 10% to 50%; Preferably, the saponification rate of the extractant used in the extraction and purification process is 5% to 60%; Preferably, the diluent used in the extraction and purification process includes kerosene and / or light white oil; Preferably, the extraction and purification process has 1 to 9 extraction stages; Preferably, the number of washing stages in the extraction and purification process is 1 to 8.

9. The preparation method according to any one of claims 1-8, characterized in that, The acid solution used for pickling in step (3) includes any one or a combination of at least two of sulfuric acid, hydrochloric acid, or nitric acid; Preferably, the amount of acid solution added is 2 mol / L to 6 mol / L.

10. The preparation method according to any one of claims 1-9, characterized in that, The number of stages of the back-extraction process in step (3) is 5 to 8.

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