CN113307313A - Preparation method of battery-grade nickel-cobalt sulfate solution - Google Patents
Preparation method of battery-grade nickel-cobalt sulfate solution Download PDFInfo
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- CN113307313A CN113307313A CN202110609986.2A CN202110609986A CN113307313A CN 113307313 A CN113307313 A CN 113307313A CN 202110609986 A CN202110609986 A CN 202110609986A CN 113307313 A CN113307313 A CN 113307313A
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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Abstract
The invention discloses a preparation method of a battery-grade nickel-cobalt sulfate solution, belonging to the technical field of resource recovery of waste lithium batteries. The preparation method of the battery-grade nickel-cobalt sulfate solution at least comprises the following steps: carrying out multiple rounds of first column adsorption and first desorption on the raw material on a first adsorption column, wherein each round of first column adsorption takes deoiled P507 raffinate as the raw material, a first desorption solution obtained in the previous round of first desorption is used as at least part of desorbent in the subsequent round of first desorption process, and the concentration of the first desorption solution is not more than 0.1 equivalent to obtain a nickel-cobalt-magnesium sulfate solution; and adjusting the pH value of the nickel-cobalt-magnesium sulfate solution to be not less than 5, and performing second column adsorption and second desorption on a second adsorption column to obtain the battery-grade nickel-cobalt sulfate solution. Wherein, the resins used for the first column adsorption and the second column adsorption both contain iminodiacetic acid functional groups. The preparation method is simple, short in flow, low in cost, high in efficiency, capable of effectively avoiding the generation of hydrogen sulfide, and green and environment-friendly.
Description
Technical Field
The invention relates to the technical field of resource recovery of waste lithium batteries, in particular to a preparation method of a battery-grade nickel-cobalt sulfate solution.
Background
At present, the P507 raffinate in the cobalt industry is directly precipitated by sodium sulfide, and the nickel sulfate can be obtained only by oxygen pressure leaching, impurity removal and extraction when the nickel sulfide cobalt is generated.
The chemical reaction equations involved in the above process include:
Na2S+CoSO4＝CoS+Na2SO4；
Na2S+NiSO4＝NiS+NiSO4；
NiS+2O2＝NiSO4；
CoS+2O2＝CoSO4。
however, direct precipitation by sodium sulfide results in the production of hydrogen sulfide and the solution being rich in sulfide ions, while excessive sodium sulfide is required, while recovery of nickel sulfide cobalt has a high impurity content and requires a high cost for processing into nickel sulfate.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a battery-grade nickel cobalt sulfate solution, which has the advantages of simplicity, short flow, low cost, high efficiency, capability of effectively avoiding the generation of hydrogen sulfide, and environmental protection.
The application can be realized as follows:
the application provides a preparation method of a battery-grade nickel cobalt sulfate solution, which at least comprises the following steps:
carrying out multiple rounds of first column adsorption and first desorption on the raw material on a first adsorption column, wherein each round of first column adsorption takes deoiled P507 raffinate as the raw material, and a first desorption solution obtained in the previous round of first desorption is used as at least part of desorbent in the subsequent round of first desorption process until the concentration of the first desorption solution is not more than 0.1 equivalent, so as to obtain a nickel-cobalt-magnesium sulfate solution;
adjusting the pH value of the nickel-cobalt-magnesium sulfate solution to be not lower than 5, and then performing second adsorption and second desorption on a second adsorption column to obtain a battery-grade nickel-cobalt sulfate solution;
wherein, the resins used for the first column adsorption and the second column adsorption both contain iminodiacetic acid functional groups.
In an alternative embodiment, the first desorption liquid resulting from the first desorption of the previous round is 25 to 75 wt% of the desorbent used in the first desorption of the subsequent round.
In an optional embodiment, when the pH value of the nickel-cobalt-magnesium sulfate solution needs to be adjusted to exceed 6.5, before the second column adsorption, solid-liquid separation is further performed on the nickel-cobalt-magnesium sulfate solution after the pH adjustment, and the liquid obtained by the separation is subjected to the second column adsorption.
In an alternative embodiment, the resins used for the first column adsorption and the second column adsorption are both macroporous styrene chelating resins containing iminodiacetic acid groups;
in an alternative embodiment, the resin used for both the first column adsorption and the second column adsorption is selected from S930PLUS or blantt S940.
In an alternative embodiment, the pH of the P507 raffinate used for the first column adsorption is 1.5 to 6.5.
In an alternative embodiment, the flow rates of the first column adsorption process and the second column adsorption process are both 300-900 mL/h.
In an alternative embodiment, the desorbent used in the first round of the first desorption process and the second round of the second desorption process is selected from a sulfuric acid solution or a hydrochloric acid solution.
In an alternative embodiment, when the first desorption solution obtained in the first desorption process of the previous round is only used as a part of the desorbent in the first desorption process of the subsequent round, the desorbent used in the first desorption process of the subsequent round further comprises a sulfuric acid solution or a hydrochloric acid solution.
In an alternative embodiment, the first round of first desorption and the second desorption process use a desorbent concentration of 1-4 equivalents.
In an alternative embodiment, the volumes of desorbent used in the first desorption process and the second desorption process are each at least 2 times the volume of resin.
In an alternative embodiment, the flow rate of desorbent in both the first desorption process and the second desorption process is 450 mL/h.
In alternative embodiments, the agent used to adjust the pH of the nickel cobalt magnesium sulfate solution comprises nickel carbonate, cobalt hydroxide, or nickel hydroxide.
The beneficial effect of this application includes:
according to the method, the deoiled P507 raffinate is subjected to resin separation on the first adsorption column, most elements except Ni and Co are removed, and then the Ni and Co adsorbed on the resin are desorbed through desorption liquid, so that the desorption liquid still contains more H+And recycling the partial desorption liquid, and desorbing the P507 raffinate adsorbed by the new round of resin as at least the partial desorption liquid until H in the first desorption liquid is finally obtained+Not higher than 0.1 equivalent, thereby obtaining Ni and Co enriched nickel cobalt magnesium sulfate solution. Furthermore, by adjusting the pH value and then performing second adsorption and second desorption on a second adsorption column, the content of Mg element can be effectively reduced, and the battery-grade nickel cobalt sulfate solution meeting the requirements can be obtained.
The preparation method is simple, short in flow, low in cost, high in efficiency, capable of effectively avoiding the generation of hydrogen sulfide in the prior art, and green and environment-friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a specific description of the preparation method of the battery grade nickel cobalt sulfate solution provided in the present application.
The application provides a preparation method of a battery-grade nickel-cobalt sulfate solution, which at least comprises the following steps:
carrying out multiple rounds of first column adsorption and first desorption on the raw material on a first adsorption column, wherein each round of first column adsorption takes deoiled P507 raffinate as the raw material, and a first desorption solution obtained in the previous round of first desorption is used as at least part of desorbent in the subsequent round of first desorption process until the concentration of the first desorption solution is not more than 0.1 equivalent, so as to obtain a nickel-cobalt-magnesium sulfate solution;
adjusting the pH value of the nickel-cobalt-magnesium sulfate solution to be not less than 5, and then performing second adsorption and second desorption on a second adsorption column to obtain a battery-grade nickel-cobalt sulfate solution (the battery-grade nickel-cobalt sulfate solution can contain a small amount of Mg);
wherein the resins used for the first column adsorption and the second column adsorption both contain iminodiacetic acid functional groups (-CH)2N(CH2CO2-)2)。
In a preferred embodiment, the first desorption solution obtained in the first desorption of the previous round is 25-75 wt% of the desorbent used in the first desorption of the subsequent round, such as 25 wt%, 40 wt%, 50 wt%, 60 wt% or 75 wt%.
For ease of understanding, taking the cycle of the first column adsorption and the first desorption as an example of 3 times, reference may be made to the following:
30L of P507 raffinate is used as a raw material for first-time first column adsorption, an ion exchange column containing imino diacetic acid functional group resin is arranged, the resin selectively adsorbs Co ions and Ni ions, and most of the rest ions are separated from Co ions and Ni ions in the first column adsorption process and are primarily removed. And then carrying out first desorption to desorb Co and Ni ions adsorbed by the resin to obtain a first desorption solution containing Co and Ni ions.
Then, another 30L of P507 raffinate is used as a raw material for the second adsorption of the first column, and the resin also selectively adsorbs Co ions and Ni ions in the ion exchange column, and most of the rest ions are separated from Co ions and Ni ions in the second adsorption of the first column and are primarily removed. And then carrying out second first desorption to obtain a second desorption solution containing Co and Ni ions. The desorbent used in the second first desorption process may be the first desorption liquid obtained after the first desorption, or may be obtained by mixing the first desorption liquid with other desorbents.
By using the first desorption liquid as the second desorption processAt least part of the desorbent in the first stripping solution can make the first stripping solution contain H+Is fully utilized and exchanged.
Then, another 30L of P507 raffinate is used as a raw material for third-time first column adsorption, in the ion exchange column, Co and Ni ions are also selectively adsorbed by the resin, and most of the rest ions are separated from Co and Ni and are primarily removed in the third-time first column adsorption process. And then carrying out third first desorption to obtain a third desorption solution containing Co and Ni ions. The desorbent used in the third first desorption process may be the second desorption liquid obtained after the second first desorption, or may be obtained by mixing the second desorption liquid with other desorbents.
The second desorption liquid can be used as at least part of desorbent in the third first desorption process to enable H contained in the second desorption liquid+Is fully utilized and exchanged.
After the three first column adsorption and first desorption processes, the concentration of the obtained third desorption liquid is not more than 0.1 equivalent. It is to be noted that the equivalent weights referred to in this application are all H+The concentration of the third stripping liquid is understood to mean here that no more than 0.1 equivalent of H is present+It is also understood that 0.1mol/L of H+。
Through the multiple rounds of first column adsorption and first desorption processes, Ni and Co in multiple groups of P507 raffinate raw materials can be enriched in the finally obtained first desorption solution (namely, the nickel-cobalt-magnesium sulfate solution), and most of other elements are effectively removed compared with the elements before passing through the columns.
Because the nickel-cobalt-magnesium sulfate solution still contains higher Mg element, the pH value of the nickel-cobalt-magnesium sulfate solution is adjusted to be not lower than 5, then second column adsorption and second desorption are carried out on the second adsorption column, and the second desorption solution only contains the Mg element with lower content, so that the requirement of the battery-grade nickel-cobalt sulfate solution is met.
It is worth noting that the adjustment of the pH of the nickel-cobalt-magnesium sulfate solution to not less than 5 is divided into two cases, one is adjusted to 5 to 6.5 (containing 6.5), and the other is adjusted to more than 6.5, such as 6.5 to 8. The specific process corresponding to the above different situations is different, when the pH of the nickel-cobalt-magnesium sulfate solution needs to be adjusted to 5-6.5 (containing 6.5), it may be that the nickel-cobalt-magnesium sulfate solution after pH adjustment is directly subjected to the second adsorption and the second desorption. However, after the pH value of the nickel-cobalt-magnesium sulfate solution needs to be adjusted to exceed 6.5, before the second column adsorption, the solid-liquid separation of the nickel-cobalt-magnesium sulfate solution after the pH adjustment is further performed, and then the liquid obtained by the separation is subjected to the second column adsorption.
In the second case, after the pH exceeds 6.5 (especially, the pH is 8-9), part of Ni in the nickel-cobalt-magnesium sulfate solution forms nickel hydroxide precipitate, the part of Ni is separated by solid-liquid separation (which plays a role in recovering part of Ni in P507 raffinate), the remaining liquid still contains higher Mg and also contains part of Ni, and then the remaining liquid is adsorbed by the second column, so that Ni is further adsorbed and separated from Mg, and the final second desorption solution has a high Ni content and almost contains no Mg.
In an alternative embodiment, the pH of the P507 raffinate used for the first column adsorption is 1.5 to 6.5. At a pH below 1.5 or above 6.5, the Ni and Co in the raffinate cannot be adsorbed by the resin.
As a reference, the size of the ion exchange column used in the first column adsorption and the second column adsorption process may be 4cm in diameter and 100cm in height. The amount of resin added to the ion exchange column may be 300 mL.
In an alternative embodiment, the resin used for the first column adsorption and the second column adsorption can be macroporous styrene chelating resin containing iminodiacetic acid groups. For example, both of them may be selected from S930PLUS or bleach S940 (in this case, the case where the first adsorption column and the second adsorption column are the same adsorption column is also included), or one may be selected from S930PLUS and the other may be selected from bleach S940.
In alternative embodiments, the flow rate of the first column adsorption process and the flow rate of the second column adsorption process may be 900mL/h, such as 300mL/h, 400mL/h, 500mL/h, 600mL/h, 700mL/h, 800mL/h, 900mL/h, etc.
In an alternative embodiment, the desorbent used in the first round of the first desorption process and the second desorption process may be selected from a sulfuric acid solution or a hydrochloric acid solution.
When the first desorption solution obtained in the previous round of first desorption is only used as a part of the desorbent in the subsequent round of first desorption, the desorbent used in the subsequent round of first desorption also comprises a sulfuric acid solution or a hydrochloric acid solution.
The first round of the first desorption process and the second desorption process may be referred to as having a desorbent concentration of 1-4 equivalents (e.g., 1 equivalent, 2 equivalents, 3 equivalents, or 4 equivalents, etc.).
The volume of the desorbent used in the first desorption process and the second desorption process is at least 2 times, such as 2 times, 5 times, 8 times or 10 times, etc., of the volume of the resin.
The flow rate of the desorbent used in the first desorption process and the second desorption process may be 450 mL/h.
The reagents used to adjust the pH of the nickel cobalt magnesium sulfate solution include, by reference, nickel carbonate, cobalt hydroxide, or nickel hydroxide. Wherein, when the pH value of the nickel-cobalt-magnesium sulfate solution is required to be adjusted to 5-6.5 (containing 6.5), nickel carbonate or cobalt carbonate is adopted, and other carbonates are not excluded, but the other carbonates have the defect of introducing new elements. When it is desired to adjust the pH of the nickel cobalt magnesium sulphate solution to above 6.5, cobalt hydroxide or nickel hydroxide is used, and similarly, the use of other hydroxides is not excluded, but other hydroxides have the disadvantage of introducing new elements.
The first column adsorption, the first desorption, the second column adsorption and the second desorption processes can be carried out at room temperature. The conditions for the first column adsorption may or may not be the same as the conditions for the second column adsorption (which may include, for example, the specification of the ion exchange column, the type of resin, the amount of resin used, the flow rate through the column, etc.); the conditions for the first desorption may or may not be identical to the conditions for the second desorption (which may include, for example, the type of desorbent, the concentration of desorbent, the volume of desorbent, the flow rate of desorbent, etc.).
Further, the above method provided herein further comprises transforming the second desorbed resin with an alkali solution for recycling.
The above-mentioned alkali solution may be, for example, a 4 wt% NaOH solution. The flow rate of the alkali solution during the transformation may be 450 mL/h. The volume of the alkali solution may be, for example, the same as the volume of the resin or 1.5 times the volume of the resin.
Further, after transformation, the resin was washed with water until the pH was neutral (pH 7-7.5).
Correspondingly, the application provides the battery-grade nickel cobalt sulfate solution prepared by the preparation method.
Further, the application also provides battery-grade nickel cobalt sulfate, which is obtained by evaporating and crystallizing the battery-grade nickel cobalt sulfate solution.
For reference, evaporative crystallization may be carried out at 85 to 100 ℃.
The obtained battery-grade nickel-cobalt sulfate has high purity and meets the relevant standard requirements of batteries.
In the application, most elements except Ni and Co in P507 raffinate are removed by resin separation, and then Ni and Co adsorbed on the resin are desorbed by desorption liquid, wherein the desorption liquid still contains more H+And recycling the partial desorption liquid, and desorbing the P507 raffinate adsorbed by the new round of resin as at least the partial desorption liquid until H in the first desorption liquid is finally obtained+Not higher than 0.1 equivalent, thereby obtaining Ni and Co enriched nickel cobalt magnesium sulfate solution. Furthermore, by adjusting the pH value and then performing second adsorption and second desorption, the content of Mg element can be effectively reduced, and the battery-grade nickel cobalt sulfate solution meeting the requirements can be obtained.
The preparation method is simple, short in flow, low in cost, high in efficiency, capable of effectively avoiding the generation of hydrogen sulfide in the prior art, and green and environment-friendly.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a battery-grade nickel sulfate, which is obtained by evaporating and crystallizing a battery-grade nickel cobalt sulfate solution at 85-100 ℃.
The battery-grade nickel-cobalt sulfate solution is prepared by the following steps:
30L of P507 raffinate was used as a raw material for the first column adsorption, and the first column adsorption was carried out at room temperature on an ion exchange column (. PHI.4 cm. times.100 cm) containing 300mL of S930PLUS resin. The P507 raffinate had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of the P507 raffinate in the first adsorption column was 600 mL/h.
After the first column adsorption, carrying out first desorption on the resin loaded with Ni and Co after the first column adsorption by using a sulfuric acid solution as a desorbent to obtain a first desorption solution containing Co and Ni ions. The volume of the sulfuric acid solution is 2 times of the volume of the resin, the concentration of the sulfuric acid is 2 equivalents, and the flow rate of the sulfuric acid is 450 mL/h.
Another 30L of P507 raffinate was used as the raw material for the second first column adsorption, and the second first column adsorption was performed at room temperature by passing through the above-mentioned ion exchange column containing S930PLUS resin. The P507 raffinate used in the process also had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of P507 raffinate in the second adsorption of the first column was also 600 mL/h.
And (3) taking the first desorption liquid obtained by the first column adsorption as a desorbent, and carrying out second first desorption on the loaded resin adsorbed by the second column to obtain a second first desorption liquid with the concentration not exceeding 0.1 equivalent, namely the nickel-cobalt-magnesium sulfate solution. Wherein the flow rate of the desorbent used in the second first desorption process is 450 mL/h.
Adding nickel carbonate into the nickel cobalt magnesium sulfate solution until the pH value of the nickel cobalt magnesium sulfate solution is 6, and then carrying out second adsorption on the nickel cobalt magnesium sulfate solution, wherein an ion exchange column (phi 4cm multiplied by 100cm) containing 300mL of S930PLUS resin is also used in the second adsorption process, and the flow rate of the nickel cobalt magnesium sulfate solution in the second adsorption process is 600 mL/h.
And then carrying out second desorption on the resin loaded with Ni and Co after the second column adsorption by using sulfuric acid as a desorbent to obtain a second desorption solution (battery-grade nickel-cobalt sulfate solution) containing Co and Ni ions. The volume of the sulfuric acid solution is 2 times of the volume of the resin, the concentration of the sulfuric acid is 2 equivalents, and the flow rate of the sulfuric acid is 450 mL/h.
After the second desorption, the resin was transformed with 4 wt% NaOH at a flow rate of 450mL/h and a volume of 300mL, and then washed with water to neutrality for the next cycle.
In the above process, the content of Co, Ni and Mg in the P507 raffinate as the raw material for the first column adsorption is shown in table 1, the content of Co, Ni and Mg in the nickel-cobalt-magnesium sulfate solution obtained after the first column adsorption and the first desorption is shown in table 2, and the content of Co, Ni and Mg in the battery-grade nickel-cobalt sulfate solution obtained after the second column adsorption and the second desorption is shown in table 3.
TABLE 1
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.012 | 0.43 | 6.41 |
TABLE 2
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.76 | 26.54 | 0.04 |
TABLE 3
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 1.53 | 53.23 | 0.003 |
Example 2
This example provides a battery-grade nickel sulfate, which is obtained by evaporating and crystallizing a battery-grade nickel cobalt sulfate solution at 85-100 ℃.
The battery-grade nickel-cobalt sulfate solution is prepared by the following steps:
30L of P507 raffinate was used as a raw material for the first column adsorption, and the first column adsorption was carried out at room temperature on an ion exchange column (. PHI.4 cm. times.100 cm) containing 300mL of S930PLUS resin. The P507 raffinate had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of the P507 raffinate in the first adsorption column was 600 mL/h.
And after the first column adsorption, performing first desorption on the resin loaded with Ni and Co after the first column adsorption by using a sulfuric acid solution as a desorbent to obtain a first desorption solution containing Co and Niy. The volume of the sulfuric acid solution is 4 times of the volume of the resin, the concentration of the sulfuric acid is 1 equivalent, and the flow rate of the sulfuric acid is 450 mL/h.
Another 30L of P507 raffinate was used as the raw material for the second first column adsorption, and the second first column adsorption was performed at room temperature by passing through the above-mentioned ion exchange column containing S930PLUS resin. The P507 raffinate used in the process also had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of P507 raffinate in the second adsorption of the first column was also 600 mL/h.
And (3) taking the first desorption solution obtained by the first column adsorption as a partial desorbent (specifically 50 wt% of the desorbent in the second first desorption) for the second first desorption, and the balance being sulfuric acid to obtain a second first desorption solution with the concentration not exceeding 0.1 equivalent, namely the nickel-cobalt-magnesium sulfate solution.
Adding sodium hydroxide into the nickel-cobalt-magnesium sulfate solution until the pH value of the nickel-cobalt-magnesium sulfate solution is 8, forming nickel hydroxide precipitate on part of Ni in the nickel-cobalt-magnesium sulfate solution, performing solid-liquid separation, separating the part of precipitate, and performing second column adsorption on the liquid obtained after the solid-liquid separation, wherein an ion exchange column (phi 4cm multiplied by 100cm) containing 300mL of S930PLUS resin is also used in the second column adsorption process, and the flow rate of the nickel-cobalt-magnesium sulfate solution in the second column adsorption process is 600 mL/h.
And then carrying out second desorption on the resin loaded with Ni and Co after the second column adsorption by using sulfuric acid as a desorbent to obtain a second desorption solution (battery-grade nickel-cobalt sulfate solution) containing Co and Ni ions. The volume of the sulfuric acid solution is 5 times of the volume of the resin, the concentration of the sulfuric acid is 1 equivalent, and the flow rate of the sulfuric acid is 450 mL/h.
After the second desorption, the resin was transformed with 4 wt% NaOH at a flow rate of 450mL/h and a volume of 300mL, and then washed with water to neutrality for the next cycle.
In the above process, the content of Co, Ni and Mg in the P507 raffinate as the raw material for the first column adsorption is shown in table 4, the content of Co, Ni and Mg in the nickel-cobalt-magnesium sulfate solution obtained after the first column adsorption and the first desorption is shown in table 5, and the content of Co, Ni and Mg in the battery-grade nickel-cobalt sulfate solution obtained after the second column adsorption and the second desorption is shown in table 6.
TABLE 4
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.012 | 0.43 | 6.41 |
TABLE 5
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.32 | 11.6 | 0.036 |
TABLE 6
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.74 | 26.4 | 0.003 |
Example 3
This example provides a battery grade nickel sulfate that differs from example 1 in that: the resins used in the first column adsorption and the second column adsorption are both blanc S940.
The battery-grade nickel-cobalt sulfate solution is prepared by the following steps:
30L of P507 raffinate was used as a raw material for the first column adsorption, and the first column adsorption was carried out at room temperature on an ion exchange column (. PHI.4 cm. times.100 cm) containing 300mL of a bleached S940 resin. The P507 raffinate had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of the P507 raffinate in the first adsorption column was 600 mL/h.
And after the first column adsorption, performing first desorption on the resin loaded with Ni and Co after the first column adsorption by using a sulfuric acid solution as a desorbent to obtain a first desorption solution containing Co and Niy. The volume of the sulfuric acid solution is 4 times of the volume of the resin, the concentration of the sulfuric acid is 1 equivalent, and the flow rate of the sulfuric acid is 450 mL/h.
Another 30L of P507 raffinate was used as the raw material for the second first column adsorption, and the second first column adsorption was performed at room temperature by passing through the above-mentioned ion exchange column containing S930PLUS resin. The P507 raffinate used in the process also had a nickel concentration of 0.43g/L and a pH of 5.0. The flow rate of P507 raffinate in the second adsorption of the first column was also 600 mL/h.
And (3) taking the first desorption liquid obtained by the first column adsorption as a part of desorbent (specifically 75 wt% of desorbent in the second first desorption) of the second first desorption, and the balance being sulfuric acid to obtain a second first desorption liquid with the concentration not exceeding 0.1 equivalent, namely the nickel-cobalt-magnesium sulfate solution.
Adding sodium hydroxide into the nickel-cobalt-magnesium sulfate solution until the pH value of the nickel-cobalt-magnesium sulfate solution is 8, forming nickel hydroxide precipitate on part of Ni in the nickel-cobalt-magnesium sulfate solution, performing solid-liquid separation, separating the part of precipitate, and performing second column adsorption on the liquid obtained after the solid-liquid separation, wherein an ion exchange column (phi 4cm multiplied by 100cm) containing 300mL of bolet S940 is also used in the second column adsorption process, and the flow rate of the nickel-cobalt-magnesium sulfate solution in the second column adsorption process is 600 mL/h.
And then carrying out second desorption on the resin loaded with Ni and Co after the second column adsorption by using sulfuric acid as a desorbent to obtain a second desorption solution (battery-grade nickel-cobalt sulfate solution) containing Co and Ni ions. The volume of the sulfuric acid solution is 5 times of the volume of the resin, the concentration of the sulfuric acid is 1 equivalent, and the flow rate of the sulfuric acid is 450 mL/h.
After the second desorption, the resin was transformed with 4 wt% NaOH at a flow rate of 450mL/h and a volume of 300mL, and then washed with water to neutrality for the next cycle.
In the above process, the content of Co, Ni and Mg in the P507 raffinate as the raw material for the first column adsorption is shown in table 7, the content of Co, Ni and Mg in the nickel-cobalt-magnesium sulfate solution obtained after the first column adsorption and the first desorption is shown in table 8, and the content of Co, Ni and Mg in the battery-grade nickel-cobalt sulfate solution obtained after the second column adsorption and the second desorption is shown in table 9.
TABLE 7
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.012 | 0.43 | 6.41 |
TABLE 8
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.35 | 12.35 | 0.032 |
TABLE 9
| Element(s) | Co | Ni | Mg |
| Raw material content (g/L) | 0.79 | 27.87 | 0.003 |
In summary, the P507 raffinate is subjected to resin separation to remove most elements except Ni and Co, and then Ni and Co adsorbed on the resin are desorbed by the desorption solution, at this time, the desorption solution still contains more H +, the partial desorption solution is recycled, and the P507 raffinate adsorbed by the new round of resin is desorbed as at least partial desorption solution until H in the first desorption solution is finally desorbed+Not higher than 0.1 equivalent, thereby obtaining Ni and Co enriched nickel cobalt magnesium sulfate solution. Further, by adjusting the pH value and then performing second column adsorption and second desorption, the content of Mg element can be effectively reduced to obtain the Mg-rich alloySufficient battery grade nickel cobalt sulfate solution. The preparation method is simple, short in flow, low in cost, high in efficiency, capable of effectively avoiding the generation of hydrogen sulfide in the prior art, and green and environment-friendly.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of battery-grade nickel cobalt sulfate solution is characterized by at least comprising the following steps:
carrying out multiple rounds of first column adsorption and first desorption on the raw material on a first adsorption column, wherein each round of first column adsorption takes deoiled P507 raffinate as the raw material, and a first desorption solution obtained in the previous round of first desorption is used as at least part of desorbent in the subsequent round of first desorption process until the concentration of the first desorption solution is not more than 0.1 equivalent, so as to obtain a nickel-cobalt-magnesium sulfate solution;
adjusting the pH value of the nickel-cobalt-magnesium sulfate solution to be not less than 5, and then performing second adsorption and second desorption on a second adsorption column to obtain a battery-grade nickel-cobalt sulfate solution;
wherein, the resins used for the first column adsorption and the second column adsorption both contain iminodiacetic acid functional groups;
preferably, the first desorption liquid obtained in the first desorption of the previous round is 25-75 wt% of the desorbent used in the first desorption of the next round;
preferably, when the pH value of the nickel-cobalt-magnesium sulfate solution needs to be adjusted to exceed 6.5, before the second column adsorption, solid-liquid separation is further performed on the nickel-cobalt-magnesium sulfate solution after the pH adjustment, and the liquid obtained by the separation is subjected to second column adsorption.
2. The preparation method of claim 1, wherein the resins used for the first column adsorption and the second column adsorption are macroporous styrene chelating resins containing iminodiacetic acid groups;
preferably, the resin used for both the first column adsorption and the second column adsorption is selected from S930PLUS or blantt S940.
3. The method of claim 1, wherein the pH of the P507 raffinate used for the first column adsorption is 1.5 to 6.5.
4. The method according to claim 1, wherein the flow rates of the first column adsorption process and the second column adsorption process are both 300-900 mL/h.
5. The method according to claim 1, wherein the desorbent used in the first desorption process and the desorbent used in the second desorption process are selected from sulfuric acid solution or hydrochloric acid solution.
6. The preparation method according to claim 5, wherein when the first desorption solution obtained from the previous first desorption cycle is only used as a partial desorbent in the subsequent first desorption cycle, the desorbent used in the subsequent first desorption cycle further comprises a sulfuric acid solution or a hydrochloric acid solution.
7. The method according to claim 5 or 6, wherein the first round of the first desorption process and the second desorption process use a desorbent concentration of 1 to 4 equivalents.
8. The method according to claim 7, wherein the volume of the desorbent used in each of the first desorption process and the second desorption process is at least 2 times the volume of the resin.
9. The production method according to claim 5 or 6, wherein the flow rate of the desorbent in each of the first desorption process and the second desorption process is 450 mL/h.
10. The method according to claim 1, wherein the reagent for adjusting the pH of the nickel-cobalt-magnesium sulfate solution comprises nickel carbonate, cobalt hydroxide, or nickel hydroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113789443A (en) * | 2021-09-15 | 2021-12-14 | 中国恩菲工程技术有限公司 | Resin adsorption method for nickel and cobalt in laterite-nickel ore |
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| CN107162067A (en) * | 2017-07-17 | 2017-09-15 | 中矿(赣州)国际钴业有限公司 | A kind of method that high-purity sulphuric acid nickel is reclaimed from nickeliferous old and useless battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107162067A (en) * | 2017-07-17 | 2017-09-15 | 中矿(赣州)国际钴业有限公司 | A kind of method that high-purity sulphuric acid nickel is reclaimed from nickeliferous old and useless battery |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113789443A (en) * | 2021-09-15 | 2021-12-14 | 中国恩菲工程技术有限公司 | Resin adsorption method for nickel and cobalt in laterite-nickel ore |
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