CN111268750B - Nickel salt production method - Google Patents
Nickel salt production method Download PDFInfo
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- CN111268750B CN111268750B CN202010092681.4A CN202010092681A CN111268750B CN 111268750 B CN111268750 B CN 111268750B CN 202010092681 A CN202010092681 A CN 202010092681A CN 111268750 B CN111268750 B CN 111268750B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the field of hydrometallurgy, and discloses a nickel salt production method, which comprises the following steps: preparing a leaching solution by using a nickel salt raw material; treating the leachate by using a first extraction liquid to obtain a first loaded extraction liquid and a first raffinate, wherein the concentration of specified impurity metal ions in the first raffinate is lower than that of the specified impurity metal ions in the leachate; treating the first raffinate with a second extract to obtain a second load extract and a second raffinate, wherein the first extract and the second extract are magnesium-saponified organic extracts, and the second raffinate is used for preparing magnesium sulfate; washing the second loaded extract with a detergent to obtain a first purified extract; eluting the first purified extraction liquid by using an eluent to obtain a second purified extraction liquid; and back-extracting the second purified extract by using acid liquor to obtain a purified nickel salt solution. The nickel salt prepared by the method has high purity and low production cost, and the discharge amount of discharge liquid and the salinity generated in the production process are low, so that the method is environment-friendly.
Description
Technical Field
The invention relates to the field of hydrometallurgy, in particular to a nickel salt production method.
Background
The battery-grade nickel salt is a main raw material for preparing the nickel-containing cathode material. For cost reasons, existing battery grade nickel salts are generally prepared using lower cost nickel salt raw materials containing more impurities. Lower cost nickel salt feedstocks include, but are not limited to, nickel sulfide ores, laterite-nickel ores, crude nickel sulfate, crude nickel carbonate, and crude nickel hydroxide.
The existing battery-grade nickel salt is produced by adopting a chemical method and an extraction method. Chemical methods are expensive to produce, while extraction methods produce effluent with high salinity. The salts contained in the effluent have low recovery value, and are not limited to discharge-limiting substances (such as sodium sulfate). The discharged liquid is often directly discharged into the external water body, which causes the salinity of the external water body to rise, and the water quality of the external water body is adversely affected.
Therefore, it is highly desirable to find a new method for producing nickel salt, which can reduce the discharge amount and salinity of the effluent while reducing the production cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nickel salt production method, which is used for reducing the production cost of nickel salt and simultaneously reducing the discharge amount and salinity of discharged liquid.
The nickel salt production method provided by the invention comprises the following steps:
preparing a leaching solution by using a nickel salt raw material;
treating the leachate with a first extraction solution to obtain a first loaded extraction solution and a first raffinate, wherein the concentration of specified impurity metal ions in the first raffinate is lower than that of the specified impurity metal ions in the leachate;
treating the first raffinate with a second extract to obtain a second loaded extract and a second raffinate, wherein the first extract and the second extract are magnesium-saponified organic extracts, and the second raffinate is used for preparing magnesium sulfate;
washing the second loaded extract with a detergent to obtain a first purified extract;
eluting the first purified extraction liquid by using an eluent to obtain a second purified extraction liquid;
and back-extracting the second purified extraction liquid by using acid liquor to obtain a purified nickel salt solution.
Optionally, the nickel salt raw material comprises at least one of crude nickel sulfate, crude nickel carbonate and crude nickel hydroxide;
the method for preparing the leaching solution by using the nickel salt raw material comprises the following steps:
adding water and/or a recycling solution into the nickel salt raw material, and reacting with concentrated sulfuric acid and a reducing agent under a stirring state to generate reaction slurry;
and controlling the acidity of the reaction slurry to a preset pH value range, and then carrying out solid-liquid separation to obtain the leachate.
Optionally, the organic extraction solution comprises an organic extractant and an organic solvent;
the organic extractant used to prepare the first and second extract solutions comprises at least one of versatic acid, neodecanoic acid, octadecenoic acid, isostearic acid, 2-octyldodecanoic acid, 2-hexyldecanoic acid, 2-butyl-octanoic acid, naphthenic acid, di-2-ethylhexyl phosphoric acid, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, bis (2,4, 4-trimethylpentyl) phosphinic acid;
optionally, the organic solvent includes at least one of sulfonated kerosene, straight-chain alkane solvents, isoparaffin solvents, and aromatic solvents;
the content of the organic extracting agent in the organic extracting solution is 5-60 wt%.
Optionally, the alkaline saponifying agent used for saponifying the first extract and the second extract comprises magnesium hydroxide and magnesium oxide.
Optionally, after the step of treating the first raffinate with the second extraction liquid to obtain the second loaded extraction liquid and the second raffinate, the method further includes:
adding a solid treating agent into the second raffinate to remove impurity ions in the second raffinate to obtain a magnesium sulfate treatment solution;
carrying out solid-liquid separation on the magnesium sulfate treatment liquid to obtain a magnesium sulfate solution;
and processing the magnesium sulfate solution according to a second preset crystallization treatment process to obtain a byproduct magnesium sulfate.
And washing the second load extraction liquid to obtain a first purified extraction liquid, wherein the washing agent is an acidified nickel salt solution.
And eluting the first purified extraction liquid to obtain a second purified extraction liquid, wherein the eluent comprises an acidic nickel chloride solution.
Optionally, the back extraction of the second purified extraction liquid with an acid solution to obtain a purified nickel salt solution further includes:
and processing the nickel salt solution according to a first preset crystallization treatment process to obtain a main product nickel salt.
Optionally, the back extraction of the second purified extraction liquid with an acid solution further includes, before obtaining the purified nickel salt solution:
the second purification extract is washed with a nickel salt containing wash solution.
According to the nickel salt production method provided by the invention, nickel ions are effectively separated from other impurity ions through the specific extracting agent, and the obtained nickel salt product has high purity; meanwhile, the process flow is simple and convenient, automatic operation can be realized, and the production cost is reduced; the main effluent liquid of the process is treated to obtain a byproduct, and the byproduct is recycled, so that the discharge amount and salinity of the effluent liquid are greatly reduced, and the process is an environment-friendly metallurgical process.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise.
FIG. 1 is a schematic flow chart of a method for producing nickel salt according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, a method for producing a nickel salt according to an embodiment of the present invention includes:
s10, preparing a leaching solution by using a nickel salt raw material;
s20, treating the leachate with a first extraction solution to obtain a first loaded extraction solution and a first raffinate, wherein the concentration of the specified impurity metal ions in the first raffinate is lower than that of the specified impurity metal ions in the leachate;
s30, treating the first raffinate with a second extract to obtain a second loaded extract and a second raffinate, wherein the first extract and the second extract are both magnesium-saponified organic extracts, and the second raffinate is used for preparing magnesium sulfate;
s40, washing the second loaded extraction liquid by using a detergent to obtain a first purified extraction liquid;
s50, eluting the first purified extraction liquid by using an eluent to obtain a second purified extraction liquid;
and S60, back-extracting the second purified extraction liquid by using acid liquor to obtain a purified nickel salt solution.
In step S10, the nickel salt raw material includes, but is not limited to, crude nickel sulfate, crude nickel carbonate, and crude nickel hydroxide. For cost reasons, a lower cost crude nickel hydroxide is preferred.
The nickel salt raw material can react with concentrated sulfuric acid to generate leachate. To improve the leaching efficiency, the nickel salt raw material may be pre-slurried and a reducing agent added during the reaction. The leachate is an aqueous solution rich in nickel ions and containing a large amount of impurity ions, such as magnesium ions, copper ions, manganese ions, iron ions, aluminum ions, zinc ions, cobalt ions, etc. (nickel salt raw materials are different and the types and contents of the impurity ions contained therein are different). The pH value of the prepared leaching solution is 0.5-6.5, and the concentration of nickel ions is 20-150 g/L.
In step S20, the first extraction solution is saponified and counter-current extracted to transfer a portion of the impurity ions in the leaching solution to the first loaded extraction solution, while the nickel ions remain in the first raffinate. Designated impurity metal ions include, but are not limited to, iron ions, copper ions, aluminum ions, zinc ions. The first loaded extract is an organic phase and the first raffinate is an aqueous phase. The first extraction liquid is an organic extraction liquid obtained by saponifying magnesium.
The first loaded extract can be regenerated by further purification (such as water washing) after washing and back extraction treatment. The strip liquor can recover iron ions, copper ions, aluminum ions and zinc ions by known technology.
The first raffinate is an aqueous solution which is rich in nickel ions and contains part of impurity ions, and the pH value of the aqueous solution is 2.0-6.0.
In step S30, the second extract is saponified and counter-current extracted, and the nickel ions and remaining impurities in the first raffinate can be transferred to the second loaded extract (organic phase). The second extraction liquid is an organic extraction liquid obtained by saponifying magnesium. The second raffinate solution contains mainly magnesium sulfate and small amounts of other metal ions including manganese, cobalt, nickel. The pH of the second raffinate is between 4.0 and 6.5. The second raffinate was used to make magnesium sulfate.
In step S40, the detergent is used to reduce the magnesium ion concentration in the second loaded extract and wash away a small amount of residual magnesium sulfate solution. The detergent is prepared from nickel sulfate, nickel chloride, acid and water in a certain proportion. Specifically, the detergent may be a nickel salt solution, such as a dilute nickel sulfate solution (e.g., having a concentration of 1mol/L and having a certain acidity). And washing the second load extraction liquid by using a detergent to obtain a first purified extraction liquid and a washed liquid. The post-wash liquor may be used in step S10 to prepare a leachate.
In step S50, the eluent is used to further remove other metal ions in the first purified extract. The eluent may be an acidic nickel salt solution, such as an acidic nickel chloride solution. In this example, the acidic nickel chloride solution contained nickel ions in an amount of 10 to 150g/L, chloride ions in an amount of 15 to 180 g/L, and hydrogen ions in an amount of 0.01 to 1 mol/L. The content of manganese ions and cobalt ions in the first purified extract is greatly reduced by the elution effect of the eluent. And eluting the first purified extraction liquid by using an eluent to obtain a second purified extraction liquid and an eluted liquid. The eluted solution contains nickel ions, chloride ions, manganese ions and cobalt ions, and the nickel ions, the chloride ions, the manganese ions and the cobalt ions can be recovered by a known technology. The recovered nickel ions and chloride ions are used for preparing the acidic nickel chloride solution.
In step S60, the second purified extract may be back-extracted with an acid solution to transfer the nickel ions to the aqueous phase. The acid solution can be sulfuric acid or hydrochloric acid. The hydrogen ion concentration of the acid solution may be 1 to 4.5 mol/L. After acid stripping, pure nickel salt solution and organic extractant (which can be recycled, such as used for preparing the first extract and the second extract) can be obtained. Through determination, the concentration of nickel ions in the pure nickel salt solution is 140-160g/L, the concentration of cobalt ions, manganese ions and calcium ions is less than 2mg/L, the concentration of magnesium ions is less than 3mg/L, and the concentration of iron ions, copper ions, aluminum ions and zinc ions is less than 1 mg/L. The nickel salt solution prepared in the step S60 meets the production requirements of battery-grade nickel sulfate products.
Optionally, alkaline saponifying agent used for saponification treatment such as magnesium hydroxide and magnesium oxide.
In this embodiment, the first extract and the second extract may be prepared by reacting an alkaline saponifier solution with an organic extract. The saponification rate of the first extract may be 30% to 70%. The saponification rate of the second extract may be 50% to 70%. In some cases, the first and second extract may be the same composition, but in a greater difference in amounts. Typically, the amount of the second extraction liquid is greater than the amount of the first extraction liquid.
For using magnesium oxide as the saponifier, the magnesium oxide can be converted into magnesium hydroxide solution by pre-dissolving technique, and then mixed with the organic extractant to prevent the damage of solid particles to the organic extraction liquid.
Optionally, the organic extraction solution comprises an organic extractant and an organic solvent. Wherein the organic extractant used for preparing the first extraction liquid and the second extraction liquid comprises at least one of versatic acid, neodecanoic acid, octadecenoic acid, isostearic acid, 2-octyldodecanoic acid, 2-hexyldecanoic acid, 2-butyl-octanoic acid, naphthenic acid, di-2-ethylhexyl phosphoric acid, 2-ethylhexyl phosphonic acid, mono-2-ethylhexyl ester and bis (2,4, 4-trimethylpentyl) phosphinic acid.
The organic extractant used to prepare the second extract may be the same as or different from the organic extractant of the first extract.
The organic solvent comprises at least one of sulfonated kerosene, straight-chain alkane solvents, isoparaffin solvents and aromatic solvents.
The content of the organic extractant in the organic extraction liquid is 5-60 wt%.
Optionally, the leaching solution is prepared by using a nickel salt raw material, and comprises:
adding water and/or a recycling solution into the nickel salt raw material, and reacting with concentrated sulfuric acid and a reducing agent under a stirring state to generate reaction slurry;
controlling the acidity of the reaction slurry to a preset pH value range, and then carrying out solid-liquid separation to obtain a leaching solution.
In this embodiment, water and/or a recycled solution is added to a nickel salt raw material to form slurry, and the slurry is added to a reaction kettle while stirring, to generate a reaction slurry. The solid-liquid ratio of the added materials is 1: 3-20. The water may be evaporated condensate water; reuse solutions include, but are not limited to, site wash water, other reuse water in a process flow. Reducing agents include, but are not limited to, hydrogen peroxide, sulfur dioxide gas, chloride ions, sodium metabisulfite, sodium sulfite, ferrous sulfate. The reducing agent can increase the leaching rate of the nickel salt raw material (such as the leaching rate of the crude nickel hydroxide raw material is increased from 92 percent to 98 percent). When the nickel salt raw material, concentrated sulfuric acid and a reducing agent act, steam can be introduced for heating, the reaction temperature is controlled to be 25-95 ℃, and then the reaction is carried out for 1-10 hours. The predetermined pH range may be 0.5-6.5. Controlling the pH value of the reaction slurry to be 0.5-6.5, and then carrying out solid-liquid separation by using a filter press to obtain a leaching solution and leaching residues. And washing the leached slag, and feeding the leached slag into a slag field.
Optionally, after the first raffinate is treated with the second extract to obtain the second loaded extract and the second raffinate, the method further includes:
adding a solid treating agent into the second raffinate to remove impurity ions in the second raffinate to obtain magnesium sulfate treatment liquid;
carrying out solid-liquid separation on the magnesium sulfate treatment solution to obtain a magnesium sulfate solution;
and processing the magnesium sulfate solution according to a second preset crystallization treatment process to obtain a byproduct magnesium sulfate.
In this embodiment, the first extract and/or the second extract is/are organic extractant saponified with magnesium, and the solute in the second raffinate is mainly magnesium sulfate and contains trace amounts of manganese, cobalt, nickel, and other ions. The added solid treating agent can react with manganese, cobalt, nickel and other ions to generate a precipitated substance. The solid treating agent may be magnesium oxide. And adding excessive magnesium oxide into the second raffinate, and controlling the pH value of the solution to be more than 10 so that manganese, cobalt, nickel and other ions form hydroxide precipitate to form turbid liquid. In some cases, the solid treatment agent may also include a soluble sulfide salt. Sulfide salt can make manganese, cobalt, nickel and other ions generate sulfide precipitate, so that the concentration of the sulfide precipitate is further reduced. Excessive magnesium oxide particles in the turbid liquid can adsorb hydroxide precipitates (and/or sulfide precipitates), and after standing for a certain time and solid-liquid separation, a mixture containing magnesium oxide and hydroxide precipitates (and corresponding sulfide precipitates if sulfide salts are added) and a magnesium sulfate solution can be obtained.
The magnesium sulfate solution is processed by a second preset crystallization treatment process to generate industrial-grade magnesium sulfate. The second preset crystallization treatment process includes, but is not limited to, evaporation, concentration, crystallization, solid-liquid separation, and drying.
Optionally, the back extraction of the second purified extraction liquid with an acid solution to obtain a purified nickel salt solution further includes:
and processing the nickel salt solution according to a first preset crystallization treatment process to obtain a main product nickel salt.
In this embodiment, the first predetermined crystallization process includes, but is not limited to, oil removal, evaporation concentration, cooling crystallization, solid-liquid separation, and drying. The purity of the nickel salt solution is high, so that the battery-grade nickel salt can be obtained. Here, the acid solution used for stripping the second purified extract includes, but is not limited to, sulfuric acid, hydrochloric acid; nickel salts include, but are not limited to, nickel sulfate, nickel chloride.
Optionally, the back extraction of the second purified extraction liquid with an acid solution further includes:
the second purified extract is washed with a nickel salt containing wash solution.
In this embodiment, before the second purified extraction liquid is back-extracted with the acid solution, the second purified extraction liquid may be washed with a nickel salt-containing washing solution in order to further improve the purity of the nickel salt solution. The nickel salt-containing washing solution may use the pure nickel salt solution generated in step S60. The nickel salt containing washing solution performs counter-current washing on the second purified extraction solution, so that a small amount of eluent carried in the second purified extraction solution (organic phase) can be removed.
Through a plurality of tests, the nickel salt solution is prepared by using the magnesium saponified organic extract, and the method has the best economic benefit and environmental protection benefit. Because the second raffinate is the main effluent of the process and the main component is magnesium sulfate, the magnesium sulfate can be recovered through treatment, and the discharge amount and salinity of the effluent are greatly reduced.
Example 1
The crude nickel hydroxide (MHP) produced from laterite-nickel ore is used for producing battery-grade nickel sulfate, and the main components (mass fraction) of a sample are shown in a table 1.
Table 1 example 1 composition of crude nickel hydroxide
| Element(s) | Ni％ | Co％ | Mn％ | Fe％ | Cu％ | Zn％ | Ca％ | Mg％ | Al％ |
| Content (wt.) | 41.3 | 4.05 | 6.8 | 0.35 | 0.43 | 0.15 | 0.27 | 2.28 | 0.14 |
Adding the sample into a reaction kettle, controlling the solid-to-liquid ratio to be 1:7, stirring, adding 98% concentrated sulfuric acid, introducing steam, keeping the reaction temperature at 65 ℃, adding hydrogen peroxide, reacting for 4 hours, and controlling the pH value of final acid to be 2.5. The leaching solution was subjected to solid-liquid separation using a plate and frame filter press to obtain a nickel sulfate leachate having the main component contents shown in table 2.
Table 2 example 1 main components of nickel sulfate leachate
| Element(s) | Ni | Co | Mn | Fe | Cu | Zn | Ca | Mg | Al |
| Content g/L | 48.6 | 4.8 | 7.8 | 0.33 | 0.48 | 0.17 | 0.28 | 2.7 | 0.16 |
Preparing 20 wt% of organic extract and 60% of magnesium soap by using versatic acid and 260# kerosene to obtain first extract. And carrying out countercurrent extraction on the nickel sulfate leaching solution by using the first extraction solution to obtain a first load extraction solution and a first raffinate. The first raffinate removes iron, copper, aluminum and zinc impurities in the nickel sulfate leachate. The first raffinate is subjected to counter-current extraction by a second extraction liquid (the composition of which is the same as that of the first extraction liquid but the dosage of which is different), so as to obtain a second loaded extraction liquid and a second raffinate. The second raffinate was magnesium sulfate solution before impurity removal, and the composition thereof is shown in table 3.
Table 3 example 1 main components of magnesium sulfate solution before impurity removal
| Element(s) | Mg | Ni | Mn | Ca | Co | Fe、Cu、Al、Zn |
| Content g/L | 29.7 | 0.39 | 0.17 | 0.03 | 0.07 | ＜0.001 |
Adding the light-burned magnesium oxide powder into the magnesium sulfate solution before impurity removal, stirring, keeping the solution at the pH value of 10.5, standing for a certain time, and performing solid-liquid separation on the suspension by using a plate and frame filter press to obtain the magnesium sulfate solution after impurity removal, wherein the composition of the magnesium sulfate solution is shown in Table 4.
Table 4 example 1 main components of magnesium sulfate solution after impurity removal
| Element(s) | Mg | Ni | Mn | Ca | Co | Fe、Cu、Al、Zn |
| Content g/L | 30.2 | 0.007 | 0.01 | 0.037 | 0.002 | ＜0.002 |
The solution after impurity removal meets the requirement of producing industrial-grade magnesium sulfate.
And washing the second load extraction liquid by using a washing agent nickel sulfate to obtain a first purified extraction liquid. And (3) carrying out elution treatment on the first purified extraction liquid by using an eluent acidic nickel chloride solution to obtain a second purified extraction liquid. The second purified extract was back-extracted with 2mol/L sulfuric acid in a counter-current manner to obtain a purified nickel sulfate solution, the main components of which are shown in Table 5.
Table 5 example 1 major components of nickel sulfate solution
| Element(s) | Ni | Co、Mn | Mg | Ca | Fe、Cu、Zn、Al |
| Content g/L | 143 | ＜0.002 | 0.0024 | 0.0016 | ＜0.001 |
The obtained nickel sulfate solution completely meets the production requirements of battery-grade nickel sulfate products.
Example 2
Battery grade nickel sulfate was produced from crude nickel carbonate produced from the electroplating sludge, and the main components of the samples are shown in Table 6.
Table 6 example 2 nickel carbonate composition
| Element(s) | Ni | Co | Mn | Fe | Cu | Zn | Ca | Mg |
| Content% | 45.1 | 0.02 | 0.01 | 0.13 | 0.01 | 0.01 | 0.047 | 0.28 |
Adding the sample into a reaction kettle, controlling the solid-liquid ratio to be 1:7, stirring, adding 98% concentrated sulfuric acid, introducing steam, keeping the reaction temperature at 65 ℃, reacting for 4 hours, and controlling the final acidity to be 4.0. The leached slurry was subjected to solid-liquid separation with a precision filter to obtain a nickel sulfate leachate having the main component contents as shown in table 7.
Table 7 example 2 main components of nickel sulfate leachate
| Element(s) | Ni | Co | Mn | Fe | Cu | Zn | Ca | Mg |
| Content g/L | 64.8 | 0.027 | 0.01 | 0.17 | 0.01 | 0.01 | 0.06 | 0.37 |
5 wt% of organic extractant (content of isoparaffin D70 is 5 wt%) and 60wt% of magnesium soap are prepared from isoparaffin D70 and neodecanoic acid to obtain first extract. And carrying out countercurrent extraction on the nickel sulfate leaching solution by using the first extraction solution to obtain a first load extraction solution and a first raffinate. The first raffinate removes iron, copper, aluminum and zinc impurities in the nickel sulfate leachate. Preparing 25 wt% of organic extractant and 60wt% of magnesium soap by using isoalkane D70 and neodecanoic acid to obtain a second extract. And carrying out countercurrent extraction on the first raffinate by using the second extraction liquid to obtain a second load extraction liquid and a second raffinate. The second raffinate is the magnesium sulfate solution before impurity removal, and the composition of the second raffinate is shown in table 8.
Table 8 example 2 main components of magnesium sulfate solution before impurity removal
| Element(s) | Mg | Ni | Mn | Ca | Co | Fe、Cu、Al、Zn |
| Content g/L | 26.8 | 0.51 | 0.001 | 0.01 | 0.001 | ＜0.001 |
Adding light-burned magnesium oxide powder into the magnesium sulfate solution before impurity removal, wherein the pH value of the feed liquid is 10.0, adding sodium sulfide with the amount of 1.1 times of that of impurity ions, standing for a certain time, and carrying out solid-liquid separation by using a plate-and-frame filter press to obtain the magnesium sulfate solution after impurity removal, wherein the composition of the magnesium sulfate solution is shown in Table 9.
Table 9 example 2 main components of magnesium sulfate solution after impurity removal
| Element(s) | Mg | Ni | Mn | Ca | Co | Fe、Cu、Al、Zn |
| The content is g/L | 27.1 | 0.002 | 0.001 | 0.02 | 0.001 | ＜0.001 |
The magnesium sulfate solution after impurity removal meets the requirement of producing industrial grade magnesium sulfate.
And washing the second load extraction liquid by using a washing agent nickel sulfate to obtain a first purified extraction liquid. And (3) carrying out elution treatment on the first purified extraction liquid by using an eluent acidic nickel chloride solution to obtain a second purified extraction liquid. The second purified extract was back-extracted with 2mol/L sulfuric acid in a counter-current manner to obtain a purified nickel sulfate solution, the main components of which are shown in Table 10.
Table 10 example 2 major components of nickel sulfate solution
| Element(s) | Ni | Co、Mn | Mg | Ca | Fe、Cu、Zn、Al |
| Content g/L | 147 | ＜0.001 | 0.001 | 0.0010 | ＜0.001 |
The obtained nickel sulfate solution completely meets the production requirements of battery-grade nickel sulfate products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (7)
1. A method for producing a nickel salt, comprising:
preparing a leaching solution by using a nickel salt raw material; the nickel salt raw material comprises at least one of crude nickel sulfate, crude nickel carbonate and crude nickel hydroxide;
treating the leachate with a first extraction solution to obtain a first loaded extraction solution and a first raffinate, wherein the concentration of specified impurity metal ions in the first raffinate is lower than that of the specified impurity metal ions in the leachate; the specified impurity metal ions comprise iron ions, copper ions, aluminum ions and zinc ions;
treating the first raffinate with a second extract to obtain a second loaded extract and a second raffinate, wherein the first extract and the second extract are both magnesium-saponified organic extracts, and the second raffinate is used for preparing magnesium sulfate; the alkaline saponifying agent used for saponification treatment comprises magnesium hydroxide, magnesium oxide;
washing the second loaded extract with a detergent to obtain a first purified extract;
eluting the first purified extraction liquid by using an eluent to obtain a second purified extraction liquid;
back-extracting the second purified extraction liquid with acid liquor to obtain a purified nickel salt solution;
the organic extraction liquid comprises an organic extractant and an organic solvent; the organic solvent comprises at least one of sulfonated kerosene, straight-chain alkane solvents, isoparaffin solvents and aromatic solvents;
the content of the organic extracting agent in the organic extracting solution is 5-60 wt%;
the organic extractant used for preparing the first extraction liquid and the second extraction liquid comprises at least one of versatic acid, neodecanoic acid, octadecenoic acid, isostearic acid, 2-octyldodecanoic acid, 2-hexyldecanoic acid, 2-butyl-octanoic acid and naphthenic acid.
2. The nickel salt production process of claim 1, wherein the preparation of the leach solution using a nickel salt feedstock comprises:
adding water and/or a recycling solution into the nickel salt raw material, and reacting with concentrated sulfuric acid and a reducing agent under a stirring state to generate reaction slurry;
and controlling the acidity of the reaction slurry to a preset pH value range, and then carrying out solid-liquid separation to obtain the leachate.
3. The nickel salt production process of claim 1, wherein after treating the first raffinate with the second extract to obtain a second loaded extract and a second raffinate, further comprising:
adding a solid treating agent into the second raffinate to remove impurity ions in the second raffinate to obtain a magnesium sulfate treatment solution;
carrying out solid-liquid separation on the magnesium sulfate treatment liquid to obtain a magnesium sulfate solution;
and processing the magnesium sulfate solution according to a second preset crystallization treatment process to obtain a byproduct magnesium sulfate.
4. The nickel salt production method according to claim 1, wherein the detergent is an acidified nickel salt solution.
5. The nickel salt production process of claim 1, wherein the eluent comprises an acidic nickel chloride solution.
6. The method for producing nickel salts according to claim 1, wherein the second purified extract is back-extracted with an acid solution to obtain a purified nickel salt solution, and further comprising:
and processing the nickel salt solution according to a first preset crystallization treatment process to obtain a main product nickel salt.
7. The method for producing nickel salts according to claim 1, wherein the second purified extract is back-extracted with an acid solution, and further comprising, before obtaining the purified nickel salt solution:
the second purification extract is washed with a nickel salt containing wash solution.
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| CN114150152B (en) * | 2020-09-04 | 2023-08-29 | 北京博萃循环科技有限公司 | Nickel cobalt lithium manganate and preparation method thereof |
| CN114134341B (en) * | 2020-09-04 | 2023-01-13 | 苏州博萃循环科技有限公司 | Method for recovering nickel, cobalt and manganese in feed liquid containing nickel, cobalt and manganese |
| CN112320860B (en) * | 2020-11-30 | 2023-02-17 | 北京博萃循环科技有限公司 | Method for purifying nickel sulfate |
| CN113088692B (en) * | 2021-04-06 | 2022-04-29 | 鞍山昊旻稀土科技有限公司 | Extractant for extracting naphthenic acid and yttrium extraction process |
| CN115433832B (en) * | 2021-06-02 | 2024-03-19 | 中国科学院过程工程研究所 | Nickel and cobalt synergistic extractant and application thereof |
| CN114672649A (en) * | 2022-03-02 | 2022-06-28 | 吉林吉恩镍业股份有限公司 | Process for converting magnesium oxide saponification P204 extractant into nickel soap |
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