CN114853093A - Preparation method of battery-grade nickel sulfate - Google Patents
Preparation method of battery-grade nickel sulfate Download PDFInfo
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- CN114853093A CN114853093A CN202210591069.0A CN202210591069A CN114853093A CN 114853093 A CN114853093 A CN 114853093A CN 202210591069 A CN202210591069 A CN 202210591069A CN 114853093 A CN114853093 A CN 114853093A
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- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 174
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 114
- 239000013078 crystal Substances 0.000 claims abstract description 82
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000605 extraction Methods 0.000 claims abstract description 62
- 238000005406 washing Methods 0.000 claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 57
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 229910052742 iron Inorganic materials 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 28
- 230000008025 crystallization Effects 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000005119 centrifugation Methods 0.000 claims description 21
- 239000000344 soap Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910000438 diphosphorus tetroxide Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000008213 purified water Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 230000002596 correlated effect Effects 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 25
- 239000012535 impurity Substances 0.000 abstract description 23
- 150000002500 ions Chemical class 0.000 abstract description 14
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 8
- 239000003513 alkali Substances 0.000 abstract description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- -1 aluminum ion Chemical class 0.000 description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a preparation method of battery-grade nickel sulfate. The method comprises the steps of leaching nickel-containing materials, removing iron and aluminum, extracting for three times, evaporating for crystallization, and washing with saturated nickel sulfate aqueous solution to obtain battery-grade nickel sulfate. The invention does not carry out the total extraction and the total back extraction of nickel, well separates nickel in the nickel-containing material from other impurity elements by three times of extraction, has less acid and alkali consumption and low production cost, and simultaneously washes wet nickel sulfate crystals by using saturated nickel sulfate aqueous solution, so that the content of impurity ions such as sodium ions in the carrying liquid of the wet nickel sulfate crystals is reduced, a large amount of nickel ions can not be dissolved, the high purity of the nickel sulfate product is ensured, and the requirement of battery-grade nickel sulfate is met.
Description
Technical Field
The invention relates to the field of power batteries, in particular to a preparation method of battery-grade nickel sulfate.
Background
In recent years, the new energy automobile industry is rapidly developed, the demand of lithium ion batteries containing nickel, cobalt and manganese is greatly increased, and the consumption of battery-grade nickel sulfate is driven to be rapidly increased. The preparation of battery-grade nickel sulfate from nickel-containing materials such as nickel hydroxide cobalt (MHP), ternary black powder and the like has become a hot point of attention. At present, the process for preparing battery-grade nickel sulfate by using nickel-containing materials mainly comprises the following steps:
(1) the nickel sulfate solution and the cobalt sulfate solution are respectively obtained through the treatments of leaching, removing aluminum, P204 extracting impurities, P507 extracting cobalt, P507/C272 extracting magnesium and the like, and finally, the nickel sulfate crystal and the cobalt sulfate crystal are obtained through an evaporation crystallization mode. In the process, because the nickel sulfate crystals are directly obtained from the raffinate through evaporation and crystallization, and a large amount of sodium ions are introduced into the raffinate in the refining process, the obtained nickel sulfate crystals do not meet the requirement of battery-grade nickel sulfate product standards on the sodium ions.
(2) Leaching, removing iron and aluminum, P204 extracting impurities, P507 extracting cobalt and magnesium, performing back extraction step by step to produce pure cobalt sulfate solution, P507 extracting nickel, performing back extraction step by step to produce pure nickel sulfate solution, and then performing evaporative crystallization on the nickel sulfate solution and the cobalt sulfate solution respectively to obtain battery-grade nickel sulfate and cobalt sulfate. The nickel sulfate solution and the cobalt sulfate solution are obtained by full extraction and full reaction, the product quality is good, but the full extraction and full reaction process consumes a large amount of liquid caustic soda and sulfuric acid, the production cost is high, and the investment is large.
Disclosure of Invention
The invention mainly aims to provide a preparation method of battery-grade nickel sulfate, so as to better give consideration to low cost and high purity of nickel-containing materials in the production of battery-grade nickel sulfate.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing battery grade nickel sulfate, comprising the steps of: step S1, adding sulfuric acid into the nickel-containing material for acid leaching to obtain a nickel-containing solution, wherein metal elements in the nickel-containing material comprise nickel elements, cobalt elements, magnesium elements, copper elements, manganese elements, calcium elements, zinc elements, iron elements and aluminum elements; step S2, removing iron and aluminum from the nickel-containing solution to obtain a solution after removing iron and aluminum; step S3, carrying out first extraction on the liquid after iron and aluminum removal by adopting a soap-transferring first extraction agent to obtain a first raffinate; step S4, carrying out second extraction on the first raffinate by using a soap-converted second extracting agent to obtain a second raffinate; step S5, carrying out third extraction on the second raffinate by using a soap-converted third extracting agent to obtain a third raffinate; step S6, sequentially carrying out evaporation concentration and cooling crystallization on the third raffinate, and then carrying out first centrifugal separation to obtain a first wet nickel sulfate crystal and a crystallization mother liquor; step S7, carrying out spray washing and/or slurrying washing on the first wet nickel sulfate crystal by using a saturated nickel sulfate aqueous solution, and carrying out second centrifugal separation on the obtained washing liquid to obtain a second wet nickel sulfate crystal and a washing liquid; drying the second wet nickel sulfate crystal to obtain battery-grade nickel sulfate; wherein the first extractant, the second extractant and the third extractant are respectively and independently selected from one or more of P204, P507 and C272.
Further, if the volume number of the saturated nickel sulfate aqueous solution is denoted as V, the weight of the first wet nickel sulfate crystal is denoted as M, and the water content of the first wet nickel sulfate crystal is denoted as n, the values of V and mxn are in positive correlation; preferably, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 0.25-3 mL.
Further, the saturated nickel sulfate aqueous solution is a saturated aqueous solution prepared from battery-grade nickel sulfate and purified water; preferably, the water content of the first wet nickel sulfate crystal is 2-8 wt%; the water content of the second wet nickel sulfate crystal is 2-8 wt%.
Further, when the washing mode is spray washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystal is 0.25-1 mL;
further, when the washing mode is slurry washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystal is 1-3 mL, and the washing time of the slurry washing is 10-60 min.
Further, in the first centrifugation process, the centrifugation rotating speed is 500-3000 rpm, and the centrifugation time is 5-30 min; in the second centrifugation process, the centrifugation rotating speed is 500-3000 rpm, and the centrifugation time is 5-30 min.
Further, in step S6, the cooling crystallization temperature is 35-50 ℃; preferably, the crystallization mother liquor is returned to the first extraction process, the second extraction process and the third extraction process as the pre-soap conversion liquor of the first extractant, the second extractant and the third extractant.
Further, the first extracting agent is a P204 extracting agent, the second extracting agent is a P507 extracting agent, and the third extracting agent is a P507 extracting agent and/or a C272 extracting agent; preferably, the volume ratio of the first extracting agent to the liquid after iron and aluminum removal is (0.5-2): 1, the volume ratio of the second extracting agent to the first raffinate is (0.5-2): 1, and the volume ratio of the third extracting agent to the second raffinate is (0.5-2): 1.
Further, in step S2, the reagent used in the step of removing aluminum is sodium carbonate and/or sodium hydroxide.
Further, the nickel-containing material comprises, by weight, 10-40% of nickel element, 2-10% of cobalt element, 0.1-3% of magnesium element, 2-10% of manganese element, 0.1-2% of copper element, 0.1-15% of calcium element, 0.1-2% of zinc element, 0.1-1% of aluminum element and 0.1-1% of iron element.
By applying the technical scheme of the invention, the battery-grade nickel sulfate can be obtained by leaching, removing iron and aluminum, extracting, evaporating, crystallizing and washing nickel-containing materials. The invention does not carry out the full extraction and the full back extraction of nickel, well separates the nickel in the nickel-containing material from other impurity elements by three times of extraction, has less acid and alkali consumption and low production cost, and simultaneously uses saturated nickel sulfate aqueous solution to wash wet nickel sulfate crystals, so that the content of impurity ions (such as sodium ions) in the carrying liquid of the wet nickel sulfate crystals is reduced, and the nickel ions can not be greatly dissolved, thereby ensuring the high purity of the nickel sulfate product and meeting the requirement of battery-grade nickel sulfate.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As in the background art of the present invention, the problems of low cost and high purity in the production of battery-grade nickel sulfate from nickel-containing materials in the prior art are difficult to be considered. In order to solve the above problems, in an exemplary embodiment of the present invention, there is provided a method for preparing battery grade nickel sulfate, including the steps of: step S1, adding sulfuric acid into the nickel-containing material for acid leaching to obtain a nickel-containing solution, wherein metal elements in the nickel-containing material comprise nickel element, cobalt element, magnesium element, copper element, manganese element, calcium element, zinc element, iron element and aluminum element; step S2, performing iron and aluminum removal on the nickel-containing solution to obtain iron and aluminum removed solution; step S3, carrying out first extraction on the liquid after iron and aluminum removal by adopting a first extraction agent converted into soap to obtain first raffinate; step S4, performing second extraction on the first raffinate by using a second soap-converted extracting agent to obtain a second raffinate; step S5, carrying out third extraction on the second raffinate by using a third soap-converted extracting agent to obtain a third raffinate; step S6, sequentially carrying out evaporation concentration and cooling crystallization on the third raffinate, and then carrying out first centrifugal separation to obtain a first wet nickel sulfate crystal and a crystallization mother liquor; step S7, carrying out spray washing and/or slurrying washing on the first wet nickel sulfate crystal by using a saturated nickel sulfate aqueous solution, and carrying out second centrifugal separation on the obtained washing liquid to obtain a second wet nickel sulfate crystal and a washing liquid; drying the second wet nickel sulfate crystal to obtain battery-grade nickel sulfate; wherein the first extractant, the second extractant and the third extractant are respectively and independently selected from one or more of P204, P507 and C272.
The invention designs the process flow aiming at the nickel-containing material, firstly leaches each metal ion in the nickel-containing material through acid leaching, and maximizes the utilization of the nickel-containing material. And then, removing iron and aluminum from the obtained nickel-containing solution, removing a large amount of iron and aluminum ion impurities in the nickel-containing solution to obtain iron and aluminum removed liquid, and then sequentially carrying out a series of extraction processes. The first extraction uses a first extraction agent converted into soap to treat the liquid after iron and aluminum removal, and the main purpose is to remove impurities such as manganese, calcium, copper, zinc, aluminum, iron and the like in the liquid to obtain a first raffinate. And the second extraction adopts a second extraction agent for converting soap to treat the first raffinate, and the purpose is to remove cobalt ions in the first raffinate to obtain a second raffinate. And the third extraction adopts a third extraction agent for converting soap to treat the second raffinate, and the main purpose is to remove magnesium ions in the second raffinate to obtain a third raffinate. And then, carrying out evaporative crystallization purification, namely sequentially carrying out evaporative concentration and cooling crystallization on the third raffinate, separating out nickel sulfate crystals by utilizing solubility differences of nickel sulfate at different temperatures, and carrying out first centrifugal separation to obtain first wet nickel sulfate crystals and a crystallization mother liquor.
It should be noted that, since alkaline substances such as sodium carbonate are used in the step of removing aluminum, sodium ions are inevitably introduced into the obtained solution after removing aluminum, and the sodium ions have extremely high water solubility and are difficult to remove by a conventional purification process. The invention uses the extractant after soap conversion to extract nickel, the extractant is easier to extract nickel relative to sodium, the nickel in the mother liquor of nickel sulfate evaporative crystallization returned is used to convert the organic extractant of sodium soap after saponification into the organic extractant of nickel soap, and the mother liquor of nickel sulfate evaporative crystallization used in the soap conversion process is used as the liquid before soap conversion. Particularly, the saturated nickel sulfate aqueous solution is adopted to carry out spray washing and/or slurrying washing on the first wet nickel sulfate crystal, the content of impurity ions, particularly sodium ions, in the first wet nickel sulfate crystal entrainment liquid can be diluted and reduced by adopting any washing mode, and meanwhile, the saturated aqueous solution can reduce the dissolution of nickel ions, so that the purification of a nickel sulfate product is realized; and then carrying out second centrifugal separation on the obtained washing liquid to obtain a second wet nickel sulfate crystal and a washing liquid. And finally, drying the second wet nickel sulfate crystal to obtain the high-purity battery-grade nickel sulfate with low impurity ions, particularly sodium ions. The invention does not carry out the total extraction and the total back extraction of nickel, well separates the nickel in the nickel-containing material from other impurity elements by three times of extraction, has less acid and alkali consumption and low production cost, and simultaneously uses saturated nickel sulfate aqueous solution to wash wet nickel sulfate crystals, so that the content of impurity ions (such as sodium ions) in the entrainment liquid of the wet nickel sulfate crystals is reduced, a large amount of nickel ions can not be dissolved, the high purity of the nickel sulfate products is ensured, and the requirements of battery-grade nickel sulfate are met.
In the specific preparation process, due to different characteristics of different extracting agents, the pH value of the solution after iron and aluminum removal is preferably adjusted to 2.5-3 before the first extraction is carried out, the pH value of the first raffinate is preferably adjusted to 3-4 before the second extraction is carried out, and the pH value of the second raffinate is preferably adjusted to 4-5.5 before the third extraction is carried out, so that the extraction effect is further improved.
The inventor finds that the volume of the saturated nickel sulfate aqueous solution added in the washing process has strong correlation with the weight and the water content of the first wet nickel sulfate crystal to be treated in the actual preparation process. In a preferred embodiment, when the volume of the saturated nickel sulfate aqueous solution is denoted by V, the weight of the first wet nickel sulfate crystals is denoted by M, and the water content of the first wet nickel sulfate crystals is denoted by n, V is positively correlated with the value of M × n. In order to further improve the practicability of the washing method, the volume of the saturated nickel sulfate aqueous solution used for each gram of the first wet nickel sulfate crystals is preferably 0.25-3 mL, and when the first wet nickel sulfate crystals are washed by the saturated nickel sulfate aqueous solution within the volume range, the content of impurity ions, particularly sodium ions, in the carrying liquid of the wet nickel sulfate crystals can be reduced to the maximum extent while the dissolution of nickel ions is reduced, so that the purity of the battery-grade nickel sulfate product is further improved.
In order to further reduce the preparation cost, in a preferred embodiment, the saturated nickel sulfate aqueous solution is a saturated aqueous solution prepared from battery-grade nickel sulfate and purified water, so that the recycling of the product is realized. In addition, when the moisture content of the wet nickel sulfate crystal is high, the carried impurity sodium ions are also high, and when the moisture content is too low, the energy consumption of the centrifugal equipment is high, so that the control of the moisture content of the wet nickel sulfate crystal within a proper range is very important, preferably, the moisture content of the first wet nickel sulfate crystal is 2-8 wt%, and the moisture content of the second wet nickel sulfate crystal is 2-8 wt%, so that the smooth washing and drying operation is facilitated, the impurity ions, especially the sodium ion content of the battery-grade nickel sulfate is reduced, and the high-purity product is obtained.
The volume of the saturated nickel sulfate aqueous solution used should be matched with the washing mode, otherwise the impurity ion removal is incomplete, or the loss of nickel ions in crystals is caused, thereby affecting the yield and purity of the product nickel sulfate. The first wet nickel sulfate crystals are preferably treated using spray washing. The spray washing can realize dehydration and washing in the same centrifuge, the operation is simple, the impurity sodium ions carried in the wet crystals can be more completely removed, and the purity of the product nickel sulfate is higher. Correspondingly, in a preferred embodiment, when the washing mode is spray washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 0.25-1 mL.
Accordingly, in a preferred embodiment, when the washing manner is slurry washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 1-3 mL, and the washing time of the slurry washing is 10-60 min.
Through the washing operation, the content of impurity ions, particularly sodium ions, in the first wet nickel sulfate crystal entrainment liquid can be diluted and reduced, the dissolution of nickel ions can be reduced, the purification of a nickel sulfate product is realized, the purity of the product nickel sulfate is improved, and therefore, the total extraction and total reaction of nickel are not needed any more, and the cost is further reduced.
According to the invention, the water content of the first wet nickel sulfate crystal and the second wet nickel sulfate crystal is controlled mainly by controlling the centrifugal parameters, and aiming at different states of the wet nickel sulfate crystal before and after washing, in a preferred embodiment, in the first centrifugal process, the centrifugal speed is 500-3000 rpm, and the centrifugal time is 5-30 min; in the second centrifugation process, the centrifugation rotating speed is 500-3000 rpm, the centrifugation time is 5-30 min, the water content of the wet nickel sulfate crystal can be better controlled within a proper range, and the purity of the battery-grade nickel sulfate is further improved.
In a preferred embodiment, in step S6, the cooling crystallization temperature is 35-50 deg.C, and the nickel sulfate crystal size is more uniform and larger in the above temperature range. In order to avoid bubbling during evaporation and to facilitate the growth of crystal particles and to reduce the introduction of solid impurities into the product, it is preferable to further include a step of removing oil and fine filtering of the third raffinate before the evaporation concentration and cooling crystallization of the third raffinate. After the crystallization is finished, the residual crystallization mother liquor can be recycled through the return extraction process, so that the cost is further reduced, and preferably, after the third raffinate is subjected to evaporation concentration, cooling crystallization and centrifugal separation, the crystallization mother liquor is returned to the first extraction process, the second extraction process and the third extraction process to be used as the soap-transferring precursor liquor of the first extractant, the second extractant and the third extractant, so that the content of heavy metal ions in the batch of products can be further reduced, and the content of impurity ions in the nickel sulfate product is reduced.
To further enhance the separation performance of the extraction process, in a preferred embodiment, the first extractant is a transsoap P204 extractant, the second extractant is a transsoap P507 extractant, and the third extractant is a transsoap P507 extractant and/or a transsoap C272 extractant, which can be saponified with sodium hydroxide solution and then be transsaponified with raffinate or crystallization mother liquor, which if not, can result in a product with higher sodium content and poor quality. Correspondingly, the volume ratio of the first extracting agent to the liquid after iron and aluminum removal is preferably (0.5-2): 1, the volume ratio of the second extracting agent to the first raffinate is (0.5-2): 1, the volume ratio of the third extracting agent to the second raffinate is (0.5-2): 1, and good separation of heavy metal ions, cobalt ions and magnesium ions can be realized in steps by differentiating the setting of the extracting agents and the use ratios, so that better conditions are created for obtaining a high-purity battery-grade nickel sulfate product.
In order to further reduce the influence of iron and aluminum ions in the solution before extraction on the subsequent extraction step, in a preferred embodiment, in step S2, the reagent used in the step of removing iron and aluminum is sodium carbonate and/or sodium hydroxide, and the pH value of the solution after removing iron and aluminum is 4-5.
In a preferred embodiment, the nickel-containing material comprises, by weight, 10 to 40% of nickel element, 2 to 10% of cobalt element, 0.1 to 3% of magnesium element, 2 to 10% of manganese element, 0.1 to 2% of copper element, 0.1 to 15% of calcium element, 0.1 to 2% of zinc element, 0.1 to 1% of aluminum element, and 0.1 to 1% of iron element. The content of each metal element in the nickel-containing material is more representative, and the method is also more suitable for removing each impurity ion and recovering each valuable metal according to the preparation method and the recovery operation of the invention, and has better separation effect.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The battery-grade nickel sulfate meets the national standard GB/T26524-2011, wherein the Na content is required to be less than or equal to 0.01 wt%.
Example 1
The nickel-containing material comprises the following components: 38 wt.% of nickel element, 3.6 wt.% of cobalt element, 2.7 wt.% of magnesium element, 5.9 wt.% of manganese element, 0.1 wt.% of copper element, 0.2 wt.% of calcium element, 0.8 wt.% of zinc element, 0.1 wt.% of aluminum element, and 0.2 wt.% of iron element.
Step S1, adding 0.5L of 98% sulfuric acid aqueous solution with mass concentration and 4.0L of water into 1000g of nickel-containing material, carrying out acid leaching for 2h, and then carrying out filter pressing to obtain 4.5L of nickel-containing solution and leached slag.
And step S2, adding 70g of sodium carbonate into 4.5L of nickel-containing solution to remove iron and aluminum, then performing filter pressing to obtain iron and aluminum removed liquid and iron and aluminum slag, and returning the iron and aluminum slag to the leaching process.
And step S3, adjusting the pH value of the solution after iron and aluminum removal to 2.5, adding 7L of the P204 extractant after soap conversion into 4.5L of the solution after iron and aluminum removal to perform first multistage countercurrent extraction, wherein the extraction stage number is 12, the extraction temperature is 30 ℃, and 4.5L of first raffinate is obtained.
And step S4, adjusting the pH value of the first raffinate to 4, adding 3.5L of the soap-converted P507 extractant into 4.5L of the first raffinate to perform second multi-stage countercurrent extraction, wherein the extraction stage number is 8, the extraction temperature is 30 ℃, and 4.5L of the second raffinate is obtained.
And step S5, adjusting the pH value of the second raffinate to 5, adding 9L of the C272 extracting agent subjected to soap conversion into 4.5L of the second raffinate to perform third multistage countercurrent extraction, wherein the extraction stage number is 12, the extraction temperature is 50 ℃, and 4.5L of the third raffinate is obtained.
Step S6, stirring and deoiling 4.5L of third raffinate with activated carbon, finely filtering, evaporating and concentrating, concentrating to 1/3 of the original volume, cooling and crystallizing at 40 ℃ for 4 hours, and then centrifuging at 3000rpm for 30min to obtain 1719g of first wet nickel sulfate crystal and 1.5L of crystallization mother liquor, wherein the water content of the first wet nickel sulfate crystal is 2%; and evaporating mother liquor to be used as the liquid before soap conversion of the first extractant, the second extractant and the third extractant.
Step S7, preparing 0.45L saturated nickel sulfate aqueous solution by using 270g of battery-grade nickel sulfate and 0.45L of purified water, and spraying and washing 1719g of first wet nickel sulfate crystals; carrying out second centrifugal separation on the obtained washing liquid to obtain second wet nickel sulfate crystals and washing liquid, wherein the water content of the second wet nickel sulfate crystals is 2%; drying the second wet nickel sulfate crystal to obtain 1685g of battery-grade nickel sulfate, wherein the determination results of yield, purity and sodium ion content are shown in Table 1.
Example 2
Example 2 differs from example 1 in that the first wet nickel sulfate crystals had a water content of 8% and the second wet nickel sulfate crystals had a water content of 8%, and the washing was carried out using 5L of a saturated nickel sulfate aqueous solution in a slurry washing manner for 60 min. The results of the nickel sulfate yield, purity, and sodium ion content measurements are shown in Table 1.
Example 3
Example 3 differs from example 1 in that the first wet nickel sulfate crystal had a water content of 4% and the second wet nickel sulfate crystal had a water content of 4%, and the results of the nickel sulfate yield, purity, and sodium ion content measurements were shown in table 1 by washing with 0.9L of a saturated nickel sulfate aqueous solution.
Example 4
Example 4 differs from example 1 in that the washing mode was spray washing and the volume of saturated aqueous nickel sulfate solution used per gram of first wet nickel sulfate crystals was 0.25 mL; the first centrifugal speed is 500rpm, and the first centrifugal time is 30 min; the second centrifugation speed was 500rpm and the second centrifugation time was 30 min. The results of the nickel sulfate yield, purity, and sodium ion content measurements are shown in Table 1.
Example 5
Example 5 differs from example 1 in that the washing mode is spray washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 1mL, the first centrifugation speed is 3000rpm, and the first centrifugation time is 5 min; the second centrifugation speed is 3000rpm, and the second centrifugation time is 5 min. The results of the nickel sulfate yield, purity, and sodium ion content measurements are shown in Table 1.
Example 6
Example 6 differs from example 1 in that the volume ratio of the first extractant to the iron and aluminum depleted liquor was 0.5:1, the volume ratio of the second extractant to the first raffinate was 0.5:1, and the volume ratio of the third extractant to the second raffinate was 0.5: 1. The washing mode is slurrying washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 1mL, and the slurrying time is 60 min. The results of the nickel sulfate yield, purity, and sodium ion content measurements are shown in Table 1.
Example 7
Example 7 differs from example 1 in that the volume ratio of the first extractant to the post iron and aluminum removal liquor was 2:1, the volume ratio of the second extractant to the first raffinate was 2:1, and the volume ratio of the third extractant to the second raffinate was 2: 1. The washing mode is slurrying washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 3mL, and the slurrying time is 10 min. The results of the nickel sulfate yield, purity, and sodium ion content measurements are shown in Table 1.
Comparative example 1
Comparative example 1 differs from example 1 in that the first wet nickel sulfate crystal had a water content of 10% and the second wet nickel sulfate crystal had a water content of 10%, and the results of the nickel sulfate yield, purity, and sodium ion content measurements were shown in table 1, using 0.2L of a saturated nickel sulfate aqueous solution for washing.
Comparative example 2
The difference between the comparative example 2 and the comparative example 1 is that the first extractant, the second extractant and the third extractant are not converted into soap, and the results of the nickel sulfate yield, the purity and the sodium ion content are shown in table 1.
Comparative example 3
Comparative example 3 is different from example 1 in that the third raffinate is directly subjected to evaporative crystallization, and the results of the nickel sulfate yield, purity and sodium ion content are shown in table 1.
TABLE 1
As can be seen from Table 1, compared with the comparative example, the invention does not carry out the total extraction and the total back extraction of nickel, the nickel in the nickel-containing material is well separated from other impurity elements by three times of extraction, the acid and alkali consumption is low, the production cost is low, and meanwhile, the saturated nickel sulfate aqueous solution is used for washing the wet nickel sulfate crystal, so that the content of impurity ions (such as sodium ions) in the carrying liquid of the wet nickel sulfate crystal is reduced, a large amount of dissolution of nickel ions can not be caused, the high purity of the nickel sulfate product is ensured, and the requirement of battery-grade nickel sulfate is met. And when the extracting agent is converted into soap and the process parameters are controlled within the preferable range of the invention, the purity of the nickel sulfate product is better.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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 sulfate is characterized by comprising the following steps:
step S1, adding sulfuric acid into the nickel-containing material for acid leaching to obtain a nickel-containing solution, wherein metal elements in the nickel-containing material comprise nickel elements, cobalt elements, magnesium elements, copper elements, manganese elements, calcium elements, zinc elements, iron elements and aluminum elements;
step S2, performing iron and aluminum removal on the nickel-containing solution to obtain iron and aluminum removed solution;
step S3, carrying out first extraction on the liquid after iron and aluminum removal by using a soap-transferring first extraction agent to obtain a first raffinate;
step S4, carrying out second extraction on the first raffinate by using a soap-converted second extracting agent to obtain a second raffinate;
step S5, carrying out third extraction on the second raffinate by using a soap-converted third extracting agent to obtain a third raffinate;
step S6, sequentially carrying out evaporation concentration and cooling crystallization on the third raffinate, and then carrying out first centrifugal separation to obtain a first wet nickel sulfate crystal and a crystallization mother liquor;
step S7, carrying out spray washing and/or slurry washing on the first wet nickel sulfate crystal by adopting a saturated nickel sulfate aqueous solution, and carrying out second centrifugal separation on the obtained washing liquid to obtain a second wet nickel sulfate crystal and a washing liquid; drying the second wet nickel sulfate crystal to obtain the battery-grade nickel sulfate;
wherein the first extractant, the second extractant and the third extractant are respectively and independently selected from one or more of P204, P507 and C272.
2. The production method according to claim 1, wherein when the volume of the saturated aqueous nickel sulfate solution is denoted by V, the weight of the first wet nickel sulfate crystals is denoted by M, and the water content of the first wet nickel sulfate crystals is denoted by n, V is positively correlated with mxn; preferably, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 0.25-3 mL.
3. The production method according to claim 1 or 2, wherein the saturated aqueous nickel sulfate solution is a saturated aqueous solution prepared from the battery-grade nickel sulfate and purified water; preferably, the water content of the first wet nickel sulfate crystal is 2-8 wt%; the water content of the second wet nickel sulfate crystal is 2-8 wt%.
4. The production method according to any one of claims 1 to 3, wherein when the washing manner is the shower washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 0.25 to 1 mL.
5. The production method according to any one of claims 1 to 4, wherein when the washing method is slurry washing, the volume of the saturated nickel sulfate aqueous solution used per gram of the first wet nickel sulfate crystals is 1 to 3mL, and the washing time of the slurry washing is 10 to 60 min.
6. The preparation method according to any one of claims 1 to 5, wherein in the first centrifugation process, the centrifugation speed is 500-3000 rpm, and the centrifugation time is 5-30 min; in the second centrifugation process, the centrifugation rotating speed is 500-3000 rpm, and the centrifugation time is 5-30 min.
7. The method according to any one of claims 1 to 6, wherein in the step S6, the temperature of the cooling crystallization is 35 to 50 ℃;
preferably, the crystallization mother liquor is returned to the first extraction process, the second extraction process and the third extraction process as a pre-soap conversion liquor of the first extractant, the second extractant and the third extractant.
8. The method according to any one of claims 1 to 7, wherein the first extractant is a P204 extractant, the second extractant is a P507 extractant, and the third extractant is a P507 extractant and/or a C272 extractant; preferably, the volume ratio of the first extracting agent to the liquid after iron and aluminum removal is (0.5-2): 1, the volume ratio of the second extracting agent to the first raffinate is (0.5-2): 1, and the volume ratio of the third extracting agent to the second raffinate is (0.5-2): 1.
9. The method according to any one of claims 1 to 8, wherein in step S2, the reagent used in the step of removing aluminum is sodium carbonate and/or sodium hydroxide.
10. The method according to any one of claims 1 to 9, wherein the nickel-containing material comprises, by weight, 10 to 40% of nickel, 2 to 10% of cobalt, 0.1 to 3% of magnesium, 2 to 10% of manganese, 0.1 to 2% of copper, 0.1 to 15% of calcium, 0.1 to 2% of zinc, 0.1 to 1% of aluminum, and 0.1 to 1% of iron.
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| CN116462245A (en) * | 2023-03-27 | 2023-07-21 | 厦门资生环保科技有限公司 | Sodium washing process method for preparing battery nickel sulfate solution by using high-nickel sludge |
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