CN114959252A - Method for producing nickel sulfate by using high-nickel matte - Google Patents
Method for producing nickel sulfate by using high-nickel matte Download PDFInfo
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- CN114959252A CN114959252A CN202210598100.3A CN202210598100A CN114959252A CN 114959252 A CN114959252 A CN 114959252A CN 202210598100 A CN202210598100 A CN 202210598100A CN 114959252 A CN114959252 A CN 114959252A
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- nickel
- iron
- copper
- sulfuric acid
- leaching
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 69
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 29
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 97
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010949 copper Substances 0.000 claims abstract description 46
- 238000002386 leaching Methods 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 230000008569 process Effects 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000000605 extraction Methods 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 6
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims abstract description 5
- 229940044175 cobalt sulfate Drugs 0.000 claims abstract description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 27
- 238000001704 evaporation Methods 0.000 claims description 21
- 239000002893 slag Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000008020 evaporation Effects 0.000 claims description 15
- 239000000344 soap Substances 0.000 claims description 15
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 12
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 238000007664 blowing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 6
- 229910020598 Co Fe Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B15/00—Other processes for the manufacture of iron from iron compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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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
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Abstract
The invention relates to a method for producing nickel sulfate by using high-nickel matte, the main components of the high-nickel matte are 65-69% of Ni, 4-6.5% of Cu, 0.85-1.5% of Co, 1.5-2.2% of Fe and 22-25% of S, the method comprises the steps of oxidizing roasting, sulfuric acid leaching, displacement copper removal, neutralization iron removal, deep extraction purification and concentrated crystallization; the leaching rate of nickel, copper, iron and cobalt can be more than 95 percent by leaching the high-nickel matte by sulfuric acid after oxidizing and roasting; and then, replacing and removing copper, neutralizing and removing iron, and extracting to remove impurities by adopting iron powder, so that crude copper powder, iron powder and cobalt sulfate byproducts are produced while producing a nickel sulfate product, the comprehensive utilization of resources of various valuable metal elements is realized, and the recovery rate of nickel is more than 92%. The invention opens up a brand new and high-efficiency process technology for directly producing nickel sulfate by using high-nickel matte, and has wide application value and development prospect.
Description
Technical Field
The invention relates to the technical field of non-ferrous metal hydrometallurgy, in particular to a method for producing nickel sulfate by using high-nickel matte.
Background
With the rapid development of the electric automobile market, the demand of the power battery for nickel sulfate increases the ship height, and each large enterprise increases the production strength of nickel sulfate and improves the yield and quality of nickel sulfate. The main raw materials of the nickel sulfate comprise high nickel matte, nickel wet-process intermediate products, nickel bean/nickel powder, waste nickel and the like. At present, other modes except metallic nickel raw materials are mainly used for preparing nickel sulfate in China.
The high-nickel matte is a pyrometallurgical intermediate product, mainly contains Ni 65-69%, Cu 4-6.5%, Co 0.85-1.5%, Fe 1.5-2.2% and S22-25%, and can be further treated to produce electrolytic nickel product. In order to meet the supply requirement of nickel sulfate, the invention provides a process technology for directly producing nickel sulfate from high-nickel matte.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing nickel sulfate by using high-nickel matte.
In order to solve the problems, the method for producing the nickel sulfate by using the high-nickel matte, disclosed by the invention, comprises the following main components of 65-69% of Ni, 4-6.5% of Cu, 0.85-1.5% of Co, 1.5-2.2% of Fe and 22-25% of S, and comprises the following steps:
(1) oxidizing and roasting: adding high-nickel matte into a rotary kiln for roasting, controlling roasting temperature and roasting time, and blowing air simultaneously to ensure that the conversion rate of the sulfide in the high-nickel matte roasted into oxide is more than 98 percent;
(2) sulfuric acid leaching: preparing the roasted material into slurry with the mass ratio of 20%, adding sulfuric acid, wherein the dosage of the sulfuric acid is 1.0-1.2 times of the theoretical dosage, controlling the reaction temperature to be 80-90 ℃, and reacting for 2-3h, so as to leach and convert the oxides into sulfate and realize the complete leaching of nickel, copper, iron and cobalt;
(3) and (3) displacement copper removal: adding iron powder into the sulfuric acid leaching solution, wherein the using amount of the iron powder is 0.9-0.95 time of theoretical using amount, and controlling the reaction temperature and the reaction time to ensure that the concentration of copper ions in the copper removing solution is 0.5-1.0g/L, so as to produce crude copper powder;
(4) neutralizing and deironing: adding nickel carbonate into the copper removing liquid, blowing air simultaneously, controlling the reaction temperature to be 70-80 ℃, reacting for 2-3h, and generating iron slag when the pH value of the reaction end point is 4.5-5.0;
(5) extraction and deep purification: preparing C272 with the concentration of 10-15% as an extracting agent, wherein the extracting agent is subjected to sodium soap by using a sodium hydroxide solution, and then is subjected to nickel soap by using a nickel sulfate solution; extracting the iron-removed liquid by using a nickel soap C272, controlling the ratio of O/A to be 1:2-3 and the grade number to be 4-6, and enabling impurity elements such as cobalt, copper and zinc in the iron-removed liquid to enter an organic phase;
(6) concentration and crystallization: evaporating and concentrating the raffinate to 350-400g/L, and cooling and crystallizing to obtain a nickel sulfate product.
Preferably, in the step (1), the roasting temperature is controlled to be 750-.
Preferably, the temperature is controlled to be 80-90 ℃, and the reaction time is 4-5 h.
Preferably, the step (4) further comprises the iron slag treatment: and (3) preparing iron slag obtained after neutralization and iron removal into slurry with the mass ratio of 30%, controlling the reaction temperature and the reaction time, adding sulfuric acid for pressure leaching, using the produced pressure leaching liquid for the sulfuric acid leaching process in the step (2), and using carbon reduction to prepare iron powder for the replacement and copper removal process in the step (3).
Preferably, in the iron slag treatment step, the reaction temperature is controlled to be 150-160 ℃, the reaction time is 1-2h, and the adding amount of the sulfuric acid is 8-10% of the amount of the iron slag.
Preferably, after the step (5), the method further comprises the following steps: and (3) performing back extraction on the organic phase by using a dilute sulfuric acid solution to produce a crude cobalt sulfate solution which can be used as a cobalt smelting raw material.
Preferably, step (6) further comprises: most of the evaporation mother liquor is circularly returned to the liquid before evaporation, and 3-5% of the evaporation mother liquor is separated for preparing nickel carbonate, so that the open circuit of impurity elements is realized.
Compared with the prior art, the invention has the following advantages:
in the invention, the leaching rates of nickel, copper, iron and cobalt are all more than 95 percent by leaching the high-nickel matte by sulfuric acid after oxidizing and roasting; and then, replacing and removing copper, neutralizing and removing iron, and extracting to remove impurities by adopting iron powder, so that crude copper powder, iron powder and cobalt sulfate byproducts are produced while producing a nickel sulfate product, the comprehensive utilization of resources of various valuable metal elements is realized, and the recovery rate of nickel is more than 92%.
The invention opens up a brand-new and high-efficiency process technology for directly producing nickel sulfate by using high-nickel matte, can enable production enterprises to selectively produce nickel sulfate products and electrolytic nickel products according to market supply-demand relations, realizes market supply-demand balance of the two products, and has wide application value and development prospect.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a process flow diagram provided in an embodiment of the present invention.
Detailed Description
Example 1
The composition of the high nickel matte in this example is shown in table 1.
TABLE 1 high nickel matte composition (wt%)
| Element(s) | Ni | Cu | Co | Fe | S |
| wt% | 68.38 | 4.13 | 1.06 | 1.58 | 22.76 |
(1) Oxidizing and roasting: and adding the high-nickel matte into a rotary kiln for roasting, controlling the roasting temperature to be 750 ℃, and roasting for 2 hours, and simultaneously blowing air to ensure that the sulfide in the high-nickel matte is completely roasted into oxide as far as possible.
Wherein the roasting temperature is controlled at 750 ℃ and 800 ℃, and the roasting time is controlled at 2-3h, so that the conversion rate of the sulfide is more than 98%.
(2) Sulfuric acid leaching: preparing the roasted material into 20 percent (mass percentage) slurry, adding sulfuric acid, wherein the sulfuric acid is 1.0 time of the theoretical amount, controlling the reaction temperature at 80 ℃, and reacting for 2 hours to leach and convert the oxides into sulfate, thereby realizing the complete leaching of metal elements such as nickel, copper, iron, cobalt and the like. Wherein the theoretical dosage of the sulfuric acid is 69.35mL (98% concentrated sulfuric acid)/100 g of high-nickel matte; the theoretical amount of sulfuric acid is the amount of sulfuric acid consumed by the theoretical calculation of the chemical reaction between nickel, copper, iron and cobalt oxides generated by oxidizing and roasting high-nickel matte and sulfuric acid.
(3) And (3) replacement and copper removal: adding iron powder into the sulfuric acid leaching solution, wherein the using amount of the iron powder is 0.9 time of the theoretical using amount, controlling the reaction temperature to be 80 ℃, and reacting for 4 hours.
The step can produce copper removing liquid and coarse copper powder, the copper removing liquid enters the step (4), and the coarse copper powder can be used as a copper smelting raw material. Wherein the theoretical dosage of the iron powder is the total amount of ferric ions and copper ions. The reaction temperature is 80-90 ℃, the reaction time is 4-5h, and under the condition, the concentration of copper ions in the copper removing liquid is 0.5-1.0 g/L.
(4) Neutralizing and deironing: adding nickel carbonate into the copper removing liquid, blowing air simultaneously, controlling the reaction temperature at 70 ℃, reacting for 2h, and controlling the pH value at the end point of the reaction to be 4.5.
A certain amount of iron is leached in the leaching process of sulfuric acid leaching in the step (2), a certain amount of iron ions are introduced in the replacement copper removal process of replacement copper removal in the step (3), and in order to avoid introducing other impurities and ensure the impurity removal requirement, nickel carbonate (prepared by evaporating mother liquor and sodium carbonate in the step (6)) is adopted, and air is blown in for neutralization and iron removal.
This step can produce and remove indisputable liquid and scum, removes indisputable liquid and gets into step (5), because the entrainment volume of nickel is great in the scum, adopts the nickel of smuggleing secretly in the pressurization selectivity leaching sediment, and the concrete step of scum treatment is: preparing 30 mass percent of slurry from the iron slag, controlling the reaction temperature to be 150 ℃ and the reaction time to be 1h, adding 8 mass percent of sulfuric acid into the slurry to perform pressure leaching, wherein the produced pressure leaching solution can be used for the sulfuric acid leaching process in the step (2), and the produced iron slag can be reduced by carbon to prepare iron powder for the replacement copper removal process in the step (3).
(5) Extraction and deep purification: preparing C272 with the concentration of 10% as an extracting agent, wherein the extracting agent is firstly subjected to sodium soap by using a sodium hydroxide solution, and then is subjected to nickel soap by using a nickel sulfate solution; extracting the iron-removed liquid by using the nickel soap C272, controlling the ratio of O/A to be 1:3, and controlling the grade to be 4, so that impurity elements such as cobalt, copper, zinc and the like in the iron-removed liquid enter an organic phase.
In addition, dilute sulfuric acid solution can be used for carrying out back extraction on the organic phase to produce crude cobalt sulfate solution which can be used as a cobalt smelting raw material.
(6) Concentration and crystallization: evaporating and concentrating the raffinate to 350g/L, and cooling and crystallizing to obtain a nickel sulfate product.
Most of the evaporation mother liquor is circularly returned to the liquid before evaporation, and 3-5% (mass percent) of the evaporation mother liquor is separated for preparing the nickel carbonate, so that the open circuit of the impurity elements is realized, wherein the impurity elements can be prevented from being enriched by 3-5% of the selection amount. The prepared nickel carbonate can be used for neutralizing and removing iron in the step (4).
The process effect is as follows: the leaching rate of nickel is 96.23 percent, the leaching rate of cobalt is 95.38 percent, the leaching rate of copper is 95.51 percent, and the leaching rate of iron is 97.26 percent. The nickel recovery rate of the total process flow is 93.15 percent.
In the implementation, no waste slag is discharged in the whole process, the recovery rate of valuable metals is high, no impurity element is introduced, and the method is a high-efficiency process method for comprehensively utilizing the valuable metal elements and resources.
Example 2
The composition of the high nickel matte in this example is shown in table 2.
TABLE 2 high nickel matte composition (wt%)
| Element(s) | Ni | Cu | Co | Fe | S |
| wt% | 65.47 | 5.78 | 0.86 | 1.91 | 23.62 |
(1) Oxidizing and roasting: and adding the high-nickel matte into a rotary kiln for roasting, controlling the roasting temperature to be 800 ℃, and roasting for 3 hours, and simultaneously blowing air to ensure that the sulfide in the high-nickel matte is completely roasted into oxide as far as possible.
(2) Sulfuric acid leaching: preparing the roasted material into 20 percent (mass percentage) slurry, adding sulfuric acid, wherein the sulfuric acid is 1.2 times of the theoretical amount, controlling the reaction temperature to be 90 ℃, and reacting for 3 hours to leach and convert the oxides into sulfate so as to realize the complete leaching of metal elements such as nickel, copper, iron, cobalt and the like. Wherein the theoretical amount of sulfuric acid used is 68.21mL (98% concentrated sulfuric acid)/100 g of nickel-rich sulfonium.
(3) And (3) replacement and copper removal: adding iron powder into the sulfuric acid leaching solution, wherein the dosage of the iron powder is 0.95 time of the theoretical dosage, controlling the reaction temperature to be 90 ℃, and reacting for 5 hours. The produced crude copper powder is used as a copper smelting raw material.
(4) Neutralizing and deironing: adding nickel carbonate into the copper removing liquid, blowing air simultaneously, controlling the reaction temperature to be 80 ℃, reacting for 3 hours, and controlling the pH value at the end point of the reaction to be 5.0.
Preparing 30 percent (mass percentage) of neutralized iron slag slurry, controlling the reaction temperature to be 160 ℃, reacting for 2 hours, wherein the adding amount of sulfuric acid is 8 percent (mass percentage) of the amount of the neutralized iron slag, and the produced pressurized leachate returns to the leaching process, and the produced iron slag is reduced by carbon to prepare iron powder.
(5) Extraction and deep purification: preparing 15% C272 as an extracting agent, wherein the extracting agent is subjected to sodium soap by using a sodium hydroxide solution, and then is subjected to nickel soap by using a nickel sulfate solution; extracting the iron-removed liquid by using the nickel soap C272, controlling the ratio of O/A to be 1:2, and controlling the grade to be 6, so that impurity elements such as cobalt, copper, zinc and the like in the iron-removed liquid enter an organic phase.
(6) Concentration and crystallization: evaporating and concentrating raffinate to 400g/L, and cooling and crystallizing to obtain a nickel sulfate product.
Most of the evaporation mother liquor circularly returns to the liquid before evaporation, and 3% of the evaporation mother liquor is separated for preparing nickel carbonate, so that the open circuit of impurity elements is realized.
The process effect is as follows: the leaching rate of nickel is 97.21%, the leaching rate of cobalt is 96.11%, the leaching rate of copper is 96.37% and the leaching rate of iron is 98.14%. The overall process nickel recovery was 92.76%.
Example 3
The composition of the high nickel matte in this example is shown in table 3.
TABLE 3 high nickel matte composition (wt%)
| Element(s) | Ni | Cu | Co | Fe | S |
| wt% | 66.11 | 6.07 | 1.12 | 2.05 | 24.79 |
(1) Oxidizing and roasting: and adding the high-nickel matte into a rotary kiln for roasting, controlling the roasting temperature to be 800 ℃, and roasting for 2 hours, and simultaneously blowing air to ensure that the sulfide in the high-nickel matte is completely roasted into oxide as far as possible.
(2) Sulfuric acid leaching: preparing the roasted material into 20 percent (mass percentage) slurry, adding sulfuric acid, wherein the sulfuric acid is 1.2 times of the theoretical amount, controlling the reaction temperature at 80 ℃, and reacting for 2 hours to leach and convert the oxides into sulfate, thereby realizing the complete leaching of metal elements such as nickel, copper, iron, cobalt and the like. Wherein the theoretical amount of sulfuric acid used is 69.42mL (98% concentrated sulfuric acid)/100 g of nickel matte.
(3) And (3) replacement and copper removal: adding iron powder into the sulfuric acid leaching solution, wherein the using amount of the iron powder is 0.9 time of the theoretical using amount, controlling the reaction temperature to be 90 ℃, and reacting for 4 hours. The produced crude copper powder is used as a copper smelting raw material.
(4) Neutralizing and deironing: adding nickel carbonate into the copper removing liquid, blowing air simultaneously, controlling the reaction temperature to be 80 ℃, reacting for 3 hours, and controlling the pH value at the end point of the reaction to be 4.5.
Preparing 30 percent (mass percentage) of neutralized iron slag slurry, controlling the reaction temperature to be 160 ℃, reacting for 2 hours, wherein the adding amount of sulfuric acid is 10 percent (mass percentage) of the amount of the neutralized iron slag, and the produced pressurized leachate returns to the leaching process, and the produced iron slag is reduced by carbon to prepare iron powder.
(5) Extraction and deep purification: preparing C272 with the concentration of 10% as an extracting agent, wherein the extracting agent is firstly subjected to sodium soap by using a sodium hydroxide solution, and then is subjected to nickel soap by using a nickel sulfate solution; extracting the iron-removed liquid by using the nickel soap C272, controlling the ratio of O/A to be 1:3, and controlling the grade to be 6, so that impurity elements such as cobalt, copper, zinc and the like in the iron-removed liquid enter an organic phase.
(6) Concentration and crystallization: evaporating and concentrating the raffinate to 350g/L, and cooling and crystallizing to obtain a nickel sulfate product.
Most of the evaporation mother liquor circularly returns to the liquid before evaporation, and 3% of the evaporation mother liquor is separated for preparing nickel carbonate, so that the open circuit of impurity elements is realized.
The process effect is as follows: the leaching rate of nickel is 96.18 percent, the leaching rate of cobalt is 95.73 percent, the leaching rate of copper is 95.69 percent, and the leaching rate of iron is 96.55 percent. The overall process nickel recovery was 92.82%.
The technical solution provided by the present invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (7)
1. A method for producing nickel sulfate by using high-nickel matte is characterized in that the main components of the high-nickel matte are 65-69% of Ni, 4-6.5% of Cu, 0.85-1.5% of Co, 1.5-2.2% of Fe and 22-25% of S, and the method comprises the following steps:
(1) oxidizing and roasting: adding high-nickel matte into a rotary kiln for roasting, controlling roasting temperature and roasting time, and blowing air simultaneously to ensure that the conversion rate of sulfide in the high-nickel matte roasted into oxide is more than 98 percent;
(2) sulfuric acid leaching: preparing the roasted material into slurry with the mass ratio of 20%, adding sulfuric acid, wherein the dosage of the sulfuric acid is 1.0-1.2 times of the theoretical dosage, controlling the reaction temperature to be 80-90 ℃, and reacting for 2-3h, so as to leach and convert the oxides into sulfate and realize the complete leaching of nickel, copper, iron and cobalt;
(3) and (3) replacement and copper removal: adding iron powder into the sulfuric acid leaching solution, wherein the using amount of the iron powder is 0.9-0.95 time of theoretical using amount, and controlling the reaction temperature and the reaction time to ensure that the concentration of copper ions in the copper removing solution is 0.5-1.0g/L, so as to produce crude copper powder;
(4) neutralizing and deironing: adding nickel carbonate into the copper removing liquid, blowing air simultaneously, controlling the reaction temperature to be 70-80 ℃, reacting for 2-3h, and generating iron slag when the pH value of the reaction end point is 4.5-5.0;
(5) extraction and deep purification: preparing C272 with the concentration of 10-15% as an extracting agent, wherein the extracting agent is subjected to sodium soap by using a sodium hydroxide solution, and then is subjected to nickel soap by using a nickel sulfate solution; extracting the iron-removed liquid by using a nickel soap C272, controlling the ratio of O/A to be 1:2-3 and the grade number to be 4-6, and enabling impurity elements such as cobalt, copper and zinc in the iron-removed liquid to enter an organic phase;
(6) concentration and crystallization: evaporating and concentrating the raffinate to 350-400g/L, and cooling and crystallizing to obtain a nickel sulfate product.
2. The method as claimed in claim 1, wherein in the step (1), the calcination temperature is controlled to be 750-800 ℃ and the calcination time is 2-3 h.
3. The method of claim 1, wherein in the step (3), the temperature is controlled to be 80-90 ℃ and the reaction time is 4-5 hours.
4. The method of claim 1, further comprising, in step (4): and (3) preparing iron slag obtained after neutralization and iron removal into slurry with the mass ratio of 30%, controlling the reaction temperature and the reaction time, adding sulfuric acid for pressure leaching, using the produced pressure leaching liquid for the sulfuric acid leaching process in the step (2), and using carbon reduction to prepare iron powder for the replacement and copper removal process in the step (3).
5. The method as claimed in claim 4, wherein in the step of treating the iron slag, the reaction temperature is controlled to be 150 ℃ and 160 ℃, the reaction time is 1-2h, and the amount of the sulfuric acid added is 8-10% of the amount of the iron slag.
6. The method of claim 1, further comprising, after step (5): and (3) performing back extraction on the organic phase by using a dilute sulfuric acid solution to produce a crude cobalt sulfate solution which can be used as a cobalt smelting raw material.
7. The method of claim 1, wherein step (6) further comprises: most of the evaporation mother liquor is circularly returned to the liquid before evaporation, and 3-5% of the evaporation mother liquor is separated for preparing nickel carbonate, so that the open circuit of impurity elements is realized.
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| US20240228321A1 (en) * | 2023-01-11 | 2024-07-11 | Korea Zinc Co., Ltd. | Method for producing nickel sulfate solution for secondary battery from nickel cathode |
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