CN112593080A - Method for treating laterite-nickel ore by combination of pyrogenic process and wet process - Google Patents
Method for treating laterite-nickel ore by combination of pyrogenic process and wet process Download PDFInfo
- Publication number
- CN112593080A CN112593080A CN202011518534.5A CN202011518534A CN112593080A CN 112593080 A CN112593080 A CN 112593080A CN 202011518534 A CN202011518534 A CN 202011518534A CN 112593080 A CN112593080 A CN 112593080A
- Authority
- CN
- China
- Prior art keywords
- nickel
- solution
- laterite
- extractant
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
-
- 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
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
- C22B23/02—Obtaining nickel or cobalt by dry processes
- C22B23/021—Obtaining nickel or cobalt by dry processes by reduction in solid state, e.g. by segregation processes
-
- 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
- C22B23/0423—Halogenated 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
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- 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
- C22B3/04—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
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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 provides a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, which comprises the following steps: (1) pretreating the laterite-nickel ore, including crushing, screening, forming and drying; (2) processing the laterite-nickel ore green pellets by adopting a rotary hearth furnace direct reduction process to obtain metallized pellets; (3) removing gangue components including calcium, magnesium, silicon, aluminum and the like from the metallized pellets through ore grinding and magnetic separation processes; (4) leaching and deironing the ferronickel powder obtained after ore grinding and magnetic separation to obtain leachate containing elements such as nickel, cobalt and the like; (5) extracting the leachate to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution. The nickel-iron alloy is obtained by adopting a direct reduction process, the battery-grade nickel-cobalt solution is prepared by adopting a wet process after impurities are removed, and the battery-grade nickel-cobalt sulfate solution is directly obtained by realizing the cooperative recovery of nickel and cobalt by using the carboxylic acid extracting agent.
Description
Technical Field
The invention belongs to the field of metallurgy, and particularly relates to a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process.
Background
Nickel is an important non-ferrous metal raw material and is abundant on the earth. The nickel ore mainly comprises copper nickel sulfide ore and nickel oxide ore, wherein the development and utilization of the nickel oxide ore mainly comprises laterite nickel ore. At present, the nickel product produced by the laterite-nickel ore mainly comprises two production processes of a fire method and a wet method. The pyrometallurgical processes include rotary kiln-electric furnace reduction smelting process (RKEF), shaft furnace-electric furnace reduction smelting process (NST), Dajiang mountain smelting process and rotary hearth furnace process which are not industrialized yet. The wet process comprises pre-reduction-ammonium leaching, normal pressure acid leaching, high pressure acid leaching, bacterial leaching and the like. A project for processing the laterite-nickel ore by adopting a hydrometallurgical process generally adopts a process of high-pressure acid leaching, washing and separating by a thickener, removing iron, aluminum and nickel cobalt and precipitating to prepare a nickel hydroxide cobalt intermediate product or a nickel sulfide cobalt intermediate product, and the intermediate product further adopts a process of leaching, purifying, evaporating, crystallizing or electrodepositing to produce final products such as nickel sulfate, cobalt sulfate, electrolytic nickel, electrolytic cobalt and the like. For the process using nickel cobalt hydroxide as an intermediate product, sodium hydroxide or magnesium oxide is generally used as a neutralizer for nickel cobalt precipitation, nickel cobalt is recovered through a neutralization precipitation reaction, and simultaneously sodium sulfate or magnesium sulfate is generated in the solution, so that sodium-containing or magnesium-containing process wastewater is generated.
CN109971977A discloses a method for recovering metallic nickel and cobalt from lateritic nickel leaching solution, which comprises the following steps: a, recovering nickel in a laterite-nickel ore leaching liquor by using a continuous ion exchange device, and collecting adsorption tail liquor; b, adsorbing and recovering cobalt from the adsorption tail liquid collected in the step a after the recovery of nickel ions at a certain temperature and a certain flow rate through chelating resin; c, after cobalt is recovered through chelating resin, adsorbing cobalt ions in the laterite-nickel ore leaching liquor onto the chelating resin for recovery, wherein the adsorption tail liquid is the laterite-nickel ore leaching liquor containing trace nickel and cobalt; d, cleaning the cobalt ions adsorbed on the chelating resin by a chemical reagent with a certain concentration at a certain flow rate, and then collecting the cobalt ions; and e, the chelating resin cleaned by the chemical reagent is reused in the nickel recovery adsorption tail liquid of the laterite-nickel ore leaching solution to adsorb and recover cobalt. The method can fully recover nickel ions and cobalt ions in the laterite-nickel ore leaching liquor, but the operation is complex and the control is difficult.
CN102268537B discloses a method for extracting cobalt and nickel from lateritic nickel ore, which comprises the following steps: the method comprises the following steps of roasting nickel laterite ore, mixing the roasted material with water to form slurry, directly adding ion exchange resin to leach and adsorb nickel and cobalt, separating the ion exchange resin from the slurry, removing the nickel and cobalt in the resin by acid washing, separating the nickel and cobalt from the eluent by a solvent extraction method, and directly using the obtained nickel-containing solution and cobalt-containing solution to produce metal nickel and cobalt by electrolysis or produce corresponding salts of the nickel and cobalt. The smelting process for recovering cobalt and nickel from the laterite-nickel ore by the wet method is simplified, a plurality of processes of leaching, impurity removal, concentration and enrichment of nickel and cobalt from the laterite-nickel ore are integrated in one working procedure to be completed, solid-liquid separation and slag washing steps are not needed, the water consumption, the ore pulp treatment capacity and the subsequent wastewater treatment capacity are reduced, the recovery rate of nickel and cobalt in the process is high, the operation is simple, the equipment investment cost can be saved, the consumption of chemical raw materials and a plurality of operation management links are reduced, the recovery rate is only about 90%, and residual metals cannot be recycled, so that the waste is caused.
The method has the problems of complex operation, difficult control, low recovery rate and the like, so that the development of the method for treating the laterite-nickel ore with high recovery rate and simple operation is necessary.
Disclosure of Invention
The invention aims to provide a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, which comprises the following steps: (1) the laterite-nickel ore is pretreated, including crushing, screening, forming and drying; (2) processing the laterite-nickel ore green pellets by adopting a rotary hearth furnace direct reduction process to obtain metallized pellets; (3) removing gangue components including calcium, magnesium, silicon, aluminum and the like from the metallized pellets through ore grinding and magnetic separation processes; (4) leaching and deironing the ferronickel powder obtained after ore grinding and magnetic separation to obtain leachate containing elements such as nickel, cobalt and the like; (5) extracting the leachate to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution. The nickel-iron alloy is obtained by adopting a direct reduction process, the battery-grade nickel-cobalt solution is prepared by adopting a wet process after impurities are removed, and the battery-grade nickel-cobalt sulfate solution is directly obtained by realizing the cooperative recovery of nickel and cobalt by using the carboxylic acid extracting agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, which comprises the following steps:
(1) pretreating the laterite-nickel ore to obtain raw laterite-nickel ore pellets;
(2) carrying out direct reduction treatment on the laterite-nickel ore green pellets obtained in the step (1) to obtain metallized pellets, and carrying out ore grinding and magnetic separation treatment on the metallized pellets to obtain ferronickel powder;
(3) leaching the ferronickel powder obtained in the step (2) to obtain a leaching solution, and carrying out precipitation treatment on the leaching solution to remove iron;
(4) and (4) extracting the leachate after iron removal obtained in the step (3) to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution.
According to the invention, after the laterite-nickel ore is crushed and screened by pretreatment, part of impurities in the laterite-nickel ore can be removed by direct reduction, ore grinding and magnetic separation, and a specific carboxylic acid extractant is used for extracting a leaching solution obtained by leaching treatment, so that the nickel and cobalt can be recovered cooperatively.
Preferably, the extractant for the extraction treatment in the step (4) comprises P204 and/or carboxylic acid extractant;
preferably, the carboxylic acid extractant has the following structural formula:
wherein m + n is more than or equal to 10 and less than or equal to 22.
Preferably, said CnH2n+1Is a linear or branched alkyl group having 1 to 20 carbon atoms.
Preferably, said CmH2m+1Is a linear or branched alkyl group having 1 to 20 carbon atoms.
Preferably, the pretreatment of step (1) comprises crushing, screening, forming and drying.
The carboxylic acid extractant comprises BC191
BC192
BC193
BC194
BC195
Or BC196
Any one or a combination of at least two of them.
In the invention, the carboxylic acid extractant is preferably adopted, and can better realize the synergistic recovery of nickel and cobalt.
Preferably, the crushing device comprises a ball mill crusher and/or a roller crusher.
Preferably, the screened particle size is 100 to 200 mesh, such as: 100 meshes, 120 meshes, 140 meshes, 150 meshes, 160 meshes, 180 meshes, 200 meshes and the like.
Preferably, the forming device comprises a double-roller ball press and/or a disc pelletizer.
Preferably, the drying temperature is 150-300 ℃, for example: 150 ℃, 180 ℃, 200 ℃, 230 ℃, 250 ℃ or 300 ℃ and the like.
Preferably, the drying time is 1-2.5 h, for example: 1h, 1.2h, 1.5h, 1.8h, 2h, 2.2h or 2.5h and the like.
Preferably, the direct reduction treatment apparatus of step (2) comprises a rotary hearth furnace.
Preferably, the temperature of the direct reduction treatment is 950 to 1250 ℃, for example: 950 ℃, 1000 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or 1250 ℃ and the like.
Preferably, the time of the direct reduction treatment is 25-40 min, for example: 25min, 26min, 28min, 30min, 33min, 35min, 37min or 40min and the like.
Preferably, the field strength of the magnetic separation in the step (2) is 1800-2500 Oe, for example: 1800Oe, 1900Oe, 2000Oe, 2100Oe, 2200Oe, 2300Oe, 2400Oe, 2500Oe, or the like, preferably 2000 Oe.
Preferably, the time of the magnetic separation is 8-15 min, for example: 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, etc., preferably 10 min.
Preferably, the leachate leached in the step (3) is an acid solution.
Preferably, the acid solution comprises a hydrochloric acid solution and/or a sulfuric acid solution.
Preferably, the pH of the acid solution is 0.1-2, such as: 0.1, 0.3, 0.5, 0.8, 1, 1.5, 2, etc.
Preferably, the precipitating agent for the precipitation treatment in the step (3) comprises any one of or a combination of at least two of a NaOH solution, ammonia water, a sodium carbonate solution, a sodium bicarbonate solution, oxalic acid and magnesium oxide.
Preferably, the extractant for the extraction treatment in the step (4) further comprises a diluent in addition to the P204 and/or carboxylic acid extractant.
Preferably, the carboxylic acid extractant accounts for 5-30% of the volume fraction of the whole extractant, such as: 5%, 10%, 15%, 20%, 25%, 30%, etc.
Preferably, the diluent comprises any one of mineral spirit, kerosene, Escaid110, hexane, heptane or dodecane or a combination of at least two thereof.
Preferably, the extractant of the extraction treatment in the step (4) is saponified before being used.
Preferably, the saponifying agent used for saponification is an alkaline solution.
Preferably, the alkaline solution comprises any one of sodium hydroxide solution, potassium hydroxide solution or ammonia water or a combination of at least two thereof.
Preferably, the concentration of the alkaline solution is 6-14 mol/L, such as: 6mol/L, 7mol/L, 8mol/L, 9mol/L, 10mol/L, 11mol/L, 12mol/L, 13mol/L or 14mol/L, etc.
As a preferred embodiment of the present invention, the method comprises the steps of:
(1) crushing, screening, molding and drying the laterite-nickel ore to obtain laterite-nickel ore green pellets;
(2) carrying out direct reduction treatment on the laterite-nickel ore green pellets obtained in the step (1) at 950-1250 ℃ for 25-40 min to obtain metallized pellets, and carrying out magnetic separation treatment on the metallized pellets at 1800-2500 Oe for 8-15 min to obtain ferronickel powder;
(3) leaching the ferronickel powder obtained in the step (2) by using an acid solution to obtain a leaching solution, and carrying out precipitation treatment on the leaching solution to remove iron;
(4) diluting the carboxylic acid extractant by using a diluent until the volume fraction is 5-30%, and then performing saponification treatment by using an alkaline solution with the concentration of 6-14 mol/L;
(5) and (4) extracting the leachate obtained in the step (3) after iron removal by using the saponified extractant obtained in the step (4) to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, after the laterite-nickel ore is crushed and screened by pretreatment, part of impurities in the laterite-nickel ore can be removed by direct reduction, ore grinding and magnetic separation, and a specific carboxylic acid extractant is used for extracting a leaching solution obtained by leaching treatment, so that the nickel and cobalt can be recovered cooperatively.
(2) The method has simple process flow and convenient operation, can efficiently recover valuable metals in the laterite-nickel ore by using the combined treatment of the pyrometallurgical method and the wet method, has the nickel extraction rate of more than 95.15 percent, the cobalt extraction rate of more than 91.46 percent and the impurity ion content of high-purity nickel-cobalt solution of less than 10 ppm.
Drawings
Fig. 1 is a flow schematic diagram of a method for treating laterite-nickel ore by a combination of a pyrometallurgical method and a wet method provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
BC191, BC195 and BC196 used in examples 1-5 and comparative examples 1-2 of the present invention were prepared as disclosed in CN 111592459A.
Example 1
The components of the lateritic nickel ore in the present example are shown in table 1:
TABLE 1
| Element(s) | Fe | Ni | Co | Al2O3 | CaO | MgO |
| wt％ | 20.4 | 1.56 | 0.05 | 3.0 | 3.2 | 18.0 |
The embodiment provides a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, wherein the method has the flow shown in figure 1, and comprises the following specific operation steps:
(1) crushing and screening the laterite-nickel ore to be below 150 meshes, and carrying out raw material forming and drying treatment to obtain laterite-nickel ore green pellets;
(2) directly reducing the laterite-nickel ore green pellets obtained in the step (1) for 38min at 1000 ℃ in a rotary hearth furnace to obtain metallized pellets;
(3) grinding the metallized pellets obtained in the step (2), and then carrying out magnetic separation for 10min under the condition that the magnetic field intensity is 2000Oe to remove gangue components to obtain ferronickel powder;
(4) leaching the ferronickel powder obtained in the step (3) with dilute sulfuric acid to obtain a leachate, adding ammonia water into the leachate, controlling the reaction temperature to be 88 ℃ and the pH to be 3.62, and removing iron through precipitation treatment to obtain a nickel-cobalt-containing leachate, wherein the concentration of each element in the nickel-cobalt leachate is shown in table 2:
TABLE 2
| Element(s) | Fe | Ni | Co | Al | Ca | Mg |
| g/L | 0.40 | 4.60 | 0.15 | 0.50 | 0.42 | 0.85 |
(5) Extracting 8-stage extraction (the volume ratio of an organic phase to a feed liquid is 1:4, the extraction mixing time is 3min, the standing time is 15min, countercurrent extraction is carried out by adopting a continuous extraction tank), 8-stage washing (the volume ratio of the organic phase to a washing liquid is 1: 0.1, the washing liquid is dilute sulfuric acid with the pH value of 1, countercurrent washing is carried out by adopting the continuous extraction tank), 6-stage back extraction (the volume ratio of the organic phase to the back extraction agent is 1:0.07, the back extraction agent is 2M sulfuric acid, and countercurrent back extraction is carried out by adopting the continuous extraction tank) with a saponified extractant (a carboxylic acid extractant is BC191, a diluent is Escaid110, the volume fraction of the extractant is 25%, the saponification degree is 50%, and the saponifier is 11M ammonia water) and a nickel-cobalt leaching solution to obtain a raffinate containing nickel-cobalt-magnesium, ferric sulfate and.
Carrying out 10-stage extraction (the volume ratio of an organic phase to a feed liquid is 1:2, the extraction mixing time is 5min, the standing time is 15min, countercurrent extraction is adopted in a continuous extraction tank), 8-stage washing (the volume ratio of the organic phase to a washing liquid is 1: 0.5, the washing liquid is dilute sulfuric acid with the pH value of 1, countercurrent washing is adopted in the continuous extraction tank), 6-stage back extraction (the volume ratio of the organic phase to the back extraction agent is 1:0.07, the back extraction agent is 2M sulfuric acid, and countercurrent back extraction is adopted in the continuous extraction tank) on the saponified extractant (the volume fraction of the extractant is 25%, the saponification degree of saponification is 50%, and the saponifying agent is 11M ammonia water) and the nickel-cobalt-magnesium-containing raffinate to obtain the high-purity nickel-cobalt solution and the magnesium-containing raffinate.
Example 2
The embodiment provides a method for treating lateritic nickel ore, and the components of the lateritic nickel ore in the embodiment are shown in table 3:
TABLE 3
| Element(s) | Fe | Ni | Co | Al2O3 | CaO | MgO |
| wt％ | 20.0 | 1.60 | 0.10 | 3.8 | 3.8 | 20.0 |
The embodiment provides a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, which comprises the following specific operation steps:
(1) crushing and screening the laterite-nickel ore to below 200 meshes, and carrying out raw material forming and drying treatment to obtain laterite-nickel ore green pellets;
(2) directly reducing the laterite nickel ore green pellets obtained in the step (1) for 42min at 1050 ℃ in a rotary hearth furnace to obtain metallized pellets;
(3) grinding the metallized pellets obtained in the step (2), and then carrying out magnetic separation for 10min under the condition that the magnetic field intensity is 2000Oe to remove gangue components to obtain ferronickel powder;
(4) leaching the ferronickel powder obtained in the step (3) with dilute sulfuric acid to obtain a leachate, adding ammonia water into the leachate, controlling the reaction temperature to be 85 ℃ and the pH to be 3.68, and removing iron through precipitation treatment to obtain a nickel-cobalt-containing leachate, wherein the concentration of each element in the nickel-cobalt leachate is shown in table 4:
TABLE 4
| Element(s) | Fe | Ni | Co | Al | Ca | Mg |
| g/L | 0.05 | 3.88 | 0.199 | 0.003 | 0.38 | 0.885 |
Extracting the saponified extractant (the carboxylic acid extractant is BC195, the diluent is sulfonated kerosene, the volume fraction of the extractant is 25%, the saponification degree is 45%, and the saponifier is 10.5M NaOH) and the nickel-cobalt leaching solution by 10 levels of extraction (the volume ratio of the organic phase to the feed liquid is 1: 5, the extraction mixing time is 5min, the standing time is 15min, countercurrent extraction is carried out by adopting a continuous extraction tank), 9 levels of washing (the volume ratio of the organic phase to the washing liquid is 1: 0.25, the washing liquid is dilute sulfuric acid with the pH value of 0.5, countercurrent washing is carried out by adopting the continuous extraction tank), and 6 levels of back extraction (the volume ratio of the organic phase to the back extractant is 1: 0.05, the back extractant is 2M sulfuric acid, and countercurrent back extraction is carried out by adopting the continuous extraction tank), so as to obtain the raffinate containing nickel-cobalt-magnesium and the solution of.
Using saponified extractant (carboxylic acid extractant BC196, diluent Escaid110, volume fraction of extractant 30%, saponification degree 55%, saponifier 10.5M NaOH) and nickel-cobalt-magnesium-containing raffinate to perform 8-stage extraction (organic phase to feed liquid volume ratio of 1: 3, extraction mixing time of 5min, standing time of 15min, countercurrent extraction by using a continuous extraction tank), 11-stage washing (organic phase to washing liquid volume ratio of 1: 0.4, washing liquid is dilute sulfuric acid with pH of 1, countercurrent washing by using a continuous extraction tank), 6-stage back extraction (organic phase to back extraction agent volume ratio of 1:0.07, back extraction agent is 2M sulfuric acid, countercurrent back extraction by using a continuous extraction tank), and obtaining nickel-cobalt-containing solution and magnesium-containing raffinate.
Example 3
The components of the lateritic nickel ore in this example are shown in table 5:
TABLE 5
| Element(s) | Fe | Ni | Co | Al2O3 | CaO | MgO |
| wt％ | 25 | 1.7 | 0.12 | 4.0 | 4.2 | 22.0 |
The embodiment provides a method for treating laterite-nickel ore by a combination of a pyrogenic process and a wet process, which comprises the following specific operation steps:
(1) crushing and screening the laterite-nickel ore to 200 meshes, and carrying out raw material forming and drying treatment to obtain laterite-nickel ore green pellets;
(2) directly reducing the laterite nickel ore green pellets obtained in the step (1) for 40min at 1150 ℃ in a rotary hearth furnace to obtain metallized pellets;
(3) grinding the metallized pellets obtained in the step (2), and then carrying out magnetic separation for 10min under the condition that the magnetic field intensity is 2000Oe to remove gangue components to obtain ferronickel powder;
(4) leaching the ferronickel powder obtained in the step (3) with dilute sulfuric acid to obtain a leachate, adding ammonia water into the leachate, controlling the reaction temperature to be 81 ℃ and the pH to be 3.32, and removing iron through precipitation treatment to obtain a nickel-cobalt-containing leachate, wherein the concentration of each element in the nickel-cobalt leachate is shown in table 6:
TABLE 6
| Element(s) | Fe | Ni | Co | Al | Ca | Mg |
| g/L | 0.02 | 6.88 | 0.93 | 0.005 | 0.04 | 1.33 |
(5) The extraction method comprises the steps of performing 9-stage extraction (the volume ratio of an organic phase to a feed liquid is 1:4, the extraction mixing time is 5min, the standing time is 15min, countercurrent extraction is performed by using a continuous extraction tank), 9-stage washing (the volume ratio of the organic phase to a washing liquid is 1: 0.25, the washing liquid is dilute sulfuric acid with the pH value of 0.5, countercurrent washing is performed by using the continuous extraction tank), and 6-stage back extraction (the volume ratio of the organic phase to the back extraction agent is 1:0.07, the back extraction agent is 2M sulfuric acid, and countercurrent back extraction is performed by using the continuous extraction tank) on a saponified extractant (P204 extractant, the diluent is Escaid110, the volume fraction of the extractant is 25%, the saponification degree is 50%, and the saponifying agent is 11M sodium hydroxide) and a nickel cobalt leaching solution to obtain a nickel cobalt magnesium extraction raffinate and an iron.
Using saponified extractant (carboxylic acid extractant BC196, diluent Escaid110, volume fraction of extractant 30%, saponification degree 40%, saponifier 10.5M ammonia water) and nickel-cobalt-magnesium-containing raffinate to perform 9-stage extraction (volume ratio of organic phase to feed liquid is 1: 3, extraction mixing time is 5min, standing time is 15min, countercurrent extraction is performed by using a continuous extraction tank), 12-stage washing (volume ratio of organic phase to washing liquid is 1: 0.25, washing liquid is dilute sulfuric acid with pH of 1, countercurrent washing is performed by using a continuous extraction tank), 6-stage back extraction (volume ratio of organic phase to back extraction agent is 1:0.07, back extraction agent is 2M sulfuric acid, countercurrent back extraction is performed by using a continuous extraction tank), and obtaining nickel-cobalt-containing solution and magnesium-containing raffinate.
Example 4
This example is different from example 1 only in that the temperature of the direct reduction treatment in step (2) is 950 ℃, and other conditions and parameters are exactly the same as those of example 1.
Example 5
This example differs from example 1 only in that the temperature of the direct reduction treatment in step (2) was 1250 ℃, and the other conditions and parameters were exactly the same as those in example 1.
Comparative example 1
The comparative example is different from example 1 only in that the direct reduction treatment of step (2) is not performed, the ore grinding and magnetic separation treatment of step (3) is directly performed after step (1), and other conditions and parameters are completely the same as those of example 1.
Comparative example 2
The comparative example is different from example 1 only in that step (4) is directly performed after step (2) without grinding and magnetic separation treatment in step (3), and other conditions and parameters are completely the same as those in example 1.
The test results of examples 1-5 and comparative examples 1-2 are shown in Table 7:
TABLE 7
| Nickel extraction rate/% | Cobalt extraction rate/% | Content of magnesium and calcium | Aluminum, iron, copper and zinc contents | |
| Example 1 | 98.75 | 96.33 | <10ppm | <5ppm |
| Example 2 | 99.35 | 98.64 | <10ppm | <5ppm |
| Example 3 | 99.22 | 97.88 | <10ppm | <5ppm |
| Example 4 | 95.15 | 93.23 | <10ppm | <5ppm |
| Example 5 | 97.21 | 91.46 | <10ppm | <5ppm |
| Comparative example 1 | / | / | / | / |
| Comparative example 2 | / | / | / | / |
As can be seen from Table 1, by using the method for treating the laterite-nickel ore by the combination of the pyrometallurgy and the wet method, the nickel extraction rate can reach more than 95.15%, the cobalt extraction rate can reach more than 91.46%, and meanwhile, the magnesium and calcium content in the extraction liquid is less than 10ppm, and the aluminum, iron, copper and zinc content is less than 5 ppm.
Compared with the examples 4 to 5, the temperature of the direct reduction treatment in the step (2) should be kept between 950 ℃ and 1250 ℃, if the temperature is lower than 950 ℃, completely reduced metallized pellets cannot be obtained, and if the temperature is higher than 1250 ℃, the morphology of the metallized pellets may be damaged, thereby affecting the extraction rate of nickel and cobalt.
Compared with the comparative example 1, the method has the advantages that the reduction treatment step in the step (2) is not performed, metal ions in the laterite-nickel ore exist in a non-oxidation state and do not have magnetism, so that nickel and cobalt cannot be separated from impurity metals such as iron, calcium, magnesium and the like by ore grinding and magnetic separation, the consumption of acid and alkali in subsequent leaching is high, and the economic benefit is low.
Compared with the comparative example 2, the method has the advantages that the ore grinding and magnetic separation treatment in the step (3) are not performed, the magnetic separation operation is not performed on the metal in the laterite-nickel ore, the nickel and cobalt can not be separated from impurity metals such as iron, calcium, magnesium and the like, the subsequent leaching is high in acid and alkali consumption, and the economic benefit is low.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for treating laterite-nickel ore by a pyrometallurgical-hydrometallurgical process is characterized by comprising the following steps:
(1) pretreating the laterite-nickel ore to obtain raw laterite-nickel ore pellets;
(2) carrying out direct reduction treatment on the laterite-nickel ore green pellets obtained in the step (1) to obtain metallized pellets, and carrying out ore grinding and magnetic separation treatment on the metallized pellets to obtain ferronickel powder;
(3) leaching the ferronickel powder obtained in the step (2) to obtain a leaching solution, and carrying out precipitation treatment on the leaching solution to remove iron;
(4) and (4) extracting the leachate after iron removal obtained in the step (3) to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution.
2. The method of claim 1, wherein the extractant of the extraction treatment of step (4) comprises P204 and/or a carboxylic acid-based extractant;
preferably, the carboxylic acid extractant has the following structural formula:
wherein m + n is more than or equal to 10 and less than or equal to 22;
preferably, said CnH2n+1Is a linear or branched alkyl group having 1 to 20 carbon atoms;
preferably, said CmH2m+1Is a linear or branched alkyl group having 1 to 20 carbon atoms.
3. The method of claim 1 or 2, wherein the pretreatment of step (1) comprises crushing, sieving, forming, and drying;
preferably, the crushing device comprises a ball mill crusher and/or a roller crusher;
preferably, the screened granularity is 100-200 meshes;
preferably, the forming device comprises a double-roller ball press and/or a disc pelletizer;
preferably, the drying temperature is 150-300 ℃;
preferably, the drying time is 1-2.5 h.
4. The method according to any one of claims 1 to 3, wherein the direct reduction treatment apparatus of step (2) comprises a rotary hearth furnace;
preferably, the temperature of the direct reduction treatment is 950-1250 ℃;
preferably, the time of the direct reduction treatment is 25-40 min.
5. The method of any one of claims 1 to 4, wherein the magnetic separation in step (2) has a field strength of 1800Oe to 2500Oe, preferably 2000 Oe;
preferably, the time for magnetic separation is 8-15 min, preferably 10 min.
6. A process according to any one of claims 1 to 5, wherein the leach solution from step (3) is an acid solution;
preferably, the acid solution comprises a hydrochloric acid solution and/or a sulfuric acid solution;
preferably, the pH of the acid solution is 0.1-2.
7. The method according to any one of claims 1 to 6, wherein the precipitant for the precipitation treatment in step (3) comprises any one of NaOH solution, ammonia water, sodium carbonate solution, sodium bicarbonate solution, oxalic acid, and magnesium oxide, or a combination of at least two thereof.
8. The process of any one of claims 1 to 7, wherein the extractant of the extraction treatment of step (4) comprises a diluent in addition to the P204 and/or carboxylic acid-based extractant;
preferably, the carboxylic acid extractant accounts for 5-30% of the volume fraction of the whole extractant;
preferably, the diluent comprises any one of mineral spirit, kerosene, Escaid110, hexane, heptane or dodecane or a combination of at least two thereof.
9. The method of any one of claims 1 to 8, wherein the extractive treated extractant of step (4) is saponified prior to use;
preferably, the saponifying agent used for saponification is an alkaline solution;
preferably, the alkaline solution comprises any one of sodium hydroxide solution, potassium hydroxide solution or ammonia water or a combination of at least two of the above;
preferably, the concentration of the alkaline solution is 6-14 mol/L.
10. The method according to any one of claims 1 to 9, characterized in that it comprises the steps of:
(1) crushing, screening, molding and drying the laterite-nickel ore to obtain laterite-nickel ore green pellets;
(2) carrying out direct reduction treatment on the laterite-nickel ore green pellets obtained in the step (1) at 950-1250 ℃ for 25-40 min to obtain metallized pellets, and carrying out magnetic separation treatment on the metallized pellets at 1800-2500 Oe for 8-15 min to obtain ferronickel powder;
(3) leaching the ferronickel powder obtained in the step (2) by using an acid solution to obtain a leaching solution, and carrying out precipitation treatment on the leaching solution to remove iron;
(4) diluting the carboxylic acid extractant by using a diluent until the volume fraction is 5-30%, and then performing saponification treatment by using an alkaline solution with the concentration of 6-14 mol/L;
(5) and (4) extracting the leachate obtained in the step (3) after iron removal by using the saponified extractant obtained in the step (4) to obtain a battery-grade nickel sulfate solution and a battery-grade cobalt sulfate solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011518534.5A CN112593080A (en) | 2020-12-21 | 2020-12-21 | Method for treating laterite-nickel ore by combination of pyrogenic process and wet process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011518534.5A CN112593080A (en) | 2020-12-21 | 2020-12-21 | Method for treating laterite-nickel ore by combination of pyrogenic process and wet process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112593080A true CN112593080A (en) | 2021-04-02 |
Family
ID=75199663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011518534.5A Pending CN112593080A (en) | 2020-12-21 | 2020-12-21 | Method for treating laterite-nickel ore by combination of pyrogenic process and wet process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112593080A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621831A (en) * | 2021-08-12 | 2021-11-09 | 材料科学姑苏实验室 | Method for extracting nickel from laterite-nickel ore |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230422A (en) * | 2008-02-02 | 2008-07-30 | 贵研铂业股份有限公司 | Method for enriching nickel from lateritic nickel with co-production of iron-oxide red |
| CN101338376A (en) * | 2008-08-15 | 2009-01-07 | 中南大学 | Process for comprehensively developing and utilizing nickel, cobalt, iron and magnesium from laterite-nickel ore |
| CN102010993A (en) * | 2010-11-10 | 2011-04-13 | 吉林吉恩镍业股份有限公司 | Process for extracting nickel and cobalt from laterite by ore pulp extraction technology |
| WO2013152487A1 (en) * | 2012-04-09 | 2013-10-17 | 北京神雾环境能源科技集团股份有限公司 | Laterite-nickel ore processing method for efficiently recovering nickel resources |
| CN105296744A (en) * | 2015-10-26 | 2016-02-03 | 广西银亿再生资源有限公司 | Method for laterite-nickel ore resourceful treatment and comprehensive recycling |
| WO2016171579A1 (en) * | 2015-04-21 | 2016-10-27 | Общество С Ограниченной Ответственностью "Ви Холдинг" | Low-temperature method for processing lateritic nickel ores so as to directly produce ferronickel |
| CN106957955A (en) * | 2017-04-27 | 2017-07-18 | 江苏省冶金设计院有限公司 | Handle the method and system of lateritic nickel ore |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
-
2020
- 2020-12-21 CN CN202011518534.5A patent/CN112593080A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101230422A (en) * | 2008-02-02 | 2008-07-30 | 贵研铂业股份有限公司 | Method for enriching nickel from lateritic nickel with co-production of iron-oxide red |
| CN101338376A (en) * | 2008-08-15 | 2009-01-07 | 中南大学 | Process for comprehensively developing and utilizing nickel, cobalt, iron and magnesium from laterite-nickel ore |
| CN102010993A (en) * | 2010-11-10 | 2011-04-13 | 吉林吉恩镍业股份有限公司 | Process for extracting nickel and cobalt from laterite by ore pulp extraction technology |
| WO2013152487A1 (en) * | 2012-04-09 | 2013-10-17 | 北京神雾环境能源科技集团股份有限公司 | Laterite-nickel ore processing method for efficiently recovering nickel resources |
| WO2016171579A1 (en) * | 2015-04-21 | 2016-10-27 | Общество С Ограниченной Ответственностью "Ви Холдинг" | Low-temperature method for processing lateritic nickel ores so as to directly produce ferronickel |
| CN105296744A (en) * | 2015-10-26 | 2016-02-03 | 广西银亿再生资源有限公司 | Method for laterite-nickel ore resourceful treatment and comprehensive recycling |
| CN106957955A (en) * | 2017-04-27 | 2017-07-18 | 江苏省冶金设计院有限公司 | Handle the method and system of lateritic nickel ore |
| CN111592459A (en) * | 2020-06-28 | 2020-08-28 | 北京博萃循环科技有限公司 | Carboxylic acid compound, preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621831A (en) * | 2021-08-12 | 2021-11-09 | 材料科学姑苏实验室 | Method for extracting nickel from laterite-nickel ore |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11459636B2 (en) | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore | |
| AU2019308625B2 (en) | Method for recycling iron, scandium, and aluminum from limonite type lateritic nickel ores | |
| CN101298638B (en) | Method for collecting nickel and cobalt from laterite-nickel ore lixivium | |
| CN109234526B (en) | Treatment method of laterite-nickel ore | |
| CN112430733A (en) | Method for treating laterite-nickel ore | |
| CN101225470B (en) | Method for extracting nickel and cobalt from lateritic nickel by hydrochloric acid process | |
| CN112575208B (en) | Method for preparing high-purity manganese sulfate from electrolytic manganese sulfide slag | |
| CN113387402B (en) | Method for producing nickel cobalt sulfate salt by using nickel cobalt hydroxide raw material crystallization method | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN112458280A (en) | Method for extracting valuable metals by leaching low grade nickel matte with acidic etching solution | |
| CN112226630B (en) | Method for extracting valuable metal elements from laterite-nickel ore by hydrochloric acid leaching method and acid-base regeneration circulation | |
| CN113088710A (en) | Method for separating copper and germanium from copper and germanium replacement slag | |
| CN111778404A (en) | Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material | |
| CN111500862A (en) | Method for removing iron and aluminum from mixed nickel cobalt hydroxide leachate | |
| CN100554453C (en) | A kind of leaching method of materials after nickelous oxide mine chloridization oxidation treatment | |
| CN114604837A (en) | Preparation method of iron phosphate and preparation method of lithium iron phosphate | |
| CN101693554A (en) | Method for extracting vanadium pentoxide from stone coal ores | |
| CN112593080A (en) | Method for treating laterite-nickel ore by combination of pyrogenic process and wet process | |
| CN112410568A (en) | Method for preparing cobalt ferrite from cobalt-containing slag | |
| CN101545056A (en) | Process for extracting nickel by acid dipping full-wet method at normal temperature and normal pressure | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| CN114959302A (en) | Method for preparing nickel sulfate/cobalt from laterite-nickel ore | |
| CN113999989A (en) | Method for treating laterite-nickel ore by using ferrate | |
| CN112853117A (en) | Method for selectively recovering copper from electroplating sludge through hydrothermal ammonia leaching | |
| CN114686698B (en) | Treatment method of laterite nickel ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210402 |