CN113528826A - Method for recovering metal in laterite-nickel ore slag - Google Patents
Method for recovering metal in laterite-nickel ore slag Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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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
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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Abstract
The invention relates to a method for recovering metals in laterite-nickel ore. The method takes laterite-nickel ore slag as a raw material, and the laterite-nickel ore slag is mixed with a compounding agent and then ground and sieved to prepare slag powder; mixing part of the slag powder, the charcoal powder and the regulator to prepare a material blank; placing the blank in a reducing atmosphere for roasting; crushing the roasted material blank into material blank powder; mixing and smelting the blank powder and the residual slag powder to obtain a smelted product; mixing the smelted product with mixed acid and carrying out leaching reaction to obtain a leaching solution; and stirring and mixing the leachate and the mixed crystal seeds, and cooling and crystallizing to obtain the polymetallic salt crystal. According to the recovery method, triethanolamine, glycerol and triisopropanolamine are used as compounding agents, humus soil and active lime are used as regulators, the process is simple and easy to implement, dust rising is reduced, the metal recovery rate is high, and effective utilization of the laterite-nickel ore slag is realized.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for recovering metals in laterite-nickel ore slag.
Background
At present, the mainstream technology for refining metallic nickel from laterite-nickel ore is a rotary kiln electric furnace smelting technology, and the metallic nickel produced by the method accounts for more than 70% of the world nickel yield. However, a large amount of slag can be discharged in the smelting process, and 10-15 tons of laterite-nickel ore slag can be generated when 1 ton of iron-nickel metal is produced. According to statistics, in 2020, the amount of the laterite-nickel ore slag discharged domestically exceeds 3800 ten thousand tons. The laterite nickel ore slag comprises 40-60% of silicon dioxide, 8-30% of magnesium oxide, 4-30% of aluminum oxide, 2-20% of calcium oxide, 1.5-8% of ferric oxide and the like, wherein potential extraction values of metals such as magnesium, aluminum, iron and the like are high. At present, the utilization method of the laterite-nickel ore slag mainly replaces simple processing methods such as sand and stone in engineering construction, auxiliary raw materials for producing cement and the like, and gives up secondary utilization of metal in the slag, so that the utilization value of the slag is very low. Therefore, how to better recover the metal resources in the laterite-nickel ore slag has practical significance for the industrial development of the laterite-nickel ore resources.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for recovering metals in laterite-nickel ore slag, so that development and full utilization of laterite resources are realized.
The invention provides a method for recovering metals in laterite-nickel ore slag, which is used for recovering and utilizing the slag generated after high-temperature sintering of laterite-nickel ore. The recovery method comprises the following steps:
(1) pretreatment: mixing the laterite-nickel ore slag with a compounding agent, grinding and sieving to prepare slag powder; wherein the compounding agents comprise triethanolamine, glycerol and triisopropanolamine;
preferably, the method also comprises removing large particle impurities in the laterite nickel ore slag before the step (1).
Preferably, the mass ratio of the laterite-nickel ore slag to the compounding agent is 100: (0.2 to 1); preferably, the mass ratio of the laterite-nickel ore slag to the compounding agent is 100: 0.38.
preferably, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent; the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is (30-70): (5-25): (1-10); preferably, the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is (40-60): (10-15): (1-5).
Preferably, the particles of the slag powder obtained after the sieving treatment are not larger than 200 meshes.
Preferably, in step (1), the method further comprises: grinding charcoal to obtain charcoal powder of no more than 200 meshes.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator to prepare a mixture; preparing the mixture into a blank; wherein the regulator comprises humus soil and active lime;
preferably, in the step (2), part of the slag powder, the charcoal powder and the regulator are mixed in a ratio of 100: (30-60): and (2) drying and uniformly mixing the components in the mass ratio of (2) to (5) to obtain a mixture.
Preferably, the mass ratio of the humus soil to the active lime is 100: (5-20). Preferably, the mass ratio of the humus soil to the active lime is 100: 7.
preferably, the mixture is made into a blocky, pear-shaped or spherical blank by a material pressing machine.
(3) And (3) roasting the blank: placing the blank in a reducing atmosphere for roasting; crushing the roasted material blank into material blank powder; mixing and smelting the blank powder and the residual slag powder to obtain a smelted product;
preferably, the blank is placed in a roasting furnace in a hydrogen atmosphere and roasted at the roasting temperature of 1200-1700 ℃ for 120-200 min.
Preferably, the mixture of the blank powder and the residual slag powder is mixed in a ratio of 100: (10-20) melting at a melting temperature of 1500-2100 ℃ until floating materials are removed. Preferably, the powder billet and the residual slag powder are mixed in a ratio of 100: the mass ratio of 14 was melted in an electric furnace at 2070 ℃ until the floating matter was removed.
Preferably, the blank powder, the residual slag powder and the slag former are mixed and smelted to prepare a smelted product. The slag former comprises calcium fluoride or calcium oxide; the slag former is used as a mixture for separating molten metal and oxides, and is smelted together with the laterite-nickel ore so as to form slag, which is beneficial to metal recovery and improves the utilization rate of the laterite-nickel ore.
(4) Leaching metals: mixing the smelted product with mixed acid and carrying out leaching reaction to obtain a leaching solution;
preferably, mixing the smelted product with mixed acid at the temperature of 70-95 ℃ in a proportion of 40-120 g: mixing 1L of solid-liquid ratio, carrying out leaching reaction for 80-150 min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with water for multiple times to obtain a washing solution; and mixing the water washing liquid and the filtrate to obtain the leaching liquid.
Preferably, mixing the smelted product with mixed acid at 70-75 ℃ in a ratio of 76 g: 1L of the solid-liquid ratio is stirred and mixed, and leaching reaction is carried out for 113 min.
Preferably, the mixed acid includes a plurality of sulfuric acid, hydrochloric acid, and nitric acid, and the sulfuric acid, hydrochloric acid, and nitric acid are industrial-grade acids.
Preferably, the volume ratio of the sulfuric acid to the hydrochloric acid or the nitric acid in the mixed acid is (4-6): (1-2).
Preferably, the volume ratio of sulfuric acid to hydrochloric acid in the mixed acid is 4.5: 1.2. preferably, the filter residue is washed with water for 1-5 times to obtain a water washing solution.
(5) Metal recovery: and stirring and mixing the leachate and the mixed crystal seeds, and cooling and crystallizing to obtain the polymetallic salt crystal.
Preferably, in the step (5), the leachate and the mixed seed crystal are stirred and mixed at 40-50 ℃, and then cooled to 10-25 ℃. Preferably, the leachate and the mixed seed crystal are stirred and mixed at 45 ℃ and then cooled to 19 ℃.
Preferably, in the step (5), the mixed seed crystal is one or more of magnesium sulfate, aluminum sulfate and ferric sulfate.
Preferably, between step (4) and step (5), a step of configuring a seed crystal is further included, specifically: determining seed crystals corresponding to the mixed seed crystals according to the component concentration of each metal in the leaching solution; determining the content of corresponding seed crystals according to the volume of the leachate and the component concentration of each metal in the leachate; and preparing the mixed seed crystal according to the corresponding seed crystal and the content of the corresponding seed crystal.
If the volume of the leachate in the step is 1L, the component concentration of magnesium in the leachate is 14.31g/L, the component concentration of iron is 11.54g/L, and the component concentration of aluminum is 9.27g/L, determining the mixed seed crystal as magnesium sulfate, ferric sulfate and aluminum sulfate according to the component concentrations of magnesium, iron and aluminum; correspondingly, according to the relevant formula, the corresponding concentrations of the magnesium sulfate, the ferric sulfate and the aluminum sulfate which are taken as the crystal seeds are respectively 0.91g/L, 0.56g/L and 0.35 g/L; further, according to the volume of the leaching solution, the corresponding contents of magnesium sulfate, ferric sulfate and aluminum sulfate are respectively determined to be 0.91g, 0.56g and 0.35 g.
Preferably, in the step of configuring the seed crystal, the type of the metal element with the component concentration higher than the preset concentration in the leachate is determined according to the component concentration of each metal in the leachate; and determining the sulfate corresponding to the metal element with the component concentration higher than the preset concentration in the leaching solution as the seed crystal corresponding to the mixed seed crystal.
If the volume of the leachate in the step is 1L, the magnesium component concentration in the leachate is 14.31g/L, the iron component concentration is 11.54g/L, the aluminum component concentration is 3g/L, and the preset concentration is 5g/L, determining the mixed seed crystal as magnesium sulfate and ferric sulfate according to the magnesium, iron and aluminum component concentrations and the preset concentration; correspondingly, according to the related formula, the corresponding concentrations of the magnesium sulfate and the ferric sulfate which are taken as the crystal seeds are 0.91g/L and 0.56g/L respectively; further, according to the volume of the leachate, the respective contents of magnesium sulfate and iron sulfate as the seed crystal were determined to be 0.91g and 0.56g, respectively.
Compared with the prior art, the invention has the following beneficial effects:
(1) the compounding agent is introduced in the pretreatment step, so that the problem of difficult grinding caused by large metal grains in the laterite-nickel ore slag is solved, the laterite-nickel ore slag is easier to refine, and the next step of blank preparation is facilitated.
(2) Charcoal powder and a regulator are introduced in the step of preparing the material embryo, so that the problems that the existing laterite-nickel ore furnace slag powder has hydrophobicity, is difficult to press and form, is easy to break in the roasting process and is accompanied with dust rising are solved, the viscosity of the laterite-nickel ore furnace slag powder is enhanced, the material embryo is favorable for forming, and the material embryo is difficult to crack in the roasting process.
(3) In the step of roasting the blank, the slag powder is added and smelted together with the blank in an electric furnace, so that the using amount of a slag former can be reduced.
(4) In the metal leaching stage, the mixed acid is used for leaching, so that the problem that the existing single acid cannot rapidly and completely leach metals is solved, and the recovery rate of the metals in the laterite-nickel ore slag is improved.
Drawings
Fig. 1 is a flow chart of a method for recovering metals from laterite-nickel ore slag in example 1 of the invention;
fig. 2 is an SEM image of lateritic nickel ore slag before pretreatment in example 1 of the present invention.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples and comparative examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
The laterite-nickel ore slag adopted in the embodiment 1 of the invention is the slag generated after high-temperature sintering of laterite-nickel ore.
Fig. 1 is a flow chart of a method for recovering metals from laterite-nickel ore slag in embodiment 1 of the invention. The method for recovering the metals in the laterite-nickel ore slag in the embodiment 1 comprises the steps of slag pretreatment, material blank preparation, material blank roasting, metal leaching and metal recovery.
Fig. 2 is an SEM image of lateritic nickel ore slag before pretreatment in example 1 of the present invention. As can be seen from the SEM picture of the lateritic nickel ore slag, the lateritic nickel ore slag is abundant in loose particles.
The following are the specific steps of the method for recovering metals from the laterite-nickel ore slag in embodiment 1 of the invention:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore after impurity removal, mixing with a compounding agent in a proportion of 100: 0.38 of mass ratio; uniformly mixing, grinding and sieving to obtain slag powder with a particle size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes. Wherein the compounding ingredient comprises triethanolamine, glycerol and triisopropanol, and the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is 46: 11: 2.5, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator in a proportion of 100: 43: 2.11, drying and uniformly mixing to obtain a mixture; and then the mixture is made into blocks by a material pressing machine. The main raw materials of the regulator are uniformly mixed humus soil and active lime, and the mass ratio of the humus soil to the active lime is 100: 7.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting at 1215-1280 ℃ for 136 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the residual slag powder in a ratio of 100: the mass ratio of 14 is put into an electric furnace at about 2070 ℃ for smelting until floating materials are removed, and a product after smelting is prepared.
(4) Leaching metals: mixing the smelted product with 70-75 ℃ mixed acid in a proportion of 76 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 113min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 2 times to obtain water washing solution; and mixing the water washing liquid and the filtrate to obtain the leaching liquid. The mixed acid is sulfuric acid and hydrochloric acid, and the volume ratio of the sulfuric acid to the hydrochloric acid is 4.5: 1.2, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery: according to the concentration of each metal in the leachate (14.31 g/L of magnesium, 11.54g/L of iron and 9.27g/L of aluminum) and the volume (1L) of the leachate, preparing mixed crystal seeds containing magnesium sulfate, ferric sulfate and aluminum sulfate, wherein the adding amount of the magnesium sulfate, the ferric sulfate and the aluminum sulfate is respectively 0.91g, 0.56g and 0.35 g; adding the mixed seed crystal into the leachate at 45 ℃, and cooling to about 19 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
the metal content of the laterite-nickel ore slag in the embodiment 1 of the invention and the content of each metal in the recovered multi-metal salt crystals are respectively measured by an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite-nickel ore slag are respectively 56.82g, 28.73g and 13.09g, and the contents of magnesium, aluminum and iron in the recovered multimetal salt crystal are respectively 41.7g, 23.29g and 9.66 g. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 73.39%, 81.07% and 73.80%.
Example 2
The laterite-nickel ore slag adopted in the embodiment 2 of the invention is the slag generated after high-temperature sintering of laterite-nickel ore.
The following are the specific steps of the method for recovering metals from laterite-nickel ore slag in embodiment 2 of the invention:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore slag after impurity removal, mixing with a compounding agent in a proportion of 100: 0.75, grinding and sieving after even mixing to prepare slag powder with the grain size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes. The compounding ingredient comprises triethanolamine, glycerol and triisopropanolamine, and the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is 45: 12: 3.7, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder, charcoal powder and regulator in a proportion of 100: 45: 4.3, drying and uniformly mixing to obtain a mixture; and then the mixture is processed into spherical blank by a pressing machine. The main raw materials of the regulator are humus soil and active lime which are uniformly mixed, wherein the mass ratio of the humus soil to the active lime is 100: 13.8.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting at a roasting temperature of 1470-1550 ℃ for 136 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the slag powder in a ratio of 100: 14.6 at about 1985 ℃ until floating materials are removed, and obtaining a product after smelting.
(4) Leaching metals: mixing the smelted product with 84-89 ℃ mixed acid in a proportion of 85.4 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 94min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 2 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; wherein, the mixed acid is sulfuric acid and hydrochloric acid, and the volume ratio of the sulfuric acid to the hydrochloric acid is 5.2: 1.5, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery: preparing mixed seed crystals containing magnesium sulfate, aluminum sulfate and ferric sulfate according to the concentration of each metal in the leachate (magnesium is 15.27g/L, aluminum is 12.19g/L and iron is 8.48g/L) and the volume of the leachate (1L), wherein the adding amount of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is 0.87g, 0.56g and 0.35g respectively; adding the mixed seed crystal into the leaching solution at 41 ℃, and cooling to about 24 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the embodiment 2 of the invention are respectively measured by an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of the laterite-nickel ore slag are respectively 63.52g, 25.63g and 17.62g, and the contents of magnesium, aluminum and iron in the recovered multimetal salt crystal are respectively 46.78g, 22.09g and 13.22 g. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 73.65%, 86.19% and 75.03%.
Example 3
The laterite-nickel ore slag adopted in the embodiment 3 is the slag generated after high-temperature sintering of laterite-nickel ore. The following are the specific steps of the method for recovering metals from the laterite-nickel ore slag in embodiment 3 of the invention:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore slag after impurity removal, mixing with a compounding agent in a proportion of 100: 0.77, grinding and sieving after even mixing to prepare slag powder with the grain size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes. The compounding ingredient comprises triethanolamine, glycerol and triisopropanolamine, and the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is 55: 10: 4.8, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator in a proportion of 100: 47: 3.2, drying and uniformly mixing to obtain a mixture; then a material pressing machine is adopted to make the mixture into a spherical material blank. The main raw materials of the regulator are humus soil and active lime which are uniformly mixed, wherein the mass ratio of the humus soil to the active lime is 100: 18.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting at the roasting temperature of 1580-1660 ℃ for 127 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the residual slag powder in a ratio of 100: 17 in an electric furnace at about 1793 ℃ until floating materials are removed, and obtaining a product after smelting.
(4) Leaching metals: mixing the smelted product with mixed acid at the temperature of 88-90 ℃ in a proportion of 61.7 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 96min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 2 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; the volume ratio of sulfuric acid to nitric acid in the mixed acid is 4: 1.8, the sulfuric acid and the nitric acid are both industrial-grade acids.
(5) Metal recovery: according to the concentration of each metal in the leachate (16.54 g/L of magnesium, 14.46g/L of aluminum and 9.27g/L of iron) and the volume (1L) of the leachate, preparing mixed seed crystals containing magnesium sulfate, aluminum sulfate and ferric sulfate, wherein the adding amount of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is respectively 0.86g, 0.62g and 0.34 g; adding mixed crystal seeds into the leachate at 47 ℃, and cooling to about 24 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the embodiment 3 of the invention are respectively measured by an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite nickel ore slag are 66.07g, 26.75g and 12.58g respectively, and the contents of magnesium, aluminum and iron in the recovered polymetallic salt crystal are 58.03g, 24.28g and 10.25g respectively. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 87.83%, 90.77% and 81.48%.
Example 4
The laterite-nickel ore slag adopted in the embodiment 4 of the invention is the slag generated after high-temperature sintering of laterite-nickel ore.
The following are the specific steps of the method for recovering the metal in the laterite-nickel ore slag in the embodiment 4 of the invention:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore slag after impurity removal, mixing with a compounding agent in a proportion of 100: 0.85, grinding and sieving after even mixing to prepare slag powder with the grain size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes; the compounding ingredients comprise triethanolamine, glycerol and triisopropanol, and the mass ratio of the triethanolamine to the glycerol to the triisopropanol is 48: 10: 4.8, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator in a proportion of 100: 34: 3.9, drying and uniformly mixing to obtain a mixture; and then the mixture is made into a blocky material blank by a material pressing machine. The main raw materials of the regulator are humus soil and active lime which are uniformly mixed, wherein the mass ratio of the humus soil to the active lime is 100: 16.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting at the roasting temperature of 1400-1460 ℃ for 156 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the slag powder in a ratio of 100: 15.3 at about 1958 ℃ until floating materials are removed, and obtaining a product after smelting.
(4) Leaching metals: mixing the smelted product with mixed acid at the temperature of 90-95 ℃ in a proportion of 97 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 142min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 3 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; wherein the volume ratio of sulfuric acid to hydrochloric acid in the mixed acid is 4.8: 2, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery: preparing mixed seed crystals containing magnesium sulfate, aluminum sulfate and ferric sulfate according to the concentration of each metal in the leachate (magnesium is 15.97g/L, aluminum is 12.57g/L and iron is 8.54g/L) and the volume of the leachate (1L), wherein the adding amount of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is 0.86g, 0.61g and 0.42g respectively; adding mixed crystal seeds into the leachate at 48 ℃, and cooling to about 24 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the embodiment 4 of the invention are respectively measured by an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite-nickel ore slag are respectively 68.47g, 21.52g and 17.23g, and the contents of magnesium, aluminum and iron in the recovered multi-metal salt crystal are respectively 51.63g, 18.85g and 15.04 g. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 75.41%, 87.59% and 87.29%.
Example 5
The laterite-nickel ore slag adopted in the embodiment 5 of the invention is the slag generated after high-temperature sintering of laterite-nickel ore.
The following are the specific steps of the method for recovering metals from the laterite-nickel ore slag in embodiment 5 of the invention:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore slag after impurity removal, mixing with a compounding agent in a proportion of 100: 0.89, grinding and sieving to obtain slag powder with the particle size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes; wherein the compounding agent is prepared from triethanolamine: glycerol: triisopropanolamine in a mass ratio of 60: 14: 4.3, and the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator in a proportion of 100: 53: 4.7, drying and uniformly mixing to obtain a mixture; and then, preparing the mixture into a blocky material blank by using a material pressing machine. The main raw materials of the regulator are humus soil and active lime which are uniformly mixed, wherein the mass ratio of the humus soil to the active lime is 100: 20.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting at the roasting temperature of 1620-1680 ℃ for 181 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the residual slag powder in a ratio of 100: smelting at the mass ratio of 16.7 in an electric furnace at about 1921 ℃ until floating materials are removed, and obtaining a smelted product.
(4) Leaching metals: mixing the smelted product with 74 ℃ mixed acid, mixing the smelted product with 113 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 132min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 3 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; the volume ratio of sulfuric acid to hydrochloric acid in the mixed acid is 3.7: 2, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery: according to the concentration of each metal in the leachate (magnesium 16.39g/L, aluminum 11.21g/L and iron 9.17g/L) and the volume of the leachate (1L), preparing a mixed seed crystal containing magnesium sulfate, aluminum sulfate and ferric sulfate, wherein the adding amount of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is 0.83g/L, 0.42g/L and 0.17g/L respectively; adding mixed seed crystal into the leachate at 45 ℃, and cooling to about 25 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the embodiment 5 of the invention are respectively measured by an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite nickel ore slag are respectively 60.3g, 37.12g and 22.45g, and the contents of magnesium, aluminum and iron in the recovered multimetal salt crystal are respectively 44.01g, 29.26g and 18.69 g. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 72.99%, 78.83% and 83.25%.
Comparative example 1
The laterite-nickel ore slag adopted in the comparative example 1 is the slag generated after high-temperature sintering of laterite-nickel ore.
The recovery method comprises the following specific steps:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; 1kg of the laterite-nickel ore slag after impurity removal is ground and sieved to prepare slag powder with the grain size of not more than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes.
(2) Preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator in a proportion of 100: 45: 2.40, drying and uniformly mixing to obtain a mixture; and then the mixture is made into blocks by a material pressing machine. The raw materials of the regulator are humus soil and active lime which are uniformly mixed, wherein the mass ratio of the humus soil to the active lime is 100: 6.
(3) and (3) roasting the blank: placing the blank in a roasting furnace in a hydrogen atmosphere, and roasting for 145min at a roasting temperature of 1245-1280 ℃; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the residual slag powder in a ratio of 100: 14, smelting in an electric furnace at 1862 ℃ until floating materials are removed to obtain a smelted product.
(4) Leaching metals: mixing the smelted product with mixed acid at 78-80 ℃ in a proportion of 85 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 113min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 2 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; the volume ratio of sulfuric acid to hydrochloric acid in the mixed acid is 4.5: 1.5, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery:
preparing mixed seed crystals containing magnesium sulfate, aluminum sulfate and ferric sulfate according to the concentration of each metal in the leachate (16.43 g/L of magnesium, 12.92g/L of aluminum and 5.23g/L of iron) and the volume (1L) of the leachate; the adding amount of magnesium sulfate, aluminum sulfate and ferric sulfate is 0.75g, 0.36g and 0.19g respectively; adding mixed crystal seeds into the leachate at 48 ℃, and cooling to about 20 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
respectively measuring the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the comparative example 1 by adopting an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite nickel ore slag are respectively 58.65g, 33.46g and 19.73g, and the contents of magnesium, aluminum and iron in the recovered multimetal salt crystal are respectively 38.7g, 25.29g and 13.95 g. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 65.98%, 75.58% and 70.70%.
Comparative example 2
The laterite-nickel ore slag adopted in the comparative example 2 is the slag generated after high-temperature sintering of laterite-nickel ore.
Specifically, the recovery method comprises the following specific steps:
(1) pretreatment: removing large particle impurities in the laterite-nickel ore slag; taking 1kg of the laterite-nickel ore slag after impurity removal, mixing with a compounding agent in a proportion of 100: 0.75 mass ratio, grinding and sieving to obtain slag powder not larger than 200 meshes; grinding charcoal to obtain charcoal powder of no more than 200 meshes. The compounding agent comprises triethanolamine, glycerol and triisopropanol, wherein the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is 46: 15: 4.0, the purity of the triethanolamine, the glycerol and the triisopropanolamine is more than 95 percent.
(2) Preparing a blank: mixing part of the slag powder and the charcoal powder in a proportion of 100: 45, drying and uniformly mixing to obtain a mixture; and then the mixture is made into blocks by a material pressing machine.
(3) And (3) roasting the blank: placing the blank in a hydrogen atmosphere roasting furnace, and roasting at 1240-1280 ℃ for 139 min; crushing the roasted material blank into material blank powder with the particle size not larger than 60 meshes; mixing the blank powder and the residual slag powder in a ratio of 100: 14, smelting in an electric furnace at about 1845 ℃ until floating materials are removed to obtain a smelted product.
(4) Leaching metals: mixing the smelted product with mixed acid at 83-86 ℃ in a proportion of 110 g: stirring and mixing 1L of solid-liquid ratio, carrying out leaching reaction for 105min, and carrying out suction filtration to obtain filtrate and filter residue; washing the filter residue with hot water for 2 times to obtain water washing solution; mixing the water washing liquid and the filtrate to obtain a leaching liquid; the volume ratio of sulfuric acid to hydrochloric acid in the mixed acid is 5.5: 1.2, the sulfuric acid and the hydrochloric acid are both industrial-grade acids.
(5) Metal recovery: preparing mixed seed crystals containing magnesium sulfate, aluminum sulfate and ferric sulfate according to the concentration of each metal in the leachate (magnesium is 17.66g/L, aluminum is 10.43g/L and iron is 8.54g/L) and the volume of the leachate (1L), wherein the adding amount of the magnesium sulfate, the aluminum sulfate and the ferric sulfate is 0.87g, 0.43g and 0.26g respectively; adding the mixed seed crystal into the leaching solution at 40 ℃, and cooling to about 18 ℃ in the stirring process to obtain the polymetallic salt crystal.
And (3) testing results:
respectively measuring the metal content of the laterite-nickel ore slag and the content of each metal in the recovered multi-metal salt crystals in the comparative example 2 by adopting an atomic spectrometer, and according to the measurement results: the contents of magnesium, aluminum and iron in 1kg of laterite nickel ore slag are 64.63g, 28.44g and 16.23g respectively, and the contents of magnesium, aluminum and iron in the recovered multi-metal salt crystal are 46.63g, 21.23g and 10.49g respectively. Therefore, by the recovery method, the recovery rates of magnesium, aluminum and iron in the laterite-nickel ore slag are respectively as follows: 72.15%, 74.65% and 64.63%.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A recovery method of metals in laterite-nickel ore slag is characterized by comprising the following steps:
(1) pretreatment: mixing the laterite-nickel ore slag with a compounding agent, grinding and sieving to prepare slag powder; wherein the compounding agents comprise triethanolamine, glycerol and triisopropanolamine;
(2) preparing a blank: mixing part of the slag powder, the charcoal powder and the regulator to prepare a mixture; preparing the mixture into a blank; wherein the regulator comprises humus soil and active lime;
(3) and (3) roasting the blank: placing the blank in a reducing atmosphere for roasting; crushing the roasted material blank into material blank powder; mixing and smelting the blank powder and the residual slag powder to obtain a smelted product;
(4) leaching metals: mixing the smelted product with mixed acid and carrying out leaching reaction to obtain a leaching solution;
(5) metal recovery: and stirring and mixing the leachate and the mixed crystal seeds, and cooling and crystallizing to obtain the polymetallic salt crystal.
2. The recovery method according to the claim 1, characterized in that in step (1), the mass ratio of the lateritic nickel ore slag to the complexing agent is 100: (0.2 to 1); the mass ratio of the triethanolamine to the glycerol to the triisopropanolamine is (40-60): (10-15): (1-5).
3. The recycling method according to claim 1, wherein in the step (2), the mass ratio of the partial slag powder, the charcoal powder and the modifier is 100: (30-60): (2-5); the mass ratio of the humus soil to the active lime is 100: (5-20).
4. The recycling method according to claim 1, wherein in the step (3), the material blank is roasted at a roasting temperature of 1200 to 1700 ℃ in a hydrogen atmosphere for 120 to 200 min; mixing the blank powder and the residual slag powder in a ratio of 100: (10-20) melting at a melting temperature of 1500-2100 ℃.
5. The recycling method according to claim 1, wherein in the step (3), the billet powder and the remaining slag powder are smelted until floaters are removed.
6. The recovery method according to claim 1, wherein in the step (4), the smelted product is mixed with mixed acid at 70-95 ℃ and subjected to leaching reaction for 80-150 min; wherein the solid-to-liquid ratio of the smelted product to the mixed acid is 40-120 g: 1L, the mixed acid comprises a plurality of sulfuric acid, hydrochloric acid and nitric acid, and the volume ratio of the sulfuric acid to the hydrochloric acid or the nitric acid in the mixed acid is (4-6): (1-2).
7. The recycling method according to claim 1, wherein in the step (5), the temperature of the leachate and the mixed seed crystal is reduced to 10-25 ℃ after the leachate and the mixed seed crystal are stirred and mixed at 40-50 ℃.
8. The recycling method according to claim 1, wherein in the step (5), the mixed seed crystal is one or more of magnesium sulfate, aluminum sulfate and ferric sulfate.
9. The recovery method according to claim 1, characterized in that, between steps (4) and (5), it further comprises a step of configuring a seed crystal, in particular: determining seed crystals corresponding to the mixed seed crystals according to the component concentration of each metal in the leaching solution; determining the content of the corresponding seed crystal according to the volume of the leachate and the component concentration of each metal in the leachate; and preparing mixed crystal seeds according to the corresponding crystal seeds and the content of the corresponding crystal seeds.
10. The recycling method according to claim 9, further comprising, in the step of arranging the seed crystal: determining the types of metal elements with component concentrations higher than preset concentrations in the leachate according to the component concentrations of all metals in the leachate; and determining the sulfate corresponding to the metal element with the component concentration higher than the preset concentration in the leaching solution as the seed crystal corresponding to the mixed seed crystal.
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| PCT/CN2021/142956 WO2022267426A1 (en) | 2021-06-25 | 2021-12-30 | Method for recovering metal from laterite-nickel ore slag |
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| CN115254251A (en) * | 2022-07-14 | 2022-11-01 | 扬州一川镍业有限公司 | Laterite-nickel ore electric furnace smelting slag recovery treatment process |
| WO2022267426A1 (en) * | 2021-06-25 | 2022-12-29 | 广东邦普循环科技有限公司 | Method for recovering metal from laterite-nickel ore slag |
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| CN113528826A (en) * | 2021-06-25 | 2021-10-22 | 广东邦普循环科技有限公司 | Method for recovering metal in laterite-nickel ore slag |
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- 2021-06-25 CN CN202110712375.0A patent/CN113528826A/en active Pending
- 2021-12-30 WO PCT/CN2021/142956 patent/WO2022267426A1/en unknown
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| CN101403043A (en) * | 2008-10-27 | 2009-04-08 | 昆明理工大学 | Method for producing ferronickel granule with direct reduction of laterite nickel mine with rotary kiln |
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| WO2022267426A1 (en) * | 2021-06-25 | 2022-12-29 | 广东邦普循环科技有限公司 | Method for recovering metal from laterite-nickel ore slag |
| CN115254251A (en) * | 2022-07-14 | 2022-11-01 | 扬州一川镍业有限公司 | Laterite-nickel ore electric furnace smelting slag recovery treatment process |
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