CN110331283B - Method for treating acid leaching residues of laterite-nickel ore - Google Patents
Method for treating acid leaching residues of laterite-nickel ore Download PDFInfo
- Publication number
- CN110331283B CN110331283B CN201910765616.0A CN201910765616A CN110331283B CN 110331283 B CN110331283 B CN 110331283B CN 201910765616 A CN201910765616 A CN 201910765616A CN 110331283 B CN110331283 B CN 110331283B
- Authority
- CN
- China
- Prior art keywords
- iron
- slag
- nickel
- aluminum
- stage
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- 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
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention provides a method for treating acid leaching residues of laterite-nickel ore. The processing method comprises the following steps: carrying out pressure acid leaching treatment on the laterite-nickel ore to obtain iron-containing acid leaching slag and acid leaching liquid; pre-neutralizing the pickle liquor to obtain pre-neutralized liquor; adjusting the pH value of the pre-neutralization solution to 3.2-3.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform first-stage iron and aluminum removal to obtain first-stage iron and aluminum slag and first-stage iron and aluminum removed liquid; processing the mixture of the iron-aluminum slag and the iron-containing acid leaching slag by using a magnetizing roasting process to obtain iron ore concentrate; adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.2-4.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform second-stage iron-removal aluminum to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; carrying out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid to obtain lean solution and nickel and cobalt precipitates after nickel and cobalt precipitation; precipitating manganese and magnesium from the lean solution after nickel and cobalt precipitation in steps to obtain manganese slag and magnesium slag; the two-stage iron-aluminum slag is returned to the pressure acid leaching process, so that the metal recovery rate is improved.
Description
Technical Field
The invention relates to the technical field of metal recovery, in particular to a method for treating laterite-nickel ore acid leaching slag.
Background
With the rapid development of the battery industry, the demand of nickel and cobalt in the world rises sharply, the price of nickel and cobalt rises greatly, high-grade nickel and cobalt resources are depleted day by day, people focus on developing low-grade laterite-nickel ore with complex components, and the adopted process is generally a high-pressure acid leaching process to produce nickel and cobalt raw materials for batteries.
However, the high-pressure acid leaching process generates a large amount of leaching residues with high iron content, gypsum residues, manganese-magnesium residues and the like, and the leaching residues, the gypsum residues, the manganese-magnesium residues and the like need to be stockpiled in a tailing pond, otherwise, the environment is polluted.
Disclosure of Invention
The invention mainly aims to provide a method for treating laterite-nickel ore acid leaching slag, which aims to solve the problems of low metal recovery rate and serious environmental pollution in laterite-nickel ore acid leaching slag in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for treating acid leaching slag of lateritic nickel ore, comprising: carrying out pressure acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid; pre-neutralizing the pickle liquor, and carrying out solid-liquid separation to obtain gypsum residue and pre-neutralized liquor; adjusting the pH value of the pre-neutralization solution to 3.2-3.5 by using calcium hydroxide at 70-80 ℃ to perform first-stage iron and aluminum removal, and performing solid-liquid separation to obtain first-stage iron and aluminum slag and first-stage iron and aluminum removed liquid; treating the mixture of the iron-aluminum slag and the iron-containing acid leaching slag by using a magnetizing roasting process to obtain iron ore concentrate and harmless tailings, wherein the weight content of the iron-aluminum slag in one section of the mixture is below 25%; adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.2-4.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform second-stage iron-removal aluminum, and performing solid-liquid separation to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; carrying out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid to obtain lean solution and nickel and cobalt precipitates after nickel and cobalt precipitation; precipitating manganese and magnesium from the lean solution after nickel and cobalt precipitation in steps to obtain manganese slag and magnesium slag in sequence; and returning the second-stage iron-aluminum slag to the pressure acid leaching treatment process.
Further, the process of depositing manganese and depositing magnesium on the barren solution after nickel and cobalt deposition in steps comprises: oxidizing the barren solution after nickel and cobalt precipitation, then regulating the pH value of the barren solution after nickel and cobalt precipitation to 9.0-9.5 by using calcium hydroxide at the temperature of 0-50 ℃ for manganese precipitation, and performing solid-liquid separation to obtain manganese slag and a solution after manganese precipitation; and (3) adjusting the pH value of the solution after manganese precipitation to 10.5-11.5 by using calcium hydroxide at the temperature of 0-50 ℃ to precipitate magnesium, and performing solid-liquid separation to obtain magnesium slag and a solution after magnesium precipitation.
Further, the above-mentioned process of depositing nickel cobalt to second-stage deironing aluminium liquid includes: regulating the pH value of the second-stage iron-removed aluminum liquid to 7.0-7.2 by using calcium hydroxide at the temperature of 60-65 ℃ to carry out nickel and cobalt precipitation, and carrying out solid-liquid separation to obtain a first-stage mixed nickel and cobalt precipitate and a first-stage nickel and cobalt precipitation liquid; and (3) regulating the pH value of the solution after the first-stage nickel and cobalt precipitation to 8.0-8.5 by using calcium hydroxide at the temperature of 50-55 ℃, performing nickel and cobalt precipitation, and performing solid-liquid separation to obtain a second-stage mixed nickel and cobalt precipitate and a lean solution after nickel and cobalt precipitation.
Further, the treatment method also comprises the step of returning the second-stage mixed nickel cobalt precipitate to the pressure acid leaching treatment process.
Further, the process for treating the mixture of the section of the iron-aluminum slag and the iron-containing acid leaching slag by using the magnetizing roasting process comprises the following steps: carrying out magnetizing roasting on the mixture after blending coal to obtain roasting slag; and carrying out magnetic separation on the roasting slag to obtain iron ore concentrate and harmless tailings.
Furthermore, coal is blended in an amount of 10 to 30 wt% of the mixture, and preferably one or both of anthracite and lignite are blended.
Further, the roasting temperature of the magnetizing roasting is 700-1000 ℃, the roasting time is 1-2 hours, and water quenching is carried out on the roasted slag after the magnetizing roasting is finished and before the magnetic separation is carried out on the roasted slag.
Furthermore, the magnetic field intensity of the magnetic separation is 100-300 kA/m.
Further, the process of pre-neutralizing the acid leaching solution comprises the steps of adding limestone into the acid leaching solution for pre-neutralizing to enable the concentration of sulfuric acid in the acid leaching solution to be 10-15 g/L, adjusting the temperature of the acid leaching solution after pre-neutralizing to be 80-90 ℃, and then carrying out solid-liquid separation.
Further, the temperature for carrying out the pressure acid leaching treatment on the laterite-nickel ore is 230-260 ℃, and the pressure is 3-6 MPa.
By applying the technical scheme of the invention, the obtained gypsum slag, manganese slag and magnesium slag can be used as common solid waste for treatment, and can be sold as a byproduct due to higher manganese content in the manganese slag and higher magnesium content in the magnesium slag, so that the recovery of a small amount of manganese and magnesium in the leaching slag containing the ferrite is realized; the first-stage iron and aluminum removal is carried out under the conditions, so that iron elements are left in the slag as much as possible, and the recovery rate of iron is improved; iron in the iron-containing acid leaching slag and a section of iron-aluminum slag is efficiently recovered by utilizing a magnetizing roasting process, wherein the obtained iron concentrate has high grade and can be directly used as a raw material of other iron products, and the obtained harmless tailings have no environmental pollution and can also be used as a raw material for producing cement; meanwhile, the iron and aluminum are removed in the second stage under the conditions, so that the iron and the aluminum enter the slag as much as possible and return to the pressurized acid leaching treatment process to improve the recovery of the iron, the content of the iron and the aluminum in the second stage iron-removed aluminum liquid is reduced, and the subsequent separation efficiency of the nickel and the cobalt is improved; further, the treatment method also carries out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid, thereby realizing the recovery of nickel and cobalt. In conclusion, the treatment method realizes the recovery of valuable metal elements in the ferrous acid-containing leaching slag, further improves the metal recovery rate, realizes the efficient utilization of laterite-nickel ore resources, obviously relieves the problem of environmental pollution caused by the ferrous acid-containing leaching slag, and can further utilize the slag to realize the harmless treatment of the slag.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology of the application, the high-pressure acid leaching process generates a large amount of acid leaching residues, and at present, valuable metals in the acid leaching residues are not sufficiently recovered, so that the metal recovery rate is low, and further the environmental pollution is serious. In order to solve the problems, the application provides a method for treating acid leaching slag of laterite-nickel ore. The processing method comprises the following steps: carrying out pressure acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid; pre-neutralizing the pickle liquor, and carrying out solid-liquid separation to obtain gypsum residue and pre-neutralized liquor; adjusting the pH value of the pre-neutralization solution to 3.2-3.5 by using calcium hydroxide at 70-80 ℃ to perform first-stage iron and aluminum removal, and performing solid-liquid separation to obtain first-stage iron and aluminum slag and first-stage iron and aluminum removed liquid; treating the mixture of the iron-aluminum slag and the iron-containing acid leaching slag by using a magnetizing roasting process to obtain iron ore concentrate and harmless tailings; adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.2-4.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform second-stage iron-removal aluminum, and performing solid-liquid separation to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; carrying out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid to obtain lean solution and nickel and cobalt precipitates after nickel and cobalt precipitation; precipitating manganese and magnesium from the lean solution after nickel and cobalt precipitation in steps to obtain manganese slag and magnesium slag in sequence; and returning the second-stage iron-aluminum slag to the pressure acid leaching treatment process.
According to the treatment method, the obtained gypsum slag, manganese slag and magnesium slag can be used as common solid waste for treatment, and can be sold as byproducts due to the fact that the manganese content in the manganese slag is high and the magnesium content in the magnesium slag is high, so that the recovery of a small amount of manganese and magnesium in the leaching slag containing the ferrite is realized; the first-stage iron and aluminum removal is carried out under the conditions, so that iron elements are left in the slag as much as possible, the recovery rate of iron is improved, and the high-quality first-stage iron and aluminum slag is provided for subsequent magnetizing roasting; iron in the iron-containing acid leaching slag and a section of iron-aluminum slag is efficiently recovered by utilizing a magnetizing roasting process, wherein the obtained iron concentrate has high grade and can be directly used as a raw material of other iron products, and the obtained harmless tailings have no environmental pollution and can also be used as a raw material for producing cement; meanwhile, the iron and aluminum are removed in the second stage under the conditions, so that the iron and the aluminum enter the slag as much as possible and return to the pressurized acid leaching treatment process to improve the recovery of the iron, the content of the iron and the aluminum in the second stage iron-removed aluminum liquid is reduced, and the subsequent separation efficiency of the nickel and the cobalt is improved; further, the treatment method also carries out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid, thereby realizing the recovery of nickel and cobalt. In conclusion, the treatment method realizes the recovery of valuable metal elements in the ferrous acid-containing leaching slag, further improves the metal recovery rate, realizes the efficient utilization of laterite-nickel ore resources, obviously relieves the problem of environmental pollution caused by the ferrous acid-containing leaching slag, and can further utilize the slag to realize the harmless treatment of the slag.
In a preferred embodiment of the present application, in order to improve the recovery and separation effects of manganese and magnesium, the above-mentioned process of precipitating manganese and magnesium in the post-nickel-cobalt-precipitation barren solution sub-step preferably includes: oxidizing the lean solution after nickel and cobalt precipitation, then regulating the pH value of the lean solution after nickel and cobalt precipitation to 9.0-9.5 by using calcium hydroxide at 0-50 ℃ for manganese precipitation, and performing solid-liquid separation to obtain manganese slag and a solution after manganese precipitation, wherein the lean solution after nickel and cobalt precipitation is oxidized to oxidize manganese therein into high-valence manganese, so that manganese is more easily precipitated preferentially to realize the separation of manganese and magnesium; and (3) adjusting the pH value of the solution after manganese precipitation to 10.5-11.5 by using calcium hydroxide at the temperature of 0-50 ℃ to precipitate magnesium, and performing solid-liquid separation to obtain magnesium slag and a solution after magnesium precipitation.
In another preferred embodiment of the present application, the above process of depositing nickel and cobalt on the second-stage molten iron after removing iron includes: regulating the pH value of the second-stage iron-removed aluminum liquid to 7.0-7.2 by using calcium hydroxide at the temperature of 60-65 ℃ to carry out nickel and cobalt precipitation, and carrying out solid-liquid separation to obtain a first-stage mixed nickel and cobalt precipitate and a first-stage nickel and cobalt precipitation liquid; and (3) regulating the pH value of the solution after the first-stage nickel and cobalt precipitation to 8.0-8.5 by using calcium hydroxide at the temperature of 55-60 ℃ to precipitate nickel and cobalt, and performing solid-liquid separation to obtain a second-stage mixed nickel and cobalt precipitate and a lean solution after nickel and cobalt precipitation. The nickel and cobalt precipitation is carried out in stages, the consumption of calcium hydroxide is reduced on the premise of realizing the nickel and cobalt recovery efficiency as much as possible, and the nickel and cobalt recovery cost is saved.
In addition, in order to further improve the recovery rate of nickel in the laterite-nickel ore, the treatment method preferably further comprises the step of returning the second-stage mixed nickel-cobalt precipitate to the pressure acid leaching treatment process. So that the nickel and cobalt in the second-stage mixed nickel-cobalt precipitate can be further recovered by a pressure acid leaching treatment process.
The magnetizing roasting process used in the present application can be implemented by referring to the prior art, and preferably the above-mentioned process for treating a mixture of a section of ferroaluminum slag and iron-containing acid leaching slag by using the magnetizing roasting process comprises: carrying out magnetizing roasting on the mixture after blending coal to obtain roasting slag; and carrying out magnetic separation on the roasting slag to obtain iron ore concentrate and harmless tailings.
In order to improve the magnetization efficiency, the coal is preferably blended in an amount of 10 to 30 wt% based on the mixture, and in order to improve the utilization efficiency of the coal, one or both of anthracite and lignite are preferably blended.
In the magnetizing roasting process, weak magnetic iron trioxide is reduced into strong magnetic ferroferric oxide, in order to improve the reduction efficiency and further improve the magnetic separation efficiency, the roasting temperature of the magnetizing roasting is preferably 700-1000 ℃, the roasting time is preferably 1-2 hours, and the roasting slag is subjected to water quenching after the magnetizing roasting is finished and before the roasting slag is subjected to magnetic separation. And water quenching is carried out after roasting is finished and before magnetic separation is carried out on the roasted slag, so that the influence on the conversion efficiency of iron caused by the oxidation of the roasted slag at high temperature after roasting is finished is avoided.
In order to improve the magnetic separation efficiency, the magnetic field intensity of the magnetic separation is preferably 100-300 kA/m. After the magnetizing roasting treatment, the grade of the obtained iron ore concentrate reaches 58-65%, and the recovery rate of iron reaches 85-95%.
In order to avoid excessive influence of sulfuric acid in the pickle liquor on subsequent treatment, the process of pre-neutralizing the pickle liquor preferably comprises the steps of adding limestone into the pickle liquor for pre-neutralizing, enabling the concentration of sulfuric acid in the pickle liquor to be 10-15 g/L, adjusting the temperature of the pickle liquor after pre-neutralizing to be 80-90 ℃, and then carrying out solid-liquid separation. Part of the sulfuric acid is neutralized to form gypsum through the addition of limestone; in order to avoid precipitation of metal ions such as nickel and cobalt in the neutralization process, the concentration of sulfuric acid needs to be controlled to maintain an acidic environment, the concentration of sulfuric acid in the acid leaching solution is controlled to be 10-15 g/L through experimental verification, and when solid-liquid separation is carried out at 80-90 ℃, the content of sulfuric acid in the acid leaching solution can be reduced as far as possible, the consumption of alkaline substances in subsequent metal separation is reduced, precipitation of metal ions such as nickel and cobalt can be effectively avoided, and an ideal separation effect of the metal ions and gypsum residues is realized. The solid-liquid separation is preferably carried out by adopting a CCD counter-current washing method, so that the separation effect of the gypsum residue is improved.
In another preferred embodiment of the application, the temperature for performing the pressure acid leaching treatment on the laterite-nickel ore is 230-260 ℃, and the pressure is 3-6 MPa. By controlling the temperature and pressure range of the pressure acid leaching, the dissolution of metal elements in the laterite-nickel ore is improved as much as possible, and the metal yield is further improved.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
Carrying out high-pressure acid leaching treatment on laterite-nickel ore at 230 ℃ and 3.0MPa, carrying out solid-liquid separation to obtain ferrate-containing leaching slag and a leaching solution, adding limestone into the leaching solution for pre-neutralization until the concentration of sulfuric acid in the leaching solution is 10g/L, and controlling the temperature of the pre-neutralized leaching solution to be 90 ℃ for carrying out CCD (charge coupled device) countercurrent washing to obtain general solid waste gypsum slag and a pre-neutralized solution; adding calcium hydroxide into the preneutralized solution to adjust the pH value of the preneutralized solution to 3.2, and performing solid-liquid separation at 80 ℃ to obtain a section of ferroaluminum slag and a section of ferroaluminum removed liquid; and taking 20g of the uniformly mixed mixture of the section of the iron-aluminum slag and the acid leaching slag for coal blending, wherein the section of the iron-aluminum slag accounts for 11.3 percent of the total weight of the mixture, the coal blending is anthracite coal accounting for 20wt percent of the mixture, the mixture after the coal blending is roasted for 1h at 800 ℃ in a muffle furnace, and the roasted slag is subjected to weak magnetic separation under the condition that the magnetic field intensity is 200kA/m after the roasted slag is quenched by water, so that iron ore concentrate and harmless tailings are obtained respectively. Through chemical analysis, the grade of the iron ore concentrate reaches 65%, and the recovery rate is 95%. Adding calcium hydroxide to the first-stage iron-removed aluminum liquid to adjust the pH value to 4.2, and performing solid-liquid separation at 75 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; mixing the second-stage iron-aluminum slag and the laterite-nickel ore, and then leaching at high pressure again; adding calcium hydroxide into the second-stage iron-removed aluminum liquid to adjust the pH value to 7.0, and performing solid-liquid separation at 70 ℃ to obtain a first-stage mixed nickel-cobalt precipitate and a first-stage nickel-cobalt precipitation liquid, wherein the first-stage mixed nickel-cobalt precipitate is a high-quality nickel-cobalt hydroxide product; adding calcium hydroxide into the first-stage nickel and cobalt precipitation solution to adjust the pH value to 8.0, carrying out solid-liquid separation at 65 ℃ to obtain a second-stage mixed nickel and cobalt precipitate and a lean solution after nickel and cobalt precipitation, mixing the second-stage mixed nickel and cobalt precipitate with the laterite nickel ore, and carrying out high-pressure leaching again; continuously adding calcium hydroxide into the lean solution after nickel and cobalt precipitation to adjust the pH value to 9.0, and performing solid-liquid separation at 60 ℃ to obtain manganese slag and a solution after manganese precipitation; adding calcium hydroxide into the solution after manganese precipitation to adjust the pH value to 10.5, and performing solid-liquid separation at 40 ℃ to obtain magnesium slag and a solution after magnesium precipitation, wherein the obtained manganese slag and magnesium slag belonging to common solid wastes are sold as manganese and magnesium byproducts due to high manganese and magnesium contents.
Example 2
Carrying out 245 ℃ and 4.5MPa high-pressure acid leaching treatment on laterite-nickel ore, carrying out solid-liquid separation to obtain ferrate-containing leaching slag and a leaching solution, adding limestone into the leaching solution for pre-neutralization until the concentration of sulfuric acid in the leaching solution is 12g/L, and controlling the temperature of the pre-neutralized leaching solution to be 85 ℃ for carrying out CCD (charge coupled device) countercurrent washing to obtain general solid waste gypsum slag and a pre-neutralized solution; adding calcium hydroxide into the preneutralized solution to adjust the pH value of the preneutralized solution to 3.3, and performing solid-liquid separation at 75 ℃ to obtain a section of ferroaluminum slag and a section of ferroaluminum removed liquid; and taking 20g of the uniformly mixed mixture of the iron-aluminum slag and the acid leaching slag, blending coal, wherein the blended coal is lignite accounting for 25 wt% of the mixture, the iron-aluminum slag accounts for 14.6% of the total weight of the mixture, roasting the mixture after blending coal in a muffle furnace at 850 ℃ for 2h, performing weak magnetic separation on the roasted slag after water quenching of the roasted slag under the condition that the magnetic field intensity is 150kA/m, and respectively obtaining iron ore concentrate and harmless tailings. Through chemical analysis, the grade of the iron ore concentrate reaches 60 percent, and the recovery rate is 94 percent. Adding calcium hydroxide to the first-stage iron-removed aluminum liquid to adjust the pH value to 4.3, and performing solid-liquid separation at 73 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; mixing the second-stage iron-aluminum slag and the laterite-nickel ore, and then leaching at high pressure again; adding calcium hydroxide into the second-stage iron-removed aluminum liquid to adjust the pH value to 7.1, and performing solid-liquid separation at 65 ℃ to obtain a first-stage mixed nickel-cobalt precipitate and a first-stage nickel-cobalt precipitation liquid, wherein the first-stage mixed nickel-cobalt precipitate is a high-quality nickel-cobalt hydroxide product; adding calcium hydroxide into the first-stage nickel and cobalt precipitation solution to adjust the pH value of the first-stage nickel and cobalt precipitation solution to 8.1, carrying out solid-liquid separation at 63 ℃ to obtain a second-stage mixed nickel and cobalt precipitate and a lean solution after nickel and cobalt precipitation, mixing the second-stage mixed nickel and cobalt precipitate with the laterite nickel ore, and carrying out high-pressure leaching again; continuously adding calcium hydroxide into the lean solution after nickel and cobalt precipitation to adjust the pH value to 9.3, and performing solid-liquid separation at 55 ℃ to obtain manganese slag and a solution after manganese precipitation; adding calcium hydroxide into the solution after manganese precipitation to adjust the pH value to 11, carrying out solid-liquid separation at 50 ℃ to obtain magnesium slag and a solution after magnesium precipitation, and selling the obtained high-manganese slag and high-magnesium slag which belong to common solid wastes as manganese and magnesium byproducts due to high manganese and magnesium contents.
Example 3
Carrying out high-pressure acid leaching treatment on laterite-nickel ore at 260 ℃ and 5.0MPa, carrying out solid-liquid separation to obtain ferrate-containing leaching slag and a leaching solution, adding limestone into the leaching solution for pre-neutralization until the concentration of sulfuric acid in the leaching solution is 14g/L, and controlling the temperature of the pre-neutralized leaching solution to be 80 ℃ for carrying out CCD (charge coupled device) countercurrent washing to obtain general solid waste gypsum slag and a pre-neutralized solution; adding calcium hydroxide into the preneutralized solution to adjust the pH value of the preneutralized solution to 3.5, and performing solid-liquid separation at 70 ℃ to obtain a section of ferroaluminum slag and a section of ferroaluminum removed liquid; and taking 20g of the uniformly mixed mixture of the iron-aluminum slag and the acid leaching slag, blending coal, wherein the blended coal is 15 wt% of anthracite, the iron-aluminum slag accounts for 11.3% of the total weight of the mixture, roasting the mixture after blending coal in a muffle furnace at 750 ℃ for 1.5h, quenching the roasted slag with water, and performing weak magnetic separation on the roasted slag under the condition that the magnetic field intensity is 300kA/m to respectively obtain iron ore concentrate and harmless tailings. Through chemical analysis, the grade of the iron ore concentrate reaches 60 percent, and the recovery rate is 85 percent. Adding calcium hydroxide to the first-stage iron-removed aluminum liquid to adjust the pH value to 4.5, and performing solid-liquid separation at 70 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid; mixing the second-stage iron-aluminum slag and the laterite-nickel ore, and then leaching at high pressure again; adding calcium hydroxide into the second-stage iron-removed aluminum liquid to adjust the pH value to 7.2, and performing solid-liquid separation at 60 ℃ to obtain a first-stage mixed nickel-cobalt precipitate and a first-stage nickel-cobalt precipitation liquid, wherein the first-stage mixed nickel-cobalt precipitate is a high-quality nickel-cobalt hydroxide product; adding calcium hydroxide into the first-stage nickel and cobalt precipitation solution to adjust the pH value to 8.3, carrying out solid-liquid separation at 60 ℃ to obtain a second-stage mixed nickel and cobalt precipitate and a lean solution after nickel and cobalt precipitation, mixing the second-stage mixed nickel and cobalt precipitate with the laterite nickel ore, and carrying out high-pressure leaching again; continuously adding calcium hydroxide into the lean solution after nickel and cobalt precipitation to adjust the pH value to 9.5, and performing solid-liquid separation at 50 ℃ to obtain manganese slag and a solution after manganese precipitation; adding calcium hydroxide into the solution after manganese precipitation to adjust the pH value to 11.5, carrying out solid-liquid separation at 30 ℃ to obtain magnesium slag and a solution after magnesium precipitation, wherein the obtained high-manganese slag and high-magnesium slag belonging to common solid wastes are sold as manganese and magnesium byproducts due to high manganese and magnesium contents.
Example 4
The difference from the example 1 is that limestone is added into the acid leaching solution for pre-neutralization until the sulfuric acid concentration in the acid leaching solution is 18g/L, and the temperature of the acid leaching solution after pre-neutralization is controlled to be 90 ℃ for CCD counter-current washing to obtain general solid waste gypsum slag and pre-neutralization solution, and a small amount of gypsum exists in the first section of the obtained iron-aluminum slag, so that the grade of the obtained iron ore concentrate is 60%, and the recovery rate is 91%.
Example 5
The difference from the embodiment 1 is that limestone is added into the acid leaching solution for pre-neutralization until the sulfuric acid concentration in the acid leaching solution is 10g/L, and the temperature of the acid leaching solution after the pre-neutralization is controlled to be 70 ℃ for CCD countercurrent washing to obtain general solid waste gypsum slag and pre-neutralization solution, wherein the iron ore concentrate grade reaches 62%, and the recovery rate is 89%.
Example 6
The difference from the embodiment 1 is that 20g of a uniformly mixed mixture of the section of the iron-aluminum slag and the acid leaching slag is taken for coal blending, wherein the coal blending is 30 wt% of lignite in the mixture, the mixture after the coal blending is roasted in a muffle furnace at 700 ℃ for 1h, and after water quenching of the roasting slag, the roasting slag is subjected to weak magnetic separation under the magnetic field intensity of 200kA/m, so that iron ore concentrate and harmless tailings are respectively obtained. Through analysis, the grade of the iron ore concentrate reaches 63%, and the recovery rate is 90%.
Example 7
The difference from the embodiment 1 is that 20g of the uniformly mixed mixture of the section of the iron-aluminum slag and the acid leaching slag is mixed, wherein the coal is mixed by roasting the mixture of anthracite coal accounting for 10 wt% of the mixture after mixing in a muffle furnace at 1000 ℃ for 1h, and the roasted slag is subjected to weak magnetic separation under the magnetic field intensity of 200kA/m after water quenching to obtain iron ore concentrate and harmless tailings respectively. Through analysis, the grade of the iron ore concentrate reaches 62 percent, and the recovery rate is 89 percent.
Example 8
The difference from the embodiment 1 is that calcium hydroxide is added to the first-stage iron-removed aluminum liquid to adjust the pH value to 4.2, solid-liquid separation is carried out at 80 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid, wherein the gypsum content in the second-stage iron-aluminum slag is slightly higher than that in the embodiment 1, the grade of the finally obtained iron concentrate is 63%, and the recovery rate is 92%.
Example 9
The difference from the embodiment 1 is that calcium hydroxide is added into the second-stage iron-removed aluminum liquid to adjust the pH value to 7.5, and solid-liquid separation is carried out at 70 ℃ to obtain first-stage mixed nickel cobalt precipitation and first-stage nickel cobalt precipitation liquid, wherein the recovery rates of nickel and cobalt are slightly reduced.
Example 10
The difference from the example 1 is that calcium hydroxide is added into the first-stage nickel and cobalt precipitation solution to adjust the pH value to 8.5, solid-liquid separation is carried out at 65 ℃, and second-stage mixed nickel and cobalt precipitation and lean solution after nickel and cobalt precipitation are obtained, wherein the recovery rate of magnesium and manganese is slightly reduced.
Comparative example 1
The difference from the example 1 is that calcium hydroxide is added into the preneutralized solution to adjust the pH value to 3.7, solid-liquid separation is carried out at 80 ℃ to obtain a section of iron-aluminum slag and a section of iron-removed aluminum liquid, wherein the grade of iron-iron concentrate is 58%, and the recovery rate is 83%.
Comparative example 2
The difference from the example 1 is that calcium hydroxide is added into the preneutralized solution to adjust the pH value to 3.0, solid-liquid separation is carried out at 80 ℃ to obtain a section of iron-aluminum slag and a section of iron-removed aluminum liquid, wherein the grade of iron concentrate is 60 percent, and the recovery rate is 80 percent.
Comparative example 3
The difference from the example 1 is that the pH value of the first-stage iron-removed aluminum liquid is adjusted to 4.6 by adding calcium hydroxide, and solid-liquid separation is carried out at 75 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid, wherein the grade of iron concentrate is 56%, and the iron recovery rate is 80%.
Comparative example 4
The difference from the example 1 is that the pH value of the first-stage iron-removed aluminum liquid is adjusted to 4.0 by adding calcium hydroxide, and solid-liquid separation is carried out at 75 ℃ to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid, wherein the grade of iron concentrate is 54%, and the iron recovery rate is 81%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the obtained gypsum slag, manganese slag and magnesium slag can be used as general solid waste for treatment, and can be sold as byproducts due to higher manganese content in the manganese slag and higher magnesium content in the magnesium slag, so that the recovery of a small amount of manganese and magnesium in the leaching slag containing the ferrite is realized; the first-stage iron and aluminum removal is carried out under the conditions, so that iron elements are left in the slag as much as possible, and the recovery rate of iron is improved; iron in the iron-containing acid leaching slag and a section of iron-aluminum slag is efficiently recovered by utilizing a magnetizing roasting process, wherein the obtained iron concentrate has high grade and can be directly used as a raw material of other iron products, and the obtained harmless tailings have no environmental pollution and can also be used as a raw material for producing cement; meanwhile, the iron and aluminum are removed in the second stage under the conditions, so that the iron and the aluminum enter the slag as much as possible and return to the pressurized acid leaching treatment process to improve the recovery of the iron, the content of the iron and the aluminum in the second stage iron-removed aluminum liquid is reduced, and the subsequent separation efficiency of the nickel and the cobalt is improved; further, the treatment method also carries out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid, thereby realizing the recovery of nickel and cobalt. In conclusion, the treatment method realizes the recovery of valuable metal elements in the ferrous acid-containing leaching slag, further improves the metal recovery rate, realizes the efficient utilization of laterite-nickel ore resources, obviously relieves the problem of environmental pollution caused by the ferrous acid-containing leaching slag, and can further utilize the slag to realize the harmless treatment of the slag.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for treating acid leaching slag of laterite-nickel ore is characterized by comprising the following steps:
carrying out pressure acid leaching treatment on the laterite-nickel ore, and carrying out solid-liquid separation to obtain iron-containing acid leaching slag and acid leaching liquid;
pre-neutralizing the pickle liquor, and carrying out solid-liquid separation to obtain gypsum residue and pre-neutralized liquor;
adjusting the pH value of the pre-neutralization solution to 3.2-3.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform first-stage iron and aluminum removal, and performing solid-liquid separation to obtain first-stage iron and aluminum slag and first-stage iron and aluminum removed liquid;
treating the mixture of the section of iron-aluminum slag and the iron-containing acid leaching slag by using a magnetizing roasting process to obtain iron ore concentrate and harmless tailings, wherein the weight content of the section of iron-aluminum slag in the mixture is below 25%;
adjusting the pH value of the first-stage iron-removed aluminum liquid to 4.2-4.5 by using calcium hydroxide at the temperature of 70-80 ℃ to perform second-stage iron-removal aluminum, and performing solid-liquid separation to obtain second-stage iron-aluminum slag and second-stage iron-removed aluminum liquid;
carrying out nickel and cobalt precipitation on the second-stage iron-removed aluminum liquid to obtain lean solution and nickel and cobalt precipitates after nickel and cobalt precipitation;
carrying out manganese precipitation and magnesium precipitation on the lean solution after nickel and cobalt precipitation in steps to obtain manganese slag and magnesium slag in sequence; and
returning the two sections of iron-aluminum slag to the pressure acid leaching treatment process,
the process for treating the mixture of the section of the iron-aluminum slag and the iron-containing acid leaching slag by using the magnetizing roasting process comprises the following steps:
carrying out magnetization roasting on the mixture after coal blending to obtain roasting slag, and carrying out coal blending according to the coal blending amount which is 10-30 wt% of the mixture, wherein the coal blending is blended with one or two of anthracite and lignite;
performing magnetic separation on the roasting slag to obtain the iron ore concentrate and harmless tailings,
the process of precipitating manganese and magnesium from the lean solution after nickel and cobalt precipitation in steps comprises the following steps:
oxidizing the lean solution after nickel and cobalt precipitation, then regulating the pH value of the lean solution after nickel and cobalt precipitation to 9.0-9.5 by using calcium hydroxide at the temperature of 0-50 ℃ for manganese precipitation, and performing solid-liquid separation to obtain manganese slag and a solution after manganese precipitation;
and (3) adjusting the pH value of the manganese-precipitated liquid to 10.5-11.5 by using calcium hydroxide at the temperature of 0-50 ℃ to precipitate magnesium, and performing solid-liquid separation to obtain magnesium slag and magnesium-precipitated liquid.
2. The treatment method according to claim 1, wherein the step of performing nickel-cobalt precipitation on the secondary molten iron-removed aluminum comprises the following steps:
at the temperature of 60-65 ℃, adjusting the pH value of the second-stage iron-removed aluminum liquid to 7.0-7.2 by using calcium hydroxide to carry out nickel and cobalt precipitation, and carrying out solid-liquid separation to obtain a first-stage mixed nickel and cobalt precipitate and a first-stage nickel and cobalt precipitation liquid;
and at the temperature of 50-55 ℃, adjusting the pH value of the first-stage nickel-cobalt-precipitated solution to 8.0-8.5 by using calcium hydroxide to precipitate nickel and cobalt, and performing solid-liquid separation to obtain a second-stage mixed nickel-cobalt precipitate and the lean solution after nickel and cobalt precipitation.
3. The process of claim 2 further comprising returning the second stage mixed nickel cobalt precipitate to the pressure acid leach process.
4. The treatment method as claimed in claim 1, wherein the roasting temperature of the magnetizing roasting is 700-1000 ℃, the roasting time is 1-2 h, and the roasting slag is water quenched after the magnetizing roasting and before the magnetic separation of the roasting slag.
5. The process of claim 1, wherein the magnetic field strength of the magnetic separation is 100-300 kA/m.
6. The method according to claim 1, wherein the step of pre-neutralizing the acid-leached solution comprises adding limestone to the acid-leached solution to pre-neutralize the acid-leached solution so that the concentration of sulfuric acid in the acid-leached solution is 10 to 15g/L, and adjusting the temperature of the acid-leached solution after pre-neutralization to 80 to 90 ℃ to perform solid-liquid separation.
7. The treatment method according to the claim 1, characterized in that the temperature of the pressure acid leaching treatment of the lateritic nickel ore is 230-260 ℃, and the pressure is 3-6 MPa.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910765616.0A CN110331283B (en) | 2019-08-19 | 2019-08-19 | Method for treating acid leaching residues of laterite-nickel ore |
| PH12020050207A PH12020050207A1 (en) | 2019-08-19 | 2020-07-07 | Processing method for laterite nickel ore acid leaching slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910765616.0A CN110331283B (en) | 2019-08-19 | 2019-08-19 | Method for treating acid leaching residues of laterite-nickel ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110331283A CN110331283A (en) | 2019-10-15 |
| CN110331283B true CN110331283B (en) | 2021-08-31 |
Family
ID=68149870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910765616.0A Active CN110331283B (en) | 2019-08-19 | 2019-08-19 | Method for treating acid leaching residues of laterite-nickel ore |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110331283B (en) |
| PH (1) | PH12020050207A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111534686A (en) * | 2020-05-27 | 2020-08-14 | 浙江工贸职业技术学院 | Iron removal equipment and iron removal method for nickel cobalt raffinate |
| CN111424172A (en) * | 2020-06-01 | 2020-07-17 | 中国恩菲工程技术有限公司 | Wet treatment process of laterite-nickel ore |
| CN111621641A (en) * | 2020-06-03 | 2020-09-04 | 中国恩菲工程技术有限公司 | Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore |
| CN111498916B (en) * | 2020-06-03 | 2022-07-26 | 中国恩菲工程技术有限公司 | Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore |
| CN111498917B (en) * | 2020-06-04 | 2022-07-26 | 中国恩菲工程技术有限公司 | Treatment method of laterite-nickel ore |
| CN112760498A (en) * | 2020-12-25 | 2021-05-07 | 浙江天能新材料有限公司 | Method for preparing high-purity cobalt sulfate and recovering germanium by removing iron in sections |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2528137A1 (en) * | 1975-04-04 | 1976-10-21 | Financial Mining Ind Ship | METHOD OF INCREASING THE NICKEL CONTENT IN NICKEL LATERITE IRON ORES |
| CN101899571A (en) * | 2009-11-05 | 2010-12-01 | 中国恩菲工程技术有限公司 | Process for producing nickel and cobalt from nickel and cobalt ores |
| CN102041381A (en) * | 2011-01-17 | 2011-05-04 | 河南永通镍业有限公司 | Method for recovering nickel, cobalt, iron, manganese and magnesium from oxidized nickel ore |
| CN102345019A (en) * | 2011-10-25 | 2012-02-08 | 北京矿冶研究总院 | Method for treating brown iron type laterite-nickel ore |
| CN103205569A (en) * | 2013-03-27 | 2013-07-17 | 凉山矿业股份有限公司 | Method for treating nickel laterite ores |
-
2019
- 2019-08-19 CN CN201910765616.0A patent/CN110331283B/en active Active
-
2020
- 2020-07-07 PH PH12020050207A patent/PH12020050207A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2528137A1 (en) * | 1975-04-04 | 1976-10-21 | Financial Mining Ind Ship | METHOD OF INCREASING THE NICKEL CONTENT IN NICKEL LATERITE IRON ORES |
| CN101899571A (en) * | 2009-11-05 | 2010-12-01 | 中国恩菲工程技术有限公司 | Process for producing nickel and cobalt from nickel and cobalt ores |
| CN102041381A (en) * | 2011-01-17 | 2011-05-04 | 河南永通镍业有限公司 | Method for recovering nickel, cobalt, iron, manganese and magnesium from oxidized nickel ore |
| CN102345019A (en) * | 2011-10-25 | 2012-02-08 | 北京矿冶研究总院 | Method for treating brown iron type laterite-nickel ore |
| CN103205569A (en) * | 2013-03-27 | 2013-07-17 | 凉山矿业股份有限公司 | Method for treating nickel laterite ores |
Also Published As
| Publication number | Publication date |
|---|---|
| PH12020050207A1 (en) | 2021-02-22 |
| CN110331283A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110331283B (en) | Method for treating acid leaching residues of laterite-nickel ore | |
| CN101818250B (en) | Method for processing cobalt-copper-iron alloy | |
| CN105803191B (en) | A kind of Zinc Hydrometallurgy Process zinc-iron separation method | |
| CN107630146B (en) | Nickel recovery process | |
| CN102312083A (en) | Method for extracting zinc indium and recovering iron from high-iron high indium zinc concentrate | |
| CN113897491B (en) | Method for comprehensively and efficiently treating zinc leaching slag | |
| CN110616328B (en) | Method for preparing iron-chromium black from chromium-containing electroplating sludge | |
| CN113621819B (en) | Method for extracting valuable metals from low-grade nickel matte converter slag | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN102041377A (en) | Method for recovering iron, vanadium and chromium in vanadium-titanium magnetite concentrate | |
| WO2023000847A1 (en) | Nickel-iron wet treatment method and application thereof | |
| CN102676803B (en) | Resource utilization method for catalytic oxidation leaching of molybdenum and nickel from molybdenum-nickel ore | |
| CN104195345A (en) | Process for recovering sulfur, lead, zinc and silver from oxygen-enriched directly leached residues of zinc concentrates or lead-zinc mixed ores | |
| CN102660690A (en) | Method for recovering valuable metal from zinc hydrometallurgy high acid leach residue | |
| CN105568001A (en) | Combined high-pressure acid leaching method for cobalt alloy and oxide cobalt minerals | |
| WO2023024592A1 (en) | Method for preparing nickel sulfate from ferronickel | |
| CN104232924A (en) | Copper extraction and iron removal method of copper ore acid leaching liquid | |
| AU2017344873A1 (en) | Process for recycling cobalt-bearing materials | |
| WO2012171480A1 (en) | Hydrometallurgical method for comprehensive recycling of lateritic nickel ore components as products | |
| CN110564961B (en) | Method for reducing leached hydrocobaltite | |
| CN102021332B (en) | Technology for recycling Ni, Co, Fe, and Mg from nickel oxide mineral | |
| CN111470534A (en) | Preparation process of vanadium pentoxide | |
| CN111424172A (en) | Wet treatment process of laterite-nickel ore | |
| CN108441649B (en) | Method for extracting nickel from chemical precipitation nickel sulfide material | |
| US9776885B2 (en) | Method for producing hematite for ironmaking |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |