US20170175227A1 - Hydrometallurgical process for nickel oxide ore - Google Patents

Hydrometallurgical process for nickel oxide ore Download PDF

Info

Publication number
US20170175227A1
US20170175227A1 US15/304,898 US201515304898A US2017175227A1 US 20170175227 A1 US20170175227 A1 US 20170175227A1 US 201515304898 A US201515304898 A US 201515304898A US 2017175227 A1 US2017175227 A1 US 2017175227A1
Authority
US
United States
Prior art keywords
slurry
ore
nickel
chromite
nickel oxide
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.)
Abandoned
Application number
US15/304,898
Other languages
English (en)
Inventor
Go Ohara
Yasumasa Kan
Masaki Imamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Assigned to SUMITOMO METAL MINING CO. LTD. reassignment SUMITOMO METAL MINING CO. LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMAMURA, MASAKI, OHARA, GO
Publication of US20170175227A1 publication Critical patent/US20170175227A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043Sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00Preliminary treatment of ores or scrap
    • C22B1/14Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24Binding; Briquetting ; Granulating
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/005Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0407Leaching processes
    • C22B23/0415Leaching processes with acids or salt solutions except ammonium salts solutions
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00Obtaining nickel or cobalt
    • C22B23/04Obtaining nickel or cobalt by wet processes
    • C22B23/0453Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06Extraction 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
    • C22B3/08Sulfuric acid, other sulfurated acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to a hydrometallurgical process for nickel oxide ore, specifically relates to a hydrometallurgical process for nickel oxide ore for recovering nickel and cobalt from nickel oxide ore using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, in which problems are solved by suppressing the wear, caused by an ore slurry produced from the ore processing step, of facilities such as conveyance piping and a pump for conveying the ore slurry and improving the durability of the facilities to thereby reduce the amount of a final neutralized residue produced from the final neutralization step and allow the compression of the capacity of a tailings dam for storing a leach residue, a neutralized precipitate, and the like to be discarded to thereby reduce cost and environmental risk; and impurity components which can be recycled and effectively used as a resource can be separated and recovered.
  • the high pressure acid leach process is advantageous in terms of energy cost since it does not have dry process steps such as a reduction step and a drying step unlike a pyrometallurgical process which is a conventional common smelting method for nickel oxide ore, and the high pressure acid leach process is continuously considered to be a promising technique as a smelting method for low-grade nickel oxide ore.
  • the nickel leaching rate from ores is improved by performing two-stage leaching in which the ore slurry is subjected to atmospheric leach (step (a)) and then the atmospheric leach residue is subjected to high pressure acid leach (step (b)), and at the same time, the load of the neutralization step (step (c)) is reduced by neutralizing the excess acid contained in the leachate from the high pressure acid leach with the alkali component contained in the atmospheric leach residue.
  • Patent Literature 2 a method including steps (1) to (4) described below has been proposed (refer to, for example, Patent Literature 2) as another process of utilizing leaching at high temperature under pressure.
  • Leaching step forming a slurry of nickel oxide ore, adding sulfuric acid to the slurry, and stirring the slurry at a temperature of 220 to 280° C. to form a leach slurry;
  • Solid-liquid separation step washing the leach slurry obtained in the previous leaching step using a multi-stage thickener to separate it into a leachate containing nickel and cobalt and a leach residue;
  • Neutralization step adjusting the leachate obtained in the solid-liquid separation step with calcium carbonate to a pH of or less while suppressing the oxidation of the leachate to produce a neutralized precipitate containing trivalent iron and separate the leachate into a neutralized precipitate slurry and mother liquor for nickel recovery;
  • Sulfurization step blowing hydrogen sulfide gas into the mother liquor for nickel recovery obtained in the neutralization step to produce a sulfide containing nickel and cobalt and separate the sulfide from a barren liquor.
  • FIG. 2 is a smelting process diagram illustrating an example of practical plants based on the hydrometallurgical process for nickel oxide ore disclosed in Japanese Patent Laid-Open No. 2005-350766.
  • nickel oxide ore 8 first forms a mixed solution with water, and the mixed solution is then subjected to foreign matter removal therefrom and ore particle size adjustment to form an ore slurry 9 .
  • the resulting ore slurry 9 is subjected to high pressure acid leach using sulfuric acid to form a leach slurry 10 .
  • the resulting leach slurry 10 is subjected to ( 3 ) solid-liquid separation step followed by multi-stage washing to be separated into a leachate 11 containing nickel and cobalt and a leach residue slurry 12 .
  • the separated leachate 11 is subjected to ( 4 ) neutralization step to be separated into a neutralized precipitate slurry 13 containing trivalent iron hydroxide and mother liquor ( 1 ) 14 for nickel recovery ( 1 ).
  • the separated mother liquor ( 1 ) 14 as one product is subjected to ( 5 ) zinc removal step of adding a sulfurizing agent to be separated into a zinc sulfide precipitate 15 containing zinc sulfide and mother liquor ( 2 ) 16 for nickel recovery.
  • the mother liquor ( 2 ) 16 as the other product is subjected to ( 6 ) sulfurization step to be separated into a mixed sulfide 17 containing nickel and cobalt and a barren liquor 18 from which nickel and the like are removed.
  • the barren liquor 18 is used as washing water for a leach residue in ( 3 ) solid-liquid separation step.
  • the features of the method disclosed in Japanese Patent Laid-Open No. 2005-350766 include the following: the consumption of a neutralizing agent and the amount of precipitates in the neutralization step can be reduced by the multi-stage washing of the leach slurry in the solid-liquid separation step; since the true density of the leach residue can be increased, solid-liquid separation characteristics can be improved; and the process is simplified by performing the leaching step only by high pressure acid leach.
  • the method disclosed in Japanese Patent Laid-Open No. 2005-350766 is considered to be advantageous against the method proposed in Japanese Patent Laid-Open No. H06-116660.
  • a first problem is the wear of facilities, which is required to be suppressed.
  • the nickel oxide ore is conveyed between the steps in the form of a slurry.
  • the wear of the materials of facilities is significantly accelerated by the conveyed slurry, and especially the frequency of maintenance of the facilities such as piping and pumps in the leaching step is high, which greatly causes an increase in maintenance cost and a reduction in the rate of plant operation.
  • a second problem is the amount of the final neutralized residue, which is required to be reduced.
  • the leach residue obtained in the solid-liquid separation step is combined with the excess barren liquor produced from the sulfurization step, and the resulting mixture is rendered harmless by the neutralization of adding a limestone slurry or a slaked lime slurry thereto.
  • the final neutralized residue produced from the final neutralization step (hereinafter, may be referred to as final neutralization step), which is stored in a tailings dam, contains not only impurity components such as hematite and chromite in the leach reside but also gypsum formed by the neutralization. Therefore, the final neutralized residue cannot be recycled, and the construction and the maintenance of the tailings dam have been a heavy cost burden.
  • a hydrometallurgical process for nickel oxide ore including, in the hydrometallurgical steps based on a high pressure acid leach process, a step of a physically separating and recovering, from an ore slurry, particles containing at least one selected from silica mineral, chromite, and silica-magnesia mineral and a step of a physically separating and recovering hematite particles in a leach residue slurry.
  • a hydrometallurgical process for nickel oxide ore including, in the hydrometallurgical steps based on a high pressure acid leach process, a step of a physically separating and recovering, from an ore slurry, particles containing at least one selected from silica mineral, chromite, and silica-magnesia mineral and a step of a physically separating and recovering hematite particles in a leach residue slurry.
  • further improvement has been required for efficiently separating and recovering the impurity components contained in the ore or the leach residue.
  • an object of the present invention is to provide, in view of the problems of conventional art, a hydrometallurgical process for nickel oxide ore for recovering nickel and cobalt from nickel oxide ore using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, in which the problems are solved by suppressing the wear, caused by an ore slurry produced from the ore processing step, of facilities such as conveyance piping and a pump for conveying the ore slurry and improving the durability of the facilities to thereby increase the percentage of a solid in the ore slurry to simplify the facilities in the ore processing step, and by reducing the amount of a final neutralized residue produced from the final neutralization step and compressing the capacity of a tailings dam for storing a leach residue, a neutralized precipitate, and the like to be discarded to thereby reduce cost and environmental risk; and im
  • the first aspect of the present invention is a hydrometallurgical process for nickel oxide ore for recovering nickel and cobalt using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, the method further including step (A): a step of separating chromite particles from an ore slurry produced in the ore processing step by a recovery process including specific gravity separation, and then classifying the chromite particles to recover a high-concentration chromite concentrate having the grade of chromium(III) oxide of at least more than 50% by weight.
  • the second aspect of the present invention is a hydrometallurgical process for nickel oxide ore for recovering nickel and cobalt using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, the method including step (A) and, after passing through step (A), further including step (B- 1 ) or step (B- 2 ):
  • the third aspect of the present invention is a hydrometallurgical process for nickel oxide ore for recovering nickel and cobalt using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, the method including step (A), step (B- 1 ), and step (B- 2 ):
  • the fourth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to third aspects, wherein the recovery process in step (A) includes subjecting the ore slurry to classification with a cyclone to form a particulate iron-leaned ore slurry in which fine iron hydroxide particles have been reduced, and then recovering chromite particles from the particulate iron-leaned ore slurry having contained the chromite particles as a chromite concentrate using specific gravity separation.
  • the fifth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the fourth aspect, wherein the recovery process in step (A) includes subjecting the ore slurry to classification with a cyclone without diluting the slurry concentration of the ore slurry.
  • the sixth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to fifth aspects, wherein the recovery process in step (A) includes collecting the whole amount of the chromite excluding unavoidable loss into the underflow in the classification with a cyclone.
  • the seventh aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to sixth aspects, wherein the specific gravity separation includes a step of using a density separator.
  • the eighth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to sixth aspects, wherein the specific gravity separation includes a step of using a spiral concentrator.
  • the ninth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to sixth aspects, wherein the specific gravity separation includes a step of using a density separator and a step of using a spiral concentrator.
  • the tenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the seventh and ninth aspects, wherein the step of using a density separator includes treating a concentrated slurry with the density separator twice or more.
  • the eleventh aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the eighth and ninth aspects, wherein the step of using a spiral concentrator includes treating a concentrated slurry with the spiral concentrator twice or more.
  • the twelfth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the eighth, ninth, and eleventh aspects, wherein the pulp content of the slurry fed to the spiral concentrator is 15 to 35% by weight of solid, preferably 20 to 30% by weight of solid.
  • the thirteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the seventh, ninth, and tenth aspects, wherein the amount of Teeter water fed to the density separator is 0.5 to 7.0 [m3 ⁇ h-1/m2].
  • the fourteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to thirteenth aspects, wherein the chromite concentrate separated by specific gravity separation is subjected to magnetic separation which is a physical separation to remove magnetite from the chromite concentrate as a magnetic material and recover a non-magnetic material as a high-concentration chromite concentrate.
  • the fifteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the second or third aspect, wherein step (B- 2 ) includes setting pH after neutralization at 4 to 7 and after the neutralization, performing final neutralization with an alkali other than the magnesium-based neutralizing agent.
  • the sixteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the second or third aspect, wherein step (B- 2 ) includes subjecting the leach residue slurry or a neutralized residue slurry including the leach residue slurry to classification with a cyclone to recover a classified fine particle portion obtained by the classification as a concentrate of hematite.
  • the seventeenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to sixteenth aspects, wherein the ore processing step is a step of performing removal of foreign matter contained in the mined raw material ore and particle size adjustment of the ore to form an ore slurry; the leaching step is a step of adding sulfuric acid to the ore slurry and stirring the resulting mixture at high temperature and high pressure to form a leach slurry including a leach residue and a leachate; the solid-liquid separation step is a step of subjecting the leach slurry to multi-stage washing to obtain a leachate containing nickel and cobalt and a leach residue slurry; the neutralization step is a step of adding an alkali to the leachate to form a neutralized precipitate slurry containing trivalent iron and mother liquor for recovering nickel; the zinc removal step is a step of blowing hydrogen sulfide gas into the mother liquor to form a zinc sulfide precipitate slurry and
  • the eighteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to seventeenth aspects, wherein the particle size adjustment of the ore in the ore processing step is performed by sieving with a particle size of 2 mm or less.
  • the nineteenth aspect of the present invention is the hydrometallurgical process for nickel oxide ore according to the first to eighteenth aspects, wherein the grade of chromium(III) the concentrated chromite is 41% by weight or more.
  • step (A) and step (B) in a hydrometallurgical process for recovering nickel and cobalt from nickel oxide ore using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step.
  • step (A) in the present invention particles containing chromite in the ore slurry produced from the ore processing step can be separated and recovered to thereby significantly suppress the wear of facilities such as piping and a pump during the conveyance of the ore slurry.
  • chromite is separated before the hydrometallurgy, a reduction in the amount of the leach residue can be expected, and the amount of a final neutralized residue can also be reduced. Furthermore, if the separated chromite is concentrated, the concentrate can also be effectively used as a resource.
  • step (B) in the present invention hematite in the leach residue produced from the solid-liquid separation step is separated and recovered to thereby achieve a reduction in the amount of a final neutralized residue produced from the final neutralization step, thereby capable of compressing the capacity of a tailings dam for storing a leach residue, a neutralized precipitate, and the like to be discarded to thereby reduce cost and environmental risk, and the hematite separated and recovered can also be effectively used as an iron resource.
  • FIG. 1 is a smelting process diagram showing an embodiment of the hydrometallurgical process for nickel oxide ore according to the present invention.
  • FIG. 2 is a smelting process diagram showing an example of a practical plant based on a conventional hydrometallurgical process for nickel oxide ore.
  • FIG. 3 is an execution flow chart in Example 1 of the present invention.
  • FIG. 4 is an execution flow chart in Example 2 of the present invention.
  • FIG. 5 is an execution flow chart in Comparative Example 1 of the present invention.
  • FIG. 6 is an execution flow chart in Comparative Example 4 of the present invention.
  • the hydrometallurgical process for nickel oxide ore of the present invention for recovering nickel and cobalt using a high pressure acid leach process including an ore processing step, a leaching step, a solid-liquid separation step, a neutralization step, a zinc removal step, a sulfurization step, and a final neutralization step, includes step (A), or after passing through step (A), includes step (B- 1 ) and/or step (B- 2 ).
  • Step (A) is a step of separating chromite particles from an ore slurry produced in the ore processing step by a recovery process including specific gravity separation, and then classifying the chromite particles to recover a high-concentration chromite concentrate.
  • the ore slurry, in which the Cr grade has been reduced in step (A), is treated in the leaching step and the solid-liquid separation step, and a leachate after the solid-liquid separation step is neutralized in step (B- 1 ) with a Mg-based neutralizing agent such as Mg(OH) 2 and MgO and a Ca-based neutralizing agent such as CaCO 3 and Ca(OH) 2 .
  • a Mg-based neutralizing agent such as Mg(OH) 2 and MgO
  • Ca-based neutralizing agent such as CaCO 3 and Ca(OH) 2 .
  • the ore slurry, in which the Cr grade has been reduced in step (A), is treated in the leaching step and the solid-liquid separation step, and a leach residue slurry after the solid-liquid separation step is neutralized in step (B- 2 ) with a Mg-based neutralizing agent such as Mg(OH) 2 and MgO to recover hematite particles.
  • a Mg-based neutralizing agent such as Mg(OH) 2 and MgO
  • step (A) As an essential step.
  • step (A) particles containing chromite in the ore slurry produced from the ore processing step as the previous step are separated and recovered to thereby impart the effect of suppressing the wear of facilities such as piping and a pump during the conveyance of the ore slurry.
  • the wear is suppressed by separating chromite having extremely high hardness generally contained in nickel oxide ore. Further, a reduction in the amount of a leach residue can be expected by removing chromite in advance from the ore slurry before hydrometallurgy, and, as a result, the amount of a final neutralized residue can also be reduced.
  • the chromite which has been separated and recovered can be sufficiently concentrated, it can also be effectively used as a resource.
  • step (B) including step (B- 1 ) and step (B- 2 ), hematite in the leach residue produced from the solid-liquid separation step is separated and recovered to thereby reduce the amount of a final neutralized residue produced from the final neutralization step, thereby capable of compressing the capacity of a tailings dam for storing a leach residue, a neutralized precipitate, and the like to be discarded to thereby reduce cost and environmental risk.
  • the hematite separated and recovered can also be effectively used as an iron resource.
  • iron in the nickel oxide ore is hydrolyzed at a high temperature in the leaching step, iron is contained in the form of hematite in the final neutralized residue.
  • the final neutralized residue contains not only chromite in the leach residue but also gypsum formed by neutralization using a neutralizing agent containing Ca, the iron grade is as low as 30 to 40% by weight, and it is difficult to effectively use the final neutralized residue as it is as an ironmaking raw material or the like.
  • sulfur (gypsum; calcium sulfate), chromium (chromite), and the like contained in the final neutralized residue are components that influence the distribution of minor components into pig iron, the quality of steel products, and the like, and it is required to suppress the inclusion of these impurity elements.
  • step (B- 2 ) of the present invention is performed only by using a Mg-based neutralizing agent, MgSO4 having high solubility is produced to suppress the fixing of sulfur to a solid and allow hematite having a low sulfur grade to be separated and recovered.
  • FIG. 1 is a smelting process diagram showing an embodiment of the hydrometallurgical process for nickel oxide ore according to the present invention.
  • nickel oxide ore 8 first forms a mixed solution with water, and foreign matter removal from the mixed solution and ore particle size adjustment are then performed to form an ore slurry 9 .
  • step (A) the ore slurry 9 is subjected to newly provided step (A) to separate and recover chromite 23 .
  • An autoclave feed slurry 22 as the other product is subjected to [ 2 ] leaching step.
  • valuable components such as nickel and cobalt are leached with sulfuric acid from the autoclave feed slurry 22 using an autoclave or the like to form a leach slurry 10 .
  • the formed leach slurry 10 is subjected to [ 3 ] solid-liquid separation step using a multi-stage thickener or the like to be separated into a leachate 11 containing nickel and cobalt and a leach residue slurry 12 .
  • step (B- 1 ) The separated leachate 11 is subjected to step (B- 1 ) to be separated into a residue after step (B- 1 ) 26 containing trivalent iron hydroxide as a main component and mother liquor ( 1 ) 14 containing nickel.
  • the separated mother liquor ( 1 ) 14 as one product is subjected to [ 5 ] zinc removal step of adding a sulfurizing agent to be separated into a zinc sulfide precipitate 15 containing zinc sulfide and mother liquor ( 2 ) 16 for nickel recovery.
  • the mother liquor ( 2 ) 16 as the other product is subjected to [ 6 ] sulfurization step of adding a sulfurizing agent to be separated into a mixed sulfide 17 containing nickel and cobalt and a barren liquor 18 .
  • barren liquor 18 is used as washing water for a leach residue in [ 3 ] solid-liquid separation step.
  • the barren liquor 18 may also be fed to the final neutralization step.
  • a part of the leach residue slurry 12 is fed to step (B- 2 ) together with excess barren liquor 18 and subjected to neutralization to separate and recover hematite 28 .
  • step (B- 2 ) 27 and the leach residue slurry 12 which has not be fed to step (B- 2 ) are fed to [ 7 ] final neutralization step and neutralized to a pH of about 8 to 9.
  • a resulting final neutralized residue 19 is stored in a tailings dam 20 .
  • the ore processing step is a step of performing foreign matter removal and ore particle size adjustment to form an ore slurry.
  • nickel oxide ore is sieved by elutriation or the like to separate foreign matter that cannot be leached in the leaching step, an ore that is hardly transported with a pump, and the like.
  • the sieving particle size is about 2 mm, and an ore having a particle size larger than about 2 mm is classified and separated.
  • a slurry is formed of an ore passed through the sieving treatment, and the slurry is then settled and concentrated to prepare an autoclave feed slurry in which the solid concentration in the slurry (hereinafter, referred to as slurry concentration) has been adjusted.
  • slurry concentration may be generally suitably adjusted to about 30 to 45% by weight.
  • the nickel oxide ore serving as a raw material to be treated by the hydrometallurgical process of the present invention is mainly so-called lateritic ore, such as limonite ore and saprolite ore.
  • the nickel content of the lateritic ore is normally 0.8 to 2.5% by weight, and nickel is contained as hydroxide or hydrous silica-magnesia (magnesium silicate) mineral.
  • the iron content is 10 to 50% by weight, and although iron is mainly in the form of trivalent hydroxide (goethite), divalent iron is partly contained in hydrous silica-magnesia mineral or the like.
  • Silicic acid components are contained in silica mineral, such as quartz and cristobalite (amorphous silica), and hydrous silica-magnesia mineral.
  • chromium components are contained in an amount of 1 to 5% by weight as chromite mineral containing iron or magnesium.
  • magnesia components are contained not only in hydrous silica-magnesia mineral but also in silica-magnesia mineral substantially containing no nickel which is unweathered and has high hardness.
  • silica mineral, chromite mineral, and silica-magnesia mineral are so-called gangue components which do not substantially contain nickel.
  • the ore slurry produced from the ore processing step contains chromite which generally gives significant influence on the wear of facilities such as piping and a pump in the leaching step.
  • the EPMA observation of nickel oxide ore shows that a portion having high chromium content is present as a single phase independent of a portion having high iron content in a relatively high ratio, and a large number of the portion having high chromium content has a particle size of 20 to 1000 ⁇ m.
  • the crushed particle size at this time which is determined in consideration of the original purpose for forming the ore slurry, is preferably about 2 mm or less.
  • Table 1 shows an example of the ore particle size distribution of the ore slurry obtained by crushing the ore to a particle size of about 2 mm or less and the grade of each component in each particle size section.
  • step (A) is a step of separating and recovering chromite in the ore slurry produced from the ore processing step.
  • Mineral particles of silica mineral, silica-magnesia mineral, or the like can also be separated and removed as intermediates of the step.
  • step (A) may also be performed included in the ore processing step or performed following the ore processing step.
  • the method of step (A) is not particularly limited, but methods using various physical separation means to separate chromite from the ore slurry can be applied to the method of step (A).
  • the physical separation means in order to concentrate chromite up to, for example, 41 to 50% by weight Cr 2 O 3 in which chromite is easily recycled as a resource after it is separated and recovered, a wet-physical separation method including specific gravity separation and classification for recovery of the ore in the particle-size range in which chromite is concentrated are essential from the analysis of the distribution state of each component in the ore particles constituting the ore slurry.
  • the classification particle size in the classification may be any particle size as long as goethite containing nickel in the fine particle portion is efficiently separated, and is preferably selected from the range of 20 to 150 ⁇ m, more preferably 45 to 75 ⁇ m.
  • the lower limit of the classification point that can be industrially performed is about 20 and when the classification particle size is less than 20 the concentration of chromite in the coarse particle portion will be insufficient, and nickel in the ore slurry used in the leaching step will be lost.
  • the classification particle size is more than 150 ⁇ m, the removal of silica mineral, chromite, and silica-magnesia in the fine particle portion will be insufficient.
  • the technique in the classification is not particularly limited, but it is desirable to select cyclone classification which has high performance and is capable of large-amount treatment.
  • the specific gravity of chromite is higher than that of iron hydroxide such as goethite, and chromite that is coarse and has a high specific gravity and goethite that is fine and has a low specific gravity can be efficiently separated with a cyclone.
  • the operating pressure of the cyclone is desirably 0.1 to 0.3 MPa when separation performance and treatment speed are taken into consideration.
  • the shape of the cyclone is desirably adjusted so that the pulp content of the underflow may be 50% by weight or more.
  • the pulp content of the ore slurry to be fed to the cyclone is, but not particularly limited to, preferably 10 to 30% by weight, more preferably 15 to 20% by weight.
  • the separation with the cyclone can be performed even if the pulp content is less than 10% by weight, but such a pulp content requires a large amount of water and is disadvantageous for the settling and concentration in a subsequent step. Further, if the pulp content is higher than 30% by weight, the viscosity of the slurry may increase to disturb the separation.
  • the pulp content after the ore processing step is set to the above range of 10 to 30% by weight, additional feeding of water is not required, and a tank for dilution is also not required. Therefore, the above pulp content range is preferred.
  • the specific gravity separation apparatus to be used is not particularly limited, but it is preferred to select at least one of a shaking table, a density separator, and a spiral concentrator, and it is more preferred to select at least one of a density separator and a spiral concentrator, which are suitable for large-amount treatment.
  • the pulp content of the slurry fed thereto is preferably more than 15% by weight and less than 35% by weight, more preferably more than 20% by weight and less than 30% by weight.
  • the separation performance may be deteriorated, and when the pulp content is 35% by weight or more, the flow of particles on the chromite concentration side (inner side) may stagnate during the separation with a spiral concentrator to produce build-up to prevent sufficient separation.
  • the recovery rate of chromite will be increased by subjecting chromite (outer side) concentrated to 15% by weight or more and 40% by weight or less to spiral treatment several times.
  • the amount of Teeter water is desirably set to 0.5 to 7.0 [m3 ⁇ h-1/m2].
  • Teeter water refers to water for floating the above ore particles in the density separator. Teeter water floats the ore particles to form a fluidized bed to gather heavy particles in a lower layer. Teeter water may also be referred to as fluidization water.
  • the Cr 2 O 3 grade is increased by treating the slurry with a density separator several times.
  • the Cr 2 O 3 grade in chromite can be concentrated up to 41 to 50% by weight or more only by the specific gravity separation, but in order to concentrate chromite to higher concentration, it is desired to separate and remove magnetite contained in a very small amount.
  • the magnetic field strength in the magnetic separation is not particularly limited but varies depending on belt speed, belt thickness, and apparatus, and it is preferably in the range of 200 [Oe] to 2000 [Oe].
  • the magnetic field strength is less than 200 [Oe]
  • the magnetic field may be so weak that separation and removal of magnetite may be insufficient.
  • the magnetic field strength is more than 2000 [Oe]
  • the removal of magnetite will be no problem, but even chromite may be magnetized to prevent magnetic separation.
  • a low-intensity magnetic separator may be used.
  • a Non-Mag slurry obtained by low-intensity magnetic separation can be subjected to classification with a classifier provided with a 53 ⁇ m-mesh screen and a 300 ⁇ m-mesh screen to thereby increase the Cr 2 O 3 grade obtained by the classification.
  • the leaching step is a step of adding sulfuric acid to the ore slurry obtained through the ore processing step and step (A) and then stirring the resulting mixture at a temperature of 220 to 280° C. to form a leach slurry including a leach residue and a leachate.
  • a preheater, an autoclave, and a flash tank are used as main facilities.
  • the leaching of nickel, cobalt and the like as sulfates and the fixation of leached iron sulfate as hematite are performed by the leaching reaction represented by reaction formulas (1) to (3) and the high temperature thermal hydrolysis reaction represented by reaction formulas (4) and (5).
  • the liquid portion of the resulting leach slurry usually contains divalent and trivalent iron ions in addition to nickel, cobalt and the like.
  • M represents Ni, Co, Fe, Zn, Cu, Mg, Cr, Mn, or the like.
  • the reaction temperature in the leaching step is 220 to 280° C., preferably 240 to 270° C.
  • iron is fixed as hematite by performing the reactions in this temperature range.
  • reaction temperature is lower than 220° C.
  • iron will remain dissolved in the reaction solution since the rate of the high temperature thermal hydrolysis reaction is slow. Therefore, the solution purification load for removing iron will increase, making it very difficult to separate iron from nickel.
  • the temperature is higher than 280° C.
  • the high temperature thermal hydrolysis reaction itself will be accelerated, but it will be difficult to select a material of a vessel used in high pressure acid leach, and the steam cost for increasing temperature will also increase. Therefore, a temperature of higher than 280° C. is not suitable.
  • the amount of sulfuric acid used in the leaching step is, but not particularly limited to, a slightly excessive amount relative to the stoichiometric amount required for iron in the ore to be leached and converted to hematite, for example, 300 to 400 kg per ton of the ore. Particularly, if the amount of sulfuric acid added per ton of the ore is more than 400 kg, the cost of sulfuric acid and the cost of a neutralizing agent in a subsequent step will increase. Therefore, such an amount is not preferred. Further, the amount of sulfuric acid used in view of a leaching step product is aimed to be 25 to 50 g/L, preferably 35 to 45 g/L, in terms of the concentration of free sulfuric acid at the completion of leaching.
  • the true density of the leach residue is increased; a high density leach residue is stably produced; and the solid-liquid separability of the slurry is improved.
  • the facilities of the solid-liquid separation step, which is the subsequent step, can be simplified.
  • the solid-liquid separation step is a step of subjecting the leach slurry formed in the previous leaching step to multi-stage washing to obtain a leachate containing nickel and cobalt and a leach residue. Thereby, nickel and the like which adhere to the leach residue and are discarded are recovered in the leachate
  • Step (B- 1 ) is a step of neutralizing the leachate 11 separated in the previous solid-liquid separation step, specifically a step of adding a neutralizing agent (pH adjuster) to the leachate 11 obtained in the leaching step so that it has a pH in the range of 4 or less, preferably 3.2 to 3.8, while suppressing the oxidation of the leachate 11 , to form a residue after step (B- 1 ) 26 as a neutralized precipitate slurry containing trivalent iron and mother liquor ( 1 ) 14 for nickel recovery.
  • a neutralizing agent pH adjuster
  • the excess acid used in the leaching step is neutralized, and trivalent iron ions remaining in the leachate are removed.
  • a neutralizer which does not contain Ca, such as a Mg-based alkali such as Mg(OH) 2 , and MgO which dissolves in the leachate and shows alkalinity.
  • gypsum When a neutralizing agent containing Ca, such as CaCO 3 , is used, gypsum will be produced. A part of the residue after step (B- 1 ) 26 as the neutralized precipitate slurry produced in this step is returned to the solid-liquid separation step and repeatedly used. Therefore, incorporation of gypsum into the leach residue slurry may occur, which does not give significant influence on the hematite grade since the amount of gypsum is small.
  • a Ca-based neutralizer may be used without problems.
  • the zinc removal step is a step of blowing hydrogen sulfide gas into the mother liquor obtained in the previous step to produce a sulfide containing zinc to form a zinc sulfide precipitate slurry and mother liquor for nickel and cobalt recovery, prior to the step of separating nickel and cobalt as sulfides.
  • the resulting zinc sulfide precipitate slurry can be sent to the final neutralization step ( 7 ) and treated, similar to the neutralized precipitate slurry obtained in the neutralization step.
  • the sulfurization step is a step of blowing hydrogen sulfide into the mother liquor ( 2 ) for nickel and cobalt recovery obtained in the zinc removal step to produce a mixed sulfide (zinc sulfide precipitate) 17 containing nickel and cobalt and barren liquor 18 .
  • the resulting barren liquor 18 has a pH of about 1 to and contains not only impurities such as iron, magnesium, and manganese which are contained without being sulfurized, but also a very small amount of nickel and cobalt as a recovery loss. Therefore, the barren liquor 18 is used as washing water for the leach residue in the solid-liquid separation step and as washing water for the neutralization residue produced in the neutralization step.
  • Step (B- 2 ) is a step of neutralizing a part of the leach residue (leach residue slurry: represented by reference numeral 12 in FIG. 1 ) produced in the solid-liquid separation step with a Mg-based neutralizing agent, such as a Mg-based alkali, such as Mg(OH)2, and MgO to recover hematite particles.
  • a Mg-based neutralizing agent such as a Mg-based alkali, such as Mg(OH)2, and MgO to recover hematite particles.
  • the method for step (B- 2 ) is not particularly limited, but a Ca-based alkali is not used as a neutralizing agent.
  • a Ca-based alkali is not used as a neutralizing agent.
  • CaCO 3 is used as a neutralizing agent, it will react with adhering sulfuric acid to produce gypsum. Since the gypsum has low solubility, it is precipitated as a solid and increases the sulfur grade in the residue. On the other hand, since MgSO 4 has high solubility, it is not easily precipitated as a solid and effective for reducing sulfur.
  • Mg(OH)2 which is a Mg-based alkali is preferred, but a Mg-based neutralizing agent such as MgO may be used.
  • Table 2 shows an example of the ore particle size distribution of the leach residue obtained by leaching the ore slurry obtained by crushing the ore to a particle size of about 2 mm or less and the grade of each component in each particle size section.
  • the particles containing iron in a high content are finer particles than particles containing chromium, silicon, and the like in high contents
  • the particles containing iron in a high content can be separated from the coarse particle portion containing chromium, silicon, and the like in high contents and driven away out of the system to recover hematite as a resource by screening means such as a classification method.
  • the classification method is preferably a treatment with a cyclone or the like which is capable of large-amount treatment.
  • the final neutralization step is a step of adding the treatment solution after step (B- 2 ) 27 obtained in step (B- 2 ), the leach residue slurry 12 after the solid-liquid separation step which has not been treated in step (B- 2 ), the residue after step (B- 1 ) 26 , and optionally a slurry formed from the zinc sulfide precipitate 15 obtained in the zinc removal step to prepare a mixture and further adding a limestone slurry and a slaked lime slurry to the mixture to adjust the pH to about 8 or 9, thereby precipitating metal ions in the solution as a neutralized precipitate to obtain a final neutralized residue 19 .
  • the resulting final neutralized residue 19 is stored in the tailings dam 20 .
  • step (A) the ore slurry 9 was subjected to step (A) according to the execution flow chart shown in FIG. 3 , in which the ore slurry 9 was subjected to classification with a hydrocyclone to separate goethite and then subjected to specific gravity separation once with a density separator and a spiral concentrator in combination in this order.
  • the ore slurry having the composition shown in Table 3 was classified using a hydrocyclone (manufactured by Daiki Ataka Engineering Co., Ltd., Model MD-9) as a classifier used in step (A).
  • a hydrocyclone manufactured by Daiki Ataka Engineering Co., Ltd., Model MD-9
  • Example 1 the classification was performed under the conditions of a slurry concentration of 15% by weight, a slurry temperature of normal temperature, and an operating pressure of 0.2 MPa.
  • the level of Cr 2 O 3 increased to 13.5% by weight versus 2.5% by weight in the feed, and the level of SiO 2 increased to 6.0% by weight versus 4.4% by weight in the feed; on the other hand, the level of Fe decreased to 45.2% by weight versus the iron grade of 51.5% by weight in the feed.
  • the hydrocyclone U/F (slurry concentration: 33% by weight) was fed to a density separator (manufactured by Outotec, Inc., “Tanksizer TS-Lab”, tank inside diameter: 228.6 mm).
  • the feed rate of the slurry was set to 56 [kg/Hr], and the slurry temperature was set to normal temperature.
  • the treatment was performed by setting the amount of Teeter water at this time to 6.9 [m3 ⁇ h-1/m2] and the set point (set value of a density meter) to 20.
  • compositions of the feed to the density separator (hydrocyclone U/F) and the underflow from the density separator (density separator U/F) are shown in Table 4.
  • the hydrocyclone U/F (slurry concentration: 33% by weight) was subjected to a separation test with a spiral concentrator (manufactured by Outotec, Inc., “MC7000”).
  • the level of Cr 2 O 3 increased to 24.4% by weight in the Middling. On the other hand, the level of Cr 2 O 3 was 5.3% by weight in the Tailing.
  • the density separator U/F ( 1 ) (slurry concentration: 75% by weight) obtained from the density separator was diluted with water to a slurry concentration of 25% by weight, and the diluted slurry was subjected to a separation test with a spiral concentrator (manufactured by Outotec, Inc., “MC7000”).
  • the level of Cr 2 O 3 increased to 24.3% by weight.
  • the level of Cr 2 O 3 was 5.0% by weight.
  • the “Concentrate” obtained from the spiral test was diluted to a slurry concentration of 20% by weight, and the diluted slurry was fed to a low-intensity magnetic separator (manufactured by Outotec, Inc., “Inprosys benchtop LIMS”) at a feed rate of 45.4 [kg/Hr] to obtain a magnetic material (Mag) and a non-magnetic material (Non-Mag).
  • a low-intensity magnetic separator manufactured by Outotec, Inc., “Inprosys benchtop LIMS”
  • the level of Cr 2 O 3 obtained from the low-intensity magnetic separation increased to 45.3% by weight versus 41.2% by weight in the feed.
  • the level of Fe decreased to 23.1% by weight from 28.5% by weight.
  • the ore slurry can be concentrated to a concentration exceeding the Cr 2 O 3 grade of generally commercially available chromite by sequentially treating the ore slurry with a hydrocyclone, with a density separator twice, and with a spiral concentrator.
  • the recovery rate of the resulting chromite was 42.5% by weight.
  • the chromite obtained by the low-intensity magnetic separation treatment was subjected to classification as shown below.
  • the non-magnetic slurry obtained by the low-intensity magnetic separation was subjected to classification with a classifier (manufactured by DALTON Co., Ltd.: vibrating screen 702CB) provided with a 53 ⁇ m-mesh screen and a 300 ⁇ m-mesh screen.
  • a classifier manufactured by DALTON Co., Ltd.: vibrating screen 702CB
  • the level of Cr 2 O 3 obtained by the classification increased to 51.4% by weight versus 45.3% by weight in the feed.
  • the level of Fe increased from 23.1% by weight to 31.2% by weight.
  • the ore slurry can be concentrated to a concentration exceeding the Cr 2 O 3 grade of generally commercially available chromite.
  • the recovery rate of the chromite obtained in Example 1 was 19%. Note that the recovery rate was determined by the Formula (6).
  • step (A) In the production flow of the present invention in FIG. 1 , the ore slurry was subjected to step (A) as shown in the execution flow chart of step (A) in FIG. 4 , in which the ore slurry was subjected to specific gravity separation repeatedly twice with a density separator and then subjected to specific gravity separation with a spiral concentrator.
  • the ore slurry having the composition shown in Table 9 was classified using a hydrocyclone (manufactured by Daiki Ataka Engineering Co., Ltd., Model MD-9) as a classifier used in step (A).
  • a hydrocyclone manufactured by Daiki Ataka Engineering Co., Ltd., Model MD-9
  • Example 2 the classification was performed under the conditions of a slurry concentration of 15% by weight, a slurry temperature of normal temperature, and an operating pressure of 0.2 MPa.
  • the level of Cr 2 O 3 increased to 13.5% by weight versus 2.5% by weight in the feed, and the level of SiO 2 increased to 6.0% by weight versus 4.4% by weight in the feed; on the other hand, the level of Fe decreased to 45.2% by weight versus the iron grade of 51.5% by weight in the feed.
  • the hydrocyclone U/F (slurry concentration: 33% by weight) was fed to a density separator (manufactured by Outotec, Inc., “Tanksizer TS-Lab”, tank inside diameter: 228.6 mm).
  • the feed rate of the slurry was set to 56 [kg/Hr], and the slurry temperature was set to normal temperature.
  • the treatment was performed by setting the amount of Teeter water at this time to 6.9 [m3 ⁇ h-1/m2] and the set point (set value of a density meter) to 20.
  • compositions of the feed to the density separator ( 1 ) hydrocyclone U/F
  • the underflow from the density separator ( 1 ) density separator U/F ( 1 )
  • the density separator U/F ( 1 ) (slurry concentration: 75% by weight) was diluted with water to a slurry concentration of 40% by weight, and the diluted slurry was subjected to the density separator treatment again.
  • the compositions of the feed to the density separator ( 2 ) (density separator U/F ( 1 ) obtained by the first density separator treatment) and the underflow from the density separator ( 2 ) (density separator U/F ( 2 ) obtained by the second density separator treatment) are shown in Table 11.
  • Table 11 shows that the level of Cr 2 O 3 increased from 16.9% by weight to 21.1% by weight. It can be verified that the concentration of chromite proceeds by repeating the treatment with a density separator in this way.
  • the density separator U/F ( 2 ) (slurry concentration: 75% by weight) obtained from the density separator ( 2 ) was diluted with water to a slurry concentration of 25% by weight, and the diluted slurry was subjected to a spiral test with a spiral concentrator (manufactured by Outotec, Inc., “MC7000”).
  • the level of Cr 2 O 3 increased to 42.5% by weight versus 30.3% by weight in the feed by subjecting the Middling ( 1 ) to the spiral treatment again.
  • the level of Cr 2 O 3 decreased to 19.4% by weight in the Middling ( 2 ) and to 19.5% by weight in the Tailing.
  • These Middling ( 2 ) and Tailing may optionally be subjected to the spiral treatment again.
  • the “Concentrates” obtained by the two spiral tests were mixed and diluted to a slurry concentration of 20% by weight, and the diluted slurry was fed to a low-intensity magnetic separator (manufactured by Outotec, Inc., “Inprosys benchtop LIMS”) at a feed rate of 45.4 [kg/Hr] to obtain a magnetic material (Mag) and a non-magnetic material (Non-Mag).
  • a low-intensity magnetic separator manufactured by Outotec, Inc., “Inprosys benchtop LIMS”
  • the level of Cr 2 O 3 obtained from the low-intensity magnetic separation increased to 48.5% by weight versus 44.1% by weight in the feed.
  • the level of Fe decreased to 20.0% by weight from 24.7% by weight.
  • the ore slurry can be concentrated to a concentration exceeding the Cr 2 O 3 grade of generally commercially available chromite by sequentially treating the ore slurry with a hydrocyclone, with a density separator twice, and with a spiral concentrator.
  • the recovery rate of the resulting chromite was 44% by weight.
  • the chromite obtained by the low-intensity magnetic separation treatment was subjected to classification as shown below.
  • the non-magnetic slurry obtained by the low-intensity magnetic separation was subjected to classification with a classifier (manufactured by DALTON Co., Ltd.: vibrating screen 702CB) provided with a 53 ⁇ m-mesh screen and a 300 ⁇ m-mesh screen.
  • a classifier manufactured by DALTON Co., Ltd.: vibrating screen 702CB
  • the level of Cr 2 O 3 obtained by the classification increased to 55.0% by weight versus 48.5% by weight in the feed.
  • the level of Fe increased from 20.0% by weight to 27.0% by weight.
  • the ore slurry can be concentrated to a concentration exceeding the Cr2O3 grade of generally commercially available chromite.
  • the recovery rate of the chromite obtained in Example 2 was 20%. Note that the recovery rate was determined by the Formula (6) in the same manner as in Example 1.
  • the ore slurry was classified using a hydrocyclone (manufactured by Daiki Ataka Engineering Co., Ltd., Model “MD-9”) as a classifier.
  • a hydrocyclone manufactured by Daiki Ataka Engineering Co., Ltd., Model “MD-9”
  • the classification was performed under the conditions of a slurry concentration of 9.8% by weight, a slurry temperature of normal temperature, and an operating pressure of 0.22 MPa.
  • hydrocyclone underflow (hydrocyclone U/F) having a slurry concentration of 33% by weight was diluted to a slurry concentration of 4.9% by weight, and the diluted slurry was charged into a high-mesh separator (manufactured by Kikosha Co., Ltd., “KUC-612S”).
  • the feed rate to the high-mesh separator was 0.98 [m 3 /hour]; the rotation speed of the bucket was 0.8 rpm; the bucket length was 75 mm; and the bucket had holes each having a diameter of 4 mm opened at a pitch of 6 mm, in which the rate of hole area was 40%.
  • the amount of washing water was set to 6 m3/hour.
  • compositions of the ore slurry and the hydrocyclone underflow (hydrocyclone U/F) and the composition of the underflow of the high-mesh separator (high-mesh separator U/F) are shown in Table 16.
  • the Cr 2 O 3 grade was concentrated from 4.1% by weight in the ore slurry to 13.0% by weight in the coarse particle portion of the hydrocyclone (hydrocyclone U/F), and to 19.1% by weight in the coarse particle portion of the high-mesh separator (high-mesh separator U/F), but the target level of the composition of commercially available products was not obtained.
  • Example 2 The overflow of the hydrocyclone and the overflow of the density separator in Example 1 were charged into an autoclave at a solid weight ratio of 77:15, and thereto was added 98% sulfuric acid. The resulting mixture was subjected to high pressure acid leach under the following conditions to produce a leach slurry 10 .
  • the produced leach slurry was separated into a leachate 11 and a leach residue slurry 12 by a solid-liquid separation step.
  • Leaching temperature 245° C.
  • Mg(OH) 2 slurry having a concentration of 20% by weight as a neutralizing agent was added to the leach residue slurry 12 to neutralize the leach residue slurry so that it might have a pH of 2.5 at 70° C.
  • the slurry was subjected to solid-liquid separation using 5C filter paper followed by adding the Mg(OH) 2 slurry until the resulting slurry has a pH of 6, and the resulting slurry was then further subjected to solid-liquid separation using 5 C filter paper.
  • the Cr 2 O 3 grade of the resulting final neutralized residue was 0.9% by weight. Since MgSO 4 produced has high solubility, the residue had a sulfur grade of 0.53% by weight.
  • Example 1 When the ore slurry in Example 1 was treated in the same manner as in Example 3 except that the ore slurry was charged into an autoclave without treating the slurry with the hydrocyclone and the density separator, the Cr 2 O 3 grade of the resulting final neutralized residue was 2.1% by weight.
  • Example 3 As is obvious from a comparison between Example 3 and Comparative Example 2, chromite in the ore slurry was able to be separated and removed to halve the Cr 2 O 3 grade in the residue by first classifying the ore slurry with the hydrocyclone and then treating with the density separator which is one of the specific gravity separation apparatuses.
  • a leach residue slurry 12 was prepared in the same manner as in Example 3; a slaked lime slurry with a concentration of 25% by weight was added as a neutralizing agent to the entire amount of the leach residue slurry to neutralize the slurry to a pH of 8.5 at 60° C. to precipitate metal ions as a precipitate; and a neutralization residue and a treatment solution after neutralization were obtained by solid-liquid separation.
  • the neutralization residue was subjected to cyclone classification to separate hematite 28 .
  • a slaked lime slurry with a concentration of 25% by weight was added to a mixed solution obtained by mixing the treatment solution after neutralization with a remaining neutralization residue from which hematite 28 had been separated, and the resulting mixture was then repeatedly subjected to solid-liquid separation with 5C filter paper to obtain a final neutralized residue.
  • the resulting final neutralized residue had a Cr 2 O 3 grade of 0.8% by weight. Since CaSO4 produced has low solubility, the residue had a sulfur grade of 5.72% by weight and a Ca grade of 8.49% by weight.
  • Example 1 As shown in the execution flow chart of Comparative Example in FIG. 6 , the separation test was performed under the same conditions as in Example 1 except that the ore slurry was subjected to the specific gravity separation once in the same manner as in Example 1 without the classification with the hydrocyclone and finally subjected to the classification with the hydrocyclone.
  • Table 18 shows the results obtained by subjecting the ore, which had not been subjected to the classification with the hydrocyclone, to the specific gravity separation with the density separator.
  • the Cr2O3 concentration of the underflow from the density separator was not as high as that of the underflow obtained by treating a feed which had been subjected to classification (refer to the density separator U/F in Table 4), probably because the feed (ore slurry) had a high viscosity.
  • the concentration of Cr2O3 was 35.3% by weight, which did not satisfy 41% by weight or more.
  • the hydrometallurgical process for nickel oxide ore of the present invention is suitable as a smelting method based on high pressure acid leach utilized in the hydrometallurgical field of nickel oxide ore.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
US15/304,898 2014-04-18 2015-03-27 Hydrometallurgical process for nickel oxide ore Abandoned US20170175227A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014086590A JP6183788B2 (ja) 2014-04-18 2014-04-18 ニッケル酸化鉱石の湿式製錬方法
JP2014-086590 2014-04-18
PCT/JP2015/059674 WO2015159685A1 (ja) 2014-04-18 2015-03-27 ニッケル酸化鉱石の湿式製錬方法

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/059674 A-371-Of-International WO2015159685A1 (ja) 2014-04-18 2015-03-27 ニッケル酸化鉱石の湿式製錬方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US16/554,982 Division US20190382870A1 (en) 2014-04-18 2019-08-29 Hydrometallurgical process for nickel oxide ore

Publications (1)

Publication Number Publication Date
US20170175227A1 true US20170175227A1 (en) 2017-06-22

Family

ID=54323896

Family Applications (2)

Application Number Title Priority Date Filing Date
US15/304,898 Abandoned US20170175227A1 (en) 2014-04-18 2015-03-27 Hydrometallurgical process for nickel oxide ore
US16/554,982 Abandoned US20190382870A1 (en) 2014-04-18 2019-08-29 Hydrometallurgical process for nickel oxide ore

Family Applications After (1)

Application Number Title Priority Date Filing Date
US16/554,982 Abandoned US20190382870A1 (en) 2014-04-18 2019-08-29 Hydrometallurgical process for nickel oxide ore

Country Status (8)

Country Link
US (2) US20170175227A1 (https=)
EP (1) EP3133177B1 (https=)
JP (1) JP6183788B2 (https=)
CN (1) CN106232842A (https=)
AU (1) AU2015247229B2 (https=)
CA (1) CA2946106C (https=)
PH (1) PH12016502070A1 (https=)
WO (1) WO2015159685A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230227326A1 (en) * 2020-08-17 2023-07-20 Guangdong Brunp Recycling Technology Co., Ltd. Method for producing battery-grade nickel sulfate by using laterite nickel ore

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6202083B2 (ja) * 2015-12-25 2017-09-27 住友金属鉱山株式会社 硫化剤の除去方法
CN105567964B (zh) * 2015-12-28 2017-05-17 中南大学 一种含钒铬溶液选择性还原分离回收钒和铬的方法
JP7087601B2 (ja) * 2018-04-06 2022-06-21 住友金属鉱山株式会社 硫化剤の除去方法及びニッケル酸化鉱石の湿式製錬方法
JP7687079B2 (ja) * 2021-06-23 2025-06-03 住友金属鉱山株式会社 含クロマイトスラリーの分配装置及びこれを用いたクロマイトの回収方法
JP2023042898A (ja) * 2021-09-15 2023-03-28 住友金属鉱山株式会社 クロム鉄鉱石の回収方法
JP7151848B1 (ja) 2021-09-15 2022-10-12 住友金属鉱山株式会社 クロム鉄鉱石の回収方法
JP2023050767A (ja) * 2021-09-30 2023-04-11 住友金属鉱山株式会社 クロム鉄鉱石の回収方法
JP7848511B2 (ja) * 2022-02-25 2026-04-21 住友金属鉱山株式会社 クロム鉄鉱石の分離回収設備、及び、クロム鉄鉱石の回収方法
JP7658359B2 (ja) * 2022-12-29 2025-04-08 住友金属鉱山株式会社 ニッケル酸化鉱石の高圧硫酸浸出における制御方法
CN116790875B (zh) * 2023-06-15 2025-02-18 四川顺应动力电池材料有限公司 一种红土镍矿脱硫的方法
WO2025020179A1 (zh) * 2023-07-27 2025-01-30 青美邦新能源材料有限公司 红土镍矿酸浸提取镍钴锰的方法
WO2026049131A1 (ko) * 2024-08-30 2026-03-05 고려아연 주식회사 황화물 형태의 니켈 매트로부터의 니켈 회수 방법
WO2026049200A1 (ko) * 2024-08-30 2026-03-05 고려아연 주식회사 황화물 형태의 니켈 매트로부터의 니켈 회수 방법

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961908A (en) * 1974-02-27 1976-06-08 Freeport Minerals Company Autoclave system for leaching sulfide concentrates
AU2009212947A1 (en) * 2008-09-19 2010-04-08 Sumitomo Metal Mining Co., Ltd. Hydrometallurgical process of nickel laterite ore
JP2012107289A (ja) * 2010-11-17 2012-06-07 Sumitomo Metal Mining Co Ltd クロマイト回収方法、並びにニッケル酸化鉱石の湿式製錬方法
JP2013095971A (ja) * 2011-11-01 2013-05-20 Sumitomo Metal Mining Co Ltd ニッケル酸化鉱石の湿式製錬方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101638730B (zh) * 2008-07-31 2015-03-25 塔塔钢铁有限公司 用于从冶金级铬铁矿精矿细粉生产海绵铬的方法
JP5446226B2 (ja) * 2008-09-19 2014-03-19 住友金属鉱山株式会社 ニッケル酸化鉱石の湿式製錬方法
JP2010100915A (ja) * 2008-10-27 2010-05-06 Jfe Steel Corp 竪型炉の操業方法
WO2014125558A1 (ja) * 2013-02-12 2014-08-21 住友金属鉱山株式会社 ニッケル酸化鉱石の湿式製錬方法
JP5757442B2 (ja) * 2013-04-23 2015-07-29 住友金属鉱山株式会社 ニッケル酸化鉱石の湿式製錬方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961908A (en) * 1974-02-27 1976-06-08 Freeport Minerals Company Autoclave system for leaching sulfide concentrates
AU2009212947A1 (en) * 2008-09-19 2010-04-08 Sumitomo Metal Mining Co., Ltd. Hydrometallurgical process of nickel laterite ore
JP2012107289A (ja) * 2010-11-17 2012-06-07 Sumitomo Metal Mining Co Ltd クロマイト回収方法、並びにニッケル酸化鉱石の湿式製錬方法
JP2013095971A (ja) * 2011-11-01 2013-05-20 Sumitomo Metal Mining Co Ltd ニッケル酸化鉱石の湿式製錬方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
IN 200200512 ABSTRACT (YEAR:2006) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230227326A1 (en) * 2020-08-17 2023-07-20 Guangdong Brunp Recycling Technology Co., Ltd. Method for producing battery-grade nickel sulfate by using laterite nickel ore
US11952288B2 (en) * 2020-08-17 2024-04-09 Guangdong Brunp Recycling Technology Co., Ltd. Method for producing battery-grade nickel sulfate by using laterite nickel ore

Also Published As

Publication number Publication date
EP3133177B1 (en) 2020-09-02
EP3133177A1 (en) 2017-02-22
CN106232842A (zh) 2016-12-14
CA2946106A1 (en) 2015-10-22
JP6183788B2 (ja) 2017-08-23
AU2015247229B2 (en) 2019-05-02
AU2015247229A1 (en) 2016-11-10
CA2946106C (en) 2019-08-20
EP3133177A4 (en) 2017-12-27
JP2015206068A (ja) 2015-11-19
WO2015159685A1 (ja) 2015-10-22
US20190382870A1 (en) 2019-12-19
PH12016502070A1 (en) 2016-12-19

Similar Documents

Publication Publication Date Title
US20190382870A1 (en) Hydrometallurgical process for nickel oxide ore
US20160076121A1 (en) Hydrometallurgical process for nickel oxide ore
JP5403033B2 (ja) ニッケル酸化鉱石の湿式製錬方法
JP5446226B2 (ja) ニッケル酸化鉱石の湿式製錬方法
US9783869B2 (en) Hydrometallurgical process for nickel oxide ore
JP2015206068A5 (https=)
AU2009212947A1 (en) Hydrometallurgical process of nickel laterite ore
JP2013095971A5 (https=)
US10273558B2 (en) Ore slurry pre-treatment method and ore slurry manufacturing method
JP6565511B2 (ja) 鉱石スラリーの処理方法、ニッケル酸化鉱石の湿式製錬方法
JP6969262B2 (ja) ニッケル酸化鉱石の湿式製錬方法
US10626481B2 (en) Mineral ore slurry pretreatment method, and method for manufacturing mineral ore slurry
JP2019065340A (ja) ニッケル酸化鉱石の湿式製錬方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: SUMITOMO METAL MINING CO. LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OHARA, GO;IMAMURA, MASAKI;REEL/FRAME:040042/0022

Effective date: 20160915

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION