AU2017218246B2 - Sulfuration treatment method, sulfide production method, and hydrometallurgical process for nickel oxide ore - Google Patents
Sulfuration treatment method, sulfide production method, and hydrometallurgical process for nickel oxide ore Download PDFInfo
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- 238000005987 sulfurization reaction Methods 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910000480 nickel oxide Inorganic materials 0.000 title claims description 25
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims description 25
- 238000009854 hydrometallurgy Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 230000019086 sulfide ion homeostasis Effects 0.000 title claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 194
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 160
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 98
- 239000007789 gas Substances 0.000 claims abstract description 77
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 70
- 239000003929 acidic solution Substances 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 67
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 60
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims description 35
- 238000011084 recovery Methods 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 20
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 73
- 239000003795 chemical substances by application Substances 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 description 63
- 229910017052 cobalt Inorganic materials 0.000 description 32
- 239000010941 cobalt Substances 0.000 description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000006386 neutralization reaction Methods 0.000 description 20
- 150000004763 sulfides Chemical class 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 239000002562 thickening agent Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- -1 for example Chemical compound 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910015853 MSO4 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 229910001710 laterite Inorganic materials 0.000 description 3
- 239000011504 laterite Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000011019 hematite Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009283 thermal hydrolysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical class [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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
-
- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Provided is a method with which it is possible, when causing a sulfuration reaction to occur from a sulfuric acid acidic solution containing at least nickel through use of a sulfuration agent and generating a sulfide of nickel, to suitably control the grain size of the generated sulfide while maintaining high reaction efficiency. The sulfuration treatment method according to the present invention comprises supplying a sulfuric acid acidic solution that contains nickel to a reactor, adding hydrogen sulfide gas to the sulfuric acid acidic solution, and generating nickel sulfide, wherein unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to the recovered hydrogen sulfide gas, sodium hydrosulfide is generated, and the resulting solution of sodium hydrosulfide is added to sulfuric acid acidic solution. At this time, when the sodium hydrosulfide solution is added, the grain size of the generated sulfide of nickel is set to 50 μm or higher by 50% particle size (D50) by controlling the amount of sodium hydrosulfide solution added to the reactor to which the sulfuric acid acidic solution is supplied.
Description
The present invention relates to a sulfuration treatment method for generating a nickel sulfide from a sulfuric acid acidic solution containing nickel based on a sulfuration reaction using a sulfuration agent.
BACKGROUND ART
In recent years, recovery of valuable metals from lowgrade nickel ores by high pressure acid leach (HPAL) method in which acid leaching is conducted at high temperature and high pressure has been put to practical use in the field of nickel hydrometallurgy using nickel oxide ore as a raw material. Moreover, with regard to the recovery of valuable metals such as nickel and cobalt leached from nickel oxide ore by the HPAL method, a method is generally used in which the valuable metals are recovered as a sulfide by adding a sulfuration agent such as hydrogen sulfide gas to a sulfuration bath containing the valuable metals under pressure.
In the sulfuration treatment, a method in which the pressure of the reaction vessel, the reaction time, the pH of the reaction solution, the addition of a seed crystal, and the
SMMF-114PCT like are adjusted is known as a method for efficiently causing the sulfuration reaction to occur.
In addition, as one means for improving the reaction efficiency of the sulfuration reaction, for example, a method in which sodium hydrosulfide is added into the reaction vessel is disclosed in Patent Document 1. Specifically, in this method, a sodium hydrosulfide solution obtained by recovering hydrogen sulfide gas, which has been excessively blown into a sulfuration reaction vessel, using a caustic soda solution is added into the sulfuration reaction vessel again. According to this method, it is possible to suppress a decrease in the pH of the reaction solution accompanying the progress of the sulfuration reaction and to suppress redissolution of the generated sulfide. In addition, it is possible to maintain the concentrations of nickel and cobalt in the final reaction liquid low since redissolution of the sulfide can be suppressed, and as a result, it is possible to improve the reaction efficiency of the sulfuration reaction and to recover valuable metals such as nickel and cobalt at a high efficiency.
Meanwhile, in the step of conducting such a sulfuration treatment, it is advantageous to increase the residence time in order to efficiently conduct the sulfuration reaction and there is a case in which two or more reactors are arranged in
SMMF-114PCT series in order to prevent short pass of the solution supplied to the reaction vessel. In such a case, the entire amount of hydrogen sulfide gas and a sodium hydrosulfide solution, which are a sulfuration agent, are added to the initial reactor (first reactor) close to the liquid supply side of the reaction starting liquid.
However, in the method as described above, it is difficult to control the grain size of sulfides (mixed nickel and cobalt sulfides) of nickel and cobalt to be generated and there is often a case in which sulfides are generated which have a small grain size so that the average particle size represented by 50% particle size (D50) is less than 50 pm.
A sulfide having a fine grain size deteriorates the dehydrating property when conducting solid-liquid separation by using a filter press or the like in the subsequent step, a corresponding large scale facility and the corresponding time are required in order to secure the treatment capacity, and the treatment efficiency remarkably decreases. In addition, a sulfide having a fine grain size is likely to be oxidized and this also affects the operation and the quality in some cases.
In view of the above, there is a demand for a technique for stabilizing the grain size of a sulfide to be generated while maintaining a high reaction efficiency in a sulfuration
SMMF-114PCT
2017218246 15 Jan 2019 treatment for generating sulfides of nickel and cobalt. Patent Document 1: Japanese Unexamined Patent Application, Publication No. 2010-126778
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
The present invention has been proposed in view of such circumstances, and seeks to provide a method by which it is possible to appropriately control the grain size of a sulfide to be generated while maintaining a high reaction efficiency when causing a sulfuration reaction to occur from a sulfuric acid acidic solution containing at least nickel through use of a sulfuration agent and generating a nickel sulfide.
Means for Solving the Problems
The inventors of the present invention have conducted intensive investigations to solve the problems described above. As a result, it has been found out that it is possible to suppress miniaturization of a sulfide to be generated while maintaining a high reaction efficiency by using hydrogen sulfide gas as a sulfuration agent and also recovering the unreacted portion of the hydrogen sulfide gas, generating sodium hydrosulfide, and controlling the amount of the resulting sodium hydrosulfide solution to be added, and thus the present invention has been completed.
(1) A first aspect of the present invention is a sulfuration treatment method, including supplying a sulfuric acid acidic solution containing nickel to a reactor, adding hydrogen sulfide gas to the sulfuric acid acidic solution, and generating a nickel sulfide, in which unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the sulfuric acid acidic solution, and a grain size of a sulfide to be generated of nickel is set to 50 pm or more as 50% particle size (D50) by controlling an amount of the sodium hydrosulfide solution to be added to a reactor to which the sulfuric acid acidic solution is supplied when the sodium hydrosulfide solution is added.
(2) A second aspect of the present invention is the sulfuration treatment method according to the first aspect, in which the reactor includes two or more reactors connected in series, and the sulfuric acid acidic solution is supplied to a first reactor located most upstream among the two or more reactors connected in series.
SMMF-114PCT (3) A third aspect of the present invention is the sulfuration treatment method according to the second aspect, in which amounts of hydrogen sulfide gas and a sodium hydrosulfide solution to be added into the first reactor are controlled so that a nickel recovery rate in the first reactor becomes less than 90%.
(4) A fourth aspect of the present invention is the sulfuration treatment method according to the second or third aspect, in which an amount of a sodium hydrosulfide solution to be added into the first reactor is controlled to a proportion to be 0.20% or less of a flow rate of the sulfuric acid acidic solution to be supplied to the first reactor.
(5) A fifth aspect of the present invention is the sulfuration treatment method according to any one of the first to fifth aspects, in which the sulfuric acid acidic solution is a leachate obtained by subjecting a slurry of nickel oxide ore to a leaching treatment using sulfuric acid at high temperature and high pressure in a hydrometallurgical process for nickel oxide ore.
(6) A sixth aspect of the present invention is a nickel sulfide production method, including supplying a sulfuric acid acidic solution containing nickel to a reactor, adding hydrogen sulfide gas to the sulfuric acid acidic solution, and
SMMF-114PCT obtaining a nickel sulfide, in which unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the sulfuric acid acidic solution, and a nickel sulfide and cobalt having a grain size of 50 pm or more as 50% particle size (D50) is obtained by controlling an amount of the sodium hydrosulfide solution to be added to a reactor to which the sulfuric acid acidic solution is supplied when the sodium hydrosulfide solution is added.
(7) A seventh aspect of the present invention is a hydrometallurgical process for nickel oxide ore, including leaching nickel from nickel oxide ore using sulfuric acid at high temperature and high pressure and generating a nickel sulfide from a resulting leachate, in which the method includes a sulfuration step of supplying the leachate to a reactor, adding hydrogen sulfide gas to the leachate, and generating a nickel sulfide, and in the sulfuration step, unreacted gas among the hydrogen sulfide gas added to the leachate is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the
SMMF-114PCT leachate, and a grain size of a sulfide to be generated of nickel is set to 50 μιη or more as 50% particle size (D50) by controlling an amount of the sodium hydrosulfide solution to be added to the reactor to which the leachate is supplied when the sodium hydrosulfide solution is added. Effects of the Invention
According to the present invention, it is possible to appropriately control the grain size of a sulfide to be generated while maintaining a high reaction efficiency in a treatment for generating a nickel sulfide from a sulfuric acid acidic solution containing at least nickel by a sulfuration treatment using a sulfuration agent.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a process chart which illustrates an example of the flow of a hydrometallurgical process for nickel oxide ore. Fig. 2 is a graph chart which illustrates the results of a sulfuration treatment conducted in Examples and Comparative Examples .
PREFERRED MODE FOR CARRYING OUT THE INVENTION
Hereinafter, specific embodiments of the present invention (hereinafter referred to as the present embodiments) will be
SMMF-114PCT described in detail with reference to the drawings. However, the present invention is not limited to the following embodiments, and various modifications can be made without changing the gist of the present invention.
Incidentally, the expression X to Y (X and Y are arbitrary numerical values) in the present specification means X or more and Y or less unless otherwise specified.
<<1. Sulfuration treatment method>>
The sulfuration treatment method according to the present embodiment is a sulfuration treatment method, which includes supplying a sulfuric acid acidic solution containing at least nickel to a reactor, adding hydrogen sulfide gas to the gas phase in the reactor containing the sulfuric acid acidic solution, causing a sulfuration reaction to occur, and generating a nickel sulfide.
In this sulfuration treatment method, for example, hydrogen sulfide gas having a purity of about 95% to 99% to be used as a sulfuration agent is added to the sulfuric acid acidic solution, which is a sulfuration reaction starting liquid, in an excessive amount to be larger than the theoretical equivalent amount required for generating a sulfide by the sulfuration reaction. This makes it possible to recover nickel contained in the sulfuric acid acidic solution
SMMF-114PCT as a sulfide at a high recovery rate.
Meanwhile, an excessive amount of hydrogen sulfide gas is added and thus unreacted gas, which has not been involved in the sulfuration reaction, remains in the reactor. Hence, in this sulfuration treatment method, the unreacted gas among the added hydrogen sulfide gas is recovered, sodium hydroxide is added to the recovered hydrogen sulfide gas, sodium hydrosulfide is generated, and the resulting solution of sodium hydrosulfide is added to the sulfuric acid acidic solution. This makes it possible to recover nickel in the sulfuric acid acidic solution as a nickel sulfide at a still higher recovery rate and also to improve the utilization efficiency of hydrogen sulfide gas.
Moreover, the sulfuration treatment method according to the present embodiment is characterized in that the amount of the resulting sodium hydrosulfide solution to be added is controlled at this time. More specifically, the amount of the sodium hydrosulfide solution to be added to the reactor, to which the sulfuric acid acidic solution is supplied, is controlled so that the grain size of the nickel sulfide to be generated becomes 50 pm or more as 50% particle size (D50).
According to such a sulfuration treatment method, it is possible to improve the recovery rate of nickel contained in
SMMF-114PCT the sulfuric acid acidic solution as a sulfide and also to prevent miniaturization of the grain size of a sulfide to be generated by increasing the reaction efficiency of the sulfuration reaction using a sulfuration agent.
Here, in the sulfuration treatment method according to the present embodiment, unreacted hydrogen sulfide gas is recovered, sodium hydrosulfide is generated, and the entire amount thereof is repeatedly used in the sulfuration reaction as described above. Accordingly, in the sulfuration treatment, a sulfuration reaction using sodium hydrosulfide as presented in the following Formula (2) occurs in addition to the sulfuration reaction using hydrogen sulfide gas as presented in the following Formula (1). Incidentally, M in the following Formulas (1) and (2) represents Ni or Co. MSO4 + H2S MS + H2SO4 ... (1)
2NaHS + MSO4 Na2SO4 + MS + H2S ... (2)
In addition, in the sulfuration treatment, a sulfuric acid acidic solution, which is a starting liquid, is supplied to a sulfuration reactor, in which a sulfuration reaction occurs, hydrogen sulfide gas is added to the gas phase portion in the reactor containing the sulfuric acid acidic solution by being blown thereinto, and hydrogen sulfide gas blown into the gas phase is dissolved in the liquid phase, thereby conducting the
SMMF-114PCT sulfuration reaction.
The sulfuration reactor is not particularly limited, but it is possible to use a reactor composed of two or more tanks, preferably three or more tanks, and more preferably four or more tanks connected in series. In a sulfuration reactor composed of two or more tanks, the sulfuric acid acidic solution containing nickel, which is a sulfuration reaction starting liquid, is supplied to the reactor (first reactor) located most upstream and the sulfuration reaction sequentially and continuously occurs in the respective reactors. In addition, a gas blowing port for blowing hydrogen sulfide gas is provided to the first reactor, and hydrogen sulfide gas is blown into the first reactor therethrough.
More specifically, for example, in a sulfuration reactor composed of three tanks, first, a sulfuric acid acidic solution containing nickel, which is a sulfuration reaction starting liquid, is supplied into the first reactor, which is the initial reactor (reactor located most upstream) among the three reactors continuously provided, and hydrogen sulfide gas is blown into the gas phase portion in the reactor through the gas blowing port. Thereafter, a sulfuration reaction proceeds in the first reactor over a predetermined time, next, the solution containing the generated nickel sulfide is
SMMF-114PCT transferred to the second reactor, and the sulfuration reaction subsequently proceeds in the second reactor. In the same manner, the sulfuration reaction also proceeds in the third reactor, which is the final stage, and the nickel sulfide and the barren solution, which is the final reaction liquid, are separated from the slurry after reaction final reaction liquid) obtained from the third reactor by using a solid-liquid separator such as a thickener
Incidentally, the third reactor of the final stage may be a storage tank.
In this manner in a reactor composed of plural tanks for example two or more tanks a sulfide generating reaction based on the sulfuration reaction occurs mainly in the first reactor and the so-called growth of the generated nickel sulfide occurs in the subsequent second reactor and after.
However, as a result of intensive studies by the inventors of the present invention, it has been found out that the grain size of the sulfide to be finally obtained tends to be small in a case in which the nickel recovery rate in the first reactor is 90% or more. Incidentally, the nickel recovery rate in the first reactor herein is defined by the following formula. Nickel recovery rate = (volume of starting liquid χ nickel concentration in starting liquid - volume of final liquid in first reactor χ nickel concentration in final liquid
SMMF-114PCT in first reactor) a (volume of starting liquid χ nickel concentration in starting liquid)
In other words, the sulfuration reaction due to nucleation is dominant in the first reactor, and thus it is considered that a large amount of sulfide having a fine grain size is generated and nuclear growth cannot sufficiently proceed in the subsequent stage reactor in a case in which the nickel recovery rate in the first reactor is high (90% or more). Moreover, this is presumed to be a factor of generation of a sulfide having a small grain size.
From this fact, the inventors of the present invention have found out that a high nickel recovery rate can be achieved in the sulfuration treatment while sufficiently causing nuclear growth of the sulfide to occur in the subsequent stage reactors of the second reactor and after by controlling the amount of the sulfuration agent to be added to the reactor, particularly the first reactor. Incidentally, the nickel recovery rate by the sulfuration treatment herein is defined by the following formula. Nickel recovery rate = (volume of starting liquid χ nickel concentration in starting liquid - volume of final liquid χ nickel concentration in final liquid) a (volume of starting liquid χ nickel concentration in starting liquid)
SMMF-114PCT
As described above, in the sulfuration treatment method according to the present embodiment, hydrogen sulfide gas and also a sodium hydrosulfide solution generated by recovering unreacted gas, which has not been involved in the sulfuration reaction, are added as a sulfuration agent. At this time, for example, when the addition of hydrogen sulfide gas is changed to the subsequent stage reactors of the second reactor and after, it is difficult to control the pressure and liquid level in each reactor and it is impossible to continuously conduct a stable operation.
Hence, the amount of the sodium hydrosulfide solution generated by recovering unreacted hydrogen sulfide gas to be added is controlled so that the grain size of a nickel sulfide to be generated becomes 50 pm or more as 50% particle size (D50) .
It is possible to suppress the miniaturization of a sulfide to be obtained and to control the grain size to an appropriate value while maintaining a stable operation without affecting the pressure and liquid level in the reactor by controlling the amount of the sodium hydrosulfide solution to be added in this manner.
More specifically, it is preferable that the amount of the sodium hydrosulfide solution to be added into the first
SMMF-114PCT reactor is controlled to a proportion to be 0.20% or less of the flow rate of the sulfuric acid acidic solution, which is the reaction starting liquid, to be supplied to the first reactor. Moreover, the excessive portion of the sodium hydrosulfide solution is added to the subsequent stage reactors of the second reactor and after.
It is possible to more effectively suppress the miniaturization of a sulfide to be obtained, specifically, to produce a sulfide having a controlled grain size of 50 pm or more as 50% particle size (D50) while maintaining a high reaction efficiency by effectively utilizing hydrogen sulfide gas by controlling the amount of the sodium hydrosulfide solution to be added into the first reactor in this manner. In addition, quality deterioration due to oxidation of the sulfide can be prevented as the grain size of the sulfide can be appropriately controlled. Furthermore, it is possible to prevent deterioration in filterability when conducting a filtration treatment and the like of the slurry containing a sulfide after the sulfuration treatment and thus to conduct an efficient operation.
The method for adding the sodium hydrosulfide solution is not particularly limited, but it is possible to use a pump such as a diaphragm pump, which can generally add and supply
SMMF-114PCT the sodium hydrosulfide solution to a high pressure vessel, for example, in the case of using a pressure reaction vessel as a reactor.
«2. Application to hydrometallurgical process for nickel oxide ore»
In the sulfuration treatment method according to the present embodiment, a sulfuric acid acidic solution containing at least nickel is used as a target of the sulfuration treatment as described above. This sulfuric acid acidic solution containing nickel is a reaction starting liquid of a sulfuration reaction, and is, for example, an aqueous sulfuric acid acidic solution having a nickel concentration of about 0.5 g/L to 5.0 g/L. In addition, this sulfuric acid acidic solution may contain cobalt, iron, manganese, magnesium, aluminum, chromium, lead, and the like as an element other than nickel.
The sulfuration treatment method according to the present embodiment can be applied to a treatment in a sulfuration step in a hydrometallurgical process for nickel oxide ore, for example. At this time, a leachate obtained by subjecting a slurry of nickel oxide ore of a raw material to a leaching treatment using sulfuric acid at high temperature and high pressure can be used as a sulfuric acid acidic solution
SMMF-114PCT containing nickel. This leachate contains cobalt as a valuable metal in addition to nickel. Incidentally, a postneutralization liquid obtained by conducting a neutralization treatment of the leachate obtained through the leaching treatment using a neutralizing agent may be used as to be described later.
Hereinafter, the outline of the hydrometallurgical process for nickel oxide ore will be described and a specific mode in which the sulfuration treatment method described above is applied to a treatment in the sulfuration step in the hydrometallurgical process will be described. Incidentally, the hydrometallurgical process for nickel oxide ore will be described by taking a hydrometallurgical process by high pressure acid leach method (HPAL method) in which leaching is conducted at high temperature and high pressure as an example. <2-1. Respective steps in hydrometallurgical process for nickel oxide ore>
Fig. 1 is a process chart which illustrates an example of the flow of a hydrometallurgical process for nickel oxide ore. As illustrated in Fig. 1, the hydrometallurgical process for nickel oxide ore includes a leaching step SI in which sulfuric acid is added to a slurry of nickel oxide ore of a raw material and a leaching treatment is conducted at high
SMMF-114PCT temperature and high pressure, a solid-liquid separation step S2 in which the residue is separated from the leaching slurry and a leachate containing nickel and cobalt is obtained, a neutralization step S3 in which the pH of the leachate is adjusted, the impurity elements in the leachate are separated as a neutralization precipitate slurry, and a postneutralization liquid is obtained, and a sulfuration step (nickel recovery step) S4 in which sulfides of nickel and cobalt are generated by adding hydrogen sulfide gas to the post-neutralization liquid.
(1) Leaching step
In the leaching step SI, sulfuric acid is added to a slurry (ore slurry) of nickel oxide ore and the mixture is stirred under conditions of a temperature of about 230°C to 270°C and a pressure of about 3 to 5 MPa by using a high temperature pressurization reactor such as an autoclave, thereby generating a leaching slurry composed of a leachate and a leaching residue.
Examples of the nickel oxide ore may mainly include socalled laterite ore such as limonite ore and saprolite ore. The nickel content in the laterite ore is usually 0.8 wt% to 2.5 wt%, and nickel is contained as a hydroxide or a silica magnesia (magnesium silicate) mineral. In addition, the
SMMF-114PCT content of iron is 10 wt% to 50 wt%, and iron is mainly in the form of a trivalent hydroxide (goethite), but divalent iron is partly contained in the silica magnesia mineral. In addition, in the leaching step SI, an oxide ore containing valuable metals such as nickel, cobalt, manganese, and copper, for example, manganese nodules reserved in the deep ocean can be used in addition to such laterite ore.
In the leaching treatment in the leaching step SI, for example, a leaching reaction and a high temperature thermal hydrolysis reaction represented by the following Formulas (i) to (v) occur and leaching as sulfates of nickel, cobalt, and the like and immobilization of leached iron sulfate as hematite proceed. However, immobilization of iron ions does not completely proceed and thus the liquid portion of the leaching slurry to be obtained usually contains divalent and trivalent iron ions in addition to nickel, cobalt, and the like. Incidentally, in this leaching step SI, it is preferable to adjust the pH of the leachate to be obtained to 0.1 to 1.0 from the viewpoint of the filterability of the leaching residue containing hematite to be generated in the solidliquid separation step S2 of the next step.
• Leaching reaction
MO + H2SO4 - MSO4 + H2O ...(i)
SMMF-114PCT (incidentally, M in Formula (i) represents Ni, Co, Fe, Zn, Cu, Mg, Cr, Mn, or the like)
2Fe(OH)3 + 3H2SO4 - Fe2(SO4)3 + 6H2O ...(ii)
FeO + H2SO4 —> FeSO4 + H2O . . . (iii) • High temperature thermal hydrolysis reaction
2FeSO4 + H2SO4 + l/2O2 Fe2(SO4)3 + H20 ...(iv)
Fe2(SO4)3 + 3H2O - Fe2O3 + 3H2SO4 . .. (v)
Incidentally, the amount of sulfuric acid to be added to the autoclave charged with the ore slurry is not particularly limited, but an excessive amount, in which iron in the ore may be leached, is used. For example, the amount is set to about 300 kg to 400 kg per 1 ton of ore.
(2) Solid-liguid separation step
In the solid-liguid separation step S2, the leaching slurry generated in the leaching step SI is subjected to multi-stage washing and separated into a leachate containing valuable metals such as nickel and cobalt and a leaching residue .
In the solid-liguid separation step S2, the leaching slurry is mixed with a washing liguid and then subjected to a solid-liguid separation treatment using a solid-liguid separator such as a thickener. Specifically, first, the leaching slurry is diluted with the washing liguid, and then
SMMF-114PCT the leaching residue in the leaching slurry is concentrated as a precipitate in the thickener. This makes it possible to decrease nickel and cobalt to be attached to the leaching residue depending on the degree of dilution. Incidentally, it is possible to attempt improvement in the recovery rates of nickel and cobalt by using thickeners, which have such a function and are connected in multiple stages in the actual operation .
(3) Neutralization step
In the neutralization step S3, a neutralizing agent such as magnesium oxide or calcium carbonate is added to the leachate so as to adjust the pH to 4 or less while suppressing oxidation of the leachate and a neutralization precipitate slurry containing trivalent iron and a post-neutralization liquid, which is a mother liquid for nickel recovery, are obtained.
In the neutralization step S3, a neutralizing agent such as calcium carbonate is added to the leachate so as to adjust the pH of a post-neutralization liquid to be obtained to 4 or less, preferably 3.0 to 3.5, and more preferably 3.1 to 3.2 while suppressing oxidation of the separated leachate and a post-neutralization liquid to be a base of the mother liquid for nickel recovery and a neutralization precipitate slurry
SMMF-114PCT containing trivalent iron as an impurity element are formed. In the neutralization step S3, the excessive acid used in the leaching treatment by the HPAL method is neutralized, a final neutralization liquid is generated, and also impurities such as trivalent iron ions and aluminum ions remaining in the solution are removed as a neutralization precipitate by subjecting the leachate to a neutralization treatment (liquid purification treatment) in this manner.
Incidentally, the post-neutralization liquid is a solution based on a leachate obtained by subjecting nickel oxide ore of a raw material to a leaching treatment (leaching step SI) using sulfuric acid and is a sulfuric acid acidic solution containing nickel and cobalt as described above. This postneutralization liquid is a reaction starting liquid of the sulfuration reaction in the sulfuration step S4 to be described later, and the nickel concentration and cobalt concentration in the post-neutralization liquid are in a range of approximately 0.5 g/L to 5.0 g/L, respectively. In addition, iron, manganese, magnesium, aluminum, chromium, lead, and the like remaining in trace amounts may be contained in this postneutralization liquid in addition to nickel and cobalt.
(4) Sulfuration step (nickel recovery step)
In the sulfuration step S4, the post-neutralization liquid,
SMMF-114PCT which is a sulfuric acid acidic solution containing nickel and cobalt, is used as a sulfuration reaction starting liquid, a sulfuration reaction is caused to occur by blowing hydrogen sulfide gas into the sulfuration reaction starting liquid, and sulfides of nickel and cobalt containing a small amount of impurity components and a barren liquor (post-sulfuration liquor) in which the concentrations of nickel and cobalt are stabilized at a low level are generated.
Incidentally, zinc can be selectively separated as a sulfide prior to separation of nickel and cobalt as a sulfide in a case in which zinc is contained in the postneutralization liquid.
The sulfuration treatment in the sulfuration step S4 can be conducted by using a sulfuration reactor and the like, and hydrogen sulfide gas is blown into the gas phase portion in the reactor with respect to the sulfuration reaction starting liquid introduced into the sulfuration reactor and the hydrogen sulfide gas is dissolved in the solution to cause a sulfuration reaction to occur. By this sulfuration treatment, nickel and cobalt contained in the sulfuration reaction starting liquid are immobilized as a sulfide and recovered.
Incidentally, after completion of the sulfuration reaction, the resulting slurry containing sulfides of nickel and cobalt
SMMF-114PCT is charged into a precipitator such as a thickener and subjected to a precipitation separation treatment and only the sulfides are separated and recovered from the bottom of the thickener. Meanwhile, the aqueous solution component is caused to overflow from the top of the thickener and recovered as a barren solution.
<2-2. Sulfuration treatment method in sulfuration step>
Here, the sulfuration treatment method described above can be applied to the treatment in the sulfuration step S4, namely, the sulfuration treatment for generating sulfides of nickel and cobalt from the final neutralization liquid, which is a sulfuric acid acidic solution containing nickel and cobalt.
In other words, in the hydrometallurgical process for nickel oxide ore according to the present embodiment, the unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to the recovered hydrogen sulfide gas, sodium hydrosulfide is generated, and the resulting sodium hydrosulfide solution is added to the sulfuric acid acidic solution in the sulfuration step S4. Moreover, the grain sizes of sulfides of nickel and cobalt to be generated are set to 50 pm or more as 50% particle size (D50) by controlling the amount of the sodium hydrosulfide solution to be added to the
SMMF-114PCT reactor to which the sulfuric acid acidic solution, which is a reaction starting liquid, is supplied when the sodium hydrosulfide solution is added.
More specifically, for example, a sulfuration treatment is conducted by using two or more reactors connected in series, the amount of the sodium hydrosulfide solution to be added to the first reactor, to which the sulfuric acid acidic solution, which is a reaction starting liquid, is supplied and which is located most upstream among the two or more reactors connected in series, is controlled to a proportion to be 0.20% or less of the flow rate of the sulfuric acid acidic solution to be supplied to the first reactor.
The details of the specific sulfuration treatment method are the same as those described above, thus the description here will be omitted, but in the present embodiment, it is possible to suppress the miniaturization of particles of sulfides to be obtained and to control the grain size to an appropriate value while maintaining the reaction efficiency of the sulfuration reaction by controlling the amount of the sodium hydrosulfide solution to be added among the compounds to be used as sulfuration agents in this manner. This prevents the deterioration in filterability in the filtration treatment of the subsequent stage and it is thus possible to increase
SMMF-114PCT the recovery rates of nickel and cobalt as a sulfide and to realize a stable operation.
Incidentally, it is preferable to repeatedly use a part of the sulfides of nickel and cobalt obtained in this sulfuration step S4 in the sulfuration reaction in the sulfuration step S4 as a seed crystal (arrow R in Fig. 1) as also illustrated in the process chart of Fig. 1. In the sulfides of nickel and cobalt obtained through the sulfuration treatment as described above, miniaturization of the grain size is suppressed, specifically, the grain size is 50 pm or more as 50% particle size (D50). Consequently, it is possible to suitably use the sulfides of nickel and cobalt thus obtained as a seed crystal by repeatedly using the sulfides and to control the grain size of sulfides to be obtained in a continuous operation to a more appropriate range.
EXAMPLES
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to the following Examples at all.
Analysis of the metals used in Examples and Comparative Examples was conducted by ICP emission spectrometry. In addition, the grain size of sulfides was determined by
SMMF-114PCT particle size distribution measurement by a laser diffraction scattering method using a Microtrac particle size analyzer. [Example 1]
A sulfuration treatment was conducted by blowing hydrogen sulfide gas into a sulfuric acid acidic solution containing nickel to be used as a reaction starting liquid by using a reactor composed of three tanks connected in series. Incidentally, the sulfuric acid acidic solution, which was a reaction starting liquid, was supplied to the first reactor located most upstream among the three reactors connected in series, and the sulfuration reaction was caused to occur in the first reactor and the second reactor of the next second tank. The third reactor of the third tank was used as a storage tank.
Specifically, the nickel concentration in the sulfuric acid acidic solution was 4.0 g/L to 4.3 g/L, and the flow rate of the sulfuric acid acidic solution supplied to the first reactor was set to 300 m3/Hr to 350 m3/Hr. In addition, the entire amount of hydrogen sulfide gas was blown into the first reactor by setting the flow rate of hydrogen sulfide gas blown to 500 Nm3/Hr to 550 Nm3/Hr.
In addition, the gas remaining in the reactor, which was an unreacted portion among the blown hydrogen sulfide gas, was
SMMF-114PCT recovered, sodium hydroxide was added to the recovered hydrogen sulfide gas, and a sodium hydrosulfide solution was generated. The amount of sodium hydrosulfide solution generated was 2.5 m3/Hr, and the entire amount of the sodium hydrosulfide solution was repeatedly used in the sulfuration treatment.
At this time, the flow rate of the sodium hydrosulfide solution supplied to the first reactor was adjusted to 0.20% of the flow rate of the starting liquid supplied, and the rest
| of the sodium | hydrosulfide | solution | was supplied | to | the second |
| reactor . | |||||
| The grain | size of the | sulfide generated by such | a | ||
| treatment was | 50 pm as 50% | particle | size (D50). | In | addition, |
the nickel recovery rate by the sulfuration treatment at this time was 99.0%. Nickel recovery rate = (volume of starting liquid χ nickel concentration in starting liquid - volume of final liquid χ nickel concentration in final liquid) a (volume of starting liquid χ nickel concentration in starting liquid) [Example 2]
In Example 2, the sodium hydrosulfide solution was not supplied to the first reactor but the entire amount thereof was supplied to the second reactor. Incidentally, the treatment was conducted in the same manner as in Example 1
SMMF-114PCT except this.
The grain size of the sulfide generated by such a treatment was 62 pm as 50% particle size (D50). In addition, the nickel recovery rate by the sulfuration treatment at this time was 98.1%.
[Comparative Example 1]
In Comparative Example 1, the entire amount of the sodium hydrosulfide solution was supplied to the first reactor. Incidentally, the flow rate of the sodium hydrosulfide solution supplied with respect to the flow rate of the starting liquid supplied was 0.68%. The treatment was conducted in the same manner as in Example 1 except these.
The grain size of the sulfide generated by such a treatment was 23 pm as 50% particle size (D50), and the sulfide was a fine sulfide. Incidentally, the nickel recovery rate by the sulfuration treatment at this time was 99.0%. [Comparative Example 2]
In Comparative Example 2, the flow rate of the sodium hydrosulfide solution supplied to the first reactor was adjusted to 0.29% of the flow rate of the starting liquid supplied, and the rest of the sodium hydrosulfide solution was supplied to the second reactor. Incidentally, the treatment was conducted in the same manner as in Example 1 except this.
SMMF-114PCT
The grain size of the sulfide generated by such a treatment was 35 gm as 50% particle size (D50), and the sulfide was a fine sulfide. Incidentally, the nickel recovery rate by the sulfuration treatment at this time was 99.1%.
Fig. 2 illustrates the results on the sulfuration treatment conducted in Examples and Comparative Examples described above, and it is a graph chart which illustrates the relation of the D50% particle size of the generated sulfide to the amount of the sodium hydrosulfide solution added to the first reactor (ratio to flow rate of starting liquid supplied).
From the results of Examples and Comparative Examples, it can be seen that it is possible to suppress the miniaturization of a sulfide to be generated and to appropriately control the grain size while maintaining a high reaction efficiency by using hydrogen sulfide gas and a sodium hydrosulfide solution generated from the unreacted portion of the hydrogen sulfide gas as a sulfuration agent and further controlling the amount of the sodium hydrosulfide solution to be added to the first reactor to which the reaction starting liquid is supplied.
SMMF-114PCT
ΙΑ
2017218246 15 Jan 2019
Throughout this specification and the claims which follow, unless the context requires otherwise, the word comprise, and variations such as comprises or comprising, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
The reference in this specification to any prior publication (or information derived from it) , or to any matter which is known, is not, and should not be taken as, an acknowledgement or admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of endeavour to which this specification relates.
Claims (7)
1. A sulfuration treatment method, comprising: supplying a sulfuric acid acidic solution containing nickel to a reactor, adding hydrogen sulfide gas to the sulfuric acid acidic solution, and generating a nickel sulfide, wherein unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the sulfuric acid acidic solution, and a grain size of a sulfide to be generated of nickel is set to 50 pm or more as 50% particle size (D50) by controlling an amount of the sodium hydrosulfide solution to be added to a reactor to which the sulfuric acid acidic solution is supplied when the sodium hydrosulfide solution is added.
2. The sulfuration treatment method according to claim 1, wherein the reactor includes two or more reactors connected in series, and the sulfuric acid acidic solution is supplied to a first reactor located most upstream among the two or more reactors connected in series.
3. The sulfuration treatment method according to claim 2, wherein amounts of hydrogen sulfide gas and a sodium hydrosulfide solution to be added into the first reactor are controlled so that a nickel recovery rate in the first reactor to be defined by the following formula becomes less than 90%. Nickel recovery rate = (volume of sulfuric acid acidic solution x nickel concentration in sulfuric acid acidic solution - volume of final reaction liquid in first reactor * nickel concentration in final reaction liquid in first reactor) + (volume of sulfuric acid acidic solution * nickel concentration in sulfuric acid acidic solution).
4. The sulfuration treatment method according to claim 2 or 3, wherein an amount of a sodium hydrosulfide solution to be added into the first reactor is controlled to a proportion to be 0.20% or less of an amount of the sulfuric acid acidic solution supplied to the first reactor.
5. The sulfuration treatment method according to any one of claims 1 to 4, wherein the sulfuric acid acidic solution is a leachate obtained by subjecting a slurry of nickel oxide ore to a leaching treatment using sulfuric acid at high temperature and high pressure in a hydrometallurgical process for nickel oxide ore.
6. A nickel sulfide production method, comprising: supplying a sulfuric acid acidic solution containing nickel to a reactor, adding hydrogen sulfide gas to the sulfuric acid acidic solution, and obtaining a nickel sulfide, wherein unreacted gas among the hydrogen sulfide gas added to the sulfuric acid acidic solution is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the sulfuric acid acidic solution, and a nickel sulfide having a grain size of 50 pm or more as
50% particle size (D50) is obtained by controlling an amount of the sodium hydrosulfide solution to be added to a reactor to which the sulfuric acid acidic solution is supplied when the sodium hydrosulfide solution is added.
7. A hydrometallurgical process for nickel oxide ore, comprising: leaching nickel from nickel oxide ore using sulfuric acid at high temperature and high pressure and generating a nickel sulfide from a resulting leachate, wherein the method comprises a sulfuration step of supplying the leachate to a reactor, adding hydrogen sulfide gas to the leachate, and generating a nickel sulfide, and in the sulfuration step, unreacted gas among the hydrogen sulfide gas added to the leachate is recovered, sodium hydroxide is added to recovered hydrogen sulfide gas, sodium hydrosulfide is generated, the resulting solution of sodium hydrosulfide is added to the leachate, and a grain size of a sulfide to be generated of nickel is set to 50 pm or more as 50% particle size (D50) by controlling an amount of the sodium hydrosulfide solution to be added to the reactor to which the leachate is supplied when the sodium hydrosulfide solution is added.
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| JP2016-024712 | 2016-02-12 | ||
| PCT/JP2017/003684 WO2017138421A1 (en) | 2016-02-12 | 2017-02-02 | Sulfuration treatment method, sulfide production method, and wet smelting method for nickel oxide ore |
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| JP7035735B2 (en) * | 2018-04-03 | 2022-03-15 | 住友金属鉱山株式会社 | Method for producing nickel-cobalt mixed sulfide from low nickel grade oxide ore |
| JP7196630B2 (en) * | 2019-01-22 | 2022-12-27 | 住友金属鉱山株式会社 | Method and equipment for recovering valuable metals from aqueous sulfuric acid solution |
| CN110127629B (en) * | 2019-04-25 | 2020-11-17 | 南京聚拓化工科技有限公司 | Device and process for preparing sulfuric acid from sulfide by wet process |
| JP7293873B2 (en) * | 2019-05-30 | 2023-06-20 | 住友金属鉱山株式会社 | Method for producing nickel sulfide, hydrometallurgical method for nickel oxide ore |
| JP7355186B1 (en) | 2022-08-29 | 2023-10-03 | 住友金属鉱山株式会社 | Particle size control method for nickel-cobalt mixed sulfide |
| JP7533807B1 (en) | 2023-02-13 | 2024-08-14 | 三菱マテリアル株式会社 | METHOD AND APPARATUS FOR RECOVERING METALS |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| DA3 | Amendments made section 104 |
Free format text: THE NATURE OF THE AMENDMENT IS: AMEND THE INVENTION TITLE TO READ SULFURATION TREATMENT METHOD, SULFIDE PRODUCTION METHOD, AND HYDROMETALLURGICAL PROCESS FOR NICKEL OXIDE ORE |
|
| FGA | Letters patent sealed or granted (standard patent) |