PH12016501121B1 - Facility of manufacturing sulfide and method of manufacturing same - Google Patents
Facility of manufacturing sulfide and method of manufacturing same Download PDFInfo
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- PH12016501121B1 PH12016501121B1 PH12016501121A PH12016501121A PH12016501121B1 PH 12016501121 B1 PH12016501121 B1 PH 12016501121B1 PH 12016501121 A PH12016501121 A PH 12016501121A PH 12016501121 A PH12016501121 A PH 12016501121A PH 12016501121 B1 PH12016501121 B1 PH 12016501121B1
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- reaction
- solution
- gas
- sodium hydrosulfide
- discharged
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims description 51
- 239000007789 gas Substances 0.000 claims abstract description 166
- 239000000243 solution Substances 0.000 claims abstract description 151
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 129
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 103
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 90
- 239000007864 aqueous solution Substances 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 136
- 238000005987 sulfurization reaction Methods 0.000 claims description 85
- 229910052759 nickel Inorganic materials 0.000 claims description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 55
- 238000011084 recovery Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000001180 sulfating effect Effects 0.000 claims description 14
- 238000002386 leaching Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 abstract 4
- 238000005486 sulfidation Methods 0.000 abstract 3
- 229910017052 cobalt Inorganic materials 0.000 description 25
- 239000010941 cobalt Substances 0.000 description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 25
- 239000000126 substance Substances 0.000 description 12
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 4
- 238000001784 detoxification Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009854 hydrometallurgy Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- IPRPPFIAVHPVJH-UHFFFAOYSA-N (4-hydroxyphenyl)acetaldehyde Chemical compound OC1=CC=C(CC=O)C=C1 IPRPPFIAVHPVJH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/32—Hydrosulfides of sodium or potassium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Treating Waste Gases (AREA)
Abstract
Provided are: a sulfide-manufacturing facility which can attain effective utilization of hydrogen sulfide gas and thus improve the reaction efficiency of hydrogen sulfide; and a sulfide-manufacturing process. This sulfide-manufacturing facility is provided with: a sulfidation vessel (1) to which a reaction start liquid (11), hydrogen sulfide gas (12) and a sodium hydrogen sulfide-containing aqueous solution (13) are supplied; a reaction finish liquid reserving tank (2) to which a reaction finish liquid (14) is supplied; a first gas washing tower (3) in which hydrogen sulfide gas (17) discharged from the sulfidation vessel (1) is absorbed by an aqueous sodium hydroxide solution (19); a second gas washing tower (4) in which hydrogen sulfide gas (21) discharged from the reaction finish liquid reserving tank (2) is absolved by an aqueous sodium hydroxide solution (20) discharged from the first gas washing tower; and a circulating system (6) for supplying a sodium hydrogen sulfide-containing aqueous solution (13) discharged from the second gas washing tower (4) to the sulfidation vessel (1). Thus, the hydrogen sulfide gas (17,21) can be effectively utilized, whereby the reaction efficiency of hydrogen sulfide can be improved.
Description
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Title of Invention: ~~ FACILITY OF MANUFACTURING SULFIDE AND METHOD
OF MANUFACTURING SAME
The present invention relates to a facility of manufacturing a sulfide and a method of manufacturing the sulfide. More specifically, the present invention relates to a facility of manufacturing a sulfide of a valuable metal by adding a sulfating agent to a sulfuric acid aqueous solution containing a valuable metal and a method of manufacturing the sulfide.
As a method of selectively recovering a valuable metal contained in a sulfuric acid aqueous solution which includes an impurity, a method of adding a sulfating agent to the sulfuric acid aqueous solution to precipitate the valuable metal as a sulfide with a sulfurization reaction is known. As the sulfating agent, for example, a hydrogen sulfide gas or an alkali sulfide is used.
In a method of using the hydrogen sulfide gas as the sulfating agent, unreacted hydrogen sulfide gas is discharged. Since the hydrogen sulfide gas is a toxic gas, a detoxification facility is necessary. Since an acid is produced in the sulfurization reaction by the hydrogen sulfide gas, the pH of its reaction solution is lowered. When the pH of the reaction solution is lowered below a specific value, the sulfide is redissolved, and thus the sulfurization reaction is prevented from proceeding. Hence, in order for the sulfurization reaction to be made to proceed efficiently, the lowering of the pH is controlled by adjusting the concentration of the valuable metal in the reaction solution such that the concentration is equal to or less than a specific concentration or the sulfurization reaction is made to proceed while the produced acid is being neutralized by the addition of an alkali.
In a method of using the alkali sulfide (for example, sodium hydrosulfide or sodium sulfide) as the sulfating agent, since the alkali sulfide is chemically stable, a large detoxification facility is not necessary, with the result that it is possible to use the method in a simple manner. Since the alkali sulfide itself is alkaline, the method is advantageous in that unlike the method using the hydrogen sulfide gas, the pH of the reaction solution is not lowered so as to prevent the sulfide from being redissolved accordingly. Thus, it is possible to recover the sulfide with a high yield.
Patent literature 1 discloses a method of manufacturing a nickel-cobalt mixed sulfide. As shown in Fig. 8, a reaction initial solution 101 formed of a sulfuric acid aqueous solution containing nickel and cobalt is introduced into a reaction container 109.
As sulfating agents, a hydrogen sulfide gas 102 and an aqueous solution 103 containing sodium hydrosulfide are supplied to the reaction container 109. In the reaction container 109, a sulfurization reaction of nickel and cobalt occurs, and a reaction last solution 104 containing the nickel-cobalt mixed sulfide is discharged. A discharge gas 105 discharged from the reaction container 109 contains unreacted hydrogen sulfide gas.
The discharge gas 105 is processed by a gas scrubber 107, and the detoxified gas is discharged to the atmosphere 108. In the gas scrubber 107, a sodium hydroxide aqueous solution 106 is used as an absorbing solution, and the hydrogen sulfide gas in the discharge gas 105 is recovered, and thus the aqueous solution 103 containing sodium hydrosulfide is obtained. The aqueous solution 103 is returned repeatedly as the sulfide to the reaction container 109. In this way, it is possible to enhance the efficiency of utilization of the hydrogen sulfide gas, and thus it is possible to recover nickel and cobalt with a high yield.
However, in the conventional method described above, it is practically difficult to return repeatedly the total amount of aqueous solution 103 containing sodium hydrosulfide to the reaction container 109. This is because since the aqueous solution 103 is directly transferred from the gas scrubber 107 to the reaction container 109 in the conventional method, when a large amount of hydrogen sulfide gas is supplied to the gas scrubber 107, and the amount of aqueous solution 103 produced is larger than the amount supplied to the reaction container 109, it is necessary to feed a surplus part of the aqueous solution 103 to a wastewater processing process outside the system to reduce the amount of solution.
When the reaction last solution 104 is discharged from the reaction container 109, and the temperature and pressure thereof are lowered, part of the hydrogen sulfide dissolved in the reaction last solution 104 is discharged as a gas. However, since a small amount of hydrogen sulfide gas is discharged from the reaction last solution 104, the hydrogen sulfide gas is processed without being recycled.
As described above, the effective utilization of hydrogen sulfide gas cannot be sufficiently achieved in the conventional method.
Patent Literature
Patent Literature 1: Japanese Unexamined Patent Application Publication No. 2010-126778
In view of the foregoing situations, the present invention is intended to provide a facility of and a method of manufacturing a sulfide in which a hydrogen sulfide gas is utilized effectively and thus it is possible to enhance the reaction efficiency of a hydrogen sulfide.
A facility of manufacturing a sulfide according to a first invention includes: a sulfurization reaction container to which a sulfuric acid aqueous solution containing a valuable metal is supplied as a reaction initial solution, to which a hydrogen sulfide gas and an aqueous solution containing sodium hydrosulfide are supplied as sulfating agents and in which a sulfide of the valuable metal is produced by a sulfurization reaction; a reaction last solution storage tank to which a reaction last solution discharged from the sulfurization reaction container is supplied; a first gas scrubber in which the hydrogen sulfide gas discharged from the sulfurization reaction container is absorbed by an absorbing solution formed of a sodium hydroxide aqueous solution such that sodium hydrosulfide is produced; a second gas scrubber in which the hydrogen sulfide gas discharged from the reaction last solution storage tank is absorbed by the absorbing solution such that sodium hydrosulfide is produced; and a circulation device which supplies, as the aqueous solution containing sodium hydrosulfide, the absorbing solution discharged from the second gas scrubber to the sulfurization reaction container, where the absorbing solution is newly supplied to the first gas scrubber and the absorbing solution containing sodium hydrosulifide is discharged from the first gas scrubber, and the absorbing solution discharged from the first gas scrubber is supplied to the second gas scrubber and the absorbing solution containing sodium hydrosulfide is discharged from the second gas scrubber.
A facility of manufacturing a sulfide according to a second invention is characterized in that, in the first invention, the circulation device includes a sodium hydrosulfide storage tank in which the aqueous solution. containing sodium hydrosulfide discharged from the second gas scrubber is temporarily stored.
A facility of manufacturing a sulfide according to a third invention is characterized in that, in the first or second invention, the reaction initial solution is a nickel recovery mother liquid which is obtained by removing an impurity from a leachate obtained by subjecting a slurry containing a nickel oxide ore to sulfuric acid leaching.
A method of manufacturing a sulfide according to a fourth invention includes: supplying, as sulfating agents, a hydrogen sulfide gas and an aqueous solution containing sodium hydrosulfide to a sulfuric acid aqueous solution containing a valuable metal serving as a reaction initial solution so as to produce a sulfide of the valuable metal by a sulfurization reaction; newly supplying an absorbing solution formed of a sodium hydroxide aqueous solution to a first gas scrubber; absorbing, in the first gas scrubber, an unreacted hydrogen sulfide gas in the sulfurization reaction by the absorbing solution such that sodium hydrosulfide is produced; supplying the absorbing solution discharged from the first gas scrubber to a second gas scrubber: absorbing, in the second gas scrubber, a hydrogen sulfide gas discharged from a reaction last solution in the sulfurization reaction by the absorbing solution such that sodium hydrosulfide is produced; and supplying, as the aqueous solution containing sodium hydrosulfide, the absorbing solution discharged from the second gas scrubber to the reaction initial solution.
A method of manufacturing a sulfide according to a fifth invention is characterized in that, in the fourth invention, the aqueous solution containing sodium hydrosulfide is temporarily stored and is thereafter supplied to the reaction initial solution.
A method of manufacturing a sulfide according to a sixth invention is characterized in that, in the fourth or fifth invention, the reaction initial solution is a nickel recovery mother liquid which is obtained by removing an impurity from a leachate obtained by subjecting a slurry containing a nickel oxide ore to sulfuric acid leaching.
According to the first invention, since the absorbing solution obtained from the first gas scrubber is used in the second gas scrubber, it is possible to reduce the amount of sodium hydroxide aqueous solution used, and thus it is possible to reduce the specific consumption of sodium hydroxide.
According to the second invention, since the aqueous solution containing sodium hydrosulfide is temporarily stored, when the amount of aqueous solution containing sodium hydrosulfide which is produced is larger than the amount supplied to the sulfurization reaction container, a surplus part of the solution can be stored whereas when the amount of aqueous solution containing sodium hydrosulfide which is produced is lower than the amount supplied to the sulfurization reaction container, the aqueous solution containing sodium hydrosulfide which is temporarily stored can be supplied to the sulfurization reaction container. Consequently, the total amount of sodium hydrosulfide can be returned repeatedly to the sulfurization reaction container, and thus the amount of sodium hydrosulfide supplied is increased, with the result that it is possible to enhance the reaction efficiency of a hydrogen sulfide.
According to the third invention, it is possible to recover a nickel sulfide with a high yield.
According to the fourth invention, since the absorbing solution obtained from the first gas scrubber is used in the second gas scrubber, it is possible to reduce the amount of sodium hydroxide aqueous solution used, and thus it is possible to reduce the specific consumption of sodium hydroxide.
According to the fifth invention, since the aqueous solution containing sodium hydrosulfide is temporarily stored, when the amount of aqueous solution containing sodium hydrosulfide which is produced is larger than the amount supplied to the reaction initial solution, a surplus part of the solution can be stored whereas when the amount of aqueous solution containing sodium hydrosulfide which is produced is lower than the amount supplied to the reaction initial solution, the aqueous solution containing sodium hydrosulfide which is temporarily stored can be supplied to the reaction initial solution.
Consequently, the total amount of sodium hydrosulfide can be returned repeatedly to the reaction initial solution, and thus the amount of sodium hydrosulfide supplied is increased, with the result that it is possible to enhance the reaction efficiency of a hydrogen sulfide.
According to the sixth invention, it is possible to recover a nickel sulfide with a high yield.
Fig. 1 is an illustrative diagram of a facility of manufacturing a sulfide according to an embodiment of the present invention;
Fig. 2 is an overall process diagram of a hydrometallurgical method;
Fig. 3 is an illustrative diagram of a facility of manufacturing a sulfide in comparative example 1;
Fig. 4 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the pH of a nickel barren solution;
Fig. 5 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and a nickel recovery rate;
Fig. 6 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the reaction efficiency of a hydrogen sulfide;
Fig. 7 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the specific consumption of sodium hydroxide; and
Fig. 8 is an illustrative diagram of a conventional manufacturing facility.
An embodiment of the present invention will then be described with reference to drawings. (Hydrometallurgy)
Hydrometallurgy in which a nickel-cobalt mixed sulfide is obtained from a nickel oxide ore will first be described. As a hydrometallurgical method of recovering valuable metals such as nickel and cobalt from a low-grade nickel oxide ore such as a limonite ore, a high-temperature and high-pressure sulfuric acid leaching method which is a high-pressure acid leaching method (HPAL: High Pressure Acid Leaching) using sulfuric acid is known.
As shown in Fig. 2, the hydrometallurgy using the high-temperature and high- pressure sulfuric acid leaching method includes a preprocessing step (1), a high- temperature and high-pressure sulfuric acid leaching step (2), a solid-liquid separation step (3), a neutralization step (4), a dezincification step (5), a sulfurization step (6) and a detoxification step (7).
In the preprocessing step (1), an ore slurry is manufactured by crushing and classifying the nickel oxide ore. In the high-temperature and high-pressure sulfuric acid leaching step (2), sulfuric acid is added to the ore slurry obtained in the preprocessing step (1), and they are agitated at 220 to 280°C and are subjected to the high-temperature and high-pressure acid leaching, with the result that the leach slurry is obtained. In the solid-liquid separation step (3), the leach slurry obtained in the high-temperature and high-pressure sulfuric acid leaching step (2) is subjected to solid-liquid separation, and thus a leachate (crude nickel sulfate aqueous solution) containing nickel and cobalt and a leach residue are obtained.
In the neutralization step (4), the crude nickel sulfate aqueous solution obtained in the solid-liquid separation step (3) is neutralized. In the dezincification step (5), a hydrogen sulfide gas is added to the crude nickel sulfate aqueous solution neutralized in the neutralization step (4), and thus zinc is precipitated as zinc sulfide and is removed.
In the sulfurization step (6), a sulfating agent is added to a nickel recovery mother liquid obtained in the dezincification step (5), and thus the nickel-cobalt mixed sulfide and a nickel barren solution are obtained. In the detoxification step (7), the leach residue produced in the solid-liquid separation step (3) and the nickel barren solution produced in the sulfurization step (6) are detoxified.
A facility of and a method of manufacturing a sulfide according to the embodiment of the present invention are preferably applied to the sulfurization step in the hydrometallurgy described above. Specifically, the nickel recovery mother liquid obtained by removing an impurity such as zinc from the leachate (crude nickel sulfate aqueous solution) obtained by subjecting the slurry containing the nickel oxide ore to the sulfuric acid leaching is used as a reaction initial solution, the sulfating agent is added to the reaction initial solution and thus nickel and cobalt contained in the reaction initial solution are precipitated by a sulfurization reaction as the nickel-cobalt mixed sulfide.
Although the total concentration of nickel and cobalt in the nickel recovery mother liquid is not particularly limited, it is normally 2 to 6 g/L. Here, the concentration of nickel is 2 to 5 g/L, and the concentration of cobalt is 0.1 to 0.6 g/L.
The reaction initial solution is not limited to the nickel recovery mother liquid as long as the reaction initial solution is a sulfuric acid aqueous solution containing a valuable metal such as nickel or cobalt. (Manufacturing facility and manufacturing method)
A facility A of manufacturing a sulfide according to the embodiment of the present invention and a method of manufacturing the sulfide with the manufacturing facility A will then be described.
As shown in Fig. 1, the manufacturing facility A according to the embodiment includes a sulfurization reaction container 1, a reaction last solution storage tank 2, a first gas scrubber 3, a second gas scrubber 4 and a sodium hydrosulfide storage tank 5.
The sulfurization reaction container 1 is a pressurization-type reaction container that has pressure resistance. As a reaction initial solution 11, a nickel recovery mother liquid (sulfuric acid aqueous solution containing nickel and cobalt) is supplied to the sulfurization reaction container 1. As sulfating agents, a hydrogen sulfide gas 12 and an aqueous solution 13 containing sodium hydrosulfide are supplied.
The number of sulfurization reaction containers 1 is not limited to one, and a plurality of sulfurization reaction containers 1, for example, four sulfurization reaction containers 1 may be connected in series to continuously perform the sulfurization reaction.
As shown in chemical formula 1 below, when the hydrogen sulfide gas 12 is supplied to the reaction initial solution 11, nickel and cobalt in the reaction initial solution 11 are transformed into a nickel sulfide and a cobalt sulfide by the sulfurization reaction of hydrogen sulfide (H2S), and they are precipitated. Sulfuric acid (H2SO4) is produced by the reaction of chemical formula 1. (Chemical formula 1)
MSO; + H2S — MS + H,S04 (where M represents Ni or Co)
When the aqueous solution 13 containing sodium hydrosulfide is supplied to the reaction initial solution 11, the sulfuric acid produced by the reaction of chemical formula 1 is neutralized by the sodium hydrosulfide (NaSH) through the neutralization reaction of chemical formula 2 below. At the same time, nickel and cobalt in the reaction initial solution 11 are transformed into a nickel sulfide and a cobalt sulfide by the sulfurization reaction of sodium hydrosulfide represented by chemical formula 3 below, and they are precipitated. (Chemical formula 2)
H,SO4 + 2NaSH — Na;SO4 + 2H,S (Chemical formula 3)
MSO; + 2NaSH — NaxSO4 + MS + HaS (where M represents Ni or Co)
When the aqueous solution 13 containing sodium hydrosulfide is supplied to the reaction initial solution 11, the sulfuric acid produced by the reaction of chemical formula 1 is neutralized, at the same time, the sulfide is produced by the sulfurization reaction of sodium hydrosulfide and thus it is possible to reduce the lowering of the pH.
Consequently, it is possible to recover the nickel sulfide and the cobalt sulfide with a high yield. In this way, it is possible to realize a nickel recovery rate of 97.5% or more.
As described above, the hydrogen sulfide gas 12 and the aqueous solution 13 containing sodium hydrosulfide are supplied to the reaction initial solution 11, and thus the sulfurization reaction occurs, with the result that the nickel-cobalt mixed sulfide is produced.
Although the pressure of the sulfurization reaction container 1 is not particularly limited, in order to make the sulfurization reaction of nickel and cobalt proceed, the pressure is preferably 100 to 300 kPa. It is efficient to couple the sulfurization reaction containers 1 together in a plurality of stages and to use them, and in this case, preferably, in the first stage, the pressure is set at 250 to 300 kPa, the pressure is gradually lowered and at the final stage, the pressure reaches 100 to 150 kPa. In this way, the hydrogen sulfide gas is efficiently used in the sulfurization reaction.
Although the pH of the reaction initial solution 11 is not particularly limited, in order to make the sulfurization reaction of nickel and cobalt proceed, the pH is preferably 3.0 to 3.8. This is because when the pH of the reaction initial solution 11 is less than 3.0, in the neutralization step in the preceded stage, iron, aluminum and the like are not sufficiently removed. On the other hand, that is because when the pH of the reaction initial solution 11 exceeds 3.8, the hydroxides of nickel and cobalt may be produced.
Although the temperature of the reaction initial solution 11 is not particularly limited, the temperature is preferably 65 to 90°C. Although the sulfurization reaction itself is generally promoted as the temperature is increased, when the temperature exceeds 90°C, it costs significantly and disadvantageously to increase the temperature, and the sulfide may be disadvantageously adhered to the sulfurization reaction container 1 because the reaction speed is high.
Although the amount of hydrogen sulfide gas 12 supplied is not particularly limited, in order for nickel and cobalt to be recovered as the sulfides with a desired high yield, the supplied amount is preferably about 1.0 to 1.1 times as high as a reaction equivalent required when nickel and cobalt contained in the reaction initial solution 11 are sulfurized according to chemical formula 1. When the hydrogen sulfide gas 12 is added excessively beyond the amount described above, unreacted hydrogen sulfide gas which is discharged from the sulfurization reaction container 1 is increased.
A reaction last solution 14 containing the nickel-cobalt mixed sulfide produced by the suifurization reaction is discharged from the sulfurization reaction container 1, is supplied to the reaction last solution storage tank 2 and is temporarily stored. The reaction last solution storage tank 2 is a container that has hermeticity. The nickel- cobalt mixed sulfide 15 precipitated in the reaction last solution storage tank 2 and a nickel barren solution 16 which is a supernatant solution are separated and discharged.
In the sulfurization reaction container 1, in order for nickel and cobalt to be recovered as the sulfides with a high yield, the sulfating agent is added excessively as compared with a necessary theoretical equivalent. The unreacted hydrogen sulfide gas in the sulfurization reaction is discharged from the sulfurization reaction container 1. : Hence, a discharge gas 17 discharged from the sulfurization reaction container 1 contains the hydrogen sulfide gas.
The discharge gas 17 (which contains the hydrogen sulfide gas) discharged from the sulfurization reaction container 1 is detoxified in the first gas scrubber 3, and is thereafter discharged as the detoxified discharge gas 18 to the outside of the system. In the first gas scrubber 3, a sodium hydroxide aqueous solution 19 is used as an absorbing solution, and the hydrogen sulfide gas in the discharge gas 17 is absorbed by the sodium hydroxide aqueous solution 19.
As shown in chemical formula 4 below, when the hydrogen sulfide gas is absorbed by the sodium hydroxide aqueous solution, hydrogen sulfide (H2S) and sodium hydroxide (NaOH) react with each other, and thus an aqueous solution that contains sodium hydrosulfide (NaSH) is produced. In this way, the hydrogen sulfide gas which is a toxic gas is removed. (Chemical formula 4)
H.S + NaOH — NaSH + H20
The concentration of the sodium hydroxide aqueous solution 19 and the supplied amount thereof are adjusted such that the hydrogen sulfide gas contained in the discharge gas 17 is detoxified sufficiently. For example, when 15 to 25 mass % of sodium hydroxide aqueous solution is used, an aqueous solution that contains 20 to 35 mass % of sodium hydrosulfide is obtained.
Inside the first gas scrubber 3, the absorbing solution 19 is circulated, and the hydrogen sulfide gas in the discharge gas 17 is absorbed. The absorbing solution 19 is newly supplied to the first gas scrubber 3, and instead, an absorbing solution 20 in which the hydrogen sulfide gas is absorbed is discharged. In the absorbing solution 20, the produced sodium hydrosulfide and unreacted sodium hydroxide are contained. The absorbing solution 20 (sodium hydroxide aqueous solution containing sodium hydrosulfide) discharged from the first gas scrubber 3 is supplied as an absorbing solution to the second gas scrubber 4.
In the reaction last solution 14 stored in the reaction last solution storage tank 2, hydrogen sulfide is dissolved. When the hydrogen sulfide is discharged from the sulfurization reaction container 1, and the temperature and pressure thereof are lowered,
part thereof is discharged as a gas. Hence, a discharge gas 21 that is discharged from the reaction last solution storage tank 2 contains the hydrogen sulfide gas. The amount of hydrogen sulfide gas discharged from the reaction last solution storage tank 2 is lower than the amount of hydrogen sulfide gas discharged from the sulfurization reaction container 1. Hence, the concentration of the hydrogen sulfide in the discharge gas 21 discharged from the reaction last solution storage tank 2 is lower than the concentration of the hydrogen sulfide in the discharge gas 17 discharged from the sulfurization reaction container 1.
The discharge gas 21 (which contains the hydrogen sulfide gas) discharged from the reaction last solution storage tank 2 is detoxified in the second gas scrubber 4, and is thereafter discharged as the detoxified discharge gas 22 to the outside of the system. In the second gas scrubber 4, the absorbing solution 20 (sodium hydroxide aqueous solution containing sodium hydrosulfide) discharged from the first gas scrubber 3 is used as an absorbing solution, and the hydrogen sulfide gas in the discharge gas 21 is absorbed by the absorbing solution 20. Hydrogen sulfide and sodium hydroxide react with each other, and thus sodium hydrosulfide is produced. Here, the unreacted sodium hydroxide left in the absorbing solution 20 contributes to the reaction. In this way, the hydrogen sulfide gas which is a toxic gas is removed.
Inside the second gas scrubber 4, the absorbing solution 20 is circulated, and the hydrogen sulfide gas in the discharge gas 21 is absorbed. The absorbing solution 20 is supplied to the second gas scrubber 4, and instead, an absorbing solution 23 in which the hydrogen sulfide gas is absorbed is discharged. The absorbing solution 23 (aqueous solution containing sodium hydrosulfide) discharged from the second gas scrubber 4 is supplied to the sodium hydrosulfide storage tank 5.
In the sodium hydrosulfide storage tank 5, the absorbing solution 23 discharged from the second gas scrubber 4, that is, the aqueous solution 13 containing sodium hydrosulfide is temporarily stored. The sodium hydrosulfide storage tank 5 and the sulfurization reaction container 1 are connected with a pipe 6, and a pump 7 is provided in the pipe 6. Hence, by the drive of the pump 7, the aqueous solution 13 containing sodium hydrosulfide stored in the sodium hydrosulfide storage tank 5 can be supplied to the sulfurization reaction container 1. In other words, the aqueous solution 13 containing sodium hydrosulfide is temporarily stored, and is thereafter supplied to the reaction initial solution 11.
The sodium hydrosulfide storage tank 5, the pipe 6 and the pump 7 correspond to a “circulation device” in scope of claims. As long as the circulation device can supply, as the aqueous solution 13 containing sodium hydrosulfide, the absorbing solution 23 discharged from the second gas scrubber 4, to the sulfurization reaction container 1, the configuration thereof is not particularly limited. The sodium hydrosulfide storage tank 5 may be omitted.
As described above, with the first gas scrubber 3 and the second gas scrubber 4, the unreacted hydrogen sulfide gas 17 in the sulfurization reaction and the hydrogen sulfide gas 21 discharged from the reaction last solution 14 in the sulfurization reaction are absorbed by the absorbing solution 19 formed of the sodium hydroxide aqueous solution, and thus the aqueous solution 13 containing sodium hydrosulfide is obtained.
Then, the obtained aqueous solution 13 containing sodium hydrosulfide is supplied to the reaction initial solution 11.
As described above, not only the unreacted hydrogen sulfide gas 17 in the sulfurization reaction but also the hydrogen sulfide gas 21 discharged from the reaction last solution 14 are absorbed by the sodium hydroxide aqueous solution 19, and thus sodium hydrosulfide is produced and is returned repeatedly to the sulfurization reaction container 1, with the result that it is possible to utilize effectively the hydrogen sulfide gases 17 and 21. Consequently, since the amount of sodium hydrosulfide 13 supplied to the sulfurization reaction container 1 is increased, it is possible to enhance the reaction efficiency of a hydrogen sulfide.
Since the aqueous solution 13 containing sodium hydrosulfide is temporarily stored in the sodium hydrosulfide storage tank 5, when the amount of aqueous solution 13 containing sodium hydrosulfide which is produced by the first gas scrubber 3 and the second gas scrubber 4 is larger than the amount supplied to the sulfurization reaction container 1 (the reaction initial solution 11), a surplus part of the solution can be stored.
On the other hand, when the amount of aqueous solution 13 containing sodium hydrosulfide which is produced by the first gas scrubber 3 and the second gas scrubber 4 is lower than the amount supplied to the sulfurization reaction container 1 (the reaction initial solution 11), the aqueous solution 13 containing sodium hydrosulfide which is temporarily stored can be supplied to the sulfurization reaction container 1 (the reaction initial solution 11). Consequently, the total amount of sodium hydrosulfide which is conventionally and inevitably discarded partially can be returned repeatedly to the sulfurization reaction container 1 (the reaction initial solution 11), and thus the amount of sodium hydrosulfide supplied is increased. Hence, even with this effect, it is possible to enhance the reaction efficiency of a hydrogen sulfide.
Furthermore, since the absorbing solution 20 obtained from the first gas scrubber 3 is used in the second gas scrubber 4, it is possible to reduce the amount of sodium hydroxide aqueous solution 19 used. Specifically, since the unreacted sodium
So hydroxide left in the absorbing solution 20 without being used for detoxifying the hydrogen sulfide gas in the first gas scrubber 3 can be used effectively in the second gas scrubber 4, it is possible to reduce the used amount of sodium hydroxide which is necessary for recovering the hydrogen sulfide gas as sodium hydrosulfide, with the result that it is possible to reduce the specific consumption of sodium hydroxide.
Consequently, it is possible to reduce the operation cost. [Examples]
Examples will then be described. (Example 1)
The manufacturing facility A shown in Fig. 1 was used to recover the nickel- cobalt mixed sulfide. Four sulfurization reaction containers 1 were connected in series to continuously perform the sulfurization reaction. The reaction initial solution 11 was a nickel recovery mother liquid (sulfuric acid aqueous solution containing nickel and cobalt), and the concentration of nickel was 4.2 to 4.5 g/L, and the concentration of cobalt was 0.26 to 0.34 g/L. A nickel load on the sulfurization reaction container 1 was 1.9 to 2.2 kg/hour/m*®. The pH of a nickel barren solution, a nickel recovery rate, the reaction efficiency of a hydrogen sulfide and the specific consumption of sodium hydroxide obtained by this operation were evaluated. (Comparative example 1)
A manufacturing facility B shown in Fig. 3 was used to recover the nickel-cobalt mixed sulfide. The manufacturing facility B had a configuration in which in the manufacturing facility A, the aqueous solution 13 containing sodium hydrosulfide discharged from the first gas scrubber 3 was returned directly and repeatedly to the sulfurization reaction container 1. A surplus part 20 of the aqueous solution 13 containing sodium hydrosulfide discharged from the first gas scrubber 3 was discharged to a wastewater processing process outside the system. The sodium hydroxide aqueous solution 19 is newly supplied to the second gas scrubber 4, and the aqueous solution 23 containing sodium hydrosulfide discharged from the second gas scrubber 4 was discharged to the wastewater processing process outside the system.
Four sulfurization reaction containers 1 were connected in series to continuously perform the sulfurization reaction. The reaction initial solution 11 was a nickel recovery mother liquid (sulfuric acid aqueous solution containing nickel and cobalt), and the concentration of nickel was 4.2 to 4.5 g/L, and the concentration of cobalt was 0.27 to 0.37 g/L. A nickel load on the sulfurization reaction container 1 was 1.9 to 2.2 kg/hour/m3. The pH of a nickel barren solution, a nickel recovery rate, the reaction efficiency of a hydrogen sulfide and the specific consumption of sodium hydroxide obtained by this operation were evaluated.
The results of the evaluations of example 1 and comparative example 1 are shown in Figs. 4 to 7. Fig. 4 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the pH of the nickel barren solution, Fig. 5 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and a nickel recovery rate, Fig. 6 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the reaction efficiency of a hydrogen sulfide, and Fig. 7 is a graph showing a relationship between the addition ratio of sodium hydrosulfide and the specific consumption of sodium hydroxide.
Here, the addition ratio of sodium hydrosulfide is defined by formula 1 below. (Formula 1)
A = Vyasu+ Vs ”
where A represents the addition ratio of sodium hydrosulfide, Vasu represents the volume of a sodium hydrosulfide aqueous solution and Vs represents the volume of a reaction initial solution.
The nickel recovery rate of a nickel sulfide and a cobalt sulfide in the sulfurization reaction is defined by formula 2 below. (Formula 2)
R = (Vs x ps.ni- VB x pei) + (Vs X ps-ni) where R represents the nickel recovery rate, Vs represents the volume of the reaction initial solution, ps.ni represents the concentration of nickel in the reaction initial solution, Vg represents the volume of the nickel barren solution and ps.ni represents the concentration of nickel in the nickel barren solution.
The reaction efficiency of a hydrogen sulfide is defined by formula 3 below. (Formula 3)
E = ((Vs x psni- VB Xx pi) + Ar(Ni) + (Vs X ps.co- VB X ppco) + Ar(Co)) + (Vms+22.4) where E represents the reaction efficiency of a hydrogen sulfide, Vs represents the volume of the reaction initial solution, ps; represents the concentration of nickel in the reaction initial solution, ps.co represents the concentration of cobalt in the reaction initial solution, Vp represents the volume of the nickel barren solution, ps.ni represents the concentration of nickel in the nickel barren solution, pp.co represents the concentration of cobalt in the nickel barren solution, Ar(Ni) represents the atomic weight of nickel, Ar(Co) represents the atomic weight of cobalt, and Vuzs represents the volume of hydrogen sulfide used.
The specific consumption of sodium hydroxide is defined by formula 4 below.
(Formula 4)
U = Wnaon + Wi where U represents the specific consumption of sodium hydroxide, Wnaon represents the amount of sodium hydroxide used in the first gas scrubber 3 and the second gas scrubber 4 and Wh; represents the amount of nickel obtained as the sulfide.
As is understood from Fig. 4, the average of the addition ratio of sodium hydrosulfide is 0.50% in example 1 whereas the average of the addition ratio of sodium hydrosulfide is 0.37% in comparative example 1. In other words, in example 1, the addition ratio of sodium hydrosulfide is increased to about 1.35 times the addition ratio of sodium hydrosulfide in comparative example 1. In this way, it is confirmed that in example 1, the amount of sodium hydrosulfide supplied to the sulfurization reaction container 1 is increased.
As compared with comparative example 1, in example 1, the average of the pH of the nickel barren solution is high by 0.15. In this way, it is confirmed that in example 1, the amount of sodium hydrosulfide supplied to the sulfurization reaction container 1 is increased and that thus it is possible to reduce the lowering of the pH caused by the sulfurization reaction.
As is understood from Fig. 5, the average of the nickel recovery rate is 98.2% in example 1 whereas the average of the nickel recovery rate is 98.1% in comparative example 1, and an equivalent nickel recovery rate is obtained.
On the other hand, as is understood from Fig. 6, the average of the reaction efficiency of a hydrogen sulfide is 93.7% in example 1 whereas the average of the reaction efficiency of a hydrogen sulfide is 89.9% in comparative example 1, and the reaction efficiency of a hydrogen sulfide in example 1 is higher. In this way, it is confirmed that in example 1, the amount of sodium hydrosulfide supplied to the sulfurization reaction container 1 is increased and that thus it is possible to reduce the amount of hydrogen sulfide used while maintaining a nickel recovery rate of 97.5% or more in the sulfurization reaction.
As is understood from Fig. 7, the average of the specific consumption of sodium hydroxide is 0.25 (NaOH-tNi-t) in example 1 whereas the average of the specific consumption of sodium hydroxide is 0.29 (NaOH-t/Ni-t) in comparative example 1. In this way, it is confirmed that in example 1, since the unreacted sodium hydroxide in the first gas scrubber 3 is used in the second gas scrubber 4, it is possible to reduce the amount of sodium hydroxide used, and thus it is possible to reduce the specific consumption of sodium hydroxide.
Reference Signs List
A manufacturing facility 1 sulfurization reaction container 2 reaction last solution storage tank 3 first gas scrubber 4 second gas scrubber 5 sodium hydrosulfide storage tank 6 pipe 7 pump 11 reaction initial solution 12 hydrogen sulfide gas 13 aqueous solution containing sodium hydrosulfide 14 reaction last solution
15 nickel-cobalt mixed sulfide 16 nickel barren solution 17 discharge gas 18 detoxified discharge gas 19 absorbing solution (sodium hydroxide aqueous solution) 20 absorbing solution 21 discharge gas 22 detoxified discharge gas 23 absorbing solution
Claims (1)
- CTTLLECTIAL FROPLATE CTTICE Re: or je ; : ) foConTD I 201; os on), ier Claims I “Ld 0. a futivay =a TH Ei Claim 1 "55 A facility of manufacturing a sulfide, the facility comprising: a sulfurization reaction container to which a sulfuric acid aqueous solution containing a valuable metal is supplied as a reaction initial solution, to which a hydrogen sulfide gas and an aqueous solution containing sodium hydrosulfide are supplied as sulfating agents and in which a sulfide of the valuable metal is produced by a sulfurization reaction;a reaction last solution storage tank to which a reaction last solution discharged from the sulfurization reaction container is supplied;a first gas scrubber in which the hydrogen sulfide gas discharged from the sulfurization reaction container is absorbed by an absorbing solution formed of a sodium hydroxide aqueous solution such that sodium hydrosulfide is produced;a second gas scrubber in which the hydrogen sulfide gas discharged from the reaction last solution storage tank is absorbed by the absorbing solution such that sodium hydrosulfide is produced; and a circulation device which supplies, as the aqueous solution containing sodium hydrosulfide, the absorbing solution discharged from the second gas scrubber to the sulfurization reaction container,wherein the absorbing solution is newly supplied to the first gas scrubber and the absorbing solution containing sodium hydrosulfide is discharged from the first gas scrubber, and the absorbing solution discharged from the first gas scrubber is supplied to the second gas scrubber and the absorbing solution containing sodium hydrosulfide is discharged from the second gas scrubber.Claim 2 The facility of manufacturing a sulfide according to claim 1,wherein the circulation device includes a sodium hydrosulfide storage tank in which the aqueous solution containing sodium hydrosulfide discharged from the second gas scrubber is temporarily stored.Claim 3 The facility of manufacturing a sulfide according to claim 1 or 2, wherein the reaction initial solution is a nickel recovery mother liquid which is obtained by removing an impurity from a leachate obtained by subjecting a slurry containing a nickel oxide ore to sulfuric acid leaching.Claim 4 (Amended) A method of manufacturing a sulfide, the method comprising: supplying, as sulfating agents, a hydrogen sulfide gas and an aqueous solution containing sodium hydrosulfide to a sulfuric acid aqueous solution containing a valuable metal serving as a reaction initial solution so as to produce a sulfide of the valuable metal by a sulfurization reaction; newly supplying an absorbing solution formed of a sodium hydroxide aqueous solution to a first gas scrubber; absorbing, in the first gas scrubber, an unreacted hydrogen sulfide gas in the sulfurization reaction by the absorbing solution such that sodium hydrosulfide is produced; supplying the absorbing solution discharged from the first gas scrubber to a second gas scrubber; absorbing, in the second gas scrubber, a hydrogen sulfide gas discharged from a reaction last solution in the sulfurization reaction by the absorbing solution such that sodium hydrosulfide is produced; and supplying, as the aqueous solution containing sodium hydrosulfide, the absorbing solution discharged from the second gas scrubber to the reaction initial solution.Claim 5 The method of manufacturing a sulfide according to claim 4, wherein the aqueous solution containing sodium hydrosulfide is temporarily stored and is thereafter supplied to the reaction initial solution.Claim 6 The method of manufacturing a sulfide according to claim 4 or 5, wherein the reaction initial solution is a nickel recovery mother liquid which is obtained by removing an impurity from a leachate obtained by subjecting a slurry containing a nickel oxide ore to sulfuric acid leaching.
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|---|---|---|---|
| JP2014012915A JP5807689B2 (en) | 2014-01-28 | 2014-01-28 | Sulfide production equipment and method |
| PCT/JP2014/080426 WO2015114913A1 (en) | 2014-01-28 | 2014-11-18 | Sulfide-manufacturing facility and process |
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| PH12016501121A1 PH12016501121A1 (en) | 2016-07-18 |
| PH12016501121B1 true PH12016501121B1 (en) | 2016-07-18 |
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| PH12016501121A PH12016501121B1 (en) | 2014-01-28 | 2016-06-10 | Facility of manufacturing sulfide and method of manufacturing same |
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| JP (1) | JP5807689B2 (en) |
| AU (1) | AU2014380678B2 (en) |
| PH (1) | PH12016501121B1 (en) |
| WO (1) | WO2015114913A1 (en) |
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| JP6213586B2 (en) * | 2016-02-12 | 2017-10-18 | 住友金属鉱山株式会社 | Sulfidation treatment method, sulfide production method, and nickel oxide ore hydrometallurgy method |
| JP6388043B2 (en) * | 2017-02-24 | 2018-09-12 | 住友金属鉱山株式会社 | Sulfide production method, nickel oxide ore hydrometallurgy method |
| JP7200698B2 (en) * | 2019-01-28 | 2023-01-10 | 住友金属鉱山株式会社 | Hydrometallurgical method for nickel oxide ore |
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| JP2658799B2 (en) * | 1993-03-09 | 1997-09-30 | 株式会社デンソー | Aluminum vacuum brazing furnace |
| KR100246031B1 (en) * | 1993-02-12 | 2000-04-01 | 오카메 히로무 | Aluminum vacuum brazing furnace and aluminum brazing method |
| JP3726107B2 (en) * | 1997-12-26 | 2005-12-14 | 三井金属エンジニアリング株式会社 | Method for wet recovery of crude zinc oxide dust |
| JP5572928B2 (en) * | 2008-07-25 | 2014-08-20 | 住友金属鉱山株式会社 | Method for hydrometallizing nickel oxide ore |
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| AU2014380678A1 (en) | 2016-06-23 |
| WO2015114913A1 (en) | 2015-08-06 |
| JP5807689B2 (en) | 2015-11-10 |
| PH12016501121A1 (en) | 2016-07-18 |
| AU2014380678B2 (en) | 2017-01-05 |
| JP2015140448A (en) | 2015-08-03 |
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