EP3550040A1 - Wet metallurgy method for nickel oxide ore - Google Patents
Wet metallurgy method for nickel oxide ore Download PDFInfo
- Publication number
- EP3550040A1 EP3550040A1 EP17876261.3A EP17876261A EP3550040A1 EP 3550040 A1 EP3550040 A1 EP 3550040A1 EP 17876261 A EP17876261 A EP 17876261A EP 3550040 A1 EP3550040 A1 EP 3550040A1
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- European Patent Office
- Prior art keywords
- nickel
- post
- dezincification
- hydrogen sulfide
- precipitate
- Prior art date
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 27
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000005272 metallurgy Methods 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 55
- 239000002244 precipitate Substances 0.000 claims abstract description 41
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 37
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 37
- 239000007789 gas Substances 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 27
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 229910052984 zinc sulfide Inorganic materials 0.000 description 44
- 239000005083 Zinc sulfide Substances 0.000 description 43
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 42
- 239000002245 particle Substances 0.000 description 34
- 238000007664 blowing Methods 0.000 description 29
- 239000007788 liquid Substances 0.000 description 24
- 239000002002 slurry Substances 0.000 description 20
- 238000000926 separation method Methods 0.000 description 19
- 229910017052 cobalt Inorganic materials 0.000 description 16
- 239000010941 cobalt Substances 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 239000004744 fabric Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000005987 sulfurization reaction Methods 0.000 description 8
- 239000010419 fine particle Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910001710 laterite Inorganic materials 0.000 description 1
- 239000011504 laterite Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
Images
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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
Definitions
- the present invention relates to a hydrometallurgical method in which nickel oxide ore is subjected to highpressure acid leaching, and more particularly relates to a hydrometallurgical method capable of increasing a nickel recovery rate.
- HPAL high pressure acid leach
- This process is different from a conventional pyrometallurgical process generally used as a smelting method for nickel oxide ore in that nickel oxide ore is processed under wet conditions throughout the process without performing an oxide ore reduction step and drying step at high temperature, and is therefore advantageous in terms of energy and cost.
- the HPAL process allows to obtain a nickel- and cobalt-containing sulfide (hereinafter also referred to as a nickel/cobalt mixed sulfide) which is concentrated to a nickel grade of about 50 to 60% by mass, and therefore high purity nickel can easily be obtained by refining.
- nickel oxide ore as a raw material is subjected to high pressure acid leaching to recover nickel as a product
- the nickel oxide ore is generally often processed through the following steps (a) to (d):
- Patent Literature 1 discloses a hydrometallurgical method based on the above-described high pressure acid leaching, which includes a leaching step in which nickel oxide ore is subjected to leaching using sulfuric acid and then to solid-liquid separation to obtain a leachate; a neutralization step in which a neutralizer is added to the leachate to generate a neutralized precipitate containing an impurity, and the neutralized precipitate is removed to obtain a post-neutralization solution; a dezincification step in which hydrogen sulfide gas is added to the post-neutralization solution to generate zinc sulfide, and the zinc sulfide is removed to obtain a mother liquor for nickel recovery; and a nickel recovery step in which hydrogen sulfide gas is added to the mother liquor to recover nickel and cobalt as a mixed sulfide.
- a leach residue is appropriately added to the leachate and the pH of the post-neutralization solution is adjusted to 3.0 to 3.5 in the neutralization step, and further a sulfurization reaction is performed in the dezincification step in a state where suspended solids including the neutralized precipitate and the leach residue remain in the post-neutralization solution so that the turbidity of the post-neutralization solution is 100 to 400 NTU (Nephelometric Turbidity Unit).
- NTU Nephelometric Turbidity Unit
- Patent Literature 1 JP 2010-37626 A
- the present inventors have found that the recovery rate of nickel can be increased by providing two or more reaction tanks connected in series for the dezincification reaction, and by adjusting the distribution ratio of hydrogen sulfide gas blown into the reaction tanks when a dezincification reaction (sulfurization reaction) is performed by sulfurization by adding a sulfurizing agent to a post-neutralization solution obtained by neutralizing a leachate obtained by subjecting nickel oxide ore to high pressure acid leaching.
- the present invention is directed to a hydrometallurgical method for nickel oxide ore, including: a leaching step in which nickel oxide ore is subjected to acid leaching under high pressure, and a leach residue is then removed to obtain a leachate; a neutralization step in which a neutralizer is added to the leachate to generate a neutralized precipitate, and the neutralized precipitate is removed to obtain a post-neutralization solution; a dezincification step in which hydrogen sulfide gas is blown into the post-neutralization solution to generate a zinc precipitate, and the zinc precipitate is removed to obtain a post-dezincification solution; and a nickel recovery step in which a sulfurizing agent is added to the post-dezincification solution to recover nickel as a sulfide, wherein in the dezincification step, the hydrogen sulfide gas is blown into two or more reaction tanks connected in series to allow the post-neutralization solution to flow therethrough in order in such a manner that an amount of the
- the present invention it is possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper when zinc contained in nickel oxide ore is removed, thereby increasing the recovery rate of nickel.
- the hydrometallurgical method starts from a leaching step S1 in which nickel oxide ore as a raw material is crushed into small pieces by a crushing means such as a crusher, and water is added thereto to obtain a slurry. Then, sulfuric acid is added to the slurry, and the mixture is placed in a pressure vessel such as an autoclave and subjected to sulfuric acid leaching under high temperature and pressure at, for example, 240 to 280°C to leach nickel and cobalt as valuables.
- a leaching step S1 in which nickel oxide ore as a raw material is crushed into small pieces by a crushing means such as a crusher, and water is added thereto to obtain a slurry. Then, sulfuric acid is added to the slurry, and the mixture is placed in a pressure vessel such as an autoclave and subjected to sulfuric acid leaching under high temperature and pressure at, for example, 240 to 280°C to leach nickel and cobalt as valuables.
- a solid-liquid separation step S2 a slurry obtained by the above-described sulfuric acid leaching is subjected to multistep washing, and then a leach residue is removed from the slurry by solid-liquid separation to obtain a leachate containing nickel, cobalt, and impurity elements.
- a neutralization step S3 an alkali such as calcium hydroxide or calcium carbonate is added as a neutralizer to the leachate to adjust the pH of the leachate to precipitate the impurity elements as a neutralized precipitate.
- a flocculant coagulant
- a flocculant coagulant
- the neutralized precipitate obtained in the neutralization step S3 may be returned to the solid-liquid separation step S2.
- at least part of the leach residue obtained in the solid-liquid separation step S2 may be added to the leachate in the neutralization step S3.
- a dezincification step S4 hydrogen sulfide gas is blown as a sulfurizing agent into the post-neutralization solution to generate a zinc-containing sulfide precipitate (zinc sulfide), and a slurry containing the sulfide precipitate is subjected to solid-liquid separation to remove the zinc sulfide to obtain a post-dezincification solution.
- zinc sulfide zinc-containing sulfide precipitate
- a sulfurizing agent such as hydrogen sulfide gas is added to the post-dezincification solution to generate a nickel/cobalt mixed sulfide containing nickel and cobalt, and a slurry containing the nickel/cobalt mixed sulfide is subjected to sold-liquid separation to recover the nickel/cobalt mixed sulfide and to obtain a post-sulfurization solution (barren solution).
- barren solution post-sulfurization solution
- the barren solution may be returned to the solid-liquid separation step S2.
- zinc is selectively precipitated and settled as a sulfide in the dezincification step S4 so as to be separated from nickel and cobalt.
- two or more reaction tanks for blowing hydrogen sulfide gas into the post-neutralization solution are provided to perform a sulfurization reaction, and are connected in series so that the post-neutralization solution obtained in the neutralization step flows therethrough in order.
- the ratio of the amount of hydrogen sulfide gas blown into the second and following reaction tanks from the top out of the reaction tanks connected in series to the amount of hydrogen sulfide gas blown into all the reaction tanks (hereinafter also referred to as "blowing ratio”) is adjusted to be in an appropriate range. This makes it possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper, thereby increasing the recovery rate of nickel.
- the dezincification step S4 when n-number of reaction tanks for performing a dezincification reaction are provided in the order of a No. 1 reaction tank, a No. 2 reaction tank, a No. 3 reaction tank, ... and a No. n reaction tank from the top so that the post-neutralization solution flows therethrough in this order, the ratio of the amount of hydrogen sulfide gas blown into (n-1)-number of reaction tanks including the No. 2 and following reaction tanks to the amount of hydrogen sulfide gas blown into all the reaction tanks from the No. 1 reaction tank to the No. n reaction tank (i.e., blowing ratio) is adjusted to 50% to 90%. This makes it possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper.
- the blowing ratio when the blowing ratio is set to such a high value, particles of the sulfide precipitate can grow to have a large particle size. As a result, solid-liquid separability in the dezincification step can also be improved. In the dezincification step, fine particles of the sulfide precipitate are likely to be formed. Therefore, when a slurry containing such fine particles is subjected to solid-liquid separation using a filtration device such as a filter press, a filter cloth is quickly clogged so that the volume of a liquid that can pass through the filter cloth reduces. In order to recover the filter cloth, the filter cloth needs to be frequently backwashed or replaced, which may reduce production efficiency. However, when the blowing ratio is set to such a high value as described above, particles of the sulfide precipitate have a large diameter so that filterability improves.
- the blowing ratio is preferably adjusted to 60% to 90%, more preferably 60% to 85%.
- the ability of the filtration device to allow a liquid to pass through it improves, which makes it possible to improve productivity.
- the blowing ratio is less than 60%, the ratio of hydrogen sulfide gas blown into the No. 1 reaction tank is relatively high. In this case, fine particles of zinc sulfide as nuclei are excessively generated in the No.1 reaction tank, and particles of sulfides grow using these large number of fine particles as nuclei in the No. 2 and following reaction tanks, which makes it difficult to obtain particles of zinc sulfide having a large particle diameter.
- the blowing ratio exceeds 90%, generation of fine particles of zinc sulfide as nuclei is suppressed in the No. 1 reaction tank, which leads to a shortage of seeds. In this case, there is a fear that particle grow is insufficient in the No. 2 and following reaction tanks.
- the blowing ratio may be appropriately adjusted so that the particles grow to the extent that a filter cloth is not easily clogged in subsequent filtration treatment.
- the last reaction tank may serve as a buffer tank into which a large amount of hydrogen sulfide gas is not blown.
- the last reaction tank serves as a buffer tank, a reaction time can be secured by the buffer tank even when the short pass of a processed liquid occurs in the reaction tanks located upstream from the last reaction tank, which prevents a reduction in total reaction efficiency.
- the number of reaction tanks for dezincification reaction is preferably 3 or less.
- a dezincification reaction is preferably performed at a pH of 2.5 or higher but 3.5 or lower. If the pH is lower than 2.5, zinc is insufficiently separated due to redissolution of zinc sulfide that has once been generated. On the other hand, if the pH exceeds 3.5, elements, such as iron and nickel, that should not be removed may also be precipitated, which increases a precipitate load on a filter cloth or a filtration device used in subsequent filtration treatment. Particularly, in the case of iron, a large amount of fine precipitate is generated, which promotes the clogging of a filter cloth. Therefore, in order to achieve a sufficient flow rate of the filter cloth, the filter cloth needs to be frequently backwashed, which may reduce production efficiency.
- the dezincification reaction is preferably performed while the pH is maintained at 2.7 or higher but 3.0 or lower so that the pH falls within the above range even when an acid is generated.
- Nickel oxide ore was subjected to hydrometallurgical leaching at high temperature and pressure in accordance with a process flow chart shown in FIG. 1 to recover nickel in the form of a sulfide. More specifically, nickel oxide ore including laterite ore, saprolite ore, and limonite ore and sulfuric acid were placed in an autoclave as a pressure vessel and heated to a temperature of 240 to 260°C by a steam heater to perform leaching under high pressure, and then the obtained leach slurry was subjected to solid-liquid separation to remove a leach residue to obtain a leachate.
- Calcium hydroxide was added as a neutralizer to the leachate to adjust the pH of the leachate to 3.0 to 3.5 to generate a neutralized precipitate. Then, an anionic flocculant was added to remove the neutralized precipitate by solid-liquid separation to obtain a post-neutralization solution.
- reaction tanks No. 1 reaction tank, No. 2 reaction tank, No. 3 reaction tank
- the post-neutralization solution was continuously supplied to the first No. 1 reaction tank at a flow rate of 1200 to 1450 m 3 /hr so as to flow through the No. 1 reaction tank, the No. 2 reaction tank, and the No. 3 reaction tank in this order.
- hydrogen sulfide gas was blown into each of these three reaction tanks to sulfurize zinc contained in the post-neutralization solution to generate zinc sulfide.
- Table 1 shows the blowing ratio during generation of each of the zinc sulfide samples 1 to 46 and the particle dimeter of each of the zinc sulfide samples 1 to 46 generated at the shown blowing ratio.
- FIG. 2 shows a graph obtained by plotting a relationship between the blowing ratio and the particle dimeter of zinc sulfide. The particle diameter of zinc sulfide was measured by observing the sample collected during steady operation with a microscope and by using a Microtrac. It is to be noted that the pH and temperature of the slurry in the reaction tanks during generation of the zinc sulfide samples 1 to 46 were maintained at 2.7 to 2.9 and 60 to 67°C, respectively.
- the composition of the post-neutralization solution was as follows: nickel concentration 3.5 to 4.0 g/L, iron concentration 0.7 to 1.4 g/L, and zinc concentration 60 to 140 mg/L.
- the zinc concentration of the post-dezincification solution was reduced to about 5 to 12 mg/L.
- particles of the zinc sulfide samples 24 to 46 obtained by adjusting the ratio of hydrogen sulfide gas blown into the No. 2 and following reaction tanks to 60% or higher but 90% or lower were coarse and had a particle diameter of about 10 ⁇ m or more.
- These zinc sulfide samples 24 to 46 were prepared by continuously performing smelting over several days (at least 24 hours) per sample at different blowing ratios, but a filtration device to which the slurry taken out of the No. 3 reaction tank was supplied was not clogged.
- particles of all the zinc sulfide samples 1 to 23 prepared at a blowing ratio of less than 60% were fine and had a particle diameter of less than 10 ⁇ m.
- Each of these zinc sulfide samples 1 to 23 were prepared by continuously performing smelting at different blowing ratios, and as a result, a filtration device was clogged before the elapse of 24 hours.
- FIG. 3 is a graph obtained by plotting a relationship between the nickel grade and the blowing ratio.
- FIG. 4 is a graph obtained by plotting a relationship between the particle diameter and the nickel grade of the zinc sulfide.
- the nickel grade of the zinc sulfide can be reduced to 1% or less by setting the blowing ratio to 50% or more. Further, as can be seen from FIG. 4 , the nickel grade of the zinc sulfide can be reduced to 1% or less by allowing particles of the zinc sulfide to have a particle dimeter of about 10 ⁇ m or more, that is, by setting the blowing ratio of hydrogen sulfide gas to about 60% or more as can be seen from Table 1 and FIG. 2 . As described above, when the particle diameter of the zinc sulfide is 10 ⁇ m or more, the effect of improving filterability can be obtained in addition to the effect of increasing the recovery rate of nickel.
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Abstract
Description
- The present invention relates to a hydrometallurgical method in which nickel oxide ore is subjected to highpressure acid leaching, and more particularly relates to a hydrometallurgical method capable of increasing a nickel recovery rate.
- As one of hydrometallurgical method methods of nickel oxide ore, a high pressure acid leach (HPAL) process using sulfuric acid is known. This process is different from a conventional pyrometallurgical process generally used as a smelting method for nickel oxide ore in that nickel oxide ore is processed under wet conditions throughout the process without performing an oxide ore reduction step and drying step at high temperature, and is therefore advantageous in terms of energy and cost. Further, the HPAL process allows to obtain a nickel- and cobalt-containing sulfide (hereinafter also referred to as a nickel/cobalt mixed sulfide) which is concentrated to a nickel grade of about 50 to 60% by mass, and therefore high purity nickel can easily be obtained by refining.
- When nickel oxide ore as a raw material is subjected to high pressure acid leaching to recover nickel as a product, the nickel oxide ore is generally often processed through the following steps (a) to (d):
- (a) a leaching and solid-liquid separation step in which water is added to crushed nickel oxide ore to obtain a slurry, sulfuric acid is then added to the slurry, the mixture is placed in a reaction container such as an autoclave and maintained at a temperature of about 240 to 280°C under high pressure to leach valuables such as nickel and cobalt contained in the nickel oxide ore, and the slurry is taken out of the reaction container after leaching and subjected to solid-liquid separation in a sedimentation tank to separate a leachate containing nickel and cobalt from a leach residue;
- (b) a neutralization step in which the leachate is adjusted to a predetermined pH by adding a neutralizer to precipitate an impurity such as iron to obtain a neutralized slurry, a coagulant is added to the neutralized slurry containing a neutralized precipitate of the impurity to separate the neutralized precipitate by solid-liquid separation so as to obtain a post-neutralization solution containing nickel and cobalt;
- (c) a dezincification step in which a sulfurizing agent is added to the post-neutralization solution while the amount of the sulfurizing agent added is controlled to be in an appropriate range to remove only zinc and copper as sulfides without sulfurizing nickel and cobalt contained as valuables in the post-neutralization solution, the thus obtained sulfide precipitate (also referred to as zinc precipitate) is separated by solid-liquid separation to obtain a post-dezincification solution; and
- (d) a nickel recovery step in which a sulfurizing agent is added to the post-dezincification solution to generate a nickel/cobalt mixed sulfide, and the mixed sulfide is separated and recovered.
- For example,
Patent Literature 1 discloses a hydrometallurgical method based on the above-described high pressure acid leaching, which includes a leaching step in which nickel oxide ore is subjected to leaching using sulfuric acid and then to solid-liquid separation to obtain a leachate; a neutralization step in which a neutralizer is added to the leachate to generate a neutralized precipitate containing an impurity, and the neutralized precipitate is removed to obtain a post-neutralization solution; a dezincification step in which hydrogen sulfide gas is added to the post-neutralization solution to generate zinc sulfide, and the zinc sulfide is removed to obtain a mother liquor for nickel recovery; and a nickel recovery step in which hydrogen sulfide gas is added to the mother liquor to recover nickel and cobalt as a mixed sulfide. - In the method disclosed in
Patent Literature 1, a leach residue is appropriately added to the leachate and the pH of the post-neutralization solution is adjusted to 3.0 to 3.5 in the neutralization step, and further a sulfurization reaction is performed in the dezincification step in a state where suspended solids including the neutralized precipitate and the leach residue remain in the post-neutralization solution so that the turbidity of the post-neutralization solution is 100 to 400 NTU (Nephelometric Turbidity Unit). The thus obtained slurry containing a sulfide precipitate is subjected to solid-liquid separation in a filtration step in the dezincification step to obtain the sulfide precipitate and a final solution containing nickel and cobalt. - Patent Literature 1:
JP 2010-37626 A - In the above-described HPAL process using nickel oxide ore as a raw material, conditions for generating a sulfide precipitate of zinc in the dezincification step approximate to conditions for generating a sulfide precipitate of nickel, and therefore there is often a case where nickel loss occurs due to coprecipitation of zinc and nickel in the zinc precipitate. The recovery rate of nickel has a great impact on the economic efficiency of the process, and therefore it is desirable to reduce nickel loss as much as possible.
- In light of the above circumstances, it is an object of the present invention to provide a hydrometallurgical method for nickel oxide ore based on high pressure acid leaching which is capable of increasing the recovery rate of nickel by reducing the amount of nickel coprecipitated with impurities such as zinc and copper when zinc contained in the nickel oxide ore is removed.
- In order to achieve the above object, the present inventors have found that the recovery rate of nickel can be increased by providing two or more reaction tanks connected in series for the dezincification reaction, and by adjusting the distribution ratio of hydrogen sulfide gas blown into the reaction tanks when a dezincification reaction (sulfurization reaction) is performed by sulfurization by adding a sulfurizing agent to a post-neutralization solution obtained by neutralizing a leachate obtained by subjecting nickel oxide ore to high pressure acid leaching. This finding has led to the completion of the present invention.
- More specifically, the present invention is directed to a hydrometallurgical method for nickel oxide ore, including: a leaching step in which nickel oxide ore is subjected to acid leaching under high pressure, and a leach residue is then removed to obtain a leachate; a neutralization step in which a neutralizer is added to the leachate to generate a neutralized precipitate, and the neutralized precipitate is removed to obtain a post-neutralization solution; a dezincification step in which hydrogen sulfide gas is blown into the post-neutralization solution to generate a zinc precipitate, and the zinc precipitate is removed to obtain a post-dezincification solution; and a nickel recovery step in which a sulfurizing agent is added to the post-dezincification solution to recover nickel as a sulfide, wherein in the dezincification step, the hydrogen sulfide gas is blown into two or more reaction tanks connected in series to allow the post-neutralization solution to flow therethrough in order in such a manner that an amount of the hydrogen sulfide gas blown into the second and following reaction tanks from top is adjusted to 50% or more but 90% or less of a total amount of the hydrogen sulfide gas blown into all the reaction tanks.
- According to the present invention, it is possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper when zinc contained in nickel oxide ore is removed, thereby increasing the recovery rate of nickel.
-
-
FIG. 1 is a process flow chart showing a hydrometallurgical method for nickel oxide ore according to an embodiment of the present invention. -
FIG. 2 is a graph obtained by plotting a relationship between the particle diameter of each of samples of zinc sulfide obtained in Examples and the blowing ratio of hydrogen sulfide gas during generation of the zinc sulfide. -
FIG. 3 is a graph obtained by plotting a relationship between the Ni grade of each of samples of zinc sulfide obtained in Examples and the blowing ratio of hydrogen sulfide gas during generation of the zinc sulfide. -
FIG. 4 is a graph obtained by plotting a relationship between the Ni grade and the particle diameter of each of samples of zinc sulfide obtained in Examples. - Hereinbelow, a hydrometallurgical method for nickel oxide ore according to an embodiment of the present invention will be described. As shown in
FIG. 1 , the hydrometallurgical method starts from a leaching step S1 in which nickel oxide ore as a raw material is crushed into small pieces by a crushing means such as a crusher, and water is added thereto to obtain a slurry. Then, sulfuric acid is added to the slurry, and the mixture is placed in a pressure vessel such as an autoclave and subjected to sulfuric acid leaching under high temperature and pressure at, for example, 240 to 280°C to leach nickel and cobalt as valuables. - Then, in a solid-liquid separation step S2, a slurry obtained by the above-described sulfuric acid leaching is subjected to multistep washing, and then a leach residue is removed from the slurry by solid-liquid separation to obtain a leachate containing nickel, cobalt, and impurity elements. Then, in a neutralization step S3, an alkali such as calcium hydroxide or calcium carbonate is added as a neutralizer to the leachate to adjust the pH of the leachate to precipitate the impurity elements as a neutralized precipitate. Then, a flocculant (coagulant) is added to a slurry containing the neutralized precipitate, and the slurry is subjected to solid-liquid separation to remove the neutralized precipitate to obtain a post-neutralization solution containing nickel and cobalt. It is to be noted that if necessary, the neutralized precipitate obtained in the neutralization step S3 may be returned to the solid-liquid separation step S2. As shown by a dotted line in
FIG. 1 , at least part of the leach residue obtained in the solid-liquid separation step S2 may be added to the leachate in the neutralization step S3. - Then, in a dezincification step S4, hydrogen sulfide gas is blown as a sulfurizing agent into the post-neutralization solution to generate a zinc-containing sulfide precipitate (zinc sulfide), and a slurry containing the sulfide precipitate is subjected to solid-liquid separation to remove the zinc sulfide to obtain a post-dezincification solution. Finally, in a nickel recovery step S5, a sulfurizing agent such as hydrogen sulfide gas is added to the post-dezincification solution to generate a nickel/cobalt mixed sulfide containing nickel and cobalt, and a slurry containing the nickel/cobalt mixed sulfide is subjected to sold-liquid separation to recover the nickel/cobalt mixed sulfide and to obtain a post-sulfurization solution (barren solution). As shown in
FIG. 1 , if necessary, the barren solution may be returned to the solid-liquid separation step S2. - In the embodiment of the hydrometallurgical method according to the present invention, zinc is selectively precipitated and settled as a sulfide in the dezincification step S4 so as to be separated from nickel and cobalt. At this time, two or more reaction tanks for blowing hydrogen sulfide gas into the post-neutralization solution are provided to perform a sulfurization reaction, and are connected in series so that the post-neutralization solution obtained in the neutralization step flows therethrough in order. Further, the ratio of the amount of hydrogen sulfide gas blown into the second and following reaction tanks from the top out of the reaction tanks connected in series to the amount of hydrogen sulfide gas blown into all the reaction tanks (hereinafter also referred to as "blowing ratio") is adjusted to be in an appropriate range. This makes it possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper, thereby increasing the recovery rate of nickel.
- More specifically, in the dezincification step S4, when n-number of reaction tanks for performing a dezincification reaction are provided in the order of a No. 1 reaction tank, a No. 2 reaction tank, a No. 3 reaction tank, ... and a No. n reaction tank from the top so that the post-neutralization solution flows therethrough in this order, the ratio of the amount of hydrogen sulfide gas blown into (n-1)-number of reaction tanks including the No. 2 and following reaction tanks to the amount of hydrogen sulfide gas blown into all the reaction tanks from the No. 1 reaction tank to the No. n reaction tank (i.e., blowing ratio) is adjusted to 50% to 90%. This makes it possible to reduce the amount of nickel coprecipitated with impurities such as zinc and copper.
- Further, when the blowing ratio is set to such a high value, particles of the sulfide precipitate can grow to have a large particle size. As a result, solid-liquid separability in the dezincification step can also be improved. In the dezincification step, fine particles of the sulfide precipitate are likely to be formed. Therefore, when a slurry containing such fine particles is subjected to solid-liquid separation using a filtration device such as a filter press, a filter cloth is quickly clogged so that the volume of a liquid that can pass through the filter cloth reduces. In order to recover the filter cloth, the filter cloth needs to be frequently backwashed or replaced, which may reduce production efficiency. However, when the blowing ratio is set to such a high value as described above, particles of the sulfide precipitate have a large diameter so that filterability improves.
- As described above, in order to improve not only the recovery rate of nickel but also solid-liquid separability, the blowing ratio is preferably adjusted to 60% to 90%, more preferably 60% to 85%. This makes it possible to increase the particle diameter of particles of zinc sulfide (also referred to as "zinc sulfide precipitate") to be finally generated which allows to prevent the clogging of a filter cloth of a subsequent filtration device, such as a filter press. As a result, the ability of the filtration device to allow a liquid to pass through it improves, which makes it possible to improve productivity. The reason why such an increase in blowing ratio allows particles of the zinc sulfide precipitate to grow to have a large particle diameter is because when the blowing ratio increases, the number of fine particles of sulfides of impurities including zinc which are generated in an early stage of a sulfurization reaction in the No. 1 reaction tank decreases, and particles of the sulfides grow using these small number of fine particles as nuclei (also referred to as "seeds") in the No. 2 and following reaction tanks.
- When the blowing ratio is less than 60%, the ratio of hydrogen sulfide gas blown into the No. 1 reaction tank is relatively high. In this case, fine particles of zinc sulfide as nuclei are excessively generated in the No.1 reaction tank, and particles of sulfides grow using these large number of fine particles as nuclei in the No. 2 and following reaction tanks, which makes it difficult to obtain particles of zinc sulfide having a large particle diameter. On the other hand, when the blowing ratio exceeds 90%, generation of fine particles of zinc sulfide as nuclei is suppressed in the No. 1 reaction tank, which leads to a shortage of seeds. In this case, there is a fear that particle grow is insufficient in the No. 2 and following reaction tanks. That is, when more than 10% but less than 40% of hydrogen sulfide gas supplied to all the reaction tanks is blown into the No. 1 reaction tank, seeds can be stably generated. More specifically, the blowing ratio may be appropriately adjusted so that the particles grow to the extent that a filter cloth is not easily clogged in subsequent filtration treatment.
- It is to be noted that when three or more reaction tanks are provided in series, the last reaction tank may serve as a buffer tank into which a large amount of hydrogen sulfide gas is not blown. When the last reaction tank serves as a buffer tank, a reaction time can be secured by the buffer tank even when the short pass of a processed liquid occurs in the reaction tanks located upstream from the last reaction tank, which prevents a reduction in total reaction efficiency. However, the number of reaction tanks for dezincification reaction is preferably 3 or less. This is because when there are a large number of reaction tanks in which substantially no sulfurization reaction occurs, problems occur such as waste of equipment costs and energy costs and redissolution of the zinc sulfide precipitate due to the oxidation of the slurry staying in the excess reaction tanks by air contained in the slurry. Further, zinc sulfide particles separately prepared or zinc sulfide particles recovered by solid-liquid separation may be supplied to the No. 1 reaction tank as seeds, which makes it possible to generate coarser zinc sulfide particles.
- In the dezincification step S4, a dezincification reaction is preferably performed at a pH of 2.5 or higher but 3.5 or lower. If the pH is lower than 2.5, zinc is insufficiently separated due to redissolution of zinc sulfide that has once been generated. On the other hand, if the pH exceeds 3.5, elements, such as iron and nickel, that should not be removed may also be precipitated, which increases a precipitate load on a filter cloth or a filtration device used in subsequent filtration treatment. Particularly, in the case of iron, a large amount of fine precipitate is generated, which promotes the clogging of a filter cloth. Therefore, in order to achieve a sufficient flow rate of the filter cloth, the filter cloth needs to be frequently backwashed, which may reduce production efficiency.
- It is to be noted that in the dezincification reaction, an acid is generated after the reaction as shown in the following
formula 1. Therefore, the dezincification reaction is preferably performed while the pH is maintained at 2.7 or higher but 3.0 or lower so that the pH falls within the above range even when an acid is generated.
[Formula 1] ZnSO4+H2S→ZnS+H2SO4
- Nickel oxide ore was subjected to hydrometallurgical leaching at high temperature and pressure in accordance with a process flow chart shown in
FIG. 1 to recover nickel in the form of a sulfide. More specifically, nickel oxide ore including laterite ore, saprolite ore, and limonite ore and sulfuric acid were placed in an autoclave as a pressure vessel and heated to a temperature of 240 to 260°C by a steam heater to perform leaching under high pressure, and then the obtained leach slurry was subjected to solid-liquid separation to remove a leach residue to obtain a leachate. Calcium hydroxide was added as a neutralizer to the leachate to adjust the pH of the leachate to 3.0 to 3.5 to generate a neutralized precipitate. Then, an anionic flocculant was added to remove the neutralized precipitate by solid-liquid separation to obtain a post-neutralization solution. - Then, three reaction tanks (No. 1 reaction tank, No. 2 reaction tank, No. 3 reaction tank) were prepared which were connected in series and each of which had an almost cylindrical shape having a diameter of 7.7 m and a height of 12 m (capacity: 460 m3). The post-neutralization solution was continuously supplied to the first No. 1 reaction tank at a flow rate of 1200 to 1450 m3/hr so as to flow through the No. 1 reaction tank, the No. 2 reaction tank, and the No. 3 reaction tank in this order. Further, hydrogen sulfide gas was blown into each of these three reaction tanks to sulfurize zinc contained in the post-neutralization solution to generate zinc sulfide. At this time, the ratio of the amount of hydrogen sulfide gas blown into the No. 2 reaction tank and the No. 3 reaction tank to the amount of hydrogen sulfide gas blown into all the three reaction tanks, that is, the blowing ratio was changed little by little from 5.1% to 86.3%.
- Then, a post-sulfurization solution taken out of the last No. 3 reaction tank was supplied to a Buchner funnel, in which a filter cloth was placed on a perforated plate having a plurality of pores and a diameter of 60 cm, and subjected to solid-liquid separation by vacuum suction on the filtrate side. In this way, zinc sulfide (zinc sulfide precipitate)
samples 1 to 46 generated at different blowing ratios were obtained. It is to be noted that blowing of hydrogen sulfide gas into the No. 2 reaction tank and the No. 3 reaction tank was performed in such a manner that most of the hydrogen sulfide gas was blown into the No. 2 reaction tank, that is, the No. 3 reaction tank was used to react zinc sulfide particles grown in the No. 2 reaction tank with remaining dissolved hydrogen sulfide gas to finally grow the zinc sulfide particles. More specifically, the amount of hydrogen sulfide gas blown into the No. 3 reaction tank was appropriately increased or decreased without changing the blowing ratio on the basis of the particle diameter of sampled grown zinc sulfide particles. - The following Table 1 shows the blowing ratio during generation of each of the
zinc sulfide samples 1 to 46 and the particle dimeter of each of thezinc sulfide samples 1 to 46 generated at the shown blowing ratio.FIG. 2 shows a graph obtained by plotting a relationship between the blowing ratio and the particle dimeter of zinc sulfide. The particle diameter of zinc sulfide was measured by observing the sample collected during steady operation with a microscope and by using a Microtrac. It is to be noted that the pH and temperature of the slurry in the reaction tanks during generation of thezinc sulfide samples 1 to 46 were maintained at 2.7 to 2.9 and 60 to 67°C, respectively. The composition of the post-neutralization solution was as follows: nickel concentration 3.5 to 4.0 g/L, iron concentration 0.7 to 1.4 g/L, andzinc concentration 60 to 140 mg/L. The zinc concentration of the post-dezincification solution was reduced to about 5 to 12 mg/L.[Table 1] Samples Blowing ratio (%) Particle diameter of Zn sulfide (µm) 1 5.1 8.1 2 7.6 8.4 3 11.0 9.1 4 11.6 6.9 5 12.9 9.1 6 13.2 7.2 7 13.9 7.9 8 23.7 8.1 9 23.8 9.9 10 23.8 7.7 11 24.1 7.7 12 24.1 9.3 13 28.5 6.6 14 28.6 6.4 15 28.6 8.3 16 30.8 7.7 17 30.8 6.9 18 48.1 7.7 19 48.3 7.0 20 48.8 6.9 21 49.0 8.2 22 51.5 7.9 23 53.5 9.8 24 60.1 11.4 25 63.8 18.1 26 66.4 14.1 27 66.5 10.7 28 66.7 17.8 29 67.3 10.6 30 67.9 12.5 31 68.4 15.6 32 68.6 11.5 33 69.0 13.6 34 80.1 14.3 35 81.0 19.0 36 81.6 11.0 37 82.0 10.1 38 82.2 16.7 39 83.4 22.6 40 84.1 16.8 41 84.5 28.1 42 84.6 15.0 43 84.8 30.1 44 84.9 18.7 45 86.2 22.0 46 86.3 16.7 - As can be seen from the results shown in Table 1 and
FIG. 2 , particles of the zinc sulfide samples 24 to 46 obtained by adjusting the ratio of hydrogen sulfide gas blown into the No. 2 and following reaction tanks to 60% or higher but 90% or lower were coarse and had a particle diameter of about 10 µm or more. These zinc sulfide samples 24 to 46 were prepared by continuously performing smelting over several days (at least 24 hours) per sample at different blowing ratios, but a filtration device to which the slurry taken out of the No. 3 reaction tank was supplied was not clogged. On the other hand, particles of all thezinc sulfide samples 1 to 23 prepared at a blowing ratio of less than 60% were fine and had a particle diameter of less than 10 µm. Each of thesezinc sulfide samples 1 to 23 were prepared by continuously performing smelting at different blowing ratios, and as a result, a filtration device was clogged before the elapse of 24 hours. - Then, 37 zinc sulfide samples were randomly selected from the
zinc sulfide samples 1 to 46, and their nickel grades were measured by ICP. The nickel grade of the zinc sulfide and the blowing ratio are shown in the following Table 2.FIG. 3 is a graph obtained by plotting a relationship between the nickel grade and the blowing ratio. Further,FIG. 4 is a graph obtained by plotting a relationship between the particle diameter and the nickel grade of the zinc sulfide.[Table 2] Samples Blowing ratio (%) Ni grade of Zn sulfide (%) 1 5.1 1.7 2 7.6 1.2 5 12.9 1.7 6 13.2 1.7 7 13.9 1.0 8 23.7 1.2 9 23.8 1.2 10 23.8 1.1 11 24.1 1.3 16 30.8 1.7 17 30.8 1.2 18 48.1 1.0 19 48.3 1.3 20 48.8 1.3 21 49.0 1.4 22 51.5 0.6 23 53.5 0.7 24 60.1 0.7 25 63.8 0.5 26 66.4 0.6 27 66.5 0.8 29 67.3 0.6 30 67.9 0.5 31 68.4 0.6 32 68.6 0.4 33 69.0 0.5 34 80.1 0.4 35 81.0 0.8 36 81.6 0.4 37 82.0 0.7 39 83.4 0.4 41 84.5 0.6 42 84.6 0.4 43 84.8 0.6 44 84.9 0.5 45 86.2 0.7 46 86.3 0.8 - As can be seen from Table 2 and
FIG. 3 , the nickel grade of the zinc sulfide can be reduced to 1% or less by setting the blowing ratio to 50% or more. Further, as can be seen fromFIG. 4 , the nickel grade of the zinc sulfide can be reduced to 1% or less by allowing particles of the zinc sulfide to have a particle dimeter of about 10 µm or more, that is, by setting the blowing ratio of hydrogen sulfide gas to about 60% or more as can be seen from Table 1 andFIG. 2 . As described above, when the particle diameter of the zinc sulfide is 10 µm or more, the effect of improving filterability can be obtained in addition to the effect of increasing the recovery rate of nickel.
Claims (2)
- A hydrometallurgical method for nickel oxide ore, comprising: a leaching step in which nickel oxide ore is subjected to acid leaching under high pressure, and a leach residue is then removed to obtain a leachate; a neutralization step in which a neutralizer is added to the leachate to generate a neutralized precipitate, and the neutralized precipitate is removed to obtain a post-neutralization solution; a dezincification step in which hydrogen sulfide gas is blown into the post-neutralization solution to generate a zinc precipitate, and the zinc precipitate is removed to obtain a post-dezincification solution; and a nickel recovery step in which a sulfurizing agent is added to the post-dezincification solution to recover nickel as a sulfide, wherein in the dezincification step, the hydrogen sulfide gas is blown into two or more reaction tanks connected in series to allow the post-neutralization solution to flow therethrough in order in such a manner that an amount of the hydrogen sulfide gas blown into the second and following reaction tanks from top is adjusted to 50% or more but 90% or less of a total amount of the hydrogen sulfide gas blown into all the reaction tanks.
- The hydrometallurgical method for nickel oxide ore according to claim 1, wherein in the dezincification step, the sulfurizing reaction is performed in a pH range of 2.5 or higher but 3.5 or lower.
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| JP2016232416 | 2016-11-30 | ||
| JP2017002344A JP6350684B2 (en) | 2016-11-30 | 2017-01-11 | Method for hydrometallizing nickel oxide ore |
| PCT/JP2017/041381 WO2018101069A1 (en) | 2016-11-30 | 2017-11-16 | Wet metallurgy method for nickel oxide ore |
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| JP7095606B2 (en) * | 2019-01-17 | 2022-07-05 | 住友金属鉱山株式会社 | Method for producing nickel-cobalt mixed sulfide from nickel oxide ore by hydrometallurgy |
| JP7508977B2 (en) | 2020-09-29 | 2024-07-02 | 住友金属鉱山株式会社 | Dezincification treatment method, nickel oxide ore hydrometallurgy method |
| JP7585921B2 (en) * | 2021-03-24 | 2024-11-19 | 住友金属鉱山株式会社 | Hydrometallurgical process for nickel oxide ore |
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| CA1116412A (en) * | 1979-05-10 | 1982-01-19 | Kohur N. Subramanian | Recovery of nickel and cobalt from leach slurries |
| JP2004305917A (en) * | 2003-04-07 | 2004-11-04 | Sumitomo Metal Mining Co Ltd | Method for removing zinc from nickel sulfate aqueous solution |
| JP5572928B2 (en) * | 2008-07-25 | 2014-08-20 | 住友金属鉱山株式会社 | Method for hydrometallizing nickel oxide ore |
| JP5682567B2 (en) * | 2009-10-19 | 2015-03-11 | 住友金属鉱山株式会社 | Nickel oxide ore wet refining plant and method of operation thereof |
| JP6222141B2 (en) * | 2015-03-05 | 2017-11-01 | 住友金属鉱山株式会社 | Method for producing nickel sulfide, method for hydrometallizing nickel oxide ore |
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