AU725800B2 - Process for recovering valuable metals from oxide ore - Google Patents
Process for recovering valuable metals from oxide ore Download PDFInfo
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- AU725800B2 AU725800B2 AU60618/99A AU6061899A AU725800B2 AU 725800 B2 AU725800 B2 AU 725800B2 AU 60618/99 A AU60618/99 A AU 60618/99A AU 6061899 A AU6061899 A AU 6061899A AU 725800 B2 AU725800 B2 AU 725800B2
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- leached
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- cobalt
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- 229910052751 metal Inorganic materials 0.000 title claims description 43
- 239000002184 metal Substances 0.000 title claims description 41
- 150000002739 metals Chemical class 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 109
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 86
- 239000011572 manganese Substances 0.000 claims description 70
- 229910052748 manganese Inorganic materials 0.000 claims description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 239000011701 zinc Substances 0.000 claims description 55
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 53
- 229910052725 zinc Inorganic materials 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 48
- 229910017052 cobalt Inorganic materials 0.000 claims description 44
- 239000010941 cobalt Substances 0.000 claims description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 44
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 41
- 238000002386 leaching Methods 0.000 claims description 31
- 239000011777 magnesium Substances 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 28
- 239000002244 precipitate Substances 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 19
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 150000004679 hydroxides Chemical class 0.000 claims description 15
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 9
- 229940044175 cobalt sulfate Drugs 0.000 claims description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229940053662 nickel sulfate Drugs 0.000 claims description 8
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 description 30
- 238000011084 recovery Methods 0.000 description 23
- 238000000926 separation method Methods 0.000 description 18
- 238000006386 neutralization reaction Methods 0.000 description 16
- 239000012535 impurity Substances 0.000 description 13
- 150000004763 sulfides Chemical class 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 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 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical class [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- -1 specifically Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Description
AUSTRALIA
Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): PACIFIC METALS CO., LTD.
Invention Title: PROCESS FOR RECOVERING VALUABLE METALS FROM OXIDE ORE 0 0 *0 0 000.
0 0**00 The following statement is a full description of this invention, including the best method of performing it known to me/us: PROCESS FOR RECOVERING VALUABLE METALS FROM OXIDE ORE BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a process for recovering valuable metals, specifically, nickel, cobalt, zinc and manganese, from oxide ore by sulfuric acidleaching an oxide ore containing nickel, cobalt, zinc, manganese, iron, aluminum, magnesium, chromium and the "'"like.
10 Description of the Background Art One process for recovering valuable metal from an oxide ore is the sulfuric acid-leaching process. Processes for sulfuric acid-leaching of nickel oxide ore are described in detail in, for example, U.S. Patent No.
2,872,306 and the Journal of Metals, March 1960, p206.
Various processes are used for recovering valuable metals from nickel oxide ore by sulfuric acidleaching, such as that of dissolving the ore in sulfuric :acid, blowing hydrogen sulfide gas into the solution to precipitate nickel and cobalt as sulfides, oxidizing and dissolving the sulfides under high temperature and high pressure, and carrying out reduction with hydrogen.
When a nickel oxide ore is treated using this type of sulfuric acid-leaching process, difficulties are encountered in each step of the operation. First, in the step for obtaining the solution by dissolving the nickel 1Aoxide ore in sulfuric acid, a problem of poor economy arises owing to the simultaneous leaching of iron.
Specifically: 1) When the nickel oxide ore is dissolved under atmospheric pressure, a large amount of sulfuric acid is consumed because iron present in the ore leaches out together with the desired nickel and cobalt.
2) A large amount of neutralizer is required in the neutralization step for removing the iron.
10 Various references, including the Journal of Metals mentioned above, point out that these problems can be overcome by dissolving the ore in sulfuric acid under high temperature and high pressure in an autoclave, because iron leaching is suppressed under these conditions.
In processing of nickel oxide ore by the sulfuric acid-leaching process, problems also arise in the step of blowing hydrogen sulfide gas into the solution to precipitate nickel and cobalt as sulfides.
Specifically: 1) The autoclave operated at a high pressure of 2-10kg/cm 2 and a high temperature of 100°C or higher in this step is expensive and complicated to operate.
2) Since the produced sulfides adhere to the wall of the autoclave, the operation has to be frequently interrupted for sulfide removal.
3) The rate of sulfide production is slow because the reaction between the hydrogen sulfide gas and the -2r, solution containing nickel and cobalt is a gas phase reaction. Large equipment therefore becomes necessary.
4) In order to produce sulfides with good filterseparation property, a large amount of sulfides must be made present as seed crystals beforehand. Large equipment therefore becomes necessary.
Owing to its toxicity, hydrogen sulfide gas is hard to handle from various aspects and requires use of complex equipment.
10 The step of dissolving the sulfides obtained in the preceding step involves addition of oxygen under high temperature and high pressure and therefore requires use of an expensive autoclave and complex equipment.
SUMMARY OF THE INVENTION 15 An intention of an embodiment of the present invention is to i provide a novel process for recovering valuable metals from oxide ore, which overcomes the aforesaid problems heretofore encountered in the recovery of valuable metals from oxide ore, particularly nickel oxide ore, by the sulfuric acid leaching process.
More specifically, an intention of an embodiment of the present invention is to provide a process for recovering valuable metals from oxide ore having the following features: 1) Ability to recover valuable metals from a solution without use of an autoclave or hydrogen sulfide, 3 2) Ability to recover valuable metals that can be used industrially without further processing, 3) Ability to discretely separate nickel, cobalt and other valuable metals, thereby eliminating the need for an autoclave or other expensive equipment when the separated materials are dissolved out of the solution.
4) Ability to recover metals liable to pollute the environment as valuable metals.
9.. 10 o o go• oo o o The inventors carried out various experiments and tests regarding recovery o valuable metals from oxide ore, particularly nickel oxide ore, by the sulfuric acid-leaching process. These efforts led to the discovery that the intentions outlined above could be achieved by the following two processes according to the present invention. As termed with respect to the present invention, "valuable metals" means nickel, cobalt, zinc and manganese.
The process for recovering valuable metals from oxide ore according to the first aspect of the invention is characterized in sequentially carrying out the following steps: a step of subjecting a previously prepared slurry of an oxide ore to atmospheric leaching under an acidic sulfuric acid condition using a pressure-leached solution obtained in a step thereby obtaining an atmospheric leached solution and an atmospheric leached residue, 4 a step of reacting the atmospheric leached residue obtained in the step with sulfuric acid under sufficiently high temperature and high pressure to form a pressure-leached solution, a step of adding a neutralizer to the atmospheric leached solution obtained in the step to separate iron and aluminum from the atmospheric leached solution as precipitates, a step of adding neutralizer to the atmospheric leached solution separated of iron and aluminum in the step to precipitate and recover nickel, cobalt and zinc from the atmospheric leached solution as •go• hydroxides or carbonates, and a step of adding neutralizer and oxidizer to S 15 the atmospheric leached solution separated of nickel, cobalt and zinc in the step to precipitate and recover manganese from the atmospheric leached solution as oxide and hydroxide or oxide and carbonate.
:The process for recovering valuable metals from oxide ore according to the second aspect of the invention is characterized in sequentially carrying out the following steps: a step of subjecting a previously prepared slurry of an oxide ore to atmospheric leaching under an acidic sulfuric acid condition using a pressure-leached solution obtained in a step thereby obtaining an 5 atmospheric leached solution and an atmospheric leached residue, a step of reacting the atmospheric leached residue obtained in the step with sulfuric acid under sufficiently high temperature and high pressure to form a pressure-leached solution, a step of adding a neutralizer to the atmospheric leached solution obtained in the step to separate iron and aluminum from the atmospheric leached 10 solution as precipitates, a step of adding neutralizer to the atmospheric leached solution separated of iron and aluminum ioo.
in the step to precipitate and recover nickel, cobalt and zinc from the atmospheric leached solution as 15 hydroxides or carbonates, a step of adding neutralizer and oxidizer to the atmospheric leached solution separated of nickel, cobalt and zinc in the step to precipitate and recover .i manganese from the atmospheric leached solution as oxide and hydroxide or oxide and carbonate, a step of dissolving the hydroxide or carbonate of the nickel, cobalt and zinc obtained in the step with sulfuric acid to obtain a solution containing nickel sulfate, cobalt sulfate and zinc sulfate, and a step of crystallizing the solution containing nickel sulfate, cobalt sulfate and zinc sulfate 6 obtained in the step to recover a mixture of crystals of nickel sulfate, cobalt sulfate and zinc sulfate.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing an embodiment of a process according to the invention for recovering nickel, cobalt and zinc (mixture of nickel, cobalt and zinc hydroxides or carbonates) by neutralization/recovery/precipitation and manganese as manganese precipitate (mixture of manganese oxide and hydroxide or oxide and carbonate) from oxide ore.
Figure 2 is a flow chart showing another embodiment of a process CO l according to the invention for recovering nickel, cobalt and zinc as sulfuric acid crystallization product (mixture of nickel, cobalt and zinc sulfates)and manganese as manganese precipitate (mixture of manganese oxide and 15 hydroxide or oxide and carbonate) from oxide ore.
DETAILED DESCRIPTION OF THE INVENTION .i Embodiments of the present invention will now be explained in detail with reference to Figures 1 and 2. A first aspect of the invention is shown in the form of a flow chart in Figure 1.
An oxide ore A is slurried, a pressure-leached solution D is added to the slurry, and an atmospheric leaching step 1 is conducted at 80-100°C for 2-3 hours.
During the atmospheric leaching step i, free sulfuric acid in the pressure-leached solution D and magnesium of the 7 oxide ore A react to reduce the amount of free sulfuric acid and simultaneously lower the amount of magnesium. This saves neutralizer consumption in a step 5 (explained later) for impurity removal by neutralization.
After the atmospheric leaching step i, the atmospheric leached slurry is separated with a thickener 2 into an atmospheric leached residue B and an atmospheric leached solution C. Optionally, a commercially available coagulant, a polyacrylamide type coagulant, can be added to the thickener to promote the separation.
:00. The whole amount of the atmospheric leached residue B is supplied to a pressure-leaching step 3.
o .o Sulfuric acid is added to the atmospheric leached residue B and the pressure-leaching step 3 is conducted at 220- 0 15 270°C and 20-50atm (gage pressure) for 10-60min. Since magnesium was leached from the oxide ore A in the atmospheric leaching step 1, the atmospheric leached residue B supplied to the pressure-leaching step 3 can be subjected to the pressure-leaching step 3 at a lower magnesium content than was originally contained in the oxide ore A. This has the effect of reducing the amount of sulfuric acid used. Owing to the reaction between magnesium and free sulfuric acid during the atmospheric leaching step i, moreover, the particles of the atmospheric leached residue B become finer than those of the oxide ore A. As the specific surface area of the atmospheric leached residue B therefore increases, nickel, cobalt, zinc and 8 manganese can be leached using a smaller amount of sulfuric acid.
Further, by setting the temperature and pressure during the pressure-leaching step 3 in the foregoing manner, it becomes possible to leach substantially all of the nickel, cobalt, zinc, manganese and magnesium from the oxide ore A and, on the other hand, to suppress leaching of iron, aluminum and chromium to a considerable extent. This has the effect of reducing the amount of sulfuric acid used and also reduces the amount of neutralizer used in the impurity removal step 5. The pressure-leached solution D is separated of pressure-leached residue in a thickener 4 and is then supplied to the atmospheric leaching step 1, as indicated earlier. The pressure-leached solution D supplied to the atmospheric leaching step 1 is therefore low in iron, aluminum and chromium content. This in turn has the effect of lowering the iron, aluminum and chromium content of the atmospheric leached solution C obtained.
Specifically, substantially the total amount of nickel, cobalt, zinc, manganese and magnesium contained in the oxide ore A has been leached into the atmospheric leached solution C and, further, the atmospheric leached solution C has been made low in content of the impurities iron, aluminum and chromium. The atmospheric leached solution C is added with neutralizer to effect the impurity removal step 5 for removing the impurities iron, aluminum and chromium by neutralization. Usable neutralizers include -9oxides of magnesium, calcium and sodium, carbonates of magnesium, calcium, sodium and ammonia, and hydroxides of magnesium, calcium, sodium and ammonia.
In the impurity removal step 5, the pH of the atmospheric leached solution C is adjusted to 1.5-6.0 during the impurity removal in order to separate it into neutralized wastes and neutralized solution E. The reasons for limiting the pH to this range are as follows: 1) At a pH below 1.5, the reaction of the impurity iron, aluminum and chromium with the neutralizer is insufficient, so that iron, aluminum and chromium are *0eo not neutralized and removed as iron, aluminum and chromium hydroxides or carbonates.
2) At a pH above 6.0, nickel, cobalt and zinc are *696 simultaneously coprecipitated as hydroxides or carbonates in addition to iron, aluminum and chromium.
S.-I The pH is therefore adjusted to 1.5-6.0, preferably 3.5-5.5.
go9* The neutralized solution (atmospheric leached solution) E from the impurity removal step 5 is sent to a neutral i zation/recovery step 6, where nickel, cobalt and zinc are recovered. The neutralization/recovery step 6 is carried out by adding neutralizer to the neutralized solution E and reacting the neutralized solution E and the neutralizer under atmospheric pressure, at a temperature of or higher and a pH in the range of 6.0-7.8. Points requiring attention from the operational viewpoint 10 regarding the neutralization/recovery step 6 and the reasons for the aforesaid condition limits are as follows: 1) Usable neutralizers include oxides of magnesium and sodium, carbonates of magnesium andsodium, and hydroxides of magnesium and sodium.
2) Recovery diminishes at a pH below 6.0 because precipitation of nickel, cobalt and zinc does not proceed.
3) Manganese and magnesium coprecipitate in addition to nickel, cobalt and zinc at a pH exceeding 7.8.
10 4) The pH should therefore be adjusted to •0047.8, more preferably 7.0-7.8.
5) At a temperature below 60°C, the reaction is slow, so that the productionof hydroxides or carbonates of .nickel, cobalt and zinc takes a long time. The nickel, a._ai 15 cobalt and zinc recovery rates therefore fall. In addition, the hydroxide and carbonate precipitates gel and impede e solid-liquid separation.
6) A temperature of 60°C or higher is therefore preferable.
When the operation is conducted under the foregoing conditions, the neutralization/recovery step 6 precipitates nickel, cobalt and zinc from the neutralized solution E as hydroxides or carbonates, depending on the type of neutralizer used. The precipitate is a mixture of the hydroxides or carbonates of nickel, cobalt and zinc (and is hereinafter called "neutralized recovered product 11 The process of this embodiment of the present invention for recovering nickel, cobalt and zinc from the neutralized solution E as hydroxides or carbonates has the following advantages over the prior art: 1) Unlike in the prior .art, the recovery of the valuable metals from the leached solution can be conducted without use of an autoclave. The equipment is therefore simple and inexpensive.
2) Safety is high because no hydrogen sulfide gas 10 or other toxic material is used.
3) No harmful substance is discharged into the environment. In particular, the invention enables complete compliance with regulations regarding the concentration of zinc in effluents. This is because all of the zinc contained in the neutralized solution E is separated into the neutralized recovered product F and, therefore, no zinc is contained in the final waste.
4) The neutralized recovered product F can optionally be used as a ferro-nickel production material without further processing. Otherwise it can be processed by drying or the like and used as a stainless steel production material. However, since such processing volatilizes the zinc contained in the neutralized recovered product F, the zinc should be separately recovered.
The neutralized recovered product F produced in the neutralization/recovery step 6 is filtered to separate a neutralized postharvest solution G. As the neutralized 12 postharvest solution G contains manganese, this metal is separated and recovered in a manganese separation step 7.
The manganese separation step 7 is conducted by adding a neutralizer and an oxidizer to the neutralized postharvest solution G and reacting the neutralized postharvest solution G with the neutralizer and the oxidizer while keeping the pH adjusted within the range of 7.8-8.5 and the redox potential adjusted within the range of 20-200mV. Points requiring attention from the 5 1 0 operational viewpoint regarding the manganese separation Sr, step 7 and the reasons for the aforesaid condition limits oo are as follows: 1) Usable neutralizers include oxides, carbonates or hydroxides of magnesium and sodium.
00 SI 15. 2) Usable oxidizers include air, oxygen, ozone and hydrogen peroxide.
3) At a pH below 7.8, manganese is not neutralized and its recovery rate declines.
r~r 4) At a pH above 8.5, the amount of neutralizer *5 used increases and undissolved neutralizer remains.
At a redox potential below 20mV, manganese oxidation is inadequate and its neutralization does not proceed sufficiently. At a redox potential below maintenance of the concentration of the manganese remaining in the solution following the manganese separation step 7 at or below 10ppm, the stipulated effluent standard, requires use of an excessive amount of neutralizer even at 13 a pH of 7.8 or above. When neutralizer is used in excess, the pH of the solution following the manganese separation step 7 is liable to rise above the stipulated effluent standard.
6) At a redox potential above 200mV, manganese oxidization is insufficient. Although manganese does not remain in the solution following the manganese separation step 7, an excessive amount of oxidizer is required.
When the manganese separation step 7 is conducted 10 under the foregoing conditions, the manganese of the neutralized postharvest solution G is precipitated as a mixture of oxide and hydroxide or as a mixture of oxide and carbonate, depending on the type of neutralizer used (this precipitate hereinafter being called "manganese precipitate 9&t* The manganese precipitate H is filtered to separate a manganese-separated solution I.
the process of this embodiment of the present invention, the method separating and recovering manganese from the neutralized postharvest solution G has the following advantages over the prior art: 1) It enables recovery of manganese, which is not possible with the prior art.
2) The recovered manganese can be used as a ferro-manganese production material in the form of the manganese precipitate H without further processing or can be dissolved in sulfuric acid and used as a production 14 material for electrolytic manganese dioxide or electrolytic metallic manganese.
3) No harmful substance is discharged into the environment. In particular, regulations regarding the concentration of manganese in effluents can be met. This is because all manganese is separated and recovered as the manganese precipitate H.
4) Specifically, the manganese-separated solution I after separation of manganese as the manganese 0 09 SO 0 precipitate H does not contain any metal other than e magnesium, calcium or sodium, particularly does not include S. any heavy metal, and therefore does not cause pollution even when discharged into the sea or other water body.
A second aspect of the invention is shown in the 0905 form of a flow chart in Figure 2. The second aspect of the invention adds to the first aspect of the invention steps for refining the neutralized recovered product F produced by the first aspect of the invention. This is for enhancing the utility of the neutralized recovered product F by converting it to a water-soluble substance. As set out in the foregoing, this type of conversion has also been conducted with respect to sulfides produced by conventional technologies, which use an autoclave to dissolve the sulfides under high temperature and high pressure while adding oxygen, thereby obtaining a solution containing nickel sulfate and cobalt sulfate.
15 In the second aspect of the invention, such conversion operation is conducted by adding water to the neutralized recovered product F to obtain a slurry and adding sulfuric acid to the slurry to conduct a sulfuric acid dissolving step 8.
The neutralized recovered product F is a mixture of hydroxides of nickel, cobalt and zinc or a mixture of carbonates of nickel, cobalt and zinc, depending on the type of neutralizer used in the neutralization/recovery 10 step 6. Since these mixtures readily dissolve in sulfuric acid at normal temperature and atmospheric pressure, the ooo.
invention process is advantageous in that it does not oe require special, expensive equipment such as an autoclave needed in the case of sulfides.
S 15 The sulfuric acid dissolving step 8 is preferably conducted with respect to the neutralized recovered product F with the pH adjusted to within the range of 1.0-6.0. At a pH below 1.0, the amount of sulfuric acid used increases, *555 which is uneconomical, and the free sulfuric acid 66 concentration of a resulting sulfuric acid solution J increases, which makes it difficult to conduct an ensuing crystallization step 9 with respect to the sulfuric acid solution J. At a pH above 6.0, some of the neutralized recovered product F undesirably remains undissolved.
When the neutralized recovered product F is subjected to the sulfuric acid dissolving step 8, the sulfuric acid solution J is obtained. The sulfuric acid 16 solution J contains dissolved nickel sulfate, cobalt sulfate and zinc sulfate. Its impurity content is low.
After being removed of excess water by evaporation, the sulfuric acid solution J is subjected to the crystallization step 9, whereby there is readily obtained a mixture of crystals of nickel sulfate, cobalt sulfate and zinc sulfate (hereinafter called "mixed crystals The mixed crystals K are easy to package and transport. As they can be dissolved with only water, they are also simple to 1 0 use.
•EXAMPLES
6e Specific examples of the invention will now be explained together with comparative examples. All percentages referred to in the examples and comparative 15 examples are percentages by weight.
.Example 1 An oxide ore A having as constituents 1.75% of e Ni, 0.13% of Co, 0.08% of Zn, 0.75% of Mn, 38% of Fe, 1.8% 0e of Al, 2.7% of Cr, and 3.6% of Mg was processed in accordance with the steps of Figure 1.
First, the oxide ore A was prepared into a slurry and the slurry was mixed with pressure-leached solution D obtained from the thickener 4. The result was subjected to the atmospheric leaching step 1 at 95°C for 3hr. The resulting reaction of free sulfuric acid in the pressureleached solution D and Mg in the oxide ore A reduced the 17 free sulfuric acid content from ll.0g/l to 2.0Og/l and increased the pH of the atmospheric leached solution C from to 1.7. On the other hand, 46% of the Mg was leached out of the oxide ore A and passed to the atmospheric leached solution C. Owing to the rise in the pH, 90% of the Fe in the pressure-leached solution D precipitated as hydroxide and was passed to the atmospheric leached residue
B.
The slurry from the atmospheric leaching step 1 10 was separated into the atmospheric leached solution C and ooo:the atmospheric leached residue B in the thickener 2. The atmospheric leached residue B was passed to the pressureleaching step 3 in the form of slurry and the atmospheric leached solution C was passed to the impurity removal step 15 S"In the pressure-leaching step 3, sulfuric acid was added to the slurry of atmospheric leached residue B at the rate of 0.242kg per kilogram of oxide ore and leaching was conducted in an autoclave made of titanium under conditions of a temperature of 240°C and a pressure of 36kg/cm 2 As a result, valuable metals were leached at leaching rates of 94.0% of Ni, 94.5% of Co, and 94.0% of Zn. The impurity-to-Ni concentration ratios in the pressure-leached solution D were Fe/Ni: 0.20, Al/Ni: 0.11, and Cr/Ni: 0.004.
The atmospheric leached solution C from the atmospheric leaching step 1 was added with limestone to 18 conduct the impurity removal step 5 at a pH of 4.0. The produced precipitate and neutralized solution E were separated by filtering with a filter press. The impurity removal step 5 removed Fe, Al and Cr from the atmospheric leached solution C at the rates of 95%, 90% and 92%, respectively.
The neutralized solution E was adjusted to a pH of 7.6 by addition of magnesium oxide as a neutralizer and the neutralization/recovery step 6 was conducted at a 10 temperature of 80 0 C for 60min. The neutralization/recovery *.*.step 6 produced neutralized recovered product F comprising hydroxides of nickel, cobalt and zinc. Valuable metals were recovered to the neutralized recovered product F at the rates of Ni: 99.5%, Co: 99.0% and Zn: 99.2%. The i 15 neutralized recovered product F had an average particle diameter of 20gm and exhibited excellent filter-separation property. The composition of the neutralized recovered .i product F included Ni: 43.2%, Co: 3.12%, Zn: 1.95%, Fe: 0.43%, Al: 0.47%, Cr: 0.02%, Mn: 3.50% and Mg: 1.50%.
The neutralized recovered product F obtained in this manner was filtered with a filter press to separate neutralized postharvest solution G. The neutralized postharvest solution G was adjusted to a pH of 8.0 by addition of magnesium oxide as a neutralizer, adjusted to a redox potential of 80mV by blowing in air, and subjected to the manganese separation step 7 at 80 0 C for 60min. This yielded manganese precipitate H. The recovery rate of Mn to 19 t t .1 the manganese precipitate H was 99.9%. Components of the manganese precipitate H included Mn: 31.7%, Ni: 0.36%, Co: 0.05%, Zn: 0.02% and Mg: 6.31%. After separation of the manganese precipitate H, the manganese-separated solution I had a Mn concentration of 0.005g/l and was acceptable for discharge as an effluent.
Example 2 The neutralized solution E obtained in Example 1 was adjusted to a pH of 7.6 by addition of sodium carbonate as a neutralizer and subjected to the neutralization/recovery step 6 at a temperature of 80°C for The neutralization/recovery step 6 yielded a neutralized recovered product F comprising carbonates of nickel, cobalt and zinc. The metals were recovered to the 15 neutralized recovered product F at the rates of Ni: 99.7%, Co: 99.3% and Zn: 99.2%. The neutralized recovered product F had an average particle diameter of 27Mm and exhibited excellent filter-separation property. The composition of the neutralized recovered product F included Ni: 40.5%, Co: 2.91%, Zn: 1.83%, Fe: 0.40%, Al: 0.41%, Cr: 0.02%, Mn: 2.65% and Mg: 1.03%.
The neutralized postharvest solution G obtained was adjusted to a pH of 8.2 by addition of sodium carbonate as a neutralizer, adjusted to a redox potential of 120mV by blowing in air, and subjected to the manganese separation step 7 at 80°C for 60min. This yielded manganese 20 precipitate H. The recovery rate of Mn to the manganese precipitate H was 99.9%. Components of the manganese precipitate H included Mn: 33.7%, Ni: 0.34%, Co: 0.05%, Zn: 0.02% and Mg: 3.65%. After separation of the manganese precipitate H, the manganese-separated solution I had a Mn concentration of 0.003g/l and was acceptable for discharge as an effluent.
Example 3 The neutralized recovered product F obtained in *oeo 1 0 Example 1 was added with water and sulfuric acid to conduct the sulfuric acid dissolving step 8, thereby obtaining a sulfuric acid solution J having a Ni concentration of a Co concentration of 7.2g/l, a Zn concentration of and a pH of 3.5. The sulfuric acid solution J was subjected to the crystallization step 9 by evaporation :i removal of water by processing in a jacket-type evaporation crystallizer using steam, thereby obtaining mixed crystals K. The mixed crystals K included Ni: 21.8%, Co: 1.57%, Zn: 0.98%, Fe: 0.22%, Al: 0.24%, Mn: 1.77% and Mg: 0.76%.
Example 4 The neutralized recovered product F obtained in Example 2 was subjected to the same sulfuric acid dissolving step 8 and crystallization step 9 of Example 3 to obtain mixed crystals K. The mixed crystals K included 21 Ni: 22.6%, Co: 1.62%, Zn: 1.02%, Fe: 0.22%, Al: 0.23%, Mn: 1.48% and Mg: 0.57%.
Comparative Example 1 The neutralized solution E obtained in Example 1 was adjusted to a pH of 8.0 by addition of magnesium oxide as a neutralizer and subjected to the neutralization/recovery step 6 at a temperature of 80*C for 60min. The neutralization/recovery step 6 yielded a neutralized recovered product F comprising hydroxides of 10 nickel, cobalt and zinc. The metals were recovered to the neutralized recovered product.F at the rates of Ni: 99.7%, Co: 99.8% and Zn: 99.6%, but 57% of Mn was simultaneously coprecipitated and a large amount of unreacted magnesium oxide was also present. The composition of the neutralized 15 recovered product F included Ni: 27.6%, Co: 1.98%, Zn: 1.24%, Fe: 0.07%, Al: 0.29%, Mn: 7.2% and Mg: A decrease in Ni and increases in Mn and Mg were thus observed.
Comparative Example 2 The neutralized postharvest solution G obtained in Example 1 was adjusted to a pH of 8.2 by addition of magnesium oxide as a neutralizer and, without use of air, oxygen or other oxidizer, was subjected to the manganese separation step 7 at 80*C for 60min. The redox potential at this time was -60mV. The recovery rate of Mn to the 22 manganese precipitate H was 92% and a large amount of unreacted MgO was present. The manganese precipitate H included Mn: 21.3%, Ni: 0.24%, Co: 0.03%, Zn: 0.02% and Mg: 18.6%. After separation of the manganese precipitate H, the manganese-separated solution I had a Mn concentration of 0.28g/l and was unacceptable for discharge as an effluent.
According to the first aspect of the invention, no autoclave or hydrogen sulfide is required for recovering valuable metal from the leached solution and the recovered S 1 0 products can be used industrially without further oooo processing. Moreover, metals liable to pollute the environment can be recovered safely and efficiently as valuable metals.
i 9o The second aspect of the invention offers a .15 number of outstanding technological features including that *99999 S"no autoclave or hydrogen sulfide is required for recovering valuable metal from the leached solution, that the 999o .recovered products can be used industrially without further processing, that metals liable to pollute the environment can be recovered safely and efficiently as valuable metals, and that in the case of discretely separating nickel, cobalt and other valuable metals, the recovered products can be dissolved without need for an autoclave or other expensive equipment.
23
Claims (3)
1. A process for recovering valuable metals from oxide ore, which is a process for recovering nickel, cobalt, zinc and manganese as valuable metals from oxide ore containing such metals as nickel, cobalt, zinc, manganese, magnesium, iron, aluminum and chromium, comprising: a step of subjecting a previously prepared slurry of an oxide ore to atmospheric leaching under an 1' 0 acidic sulfuric acid condition using a pressure-leached oooo solution obtained in a step thereby obtaining an atmospheric leached solution and an atmospheric leached residue, a step of reacting the atmospheric leached residue obtained in the step with sulfuric acid under sufficiently high temperature and high pressure to form a pressure-leached solution, a step of adding a neutralizer to the atmospheric leached solution obtained in the step to separate iron and aluminum from the atmospheric leached solution as precipitates, a step of adding neutralizer to the atmospheric leached solution separated of iron and aluminum in the step to precipitate and recover nickel, cobalt and zinc from the atmospheric leached solution as hydroxides or carbonates, and 24 a step of adding neutralizer and oxidizer to the atmospheric leached solution separated of nickel, cobalt and zinc in the step to precipitate and recover manganese from the atmospheric leached solution as oxide and hydroxide or oxide and carbonate.
2. A process for recovering valuable metals from oxide ore, which is a process for recovering nickel, cobalt, zinc and manganese as valuable metals from oxide ore containing such metals as nickel, cobalt, zinc, o5e manganese, magnesium, iron, aluminum and chromium, comprising: a step of subjecting a previously prepared slurry of an oxide ore to atmospheric leaching under an acidic sulfuric acid condition using a pressure-leached *ooS*S S 15 solution obtained in a step thereby obtaining an atmospheric leached solution and an atmospheric leached residue, a step of reacting the atmospheric leached residue obtained in the step with sulfuric acid under sufficiently high temperature and high pressure to form a pressure-leached solution, a step of adding a neutralizer to the atmospheric leached solution obtained in the step to separate iron and aluminum from the atmospheric leached solution as precipitates, a step of adding neutralizer to the atmospheric leached solution separated of iron and aluminum in the step to precipitate and recover nickel, cobalt and zinc from the atmospheric leached solution as hydroxides or carbonates, a step of adding neutralizer and oxidizer to the atmospheric leached solution separated of nickel, cobalt and zinc in the step to precipitate and recover manganese from the atmospheric leached solution as oxide 10 and hydroxide or oxide and carbonate, oo o step of dissolving the hydroxide or carbonate of the nickel, cobalt and zinc obtained in the step with sulfuric acid to obtain a solution containing nickel sulfate, cobalt sulfate and zinc sulfate, and 15 a step of crystallizing the solution e S"containing nickel sulfate, cobalt sulfate and zinc sulfate obtained in the step to recover a mixture of crystals of nickel sulfate, cobalt sulfate and zinc sulfate.
3. A process for recovering valuable metals from oxide ore, said process being substantially as herein described with reference to examples 1 to 4 and the accompanying flowcharts. Dated this 24th day of November 1999 PACIFIC METAL CO., LTD. By their Patent Attorneys GRIFFITH HACK 26
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07243099A JP3385997B2 (en) | 1999-02-12 | 1999-02-12 | Method of recovering valuable metals from oxide ore |
| JP11-72430 | 1999-02-12 |
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| AU6061899A AU6061899A (en) | 2000-08-17 |
| AU725800B2 true AU725800B2 (en) | 2000-10-19 |
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| AU (1) | AU725800B2 (en) |
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1999
- 1999-02-12 JP JP07243099A patent/JP3385997B2/en not_active Expired - Fee Related
- 1999-11-24 AU AU60618/99A patent/AU725800B2/en not_active Expired
Cited By (8)
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| FR2843315A1 (en) * | 2002-08-08 | 2004-02-13 | Dynatec Corp | SELECTIVE PROCESSING OF MANGANESE FROM ACID SOLUTIONS CONTAINING MAGNESIUM AND ALUMINUM. |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU6061899A (en) | 2000-08-17 |
| JP2000234130A (en) | 2000-08-29 |
| JP3385997B2 (en) | 2003-03-10 |
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