AU3547900A - Purification of zinc-bearing material solutions containing manganese - Google Patents
Purification of zinc-bearing material solutions containing manganese Download PDFInfo
- Publication number
- AU3547900A AU3547900A AU35479/00A AU3547900A AU3547900A AU 3547900 A AU3547900 A AU 3547900A AU 35479/00 A AU35479/00 A AU 35479/00A AU 3547900 A AU3547900 A AU 3547900A AU 3547900 A AU3547900 A AU 3547900A
- Authority
- AU
- Australia
- Prior art keywords
- zinc
- manganese
- concentration
- bearing material
- occur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000011572 manganese Substances 0.000 title claims description 37
- 239000011701 zinc Substances 0.000 title claims description 30
- 229910052748 manganese Inorganic materials 0.000 title claims description 18
- 229910052725 zinc Inorganic materials 0.000 title claims description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 17
- 239000000463 material Substances 0.000 title claims description 17
- 238000000746 purification Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims 2
- 238000007254 oxidation reaction Methods 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- SPTYHKZRPFATHJ-HYZXJONISA-N dT6 Chemical compound O=C1NC(=O)C(C)=CN1[C@@H]1O[C@H](COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)O[C@@H]2[C@H](O[C@H](C2)N2C(NC(=O)C(C)=C2)=O)CO)[C@@H](O)C1 SPTYHKZRPFATHJ-HYZXJONISA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 1
- 239000004297 potassium metabisulphite Substances 0.000 description 1
- 235000010263 potassium metabisulphite Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/26—Refining solutions containing zinc values, e.g. obtained by leaching zinc ores
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
WO 00/61826 PCT/CA00/00352 PURIFICATION OF ZINC-BEARING MATERIAL SOLUTIONS CONTAINING MANGANESE BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION The present invention relates to the purification of zinc-bearing materials, more particularly but not necessarily exclusively to zinc-bearing aqueous solutions. 2. DESCRIPTION OF THE RELATED ART Some zinc (Zn) ores, for example sphalerite, contain high levels of manganese (Mn) that cannot be separated using conventional mineral processing techniques, since the Mn is present in the crystal lattice. When Zn sulphides containing Mn impurities are roasted and then leached, they can, in some cases, produce leach solutions or electrolyte solutions containing unreasonably high levels of Mn. Although some relatively small amounts of Mn are generally acceptable in a Zn electrolyte, for example, excessive quantities can create problems, since the Mn is oxidized at the anode in the form of MnO 2 , some of which falls at the bottom of the cell and must be periodically removed. Greater concentrations of MnO, can lead to significant reductions in electrolytic efficiency. It is generally known in the prior art that precipitating zinc and manganese together, using sodium carbonate or lime as naturalizing agent, can be carried out at 70 0 C and at pH values between 5 and 7. However, in this case, zinc begins to precipitate before manganese and therefore most of the zinc would be precipitated with manganese which is obviously not acceptable, as shown in figure 1. Another solution proposed by the prior art is to oxidize Mn to Mn 4 so that MnO 2 can be removed by precipitation at a pH where Zn 2 + is soluble. Air and oxygen gas are typically used as oxidants in this case but they are generally uneconomically slow. Peroxide or stronger CIT'TTTTTT cviT TIITT rW 71.
WO 00/61826 PCT/CA00/00352 oxidants, such as Caro's acid or ozone, are in many cases too expensive. US Patent 2,816,819 to Wallis et al. discloses a system which uses S0 2 /Air to precipitate iron from a cobalt- or a nickel-bearing solution. Canadian Patent 935,650 discloses a technique by which a mixture of SO2/Air is used to precipitate a number of impurities from a cobalt or a nickel solution. However, neither reference is concerned with techniques for reducing impurities from Zn-bearing materials. It is an object of the present invention to provide an improved method to remove at least a portion of Mn from Zn-bearing materials. SUMMARY OF THE INVENTION Briefly stated, the invention involves a process for removing at least a portion of a manganese constituent from a zinc-bearing material, comprising the step of subjecting the material to mixture of SO 2 and oxygen, at conditions sufficient to oxidize the manganese constituent. Preferably, the material is maintained at a pH sufficient to precipitate manganese while minimizing precipitation of the zinc constituent. BRIEF DESCRIPTION OF THE DRAWINGS Several preferred embodiments of the present invention will now be described, by way of example only, with reference to the appended drawing in which: Figure 1 is a plot of precipitation for Mn and Zn according to pH; Figure 2 is a plot of precipitation using S0 2 /0 2 mixture as an oxidant; -2 SUBSTTITTi r r'T arTrT - - WO 00/61826 PCT/CA00/00352 DESCRIPTION OF THE PREFERRED EMBODIMENTS Briefly stated, the invention involves a process for removing at least a portion of a manganese constituent from a zinc-bearing material, comprising the step of subjecting the material to mixture of SO 2 and oxygen, at conditions sufficient to oxidize the manganese constituent. Preferably, the material is maintained at a pH sufficient to precipitate manganese while minimizing precipitation of the zinc constituent. Preferably, the process is carried out at a pH between about 3 and about 5, more preferably between 3 and 4. Still more preferably, the pH is 3. If the pH is higher than 5, for example up to 7, at least some residual Zn may be precipitated with the Mn. The higher the pH in this range, the greater the quantity of Zn being precipitated with Mn. In this case, it may be feasible either to process the Mn subsequently with the residual Zn in place or alternatively to subject the co-precipitate to a mildly acidic solution (such as at a pH of 3 to 4) to re-dissolve the residual zinc. The pH limit of 4 is significant because, as the following examples illustrate, residual Zn has been found to appear in the precipitate at a pH value above 4 while there appears to be no Zn co-precipitate at pH values below 4. Therefore, it may be desirable, in some circumstances, to maintain the reaction at the lower end of the pH range, that is in the vicinity of pH 3 in order to minimize the likelihood of a Zn co-precipitate. This route may also be enhanced by maintaining a distribution of nucleation sites in the reaction, such as MnO 2 crystals. The oxygen may be in the form of O2 or air or a mixture of both. Preferably, the process occurs at a temperature ranging from about 40 to about 80 0 C, -3- WO 00/61826 PCT/CA00/00352 more preferably at a temperature ranging from 50 to 80 0 C, still more preferably at a temperature ranging from 58 to 78 0 C. For example, the process may be carried out at about 70 0 C or, alternatively, at about 60 0 C. It may also be desirable, in some cases, to raise the temperature above 80 0 C, for example to an upper limit of about 130 0 C or higher in order to increase the reaction kinetics of the process, though this would need to be done under pressure, depending on the chosen temperature. For example, a temperature of 130 0 C would require a pressure of about 50 psi. Preferably, in the case where the oxygen is present in the form of 02 gas, the SO 2 is at a concentration from about 0.5% to 10%, with the balance 02 gas, more preferably from 1 to 8%, still more preferably at a concentration from 2 to 3%. In the case where the oxygen is present in air, the SO 2 is preferably at a concentration ranging from about 0.1% to 2%, with the balance being Air, more preferably from about 0.2 to 1.4%, still more preferably from about 0.4 to 0.6%. For example, the concentration may be about 0.5%. The zinc material may be in a number of forms including an aqueous solution, such as a leach solution or an electrolyte solution. The present process is beneficial in that it makes use of a relatively inexpensive and plentiful oxidant, a gas mixture of 2 Oz/SO2, or alternatively Air/SO 2 , or still alternatively 100% pure Air can be used together with equivalent amounts of SO 2 , preferably added as SO 2 in a gaseous or liquid form, or added as a constituent in a solution containing, for example, sodium metabisulphite, ammonium metabisulphite, potassium metabisulphite or other suitable forms of metabisulphite. Embodiments of the present invention will be described with reference to the following -4- WO 00/61826 PCT/CA00/00352 Examples which are presented for illustrative purposes only and are not intended to limit the scope of the invention. EXAMPLE 1 A solution containing 5 g/L Mn as MnSO 4 was sparged with a mixture of SO 2 and 02 at different pH levels. The amount of Mn removed at each pH is shown in figure 2. A comparison can be made between the precipitation of pH's of manganese oxidized with S0 2 /0 2 as shown in figure 2 with the precipitation of zinc as shown in figure 1. The Mn is removed from solution at pH levels ranging from about 3 to 5. However, in the region from about 3 to 4, the Mn is removed from solution while the Zn is soluble and therefore remains in solution. EXAMPLE 2 A solution containing 18 g/L Mn as MnSO 4 was sparged at 60 0 C and at a pH of 6.5 with
SO
2 /0 2 mixtures containing 2% (v/v) SO2. After one hour, 25% of the manganese had precipitated. After 2 hours, 57% of the Mn had precipitated and after 4 hours, 99.5% of the Mn had precipitated. -5-
Claims (20)
1. A process for removing at least a portion of a manganese constituent from a zinc-bearing material, comprising the step of subjecting said material to a first oxidation mixture of SO2 and oxygen, at conditions sufficient to oxidize said manganese constituent.
2. A process as defined in claim 1 wherein the material is maintained at a pH sufficient to precipitate manganese while minimizing precipitation of said zinc constituent.
3. A process as defined in claim 2 wherein said pH is between about 3 and about 5.
4. A process as defined in claim 3 wherein said pH is between 3 and 4.
5. A process as defined in claim 4 wherein said pH is 3.
6. A process as defined in claim 1 wherein said oxygen is in the form of 02.
7. A process as defined in claim 6 wherein said oxidation mixture includes Air.
8. A process as defined in claim 7 wherein steps (a) and (c) occur at a temperature ranging from about 40 to about 80 0 C.
9. A process as defined in claim 8 wherein steps (a) and (c) occur at a temperature ranging from 50 to 800C.
10. A process as defined in claim 9 wherein steps (a) and (c) occur at a temperature ranging from 58 to 78 0 C.
11. A process as defined in claim 10 wherein steps (a) and (c) occur at about 70 0 C. -6- WO 00/61826 PCT/CA00/00352
12. A process as defined in claim 10 wherein steps (a) and (c) occur at about 60 0 C.
13. A process as defined in claim 6 wherein said SO 2 is at a concentration from 0.5% to 10%, with the balance 02 gas.
14. A process as defined in claim 13 wherein said SO 2 is at a concentration from 1 to 8%.
15. A process as defined in claim 14 wherein SO 2 is at a concentration from 2 to 3%.
16. A process as defined in claim 7 wherein SO2 is at a concentration from 0.1% to 2%, with the balance being Air.
17. A process as defined in claim 16 wherein said SO2 is at a concentration from 0.2 to 1.4%.
18. A process as defined in claim 17 wherein SO 2 is at a concentration from 0.4 to 0.6%.
19. A process as defined in claim I wherein said zinc bearing material is a leach solution.
20. A process as defined in claim 1 wherein said zinc material is an electrolyte solution. -7-
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2268496 | 1999-04-09 | ||
| CA002268496A CA2268496A1 (en) | 1999-04-09 | 1999-04-09 | Purification of zinc materials |
| PCT/CA2000/000352 WO2000061826A1 (en) | 1999-04-09 | 2000-04-05 | Purification of zinc-bearing material solutions containing manganese |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU3547900A true AU3547900A (en) | 2000-11-14 |
Family
ID=4163451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU35479/00A Abandoned AU3547900A (en) | 1999-04-09 | 2000-04-05 | Purification of zinc-bearing material solutions containing manganese |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20020083795A1 (en) |
| AU (1) | AU3547900A (en) |
| CA (1) | CA2268496A1 (en) |
| WO (1) | WO2000061826A1 (en) |
| ZA (1) | ZA200109183B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU776311B2 (en) * | 1999-12-23 | 2004-09-02 | Mcgill University | Method to control manganese in zinc leach circuits |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040040460A (en) * | 2001-09-13 | 2004-05-12 | 인텍 엘티디 | Zinc recovery process |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2816819A (en) * | 1949-09-07 | 1957-12-17 | Int Nickel Co | Process of removing ferrous sulfate from sulfate solutions containing nickel and/or cobalt |
| CA935650A (en) * | 1968-12-03 | 1973-10-23 | Kniprath Elmar | Redox precipitation of non-ferrous heavy metals from aqueous solutions |
| US4067789A (en) * | 1975-07-09 | 1978-01-10 | Newmont Exploration Limited | Process for manganese removal from zinc metal bearing solutions |
| CA1141172A (en) * | 1978-12-20 | 1983-02-15 | Gerald L. Bolton | Removal of manganese ions from zinc and manganese containing solutions |
| SU947055A1 (en) * | 1981-02-06 | 1982-07-30 | Всесоюзный Ордена Трудового Красного Знамени Научно-Исследовательский Горнометаллургический Институт Цветных Металлов | Method for purifying zinc electrolyte from impurities |
| US4439288A (en) * | 1983-07-11 | 1984-03-27 | Exxon Research & Engineering Company | Process for reducing Zn consumption in zinc electrolyte purification |
| SU1411348A1 (en) * | 1986-10-08 | 1988-07-23 | Северо-Кавказский горно-металлургический институт | Method of cleaning zinc solutions of iron (ii) and manganese (ii) |
-
1999
- 1999-04-09 CA CA002268496A patent/CA2268496A1/en not_active Abandoned
-
2000
- 2000-04-05 WO PCT/CA2000/000352 patent/WO2000061826A1/en active Application Filing
- 2000-04-05 AU AU35479/00A patent/AU3547900A/en not_active Abandoned
-
2001
- 2001-10-09 US US09/977,917 patent/US20020083795A1/en not_active Abandoned
- 2001-11-07 ZA ZA200109183A patent/ZA200109183B/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU776311B2 (en) * | 1999-12-23 | 2004-09-02 | Mcgill University | Method to control manganese in zinc leach circuits |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000061826A1 (en) | 2000-10-19 |
| US20020083795A1 (en) | 2002-07-04 |
| ZA200109183B (en) | 2002-07-31 |
| CA2268496A1 (en) | 2000-10-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK1 | Application lapsed section 142(2)(a) - no request for examination in relevant period |