AU2002308793B2 - Dissolution Method of Co Precipitate with Acid - Google Patents
Dissolution Method of Co Precipitate with Acid Download PDFInfo
- Publication number
- AU2002308793B2 AU2002308793B2 AU2002308793A AU2002308793A AU2002308793B2 AU 2002308793 B2 AU2002308793 B2 AU 2002308793B2 AU 2002308793 A AU2002308793 A AU 2002308793A AU 2002308793 A AU2002308793 A AU 2002308793A AU 2002308793 B2 AU2002308793 B2 AU 2002308793B2
- Authority
- AU
- Australia
- Prior art keywords
- precipitate
- processing solution
- range
- acid
- solution
- 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.)
- Ceased
Links
- 239000002244 precipitate Substances 0.000 title claims description 31
- 239000002253 acid Substances 0.000 title claims description 9
- 238000011978 dissolution method Methods 0.000 title claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000004679 hydroxides Chemical class 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 14
- 239000010941 cobalt Substances 0.000 description 14
- 238000002386 leaching Methods 0.000 description 12
- 238000000638 solvent extraction Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Description
.0 S&F Ref: 617954
AUSTRALIA
PATENTS ACT 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT
ORIGINAL
Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: Sumitomo Metal Mining Co., Ltd.
11-3, Shimbashi 5-chome, Minato-ku Tokyo Japan Isao Nishikawa, Kazuyuki Takaishi, Nobumasa Kemori Spruson Ferguson St Martins Tower,Level 31 Market Street Sydney NSW 2000 (CCN 3710000177) Dissolution Method of Co Precipitate with Acid The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5845c 1 Title of the Invention Dissolution Method of Co Precipitate with Acid Background of the Invention Field of the Invention This invention relates to a dissolution method of dissolving Co precipitate, mainly comprised of Co and Fe hydroxides, with acid in nickel and cobalt refining.
Description of the Related Art Generally, in nickel refining, nickel matte having concentrated Ni is obtained from raw ore, and the metallic components such as Ni, Co and Fe are leached from this matte ;o into a leaching liquid, then Co and Fe are removed as hydroxides from the obtained leaching liquid by an oxidation-neutralization method, and nickel is produced as pure nickel solution by electrolytic refining.
The Co precipitate mainly comprised of Co and Fe hydroxides that are removed by an oxidation-neutralization method from the leaching liquid is dissolved in sulfuric acid or hydrochloric acid, and then the obtained solution is used as the raw material for electrolytic cobalt or cobalt chemical products.
Recently, a solvent extraction method is widely used in the separation and refinement of cobalt from this solution, however, much of the organic solvent used industrially extracts Fe easier than Co. Accordingly, when processing the solution as is in the solvent extraction process, there is a problem occurring such as insufficient Co extract, the cobalt being the target metal, or having Fe concentrated in the organic solvent.
Therefore, as shown in Fig. 4, normally there is an Fe removal process performed in the stage before the solvent extraction process, to remove the Fe from the solution by an oxidation-neutralization method.
As described above, the Fe removal process is indispensable in the stage before the solvent extraction process for separating and refining Co from the solution of Co precipitate. However, the amount of necessary equipment increases when setting up the Fe removal process. In addition, a neutralizing agent is necessary for removing Fe by the oxidation-neutralization method, so this brings about an increase in the cost of equipment as well as in operating costs.
Summary of the Invention In order to solve the problems described above, an object of this invention is to provide a method of processing the Co precipitate solution directly in the solvent extraction process without using the Fe removal process.
[R:ALIBFF] 1083 3speci.doc:njc O 2 O Brief Description of the Drawings Fig. 1 is a flowchart to show a selective solvent extraction process for cobalt Sprecipitate solution with pH adjusted according to the present invention.
0Fig. 2 is a graph to show a relationship between a dissolution pH and Fe concentration in a cobalt precipitate solution.
Fig. 3 is a graph to show a change in Co leaching ratio in a cobalt precipitate solution.
00 Fig. 4 is a flowchart to show the conventional process of cobalt solvent extraction Mc, for cobalt precipitation solution including a Fe-removal step.
N1 0 Description of the Preferred Embodiments SIn the dissolution processing method of this invention for Co precipitate, Co precipitate containing at least Co and Fe hydroxides is dissolved by acid, wherein the pH of the processing solution is kept in the range between 0.5 and 2.0, and wherein the Co is dissolved by the processing solution together with the Fe, after which the pH of the is processing solution is raised to the range between 2.0 and 3.0 to deposit the Fe first into a precipitate.
That is, it is desirable that the pH of the processing solution is once kept in the range between 0.5 and 2.0 by adding sulfuric acid (plus reducing agent) or hydrochloric acid, and then after Fe and Co have been dissolved into the processing solution, Co precipitate, Co carbonate or Ni carbonate is added to raise the pH of the processing solution to the range between 2.0 and 3.0, to deposit the Fe in a precipitate. In this disclosure, the terms 'Dissolve' and 'Deposit' will be for the all or part of the Fe or Co depending on conditions. With the process described above, Fe is, in effect, left remaining in the precipitate in a solid state, and part or substantially all of the Co is dissolved in the processing solution.
The Co and Fe in the Co precipitate exist as trivalent hydroxides. The reactions for dissolving these hydroxides are given in Equations 1 and 2.
Equation 1: 2Co (OH) 3 6H 2e 2Co 2 6H 2 0 Equation 2: Fe (OH) 3 3H Fe 3 3H 2 0 From these equations it can be seen that for Co it is possible to dissolve its hydroxide by lowering the pH and combining the equation with a reductive reaction, on the other hand, for Fe, it is possible to control its dissolution by exactly adjusting the pH.
[R:\A1113FF] 10833speci.doc:njc INO 3 0 0Also, to adjust the pH, it is possible to use hydrochloric acid or sulfuric acid as a pH regulator. However, when sulfuric acid is used as a pH regulator, a reducing agent such Sas S02 gas or sodium sulfite must be added to cause the Co dissolution reaction to 00 progress. On the other hand, when hydrochloric acid is used as the pH regulator, chlorine ions are oxidized to be chlorine gas, so there is no need to add a reducing agent.
It is difficult to fix the Fe in the Co precipitate only by adding acid to simply lower C0\ the pH, because Fe is dissolved together with the Co. Therefore, the pH is lowered once 00 in the range from 0.5 to 2.0, and after the Co and Fe are dissolved, the pH is adjusted
O
C again using cobalt carbonate, nickel carbonate or Co precipitate in the range from 2.0 to io 3.0. In doing this, the Co remains dissolved and the Fe is re-deposited. Utilizing the C difference in the stability of Fe and Co hydroxides in this way is effective in preferentially precipitating Fe first. The ratio of leaching the cobalt does not become high even when the pH is kept between 2.0 and 3.0 without the need to lower it once to between 0.5 and The reactions above are given by Equations 3 to 6.
Equation 3:
M
3 3CoCO 3 3H M (OH) 3 3CO 2 3Co 2 Equation 4: M 3NiCO 3 3H+ M(OH) 3 3C0 2 3Ni 2 Equation
M
3 3Ni (OH) 2 3H M (OH) 3 3Ni 2 3H 2 0 Equation 6:
M
2 Ni (OH) 3
M(OH)
3 Ni 2 Equation 3 shows the case of adjusting the pH with cobalt carbonate, Equation 4 shows the case of adjusting the pH with nickel carbonate, and Equations 5 and 6 shows the case of adjusting the pH with Co precipitate. In all of the equations, M is Fe or Co.
Using Co precipitate itself as the pH regulator has the objective of lowering the operating cost when compared to a method of adding new chemicals for regulating the pH. However, in this case, as shown in Equation 5 and Equation 6, it is necessary to include Ni divalent hydroxide and/or Ni trivalent hydroxide in the Co precipitate.
The nickel ions that are leached into the solution can be separated from cobalt in a solvent extraction process.
[Rl:\1131F]10833speci.doc:tnjc Example Co precipitate was made into a 400g/L repulped slurry and hydrochloric acid was added to the slurry to adjust the pH. The Fe concentration in the slurry or solution is shown in Fig. 2 (plot Also, the leaching ratio of Co is shown in Fig. 3 (plot 0).
Also, Fig. 2 shows the change in Fe concentration of the slurry or solution when the pH was raised with Co precipitate (Co-ppt) after lowering the pH to 1.5 once (plot Moreover, Fig. 3 shows the change in the Co leaching ratio (plot L shows the measurement results, and the dotted line represents the tendency of the change).
Furthermore, Fig. 2 shows the change in Fe concentration of the slurry or solution io when the pH was raised with nickel carbonate (NiCO 3 after lowering the pH to 1.5 once (plot Moreover, Fig. 3 shows the change in the Co leaching ratio (plot A shows the measurement results, and the dotted line represents the tendency of the change).
As can be seen in Fig. 2, by adjusting the pH to 2.0 or higher, the Fe concentration becomes O.lg/L or less. Furthermore, by adjusting the pH to 2.5 or higher, the Fe concentration becomes O.1g/L or less. In this way, no matter what pH adjustment is performed, the Fe concentration takes a value that depends mainly on the pH, and it is seen that nearly all of the Fe is fixed in the precipitate.
However, it was not possible to obtain a sufficient dissolution rate in the pH range of 2.0 to 3.0 only by adjusting the pH in this pH range by just adding acid, as it can be seen in Fig. 3 that the Co leaching ratio is about 20% at a pH of 2.0, and 5% or less at a pH of On the other hand, when the pH was adjusted in the range from 2.0 to 3.0 using Co precipitate (Co-ppt) after lowering the pH once in the range from 0.5 to 2.0 (plot the Co leaching ratio was about 50% at a pH of Also, when the pH was adjusted to be in the range from 2.0 to 3.0 using nickel carbonate (NiCO 3 after lowering the pH once in the range from 0.5 to 2.0 (plot the Co leaching ratio was about 90% at pH of 2.5. In comparison with the case of simply adding hydrochloric acid to adjust the pH to 2.5, a very good Co leaching ratio was obtained.
With the method of this invention, it becomes possible to easily remove Fe from a solution in which Co precipitate is dissolved, and thus it is possible to economically produce electrolytic Cobalt and Cobalt chemicals.
[R:LIBFF] 10833 speci.doc:njc
Claims (2)
1. A dissolution method for Co precipitate containing at least Co and Fe Shydroxides, comprising the step of dissolving the Co precipitate with acid to form a 00 processing solution, wherein the pH of the processing solution is kept in the range between 0.5 and 2.0, so that Fe and Co are dissolved into the processing solution, and then the pH of the processing solution is raised to the range between 2.0 and 3.0 to C deposit the Fe. 00
2. A dissolution method for Co precipitate containing at least Co and Fe Mc, hydroxides according to claim 1, comprising the step of dissolving the Co precipitate with o0 acid to form a processing solution, wherein the pH of processing solution is kept in the C range between 0.5 and 2.0 by adding sulfuric acid plus a reducing agent or by adding hydrochloric acid, so that Fe and Co are dissolved into the processing solution, and then one member selected from the group of Co precipitate, Co carbonate and Ni carbonate is added to raise the pH of the processing solution to the range between 2.0 and 3.0 to is deposit the Fe. Dated 2 March, 2006 Sumitomo Metal Mining Co., Ltd. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON [R:\1,13H 1I 833speci.cioc:njc
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-364006 | 2001-11-29 | ||
| JP2001364006A JP4035985B2 (en) | 2001-11-29 | 2001-11-29 | Method for dissolving Co precipitate with acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2002308793A1 AU2002308793A1 (en) | 2003-06-12 |
| AU2002308793B2 true AU2002308793B2 (en) | 2007-10-04 |
Family
ID=19174254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2002308793A Ceased AU2002308793B2 (en) | 2001-11-29 | 2002-11-28 | Dissolution Method of Co Precipitate with Acid |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4035985B2 (en) |
| AU (1) | AU2002308793B2 (en) |
| CA (1) | CA2413207C (en) |
| GB (1) | GB2382573B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826523A (en) * | 2020-06-28 | 2020-10-27 | 广东邦普循环科技有限公司 | Method for refining nickel cobalt hydroxide |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6760793B2 (en) * | 2016-08-03 | 2020-09-23 | Ｊｘ金属株式会社 | How to recover valuable metals from cobalt / tungsten raw materials |
| CN107881341A (en) * | 2017-12-08 | 2018-04-06 | 上海产业技术研究院 | Method of comprehensive utilization based on hydrometallurgical processes middle and high concentration sodium sulfate wastewater |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1332830A1 (en) * | 1985-07-23 | 1992-08-07 | Государственный проектный и научно-исследовательский институт "Гипроникель" | Method of ferrocobaltic hydrate cakes |
| RU2041276C1 (en) * | 1988-11-30 | 1995-08-09 | Институт металлофизики АН Украины | Cobalt cake reprocessing method |
| JP2000234130A (en) * | 1999-02-12 | 2000-08-29 | Taiheiyo Kinzoku Kk | Method for recovering valuable metals from oxide ore |
-
2001
- 2001-11-29 JP JP2001364006A patent/JP4035985B2/en not_active Expired - Fee Related
-
2002
- 2002-11-28 GB GB0227732A patent/GB2382573B/en not_active Expired - Fee Related
- 2002-11-28 AU AU2002308793A patent/AU2002308793B2/en not_active Ceased
- 2002-11-28 CA CA2413207A patent/CA2413207C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1332830A1 (en) * | 1985-07-23 | 1992-08-07 | Государственный проектный и научно-исследовательский институт "Гипроникель" | Method of ferrocobaltic hydrate cakes |
| RU2041276C1 (en) * | 1988-11-30 | 1995-08-09 | Институт металлофизики АН Украины | Cobalt cake reprocessing method |
| JP2000234130A (en) * | 1999-02-12 | 2000-08-29 | Taiheiyo Kinzoku Kk | Method for recovering valuable metals from oxide ore |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111826523A (en) * | 2020-06-28 | 2020-10-27 | 广东邦普循环科技有限公司 | Method for refining nickel cobalt hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2003166022A (en) | 2003-06-13 |
| JP4035985B2 (en) | 2008-01-23 |
| GB2382573A (en) | 2003-06-04 |
| GB0227732D0 (en) | 2003-01-08 |
| GB2382573B (en) | 2005-09-14 |
| CA2413207C (en) | 2010-07-27 |
| CA2413207A1 (en) | 2003-05-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) | ||
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |