EP2528704B1 - Method and arrangement for producing metal powder - Google Patents
Method and arrangement for producing metal powder Download PDFInfo
- Publication number
- EP2528704B1 EP2528704B1 EP11736667.4A EP11736667A EP2528704B1 EP 2528704 B1 EP2528704 B1 EP 2528704B1 EP 11736667 A EP11736667 A EP 11736667A EP 2528704 B1 EP2528704 B1 EP 2528704B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- metal
- anolyte
- electrolytic cell
- catholyte
- 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.)
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- 229910052751 metal Inorganic materials 0.000 title claims description 209
- 239000002184 metal Substances 0.000 title claims description 209
- 238000000034 method Methods 0.000 title claims description 95
- 239000000843 powder Substances 0.000 title claims description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- 238000001556 precipitation Methods 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 32
- 229910052802 copper Inorganic materials 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000002028 premature Effects 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052713 technetium Inorganic materials 0.000 claims description 2
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 164
- 230000008569 process Effects 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000005406 washing Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 Cu2+ cations Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 6
- 230000002706 hydrostatic effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000002301 combined effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000003134 recirculating effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Definitions
- the metal received as the end product of the manufacturing process would be obtained in some other form than as a uniform solid object, such as a cathode plate.
- a uniform solid object such as a cathode plate.
- Particularly methods where the end product is obtained as pure metal powder would be extremely useful.
- the arrangement according to the invention is an arrangement for producing metal powder by precipitating yield metal powder by mixing dissolved yield metal powder with a solution containing at least one intermediary metal.
- the arrangement according to the invention comprises an electrolytic cell for dissolving the yield metal located on the anode side of the electrolytic cell and for oxidizing it in the anolyte, and for reducing, on the cathode side, the dissolved intermediary metal located on the cathode side of the electrolytic cell; a precipitation chamber arranged essentially separately from the electrolytic cell; as well as means for feeding anolyte solution and cathode solution respectively from the anode side and the cathode side of the electrolytic cell to the precipitation chamber for mixing the oxidized yield metal that is dissolved in the anolyte, and the cathode solution containing reduced intermediary metal, outside the electrolytic cell.
- a correct mixing ratio With a correct mixing ratio and an effective precipitate recovery, the creation of yield metal agglomerates can be prevented in the precipitation step, and consequently the homogeneity of the yield metal particles contained in the powder is enabled with respect to their size.
- a correct mixing ratio also facilitates a process with a better efficiency, which can be utilized for reducing the amount of energy needed in the process for producing a certain quantity of yield metal mass.
- the first part of the starting solution contains intermediary metal for boosting the dissolution of yield metal on the anode side.
- the first part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to anolyte.
- the first part of the starting solution is composed of the first part of the circulating solution.
- the second part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to catholyte.
- the second part of the starting solution is composed of the second part of the circulating solution.
- the purpose of the diaphragm is to mechanically separate the solutions located on different sides of the diaphragm, i.e. to serve as a mechanical obstacle, while at the same time being electroconductive to that extent that the electrolytic cell is capable of functioning effectively.
- This diaphragm divides the electrolytic cell to an anode part (or anode side), where the anolyte is located, and to a cathode part (or cathode side), where the catholyte is located.
- the anolyte and the catholyte cannot be mixed together without disturbing the anode and cathode reactions, and metal powder cannot be formed in the vicinity of those electrodes in the electrolytic cell.
- the kinetics in the dissolution step are rapid, as the quantity of yield metal dissolved in the anolyte is directly proportional to the charge that has flown through the anode.
- the quantity of yield metal that is dissolved in the anolyte can be efficiently and accurately controlled, which facilitates a more precise control of the process dynamics, and an improvement in reliability.
- the starting solution contains sulfuric acid. Further, in an embodiment of the invention the sulfuric acid content in the starting solution is at least 50 g/l and preferably within the range 50 g/l - 1,500 g/l. In an embodiment of the invention, the starting solution contains hydrochloric acid or nitric acid. Further, in an embodiment of the invention the hydrochloric acid content in the starting solution is within the range 15 g/l - 500 g/l. Yet in an embodiment of the invention the starting solution contains, in addition to hydrochloric acid, also alkaline chloride, the content of which in the starting solution is within the range 15 g/l - 500 g/l.
- a suitable acid, and content for said acid must be chosen so that the yield metal is dissolved from the supply material to the anolyte, instead of the oxidation of the intermediary metal. Therefore the anolyte pH (i.e. oxygen content) must be suitable.
- the oxygen content must be as high as possible.
- the part that is fed as the anolyte may contain intermediary metal in its high potential value.
- the starting solution may contain two or even several different intermediary metals.
- the first and second part of the starting solution are identical in composition.
- vanadium when the yield metal is copper and the intermediary metal is vanadium, vanadium may be oxidized on the anode side 6 into an intermediary oxidation state V 5+ , which is even higher than the V 3+ state, whereafter the V 5+ reacts with copper, thus oxidizing and dissolving copper. Now the "over-oxidized” vanadium V 5+ is reduced back to its original high-potential value V 3+ . On the anode side 6, a corresponding "overoxidation" to an intermediate oxidation state is also possible with other intermediary metals than vanadium.
- the efficiency and reliability of the process it is useful to ensure that any remarkable amounts of V 2+ and/or Cu 2+ cations are not left in the circulating solution.
- the real mixing ratio of anolyte and catholyte can be 1:N, where N > 2.
- the value of the parameter N also depends on how the circulating solution is cleaned before feeding it back to the electrolytic cell.
- the finding of a suitable mixing ratio is obvious routine testing for a man skilled in the art.
- the solid yield metal powder 14 separated from the solution is finished ( Figure 1 , step S6) in a finish treatment arrangement.
- the separation and finish treatment processes can include many different steps, depending on the desired properties of the end product.
- the yield metal powder 14 separated from the circulation electrolyte is washed in water for minimizing impurities carried along from the solution, whereafter the yield metal powder 14 is dried and coated with a passivation layer for preventing an oxidation of the powder, among others.
Description
- The invention relates to the production of finely divided metal powder. In particular, the invention relates to a dissolution-precipitation method and arrangement for producing metal powder.
- Generally the end product in many metal manufacturing processes is a plate-like object in cathode form. This kind of end product is obtained for example by means of pyrometallurgical production routes utilizing electrolysis. In these methods, a metal anode that is pyrometallurgically made of a concentrate is electrolytically refined to cathode copper, which can for example be cast into products with various different forms. These types of methods can be used for producing copper, nickel or cobalt products, among others.
- However, in the production of metals, in many cases it would be advantageous for instance with respect to further processing, if the metal received as the end product of the manufacturing process would be obtained in some other form than as a uniform solid object, such as a cathode plate. Particularly methods where the end product is obtained as pure metal powder would be extremely useful.
- In the patent application
JP2002327289 - The patent publication
US2005/0023151 introduces a method where copper powder is made by electrolytically precipitating copper from copper sulfate on a cathode. The method makes use of a ferrous/ferric anode reaction, by which the energy consumption of the method is reduced. Said publication also describes a through-flow arrangement where the precipitated copper powder is recovered from the electrodes by means of an electrolyte flowing through the electrodes. A drawback with the method and arrangement illustrated in the publicationUS2005/0023151 is, among others, an unreliable recovery of copper from the cathodes, owing for example to the precipitation of copper in various different locations in the chamber containing electrodes, and to the attachment of copper on the cathode. Owing to the above mentioned drawbacks, among others, it is difficult to control the grain size of copper powder and of the morphology of copper particles, as well to achieve a homogeneous quality with separate electrodes. In addition, the precipitation of copper directly onto the cathode also depends on the cathode material and on the surface morphology, which in part increases the unreliability of the method. - The patent application
WO2008/017731 introduces a method for manufacturing metal powder. In this method, valuable metal powder is precipitated by reducing the valuable metal dissolved in the method by means of another metal. In said method, also the dissolution of precious metal takes place in a reaction with said other metal, which weakens the control of the process kinetics as well as the efficiency thereof, and makes the method and the arrangement used therein fairly complicated. - Further, document
US2005/067299 discloses an electrolytic method in diaphragm-type cell; documentEP1552896 discloses a method for producing fine metal powder; documentJP2003328198 EP0221685 discloses an electrolytic process for the manufacture of salts; andUS5882502 discloses an electrochemical system and method. - The object of the invention is to eliminate above mentioned drawbacks of the prior art and to set forth a new method and arrangement for manufacturing metal powder in a solution-precipitation method making use of electrolysis.
- The method according to the invention is characterized by what is set forth in the independent claim 1.
- The arrangement according to the invention is characterized by what is set forth in the
independent claim 15. - In the method according to the invention for manufacturing metal powder, dissolved yield metal is mixed with a solution containing at least one intermediary metal for precipitating the dissolved yield metal into a yield metal powder. In the method, a first part of an acid-containing starting solution is brought to the anode side of the electrolytic cell as an anolyte, to be in contact with the anode and the supply material containing yield metal, and a second part of the acid-containing starting solution, which also contains intermediary metal in addition to acid, is brought to the cathode side of the electrolytic cell, as a catholyte to be in contact with the cathode; the yield metal is oxidized and dissolved in the anolyte by conducting electric current to the anode; the intermediary metal contained in the second part of the starting solution is reduced on the cathode side; and anolyte solution and catholyte solution are brought into a precipitation chamber for mixing the oxidized yield metal dissolved in the first part of the starting solution and the second part of the starting solution containing reduced intermediary metal.
- The arrangement according to the invention is an arrangement for producing metal powder by precipitating yield metal powder by mixing dissolved yield metal powder with a solution containing at least one intermediary metal. The arrangement according to the invention comprises an electrolytic cell for dissolving the yield metal located on the anode side of the electrolytic cell and for oxidizing it in the anolyte, and for reducing, on the cathode side, the dissolved intermediary metal located on the cathode side of the electrolytic cell; a precipitation chamber arranged essentially separately from the electrolytic cell; as well as means for feeding anolyte solution and cathode solution respectively from the anode side and the cathode side of the electrolytic cell to the precipitation chamber for mixing the oxidized yield metal that is dissolved in the anolyte, and the cathode solution containing reduced intermediary metal, outside the electrolytic cell.
- Among the advantages of the invention, let us point out for example good controllability of the particle size of the precipitating yield metal powder, which is made possible particularly by the feeding of the anolyte solution and cathode solution, to be mixed together, in a separate precipitation chamber, in which case the mixing ratio of said solutions can be controlled easily and accurately, as well as optimized according to the process conditions. Moreover, when the precipitation step takes place in a separate precipitation chamber, away from the vicinity of the electrodes, the effect of the electrodes in the precipitation process and in collecting the precipitate can be minimized, so that the reliability of the process is improved. Also the recovery of the yield metal precipitate becomes easier and more reliable. With a correct mixing ratio and an effective precipitate recovery, the creation of yield metal agglomerates can be prevented in the precipitation step, and consequently the homogeneity of the yield metal particles contained in the powder is enabled with respect to their size. A correct mixing ratio also facilitates a process with a better efficiency, which can be utilized for reducing the amount of energy needed in the process for producing a certain quantity of yield metal mass.
- Unless otherwise stated, in the present document the expressions "anode side" and "cathode side" refer to those parts of the electrolytic cell that contain anolyte or catholyte in the vicinity of the anode or cathode, respectively. The "anode side" or the "cathode side" need not be a uniform part of the electrolytic cell, but the "anode side" or the "cathode side" may consist of several mutually separate elements comprising an anode or a cathode and anolyte or catholyte, respectively.
- Unless otherwise stated, in the present document the expression "diaphragm" refers to any suitable film or thin mechanical obstacle, such as a membrane, an industrial textile or the like.
- Unless otherwise stated, in the present document the expression "oxidation state", "oxidation level" or a corresponding expression refers to a charge level where an atom appears alone or apparently in a molecule. Thus the expressions "oxidation state", "oxidation level" or a corresponding expression can also refer to the apparent charge of an atom.
- In an embodiment of the invention, the first part of the starting solution contains intermediary metal for boosting the dissolution of yield metal on the anode side. The first part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to anolyte. The first part of the starting solution is composed of the first part of the circulating solution. The second part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned to catholyte. The second part of the starting solution is composed of the second part of the circulating solution. Moreover, in an embodiment of the invention, the circulating solution is returned essentially completely back to electrolyte, in which case the circulating solution is essentially composed of the first part of the circulating solution and of the second part of the circulating solution. When an anolyte solution that is formed of the first part of the starting solution and a catholyte solution that is formed of the second part of the starting solution are mixed together, there is created yield metal powder as the yield metal that was oxidized and dissolved in the anolyte is reduced, and the intermediary metal that was reduced in the catholyte is oxidized. The obtained circulating solution is recirculated in an arrangement to be used in the process in one of the embodiments of the invention, so that the circulating solution is partly or completely, after the mixing step and after the yield metal precipitate is separated from the solution, returned back to anolyte and/or catholyte. Now the intermediary metal is again reduced in the catholyte. Thus it is possible to realize an electrolytic regeneration of the intermediary metal in the catholyte, which means that in some embodiments of the invention, it is essentially not necessary to feed in the process new solution containing intermediary metal. In addition, when also the anolyte in some embodiments of the invention contains intermediary metal, said intermediary metal intensifies the dissolution of the yield metal in such process conditions, for example with relatively low acid contents, where dissolution with the combined effect of electric current and acid solution would not be efficient.
- In an embodiment of the invention, the anolyte and the catholyte are mechanically separated by an electroconductive diaphragm. In an embodiment of the invention, the electrolytic cell comprises an electroconductive diaphragm provided in between the anode side and the cathode side of the electrolytic cell for mechanically separating the anode side and the cathode side.
- Further, in an embodiment of the invention, an electroconductive separator solution is conducted in between the two diaphragms separating the anolyte and the catholyte in order to prevent a premature mixing of the anolyte and the catholyte. In an embodiment of the invention, the electrolytic cell comprises two electroconductive diaphragms provided in between the anode side and the cathode side of the electrolytic cell for mechanically separating the anode side and the cathode side by means of an electroconductive separator solution placed in the space between the two diaphragms.
- In order to efficiently separate the precipitation step from the electrolytic cell and to realize this step in a controlled fashion and essentially completely in a separate precipitation chamber, the anolyte and the catholyte can in an embodiment of the invention be separated by means of an electroconductive diaphragm. In this document, the term "electroconductive diaphragm" refers to a diaphragm that is electroconductive to such extent that the diaphragm facilitates an effective operation of the electrolytic cell. However, in some embodiments of the invention, the electroconductivity of the diaphragm may be lower than the electroconductivity of those solutions that are mechanically separated by the diaphragm. Consequently, the purpose of the diaphragm is to mechanically separate the solutions located on different sides of the diaphragm, i.e. to serve as a mechanical obstacle, while at the same time being electroconductive to that extent that the electrolytic cell is capable of functioning effectively. This diaphragm divides the electrolytic cell to an anode part (or anode side), where the anolyte is located, and to a cathode part (or cathode side), where the catholyte is located. Thus the anolyte and the catholyte cannot be mixed together without disturbing the anode and cathode reactions, and metal powder cannot be formed in the vicinity of those electrodes in the electrolytic cell. For further intensifying the separation of the anode and the cathode, it is possible to use in between the anode side and the cathode side two partition diaphragms, and a separator solution can be fed in between said diaphragms.
- In an embodiment of the invention, the yield metal is copper. In an embodiment of the invention, the yield metal is selected among the following group: nickel, cobalt, zinc, silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, zirconium, tin, cadmium and indium.
- In an embodiment of the invention, the intermediary metal is vanadium. Further, in an embodiment of the invention, the intermediary metal is selected among the following group: titanium, chromium and iron. Further, in an embodiment of the invention, the intermediary metal is selected among the following group: manganese, zirconium, molybdenum, technetium, tungsten, quicksilver, germanium, arsenic, selenium, tin, antimony, tellurium and copper. In the various embodiments of the invention, the yield metals and intermediary metals can be selected among a group that depends on various different process parameters, particularly on the pH value of the electrolyte (i.e. on the oxygen content). On the basis of this description of the invention, a man skilled in the art is capable of finding in the above enlisted groups a suitable intermediary metal for a certain yield metal by means of routine testing. In particular, it has been found out that for example copper powder can be efficiently and reliably produced in an embodiment of the invention, when the selected intermediary metal is vanadium.
- In an embodiment of the invention, the supply material containing yield metal is placed in the anode. Further, in an embodiment of the invention, the yield metal located on the anode side of the electrolytic cell is placed in the anode of the electrolytic cell. When the supply material containing yield metal is placed in the anode, the rate per unit of time of the electric current passing through the yield metal, and consequently also the mass of the dissolving yield metal per unit of time, can be efficiently controlled. The advantage of this embodiment is a particularly precise control of the dissolving reaction by means of electricity; yield metal is dissolved accurately according to the used quantity of electricity in the course of the given time period according to Faraday's laws. Moreover, the kinetics in the dissolution step are rapid, as the quantity of yield metal dissolved in the anolyte is directly proportional to the charge that has flown through the anode. Thus also the quantity of yield metal that is dissolved in the anolyte can be efficiently and accurately controlled, which facilitates a more precise control of the process dynamics, and an improvement in reliability.
- In an embodiment of the invention, the yield metal is selected so that the selected yield metal is dissolved in the anolyte as a soluble salt of the acid that is contained in the first part of the starting solution.
- In an embodiment of the invention, the electrolytes are placed in an oxygen-free environment, in order to prevent the oxidation of the yield metal and/or intermediary metal that is contained in the electrolytes. This makes it easier to control the acid content of the electrolytes, which means that the balance of chemical reactions taking place in the different solutions of the process and containing for example yield metal and/or intermediary metal can be adjusted more accurately, which in turn improves the reliability and efficiency of the process, among others.
- In an embodiment of the invention, the starting solution contains sulfuric acid. Further, in an embodiment of the invention the sulfuric acid content in the starting solution is at least 50 g/l and preferably within the range 50 g/l - 1,500 g/l. In an embodiment of the invention, the starting solution contains hydrochloric acid or nitric acid. Further, in an embodiment of the invention the hydrochloric acid content in the starting solution is within the range 15 g/l - 500 g/l. Yet in an embodiment of the invention the starting solution contains, in addition to hydrochloric acid, also alkaline chloride, the content of which in the starting solution is within the range 15 g/l - 500 g/l. The suitability of an acid in the starting solution depends, among others, on the supply material, the yield metal and the intermediary metal in question. In some embodiments of the invention, the solutions may also contain more than one acid. On the basis of this description of the invention, a man skilled in the art is capable, by routine testing, of finding a suitable acid for a certain supply material, yield metal and intermediary metal, and a suitable content for said acid. In particular, it has been found out that in some embodiments of the invention, a sulfuric acid content of the starting solution that is at least 50 g/l provides for an efficient oxidation of a copper anode and its dissolution in the anode, when the intermediary metal is vanadium. A suitable acid, and content for said acid, must be chosen so that the yield metal is dissolved from the supply material to the anolyte, instead of the oxidation of the intermediary metal. Therefore the anolyte pH (i.e. oxygen content) must be suitable. When the employed yield metal is copper, and the intermediary metal is vanadium, the oxygen content must be as high as possible.
- In an embodiment of the invention, the electrolytic cell comprises at least one bag defined by a diaphragm in order to restrict the anolyte and/or catholyte inside the bag. Further, in an embodiment of the invention the electrolytic cell comprises means for conducting the separator solution from a space left in between two diaphragms to the anode side and/or the cathode side.
- The above described embodiments of the invention can be freely combined with each other. Several different embodiments can be combined in order to create a new embodiment. A method or arrangement that the invention relates to can include one or several of the above described embodiments of the invention.
- In the specification below, the invention is described with reference to the appended drawings, where
-
Figure 1 is a flowchart illustrating an embodiment of a method according to the invention, -
Figure 2 is a schematical illustration of an embodiment of an arrangement according to the invention, -
Figure 3 is a schematical block diagram illustrating an embodiment of a method according to the invention, -
Figure 4 is a schematical illustration of an embodiment of the electrolytic cell in an arrangement according to the invention, -
Figure 5 shows scanning electron microscope images (SEM images) of copper powder produced by an embodiment of the invention. - For the sake of simplicity, reference numbers referring to various elements of the invention remain the same in connection with corresponding repeated elements.
- In the preparation step S1 of an embodiment of the method according to
Figure 1 , there is produced and fed into the electrolytic cell, both to the anode side and to the cathode side, acid-bearing starting solution, electrolyte solution, which contains intermediary metal in its high potential value (i.e. in a higher oxidation state). In the method it is essential that at least the second part of the starting solution, which is fed to the cathode side, contains said intermediary metal in its high potential value, because in step S2, in the catholyte there is carried out the reduction of the intermediary metal to its low potential value (i.e. to a lower oxidation state), i.e. the regeneration of the intermediary metal. Also the first part of the starting solution, i.e. the part that is fed as the anolyte, may contain intermediary metal in its high potential value. In some embodiments of the invention, the starting solution may contain two or even several different intermediary metals. In some embodiments of the invention, the first and second part of the starting solution are identical in composition. By this procedure, the possibility that the composition of the electrolytes would be changed after starting the process is minimized, which means that the operating point of the process is stabilized more rapidly, and the controllability of the process is improved. - The type of intermediary metal suited in the method essentially depends on the selected yield metal, which should be dissolved in the anolyte in step S2, and which is later precipitated into powder in the mixing step S3. The intermediary metal and the selected yield metal together define the other features of the starting solution suited in the method, particularly the acid contained in the solution, and content of said acid in the solution. For example, the pH value of the solution must be such that in the prevailing process conditions, on the anode side there is more advantageously carried out the oxidation of yield metal and its dissolution in the anolyte than the oxidation of the intermediary metal in the anolyte. This kind of process conditions, i.e. functional windows, can be found for many different pairs of yield metal and intermediary metal. In the light of the description of the present invention as well as in the light of the Pourbaix diagrams of various different intermediary metals and yield metals, the finding of these functional windows represents routine testing for a man skilled in the art.
- The starting solution can be produced in many different ways, which depend, among others, on the suitable intermediary metal. One way is for example to dissolve, in an aqueous solution of a suitable acid, oxide containing the desired intermediary metal. When necessary, the acid content of the starting solution and the oxidation number of the dissolved intermediary metal can thereafter be adjusted to be suitable with respect to the starting solution. The adjusting of the oxidation number of the intermediary metal can be carried out for example electrolytically.
- When the starting solution is formed in step S1, it is fed as electrolyte in an electrolytic cell, where supply material containing yield metal is located on the anode side. In a method according to
Figure 1 , after step 1, instep 2 yield metal is dissolved on the anode side of the electrolytic cell from the supply material to the anolyte, as the yield metal is at the same time oxidized, and on the cathode side the intermediary metal of the starting solution is reduced from a high potential value to a low potential value. Because of productional considerations, among others, it is advantageous that the intermediary metal content and the content of the dissolved yield metal in the solutions is as high as possible. Thus a certain solution volume gives more precipitated yield metal powder in the mixing step S3 than in a situation where the contents of the intermediary metal and/or dissolved yield metal in the solutions are low. - The method according to
Figure 1 can be realized by means of an arrangement illustrated schematically inFigure 2 , where the employed supply material is present as ananode 2, which provides for rapid kinetics in the dissolution of yield metal, while the dissolution of the supply material is directly proportional to the charge flowing through theanode 2. Now the dissolution reactions can be controlled particularly accurately by using electricity; in a given period of time, the mass quantity of yield metal dissolved and oxidized on the anode is accurately proportional to the employed quantity of electricity, according to Faraday's laws. Respectively, an equimolar quantity of the intermediary metal is regenerated (reduced) on the cathode. The arrangement ofFigure 2 also comprises acathode 4, ananode side 6 of the electrolytic cell, acathode side 8, anolyte filtering equipment 10, aprecipitation chamber 12,separator equipment 16, and cleaningequipment 18 for the circulating solution. The anolyte 1 and thecatholyte 3 are mechanically separated by means of anelectroconductive separator solution 5 placed in theintermediate space 11 and by means of twoelectroconductive diaphragms 7 that define the intermediate space. The purpose is to ensure that the yield metal cations created on the anode side and the intermediary metal that is reduced to a low-potential value on the cathode side do not get into mutual contact in the electrolytic cell. Thus yield metal powder cannot be precipitated directly on the anode or cathode side of the electrolytic cell, which would, in case it happened, weaken the controllability of the process for example as regards the particle size of the yield metal powder as well as the process efficiency, and in addition, the recovery of the yield metal powder would become more difficult. In order to improve the separation of the anolyte 1 and thecatholyte 3, theseparator solution 5 provided in theintermediate space 11 can also be maintained at a higher hydrostatic pressure than the anolyte 1 and thecatholyte 3. - After step S2, in step S3, anolyte solution is conducted from the anode side of the electrolytic cell and catholyte solution is conducted from the cathode side thereof, for example by means of suitable pipes or in some other way, to the
precipitation chamber 12, in a suitable ratio away from the vicinity of theelectrodes separate precipitation chamber 12, the mixing ratio of the solutions can be controlled easily and accurately, and it can be optimized according to the process conditions. With a correct mixing ratio and an effective precipitate recovery, the creation of yield metal agglomerates can be prevented in the precipitation step, and consequently the homogeneity, with respect to their size, of the yield metal particles contained in theyield metal powder 14 is ensured. A correct mixing ratio also facilitates a process with a better efficiency, which results in reducing the amount of energy needed in the process for producing a certain quantity of yield metal mass. - In the
precipitation chamber 12, there is mixed, or there can be continuously mixed the anolyte solution and the catholyte solution conducted in thechamber 12. Prior to conducting the anolyte solution into theprecipitation chamber 12, it can in some embodiments of the invention be also purified of metallic impurities and/or other possible impurities disturbing the yield metal precipitation process in an anolyte filtering equipment 10 that is suited for this purpose. As a result of the mixing process, the oxidized yield metal of the anolyte solution is reduced and precipitated into solidyield metal powder 14, at the same time as the intermediary metal reduced in the catholyte solution is oxidized back to its high-potential value. From the obtained circulating solution, there is separated, in step S4, yield metal for example by centrifuging the circulating solution inseparator equipment 16 suited for the purpose. - When the
yield metal powder 14 is recovered, the created circulating solution is recirculated back to the electrolytic cell in step S5, part of it into anolyte 1 and part intocatholyte 3. Before conducting the circulating solution back to the electrolytic cell, any dissolved yield metal that is possibly left in the circulating solution is removed therefrom, as well as yield metal particles, in cleaningequipment 18 suited for this purpose. The cleaning operation can be carried out for example electrolytically by reduction and filtering. A thorough removal of yield metal, both dissolved and precipitated, from the circulating solution prior to recirculating the circulating solution back to the electrolytic cell is useful for the reliability of the process, for improving process efficiency and the controllability of the particle size of the yield metal powder. - In the above described method, the composition of the circulating solution is essentially identical with the composition of the starting solution, because in precipitation, the intermediary metal is oxidized back into its starting solution value, and the yield metal dissolved in the anolyte 1 on the anode side is precipitated and separated from the solution. Thus the circulating solution created in the method can be reused as a starting solution. If also the recirculating of the circulating solution back to anolyte and catholyte is carried out with the same ratio that was applied when a corresponding electrolyte was fed from the anode side and the cathode side to the precipitation chamber in step S3, an essentially closed electrolyte circulation can be used in the process, without a need to separately add/remove solution to or from the
anode side 6 of the electrolytic cell, or to or from thecathode side 8. - In practice, the method of
Figure 1 is generally realized as a continuous electrolyte circulation, as a result of which in theprecipitation chamber 12 there is continuously accumulatedyield metal powder 14 to be separated from the circulating solution and to be recovered, until the recirculation of the electrolyte solution (circulating electrolyte) in the arrangement is stopped, or when the yield metal contained in the supply material (anode 2) is completely dissolved in the electrolytic cell. When there is no more need to produceyield metal powder 14, or when the yield metal of the supply material is finished on theanode side 6 of the electrolytic cell, the recoveredyield metal powder 14 is treated in a finishing treatment in step S6, and the process is stopped. In some other preferred embodiments of the invention, the finishing treatment for the recoveredyield metal powder 14 can be carried out simultaneously with the other steps of the process, in the course of the process of separatingyield metal powder 14 and feeding it to the finishing treatment equipment (not illustrated). - In an example according to
Figure 3 , illustrated as a block diagram, the employed intermediary metal is vanadium, which in its high-potential value is V3+ in cations. The employed yield metal is copper, which is located in the supply material serving as theanode 2. The starting solution containing the vanadium intermediary metal in V3+ cations can be produced for instance by dissolving vanadium oxide V2O3 for instance to an aqueous solution of sulfuric acid. When the starting solution that contains V3+ cations in an aqueous solution, the sulfuric acid content of said solution being for example within the range 50 g/l - 1500 g/l, is formed, its first part is fed to theanode side 6 of the electrolytic cell as the anolyte 1, and the second part is fed to thecathode side 8 as thecatholyte 3. When electric current flows through the electrolytic cell, the V3+ cations are reduced on thecathode side 8 to V2+ cations in thecatholyte 3, and copper is dissolved from theanode 2 to the anolyte 1 as oxidized Cu2+ cations. Consequently, the anode reaction is Cu0 -> Cu2+ 2e-, and the cathode reaction is V3+ + e- -> V2+. - In the dissolution of copper and its oxidation in the anolyte 1, the intermediary metal may in some embodiments of the invention participate in corresponding reactions, thus improving both dissolution and oxidation, in such process conditions, for example with fairly low acid contents, where dissolution and oxidation with the combined effect of a mere electric current and an acid solution would not be efficient. Now the precise mechanism how the intermediary metal participates in the dissolution and oxidation of the yield metal depends on the selected yield metal and intermediary metal. In the above described example, when the yield metal is copper and the intermediary metal is vanadium, vanadium may be oxidized on the
anode side 6 into an intermediary oxidation state V5+, which is even higher than the V3+ state, whereafter the V5+ reacts with copper, thus oxidizing and dissolving copper. Now the "over-oxidized" vanadium V5+ is reduced back to its original high-potential value V3+. On theanode side 6, a corresponding "overoxidation" to an intermediate oxidation state is also possible with other intermediary metals than vanadium. - Thereafter anolyte solution and catholyte solution are conducted and mixed in a suitable ratio, for example in the ratio 1:3, in the
precipitation chamber 12, where copper is precipitated through the reaction 2V2+ + Cu2+ -> 2V3+ + Cu0. On the basis of this precipitation reaction, anolyte and catholyte are in theory needed in the mixing ratio 1:2, in order to make all V2+ and Cu2+ cations present in the solutions participate in the precipitation of copper. An optimal mixing ratio depends on the reaction state of the anode reactions and on the current efficiency, as well as on the reaction state and current efficiency of the cathode reactions. - As regards the efficiency and reliability of the process, it is useful to ensure that any remarkable amounts of V2+ and/or Cu2+ cations are not left in the circulating solution. In some embodiments of the invention, it is for example advantageous to try and make sure that all Cu2+ cations are consumed in the precipitation reaction, in which case the real mixing ratio of anolyte and catholyte can be 1:N, where N > 2. However, the value of the parameter N also depends on how the circulating solution is cleaned before feeding it back to the electrolytic cell. On the basis of the description of the present invention, the finding of a suitable mixing ratio is obvious routine testing for a man skilled in the art.
- When copper is precipitated into
powder 14 and separated from the rest of the solution by means of theseparator equipment 16, the remaining circulating solution is cleaned in thecleaning equipment 18 of any copper that is possibly left in the solution in the separation process, both of solid copper and dissolved, unprecipitated Cu2+ cations. The cleaning can be carried out for example electrolytically by precipitating and filtering. After said chemical and mechanical cleaning, the remaining circulating solution is essentially the same in composition as the starting solution, containing as a result from the precipitation reaction vanadium cations V3+ and sulfuric acid in aqueous solution. This circulating solution is again divided in a suitable ratio into anolyte 1 on theanode side 6 and intocatholyte 3 on thecathode side 8. After the above described regeneration, the same circulation electrolyte can again be conducted through the arrangement and the method for precipitating more/new copper powder 14 to theprecipitation chamber 12. - The solid
yield metal powder 14 separated from the solution is finished (Figure 1 , step S6) in a finish treatment arrangement. The separation and finish treatment processes can include many different steps, depending on the desired properties of the end product. In some embodiments of the invention, theyield metal powder 14 separated from the circulation electrolyte is washed in water for minimizing impurities carried along from the solution, whereafter theyield metal powder 14 is dried and coated with a passivation layer for preventing an oxidation of the powder, among others. In order to minimize the redissolution of the precipitatedyield metal powder 14 back into the circulating solution, it is useful to perform the separation of theyield metal powder 14 from the circulating electrolyte by theseparator equipment 16, and it is advisable to perform the washing as quickly as possible after the precipitation reaction. - In some embodiments of the invention, the
yield metal powder 14 is subjected to various separate washing operations. In between the washing operations, theyield metal powder 14 is separated from the washing liquid. In an embodiment of the invention, theyield metal powder 14 that is obtained from theseparator equipment 16, which is separated from the circulating electrolyte by centrifuging but is still wet, is mixed in water in the mass mixing ratio 1:20 (one part of wetyield metal powder 14 and 20 parts of water) three times. In between the mixing operations, theyield metal powder 14 is separated from the washing liquid. - The exact structure and operation of the washing equipment can vary even to a great extent, and for a man skilled in the art, the production of such equipment is obvious in the light of the description of the present invention. In a preferred embodiment of the invention, the washing equipment for realizing several successive washing operations can be for example a conveyor-belt type arrangement, where the wet
yield metal powder 14 is poured on a conveyor belt, which conveys theyield metal powder 14 to the washing liquid, from which the yield metal powder is poured on the next conveyor belt, etc. Now the settling of theyield metal powder 14 takes place when it is separated from the washing liquid, i.e. when the washing liquid containing yield metal powder is poured on the conveyor belt. - In addition to the above described example, or instead of the procedure described therein, the separated yield metal powder can naturally also be washed by many known methods, for example by means of a syphon.
- Various different electrolytic cell structures can be designed for dissolving and oxidizing yield metal on the anode side of an electrolytic cell, and for reducing intermediary metal on the cathode side of an electrolytic cell. The electrolytic cell structure illustrated schematically in
Figure 4 can be used in the arrangement for producingyield metal powder 14 in a reliable and efficient way, with a good efficiency. - In the electrolytic cell of
Figure 4 , both theanode side 6 and thecathode side 8 comprise several sections, i.e. diaphragm bags, defined by adiaphragm 7. Each diaphragm bag respectively includes ananode 2 or a cathode and anolyte 1 orcatholyte 3. Naturally theanodes 2 and thecathodes 4 are connected to a power source (not illustrated). In between each diaphragm bag, there is suppliedelectroconductive separator solution 5, which in one embodiment of the invention contains intermediary metal in a suitable high-potential value, i.e. in an oxidized state; in the case of the above described example, theseparator solution 5 may contain for example V3+ ions. - In addition, the electrolytic cell of
Figure 4 comprises afeed pipe 9 for feeding separator solution to theintermediate space 11 left between the diaphragm bags, anoverflow channel 13 for theseparator solution 4,drain channels 15 for the anolyte solution and the catholyte solution, as well as aprotective film 17. The electrolytic cell ofFigure 4 can be connected to another arrangement, for example to a precipitation chamber 12 (not illustrated inFigure 4 ), by intermediation of thedrain channels 15 and thefeed pipe 9. - In an embodiment of the invention, the
separator solution 5 serves as the starting solution, in which case the composition of theseparator solution 5 is identical to that of the starting solution. Now the starting solution can be fed to theintermediate space 11 of the electrolytic cell illustrated inFigure 4 through the apertures provided in thefeed pipe 9. From theintermediate space 11, theseparator solution 5 flows to the diaphragm bags as anolyte 1 andcatholyte 3 through perforations provided in thediaphragms 7. In addition or instead, the diaphragm can be semi-permeable, so that the separator solution 5 (starting solution) has access to flow in a controlled fashion through thediaphragm 7 as anolyte 1 and/orcatholyte 3. Anode reactions and cathode reactions take place in the diaphragm bags in the way described above. The obtained catholyte solution, containing reduced intermediary metal, as well as the anolyte solution containing dissolved or oxidized yield metal, can be conducted to theprecipitation chamber 12 for example throughoutlets 15. In some embodiments of the invention, theoutlets 15 can serve as overflow channels for removing excess electrolyte from the arrangement, in which case anolyte solution and/or catholyte solution can be brought in theprecipitation chamber 12 via another route, for example through suction inlets provided for this purpose. The circulating solution created in theprecipitation chamber 12 can in turn be recirculated, after possible cleaning steps, for example via afeed pipe 9 back to theintermediate space 11 and further to anolyte 1 and/orcatholyte 3. - By adjusting the permeability of the
diaphragms 7 in the cell illustrated inFigure 4 , or the size of the perforations provided in thediaphragms 7, the quantity of the solution flowing through theanode side 6 and/or thecathode side 8 per unit of time can be efficiently controlled. The permeability of thediaphragms 7 can be selected separately for thediaphragms 7 on theanode side 6 and/or for thediaphragms 7 on thecathode side 8. By suitably controlling the quantity of solution per time unit that has access to flow in the diaphragm bags on theanode side 6 and/or on thecathode side 8 through thediaphragms 7, in relation to the quantity of solution per time unit to be fed in theintermediate space 11, the hydrostatic pressure of theseparator solution 5 placed in theintermediate space 11 can be adjusted to be higher than the hydrostatic pressure of the electrolytes contained in the diaphragm bags located in theseparator solution 5. Thus it is possible to prevent an undesired flowing of the electrolyte through thediaphragm 7 towards theintermediate space 11, away from the diaphragm bag. By suitably arranging the measures of theoverflow channel 13, for example by arranging it at a suitable height, it is possible to ensure according toFigure 4 that the hydrostatic pressure difference between theintermediate space 11 and theanode side 6 and/or thecathode side 8 does not rise too high, but any excess separator solution flows out of the cell through theoverflow channel 13. Respectively, also by arranging the measures and locations of theoutlets 15, it is possible to affect the formation of said hydrostatic pressure difference. When the diameter of the perforations possibly provided in thediaphragms 7 is large, said hydrostatic pressure difference, together with the permeability of thediaphragms 7, essentially defines the quantity of solution that flows through theanode side 6 and thecathode side 8 per unit of time. On the basis of the description of the present invention, the above described design of the measures of the electrolytic cell, and the placing of the perforations, is obvious routine testing for a man skilled in the art. - As was described above, in some embodiments of the invention it is not necessary to directly feed starting solution and/or circulating solution to the
anode side 6 and/orcathode side 8 of the electrolytic cell, for example to the diaphragm bags, but essentially all solution in the arrangement circulates through theintermediate space 11. In case thediaphragms 7 are selected to be such that they are completely impermeable to solution, circulating solution and/or starting solution can be fed to theanode side 6 and/or to thecathode side 8, for example to the diaphragm bags, directly and not through theintermediate space 11. In some other embodiments of the invention, instead of thediaphragms 7, there can be used for example ion-selective membranes that only permeate ions of a certain type. - In the electrolytic cell according to
Figure 4 , the electrolytic cell structure is covered by aprotective film 17, by means of which theintermediate space 11 can be pressurized for example with nitrogen gas or with some other inert gas in order to prevent a possible oxidation caused by air or the surrounding environment. Also the diaphragm bags can be closed and pressurized with nitrogen in order to prevent oxidation. - The cell structure of
Figure 4 enables a reliable separation of the anolyte and the catholyte in the electrolytic cell, which reduces premature oxidation and/or reduction reactions. Consequently, by using the electrolytic cell structure according toFigure 4 , there is achieved a good efficiency in the method. In addition, the risk of a premature precipitation of the yield metal powder in the electrolytic cell is reduced, which improves the reliability of the method and makes the maintenance of the equipment easier. - By applying a method according to the block diagram illustrated in
Figure 3 , there was manufactured, in an arrangement representing essentially the type illustrated inFigure 2 , copper powder by employing as the starting solution an aqueous solution of sulfuric acid, said solution containing V3+ cations. In this starting solution, the measured sulfuric acid concentration was about 500 g/l, and the measured vanadium concentration was about 16 g/l. The employed supply material was Class A cathode copper plate, which also served as the anode of the electrolytic cell. The employed cathode was a lead plate, measures 275 mm x 130 mm. In test conditions, the solution temperatures were roughly 20 - 35° C. - The starting solution was fed to the electrolytic cell, where copper anode was oxidized and dissolved in the anolyte. The measured content of the dissolved copper was roughly 4 g/l. Thereafter anolyte solution was conducted from the anode side, and catholyte solution was conducted from the cathode side to the precipitation chamber, which in this example was a glass bottle. The mixing ratio of the anolyte solution and the catholyte solution was 1:3. As a result of the mixing operation, copper powder was formed in the precipitation chamber, according to the description above. The electron microscope images taken of the obtained copper powder are illustrated in
Figure 5 ; from these images it can be observed, for example, that the size distribution of the copper particles is fairly homogeneous, large particle agglomerates are not created, and the average size of the particles is below the micrometer range. - Although some examples and embodiments illustrating the invention are above described as methods for manufacturing copper powder, a man skilled in the art is on the basis of this description of the invention easily capable of manufacturing powders also of other metals than copper when applying the various embodiments of the invention. Likewise, on the basis of this description of the invention, a man skilled in the art is easily capable of using, in the various embodiments of the invention, other intermediary metals and/or acids than those enlisted in the above examples. The invention is not restricted to the above described examples only, but it can be realized in many different modifications within the scope of the appended claims.
Claims (21)
- A method for manufacturing a yield metal powder, wherein dissolved yield metal is mixed with a solution containing at least one intermediary metal for precipitating the dissolved yield metal into the yield metal powder (14), wherein in the method- a first part of an acid-containing starting solution is brought as an anolyte (1) to the anode side (6) of an electrolytic cell, to be in contact with the anode (2) and a supply material containing the yield metal; and a second part of the acid-containing starting solution, which also contains the intermediary metal, in a higher oxidation state, in addition to acid, is brought to the cathode side (8) of the electrolytic cell, as a catholyte (3) to be in contact with the cathode (4);- the yield metal is oxidized and dissolved in the anolyte (1) by conducting electric current in the anode (2);- the intermediary metal contained in the second part of the starting solution is reduced to a lower oxidation state on the cathode side (8);- anolyte solution and catholyte solution are brought into a precipitation chamber (12) for mixing the oxidized yield metal dissolved in the first part of the starting solution and the second part of the starting solution containing the reduced intermediary metal;- a first part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned back to anolyte (1); wherein the first part of the starting solution is composed of the first part of the circulating solution; and- a second part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution is returned back to catholyte (3); wherein the second part of the starting solution is composed of the second part of the circulating solution.
- A method according to claim 1, characterized in that the first part of the starting solution contains the intermediary metal for boosting the dissolution of yield metal on the anode side.
- A method according to claim 1 , characterized in that the circulating solution is conducted completely back to electrolyte, so that the circulating solution is composed of the first part of the circulating solution and of the second part of the circulating solution.
- A method according to any of the claims 1-3, characterized in that the anolyte (1) and the catholyte (3) are mechanically separated by an electroconductive diaphragm (7).
- A method according to any of the claims 1-4, characterized in that an electroconductive separator solution (5) is conducted in between two diaphragms (7) separating the anolyte (1) and the catholyte (3) in order to prevent a premature mixing of the anolyte (1) and the catholyte (3).
- A method according to any of the claims 1-5, characterized in that the yield metal is copper.
- A method according to any of the claims 1-5, characterized in that the yield metal is selected among the following group: nickel, cobalt, zinc, silver, gold, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, zirconium, tin, cadmium and indium.
- A method according to any of the claims 1-5, characterized in that the intermediary metal is vanadium.
- A method according to any of the claims 1-5, characterized in that the intermediary metal is selected among the group titanium, chromium and iron.
- A method according to any of the claims 1-5, characterized in that the intermediary metal is selected among the following group: manganese, zirconium, molybdenum, technetium, tungsten, quicksilver, germanium, arsenic, selenium, tin, antimony, tellurium and copper.
- A method according to any of the claims 1-10, characterized in that the supply material containing the yield metal is located in the anode (2) .
- A method according to any of the claims 1-11, characterized in that the starting solution contains sulfuric acid.
- A method according to claim 12, characterized in that the content of sulfuric acid in the starting solution is at least 50 g/l and preferably 50 g/l - 1500 g/l.
- A method according to any of the claims 1-13, characterized in that the starting solution contains hydrochloric acid or nitric acid.
- An arrangement for producing a yield metal powder by precipitating the yield metal powder (14) by mixing dissolved yield metal with a solution containing at least one intermediary metal in a lower oxidation state, wherein the arrangement comprises an electrolytic cell containing yield metal on an anode side and dissolved intermediary metal on a cathode side, for dissolving the yield metal located on the anode side of the electrolytic cell and for oxidizing it in the anolyte, and for reducing the dissolved intermediary metal located on the cathode side (8) of the electrolytic cell on the cathode side from a higher oxidation state to the lower oxidation state; a precipitating chamber (12) that is separate from the electrolytic cell; as well as means for feeding anolyte solution and catholyte solution respectively from the anode side (6) of the electrolytic cell and from the cathode side (8) of the electrolytic cell to the precipitating chamber (12) for mixing the yield metal dissolved in the anolyte and the catholyte solution containing the reduced intermediary metal, from outside the electrolytic cell; and means for returning a first part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution back to anolyte (1); wherein the first part of the starting solution is composed of the first part of the circulating solution; and means for returning a second part of the circulating solution created as a result of mixing the anolyte solution and the catholyte solution back to catholyte (3); wherein the second part of the starting solution is composed of the second part of the circulating solution.
- An arrangement according to claim 15, characterized in that the electrolytic cell comprises an electroconductive diaphragm (7) in between the anode side (6) and the cathode side (8) of the electrolytic cell for mechanically separating the anode side (6) and the cathode side (8).
- An arrangement according to any of the claims 15-16, characterized in that the electrolytic cell comprises two electroconductive diaphragms (7) in between the anode side (6) and cathode side (8) of the electrolytic cell for mechanically separating the anode side (6) and the cathode side (8) by means of an electroconductive separator solution (5) provided in the space left between the two diaphragms (7).
- An arrangement according to any of the claims 15-17, characterized in that the yield metal supplied on the anode side (6) of the electrolytic cell is located in the anode (2) of the electrolytic cell.
- An arrangement according to any of the claims 15-18, characterized in that the electrolytic cell comprises at least one bag, defined by a diaphragm (7), for keeping the anolyte and/or the catholyte inside the bag.
- An arrangement according to claim 17, characterized in that the electrolytic cell comprises means for conducting a separator solution (5) from the space left between the two diaphragms (7) to the anode side (6) and/or to the cathode side (8).
- An arrangement according to any of the claims 15-20, characterized in that the electrolytes are placed in an oxygen-free environment for preventing the oxidation of the yield metal and/or intermediary metal contained in the electrolytes.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI20105083A FI124812B (en) | 2010-01-29 | 2010-01-29 | Method and apparatus for the manufacture of metal powder |
PCT/FI2011/050056 WO2011092375A1 (en) | 2010-01-29 | 2011-01-25 | Method and arrangement for producing metal powder |
Publications (3)
Publication Number | Publication Date |
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EP2528704A1 EP2528704A1 (en) | 2012-12-05 |
EP2528704A4 EP2528704A4 (en) | 2016-11-23 |
EP2528704B1 true EP2528704B1 (en) | 2018-10-03 |
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EP11736667.4A Not-in-force EP2528704B1 (en) | 2010-01-29 | 2011-01-25 | Method and arrangement for producing metal powder |
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US (1) | US20120298523A1 (en) |
EP (1) | EP2528704B1 (en) |
JP (1) | JP5676649B2 (en) |
KR (1) | KR101529373B1 (en) |
CN (1) | CN102725086B (en) |
EA (1) | EA021918B1 (en) |
ES (1) | ES2703254T3 (en) |
FI (1) | FI124812B (en) |
WO (1) | WO2011092375A1 (en) |
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CN105506728B (en) * | 2014-09-29 | 2019-10-15 | 盛美半导体设备(上海)有限公司 | The device of precipitating metal ion from electrochemical polish liquid |
RU2600305C1 (en) * | 2015-05-08 | 2016-10-20 | Федеральное государственное бюджетное учреждение науки Институт высокотемпературной электрохимии Уральского отделения Российской Академии наук | METHOD FOR ELECTROCHEMICAL PRODUCTION OF IRIDIUM POWDER WITH SPECIFIC SURFACE AREA MORE THAN 5 m2/g |
CN107849716B (en) * | 2016-03-09 | 2020-04-10 | Jx金属株式会社 | High-purity tin and method for producing same |
CN107030290B (en) * | 2017-04-27 | 2019-02-01 | 上海交通大学 | A kind of preparation process of nanometer of glass putty |
CN107513730B (en) * | 2017-08-31 | 2019-06-14 | 北京工业大学 | Continuously prepare the device and method of tungsten powder and cobalt powder |
CN107955952A (en) * | 2017-11-02 | 2018-04-24 | 马鞍山市宝奕金属制品工贸有限公司 | A kind of method using scum production high-purity iron powder |
WO2019220858A1 (en) * | 2018-05-16 | 2019-11-21 | 住友金属鉱山株式会社 | Sulfuric acid solution production method, and electrolysis vessel which can be used in said production method |
JP7275629B2 (en) * | 2018-05-16 | 2023-05-18 | 住友金属鉱山株式会社 | Method for producing sulfuric acid solution |
KR102602595B1 (en) | 2021-11-22 | 2023-11-16 | (주)선영시스텍 | Metal powder washing machine |
CN114941076B (en) * | 2022-06-28 | 2023-06-02 | 中国矿业大学 | Method for extracting and recovering gold from aqueous solution |
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JPS5819752B2 (en) * | 1974-03-30 | 1983-04-19 | カガクギジユツチヨウ キンゾクザイリヨウギジユツケンキユウシヨチヨウ | dodenkaihou |
JPS54104439A (en) * | 1978-02-06 | 1979-08-16 | Tdk Corp | Recovering method for metallic copper from waste acidic solution |
US4780444A (en) * | 1984-05-03 | 1988-10-25 | Mobil Oil Corporation | Activation of metallophophates |
GB2181158B (en) * | 1985-10-08 | 1989-11-15 | Electricity Council | Electrolytic process for the manufacture of salts |
JPS62188791A (en) * | 1986-02-15 | 1987-08-18 | Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk | Electrowinning method for ni, co, zn, cu, mn and cr |
US5133948A (en) * | 1991-07-11 | 1992-07-28 | Asarco Incorporated | Process for the removal of bismuth from copper refining electrolyte by using lead oxide |
US5882502A (en) * | 1992-04-01 | 1999-03-16 | Rmg Services Pty Ltd. | Electrochemical system and method |
JP3696525B2 (en) * | 2001-05-02 | 2005-09-21 | 福田金属箔粉工業株式会社 | Copper fine powder manufacturing method |
JP2003328198A (en) * | 2002-05-10 | 2003-11-19 | Mitsubishi Materials Corp | Method of generating copper ion and apparatus therefor, method of producing copper sulfate and apparatus therefor, method of generating metallic ion and apparatus therefor, and method of producing acid water and apparatus therefor |
JP3508766B2 (en) * | 2002-06-14 | 2004-03-22 | 住友電気工業株式会社 | Method for producing metal fine powder |
JP4215583B2 (en) * | 2003-07-23 | 2009-01-28 | 住友電気工業株式会社 | Reducing agent solution, method for producing metal powder using the same, and method for forming metal film |
US7378011B2 (en) * | 2003-07-28 | 2008-05-27 | Phelps Dodge Corporation | Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction |
JP3896107B2 (en) * | 2003-09-30 | 2007-03-22 | 日鉱金属株式会社 | Diaphragm electrolysis method |
US7378010B2 (en) * | 2004-07-22 | 2008-05-27 | Phelps Dodge Corporation | System and method for producing copper powder by electrowinning in a flow-through electrowinning cell |
FI120438B (en) * | 2006-08-11 | 2009-10-30 | Outotec Oyj | A method for forming a metal powder |
-
2010
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2011
- 2011-01-25 EP EP11736667.4A patent/EP2528704B1/en not_active Not-in-force
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- 2011-01-25 CN CN201180007337.XA patent/CN102725086B/en not_active Expired - Fee Related
- 2011-01-25 ES ES11736667T patent/ES2703254T3/en active Active
- 2011-01-25 WO PCT/FI2011/050056 patent/WO2011092375A1/en active Application Filing
- 2011-01-25 KR KR1020127021205A patent/KR101529373B1/en active IP Right Grant
- 2011-01-25 US US13/575,275 patent/US20120298523A1/en not_active Abandoned
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CN102725086A (en) | 2012-10-10 |
JP2013518189A (en) | 2013-05-20 |
EP2528704A1 (en) | 2012-12-05 |
WO2011092375A1 (en) | 2011-08-04 |
EA201290714A1 (en) | 2013-02-28 |
ES2703254T3 (en) | 2019-03-07 |
FI20105083A (en) | 2011-07-30 |
JP5676649B2 (en) | 2015-02-25 |
KR101529373B1 (en) | 2015-06-16 |
FI20105083A0 (en) | 2010-01-29 |
US20120298523A1 (en) | 2012-11-29 |
EP2528704A4 (en) | 2016-11-23 |
CN102725086B (en) | 2015-04-22 |
FI124812B (en) | 2015-01-30 |
EA021918B1 (en) | 2015-09-30 |
KR20120115999A (en) | 2012-10-19 |
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