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EP0137776B1 - Verfahren zum erhalten und nachweisen der geeigneten konzentrationen von thioharnstoff in kupferraffinierenden elektrolysezellen - Google Patents

Verfahren zum erhalten und nachweisen der geeigneten konzentrationen von thioharnstoff in kupferraffinierenden elektrolysezellen Download PDF

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Publication number
EP0137776B1
EP0137776B1 EP83901288A EP83901288A EP0137776B1 EP 0137776 B1 EP0137776 B1 EP 0137776B1 EP 83901288 A EP83901288 A EP 83901288A EP 83901288 A EP83901288 A EP 83901288A EP 0137776 B1 EP0137776 B1 EP 0137776B1
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EP
European Patent Office
Prior art keywords
thiourea
copper
electrolyte
concentration
refining
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.)
Expired
Application number
EP83901288A
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English (en)
French (fr)
Other versions
EP0137776A4 (de
EP0137776A1 (de
Inventor
Martin Goffman
Thomas L. Jordan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asarco LLC
Original Assignee
Asarco LLC
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Filing date
Publication date
Application filed by Asarco LLC filed Critical Asarco LLC
Priority to AT83901288T priority Critical patent/ATE33408T1/de
Publication of EP0137776A1 publication Critical patent/EP0137776A1/de
Publication of EP0137776A4 publication Critical patent/EP0137776A4/de
Application granted granted Critical
Publication of EP0137776B1 publication Critical patent/EP0137776B1/de
Expired legal-status Critical Current

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    • 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
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper

Definitions

  • copper has been purified in a process wherein an electric current is transmitted between cast anodes of impure copper to cathodes which have a substantially pure copper deposit plated thereto, both anodes and cathodes being immersed in a suitable electrolyte.
  • the electrolyte which has found universal acceptance in the art is an aqueous solution of copper sulfate and sulfuric acid.
  • the refining process first dissolves the impure anode copper into the electrolyte solution and then transports the copper ions (Cu2+) to a nearby cathode, where the copper is plated out as virtually pure metal, Cu°. After a period of time a desired thickness of copper is deposited on the cathodes, whereupon they are removed and later melted for casting into several common product shapes.
  • an improved method for the electrolytic refining of copper comprising creating an electrolyte useful in copper refining including an aqueous solution of sulfuric acid and copper sulfate, together with minor amounts by weight of addition agents, one of which is thiourea, the electrolyte residing during plating in a suitable container means, which has both an inlet stream and an outlet stream of electrolyte passing through inlet and outlet flow passage means; adding at least a sufficient amount of thiourea to the inlet stream in order to maintain the outlet stream concentration of thiourea at a value at least above trace concentrations, that is, at least a measurable amount, the maximum acceptable concentration in the outlet stream being a value above which cathode deposited copper contamination becomes significant, that is, above which impurities present in the electrolyte materially affect the quality of the deposited copper, and at least periodically repeating the above while electrorefining copper in the container means.
  • Electrorefining is a process of first electrochemically dissolving impure copper from an anode and then selectively plating the dissolved copper in virtually pure form onto a cathode. Such a process thus serves two purposes; it virtually eliminates impurities which are harmful to the electrical and mechanical properties of copper, and it also separates valuable impurities from the copper, which can be either recovered as by-product metals if economically feasible, or otherwise disposed of.
  • Electrorefining as practiced in industrial tankhouses today is almost exclusively carried out using the "multiple" or "parallel" system, in which all the anodes and cathodes in each electrolytic cell are interleaved in an electrically parallel arrangement.
  • FIGs 1A and 1B two alternative arrangements of arranging anode-cathode and cell connections are illustrated.
  • all the anodes 2A, 2B in a particular cell are activated at one electrical potential, while all the cathodes 4A, 4B are at a second, lower potential.
  • Each anode 2A, 2B is positioned between two cathodes 4A, 4B in order that all the anodes will dissolve at a substantially uniform rate.
  • each section generally made up of about 20-45 cells, constitutes a separate independent part (module) of the refinery tankhouse, which can be electrically and chemically isolated from the other sections for such operations as inserting and removing electrodes, cleaning anode residues from the bottom of the cell, and maintenance services.
  • each adjacent cell is connected in series with its adjoining member, all the cathodes in each cell are in direct connection, i.e. the same potential, with the anodes in the adjoining cell.
  • the electrolyte used for copper refining today is an aqueous solution of about 40-50 g/I copper and 175-225 g/I sulfuric acid, along with small amounts of impurities, mainly nickel, arsenic, iron and antimony.
  • Steam heaters keep the solution at a temperature of about 60-65°C. at the refining cell inlet, and as the electrolyte circulates through the cells while processing the copper, its temperature drops to a range of about 55-60°C. at the outlet.
  • the flow rate, or circulation of the electrolyte in and out of the cell causes the typical large industrial cell to recirculate its electrolyte once every 5-6 hours. Such circulation is essential for several reasons, one of which is to transport dissolved impurities out of the cell and to insure uniform copper ion concentrations at the electrode surfaces.
  • the electrolyte has several "addition agents” which are added to it in an effort to improve performance. If these addition agents were not mixed into the electrolyte the finished plated copper deposits would become either soft or coarsely crystalline deposits.
  • Common addition agents found in refinery use today are bone glue, hydrolysed casein, sulphonated wood fibres such as goulac, bindarene and lignone and petroleum liquors, particularly the well known "Avitone A”.
  • thiourea means any organic compound containing a thiourea nucleus, viz. and in particular, commercially pure or commercial grade thiourea.
  • FIG. 2 is a schematic flowsheet of a copper refining process in which the tankhouse refinery is comprised of a single section.
  • Mixer tank 2 functions as a source of thiourea for the refining process, as well as the source of several other addition agents and salt additives.
  • Thiourea can be added either continually, or periodically, into the electrolyte, depending on the particular type of system used.
  • the thiourea in tank 2 passes through tube or other suitable flow means 4 and goes past flow regulator 6 whereupon it joins the main electrolyte circulation in tube 8.
  • the inlet concentration of thiourea in tube 8 is typically kept between about 800-2500 ppb, or most typically, about 1500-2000 ppb.
  • the inlet concentration should vary so that the outlet concentration of thiourea from each tankhouse section is present in at least trace concentrations, that is, at least a measureable amount, and preferably at least about 100 ppb.
  • thiourea concentrations of the order of 5000 ppb have been used in the inlet, with satisfactory results.
  • the electrolyte then enters into section or module 10, which is divided into many cells 12, each cell being constructed in the manner as seen in Figure 1.
  • section or module 10 which is divided into many cells 12, each cell being constructed in the manner as seen in Figure 1.
  • any suitable cell or tankhouse design can be used in the process of this invention, and this particular tankhouse design, employing but a single section, is used in order to simplify the analysis.
  • the electrolyte solution leaves through outlet tube 14.
  • the outlet concentration of thiourea in the electrolyte is sampled at orifice 16, the sample then measured by measuring means 18, the location of which is not important, so long as the correct outlet concentrations can be quickly and accurately measured so that system changes can be promptly made.
  • the effluent concentration of thiourea is an important parameter in optimizing tankhouse efficiency. More particularly, a thiourea effluent concentration at a value at least above trace concentrations, that is, at least a measurable amount, and preferably above about 100 ppb will lead to increased current efficiency, smoother cathodes, fewer short circuits between anode and cathode, and a lower impurity concentration in the cathodes.
  • electrolyte solution After circulating electrolyte solution is sampled at 16, it flows through tube 20 and enters tank 22, which functions as a source of fresh electrolyte, i.e. C U S0 4 and H 2 S0 4 .
  • tank 22 Upon exiting tank 22 the fresh electrolyte solution passes through tube 24 and pumping means 26, until entering heat exchanger 33 and tube 28, which raises the temperature of the electrolyte to about 65°C., whereupon the fluid exits through tube 32 into and out of head tank 34.
  • the electrolyte is next fortified by thiourea and other addition agents before the entry into section 10, as the cycle is continued indefinitely.
  • the invention in its preferred form consists of a novel improved process of electrolytic copper refining which occurs in a tankhouse or other suitable container means wherein the improvement comprises measuring the concentration of thiourea in the electrolyte outlet with a suitable measuring means, preferably by differential pulse polarography, readjusting the thiourea concentration by adding an effective amount of thiourea to the inlet stream so that the outlet concentration stays within a desired range, the range having a maximum value above which impurities develop in the copper cathodes and a minimum concentration being at least a measurable amount and preferably about 100 ppb, below which nodule formation accelerates; and periodically repeating the above procedure so that the measured outlet thiourea concentration stays between these upper and lower values, preferably about 100-2500 ppb for the typical electrorefining tankhouse.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Preliminary Treatment Of Fibers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)

Claims (5)

1. Verfahren zum elektrolytischen Raffinieren von Kupfer, in dem ein Kupferraffinationselektrolyt geschaffen wird, der mindestens teilweise aus einer wäßrigen Lösung von Schwefelsäure und Kupfersulfat in wirksamer Stärke besteht, wobei die Lösung in kleinen Gewichtsmengen Zusätze enthält, zu denen der Thioharnstoff gehürt, der Elektrolyt während der Raffination in einer geeigneten Behälteranordnung verweilt, durch dessen eintritts- und austrittsseitige Strömungskanalanordnungen ein Eintritts- bzw. Austrittsstrom des Elektrolyten tritt, und Kupfer in der Behälteranordnung elektroraffiniert wird, dadurch gekennzeichnet daß mit einem wirksamen Meßverfahren die Konzentration des Thioharnstoffs in dem Austrittsstrom des Elektrolyten periodisch gemessen und daß dem Eintrittsstrom Thioharnstoff in einer solchen Menge zugesetzt wird, daß die Thioharnstoffkonzentration in dem Austrittsstrom auf einem Wert zwischen Spuren und einer Konzentration gehalten wird, die niedriger ist als die niedrigste Konzentration, bei der sich auf den Kupferkathoden Verunreinigungen bilden.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Meßverfahren die Differentialimpulspolarographie ist.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Austrittskonzentration des Thioharnstoffs mindestens etwa 100 Teile pro Milliarde beträgt.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß die Thioharnstoffkonzentration im Austritt zwischen 100 und 5000 Teile pro Milliarde gehalten wird.
5. Verfahren nach einem der vorhergehenden Ansprüche dadurch gekennzeichnet, daß die Behälteranordnung eine Elektrolysehalle für die Kupferraffination ist.
EP83901288A 1983-02-28 1983-02-28 Verfahren zum erhalten und nachweisen der geeigneten konzentrationen von thioharnstoff in kupferraffinierenden elektrolysezellen Expired EP0137776B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83901288T ATE33408T1 (de) 1983-02-28 1983-02-28 Verfahren zum erhalten und nachweisen der geeigneten konzentrationen von thioharnstoff in kupferraffinierenden elektrolysezellen.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1983/000298 WO1984003307A1 (en) 1983-02-28 1983-02-28 Method of maintaining and testing for proper concentrations of thiourea in copper refining electrolysis cells

Publications (3)

Publication Number Publication Date
EP0137776A1 EP0137776A1 (de) 1985-04-24
EP0137776A4 EP0137776A4 (de) 1985-07-30
EP0137776B1 true EP0137776B1 (de) 1988-04-06

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EP83901288A Expired EP0137776B1 (de) 1983-02-28 1983-02-28 Verfahren zum erhalten und nachweisen der geeigneten konzentrationen von thioharnstoff in kupferraffinierenden elektrolysezellen

Country Status (8)

Country Link
EP (1) EP0137776B1 (de)
JP (1) JPS60500453A (de)
AT (1) ATE33408T1 (de)
AU (1) AU558737B2 (de)
DE (1) DE3376228D1 (de)
FI (1) FI77059C (de)
IN (1) IN163215B (de)
WO (1) WO1984003307A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR22348A (tr) * 1984-06-14 1987-02-23 Asorco Inc Bakir saflandirilmasinda yararh elektrolit coezeltilerine tiouere ilave etme yoentemi
JP5611633B2 (ja) * 2010-03-29 2014-10-22 パンパシフィック・カッパー株式会社 配管内のスケール状態検査方法
JP5566350B2 (ja) * 2011-08-15 2014-08-06 パンパシフィック・カッパー株式会社 金属の製造装置及び金属の製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2660555A (en) * 1950-12-20 1953-11-24 Canadian Copper Refiners Ltd Process of and electrolyte for refining copper
DE1180140B (de) * 1962-07-20 1964-10-22 Dehydag Gmbh Verfahren zur Abscheidung feinkoerniger Niederschlaege bei der Raffinations- und Reduktionselektrolyse von Nickel, Zink, Silber, Zinn, Blei und insbesondere Kupfer
US3389064A (en) * 1964-07-22 1968-06-18 Canadian Copper Refiners Ltd Electrolytic refining of copper and tank house electrolyte useful therein
CA1064852A (en) * 1975-12-31 1979-10-23 Cominco Ltd. Method for evaluating a system for electrodeposition of metals
JPS5834639B2 (ja) * 1977-07-09 1983-07-28 豊 持田 加圧掘用口元装置
JPS5690993A (en) * 1979-12-21 1981-07-23 Furukawa Electric Co Ltd:The Electrolytic refining of copper

Also Published As

Publication number Publication date
AU1472483A (en) 1984-09-10
FI77059B (fi) 1988-09-30
AU558737B2 (en) 1987-02-05
WO1984003307A1 (en) 1984-08-30
FI77059C (fi) 1989-01-10
FI844070A0 (fi) 1984-10-16
EP0137776A4 (de) 1985-07-30
JPS6230271B2 (de) 1987-07-01
FI844070L (fi) 1984-10-16
EP0137776A1 (de) 1985-04-24
JPS60500453A (ja) 1985-04-04
DE3376228D1 (en) 1988-05-11
ATE33408T1 (de) 1988-04-15
IN163215B (de) 1988-08-20

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