US3696012A - Process for preventing supersaturation of electrolytes with arsenic,antimony and bismuth - Google Patents

Process for preventing supersaturation of electrolytes with arsenic,antimony and bismuth Download PDF

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Publication number
US3696012A
US3696012A US105847A US3696012DA US3696012A US 3696012 A US3696012 A US 3696012A US 105847 A US105847 A US 105847A US 3696012D A US3696012D A US 3696012DA US 3696012 A US3696012 A US 3696012A
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United States
Prior art keywords
electrolyte
bismuth
antimony
acid
stannic acid
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Expired - Lifetime
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US105847A
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English (en)
Inventor
Reinhold Schulze
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Aurubis AG
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Norddeutsche Affinerie AG
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Priority claimed from DE19702004410 external-priority patent/DE2004410B2/de
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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
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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

  • My present invention relates to a process for preventing the accumulation of excesses of arsenic, antimony and bismuth, in electrolytes and, more particularly, for preventing the supersaturation of electrolytes used in the electrolytic refining of copper with arsenic, antimony or bismuth and'combinations thereof.
  • the cathodes formed contain undesirable impurities including the Group V-A elements, namely arsenic, anti mony and bismuth, as well as lead, nickel, selenium and other impurities.
  • the impurities may be incorporated in the cathode in solution in the electrolyte which may in part be trapped Within the cathode, i.e. in capillary cracks of the cathode, in interstices or openings such as the spaces between the metal of the cathode and the supporting loops, etc.
  • saturation of the electrolyte with antimony and bismuth eventually give rise to the formation of precipitates which can be incorporated mechanically in the growing cathode.
  • the art has determined that various measures should be found for the electrorening of copper containing large proportions of antimony and bismuth, i.e. high-antimony and high-bismuth copper.
  • the electrolyte is processed to keep the antimony and bismuth concentration below the saturation level. If the amounts of these impurities are low, it is merely necessary to use the procedures which are employed to recover nickel from a copper-anode electrode. In this procedure, high-nickel electrolyte is discarded and low-nickel electrolyte is supplied to the electrorening tank.
  • the loW- nickel electrolytic solution is supplied at a Well deiined rate with respect to the quantity of electrolyte discarded, the ratio being described as the discarding ratio and is, for example, about 1% per day.
  • Another object of this invention resides in the provision of a process for preventing supersaturation of electrolytes, in the electrowinning of copper, with members of the Group V-A series of the Periodic Table.
  • Another object of the invention is to provide an improved method of operating a system for the electrorefining of copper from anodes containing antimony, bismuth land arsenic in amounts exceeding the acceptable limits of these elements in the cathode.
  • Another object of the invention is to provide an economical method of removing members of the Group V-A series of elements of the Periodic Table from an acid electrolyte, e.g. of the type provided in the electrowinning of copper.
  • the process of the present invention comprises continuously contacting at least a portion of the electrolyte used for the electrorening of a nonferrous metal, e.g. electrorefining of copper, with a chemical adsorbent of the class described to maintain the concentration of antimony and bismuth below at a level considered detrimental to operation of the electrolytic process and, therefore, below that at which supersaturation may occur in the electrolyte.
  • a nonferrous metal e.g. electrorefining of copper
  • Chemical adsorbents which can be used to advantage in the present process include a low-solubility metal-oxide hydrate having large effective surface area and high stability in sulfuric acid and include manganese oxide hydrate (pyrolusite) and stannic acid (SnOz-xHzO).
  • stannic acid has proved to be particularly desirable.
  • Stannic acid has a particular high stability in a solution of sulfuric acid and, for this reason, may be used in much smaller quantities than other metal oxide hydrates. Furthermore, stannic acid can be regenerated much more easily and much more completely.
  • the chemical adsorbent is preferably pelletized or granular and may be simply charged into the electrolytic solution and may be removed by filtering or decantatiou. Alternatively, the chemical adsorbent may be held in porous bags which are suspended directly in the electrolyte. It has proved to be particularly desirable to contact the electrolytic solution with the chemical adsorbent in a separate adsorber which is included in the electrolyte cycle.
  • the adsorber may consist of a drum which contains the adsorbent and is covered at both ends by a filter cloth and designed so that the liquor enters the drum at one end and purified liquid leaves the drum at another end.
  • the stannic acid is desirably used in granular or pelletized form.
  • the adsorber may consist of an adsorption tower in which the chemical adsorbent is used as in the known ion-exchange columns.
  • the process can be carried out in a particularly desirable ernbodiment in which only part of the electrolytic solution which flows through the cells is contacted with the chemical adsorbent and, when purified, is combined with the main flow of the solution.
  • the technical literature contains descriptions of processes of producing stannic acid by a treatment of metallic tin, its alloys and compounds with acids and oxidizing agents or directly with oxidizing acids.
  • stannic acid in the process according to the invention affords the additional advantage that such stannic acid need not be pure. It has surprisingly been found that it is even possible to use a stannic acid which contains certain amounts of those impurities which are to be removed by the process according to the invention from the electrolytic liquors used in refining non-ferrous metals.
  • stannic acid may be used which has been formed by a reaction of acids, particularly dilute hydrochloric acid, with calcium stannate formed as a result of the refining of lead with caustic soda (Harris process).
  • This stannic acid is particularly inexpensive because the calcium stannate obtained as a result of the refining of lead bythe Harris process is a particularly inexpensive source of tin and may be easily reacted in stoichiometric amounts with dilute acids and at room temperature to produce stannic acid in stoichiometric quantities.
  • Hydrochloric acid is vpreferable for this purpose because of its low cost. Washing and filtering result in a product which may be used directly and which may have, eg., the composition stated in Table 1.
  • the stannic acid can be regenerated by a treatment with acid and the regenerated stannic acid may be reused in the process according to the invention.
  • the stannic acid may be desirably regenerated by a treatment with nitric acid, hydrochloric acid or sulfuric acid in a concentration which is higher than the acid concentration in the liquor used for the electrolysis of copper.
  • the stannic acid may be particularly effectively regenerated by being re-converted into calcuim stannate, from which stannic acid is recovered by the above-described treatment with acid.
  • the stannic acid may be reconverted into calcium stannate by a direct treatment with milk of lime. In a particularly desirable process of regenerating stannic acid, the same is recycled to a Harris process of refining lead to form calcium stannate, from which ⁇ new stannic acid is recovered.
  • a tank for the electrowinning of copper using a sulfuric acid electrolyte and having a cathode and an anode as represented at 11 and 12.
  • the anode may be relatively impure and can contain concentrations of antimony and bismuth above those which are tolerable in the cathode.
  • electrolyte may be removed by a duct 13 and a pump 14 and passed via a distribution valve 15 through the electrolyte reprocess cycle which is diagrammatically represented at 16. Depleted ingredients of the electrolyte may be replenished at this point and nickel removed, the electrolyte thereafter returning at 17 to the refining tank 10.
  • valve 15 branches at 18 a portion of the recirculating electrolyte through a drum-type adsorber 19 in which a mass 20 of stannic acid adsorber pellets is held between a pair of filter cloths 21 and 22.
  • a preferential removal of antimony and bismuth is effected, the electrolyte being returned at 23 to the refining tank 10.
  • porous bags 24 of electrolyte permeable cloth (filter cloth) containing the stannic acid adsorbent in grannular form may be suspended ⁇ at 25 in the electrolyte Within the refining tank.
  • a valve 26 may be provided to branch all or part of the electrolyte to be processed into adsorption column27 in which the electrolyte passes downwardly through the stannic acid adsorbent therein. The electrolyte may then be returned at 28 to the tank 10. Finally, a portion or all of the electrolyte may be passed through a filter 30 to recover the depleted adsorbent when the latter is deposited directly in the electrolyte of refining tank 10' as represented at 31. 'Ihe electrolyte can then be returned at 32 to the normal reprocess cycle represented at 16.
  • the depleted adsorbent is delivered at 33 from the bags 24, at 34 from the drum 19, at 35 from the filter 30 and at 36 from the column 27 to a regenerating stage 37 at which lime may be added to form calcium stannate which, in turn, is delivered at 38 to the stannic acid production stage 50.
  • the depleted stannic acid is delivered at 39, 40, 41 and 42 to the lead-refining stage 43 in which the Harris process is practiced.
  • the addition of caustic soda in the Harris process is represented at 44.
  • the calcium stannate derived at 45 from the lead-retining stage and the calcium stannate from the lime precipitator 37 are delivered to the stannic acid regenerator 50 to which a dilute mineral acid is supplied at 46 to produce stannic acid in stoichiometric quantities as described before.
  • the depleted adsorbent is delivered at 51, 52, 53 and 54 directly to the stannic acid regenerator 50, to which a mineral acid is supplied at 46.
  • the regenerated stannic acid is delivered to the column 27 as represented at 47, is introduced into the bath directly as shown at 31, is placed in the bags 24 as indicated at 48 and is supplied to the adsorbent drum 19 as shown at 49.
  • Example I 100 grams stannic acid recovered from calcium stannate that had been formed in a Harris process-this stannic acid is designated A in Table 1Were charged in a state of ltine division into 100 liters of a warm electrolytic liquor at a temperature of 60 C., which was shaken for a short time, whereafter the stannic acid was filtered off immediately. The temperature was maintained constant during these steps. The residue retained by the filter is designated B in Table 1. The duration of the entire process was only 1A hour. The conditions and results of the experiment are stated in Tables 1 and 2. The moisture values are not characteristic because they will obviously depend on the degree of suction used in the iiltration step.
  • Example II Anode copper containing 0.1% antimony and 0.015% bismuth was processed at arate of metric tons per day.
  • the electrolyte was constantly treated with stannic acid in a separate adsorber plant. and was then returned into the electrolytic cycle.
  • 1.1 metric tons of tin in the form of stannic acid was used in this process, by which the concentration of impurities in the electrolyte was held at 0.1 gram antimony per liter and 0.035 gram bismuth per liter. In this process, n-o oating slime and no deposits on the pipe walls of the electrolyte conduit system were observed.
  • yln a process for the electrolytic refining or electrowinning of a nonferrous metal with a sulphuric acid electrolyte for the electrolytic reiining of copper, the irnprovement which comprises the step of contacting at least a portion of said electrolyte with a chemical adsorbent constituted as a metal-oxide hydrate selected from the group which consists of pyrolusite and stannic acid and adapted to remove from said electrolyte at least one element selected from the group which consists of arsenic, antimony and bismuth, thereby preventing accumulations of excesses of said elements in said electrolyte.
  • a chemical adsorbent constituted as a metal-oxide hydrate selected from the group which consists of pyrolusite and stannic acid and adapted to remove from said electrolyte at least one element selected from the group which consists of arsenic, antimony and bismuth, thereby preventing accumulations of excesses

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US105847A 1970-01-31 1971-01-12 Process for preventing supersaturation of electrolytes with arsenic,antimony and bismuth Expired - Lifetime US3696012A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702004410 DE2004410B2 (de) 1970-01-31 1970-01-31 Verfahren zur vermeidung von uebersaettigung der elektrolytloesungen an einer oder mehreren der verunreinigungen arsen, antimon, wismut bei der elektrolytischen raffination von nicht eisenmetallen, insbesondere kupfer

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US (1) US3696012A (fr)
JP (1) JPS5422921B1 (fr)
BE (1) BE762340A (fr)
CA (1) CA989344A (fr)
ES (1) ES387754A1 (fr)
FI (1) FI53719C (fr)
GB (1) GB1326813A (fr)
PL (1) PL70544B1 (fr)
SE (1) SE364734B (fr)
ZA (1) ZA708241B (fr)
ZM (1) ZM171A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887448A (en) * 1972-04-19 1975-06-03 Norddeutsche Affinerie Method of preventing supersaturation of electrolytes with arsenic, antimony and bismuth
US3988225A (en) * 1973-04-17 1976-10-26 Norddeutsche Affinerie Method of preventing the supersaturation of electrolyte solutions with one or more of the impurities arsenic, antimony and bismuth, in the electrolytic refining of nonferrous metals, especially copper
US4046687A (en) * 1975-04-11 1977-09-06 Norddeutsche Affinerie Process for the adsorptive removal of arsenic, antimony and/or bismuth from an aqueous solution
US4136021A (en) * 1974-10-07 1979-01-23 Mobil Oil Corporation Sorbent for heavy metals
US5573739A (en) * 1994-10-28 1996-11-12 Noranda, Inc. Selective bismuth and antimony removal from copper electrolyte
US20090081370A1 (en) * 2004-08-27 2009-03-26 Atotech Deutschland Gmbh Method for coating substrates containing antimony compounds with tin and tin alloys
CN105132956A (zh) * 2015-10-12 2015-12-09 湖南金旺铋业股份有限公司 一种电解液连续净化除杂系统

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3887448A (en) * 1972-04-19 1975-06-03 Norddeutsche Affinerie Method of preventing supersaturation of electrolytes with arsenic, antimony and bismuth
US3988225A (en) * 1973-04-17 1976-10-26 Norddeutsche Affinerie Method of preventing the supersaturation of electrolyte solutions with one or more of the impurities arsenic, antimony and bismuth, in the electrolytic refining of nonferrous metals, especially copper
US4136021A (en) * 1974-10-07 1979-01-23 Mobil Oil Corporation Sorbent for heavy metals
US4046687A (en) * 1975-04-11 1977-09-06 Norddeutsche Affinerie Process for the adsorptive removal of arsenic, antimony and/or bismuth from an aqueous solution
US5573739A (en) * 1994-10-28 1996-11-12 Noranda, Inc. Selective bismuth and antimony removal from copper electrolyte
US20090081370A1 (en) * 2004-08-27 2009-03-26 Atotech Deutschland Gmbh Method for coating substrates containing antimony compounds with tin and tin alloys
CN105132956A (zh) * 2015-10-12 2015-12-09 湖南金旺铋业股份有限公司 一种电解液连续净化除杂系统

Also Published As

Publication number Publication date
GB1326813A (en) 1973-08-15
FI53719B (fr) 1978-03-31
BE762340A (fr) 1971-07-01
PL70544B1 (en) 1974-04-30
ZA708241B (en) 1971-09-29
ES387754A1 (es) 1973-05-16
ZM171A1 (en) 1971-12-22
FI53719C (fi) 1978-07-10
JPS5422921B1 (fr) 1979-08-10
SE364734B (fr) 1974-03-04
CA989344A (en) 1976-05-18

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