US3887448A - Method of preventing supersaturation of electrolytes with arsenic, antimony and bismuth - Google Patents

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

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Publication number
US3887448A
US3887448A US352079A US35207973A US3887448A US 3887448 A US3887448 A US 3887448A US 352079 A US352079 A US 352079A US 35207973 A US35207973 A US 35207973A US 3887448 A US3887448 A US 3887448A
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United States
Prior art keywords
electrolyte
adsorber
chemisorbent
bismuth
impurity
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Expired - Lifetime
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US352079A
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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 to US05/576,256 priority Critical patent/US3988225A/en
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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

Definitions

  • the cathodes produced contain undesirable impurities including the GROUP V (A) elements, namely arsenic, antimony and bismuth together with lead, nickel, selenic and other impurities.
  • GROUP V (A) elements namely arsenic, antimony and bismuth together with lead, nickel, selenic and other impurities.
  • the impurities may be incorporated in the cathode from solution or electrolyte which is mechanically received, e.g. in capillary cracks in the electrode, in interstices or openings such as the space between the metal of the cathode and the supporting loops, etc.
  • saturation of the electrolyte with antimony and bismuth eventually gives 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 electrorefining 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 levels below saturation. If the amounts of the impurities are low, it is merely necessary to use the processes which have been employed to recover nickel from a copper-containing electrolyte. In this process, high nickel electrolyte is discarded'and 'low nickel electrolyte is supplied to the refining tank,
  • Another'object of the invention is to provide an improved process for controlling the buildup of antimony, bismuth and arsenic in an electrolyte for the processing of non-ferrous metals, especially copper.
  • Another object of this invention resides in the provision of a process for preventing supersaturation of coppperelectrowinning electrolytes with members of GROUP V (A) of the PERIODIC TABLE.
  • Still another object of the invention is to provide an improved method of operating a system for the electrorefining of copper from anodes containing antimony,
  • Another object of the invention is to provide an economical method of removing members of the GROUP V (A) series of elements of the PERIODICAL TABLE from'acid electrolytes as obtained in the electrolytic refining of copper.
  • the invention is carried out by regenerating the chemisorbent in the same adsorber or adsorbers as the adsorption step is carried out originally.
  • the adsorbent floats, in accordance with the invention, and the adsorption and regeneration steps are carried out with floating adsorbent particles, the sulfuric acid required to regenerate the chemisorbent being circulated and regenerated, in turn, in an electrolytic unit which is included in the sulfuric acid recirculation path.
  • the process of the present invention thus comprises removing from electrolyte solutions, especially solutions used in the electrolytic-copper process, the impurities arsenic, antimony and bismuth substantially continuously with their introduction into the electrolyte with a large-surface chemisorbent which may float in the electrolyte (preferably the chemisorbent is or includes stannic acid) and regenerating the stannic acid with sulfuric acid of a higher concentration than the sulfuric acid in the spent electrolyte.
  • a large-surface chemisorbent which may float in the electrolyte (preferably the chemisorbent is or includes stannic acid) and regenerating the stannic acid with sulfuric acid of a higher concentration than the sulfuric acid in the spent electrolyte.
  • the regeneration is carried out with agents which remain in the adsorbers or acid cycles and need not be separately treated and under such conditions that the adsorption apparatus may be relatively small.
  • the adsorbent is floated upon the solutions with which it is to be contacted, i.e. the electrolyte to be treated by the adsorbent and the acid used to treat the adsorbent, while both adsorption and regeneration are carried out with the floating adsorbent particles.
  • Each of the liquids which is passed through the adsorber can be substantially completely removed therefrom without significant rinsing so that there is virtually no mixing of the different solutions.
  • the chemisorbent is provided in a layer which is coated onto a floating support together with layer-forming or film-forming materials.
  • the supports are preferably particles of a foamed synthetic resin, especially polystyrene or polyurethane and the film-forming material is preferably a substance having a high wear resistance, high capacity (for the reaction and adsorbent) and a high degree of activity, when combined with the reactant, so that the layer possesses a high reaction rate.
  • the film-forming substance must also have high chemical stability and adhesivity or bond strength, being able to bond even the peptizable chemisorbents.
  • the coating preferably, comprises a solution or suspension of the chemisorbent in a mixture of binders, at least one of which acts as a flocculating agent for the reactant.
  • the solution or suspension containing the mixture is used to coat the supports and, after drying, forms a tough, firmly adherent and swellable film which contains the reactant (i.e. the chemisorbent).
  • a binder system consisting of a mixture of binders including a waterinsoluble component or a component which swells only slightly in the presence of water and which imparts toughness and adhesive strength to the mixture.
  • the water-insoluble synthetic resin material which may be used in alkaline and acid solutions, may be any of those hitherto employed as latex paint vehicles.
  • the water-insoluble components is an acrylic ester in the form of the homopolymer or of polymers with vinyl ester, styrene, vinyl esters, vinyl chlorides or vinylidene chlorides.
  • the soluble or swellable component of the binders which is locked into the film so as to be insoluble but as to contribute to the permeability, is preferably a flocculating agent of the polyacrylate, polya'crylic ester, polyacrylamide, acrylic acid copolymer or polyethylene imine type.
  • the mixing ratio between the water-insoluble synthetic resin component and the water-soluble or water-swellable synthetic resin components may vary within wide limits and depends only upon the ultimate properties desired in the film. For films of higher hardness or "greater toughness and lower permeability, the water-insoluble binder component may be increased in proportion whereas, for greater permeability, the proportion of water-soluble and water-swellable binder components (insoluble in the film) will be present in greater proportion.
  • the water-soluble synthetic resin generally should make up 0.1 to 5 percent by weight, preferably 1 percent by weight, of the binder components, based upon the amount of water-insoluble 'resins, while the remainder may also consist of 10 to 1,000 percent by weight, preferably 200 percent by weight of water-swellable resins based on the amount of water-insoluble synthetic resin.
  • the resulting coating has been found to have a satisfactory permeability and air resistance. It is thus desirable to use water-soluble and water-swellable synthetic resin materials in combination.
  • the activity of the coating may be increased by the addition of soluble or insoluble substances to the solution or suspension forming the coating. These substances can be removed by solubilization and/or decomposition, e.g. into a gas, once the coating has been formed upon the support to leave pores in the coating to promote the reaction.
  • the substance which may be used to form the pores includes substances which meet the aforementioned solubility requirements, e.g. simple organic compounds such as sugar, urea and the like, simple organic or inorganic salts, especially sodium and potassium salts such as chlorides, sulfates, acetates and oxyllates, substances which have thermal decomposition temperatures within the stability range of the coating-and produce gas upon heating such as the hydrogen carbonates and.
  • viscosity control is important to provide a filmforming or smooth-coating homogenous deposit and that it may be necessary to add viscosity modifiers such as monomeric or polymeric amines and amino alcohols to eliminate the film-forming or homogenous character of the coating composition.
  • viscosity modifiers such as monomeric or polymeric amines and amino alcohols to eliminate the film-forming or homogenous character of the coating composition.
  • These materials which also serve as plasticizers, may be used in amounts up to 1,000 percent by weight based upon the waterinsoluble synthetic resin component.
  • a pump 2 withdraws enriched solution from a collecting box 1 through a conduit 3 and supplies the solution into a box 4 provided with an overflow weir 5.
  • a conduit 6 connected to the upper portion of the box 4 continuously returns a major part of the solution back into the collecting box 1. In spite of the long pipeline 3, fresh solution from the box 1 will always be available at a suitable temperature in'the overflow box 4 if the solution is recycled through 6 at a sufficiently high rate.
  • Solution is supplied to an absorberl9 through a conduit 7 and a valve 8.
  • the floating active mass 12 is disposed between flange-connectedsieve plates 10.
  • Filter cloths 11 having a suitable mesh size may also be used as retaining means, if desired.
  • the air from the adsorber 12 can escape through a venting conduit 13.
  • the adsorptively treated solution is returned into the collecting box 1 through a conduit 14, which constitutes a siphon, a draining funnel 15, a valve 16, and a conduit 17.
  • valve 8 When the adsorption has been terminated, the valve 8 is closed and a valve 18 is opened so that the solution is drained from the adsorber. Rinsing water is supplied through a valve 19 into the collecting box I or can be separately withdrawn through l4, l5. and a valve 20. The rinsing water will be drained when 19 is closed and 18 is opened.
  • Valves 21 are opened to initiate the regeneration of the adsorber mass 12. Sulfuric acid now flows into the adsorber and through 14, 15 and a valve 22 into a drain container 23. A heater 24 heats the acid to the desired temperature. Under control of a float switch 25, a pump 29 discharges the acid through a valve 26 and conduits 28 and 30 into the electrolytic cell 33, which is provided with insoluble anodes 31 and with cathodes 32. Only one anode and one cathode are shown.
  • cathodes may be desirable, for instance, to use anodes of lead and cathodes of copper.
  • the shape of the cathodes is not critical. They may consist of plates, rods, tubes, perforated plates or the like. Where plates are used, however, it will be recommended to immerse only narrow webs into the solution for a supply of current so that the gas-laden, floating mud which has been formed at the cathode can be carried without obstruction together with the draining acid through an outlet 34 onto a filter 36. All conventional units may be used as filters because the mud can be filtered well. Any acid which is supplied in excess is not filtered but is conducted over an overflow 35 into a reservoir 38.
  • the collecting box 1 owing to its high capacity, can be filled to such an extent and the purity of the electrolyte solution contained in said box can be adjusted so that the time required to regenerate the chemisorbent is bridged.
  • a second adsorber may be provided and the two adsorbers can operate in alternation so that the adsorption need not be interrupted.
  • SPECIFIC EXAMPLES EXAMPLE I 0.2 kilogram of a flocculating agent consisting of polyacrylamide are dissolved in 20 kilograms of a lowviscosity dispersion (25 percent) of an acrylate copolymer which is conventional as a paint vehicle. 20 kilograms diethanolamine are added to the viscous, filament-forming solution to render it spreadable. This mixture and 40 kilograms of a high-viscosity dispersion of an acrylic ester copolymer conventional as a paint vehicle, 50 kilograms calcium stannate, l kilogram sodium hydrogen carbonate and kilograms prefoamed Styropor P 455 (polystyrene) beads are intimately blended until a uniform sticky coating has been formed on each Styropor particle.
  • Styropor P 455 polystyrene
  • the material is dried in loosened layers at temperatures up to about 100C.
  • the process can be considerably accelerated even at a low temperature by a circulation of air. the use of a vacuum, and tumbling. It will be highly desirable to tumble and at the same time to supply warm air through the tumbling mechanism.
  • any desired insoluble substances preferably barite or lead sulfate, may be admixed in the required amount to the mixtures.
  • EXAMPLE 4 100 grams stannic acid on polystyrene beads treated as above to contain calcium stannate and reformed into stannic acid as described in the aforementioned patent this stannic acid is designated A in Table l were charged into 100 liters of a warm copper-refining electrolytic liquor at a temperature of 60C, the electrolyte being drawn off from the adsorber in which the stannic acid/foamed polystyrene floated. The temperature was maintained constant during these steps. The residue retained in the adsorber is designated B in Table l. The duration of the entire process was only A; 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 elimination of electrolyte. The stannic acid was regenerated by circulating sulfuric acid downwardly through the floating particles.
  • 0.2 kilogram flocculating agent consist I ing of polyacrylamide are added as an aqueous solution of 1 percent concentration. 2 kilograms, polyethylene imine are added to thicken the mixture.
  • 1 kilogram sodium hydrogen carbonate as a pore-forming agent is replaced by a mixture of 0.5 kilogram sodium hydrogen carbonate, 10 kilograms chalk and 2.5 kilograms common salt.
  • a process for preventing supersaturation of an electrolyte with an impurity selected from the group which consists of arsenic, antimony and bismuth which comprise the steps of:
  • said particles consist of a resin selected from the group which consists of polystyrene and polyurethane and said binder system comprises a water-insoluble binder component selected from the group which consists of polymers of acrylic acid, homopolymers and copolymers of acrylic esters with vinyl esters, styrene. vinyl ethers. vinyl chloride and vinylidene chloride. a further binder component serving as a flocculating agent for said chemisorbent and selected from the group which consists of polyacrylates, polyacrylic esters, acrylic esters copolymers, polyacrylamides and poly-ethylene imines.

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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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Water Treatment By Sorption (AREA)
US352079A 1972-04-19 1973-04-17 Method of preventing supersaturation of electrolytes with arsenic, antimony and bismuth Expired - Lifetime US3887448A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05/576,256 US3988225A (en) 1973-04-17 1975-05-12 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

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2218934A DE2218934C2 (de) 1972-04-19 1972-04-19 Verfahren zur Vermeidung von Übersättigung der Elektrolytlösungen an einer oder mehreren der Verunreinigungen Arsen, Antimon, Wismut bei der elektrolytischen Raffination von Nichteisenmetallen, insb. Kupfer

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US05/576,256 Continuation-In-Part US3988225A (en) 1973-04-17 1975-05-12 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

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JP (1) JPS4947203A (en(2012))
BE (1) BE798370R (en(2012))
CA (1) CA1011280A (en(2012))
DE (1) DE2218934C2 (en(2012))
ES (1) ES413775A2 (en(2012))
FI (1) FI55055C (en(2012))
GB (1) GB1420455A (en(2012))
PL (1) PL85511B1 (en(2012))
SE (1) SE377139B (en(2012))
ZA (1) ZA732076B (en(2012))
ZM (1) ZM6473A1 (en(2012))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4404071A (en) * 1980-06-14 1983-09-13 Dowa Mining Co., Ltd. Method of treating electrolytic solution of copper for purification and reuse thereof
WO1992001457A1 (en) * 1990-07-20 1992-02-06 Slagel, David Products and processes for the treatment of the alimentary canal

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52125605U (en(2012)) * 1976-03-22 1977-09-24
DE2633451C3 (de) * 1976-07-24 1980-08-28 Hoechst Ag, 6000 Frankfurt Herstellung von Bakterienzellmasse
JPS61227190A (ja) * 1985-03-29 1986-10-09 Miyoshi Oil & Fat Co Ltd 銅電解液中の不純金属イオンの除去方法
GB2279588B (en) * 1993-06-02 1997-07-09 Isambard Services Limited Microwave and/or radio frequency sensitised catalytic oxidation

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US489632A (en) * 1893-01-10 Frank gruessner
US2793183A (en) * 1954-07-15 1957-05-21 Clayton Manufacturing Co Electrolytic and ion exchange treatment of water
US2798040A (en) * 1955-09-15 1957-07-02 Dow Chemical Co Electrowinning of metals
US2888390A (en) * 1956-11-08 1959-05-26 Anaconda Co Electrolytic refining of copper
US3536615A (en) * 1969-08-06 1970-10-27 Col Mont Corp Method of and apparatus for treating oil leakage
US3547810A (en) * 1968-05-22 1970-12-15 Hal B H Cooper Treatment of water
US3676357A (en) * 1969-03-06 1972-07-11 Snam Progetti Compositions useful for eliminating water surface pollution caused by organic substances
US3696012A (en) * 1970-01-31 1972-10-03 Norddeutsche Affinrie Process for preventing supersaturation of electrolytes with arsenic,antimony and bismuth
US3755161A (en) * 1970-02-05 1973-08-28 Osaka Soda Co Ltd Treatment process for removal of metals and treating agent therefor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US489632A (en) * 1893-01-10 Frank gruessner
US2793183A (en) * 1954-07-15 1957-05-21 Clayton Manufacturing Co Electrolytic and ion exchange treatment of water
US2798040A (en) * 1955-09-15 1957-07-02 Dow Chemical Co Electrowinning of metals
US2888390A (en) * 1956-11-08 1959-05-26 Anaconda Co Electrolytic refining of copper
US3547810A (en) * 1968-05-22 1970-12-15 Hal B H Cooper Treatment of water
US3676357A (en) * 1969-03-06 1972-07-11 Snam Progetti Compositions useful for eliminating water surface pollution caused by organic substances
US3536615A (en) * 1969-08-06 1970-10-27 Col Mont Corp Method of and apparatus for treating oil leakage
US3696012A (en) * 1970-01-31 1972-10-03 Norddeutsche Affinrie Process for preventing supersaturation of electrolytes with arsenic,antimony and bismuth
US3755161A (en) * 1970-02-05 1973-08-28 Osaka Soda Co Ltd Treatment process for removal of metals and treating agent therefor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US4404071A (en) * 1980-06-14 1983-09-13 Dowa Mining Co., Ltd. Method of treating electrolytic solution of copper for purification and reuse thereof
WO1992001457A1 (en) * 1990-07-20 1992-02-06 Slagel, David Products and processes for the treatment of the alimentary canal
GB2262286A (en) * 1990-07-20 1993-06-16 Slagel David Products and processes for the treatment of the alimentary canal
GB2262286B (en) * 1990-07-20 1994-10-12 Slagel David Products and processes for the treatment of the alimentary canal
US5843482A (en) * 1990-07-20 1998-12-01 Tillotts Pharma Ag Products and processes for the treatment of the alimentary canal

Also Published As

Publication number Publication date
ES413775A2 (es) 1976-03-01
FI55055B (fi) 1979-01-31
BE798370R (fr) 1973-10-17
FI55055C (fi) 1979-05-10
DE2218934C2 (de) 1974-04-18
PL85511B1 (en(2012)) 1976-04-30
SE377139B (en(2012)) 1975-06-23
ZM6473A1 (en) 1973-12-21
JPS4947203A (en(2012)) 1974-05-07
ZA732076B (en) 1973-12-19
DE2218934B1 (de) 1973-09-13
GB1420455A (en) 1976-01-07
CA1011280A (en) 1977-05-31
DE2218934A1 (en(2012)) 1973-09-13

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