US3753877A - Elimination of floating slime during electrolytic refining of copper - Google Patents

Elimination of floating slime during electrolytic refining of copper Download PDF

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US3753877A
US3753877A US00146663A US3753877DA US3753877A US 3753877 A US3753877 A US 3753877A US 00146663 A US00146663 A US 00146663A US 3753877D A US3753877D A US 3753877DA US 3753877 A US3753877 A US 3753877A
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electrolyte
copper
antimony
arsenic
anode
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Lindstrom N Rune
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Boliden AB
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Boliden AB
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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

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  • the present invention relates to a method for eliminating floating slime when refining copper electrolytically with copper anodes which are contaminated with antimony and/or bismuth.
  • Copper refining by electrolysis is efiected between an anode and a cathode in an electrolyte comprising an aqueous solution of copper sulphate, the copper content normally being 35-50 g./l., and in the presence of approximately 150-250 g./l. sulphuric acid, which increases the electrical conductivity of the electrolyte.
  • an electrolyte comprising an aqueous solution of copper sulphate, the copper content normally being 35-50 g./l., and in the presence of approximately 150-250 g./l. sulphuric acid, which increases the electrical conductivity of the electrolyte.
  • arsenic together with antimony and bismuth in solution forms so-called floating slime, which is deleterious to the current efliciency and the cathode quality.
  • the electrolysis is normally carried out at temperatures between 55 and 65 C. At temperatures higher than 65 C. the amount of water evaporated from the electrolyte is extremely high, which ultimately results in higher heating costs. Moreover, at such high temperatures the cathod structure and therewith the quality of the cathode copper is impaired. At temperatures below 55 C. there is a risk of anode passivation.
  • the anode normally contains from 98 to 99.5% copper.
  • metals of more noble character than copper such as silver, gold and the platina metals are insoluble and together with other insoluble impurities in the copper, such as selenides and tellurides, form a grayish-black to black slime which is initially built up as a 0.5-1 cm. thick coating on the anode surface but which gradually loosens and sinks to the bottom of the electrolytic cell.
  • the layer of slime on the anode so-called anode slime, also contains finely divided, copper powder due to the fact that the anode contains oxygen.
  • the oxygen in the anode copper is present, inter alia, as copper(I)oxide, Cu O.
  • Copper(I)oxide is dissolved in the electrolyte according to the reaction Patented Aug. 21, 1973 Cu O+H SO CuSO -l-H 'O+Cu because at equilibrium Cu ++Cu 2Cu+ the reaction is considerably moved to the left.
  • the copper powder formed is incorporated in the anode slime.
  • Copper powder is also formed in the anode slime owing to the fact that the reaction Cu- Cu ++2e is slower than the reaction Cu Cu+ +e'". in this way a surplus of Cu' -ions is formed adjacent the anode surface, which ions, in accordance with the above equilibrium, are later disproportioned to Cu -ions and finely divided copper.
  • the lead present in the system passes primarily into solution as Pb -ions, but is immediately precipitated as PbSO and follows the anode slime.
  • the tin present in the system primarily passes into solution as Sn +-ions, but is then precipitated as tin(IV)hydroxide in gel form and also follows the anode slime.
  • the nickel and arsenic present in the system pass practically completely into solution.
  • Ni +-ions are not precipitated and the concentration of Ni +-ions in the electrolyte would increase if the electrolyte were not drained OE and replaced with freshly produced nickel free electrolyte.
  • the drained electrolyte can be evaporated and the nickel sulphate and the copper sulphate can be recovered. Residual copper in the drained electrolyte is then recovered by electrolysis using insoluble anodes. The presence of nickel-ions in the solution also reduces the solubility of the copper sulphate and lowers the electrical conductivity of the electrolyte.
  • the amount of arsenic contained by the anode normally exceeds the quantity required stoichiometrically for precipitating antimony and bismuth, and hence draining off the electrolyte also assists in regulating the arsenic content in the solution. Draining of the electrolyte also serves to maintain a constant content of copper in the electrolyte. For example, if no electrolyte were drained off, the copper content of the electrolyte would increase as a result of the aforementioned reaction and because oxygen dissolved in the electrolyte oxidizes the finely divided copper powder contained in the anode slime and the electrodes which consist of copper, whereupon copper(II)ions pass into solution.
  • the fresh electrolyte which is used to replace the drained electrolyte should therefore be free from nickel and arsenic and have a low copper content. It is often an advantage to use an electrolyte which comprises solely diluted sulphuric acid.
  • the copper content in the electrolyte can also be kept at a constant level by introducing insoluble anodes, for instance lead, in one or more cells. Thus, it is possible to reduce the copper content without increasing the drainage. In this way it is possible to keep a high arsenic content in the electrolyte without taking further measures.
  • Soluble oxygen in the electrolyte also oxidizes the three valent arsenic and three valent antimony present to the five valent state. It is presumed that Cu(I) ions catalize this oxidation.
  • a thin layer of electrolyte is formed around the surfaces of the electrodes having a composition ditferent to the main body of the electrolyte.
  • Circulation in a conventional electrolysis cell cannot affect the composition of these films to any appreciable extent.
  • the cathode film becomes deplete of copper ions and slightly enriched with sulphuric acid, and consequently the density becomes lower than the density of the main 'body of the electrolyte, whereby the depleted electrolyte flows upwards along the cathode.
  • the anode film is enriched with copper ions and slightly depleted of sulphuric acid and thereby obtains a greater density than that of the main body of electrolyte, and hence the anode film enriched with copper sulphate flows downwards along the anode.
  • This behavior of the film causes an enrichment of copper sulphate in the lower parts of the electrolytic cell. To avoid an uneven result, this must be counteracted by some form of vertical circulation of the electrolyte through the cell.
  • a vertical circulation can be achieved by removing the electrolyte either from the upper part of the cell and admitting electrolyte to the lower part or vice versa, at the same time as a certain horizontal circulation is efiected by admitting the electrolyte to one end of the cell and removing it from the other.
  • the differences in the concentration of the copper sulphate between the upper part and the lower part of the cell is more effectively equilized with increasing circulation rate.
  • a normal circulation rate is -20 l./rnin. through an electrolysis tank containing 5000 l.
  • the amount of energy consumed per unit of precipitated copper increases with increasing current density.
  • the fact that with an increased current density it is possible to increase the production rate and obtain a more rapid run of material is naturally an economic advantage.
  • the consumption of energy has small economical significance in comparison with the capital costs, and therefore most plants operate with the highest possible current density, normally 200-270 a./rn.
  • the size of the cathode and anode is normally selected on the basis of a compromise made between difierent economical and technical viewpoints, and is generally approximately 1 x 1 m.
  • the electrolysis process is carried out with each electrode in series, whereby one side of the electrode serves as a cathode and the other side as an anode.
  • all cathodes and anodes of each cell are connected in parallel.
  • the distance between the centre lines of the anodes is normally 9-13 cm. and the cathodes are placed centrally therebetween.
  • a floating slime When producing electrolytic copper, a floating slime is normally formed whichconsists of an oxide complex of bismuth, arsenic and antimony in proportions which are dependent on the concentration of these substances in the electrolyte. This concentration depends primarily on the contents of said elements in the anodes. Floating slime shows very small tendency to settle, remains suspended in the electrolyte and impurifies the cathode copper and causes growths to form on the cathode, which can result in short circuiting between the anode and the cathode and thereby reduce the current efliciency. Moreover, growths on the cathode act as settling surfaces for the anode slime.
  • the quality of the cathode is valued by determining the soft annealing temperature (recrystallisation temperature).
  • the present invention is concerned with a method for electrolytically refining copper anodes which contain more than 200 grams of antimony per ton and/or more than grams of bismuth per ton without getting floating slime, and is characterized by the steps of regulating the quantities of trivalent arsenic, pentavalent arsenic and pentavalent antimony in the electrolyte so that in the steady state the content of As(1l) exceeds 1 g./l., the content of As(V) exceeds 2 g./l. and the quantity of Sb(V) is less than 0.05 g./l.
  • trivalent arsenic can be introduced to the electrolyte in quantities at which the content of trivalent arsenic at the steady state is maintained above 1 g./ 1., preferably between 25 g./l.
  • the trivalent arsenic present in the system will absorb oxygen dissolved in the electrolyte, the arsenic being, at the same time oxidized to pentavalent arsenic.
  • the electrolyte shall contain at the steady state at least 2 g. of As(V) /l. preferably 7-15 g./l., causing crystalline arsenates of trivalent antimony and bismuth to precipitate.
  • the content of pentavalent arsenic is of greater significance than the content of trivalent arsenic.
  • the increase of AS(HI)-content of the electrolyte can be caused by dissolving a suitable As(III) compound, for example AS203, in the electrolyte or by adding an aqueous solution of AS203 thereto. It is also possible to admit arsenic to the electrolyte via the anodes, from which it passes into solution as trivalent arsenic.
  • the present invention thus includes a method for completely avoiding the formation of flotation slime in the case of anodes which contain high contents of antimony, and it has been discovered that anodes having, for example, up to 2500 grams of antimony per ton can be used successfully. Furthermore, the present invention solves the problems which occur when the anodes contain large quantities of bismuth, for example, up to 2500- g./t. Theoretically, anodes which have higher contents of antimony and particularly bismuth can be used since in respect of the formation of floating slime no upper limit with regard to the antimony and bismuth contents has been observed.
  • the composition is probably SbOH AsO
  • bismuth arsenate is a defined compound which occurs in two crystal modifications, tetragonal (the stable) of monoclinic, with the composition BiAsO
  • the crystalline precipitates settle readily and behave principally in the same manner as, for example, PbSO and sink to the bottom of the tank together with other anode slime.
  • the method of the present invention thus prevents the formation of pentavalent antimony to an extent such that the concentration in the solution is maintained below 0.05 g./l., preferably below 0.02 g./l.
  • concentration in the solution is maintained below 0.05 g./l., preferably below 0.02 g./l.
  • formation of the previously described floating slime is rendered impossible and crystalline antimony arsenate and bismuth arsenate precipitate onto graft crystals present in the anode slime. If minor quantities of pentavalent antimony are formed these are removed by co-crystallisation.
  • the crystallisation also causes the total contents of antimony and bismuth in the electrolyte to be greatly reduced.
  • trivalent arsenic as a mean of preventing the formation of pentavalent antimony, oxidation of trivalent antimony by ambient air can be prevented by excluding contact of the electrolyte and atmospheric air by means of air tight pumps and an air tight circulation system, for example.
  • the content of pentavalent antimony can be maintained in this way below 0.05 g./l.
  • the electrolytic cells can be protected against atmospheric oxygen by known expedients devised for the purpose of reducing evaporation of the electrolyte surface, for example expedients as covering the electrolyte with buoyant plastic bodies, plastic cloths or an oil layer.
  • the sulphur dioxide is suitably added to the electrolyte in liquid form or in gas form and can be charged to the system through suitable metering devices, such as nozzles, and this is suitably admitted at the lower part of the electrolytic cell.
  • sulphur dioxide is supplied to a connected absorption apparatus through which a small portion of the electrolyte is circulated.
  • a connected absorption apparatus through which a small portion of the electrolyte is circulated.
  • the absorption column used to introduce sulphur dioxide into the diverted portion of the electrolyte stream can be followed by a stripper adapted to remove completely all 50 residues so that an odourless electrolyte is obtained. It is normally necessary to supply heat to the stripper in order to prevent the electrolyte from being cooled by evaporation with subsequent risks of copper sulphate crystallising out. However, in order to render it unnecessary to heat the electrolyte to boiling point in order to strip the sulphur dioxide, an inert gas can be passed through the stripper.
  • the inert gas used can be air, and since neither metallic copper nor any other catalyst is present the trivalent arsenic or trivalent antimony is not oxidized to the corresponding pentavalent state. In the case of using inert gas for stripping you might prevent cooling of the electrolyte by adding steam.
  • the mechanism of anode passivation has been established in connection with the work carried out in developing the present invention.
  • the anode slime present on the anode in the form of a thick coating renders it difficult for copper sulphate to diliuse from solution adjacent the anode surface out into the main body of the electrolyte.
  • Copper sulphate crystals then precipitate in the anode film and block the passage of the current. This blocking effect leads to an uneven dissolution of the anode and cavities and holes occur by the side of non-electrolytically dissolved areas.
  • antimony passivation The tendency of anode passivation as a result of the sealing eifect of the gel-like floating slime on the anode slime layer has been found to increase considerably with increasing contents of antimony in the anodes, and consequently such passivation is normally designated antimony passivation.
  • the present invention eliminates the sealing floating slime in the anode film. In this way, the diffusion of copper ions through the anode film is facilitated and hence a higher copper ion concentration in the electrolyte can be permitted without the phenomenon of anode passivation taking place. This involves a corresponding increase in the copper ion concentration at the cathode, which is of particular importance with respect to improving the quality of the cathode copper at high current densities.
  • the intensity of the critical impurities antimony and bismuth is also increased.
  • this causes an increased impurity pressure in the electrolyte and therewith increased infection of floating slime on the cathode. Irrespective of what takes place at the anode, this sets a limit to the extent to which it is possible to increase current density without impairing the quality of the cathode.
  • the present invention also eliminates this limit with respect to the increase of current density.
  • EXAMPLE 1 The experiment was carried out on factory scale and the electrolyte partially protected against oxidation by ambient air by using an air tight circulation system. As(III) was supplied to the system as a reduction agent.
  • a conventional electrolyte comprising 40 g./l. Cu, 170 g./l. H 4 g./l. As, of which 0.5 g./l. Was Asflll), 0.43 g./l. Sb of which 0.10 g./l. Sb(V) and 0.35 g./l. Bi was used during the initial stage of the experiment. This represents a conventional electrolyte at the steady state.
  • Trivalent arsenic was added in the form of an aqueous solution containing 30 g./l. AS203 (saturated at room temperature). During the first two weeks, an aqueous solution containing 60% A3205 was also added.
  • the anodes comprised an anode copper having 98% Cu, 0.40% Ni, 0.40% Ag, 0.11% As, 0.035% Sb and 0.020% Bi.
  • the experiment was conducted in 28 conventional copper electrolytic cells in commercial operation. The steady state was reached after three weeks, the contents of the electrolyte being approximately 4 g./l. As(III) and approximately 11 g./l. As(V). The total antimony content stabilized at less than 0.2 g./l. of which was Sb(V) less than 0.02 g./l., and the bismuth content at less than 0.15 g./l.
  • cathodes of normal quality were initially obtained. The quality of the cathodes was progressively improved, however, owing to the reduced impurities of antimony and bismuth in the cathodes.
  • the electrolysis was initially effected in a conventional manner.
  • the quantity of electrolyte drained off to reduce the increase of copper content in the solution was held at the lowest possible level in order to preserve as much arsenic as possible in the electrolyte.
  • the following electrolyte composition was obtained at the steady state: 40 g./1. Cu, 70 g./l. H 80 11 g./l. As of which 0.7 g./l. was As(III), 0.40 g./l., Sb of which 0.10 g./l. was Sb(V) and 0.30 g./l. Bi.
  • the produced cathodes had the following co-analysis calculated in g./t.:
  • the adsorption column comprised a 1500 mm. long glass tube having a diameter of 40 mm. and filled with Rasching-rings.
  • the bottom of the column was provided with means for feeding sulphur dioxide to the column while the deflected electrolyte was fed to the top of the column.
  • the ab- 10 sorption column further comprised a similar glass tube of which the electrolyte treated with the sulphur dioxide was introduced and to which air and steam were charged to strip off the surplus sulphur dioxide.
  • a column 1 is provided with an electrolyte 2 at the top of the column.
  • a small container 3 in which gas entrained with the electrolyte is separated.
  • a gas distribution filter 4 arranged in the lower portion of the column 1 is a gas distribution filter 4 to which sulphur dioxide is passed through a conduit 5.
  • the column 1 is filled with Raschig-rings 6 and the downwardly flowing electrolyte meets the sulphur dioxide in counter-flow.
  • the column communicates with atmosphere through a conduit 7 and the electrolyte flows from the container 3 up through a conduit 8 and further through a connecting pipe 9 which communicates with atmos phere via a conduit 10 and the conduit 7.
  • the electrolyte is passed from the conduit 9 to a second column 11, similarly filled with Raschig-rings 12.
  • the column is provided at the lower end thereof with a container 13 for separating gas bubbles. Air and steam are passed through the lower portion of the column 11 through a distribution filter 14 via a conduit 15. The electrolyte is removed from the container 13 through a conduit 16 and returned to the electrolytic cell.
  • the amount of electrolyte passing through the S0 system was adjusted so that the content of As(III) in the electrolyte contained in the electrolytic cell was 3 g./l. To achieve this it was only necessary to pass 2% of the deflected and circulated electrolyte through the SO system.
  • the composition of the total amount of electrolyte in steady state was: 40% g./l. Cu, g./l. H 50 8 g./l. As(V), 3 g./l. As(III), 0.20 g./l. Sb, of which less than 0.02 g./l. was Sb(V) and 0.15 g./l. Bi.
  • the produced cathodes had lower contents of antimony, bismuth and arsenic than the aforementioned contents in the cathodes from commercial electrolysis.
  • Electrolysis of anodes with elevated contents of antimony and/or bismuth gave the same good results.
  • anodes containing 1100 g./t. Sb and 800 g./t. Bi the antimony and bismuth contents in the electrolyte was still low and cathodes produced from these anodes had the following co-analysis calculated in g./t.:
  • the total content of bismuth in the cathode copper was reduced by a third and the content of antimony reduced by half as compared with a conventional electrolyte and conventional anodes having a considerably lower content of antimony and bismuth.
  • the quantity of S0 required with the two aforementioned tests was 0.55 ton per 1000 tons of cathode copper.
  • the SO -System required is also of small dimensions. It can be calculated that for a complete electrolytic system having a capacity 1 1 of 100,000 ton Cu/year, two columns each of 4 meters in height are required, i.e. an absorption column with an inner diameter of 0.3 m. and a stripper column with an inner diameter of 0.4 in.
  • EXAMPLE 3 Commercial anodes were electrolyzed in a pilot-plant comprising five cells having three electrode pairs (three anodes and four cathodes) in each cell. The system was equipped with thyristorized current reversal equipment. Each test was carried out at a temperature of 60 C.
  • the composition of the anodes was: 98% Cu, 0.40% Ni, 0.40% Ag, 0.06% As, 0.07% Sb and 0.02% Bi.
  • Test l.-Conventional electrolysis A conventional electrolyte was used containing 40 g./l. Cu at the upper edge of the electrodes and 45 g./l. at the lower edge thereof, and 170 g./l. H 80 4 g./l. As, of which 0.5 g./l. was As(lII), 0.5 g./l. Sb and 0.35 g./l. Bi.
  • Test 2 Current reversal with conventional electrolyte
  • Conventional electrolyte was used in this test and the current was periodically reversed, the current being lead in one direction for 100 sec. (toward current) and then in the opposite direction for 6 sec. (back current). It was possible to raise the effective current density (production intensity) by 23-27% with unchanged soft annealing temperature of the product compared with test 1.
  • the limits were set partly by increased intensity of floating slime, which infected the cathodes, and partly by tendencies to anode passivation.
  • Test 3.Current reversal with electrolyte according to the invention The electrolyte used was produced in accordance with the present invention and contained 46 g./l. Cu at the upper edge of the electrodes and 51 g./l. at the lower edge of the electrodes, and 170 g./l. H 80 3 g./l. As(III) and 11 g./l. As(V), 0.2 g./l. Sb and 02 g./l. Bi.
  • the principle of current reversal was applied, the forward current having a duration of 100* sec. and the back current a duration of 6 sec.
  • the elfective current density (the production intensity) could be increased from 46-50% at the same time as an improved cathode copper quality was obtained (a soft annealing temperature 179 C.).
  • an improvement for avoiding the formation of floating slime comprising using an electrolyte containing at least 3 g./l. of arsenic in the trivalent and pentavalent form and supplying sulphur dioxide to said electrolyte in a quantity sufficient to maintain at least 1 g./l. of said arsenic in the trivalent form.
  • a method according to claim 4 characterized by adding trivalent arsenic in the form of arsenic trioxide.
  • a method according to claim 4 characterized by adding the trivalent arsenic compound to a withdrawn part stream of electrolyte, and then recirculating said part stream of electrolyte.
  • a method according to claim 1 characterized by regulating the total content of arsenic and by regulating the ratio between trivalent and pentavalent arsenic by reducing pentavalent arsenic to trivalent arsenic with sulphur dioxide.
  • a method according to claim 8 characterized in that the reduction is effected by adding sulphur dioxide to the electrolyte.
  • a method according to claim 9 characterized by adding the sulphur dioxide in gas form.
  • a method according to claim 1 characterized by periodically reversing the current during the electrolysis, said periods being of the order of 1-15% of the total electrolysis period.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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US00146663A 1970-05-28 1971-05-25 Elimination of floating slime during electrolytic refining of copper Expired - Lifetime US3753877A (en)

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SE07382/70A SE348001B (no) 1970-05-28 1970-05-28
SE07381/70A SE348000B (no) 1970-05-28 1970-05-28
SE07380/70A SE347999B (no) 1970-05-28 1970-05-28

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AT (1) AT309090B (no)
BE (1) BE767811A (no)
CA (1) CA989345A (no)
DE (1) DE2126141A1 (no)
ES (1) ES391620A1 (no)
FI (1) FI52743C (no)
GB (1) GB1327525A (no)
NO (1) NO127405B (no)
PH (1) PH9417A (no)
ZM (1) ZM7171A1 (no)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179495A (en) * 1977-08-25 1979-12-18 Sumitomo Metal Mining Company Limited Method for removing As, or As and Sb and/or Bi from sulfuric acid
WO2019219821A1 (en) * 2018-05-16 2019-11-21 Metallo Belgium Improvement in copper electrorefining
CN111020634A (zh) * 2019-12-27 2020-04-17 中南大学 一种基于定向晶型调控的铜电解液沉淀分离砷的方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4179495A (en) * 1977-08-25 1979-12-18 Sumitomo Metal Mining Company Limited Method for removing As, or As and Sb and/or Bi from sulfuric acid
WO2019219821A1 (en) * 2018-05-16 2019-11-21 Metallo Belgium Improvement in copper electrorefining
CN111020634A (zh) * 2019-12-27 2020-04-17 中南大学 一种基于定向晶型调控的铜电解液沉淀分离砷的方法

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FI52743B (no) 1977-08-01
DE2126141A1 (de) 1971-12-09
PH9417A (en) 1975-11-14
FI52743C (fi) 1977-11-10
BE767811A (fr) 1971-10-18
CA989345A (en) 1976-05-18
NO127405B (no) 1973-06-18
ES391620A1 (es) 1974-08-01
ZM7171A1 (en) 1971-12-22
GB1327525A (en) 1973-08-22
AT309090B (de) 1973-08-10

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