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US3875041A - Apparatus for the electrolytic recovery of metal employing improved electrolyte convection - Google Patents

Apparatus for the electrolytic recovery of metal employing improved electrolyte convection Download PDF

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Publication number
US3875041A
US3875041A US445435A US44543574A US3875041A US 3875041 A US3875041 A US 3875041A US 445435 A US445435 A US 445435A US 44543574 A US44543574 A US 44543574A US 3875041 A US3875041 A US 3875041A
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cathodes
cathode
cell
anode
anodes
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US445435A
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Walter W Harvey
Myron R Randlett
Karlis I Bangerskis
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Kennecott Utah Copper LLC
Kennecott Corp
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Kennecott Copper Corp
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Priority to US445435A priority Critical patent/US3875041A/en
Priority to US515513A priority patent/US3928152A/en
Priority to CA219,196A priority patent/CA1068641A/en
Priority to ZA00750696A priority patent/ZA75696B/xx
Priority to GB4667/75A priority patent/GB1504332A/en
Priority to JP50016989A priority patent/JPS5830393B2/ja
Priority to BE153570A priority patent/BE825794A/xx
Priority to SE7502038A priority patent/SE419240B/sv
Priority to DE19752508094 priority patent/DE2508094A1/de
Priority to US05/553,139 priority patent/US3979275A/en
Application granted granted Critical
Publication of US3875041A publication Critical patent/US3875041A/en
Priority to US05/860,511 priority patent/USRE30005E/en
Assigned to KENNECOTT CORPORATION reassignment KENNECOTT CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MAY 7, 1980. (SEE DOCUMENT FOR DETAILS) Assignors: KENNECOTT COPPER CORPORATION
Assigned to KENNECOTT MINING CORPORATION reassignment KENNECOTT MINING CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE DEC. 31, 1986. (SEE DOCUMENT FOR DETAILS) Assignors: KENNECOTT CORPORATION
Assigned to KENNECOTT CORPORATION, 200 PUBLIC SQUARE, CLEVELAND OHIO, 44114, A CORP. OF DE. reassignment KENNECOTT CORPORATION, 200 PUBLIC SQUARE, CLEVELAND OHIO, 44114, A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KENNECOTT MINING CORPORATION
Assigned to GAZELLE CORPORATION, C/O CT CORPORATION SYSTEMS, CORPORATION TRUST CENTER, 1209 ORANGE STREET, WILMINGTON, DE., 19801, A DE. CORP. reassignment GAZELLE CORPORATION, C/O CT CORPORATION SYSTEMS, CORPORATION TRUST CENTER, 1209 ORANGE STREET, WILMINGTON, DE., 19801, A DE. CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: RENNECOTT CORPORATION, A DE. CORP.
Assigned to KENNECOTT UTAH COPPER CORPORATION reassignment KENNECOTT UTAH COPPER CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). JULY 5, 1989 - DE Assignors: GAZELLE CORPORATION
Anticipated expiration legal-status Critical
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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
    • 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
    • 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

Definitions

  • Anode for electrowinning includes a non-conductive extension on its base and non-conductive convection baffles at opposite edges of its faces. Baffles and extension prevent electrodeposition on unwanted areas of cathode. Baffles, close spacing, and bubble 204/277 t b d d t' f 1 r 1 t n 204/277 u es cause esire convec ion 0 e ec ro y e 204/277 throughout cell.
  • convection m m W m Wm m 0 WWW RA nu .I m m c maw fi mW CT n nA ee 9 W68 rTo kSTGG e wvl, 025 .1999 NHHH U314 628 234 5 1 on 6 836 NH 2 baffles are positioned on vertical support members within the tank.
  • w o o cnc 0v a are c v u e r A /////////MV //v/..
  • the present invention is directed to an electrolytic process and apparatus for recovering copper and other metals.
  • the process and apparatus of the present invention are useful in both electrowinning and electrorefining.
  • a high current density is employed to deposit metal on a cathode.
  • current density is the ratio of current in amperes to the area of cathode in square feet and is expressed in ASP units.
  • the current density normally employed in prior art electrowinning process is about 21 ASE.
  • an increase in current density decreases the time required for a given amount of copper deposition.
  • the main obstacle preventing those skilled in the art from increasing the current density is the lack of a suitable convection system for the electrolyte.
  • the process and apparatus of the present invention is directed to a convention system which permits the current density in an electrolytic deposition process to be increased, while at the same time minimizing the incremental consumption of electrical power.
  • That system includes combination convection baffles and cathode guides on the anodes, or positioned in the tank, a predetermined close cathode-anode spacing, and a gas agitation means positioned below and between the faces of the cathode and anode.
  • a major benefit to be derived from the application of the method and apparatus of this invention is the elimi nation of electrical shorts due to contacts between anodes and cathodes. This beneficial feature greatly reduces the amount ofsystems work" required in commercial practice to locate and correct electrical shorts.
  • U.S. Pat. No. 1,260,830 to F. E. Studt. entitled Electrolytic Deposition of Copper From Acid Solutions relates to the electrolytic deposition of copper from acid solutions, wherein a means is provided to continuously agitate the electrolyte, particularly across the face of the anodes.
  • the agitation is provided by a mixture of sulfur dioxide gas and steam.
  • the purpose of the steam is to insure the correct temperature conditions.
  • the pipes through which the mixture of steam and sulfur dioxide is carried contain perforations or nozzles arranged at such angles that the escaping gas and steam will tend to impinge angularly upon the faces of the anodes, so that the electrolyte will be continuously circulated and maximum agitation will occur across the anode faces.
  • US. Pat. No. 3,412,004 to .I. B. Winters, entitled Test Plating Equipment and Method relates to a laboratory test electroplating apparatus in which an air or compressed gas distribution system is used to cause bubbles to assume random paths of travel through the electrolyte.
  • the prior art methods for agitating the electrolyte have not provided a sufficient amount of convection of the electrolyte which would enable a significant increase in the current density with an attendant production of high quality copper or other metals.
  • the prior art agitation methods have not been applicable to electorefining, because of the resulting suspension of anode slimes and the consequent deterioration of deposit quality.
  • the edges of the cathode blanks are maskedwith non-conducting or insulating material to prevent the metal being deposited on each face of the cathode from joining, which would make removal of the deposit from the cathode difficult.
  • An important side benefit of the convection scheme of the present invention is that insulating edging does not have to be positioned on the edges of a non-retentive cathode in order to prevent the edges of the deposit on each face from joining.
  • the processes and apparatus of the prior art are significantly improved by the convection system of the present invention.
  • the present invention includes close cathode-anode spacing, insulating convection baffles, and means for generating a sheet of gas bubbles be tween the cathodes and anodes.
  • current density can be significantly increased while enabling lower power consumption with an attendant production of high quality metal. Since it is preferred to utilize a non-retentive cathode, starting sheets are unnecessary with the present invention.
  • Significant economic advantages of the present invention are that it minimizes plant size. systems work, power consumption and metal inventories.
  • a further object of the present invention is to provide a novel method and apparatus for effecting vigorous electrolyte convection in an electrodeposition process.
  • a further object of the present invention is to provide an electrodeposition convection system which includes insulating convection baffles, close cathode-anode spacing and means for generating a sheet of gas bubbles between the cathod and anode faces.
  • a further object of the present invention is to provide an improved method and apparatus for electrorefining copper.
  • a further object of the present invention is to provide an improved method and apparatus for electrowinning copper.
  • FIG. 1 is a view of a prior art non-retentive cathode blank with an insulating edging applied thereto;
  • FIG. 2 is a perspective view of a non-retentive cathode blank having a layer of copper applied to both faces;
  • FIG. 3 is a sectional view taken along line 33 of FIG. 2;
  • FIG. 4 is a perspective view of a non-retentive cathode and bubble tubes for forming a fluidized sheet of gas bubbles adjacent to both faces of the cathode;
  • FIG. 5 is an exploded perspective view of the cathode clamps of FIG. 4, which are required only at very high current densities;
  • FIG. 6 is a perspective view of a portion of a cell showing an insoluble anode with insulating bottom extension and edge convection baffles;
  • FIG. 7 is an exploded perspective view of an anode clamp particularly adopted for use with cast soluble anodes in very high current density electrorefining;
  • FIG. 8 is a sectional view taken along line 88 of FIG. 6;
  • FIG. 9 is a sectional view taken along line 9-9 of FIG. 6;
  • FIG. 10 is a perspective view of bubble tubes in a bubble tube support member.
  • the present invention is directed to a method and apparatus for depositing superior quality cathode metal from all conventional electrolytes, including those having a high concentration of sulfuric acid.
  • the apparatus may be used in conjunction with several anode materials.
  • a lead-antimony anode is acceptable in the apparatus of the present invention.
  • the cathode may be a starter sheet or a non-retentive cathode blank formed of a material such as stainless steel or titanium.
  • an elongate non-retentive cathode blank is used.
  • non-retentive blanks have been employed in the prior art.
  • a problem associated with the prior art use of these cathode blanks is that the edges have to be masked with an insulating material, to prevent the metal which deposits on each face from joining and thereby making removal of the metal deposited difficult.
  • FIG. 1 shows a prior art non-retentive cathode blank 10 submerged in electrolyte 12.
  • the metal deposited thereon is removed after electrodeposition is complete.
  • the layer of metal deposited on the two faces of the cathode do not join each other in the vicinity of the side edges.
  • insulating edging 16 is applied to the edges of the cathode blank 10.
  • the anode extension is positioned on the bottom of the tank, with the anode positioned above it.
  • the side baffles in an electrorefining cell may be positioned on a support member and afflxed in the cell in relationship to the soluble anode.
  • Side baffles 18 and bottom extension 20 for insoluble anodes are best shown in FIGS. 6 and 9. Details of how side baffles l8 and bottom extension 20 prevent the deposition of copper on the edges of the cathode and also prevent undesired deflection of the ascending gas bubbles are amplifled at a more appropriate point in the specification.
  • FIG. 4 includes a perspective view of a non-retentive cathode blank 22, which is usable in accordance with the present invention. It is advantageous to form cathode 22 from Type 316 stainless steel having a standard 2B rolled finish. When this material is employed, no pre-treatment or break-in period is necessary for the cathode blank 22. Furthermore, it is easy to strip deposits from this cathode blank manually. Indeed, the deposits release easily from the cathode blanks 22 once the upper edges of the deposit are loosened. Deposits can also be detached by flexing the cathodes. It should be noted, however, that other materials can be employed in fabricating cathode blanks 22. For example, titanium blanks have been employed to advantage in the process of the present invention. Sheets of other conducting materials may be employed as cathode blanks, as appropriate to the nature of the metal to be deposited and the composition of the electrolyte.
  • the second common suspension means for an insoluble anode consists of two integrally cast verical lugs 26 enveloping sections of a rectangular suspension bar,
  • Soluble anodes employed in electrorefining are typically cast with outwardly directed lugs, or ears of nonrectangular cross-section.
  • the contact clamp detailed in FIG. 7 was designed for use in very high current density electrorefining by the method of the present invention.
  • contact clamps are superfluous at current densities of about 60 ASF or below; their use is strongly indicated at current densities of about 100 ASF and above.
  • Clamps used in production could be alternatively weight-activated cam type or of other suitable design not requiring manual fastening.
  • FIG. 6 shows a perspective view of an anode 30 which is used in the present invention.
  • Anode 30 is typically formed of a lead-antimony alloy. At this point, however, it is emphasized that the material from which the anodes are formed, forms no part of the present invention.
  • anodes may be fashioned of any material of suitable electrochemical and mechanical properties. It is, of course, preferable for the most effective use of the invention that the anodes be rigid and of uniform cross-section.
  • anode 30 includes a plurality of holes 32. The square perforations are a design feature of a good quality insoluble anode, employed in conventional copper electrowinning, but afford no special advantages in the practice of gas agitation.
  • baffles 18 and extensions 20 are electrically insulating or non-conductive. They may be formed of any electrically non-conductive material which is relatively stable in the electrolyte environment. Extensions and baffles have been fabricated from a polyvinyl chloride polymer, which has been found better suited to this use than other insulating materials of construction. such as polyethylene, polyproplene and fiberglass-reinforced epoxy board.
  • edge baffles 18 form narrow passageways through which the ends of cathode blanks 22 project.
  • Confinement of the deposit spread to within the borders of the cathode faces has distinct advantages in that (a) it eliminates time-consuming maintenance and replacement ofinsulating edging, (b) facilitates removal of deposits from the cathode blanks and (c) eliminates a source of contamination, namely the nodulose bead of deposit which typically forms along an edge strip.
  • a further useful feature of the edge baffles of the present invention is that, with the anodes in place in the cell, the cathodes are thereby guided accurately into correct position relative to anodes and bubble tubes.
  • Convection of the electrolyte in the system of the present invention is powered by gas agitation.
  • Gas agitation is an old technique in the electrodeposition art.
  • the convection system produces a fluidized sheet of relatively small, rapidly ascending gas bubbles that, together with the turbulence they create, result in vigorous mixing at the cathode surface, where mixing is most needed.
  • the convection system insures optimum deposition conditions such that the cathode is smooth and free of voids throughout all stages of its growth.
  • the gas agitation provides sufficient convection to prevent suspended particulates from lodging on the faces of the cathodes. Furthermore, the convection system avoids obstructions to electrolyte flow across the faces of the cathode and eliminates physical discontinuities of the cathode surface such as edging and loops which cause entrapment and accretion of solids. These features are particularly advantageous in the case of electrorefining, where large quantities of anode slimes are generated in the cell. It has been found that, contrary to the teaching of the prior art, the anode slimes can be disturbed to an appreciable degree without incurring enhanced incorporation of impurities into the cathode deposits.
  • the convection must be exceptionally vigorous and physical obstructions avoided, as is the case with the present invention.
  • the present invention prevents incorporation of particulate impurities such as are derived from corrosion or erosion of the insoluble anodes.
  • electrowon copper of exceptional purity has been produced while employing conventional lead or lead alloy anodes in electrolytes 'which are corrosive to these anode materials.
  • the small bubbles 50 are propelled into the electrolyte 12 from bubble tubes 52 located beneath the electrodes 20 and 22 in the tanks.
  • the air flow through the bubble tubes need not be large. For a inch O.D.
  • a suitable orifice diameter is 6/l000th inch (6 mils) at an orifice spacing of one-half inch.
  • a less suitable bubbler configuration may be employed if the desired improvement in current density and deposit quality is not as great.
  • the most suitable configuration of the bubbler comprises a rigid tube with closely spaced ([2 inch apart) round holes in diameter in the range of -7 mils. It has been found that bubble tubes having smaller diameter holes, e.g., 4 mils are not more efficient and are, moreover, more difficult to manufacture. It has also been found that bubble tubes with larger holes, e.g., 8 mils, expel an unnecessarily large volume of gas, or a comparable volume at a lower bubble velocity. If one bubble tube 52 is provided per cathode, as is shown in FIG. 9, an effective air flow is in the range of 3-4 SCFH per foot of cathode width or, for full-size cathodes, about 1.5 2.0 SCFH air per square foot of cathode.
  • This flow volume is equivalent to the rate of oxygen generation at an insoluble anode at an anodic current density of 135 to 180 ASF. It has been found that it is not so much the volume of air expelled as the total bubbletube/electrode configuration that determines the effectiveness of gas agitation. Lack of appreciation of this concept has probably retarded the more widespread application of gas agitation in large scale electrodeposition.
  • the incoming air is presaturated with water vapor at a temperature close to that of the electrolyte.
  • the bubble tubes can be operated indefinitely without plugging of the orifices.
  • the invention finally provides that the electrode separation be at its practical minimum given the size of the electrode supporting means and the clearance required for inserting and withdrawing the cathodes. Together with the gas agitation, the reduced spacing provides the means of minimizing power consumption in the electrowinning or electrorefining process.
  • the reduced spacing is maintained by a bottom rack 54 which is secured together by cross-members 58. Legs 60 attached to cross-members 58 support bottom rack 54 off the cell bottom. It will be clear that sufficient space must be provided at the sides and bottom of the cell to permit the electrolyte to circulate and to allow the slimes, if any, to settle out.
  • the bottom edges of the cathodes 22 are positioned in the electrowinning tank by the bubble tube support members 56 and are guided into position by the anode edge baffles 18.
  • the anode end baffles also serve to confine the bubble flow to the volume of electrolyte immediately adjacent to the cathode faces, thereby effecting the necessary concentration depolarization and uniform mass transport of metal ions to the cathodes.
  • the separation between the cathode blank or starter sheet and the insulating edge baffle is on the order of between about one-sixteenth to about one-eighth inch.
  • the gas agitation method of the present invention also has favorable consequences for the anode reaction.
  • the electrorefining embodiment not only is anode passivation fully forestalled, but the soluble anodes are caused to corrode uniformly, thereby allowing a reduction in the amount of anode scrap.
  • Improved efficiency is derived by substitution of soluble anodes having regular cross-section for the somewhat irregular anodes cast by customary means.
  • the anode bottom extension 20 also an insulator, functions to confine the bubble flow in the lower regions and to position the anode 30.
  • the anode 30 is also maintained in position by the bottom rack 54.
  • the bubbler itself is held in position below and adjacent to the cathode surface by the bubbler support member 56.
  • the anode bottom may be inserted into the bottom rack, for which purpose the vertical members 54 are covered with insulating material.
  • the insulating barriers 20 maybe positioned in bottom rack 54 so that their upper edges are brought into contact with or in proximity to the bottoms of the soluble anodes.
  • the principal'incentive for electrowinning or electrorefining at high current density is the attendant reduction in plant size, metal inventory, and labor requirements. Further advantage is gained by elimination of several of the normal processing steps, including starter sheet production and short clearing. In order to take full advantage of electrodeposition at high current density, however, the process must I) take place at currents which are much less than the limiting current density and (2) minimize the power consumption.
  • the present invention presents a combination of factors which together accomplish these conditions by reducing the spacing of the electrodes and providing an agitation system which assures an adequate supply of metal ions to all parts of the cathode surface. The agitation has the additional benefit of mixing the electrolyte bath sufficiently to make it difficult for suspended particulate impurities to attach themselves to the faces of the cathode, thereby resulting in higher quality deposits.
  • Fine oxygen bubbles are formed at the insoluble anode during the electrowinning process. These fine bubbles reduce the concentration potential at the anode but are inadequate in providing mixing at the opposing cathode, even with close spacing of electrodes. The reason is that their small size causes them to drift ineffectively. Therefore, alternative agitation at the cathode is necessary, especially at high current densities, to bring about sufficient depolarization at the cathode. It has been found that gas agitation has the desirable characteristic in this invention of increasing the v cathodic depolarization as the electrode spacing is detem is best shown in FIG. 9, where the bottom rack 54,
  • the anode 30 and its bottom extension 20 and the anode edge baffles 18, together with the elongated cathode blank 22, form an enclosure which minimizes the lateral spreading or contraction of the sheet of bubbles.
  • Other configurations of supporting members in the tank may be used to confine the bubble flow; however, it has been found that the above configuration is most effective and convenient in allowing ease of loading and unloading of cathodes and virtual elimination of shorts due to misalignment or warping and bowing.
  • bubbler tubes may be pre-mixed into recirculating electrolyte and the mixture of bubbles and electrolyte introduced into the tank through a source located at the same approximate position as air bubbler tube 52 shown in the drawing.
  • the dimensions of the bubbler may vary and the hole size be enlarged to permit the passage of the correct volume of recirculated electrolyte and volume of entrained gas.
  • the essential criterion for the gas agitation generator is that it introduce small bubbles from a line immediately adjacent to the cathode face to form a sheet of rapidly ascending bubbles that continue in a direction immediately adjacent to the cathode surface until reaching the electrolyte surface.
  • the present invention has been applied to relatively pure electrolytes, such as are produced by liquid ion exchange extraction or are employed in starter sheet production, and to relatively impure electrolytes such as constitute electrorefining purge streams or as are produced by various processes ofv ore leaching.
  • the utility of the present invention becomes more manifest when dealing with impure electrolytes from which pure metal cannot normally be recovered at a low ratio of metal concentration to current density.
  • the lower limit for acceptable deposits is reached at a ratio of about 1.5 (grams Cu per liter- /ASF) because of the increase in the electrolyte viscosity and the consequent decrease in the mass transport coefficient of cupric ions occasioned by the presence of extraneous solutes at appreciable concentration.
  • EXAMPLE 1 (Typical high acid, high current density electrowinning)
  • the cathode-anode spacing was fixed at about 1.26 inches.
  • the copper and acid concentrations shown in Table I are those in the cell, not in the feed to the cell.
  • the suspendedmatter was held at a minimum with continuous recirculation and filtration.
  • the agitation was accomplished with the apparatus as shown in the drawings and with /8 inch O.D. stainless steel bubbler tubes with 0.020 inch wall thickness and 6 mil orifices at onehalf inch intervals.
  • Air was presaturated with water by sparging the air through heated water and supplied at about 1.0 SCFH per square foot of cathode.
  • a copper starting sheet was used as the cathode in this trial, and a commercial lead/antimony anode was used.
  • EXAMPLE 2 (Effect of liquid ion exchange contaminants) The electrolyte was deliberately saturated with a liquid ion exchange reagent and kerosene to simulate the contaminants which may enter the electrowinning tank from a prior process of liquid ion exchange. Furthermore, the contaminated electrolyte was not filtered, so as to avoid removal of entrained organic phase. The data from Table I indicates that the presence of the organic contaminants did not affect the results previously obtained. Copper concentration was here reduced to 29.5 g/l and current density remained at about 60 ASP. Electrolyte conductivity measured (for most high acid tests) about 0.54 mho/cm.
  • EXAMPLE 3 (Extreme current density) Determination of the limit of current density to produce an acceptable quality cathode was accomplished using non-retentive Type 316 stainless steel cathodes in an electrolyte of intermediate copper concentration. The copper sheets were deposited to starter sheet thickness at a current density of 141ASF in about 200 minutes. The deposits were ductile, although coarsegrained, and some areas had higher sulfur levels than previously found. The cell voltage and power consumption were reasonable for this current density, and the air agitation from the bubbler tube was increased to only 1.3 SCFH/sq. ft. of cathode surface.
  • the ratio of current invention it has been possible to electrowin pure rent density in amps per square foot to copper concencopper of acceptable mechanical integrity from impure tration in grams per liter can be as great as 5 in the vat leach electrolytes.
  • the ratio of metal present system, as compared to 0.5 in conventional concentration to current density employed was many commercial practice. times smaller than in conventional practice, which gen- Although lead-antimony anodes have been disclosed, erally produces an inferior product. By so operating, it it is apparent to those skilled in this art that anodes of was possible to take advantage of the improvement of any suitable material can be employed.
  • any cathodic substrate can be employed in the present invention, including starter sheets such as copper starter sheets and blanks coated with release agents.
  • Another significant advantage of the system of the present invention is that the face to face separation of the anode-cathode can be decreased to a value which is limited only by the dimensions of the supporting means.
  • the resistance in the cell should be decreased.
  • Three ways to accomplish the foregoing are to increase the temperature, increase the concentration of conducting solutes in the electrolyte and reduce the spacing between electrodes.
  • reduced spacing creates other serious problems, particularly by restricting convection.
  • the reduction in spacing is limited by the suspension means; thus, as a practical matter, the spacing can not usually be made less than about 0.50 inch.
  • the face to face cathode-anode separation is usually not less than 1.25 inch.
  • the invention is not restricted to the electrodeposition of copper. Indeed, the process and apparatus can be employed to great advantage for treating any metal which is normally electrodeposited from aqueous solution.
  • metals include nickel, zinc and lead.
  • An electrodeposition cell comprising:
  • non-conductive convection edge baffles positioned adjacent to opposite edges of the anode faces and extending toward the cathode faces;
  • cathodes close spaced apart from said anodes, the submerged length of the cathodes being equal to or greater than the submerged length of the anodes and anode bottom extensions, the cathodes being wider than the anodes so that the edges of the cathodes extend outwardly from the convection baffles;
  • bubble tubes having orifices for generating sheets of relatively small rapidly ascending bubbles of gas that result in agitation of the electrolyte over the cathode faces, the portion of said bubble tube having the orifices being positioned between the nonconductive anode extensions and the cathode face;
  • baffles forming enclosures between cathode and anode faces which minimize lateral spreading and contraction of the sheet of bubbles and prevents deposition of metal at the edges of cathodes extending beyond the baffles, said anode bottom extension preventing deposition of metal at the bottom of the cathode face, said means for maintaining close spacing, said bubble tubes, and said baffles providing an electrolyte convection system which enables the efficient use of high current densities in an electrodeposition process with an attendant production of high quality metal which can be easily stripped from the cathodes.
  • bubble tube supporting members which are connected to said bottom rack, said bubble tube supporting members supporting said bubble tubes, fixing the position of the bottoms of the said cathodes in relationship to said anodes, fixing the position of each bubble tube so that a sheet of bubbles from each bubble tube sweeps across a single cathode face and suspends the bubble tubes from the bottom of the cell to permit circulation of the electrolyte.
  • bottom rack is inclusive of vertical members which position the bottom of the anodes in relationship to the cathodes and which confine the flow of bubbles from said bubble tubes.
  • An electrowinning cell comprising:
  • edge baffles attached to opposite edges of the anode faces and extending toward the cathode faces;
  • cathodes close spaced apart from said anodes, the submerged length of the cathodes being equal to or greater than the submerged length of the anodes and anode bottom extensions, the cathodes being wider than the anodes so that the edges of the cathodes extend outwardly from the convection baffles;
  • bubble tubes having orifices for generating sheets of relatively small rapidly ascending bubbles of gas that result in agitation of the electrolyte over the cathode faces, the portion of said bubble tube having the orifices being positioned between the nonconductive anode extensions and the cathode faces so that each sheet of bubbles sweep across a cathode face; said baffles forming enclosures between cathode and anode faces which minimize lateral spreading and contraction of the sheet of bubbles and prevents deposition of metal at edges of cathodes extending beyond the baffles, said anode bottom extension preventing deposition of metal at the bottom of the cathode face, said means for maintaining close spacing, said bubble tubes, and said baffles providing an electrolyte convection system which enables the efficient use of high current densities in an electrodeposition process with an attendant production of high quality metal which can be easily stripped from the cathodes.
  • bubble tube supporting member which are connected to said bottom rack, said bubble tube supporting members supporting said bubble tubes, fixing the position of the bottoms of the said cathodes in relationship to said anodes, fixing the position of each bubble tube so that a sheet of bubbles from each bubble tube sweeps across a single cathode face and suspends the bubble tubes from the bottom of the cell to permit circulation of the electrolyte.
  • bottom rack is inclusive of vertical members which position the bottom of the anodes in relationship to the cathodes and which confine the flow of bubbles from said bubble tube.

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  • Chemical Kinetics & Catalysis (AREA)
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US445435A 1974-02-25 1974-02-25 Apparatus for the electrolytic recovery of metal employing improved electrolyte convection Expired - Lifetime US3875041A (en)

Priority Applications (11)

Application Number Priority Date Filing Date Title
US445435A US3875041A (en) 1974-02-25 1974-02-25 Apparatus for the electrolytic recovery of metal employing improved electrolyte convection
US515513A US3928152A (en) 1974-02-25 1974-10-17 Method for the electrolytic recovery of metal employing improved electrolyte convection
CA219,196A CA1068641A (en) 1974-02-25 1975-02-03 Method and apparatus for the electrodeposition of metal
ZA00750696A ZA75696B (en) 1974-02-25 1975-02-03 Method and apparatus for the electrodeposition of metal
GB4667/75A GB1504332A (en) 1974-02-25 1975-02-10 Method and apparatus for the electrodeposition of metal
JP50016989A JPS5830393B2 (ja) 1974-02-25 1975-02-12 キンゾクデンカイセキシユツノホウホウトソウチ
BE153570A BE825794A (fr) 1974-02-25 1975-02-21 Procede et appareil pour le depot electrolytique de metal
SE7502038A SE419240B (sv) 1974-02-25 1975-02-24 Sett och anordning for elektrolytisk utfellning av metall varvid elektrolyten omrores genom gasinblasning
DE19752508094 DE2508094A1 (de) 1974-02-25 1975-02-25 Verfahren und vorrichtung zum elektrolytischen abscheiden von metallen
US05/553,139 US3979275A (en) 1974-02-25 1975-02-26 Apparatus for series electrowinning and electrorefining of metal
US05/860,511 USRE30005E (en) 1974-02-25 1977-12-14 Method for the electrolytic recovery of metal employing improved electrolyte convection

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US05/553,139 Continuation-In-Part US3979275A (en) 1974-02-25 1975-02-26 Apparatus for series electrowinning and electrorefining of metal
US05/860,511 Division USRE30005E (en) 1974-02-25 1977-12-14 Method for the electrolytic recovery of metal employing improved electrolyte convection

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JP (1) JPS5830393B2 (sv)
BE (1) BE825794A (sv)
CA (1) CA1068641A (sv)
DE (1) DE2508094A1 (sv)
GB (1) GB1504332A (sv)
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033839A (en) * 1975-02-26 1977-07-05 Kennecott Copper Corporation Method for series electrowinning and electrorefining of metals
US4062755A (en) * 1976-05-03 1977-12-13 Bell Telephone Laboratories, Incorporated Electroplating anode plenum
US4214952A (en) * 1978-02-28 1980-07-29 Ngk Insulators, Ltd. Electrochemical treatment process
US4272334A (en) * 1979-01-12 1981-06-09 Nippon Kokan Kabushiki Kaisha Method of fluidification of liquid between plane parallel plates by jetting the liquid
US4584082A (en) * 1983-10-12 1986-04-22 Smith James W Method and apparatus for acid mist reduction
US4639302A (en) * 1982-12-10 1987-01-27 Dextec Metallurgical Pty. Ltd. Electrolytic cell for recovery of metals from metal bearing materials
US4668353A (en) * 1984-10-10 1987-05-26 Desom Engineered Systems Limited Method and apparatus for acid mist reduction
EP0486188A2 (en) * 1990-11-16 1992-05-20 Macdermid Incorporated Process for regenerating ammoniacal chloride etchants
EP0486187A2 (en) * 1990-11-16 1992-05-20 Macdermid, Incorporated Process for the electrolytic regeneration of ammoniacal copper etchant baths
US5785836A (en) * 1994-06-02 1998-07-28 British Nuclear Fuels Plc Electrolytic treatment of material
US5897756A (en) * 1995-10-26 1999-04-27 Lea Ronal Gmbh Device for chemical or electroyltic surface treatment of plate-like objects
WO2001053568A1 (en) * 2000-01-21 2001-07-26 Waterpower Systems Pty Ltd Improvements in electrolysis cells
US20030089619A1 (en) * 2000-02-22 2003-05-15 Sunil Jayasekera Process and apparatus for recovery of cyanide and metals
US20060126268A1 (en) * 2002-03-21 2006-06-15 Chien-Min Sung Carbon nanotube devices and uses therefor
US20060124454A1 (en) * 2002-12-23 2006-06-15 Metakem Gesellschaft Fur Schichtchemie Der Metalle Mbh Anode used for electroplating
US20110233055A1 (en) * 2008-09-09 2011-09-29 Steelmore Holdingd Pty Ltd cathode and a method of forming a cathode
CN106521562A (zh) * 2016-09-30 2017-03-22 云南铜业股份有限公司 一种铜电解永久不锈钢阴极的修复方法
WO2019219821A1 (en) 2018-05-16 2019-11-21 Metallo Belgium Improvement in copper electrorefining
RU2790423C2 (ru) * 2018-05-16 2023-02-20 Металло Белджиум Улучшение электрорафинирования меди

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DE2912524C2 (de) * 1979-03-29 1985-08-29 Hüttenwerke Kayser AG, 4670 Lünen Arbeitsverfahren und Vorrichtung zum elektrolytischen Abscheiden von Metallen, insbesondere Kupfer
JPS6233800A (ja) * 1985-08-02 1987-02-13 Asahi Chem Ind Co Ltd 平板めつき用エア撹拌装置
FI113280B (sv) * 2002-04-03 2004-03-31 Outokumpu Oy Vid elektrolys användbar förflyttnings- och isoleringsanordning
WO2005019502A1 (en) * 2003-08-22 2005-03-03 Bhp Billiton Innovation Pty. Ltd. Gas sparging
GB0618025D0 (en) 2006-09-13 2006-10-25 Enpar Technologies Inc Electrochemically catalyzed extraction of metals from sulphide minerals

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US846526A (en) * 1902-04-18 1907-03-12 Elmer A Sperry Apparatus for the production of pigments.
US1365032A (en) * 1918-04-29 1921-01-11 William E Greenawalt Electrolytic apparatus
US2675348A (en) * 1950-09-16 1954-04-13 Greenspan Lawrence Apparatus for metal plating

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US1700178A (en) * 1923-09-01 1929-01-29 Porzel Joseph Device for controlling electrolytic operations
US1805920A (en) * 1927-11-07 1931-05-19 Muschler Fred Making copper plated shingles

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US846526A (en) * 1902-04-18 1907-03-12 Elmer A Sperry Apparatus for the production of pigments.
US1365032A (en) * 1918-04-29 1921-01-11 William E Greenawalt Electrolytic apparatus
US2675348A (en) * 1950-09-16 1954-04-13 Greenspan Lawrence Apparatus for metal plating

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4033839A (en) * 1975-02-26 1977-07-05 Kennecott Copper Corporation Method for series electrowinning and electrorefining of metals
US4062755A (en) * 1976-05-03 1977-12-13 Bell Telephone Laboratories, Incorporated Electroplating anode plenum
US4214952A (en) * 1978-02-28 1980-07-29 Ngk Insulators, Ltd. Electrochemical treatment process
US4272334A (en) * 1979-01-12 1981-06-09 Nippon Kokan Kabushiki Kaisha Method of fluidification of liquid between plane parallel plates by jetting the liquid
US4639302A (en) * 1982-12-10 1987-01-27 Dextec Metallurgical Pty. Ltd. Electrolytic cell for recovery of metals from metal bearing materials
US4584082A (en) * 1983-10-12 1986-04-22 Smith James W Method and apparatus for acid mist reduction
US4668353A (en) * 1984-10-10 1987-05-26 Desom Engineered Systems Limited Method and apparatus for acid mist reduction
AU591662B2 (en) * 1986-03-21 1989-12-14 Desom Engineered Systems Limited Method and apparatus for acid mist reduction
EP0486188A2 (en) * 1990-11-16 1992-05-20 Macdermid Incorporated Process for regenerating ammoniacal chloride etchants
EP0486187A2 (en) * 1990-11-16 1992-05-20 Macdermid, Incorporated Process for the electrolytic regeneration of ammoniacal copper etchant baths
EP0486187A3 (en) * 1990-11-16 1992-08-19 Macdermid, Incorporated Process and apparatus for electrowinning of heavy metals from waste baths
EP0486188A3 (en) * 1990-11-16 1992-09-09 Macdermid Incorporated Process for regenerating ammoniacal chloride etchants
US5785836A (en) * 1994-06-02 1998-07-28 British Nuclear Fuels Plc Electrolytic treatment of material
US5897756A (en) * 1995-10-26 1999-04-27 Lea Ronal Gmbh Device for chemical or electroyltic surface treatment of plate-like objects
WO2001053568A1 (en) * 2000-01-21 2001-07-26 Waterpower Systems Pty Ltd Improvements in electrolysis cells
US20030089599A1 (en) * 2000-01-21 2003-05-15 King Cameron James Electrolysis cells
US6846393B2 (en) 2000-01-21 2005-01-25 Waterpower Systems Pty Ltd Electrolysis cells
US20030089619A1 (en) * 2000-02-22 2003-05-15 Sunil Jayasekera Process and apparatus for recovery of cyanide and metals
US7085125B2 (en) * 2002-03-21 2006-08-01 Chien-Min Sung Carbon nanotube devices and uses therefor
US20060126268A1 (en) * 2002-03-21 2006-06-15 Chien-Min Sung Carbon nanotube devices and uses therefor
US20060124454A1 (en) * 2002-12-23 2006-06-15 Metakem Gesellschaft Fur Schichtchemie Der Metalle Mbh Anode used for electroplating
US7943032B2 (en) * 2002-12-23 2011-05-17 Metakem Gesellschaft Fur Schichtchemie Der Metalle Mbh Anode used for electroplating
US20110233055A1 (en) * 2008-09-09 2011-09-29 Steelmore Holdingd Pty Ltd cathode and a method of forming a cathode
CN106521562A (zh) * 2016-09-30 2017-03-22 云南铜业股份有限公司 一种铜电解永久不锈钢阴极的修复方法
WO2019219821A1 (en) 2018-05-16 2019-11-21 Metallo Belgium Improvement in copper electrorefining
RU2790423C2 (ru) * 2018-05-16 2023-02-20 Металло Белджиум Улучшение электрорафинирования меди

Also Published As

Publication number Publication date
BE825794A (fr) 1975-08-21
DE2508094A1 (de) 1975-08-28
GB1504332A (en) 1978-03-22
SE7502038L (sv) 1975-08-26
USRE30005E (en) 1979-05-22
ZA75696B (en) 1976-01-28
CA1068641A (en) 1979-12-25
JPS5830393B2 (ja) 1983-06-29
JPS50115615A (sv) 1975-09-10
SE419240B (sv) 1981-07-20

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