US3855089A - Process for the electrolytic refining of heavy metals - Google Patents

Process for the electrolytic refining of heavy metals Download PDF

Info

Publication number
US3855089A
US3855089A US00309899A US30989972A US3855089A US 3855089 A US3855089 A US 3855089A US 00309899 A US00309899 A US 00309899A US 30989972 A US30989972 A US 30989972A US 3855089 A US3855089 A US 3855089A
Authority
US
United States
Prior art keywords
metal
halide
cathode
chloride
heavy metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00309899A
Other languages
English (en)
Inventor
H Mccutchen
P Cardwell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deepsea Ventures Inc
Original Assignee
Deepsea Ventures Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Deepsea Ventures Inc filed Critical Deepsea Ventures Inc
Priority to US00309899A priority Critical patent/US3855089A/en
Priority to CA185,859A priority patent/CA1029680A/en
Priority to GB5398473A priority patent/GB1447086A/en
Priority to FR7342045A priority patent/FR2221530B2/fr
Priority to JP48132268A priority patent/JPS4999901A/ja
Application granted granted Critical
Publication of US3855089A publication Critical patent/US3855089A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/04—Manganese marine modules

Definitions

  • This invention provides an improved electrolytic process for obtaining the elemental metal by electrode- [52] U.S. Cl. 204/105 M, 204/113, 204/118, positing from an aqueous solution of a halide of the 204/ 122, 204/128 metal.
  • the improvement comprises the presence of an [51] Int. Cl. C22d 1/24, C22d 1/14, C22d l/18 alkali metal halide or an alkaline earth metal halide [58] Field of Search 204/113, 105 M, 118, 122, dissolved in the electrolyte solution.
  • This process is 204/128, 98 preferably applicable to obtaining the respective metal from the halides of nickel, cobalt, tin, iron and manga- [56] References Cited nese.
  • the chloride ion is the most mobile of the halide ions and, therefore, most efficient in any electrolysis operation.
  • the electroplating operation not only results in the plating out of the pure metal at the cathode but also, under certain circumstances, results in the evolution of the elemental halogen, e.g., chlorine gas, at the anode.
  • Nickel chloride electrolysis cell is described in Chlorine, Its Manufacture, Properties and Uses, ACS Monograph Series No. 154, .l. S. Sconce, Editor (Reinhold, 1962), see page 230.
  • Nickel metal is electroplated as an intermediate step in the production of Cl from HCl.
  • Two cells are used at a given time; one cell acts as a nickel plating electrolysis cell and the second acts as a nickel dissolving cell. The roles of the two cells are periodically reversed. For example, nickel deposits on the cathode and chlorine is released at the anode of one of the cells, which contains an aqueous solution of NiCl as the electrolyte, while nickel chloride is being formed in the second cell to feed the first cell.
  • the operations of the cells are reversed: the electrolysis is halted in the first cell and the nickel deposit is dissolved by feeding hydrochloric acid to the first cell to from nickel chloride and hydrogen.
  • the nickel chloride solution produced in the first cell is fed to the second cell in which the nickel chloride is electrolyzed to plate out nickel and to form chlorine.
  • the operations of the cells are again reversed.
  • any excess hydrochloric acid in the nickel chloride solution fed to the electrolysis cell is neutralized by a base, e.g., sodium hydroxide, resulting in the formation of, e.g., sodium chloride, salt, which remains in solution, building up to a level at which it precipitates out in the nickel-dissolving cell.
  • the effluent from the nickel dissolving cell is filtered to remove any precipitated sodium chloride prior to its being recycled as a feed stream back to the chlorine-forming electrolysis cell.
  • Sconce describes a procedure for using nickel as an intermediate in the production of chlorine and requires the plated nickel to be as readily soluble in hydrochloric acid as possible.
  • the process described by Sconce is directed towards forming as reactive a nickel plate as possible, i.e., having a high surface area, and being highly porous, spongy and treed.
  • Such a nickel plate is obtained by utilizing a very high concentration of nickel in the solution in the cell. This results in a nickel plating which has the high surface area desirable for the chlorine-producing process, but not a plating suitable for the production of the metal, per se. Similarly. in the process described by Sconce. it is not necessary to maintain a constant pH because the presence of hydrochloric acid or of hypochlorous acid is not undesirable when the quality of the nickel plated out is not relevant.
  • the nickel chloride is generally admixed with a buffering agent, e.g., boric acid, to prevent the decrease in pH generally associated with such chloride electrolysis operations.
  • a buffering agent e.g., boric acid
  • the decrease in the pH is generally caused by the reaction of the chlorine gas with water to form hypohchlorous and hydrochloric acids.
  • HCLD hydrochloric and hypochlorous acid
  • HCLD hydrochloric and hypochlorous acid
  • halide electrolysis is preferable.
  • the deposits of pure nickel metal from the chloride solution compared to deposits obtained utilizing a sulfate electrolysis solution, are finer grained, harder, smoother, stronger and less brittle.
  • the halide ions are more efficient carriers of electricity and can thus operate at lower voltages and at higher current efficiencies. There is further less tendency to pit and form module growths and trees on the deposits.
  • nondiaphragm cell as opposed to a cell wherein the anode and cathode compartments are separated by a semi-permeable diaphragm, is desirable as simplifying the construction and the operation of the cell with a concomitant decrease in cost.
  • the required use of a buffering agent tends to outweigh these advantages, at least in part.
  • the feed solution to the electrolysis cell is substantially saturated in the neutral source of halide.
  • This invention therefore, provides an improved process for refining electrolytically a heavy metal to form a fine-grained, hard, smooth, strong, dense and not brittle deposit of the metal, and to evolve a halogen, from an aqueous electrolyte solution containing dissolved therein a halide of the desired heavy metal, the electrolysis being carried out utilizing an insoluble anode, the improvement comprising the presence in the electrolyte solution of an inert halide (which can be an alkali metal halide or an alkaline earth metal halide) which is inert under the conditions of the electrolysis of the heavy metal.
  • the inert halide is preferably present in an amount of at least about 60 percent of its saturation concentration in the electrolyte solution. The maximum concentration of the inert halide in the electrolyte solution is limited only by solubility and is optimally the saturation concentration of the neutral halide in the electrolyte solution.
  • the electrodepositing of metal from an aqueous solution of the metal halide is generally applicable to some of the so called heavy metals or transition" elements of Groups VIIA, VIII, IV B and II B of the Periodic Chart of the Elements.
  • this process can be used to deposit a metal which is itself not reactive with halide ion in solution at the concentration present in the electrolyte of the present invention.
  • the halide salts of the deposited metal must be soluble in all of the metals lower valence states, if the metal is a multivalent element and is fed in a compound at one of the higher valence states.
  • the process is most effectively used for the electrowinning of nickel, cobalt, manganese, tin, iron and zinc from aqueous solutions of the respective halide salts.
  • the halide used is usually the chloride, although iodides and especially bromides are also commercially useful. If desired, a mixture of halides of two different platable metals can be utilized. For example, a mixture of nickel halide and cobalt halide can be electrolyzed to obtain alloys of nickel and cobalt at the cathode.
  • the alkali metal halide or alkaline earth metal halide present in the electrolyte in accordance with the present invention must be strongly conductive and should not introduce a cation which itself is electrolyzable under the conditions of the cell or which in other ways effect the plating of the desired heavy metal.
  • the alkali metal halides and alkaline earth metal halides are useful in all cases.
  • Useful halides of an alkali metal or an alkaline earth metal include, for example, the chlorides, iodides and bromides of sodium, potassium, cesium, lithium, magnesium, barium, calcium, strontium and rubidium.
  • Mixtures of two different metal cations and different halide anions can be present, e.g., two different alkali metal halides or one alkali metal halide and one alkaline earth metal halide, can be used, as long as, e.g., the concentration of the salts is at least about 60% of their combined saturation. That is, if a certain amount of a mixture of alkali metal halides and/or alkaline earth metal halides can be added to an electrolyte solution before forming a precipitate of at least one of the alkali metal halides or alkaline earth metal halides, 60% of that amount is an operable minimum amount of the mixed halide.
  • halide ion for both the compound of the metal to be plated and for the alkali metal or alkaline earth metal halide, different halide ions can be utilized. This may create a problem in that the halogen which is generated at the anode may not be pure. However, it has been noted that the use of different halides can aid in maintenance of the desired high quality metal cathodic deposit, which is the primary consideration.
  • the pH of the electrolyte solution in the cathodic deposition operation affects the cathode current efficiency, and the quality and the internal stress properties of the metal electrodeposited on the cathode. Accordingly, it is highly desirable to maintain the pH of the electrolyte within the cell constant within certain optimum limits. This can be accomplished by the presence of the alkali metal halide or alkaline earth metal halide in the electrolyte solution in accordance with this invention.
  • the improvement of the present invention for example, is generally applicable to the so called all- Chloride" nickel electroplating or electrorefining process, wherein all of the metal to be electrowon, e.g., nickel, is present as the halide.
  • the parameters and the compositions for such procedures are generally set forth, for example, in Graham Electroplating and Engineering Handbook, (1971), page 247.
  • the improvement of the present invention is applicable to an electrowinning or an electroplating process carried out in electrolytic cells containing an aqueous solution of the metal halide, the cell having at least one each anode and cathode.
  • the reactions taking place in the cell are as follows:
  • M is the heavy metal
  • X is the halide
  • n is the valence of the metal
  • the solvent, water should not enter into any reaction.
  • a side reaction that can occur is between the elemental halogen and water which results in the formation of a hydrohalic acid and a hypohalous acid, as follows:
  • the electrolyte solution fed to the cell can contain from about 0.3 up to about 2 gm-atoms per liter of the heavy metal, present as the halide, and preferably up to about 1.5 gmatoms per liter of heavy metal.
  • the maximum desirable concentration in the solution of the heavy metal to be electrodeposited onto the cathode is limited by the quality of the metal deposit required. Concentrations of the heavy metal in the electrolyte solution fed to the cell higher than the above tend to result in less desirable physical forms of heavy metal deposits.
  • the desirable pH for the electrolysis of most of the heavy metals, such as nickel and cobalt, is optimally in the range of from about 2 to about 2.5 but can be as low as about 1 and as high as about 3.5 without decreasing efficiency or quality of the product to below a commercially acceptable level.
  • the pH, in accordance with this process can be maintained substantially constant, or at least the change in pH can be limited, at the value initially set by the presence of the inert halide, without a buffering agent.
  • Cathode current density for these electrolysis processes is not critical and can vary depending upon the rate at which it is desired to deposit the metal. It is often necessary to balance the desired rate against the desired cathode efficiency. Generally, at a cathode current density of from about to about 50 amperes per square foot, and preferably from about 30 to about 40 amperes per square foot, a useful commercial process can be effected: the cathode efficiency is at a sufficiently high level to render the process economically feasible.
  • the operation of this process is preferably carried out by feeding in rich electrolyte solution and withdrawing spent electrolyte solution continuously, thus maintaining an electrolyte concentration within the desired range in the cell.
  • a recirculating or batch cell can be utilized, i.e., the same solution is recirculated several times through a cell past the electrodes.
  • the efficiency is measured as the cathode efficiency.
  • an efficiency of at least about 75 percent and optimally at least about 85 percent should be obtained.
  • efficiency is a function of economics and is not crucial to the operation of the process of the present invention.
  • the cathodes which are preferably used in the process of the present invention are starter sheets," formed of the same metal as is to be deposited. This permits the formation of a discrete cathode product which can be removed and utilized as solid metal.
  • the so called starter sheet can be readily prepared from a conventional soluble anode-type, electrolyte cell.
  • an aqueous electrolyte comprising 300 grams per liter NiSO .6H O, 20 grams per liter sodium chloride and 30 grams per liter boric acid, is prepared having a pH of 4.0.
  • the electrolyte is maintained at a tempera ture of F.
  • the electrolysis cell utilizes a soluble metal anode e.g. nickel of the metal desired to be electroplated e.g. nickel.
  • the cathode has a surface from which a thin sheet of the metal can be readily removed or peeled.
  • Suitable cathodes for making starter sheets include specially treated stainless steel cathodes, which permit ready removal of thin ductile sheets of the electroplated metal.
  • the preparation of the starter sheet can be carried out in an all chloride bath.
  • the anode for use in the process of the present invention is of the type insoluble, or substantially inert, or nonreactive in the electrolysis system.
  • Suitable materials for forming insoluble electrodes, for use as the anode include materials such as graphite, insoluble lead anodes, especially antimonial lead, platinum, platinum-coated materials, such as platinumcoated titanium and ruthenium-coated materials, such as ruthenium-coated titanium.
  • Each cell can include a single cathode and a single anode or can include a battery of positive and negative electrodes.
  • a series of plates either all insoluble electrodes, such as platinum, but preferably alternating insoluble anode and metal starter sheet cathodes, can be utilized wherein the electrodes are separated by from about 2 to about 6 inches and preferably from about 2 to about 3 inches.
  • the two end electrodes are anodes, so that the intermediate cathodes are plated on two sides.
  • the total halide ion concentration in the cell electrolyte comes from the alkali metal halide and/or alkaline earth metal halide and from the heavy metal halide.
  • the heavy metal is electroplated at the cathode, halogen is being generated at the anode. This serves to remove halide ion from the solution.
  • the halide ion concentration is decreased.
  • the feed to the cell is optimally saturated in the salt.
  • the electrolysis feed solution can be mixed at room temperature. If there is a substantial change in saturation concentration with temperature, the electrolyte should be mixed at substantially the temperature of operation.
  • the electrolysis cell is generally operated at an elevated temperature sufficient to insure satisfactory cathode quality and a sufficiently high cathode efficiency. It is generally understood that the higher the temperature the lower the voltage required to maintain a given current density.
  • an electrolyte temperature of at least about 35 C. is desirable in order to obtain at least a fair cathode quality and a sufficiently high cathode efficiency.
  • a lower temperature could be used if necessary. It has generally been found that temperatures greater than about 70 C. are unnecessary.
  • the electrolysis cell is operated at an electrolyte temperature of from about 45 to about 60 C.
  • the process of the present invention accordingly results in an improved electrolysis procedure whereby heavy metals can be electro-refined at a high efficiency to obtain the desired heavy metals and also a most useful by-product, the pure halogen.
  • the all chloride process is believed to be superior to the use of other salts, e.g., nickel sulflate, in electrowinning procedures. It has been shown to result in a higher efficiency, generally up to a 50 percent savings in power consumption, a wide plating range, and a lower tendency to pit and form nodule growths, and trees on the cathode deposit.
  • the procedure can operate at higher cathode and anode current efficiencies and is generally easier to control because of the simple composition of the solution.
  • FIG. I is a schematic cut-away elevation view of an electrolysis cell useful in accordance with the present invention.
  • FIGS. 2 through 5 are graphs representing correlations between various parameters for operating nickel and cobalt electrolysis cells in accordance with this invention.
  • a rectangular covered electrolysis cell indicated generally by containing an anode 12 at each end and intermediate cathodes l4 and anode 12 is useful for operating the present invention.
  • Each anode l2 and cathode 14 is connected to an electric source, not shown.
  • the cathodes 14 are the preferred starter sheets of the desired plating metal.
  • Inlet and outlet 22 are located behind the anodes at each end of the cell.
  • the cell can be operated batchwise with recirculated electrolyte when recirculation line 26, indicated by dashed lines, and pump 27 are connected to the inlet 20 and outlet 22, respectively.
  • a nickel electrolyte was prepared at room temperature as an aqueous solution comprising 80 grams per liter of nickel as NiCl and substantially saturated in sodium chloride (200 g/l.), to provide a total of 4.6 gmatoms of chloride ion/liter of solution.
  • a sample of approximately three liters of the above electrolyte solution was fed to a glass-lined rectangular cell 4 inches long containing a graphitic anode at two opposite ends and a cathode formed of a thin nickel starting sheet, approximately 0.010 inches thick, midway between the anodes.
  • the cell was provided with means to recirculate the electrolyte so that it flowed past the first anode, the cathode and then past the second anode and then was recirculated to the first anode.
  • the electrolyte was heated to a temperature of 60 C., the pH measured and found to be approximately 2.0.
  • the surface area of the anode was approximately 4 by 6 inches by 1 inch and of the cathode initially 3 by 4 inches by 0.01 inch thick.
  • the cell was operated with the electrolyte recirculating until the nickel content of the electrolyte dropped to approximately ll grams per liter and the chloride ion concentration to about 3.6 gm-atoms/liter.
  • concentration of nickel was reduced to below approximately 20 grams per liter and the chloride ion reduced by an equivalent amount, to about 4.1 gm atoms/liter, Cl, the quality of the nickel plating out at the cathode was substantially reduced.
  • the pH of the solution was found to remain substantially constant during the electrolysis until the nickel concentration was decreased to about 20 grams/liter. Chlorine was generated at the anode and was removed overhead. Nickel of a high quality and even surface was deposited onto the cathode starter sheet. The nickel deposits were light colored and unusually smooth.
  • the electrodes were electrically activated initially to a voltage of about 2.13 volts. At a cathode current density of approximately 30 amperes/ft the cathode efficiency was 91 percent.
  • Example II THROUGH 6
  • the process of Example I was repeated but the pH of the electrolyte was varied as shown in Table l by the addition of HCl or NaOH.
  • the voltage and cathode current density were varied concomitantly with the changes in pH.
  • the cell operates with reasonable efficiency and at least a fair quality deposit can be obtained over a wide range of pH.
  • feed solutions of varying pHs e.g., as obtained from various ore refining operations, can be utilized.
  • the pH remains substantially constant at the initial value throughout the electrolysis procedure.
  • Example 7 The process of Example 1 was repeated except varying the voltage to obtain the cathode current density during electrolysis as shown in Table 11, and the cathode efficiencies determined; the data are set forthin Table 11.
  • Example 9 The process of Example 1 was repeated except that the voltage was changed so that a current density of 20 amperes per square foot was obtained and operating temperatures for the electrolyte were varied. The results are set forth in Table 111.
  • EXAMPLE 12 The procedure of Example 1 was repeated but utilizing calcium chloride (300 g/l) as the halide source in place of NaCl. The quality of the cathode deposit was found to be very good and the cell operated at a satisfactory cathode efficiency.
  • EXAMPLE 14 An electrolyte solution was prepared comprising 80 g/l of cobalt, as (CoCl 200 g/l of NaCl, (substantially saturated at room temperature). A sample of this electrolyte solution (3 liters) was added to the cell described in Example 1 but containing a cathode comprising a cobalt starting sheet 3 inches X 4 inches x 0.01 inch thick. The electrolyte was heated to a temperature of 60C. and a charge of 2.13 volts was applied between the electrodes at a cathode current density of 30 amperes per square foot.
  • the procedure was operated batch-wise (recirculation) until the cobalt concentration was decreased to approximately 15 g/l cobalt and 4 gram-atom/liter chloride ion. A satisfactory cathode efficiency of 86 percent was maintained during the entire process; however, at the lower concentration of cobalt the quality of the cathode deposit began to deteriorate. The cobalt deposits were light colored and extremely smooth. The pH of the electrolyte remained constant at 2.0 throughout theentire electrolysis until the lower concentration was reached.
  • Example 14 The procedure of Example 14 was repeated. except that the initial pH of the electrolytesolution was varied as shown in Table IV below, utilizing HCl to decrease pH to below 2.0 and NaOH to increase pH. The voltage and cathode current density were varied concomitantly with changes in pH.
  • Example 14 The procedure of Example 14 was repeated, except that the voltage was changed so that a current density of 30 amperes per square foot was obtained and the temperature of the electrolyte solution was varied as shown in Table V below.
  • Example 14 The procedure of Example 14 was repeated except for varying the voltage to obtain the cathode current density during electrolysis as shown inwTable V1, and the cathode efficiencies were determined: the data are set forth in Table VI.
  • halide of a second metal is selected from the group consisting of sodium chloride, magnesium chloride, calcium chloride and potassium chloride.
  • a process for obtaining an elemental heavy metal from a halide of the heavy metal by cathodically electrodepositing the heavy metal while obtaining an elemental halogen comprising subjecting to electrolysis, between an insoluble anode and a cathode, an aqueous solution comprising dissolved therein a halide of a heavy metal selected from the group consisting of cobalt, nickel, tin, zinc, iron and maganese, to be electrodeposited, and a halide of a second metal selected from the group consisting of alkali metals and alkaline earth metals, the total concentration of halide ion in the aqueous solution being sufficient to eliminate any substantial change in the pH of the aqueous solution during electrolysis without the addition of a buffer solution and being such as to provide a concentration of the halide of the second metal of at least 60% of its saturation concentration in the electrolyte solution, so as to evolve an elemental halogen at the insoluble anode and to deposit elemental heavy

Landscapes

  • 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)
US00309899A 1972-11-27 1972-11-27 Process for the electrolytic refining of heavy metals Expired - Lifetime US3855089A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US00309899A US3855089A (en) 1972-11-27 1972-11-27 Process for the electrolytic refining of heavy metals
CA185,859A CA1029680A (en) 1972-11-27 1973-11-15 Process for the electrolytic refining of heavy metals
GB5398473A GB1447086A (en) 1972-11-27 1973-11-21 Process for the electrolytic refining of heavy metals
FR7342045A FR2221530B2 (enrdf_load_stackoverflow) 1972-11-27 1973-11-26
JP48132268A JPS4999901A (enrdf_load_stackoverflow) 1972-11-27 1973-11-27

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00309899A US3855089A (en) 1972-11-27 1972-11-27 Process for the electrolytic refining of heavy metals

Publications (1)

Publication Number Publication Date
US3855089A true US3855089A (en) 1974-12-17

Family

ID=23200142

Family Applications (1)

Application Number Title Priority Date Filing Date
US00309899A Expired - Lifetime US3855089A (en) 1972-11-27 1972-11-27 Process for the electrolytic refining of heavy metals

Country Status (5)

Country Link
US (1) US3855089A (enrdf_load_stackoverflow)
JP (1) JPS4999901A (enrdf_load_stackoverflow)
CA (1) CA1029680A (enrdf_load_stackoverflow)
FR (1) FR2221530B2 (enrdf_load_stackoverflow)
GB (1) GB1447086A (enrdf_load_stackoverflow)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087339A (en) * 1976-07-02 1978-05-02 The International Nickel Company, Inc. Electrowinning of sulfur-containing nickel
US4707227A (en) * 1986-09-15 1987-11-17 Higgins Irwin R Simultaneous electro-deposition of manganese and manganese dioxide
EP1227884B1 (de) * 1999-09-28 2005-12-28 Surtec Produkte und Systeme für die Oberflächenbehandlung GmbH Verfahren zur Herstellung eines Elektrokatalysators
CN103194768A (zh) * 2013-04-16 2013-07-10 中南大学 利用高铁高磷锰矿制备电解金属锰的方法
JP2016033242A (ja) * 2014-07-31 2016-03-10 佐々木半田工業株式会社 錫の高電流密度電解精製法
CN107077901A (zh) * 2014-08-05 2017-08-18 Snip控股公司 高纯度的Sn‑117m组合物及其制备的方法
US20210276061A1 (en) * 2020-03-06 2021-09-09 Ánodos De Chile S.A. Method for the manufacture of insoluble lead anodes, used in electrowinning or electro-refining processes of high purity metals

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2758511A1 (de) * 1977-03-28 1978-10-12 Energy Dev Ass Metall-halogen-batterie
JPS56123335A (en) * 1980-03-03 1981-09-28 Furukawa Electric Co Ltd:The Recovering method for metallic nickel from copper electrolytic solution

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114687A (en) * 1961-03-10 1963-12-17 Int Nickel Co Electrorefining nickel
US3707448A (en) * 1970-10-20 1972-12-26 Intern Erfiner Und Patentansta Method for extracting metal from a metal source in an electrolytic cell

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE533113C (de) * 1928-02-16 1931-09-08 Ernst Kelsen Verfahren zur Herstellung von Elektrolyteisen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3114687A (en) * 1961-03-10 1963-12-17 Int Nickel Co Electrorefining nickel
US3707448A (en) * 1970-10-20 1972-12-26 Intern Erfiner Und Patentansta Method for extracting metal from a metal source in an electrolytic cell

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4087339A (en) * 1976-07-02 1978-05-02 The International Nickel Company, Inc. Electrowinning of sulfur-containing nickel
US4707227A (en) * 1986-09-15 1987-11-17 Higgins Irwin R Simultaneous electro-deposition of manganese and manganese dioxide
EP1227884B1 (de) * 1999-09-28 2005-12-28 Surtec Produkte und Systeme für die Oberflächenbehandlung GmbH Verfahren zur Herstellung eines Elektrokatalysators
CN103194768A (zh) * 2013-04-16 2013-07-10 中南大学 利用高铁高磷锰矿制备电解金属锰的方法
JP2016033242A (ja) * 2014-07-31 2016-03-10 佐々木半田工業株式会社 錫の高電流密度電解精製法
CN107077901A (zh) * 2014-08-05 2017-08-18 Snip控股公司 高纯度的Sn‑117m组合物及其制备的方法
US20210276061A1 (en) * 2020-03-06 2021-09-09 Ánodos De Chile S.A. Method for the manufacture of insoluble lead anodes, used in electrowinning or electro-refining processes of high purity metals
US12157153B2 (en) * 2020-03-06 2024-12-03 Ánodos De Chile S.A. Method for the manufacture of insoluble lead anodes, used in electrowinning or electro-refining processes of high purity metals

Also Published As

Publication number Publication date
FR2221530A2 (enrdf_load_stackoverflow) 1974-10-11
FR2221530B2 (enrdf_load_stackoverflow) 1978-06-23
JPS4999901A (enrdf_load_stackoverflow) 1974-09-20
CA1029680A (en) 1978-04-18
GB1447086A (en) 1976-08-25

Similar Documents

Publication Publication Date Title
US3966568A (en) Electrowinning of gallium
US3576724A (en) Electrodeposition of rutenium
US20220380921A1 (en) Compact and flat bismuth metal preparation by electrolysis method
US3855089A (en) Process for the electrolytic refining of heavy metals
US3928153A (en) Electrowinning process
US4374007A (en) Trivalent chromium electroplating solution and process
US4906340A (en) Process for electroplating metals
US2145745A (en) Electroplating method and product
Mackinnon et al. Zinc electrowinning from aqueous chloride electrolytes
US1465034A (en) Process for the electrolytic deposition of copper
US3833485A (en) Electroplating chromium and chromium alloys
US4454012A (en) Process for the preparation of methionine
US3864227A (en) Method for the electrolytic refining of copper
EP0235908A2 (en) Method for the production of L-cysteine
USRE34191E (en) Process for electroplating metals
US3799850A (en) Electrolytic process of extracting metallic zinc
US3114687A (en) Electrorefining nickel
US3772167A (en) Electrodeposition of metals
EP2606163B1 (en) METHOD FOR THE ADJUSTMENT OF NICKEL CONTENT AND pH OF A PLATING SOLUTION
Adcock et al. The importance of cathode zinc morphology as an indicator of industrial electrowinning performance
US2398614A (en) Electrodeposition of manganese
US5112447A (en) Process for electroplating
JPS5983785A (ja) 高濃度硫酸コバルト水溶液の製造方法
US2546547A (en) Electrodeposition of manganese
US3755113A (en) Method for electrorefining of nickel