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US20150021195A1 - Electrowinning cell and process - Google Patents

Electrowinning cell and process Download PDF

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Publication number
US20150021195A1
US20150021195A1 US13/947,342 US201313947342A US2015021195A1 US 20150021195 A1 US20150021195 A1 US 20150021195A1 US 201313947342 A US201313947342 A US 201313947342A US 2015021195 A1 US2015021195 A1 US 2015021195A1
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US
United States
Prior art keywords
diaphragm
diaphragms
electrochemical cell
thickness
chamber
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.)
Abandoned
Application number
US13/947,342
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English (en)
Inventor
Rohan Akolkar
Uziel Landau
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.)
Case Western Reserve University
Original Assignee
Case Western Reserve University
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 Case Western Reserve University filed Critical Case Western Reserve University
Priority to US13/947,342 priority Critical patent/US20150021195A1/en
Assigned to CASE WESTERN RESERVE UNIVERSITY reassignment CASE WESTERN RESERVE UNIVERSITY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AKOLKAR, ROHAN, LANDAU, UZIEL
Priority to PCT/US2014/047598 priority patent/WO2015013263A1/fr
Publication of US20150021195A1 publication Critical patent/US20150021195A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements
    • 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
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • 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
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • 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
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • the present invention relates to electrochemical cells, and in particular to an electrochemical cell that may be used for electrowinning processes.
  • the electrowinning process typically occurs in an electrochemical cell.
  • a metal is electrowon from electrolytes containing metal salts
  • the metal is deposited at the cathode while, depending on the electrolyte composition, chlorine or oxygen may evolve at the anode.
  • the electrowinning process may be used to extract many different types of metals, including, but not limited to titanium (Ti).
  • a permeable membrane or diaphragm is placed between the anode and cathode within the electrochemical cell to separate the electrolyte in the anode compartment (anolyte) from that in the cathode compartment (catholyte).
  • the diaphragm serves to retard the migration of metallic ions (cations) with lower oxidation states from the cathode to the anode. Without the diaphragm, cations with lower oxidation states will migrate to the anode and get oxidized at the anode, thereby degrading cell efficiency.
  • the diaphragm also serves the purpose of confining the anodically generated chlorine to the vicinity of the anode and preventing the chlorine gas from interfering with processes at the cathode.
  • titanium is extracted from its ore using the Kroll process where the ore (TiO 2 ) is first chlorinated to TiCl 4 , and the TiCl 4 is then reduced to titanium using electrolytically produced magnesium (Mg) as the reducing agent.
  • Mg electrolytically produced magnesium
  • the Kroll process is energy intensive (requiring about 100 KWh per kg of titanium), which is partly due to the need for electrowinning the reducing agent (such as magnesium) and separating the product (Ti) from the by-product (MgCl 2 ).
  • titanium can be electrowon directly from a molten salt electrolyte containing TiCl 4 in NaCl or KCl/LiCl.
  • titanium cannot be electrowon due to plugging of the diaphragm used in the cell to separate the anolyte and catholyte.
  • Titanium deposition within the diaphragm occurs due to the development of bipolarity at the diaphragm.
  • Bipolarity causes electrochemical reactions at the diaphragm, including Ti deposition on the anolyte side of the diaphragm and oxidation of dissolved Ti ions on the catholyte side of the diaphragm.
  • Bipolarity leads to cell efficiency loss and early diaphragm and cell failure.
  • the present invention provides an electrochemical cell and method for electrowinning a variety of multivalent metals including titanium.
  • the invention provides an electrochemical cell comprising an anolyte chamber comprising an anode and configured for containing an anolyte, a catholyte chamber comprising a cathode and configured for containing a catholyte comprising a metal to be electrolytically produced, and a diaphragm separating the anolyte chamber and the catholyte chamber, the diaphragm configured to control the potential drop across the diaphragm so that it is below the potential difference for bipolar reactions at the diaphragm.
  • the diaphragm has a thickness lower than a thickness that allows the onset of bipolar reactions. In another embodiment, the diaphragm has a thickness l, such that the following inequality is satisfied: il/ ⁇ E, where i is the current density, ⁇ is the effective electrolyte conductivity of an electrolyte in the cell, and ⁇ E is the reduction potential of the bipolar reactions at the diaphragm.
  • the diaphragm may have a thickness of about 0.8 cm or less. In a different embodiment, the diaphragm may have a thickness of about 0.3 cm or less.
  • the diaphragm comprises a plurality of diaphragms.
  • the diaphragms may have the same thicknesses, differing thicknesses or a combination thereof. There may be a space between successive diaphragms of the plurality of diaphragms.
  • each of the diaphragms in the plurality of diaphragms has a thickness lower than a thickness that allows the onset of bipolar reactions.
  • each of the diaphragms have a thickness l and satisfy the following inequality: il/ ⁇ E, where i is the current density, ⁇ is the effective electrolyte conductivity of an electrolyte in the cell, and ⁇ E is the reduction potential of the bipolar reaction at the diaphragm.
  • each diaphragm in the plurality of diaphragms has a thickness of about 0.8 cm or less.
  • the diaphragms each have a thickness l of about 0.3 cm or less.
  • the electrochemical cell may comprise 3 or 4 diaphragms each having a thickness of about 0.8 cm.
  • the electrochemical cell may comprise 3 or 4 diaphragms each having a thickness of about 0.3 cm.
  • the diaphragm has a porosity that is larger than a porosity that allows for the onset of bipolar reactions for the given diaphragm thickness, electrolyte conductivity, and current density.
  • each diaphragm has the same porosity. In another embodiment, each diaphragm has a different porosity.
  • the metal to be electrolytically produced is titanium.
  • the invention provides an electrowinning process for deposition of a metal from a solution comprising: providing an electrochemical cell comprising an anolyte chamber comprising an anode and an anolyte solution dispersed in the anolyte chamber, a catholyte chamber comprising a cathode and an cathode solution dispersed in the cathode chamber, the catholyte solution comprising a fluid containing at least one metal dissolved therein, and a diaphragm separating the anolyte chamber and the catholyte chamber.
  • the process further comprises establishing a predetermined voltage and current across the electrolytic cell sufficient to effect reduction and deposition of the at least one metal at the cathode and cause an oxidation reaction at the anode, wherein the diaphragm is configured to control the potential drop across the diaphragm so that it is below the onset potential for bipolarity.
  • the diaphragm has a thickness lower than a thickness that allows bipolar reactions.
  • the diaphragm l satisfies the following inequality: il/ ⁇ E, where i is the current density, ⁇ is the effective electrolyte conductivity of an electrolyte in the cell, and ⁇ E is the reduction potential of the bipolar reaction for the at least one metal.
  • the diaphragm comprises a plurality of diaphragms.
  • the diaphragms may have the same thicknesses, differing thicknesses or a combination thereof. In one embodiment, there is a space separating successive diaphragms in the plurality of diaphragms.
  • the diaphragms each have a thickness l of less than 0.8 cm. In one embodiment, the diaphragms each have a thickness l of about 0.3 cm or less.
  • the metal being deposited comprises titanium, chromium, iron, uranium, a trans-uranium metal, or a combination of two or more thereof.
  • a constant or time-varying current or potential is applied to the diaphragm.
  • the catholyte and anolyte comprise aqueous or non-aqueous solutions.
  • the diaphragm is electrically conductive, and the method comprises applying a current or potential across the diaphragm to dissolve any metal deposits that form at the diaphragm.
  • the current or potential applied across the diaphragm is chosen from a constant or a periodic current or potential.
  • the fluid is titanium tetrachloride in NaCl, LiCl—KCl, LiCl—KCl—NaCl, or LiCl—KCl—CaCl 2 .
  • FIG. 1 is a schematic illustration of an electrochemical cell in accordance with an embodiment of the present invention.
  • FIG. 2 is a schematic illustration of an electrochemical cell in accordance with another embodiment of the present invention.
  • the present invention provides an electrochemical cell suited for electrowinning of metals such as, for example, titanium.
  • metals such as, for example, titanium.
  • the apparatus and process may be discussed with reference to titanium, but it will be appreciated that the electrochemical cell and process can also be used for the electrowinning of other metals, including, but not limited to, chromium, cobalt, niobium, iron, manganese, and others.
  • FIG. 1 shows an electrochemical cell 100 suited to electrowin metal from a fused salt bath, e.g. titanium in a fused salt bath of compounds of titanium.
  • the electrochemical cell 100 includes a body 102 adapted to hold the electrolytes including a fused salt bath comprising the metal ion or metal compound to be electrowon (e.g. titanium from titanium tetrachloride) without substantial adverse effects to the material of which the body 102 is constructed.
  • the body 102 can be, formed of a metal, such as steel, nickel, hastelloy, or any other suitable material.
  • the body 102 is internally divided into at least an anolyte chamber 104 and a deposition catholyte chamber 106 .
  • An anode 108 is disposed in the anolyte chamber 104 and adapted to be at least partially immersed in the bath during operation of the electrochemical cell 100 .
  • the material of which the anode 108 is formed is resistant to the corrosive effects of the bath and also to the elemental chlorine formed at the positive charged anode 108 during operation of the cell. Suitable anode 108 materials are, for example, carbon and graphite. However, it is not necessary for the invention that the anode 108 remains impervious to the electrolyte or non-reacting during the process.
  • the invention can also be applied to cells and processes in which the anode 108 reacts and is consumed during the process, for example a carbon anode 108 that can react with oxygen to form carbon dioxide.
  • the process can be used to extract a variety of metals from a solution.
  • the metals can be chosen from titanium, chromium, iron, uranium, a trans-uranium metal, or a combination of two or more thereof.
  • a cathode 110 is suitably disposed within the catholyte chamber 106 to be at least partially immersed in the bath during operation of the electrochemical cell 100 .
  • the deposition cathode 110 is formed from a material such as carbon or a metal such as, for example, plain carbon steel, hastelloy, etc. onto which a metal of interest (e.g., metallic titanium) can be deposited or plated and subsequently recovered.
  • a metal of interest e.g., metallic titanium
  • the cathode chamber 106 can also include a means (not shown) suitable to heat, cool, or otherwise maintain the contents of the electrochemical cell 100 at a desired temperature, and/or a feed means adapted to provide a feed material comprising the metal of interest (e.g., titanium) to the bath during operation of the electrochemical cell 100 .
  • a means suitable to heat, cool, or otherwise maintain the contents of the electrochemical cell 100 at a desired temperature
  • a feed means adapted to provide a feed material comprising the metal of interest (e.g., titanium) to the bath during operation of the electrochemical cell 100 .
  • the anolyte chamber 104 and the catholyte chamber 106 are spaced apart from each other by at least one diaphragm 112 .
  • a diaphragm support (not shown) can optionally be combined with the diaphragm 112 to complement the diaphragm strength during operation of the electrochemical cell 100 .
  • the diaphragm 112 may be formed of a metal screen, sheet, or film with a multiplicity of holes or pores extending through the thickness of the diaphragm l.
  • the diaphragm 112 substrate can be, for example, iron such as steel or stainless steel, and a metal, such as cobalt, nickel or an alloy of two or more.
  • the diaphragm 112 substrate comprise, at least about 50 weight percent cobalt or nickel, which is resistant to the corrosive environment within the body 102 and retains sufficient strength at predetermined operating temperature to act as a diaphragm 112 .
  • the pores can be formed by, for example, drilling, punching, weaving, sintering, and the like.
  • the pores in the diaphragm 112 can be the same or different sizes. In one embodiment, the pores are of a substantially uniform size.
  • the diaphragm 112 may have a consistent membrane porosity and tortuosity, or these factors may vary across the thickness of the diaphragm 112 .
  • the diaphragm 112 can comprise a ceramic non-conductive material on which sufficient metal has been deposited by electrolytic or electroless procedures.
  • suitable metals for coating the ceramic diaphragm 112 include, but are not limited to, cobalt, nickel, etc.
  • the diaphragm 112 is configured to control the potential drop across the diaphragm 112 so that is below the onset potential for bipolarity. That is, the diaphragm 112 is configured to prevent oxidation and reduction reactions, involving the metal of interest, from occurring at the diaphragm 112 .
  • the inventors have found that bipolarity can be prevented by controlling the potential drop across the diaphragm 112 to a lower value than that of the standard potential for the bipolar reaction which can take place at the diaphragm 112 .
  • the potential drop across the diaphragm can be limited below the onset potential by keeping the diaphragm sufficiently thin, keeping the diaphragm sufficiently porous, keeping the current density across the diaphragm sufficiently low, or a combination of two or more thereof.
  • the electrochemical cell comprises one or more diaphragms, each having a thickness and porosity such that the ohmic potential drop ( ⁇ ) across the diaphragm is less than the difference in the reduction potentials ( ⁇ E) for the bipolar reactions at the diaphragm.
  • bipolar reaction refers to the reduction/oxidation reaction at the diaphragm surface and within its pores that would result in the formation and deposition of solid species, e.g., metal at or within the diaphragm.
  • the diaphragm 112 has a thickness such that the following inequality is satisfied:
  • ⁇ is the effective electrolyte conductivity within the diaphragm 112
  • ⁇ E is the difference between the oxidation potential and the reduction potential the bipolar reactions at the diaphragm 112 .
  • the value il/ ⁇ is equal to the ohmic potential drop ( ⁇ across the diaphragm 112 . It should be recognized that ⁇ is the effective electrolyte conductivity within the diaphragm 112 , and as such it is affected not only by the make-up of the electrolyte, but also by the porosity of the diaphragm 112 and the tortuosity of the pores.
  • Higher porosity is achieved by providing more open space within the diaphragm 112 , and lower tortuosity corresponds to having more straight and less convoluted pores; higher porosity and lower tortuosity correspond to a higher ⁇ or lower diaphragm resistance, and hence to lower potential drop across the diaphragm 112 .
  • One method of measuring the diaphragm effective conductivity, ⁇ is to (1) apply a certain measured current, I, across a diaphragm having an area, A, that is immersed into or soaked with an electrolyte, and (2) measure the voltage drop, V, across this diaphragm using a voltmeter.
  • the value of the ohmic drop across the diaphragm 112 can be controlled to be smaller than ⁇ E as indicated by the inequality above, by having a thin diaphragm 112 , i.e., making the thickness, l, small, or having highly conductive electrolyte with highly porous diaphragm with minimal tortuosity leading to high effective conductivity ⁇ , or by maintaining the average current density, i, at the diaphragm at a small value such that the inequality above is maintained.
  • the bipolar reactions at the diaphragm 112 may be:
  • the bipolar reactions at the diaphragm may be:
  • the diaphragm 112 When bipolarity develops at the diaphragm 112 , the diaphragm 112 can become plugged by deposits of the metal of interest, leading to efficiency loss and early failure. In accordance with the present technology, by keeping the voltage drop across the diaphragm 112 low, by, e.g. keeping the thickness of the diaphragm l at an appropriate low value, deposition of the metal at or within the diaphragm 112 can be prevented.
  • the diaphragm can be provided as a plurality of diaphragms 112 in a single electrochemical cell.
  • the diaphragm 112 comprises a plurality of diaphragms 112 .
  • the diaphragms 122 are disposed adjacent to one another.
  • the diaphragms 112 In arranging and configuring the diaphragms 112 , the diaphragms 112 must be oriented such there is a space or gap disposed between successive diaphragms 112 such that the individual diaphragms 112 in the stack do not touch one another. However, such gap may be filled or partially filled by an insulating porous non-conductive spacer.
  • FIG. 2 illustrates an embodiment of an electrochemical cell 100 ′ comprising a plurality of diaphragms.
  • the cell 100 ′ is similar to the cell 100 of FIG. 1 except that cell 100 ′ comprises a plurality of diaphragms 112 a, 112 b, and 112 c.
  • the diaphragms 112 are arranged such that there is a space (e.g., 114 , 116 ) disposed between excessive diaphragms 112 .
  • the space (e.g., 114 , 116 ) is maintained to avoid the individual diaphragms 112 a, 112 b and 112 c from touching each other, which can compromise their electrical isolation from one another.
  • the space (e.g., 114 , 116 ) may comprise of an open space to be filled by an electrolyte, by a perforated insulating spacer, or a porous insulator.
  • each diaphragm has a thickness whereby il/ ⁇ E.
  • the thickness of each diaphragm 112 can be the same, or the diaphragms can have different thicknesses, providing however, that the inequality above is maintained for each individual diaphragm in the stack.
  • the number of diaphragms 112 , the thickness of each diaphragm l, and the space (e.g., 114 , 116 ) between successive diaphragms can be individually chosen to provide a desired separation effect between the catholyte and the anolyte.
  • the number of diaphragms is chosen to provide sufficient diffusion resistance to the migrating titanium ions so that they do not reach the anode 108 in excessive amounts.
  • the thickness of the diaphragms l may also depend on the metal of interest to be deposited from the solution.
  • the diaphragm 112 has a thickness of about 0.8 cm or less; about 0.6 cm; or less; about 0.4 cm or less; about 0.3 cm or less; even about 0.1 cm.
  • the diaphragm 112 has a thickness of from about 0.1 cm to about 0.8 cm; from about 0.2 cm to about 0.6 cm; even about 0.3 cm to about 0.4 cm.
  • the diaphragm 112 has a thickness of from about 0.1 cm to about 0.3 cm.
  • numerical values can be combined to form new and non-disclosed ranges. As previously described, when a plurality of diaphragms 112 are employed, the thickness of the diaphragms 112 can be the same or different, and the space or distance between successive diaphragms 112 can be the same or different.
  • an electrolyte flow may be maintained through the diaphragm 112 or the stack thereof, such that the flow further reduces the undesirable transport of species across the diaphragm 112 or diaphragm stack.
  • the electrolyte on the two sides of the diaphragm or plurality of diaphragms can be maintained at the same or different levels.
  • the diaphragms 112 can be electrically conductive and connected to a power source (not shown).
  • the power source can be adjustable to provide a constant or periodic current or potential waveform to dissolve or remove any undesired bipolar reaction from accumulating on or within the diaphragms 112 .
  • the source of the metal to be electrolytically produced and deposited at the cathode 110 can be chosen as desired.
  • titanium can be electrowon from materials such as titanium tetrachloride, titanium tetrabromide, titanium trifluoride, titanium carbide, titanium dioxide etc.
  • the salt may be chosen as desired for the metal of interest to be extracted.
  • Such salts or mixtures thereof can be, for example, NaCl, LiCl—KCl, LiCl—KCl—NaCl, and LiCl—KCl—CaCl 2 .
  • the fused salt bath desirably contains a mixture of alkali or alkaline earth metal halides, preferably lithium and potassium chlorides.
  • a eutectic mixture of the salts employed in the bath is advantageous because of the low melting temperature of such mixture.
  • metal salts dissolved in aqueous medium may be employed as the electrolyte.
  • the electrowinning process is performed by applying a current across the electrodes to effectuate deposition of the metal of interest (e.g., titanium) at the cathode 110 .
  • the method comprises (a) providing an electrochemical cell 100 comprising an anolyte chamber 104 comprising an anode 108 ; a catholyte chamber 106 comprising a cathode 110 ; and a diaphragm stack separating the anolyte chamber 104 and the catholyte chamber 106 ; (b) the catholyte solution comprising an fluid containing at least one metal dissolved therein; and (d) establishing a predetermined voltage or current across the electrolytic cell sufficient to effect reduction and deposition of the at least one metal at the cathode 110 and cause an oxidation reaction at the anode 108 , wherein the diaphragm 112 is configured to prevent bipolar reactions at the diaphragm 112 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
US13/947,342 2013-07-22 2013-07-22 Electrowinning cell and process Abandoned US20150021195A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/947,342 US20150021195A1 (en) 2013-07-22 2013-07-22 Electrowinning cell and process
PCT/US2014/047598 WO2015013263A1 (fr) 2013-07-22 2014-07-22 Cellule et procédé d'extraction électrolytique

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Application Number Priority Date Filing Date Title
US13/947,342 US20150021195A1 (en) 2013-07-22 2013-07-22 Electrowinning cell and process

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167468A (en) * 1974-10-24 1979-09-11 The Dow Chemical Company Apparatus for electrowinning multivalent metals
US20060173084A1 (en) * 2004-06-25 2006-08-03 Yongchang Zheng Bipolar membrane and method of making same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098802A (en) * 1958-10-29 1963-07-23 Amalgamated Curacao Patents Co Diaphragm for use in electrolysis
US3764493A (en) * 1972-08-31 1973-10-09 Us Interior Recovery of nickel and cobalt
US4116801A (en) * 1974-10-24 1978-09-26 The Dow Chemical Company Apparatus for electrowinning multivalent metals
US4118291A (en) * 1974-10-24 1978-10-03 The Dow Chemical Company Method of electrowinning titanium

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4167468A (en) * 1974-10-24 1979-09-11 The Dow Chemical Company Apparatus for electrowinning multivalent metals
US20060173084A1 (en) * 2004-06-25 2006-08-03 Yongchang Zheng Bipolar membrane and method of making same

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