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US20080023321A1 - Apparatus for electrolysis of molten oxides - Google Patents

Apparatus for electrolysis of molten oxides Download PDF

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Publication number
US20080023321A1
US20080023321A1 US11/496,615 US49661506A US2008023321A1 US 20080023321 A1 US20080023321 A1 US 20080023321A1 US 49661506 A US49661506 A US 49661506A US 2008023321 A1 US2008023321 A1 US 2008023321A1
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Prior art keywords
anode
iridium
oxide
titanium
electrolyte
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Abandoned
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US11/496,615
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English (en)
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Donald Sadoway
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Massachusetts Institute of Technology
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Individual
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Publication date
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Priority to US11/496,615 priority Critical patent/US20080023321A1/en
Assigned to MASSACHUSETTS INSTITUTE OF TECHNOLOGY reassignment MASSACHUSETTS INSTITUTE OF TECHNOLOGY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SADOWAY, DONALD
Priority to PCT/US2007/016742 priority patent/WO2008016526A2/fr
Publication of US20080023321A1 publication Critical patent/US20080023321A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • 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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts

Definitions

  • This invention relates to electrolytic cells for the production of metals from molten electrolytes.
  • this invention provides novel anodes and cathode substrates for use with oxide melts and liquid or gaseous metal products. More particularly, an electrochemical technique for deposition of liquid titanium from titanium dioxide is described.
  • Electrolytic processes acting on molten salt electrolytes have been used to produce several important metals, examples of which are given in U.S. Pat. No. 5,185,068, the entire disclosure of which is incorporated by reference.
  • Electrolytic reduction in extractive metallurgy has seen its greatest commercial success in the production of aluminum.
  • the invention of the Hall-Héroult process in the 1880s gave birth to a new industry and transformed aluminum from a precious metal into a ubiquitous material, commonplace in construction, transportation, packaging, and electrical devices.
  • This process functions by passing an electric current through a molten fluoride electrolyte containing alumina at about 1000° C.
  • the electrochemical extraction of aluminum by the Hall-Héroult process is discussed in U.S. Pat. No. 4,999,097, the entire disclosure of which is incorporated by reference.
  • the Hall-Héroult process has persisted as the only commercial production method for aluminum with little change in its components since early implementations.
  • the anode at which oxygen from the melt is oxidized is made of carbonaceous materials as were the first Hall-Héroult cell anodes. Carbon has several useful properties that have allowed the Hall-Héroult process to become a tonnage provider of aluminum.
  • Carbon anodes are solid at the cell operating temperatures, well above the melting point of aluminum, so that the aluminum can be retrieved in liquid form. Also, the electrical conductivity of carbon is sufficiently high that the massive amperages required for practicable production rate can be conveyed to the melt without excessive voltages.
  • Carbon anodes typically are fabricated by baking carbonaceous feedstocks such as coal tar, petroleum coke and pitch at high temperatures for extended periods of time. Arranging these materials for treatment exposes workers to injurious carbon dust. Then, during this prebake process the anode outgases undesirable by-products such as hydrocarbons, polychlorinated biphenyls and sulfur dioxide. Consequently, anode fabricators must undertake expensive filtering, collecting and treatment operations. Furthermore, anode outgassing generally persists throughout the active lifetime of the electrode.
  • interactions between the anode and the molten electrolyte during cell operation consume the anode.
  • the anode reaction should be the oxidation of oxide ions to gaseous oxygen
  • the carbon anode is not inert in the aggressive high-temperature chemical environment of the cell.
  • Anode material is removed from the electrode as oxygen in the bath combines with carbon to form volatile carbon monoxide and carbon dioxide.
  • perfluorocarbon compounds mainly tetrafluoromethane and hexafluoroethane, are produced during operation at low alumina concentration, so that aluminum smelting is the greatest single contributor to perfluorocarbon compound emissions in the United States.
  • Anode consumption is problematic for several reasons. First, it makes cell operation more difficult. It is difficult to maintain uniform anode current loading during operation due to the continuously changing topology of the electrolyte-anode interface. Due to uncertainty in the position of the anode's inconstant surface, the anode-cathode spacing is maintained at a cautiously large value to preclude electrical shorting between the anode and cathode so that a greater cell voltage must be applied to the cell to drive current through the electrolyte. The anode must be continually repositioned to maintain contact with the bath as its vertical dimension shrinks. Anode changes are labor intensive and disturb the thermal balance and electrical current distribution in the cell.
  • Gases produced by the consumption reaction can remain trapped under the anode surface and contribute additional ohmic drops to the operating voltage.
  • environmental concerns about electrolytic aluminum smelting as historically practiced have become more prominent.
  • the Hall-Héroult cell has persisted despite the longfelt need for an alternative to carbon. While an inert anode has been viewed as a highly desirable target, its discovery would provide an enhancement to an already-workable system—not a pre-requisite for a viable process. However, the identification of such an oxide-compatible, high-temperature-stable electrode for aluminum extraction could also make possible new processes for extraction of other metals from their oxide compounds.
  • titanium is instructive.
  • the main sources of titanium are ilmenite and rutile, in both of which titanium is bound to oxygen. Nonelectrolytic industrial processes for titanium extraction act on titanium chlorides and so require an additional preliminary unit operation, the carbochlorination of titanium dioxide—which generates carbon dioxide—for rendering titanium chloride feed for the final reduction.
  • the principal commercial route by which titanium is produced is the Kroll process, a batch metallothermic reduction of titanium tetrachloride by magnesium.
  • the titanium sponge product is contaminated with excess magnesium and magnesium chloride.
  • the Dow-Howmet process dissolves titanium dichloride, produced from the tetrachloride, in a potassium and lithium chloride molten electrolyte. With an operating temperature of about 520° C., the Dow-Howmet cell, like other electrolytic titanium producing operations, deposits titanium well below its melting temperature (1670° C.), resulting in dendritic solid deposits into which electrolyte is entrained. The product must be washed and then remelted to render metal ingot.
  • the Fray, Farthing, & Chen (FFC) process differs in that it uses titanium dioxide feedstock in the form of a reactive cathode immersed in a molten chloride electrolyte containing calcium chloride. By passage of current, oxygen is electrochemically removed from the TiO 2 cathode leaving behind elemental titanium. On the anode, oxygen reacts as it does in the Hall cell to produce CO 2 . Although the FFC process moves in the right direction by obviating chlorination of titanium dioxide it is nonetheless environmentally suspect due to the halide electrolyte. The formation of unacceptable, albeit small, amounts of dioxin and furans undoubtedly attends the evolution of carbon dioxide on the carbon anode in such an environment. Also, the FFC process has not become economically viable owing to the long times required to remove all the oxygen from the cathode, solid-state diffusion being extremely slow.
  • the design of apparatus for electrolytic extraction from oxide media poses many challenges not faced in the Hall-Héroult cell.
  • another essential component with rigorous materials requirements is the cathode substrate upon which the metal is deposited, the deposit subsequently acting as the cathode.
  • cathode substrate material must be solid at the operating temperature of the electrolytic cell.
  • materials that may be serviceable at aluminum's relatively low melting temperature may well lack structural integrity at the higher temperatures—exceeding 1700° C.—required for deposition of titanium metal in liquid form.
  • cathode substrate material Another requirement of the cathode substrate material is that it not react chemically with the molten electrolyte or the liquid metal product.
  • the carbon substrate of the Hall-Héroult cell is not compatible with reactive metals such as titanium in this instance because these metals react, to an undesirable extent, with carbon to form carbides.
  • a third requirement concerns the electronic conductivity of the cathode substrate material.
  • the rate of electrolytic metal deposition is proportional to the flow of electrons through the cathode substrate. If the electronic conductance of this element is too low, metal deposition at a commercially acceptable rate will be achieved only by application of a large voltage, which in turn will translate into unacceptably high electric power cost. Thus, in order to maintain an economical energy efficiency for metal extraction, the substrate material must be reasonably conductive.
  • RHMs refractory hard metals
  • An object of the present invention is, accordingly, an apparatus for extraction of metal from an oxide feedstock without use of carbon-based electrodes.
  • Another object of the invention is an electrochemical apparatus for depositing liquid titanium from titanium dioxide feedstock.
  • Another object of the invention is the electrochemical extraction of metals, in liquid or gaseous form, above their melting temperatures.
  • Another object of the invention is metal smelting with significantly reduced emission of greenhouse gases.
  • Another object of the invention is nonconsumable anodes for electrochemical extraction of metals.
  • Still another object of the invention is an anode shaped with channels for ducting evolved oxygen.
  • Another object of the invention is a means for electrochemical production of oxygen by the action of electric current through an electrode immersed in a molten electrolyte containing a source of oxygen.
  • Another object of the invention is to provide conductive cathode substrates compatible with liquid reactive metals and molten reactive-metal precursors.
  • the invention relates to the discovery that materials heretofore not considered useful for electrodes and electrode substrates of cells for the electrolytic production of metals from oxide-based feedstocks in a molten electrolyte can serve as such, thereby providing improved electrolytic cells and novel methods for metal production.
  • the invention provides nonconsumable iridium anodes for accepting electrons from oxide-containing melts, thereby facilitating the oxidation of precursors in the electrolyte, with evolution of gaseous oxygen.
  • the anodes of the invention comprise an iridium-based body having a continuous iridium surface, such that substantially the entire anodic surface in contact with the electrolyte in the cell is an iridium-based material.
  • the term iridium-based denotes a material comprising iridium sufficiently concentrated and voluminous to establish a substantially continuous iridium surface over a contact interface—defined to be the entire anode-electrolyte interface—and also to confer mechanical integrity and chemical properties of the same order as those of pure bulk iridium.
  • the anode is substantially pure iridium.
  • the anode comprises an electrode foundation of a less-expensive material overlaid by a continuous film of iridium-based material.
  • the anode is made of an iridium-based alloy having an iridium content of at least 80%.
  • iridium metal With a melting point of 2446° C., iridium metal can withstand service temperatures for electrolytic smelting of reactive metals without degradation of its mechanical properties. Its excellent high-temperature oxidation resistance allows it to serve in the aggressive molten oxide environment required to achieve the objects of the invention.
  • the electrodes disclosed herein eliminate the need for the expensive dedicated anode-preparation shop necessary to maintain a smelting facility using carbon anodes. Being essentially nonconsumable, the anodes are replaced less frequently, and operating costs are reduced.
  • the stable anode contour permits closer approach to the metal product so the cell can function at lower voltage and hence lower power cost per unit of metal product.
  • the mechanical properties of iridium make possible a variety of anode geometries greatly advantageous over the block design used for carbon anodes.
  • the anode is formed with channels for conveying oxygen evolving at the anode-electrolyte interface out of the cell, preventing the aggregation of large bubbles that reduce cell efficiency.
  • a similar advantage is provided by another embodiment in which the anode has a comb-like structure.
  • the inert anode of the invention is incorporated into a conventional Hall-Héroult cell for aluminum extraction and replaces carbon-based anodes of the prior art, with improved performance with respect to difficulty of operation and undesirable emissions.
  • the iridium-based anode contacts a molten electrolyte containing titanium and oxygen precursors as part of a cell producing titanium metal, preferably operating at a temperature sufficient for production of liquid titanium.
  • the anode is used with an electrolyte comprising titanium dioxide—derived, for example, from anatase or rutile—dissolved in a molten oxide solvent containing at least one member of the group consisting of beryllium oxide, magnesium oxide, calcium oxide, aluminum oxide, and lithium oxide.
  • the iridium-based electrode of the invention serves as anode in an apparatus evolving gaseous oxygen, for example in conjunction with deposition of a reactive metal.
  • a reactive metal for liquid-phase deposition include beryllium, aluminum, silicon, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, gallium, germanium, yttrium, zirconium, hafnium, indium, tin, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium and uranium.
  • the anode of the invention could similarly serve in an electrolysis apparatus for vapor-phase production of reactive metals such as lithium, sodium, magnesium, potassium, calcium
  • the anode of the invention is equally suitable for cell configurations incorporating one or more vertically oriented, dipping cathodes, which furnish electrons for the electrochemical reduction of ions in the electrolyte but do not act as a substrate supporting the accumulated metal deposit.
  • Such a configuration may be more satisfactory in cells operating so as to produce a vapor-phase metal since the proximity of the cathode to the upper surface of the electrolyte simplifies collection of the metal product, which can readily exit the cell at the top.
  • Dipping electrodes may be similarly desirable in the case of a liquid metal product lower in density than the molten oxide electrolyte.
  • Cells may additionally include a protective wall between anode and cathode for shielding products of the respective electrodes from one another to prevent recombination or electrical shorting. Such design considerations are well known to those skilled in the art of electrochemical extraction of metals.
  • the invention provides tungsten-based cathode substrates—having a tungsten content of at least 50%—for deposition of liquid reactive metals.
  • the cathode substrate furnishes electrons to the molten electrolyte, either directly or through a liquid metal layer, during cell operation.
  • Cathode substrates constructed of a tungsten-based alloy enable deposition of an overlying liquid reactive-metal cathode without continual formation of carbides to an extent that would erode the cathode substrate.
  • Such materials are resistant to alloying with liquid titanium and are solid at the temperature range of interest.
  • unlike elemental tungsten they resist oxidation at high temperatures.
  • the tungsten-based alloy contains at least 15% rhenium by weight; an example is W-25Re, comprising 75% tungsten and 25% rhenium, which has a melting temperature above 3000° C.
  • incorporación of the anode and cathode substrate of the invention into an electrolysis cell containing molten-oxide electrolyte establishes a novel method for electrolytic extraction of reactive metals.
  • the iridium-based anode and tungsten-based cathode substrate co-operate in a cell for optimum production of liquid titanium metal directly from an oxide feedstock.
  • Titanium production according to the invention proceeds without release of greenhouse gases: Because the metal is reduced directly from oxide, preparatory processing is much cleaner and simpler. Since the invention deposits titanium in liquid form, subsequent treatment is far easier than in current methods.
  • FIG. 1 is a vertical section showing a Hall-Héroult cell such as is employed commercially for aluminum extraction;
  • FIG. 2 is a vertical section illustrating one embodiment of a Hall-Héroult cell modified to employ a nonconsumable anode of this invention, the single anode having venting channels;
  • FIG. 3 is a vertical section illustrating one embodiment of a Sadoway cell for titanium extraction according to the invention.
  • FIG. 4 is a vertical section illustrating the anode of the invention used in a cell having a dipping cathode.
  • a conventional Hall-Héroult cell 10 has a steel outer shell 12 lined by overlying thermal insulation 14 .
  • a carbon cathode substrate 16 positioned at the bottom of the cell 10 contains metallic current collector bars 18 .
  • Carbon anodes 20 are formed by prebaking carbon blocks suspended from steel anode rods 22 which supply electrical current to the anodes 20 .
  • a cell lining 24 is also formed from carbon blocks.
  • Molten electrolyte 26 contains dissolved alumina, which is continually supplied by breaking an alumina crust 28 and adding fresh alumina.
  • the alumina crust 28 forms on frozen electrolyte and helps to minimize heat loss from the top of the cell 10 .
  • cryolite Na 3 AlF 6
  • certain fluoride salts are present in the electrolyte 26 .
  • Calcium fluoride, CaF 2 decreases the freezing point of cryolite.
  • Aluminum fluoride, AlF 3 contributes to the freezing point depression and also improves current efficiency in the cell 10 .
  • the operating temperature of the cell is about 1000° C.
  • dissolved alumina is reduced to form a molten aluminum layer 32 over the cathode substrate 16 at the bottom of the cell 10 .
  • Gas consisting principally of carbon dioxide and carbon monoxide is generated at the anode 20 .
  • the carbon anode 20 is consumed during this reaction.
  • the cell 10 is operated under conditions that cause a frozen electrolyte layer 30 to form between the carbon cell lining 24 and the molten electrolyte 26 .
  • the molten electrolyte 26 is surrounded by the shell of frozen electrolyte 30 and supported by the molten aluminum layer 32 .
  • the need to maintain the frozen electrolyte layer 30 complicates control of the cell because the location of the interface between the molten and frozen electrolyte phases varies with operating conditions of the cell 10 .
  • the carbon cathode substrate 16 is covered with a deep pool of molten aluminum so that aluminum deposits onto the molten aluminum layer 32 rather than onto carbon.
  • the molten aluminum layer 32 provides electrons to the molten electrolyte and functions as cathode in the cell 10 . This arrangement prevents the degradation of the cathode substrate 16 by creation and dissolution into the electrolyte of aluminum carbide, which is formed when aluminum is electrodeposited onto carbon.
  • an electrolysis cell 40 configured for the extraction of aluminum has a steel outer shell 42 lined by overlying thermal insulation 44 .
  • a carbon cathode substrate 46 positioned at the bottom of the cell 40 contains metallic current collector bars 48 .
  • a single anode 50 is constructed from iridium metal and formed with channels 52 for venting oxygen to the extetior of the cell 40 .
  • the anode 50 is connected to a supply of electric current by an anode rod 54 , which may be of iridium or of some other conductive material.
  • Cell lining 56 is also formed from carbon blocks.
  • the cell contains molten electrolyte 58 covered with a frozen alumina layer 60 .
  • Electrolyte compositions capable of dissolving alumina such as are found in conventional Hall-Héroult cells, are compatible with the cell of the invention. Accordingly, the cell 40 is operated so as to maintain a frozen electrolyte layer 62 .
  • the operating temperature of the cell is about 1000° C.
  • dissolved alumina is reduced to build a molten aluminum layer 64 over the cathode substrate 46 at the bottom of the cell 40 .
  • Gas consisting principally of oxygen is generated at the inert, nonconsumable anode 50 and passes through the channels 52 , thus exiting the cell 40 .
  • an electrolysis cell 70 configured for the extraction of titanium has a tungsten-rhenium outer shell 72 lined by overlying thermal insulation 74 .
  • the cathode substrate 76 positioned at the bottom of the cell 70 contains metallic current collector bars 78 .
  • a single anode 80 is constructed from iridium metal and formed with channels 82 for venting oxygen to the exterior of the cell 70 .
  • the anode 80 is connected to a supply of electric current by an anode rod 84 , which is of some electrically conductive material.
  • the cell contains molten electrolyte 88 acting as a solvent for titanium dioxide.
  • the electrolyte 88 is preferably one or more molten oxides, the precise composition of which is selected for its capability of dissolving titanium dioxide as well as other physical and chemical properties known to those skilled in the art of molten salt electrochemistry.
  • the operating temperature of the cell is about 1700° C.
  • dissolved titanium dioxide is reduced to build a liquid titanium layer 94 over the cathode substrate 76 at the bottom of the cell 70 .
  • Gas consisting principally of oxygen is generated at the inert, nonconsumable anode 80 and passes through the channels 82 , thus exiting the cell 70 .
  • an electrolysis cell 90 has an iridium anode 92 and a cathode 94 which are suspended above the cell 90 and dip into a molten electrolyte 96 .
  • gaseous oxygen evolves on the anode 92 .
  • the cathode 94 provides electrons to the electrolyte 96 , thereby extracting a reactive metal, which, depending on its boiling temperature, leaves the cell 90 as a vapor or remains in the cell in the liquid phase.
  • a protective wall 98 interposed between the anode 92 and the cathode 94 shields products of the respective electrodes from one another to prevent recombination or electrical shorting.

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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)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
US11/496,615 2006-07-31 2006-07-31 Apparatus for electrolysis of molten oxides Abandoned US20080023321A1 (en)

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US11/496,615 US20080023321A1 (en) 2006-07-31 2006-07-31 Apparatus for electrolysis of molten oxides
PCT/US2007/016742 WO2008016526A2 (fr) 2006-07-31 2007-07-26 Appareil pour l'électrolyse d'oxydes fondus

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US12116684B2 (en) 2018-04-24 2024-10-15 Battelle Energy Alliance, Llc Methods of forming alloys by reducing metal oxides
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