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WO2010118368A1 - Utilisation d'une terre rare pour le retrait d'antimoine et de bismuth - Google Patents

Utilisation d'une terre rare pour le retrait d'antimoine et de bismuth Download PDF

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Publication number
WO2010118368A1
WO2010118368A1 PCT/US2010/030599 US2010030599W WO2010118368A1 WO 2010118368 A1 WO2010118368 A1 WO 2010118368A1 US 2010030599 W US2010030599 W US 2010030599W WO 2010118368 A1 WO2010118368 A1 WO 2010118368A1
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WO
WIPO (PCT)
Prior art keywords
target material
fixing agent
stream
insoluble
electrolytic
Prior art date
Application number
PCT/US2010/030599
Other languages
English (en)
Inventor
Charles F. Whitehead
Carl R. Hassler
Original Assignee
Molycorp Minerals Llc
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=42933488&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2010118368(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Molycorp Minerals Llc filed Critical Molycorp Minerals Llc
Priority to EA201171231A priority Critical patent/EA201171231A1/ru
Priority to AU2010233100A priority patent/AU2010233100A1/en
Priority to CA2757853A priority patent/CA2757853A1/fr
Priority to MX2011010666A priority patent/MX2011010666A/es
Publication of WO2010118368A1 publication Critical patent/WO2010118368A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0084—Treating solutions
    • C22B15/0089—Treating solutions by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • 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
    • C25C7/06—Operating or servicing
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates generally to a process for removing one or more contaminants from an electrolytic solution and more particularly to a process for removing the one or more contaminants in an electrorefining solution using rare earth metals.
  • Electrometallurgy is a process for recovering a metal from an electrolytic solution using electricity.
  • the electrometallurgy process comprises passing an electric current through the electrolytic solution to extract or purify the metal.
  • the electrometallurgical process of extracting the metal from the electrolytic solution is typically called electrowinning, while the process of purifying the metal by passing the electric current through the electrolytic solution is called electrorefining.
  • Electrorefining comprises dissolving the metal at an anode and re-depositing the same metal at a cathode in an electrochemical cell.
  • the metal being refined is oxidized at the anode and enters the electrolytic solution as cation according to the following half-cell reaction:
  • the oxidation process produces electrons at the anode.
  • the number (n) of electrons (e-) produced is determined by the cationic species (M n+ ) of the metal (M) produced electrochemically.
  • the anode contains species other than the metal being electrorefined, these species may have higher, lower, or similar oxidation potentials to the metal being electrorefined. Species having higher oxidation potentials that the metal being electrorefined are considered to be more noble. More noble species, such as noble metals, are not oxidized at the anode and do not enter the electrolytic solution during the anodic process. As such, a noble metal-containing sludge forms during the anodic process of dissolving of the metal.
  • Species contained within the anode having oxidization potentials substantially similar to or oxidatively more active than the metal are typically oxidized and enter the electrolytic solution as contaminants during the anodic dissolving process. These contaminants are present within the electrolytic solution as dissolved species and accumulate within the electrolytic solution. More importantly, these contaminants may interfere with the cathodic deposition of the metal.
  • the cathodic re-deposition process of the metal is represented by the chemical half-reaction:
  • the cathode contains a substantially purer form of the metal.
  • the cathodically re- deposited metal is substantially free of the more noble metals and/or the contaminants previously contained within the anode.
  • Copper is a metal that is commonly electrorefined.
  • the noble metals commonly recovered in the electrorefining of copper are gold, silver and platinum group metals.
  • the contaminants, other than the noble metals typically are arsenic, antimony, bismuth, selenium, tellurium, lead, tin, iron, cobalt, zinc, and nickel
  • arsenic, antimony and bismuth are troublesome materials in the electrorefining of copper.
  • Arsenic, antimony and bismuth typically are contained in copper anodes used in copper electrorefining. Copper, arsenic, antimony and bismuth have similar standard reduction potentials.
  • copper, arsenic, antimony and bismuth have similar standard reduction potentials.
  • arsenic, antimony, and bismuth concentrations within the electrolytic solution increase.
  • One or more of the arsenic, antimony and bismuth may be cathodically electrodeposited with the copper affecting the cathode quality, such as copper grain structure and copper purity level of the electrorefined copper. Therefore, it is important to control the concentration of arsenic, bismuth, antimony and other contaminants during the electrorefining of copper.
  • This disclosure relates generally to target material removal from an electrolytic solution and the stabilization of one or both of the target material and the electrolytic solution.
  • the process further comprises separating the target material-laded insoluble fixing agent from at least one of the rich feed stream and the electrolyzed solution to form a purified stream. In another configuration, the process further comprises at least one of recovering the target material and recycling the purified stream to electrolysis cell.
  • the electrodepositing process is one of electrowinning or electrorefining.
  • the valuable metal is a metal having an atomic number of 22-30, 40-48, and 72-79.
  • the process further comprises contacting the target material-loaded insoluble fixing agent with a stripping solution to dissolve, solublize, or otherwise displace most of the target material in the target material-loaded insoluble fixing agent to form a loaded stripping solution and barren insoluble fixing agent, wherein the stripping solution comprises at least one of a strong base, an oxalate, ethanedioate, a strongly absorbing exchange oxyanion, a reductant or reducing agent, and an oxidant or oxidizing agent.
  • the process further comprises cycling the barren insoluble fixing agent to contacting step fc), wherein the barren insoluble fixing agent is contacted with one of the rich feed stream and the electrolyzed solution to form the target material-loaded insoluble fixing agent.
  • the process further comprises removing at least most of the dissolved target material from the loaded stripping solution.
  • the insoluble fixing agent comprising at least one of yttrium, scandium, and a lanthanoid, the target material-loaded insoluble fixing agent comprising most of the target material in the electrolyte side stream, wherein the target material, in the target material-loaded insoluble fixing agent, forms a composition with the insoluble fixing agent;
  • the valuable metal is copper.
  • the target material is at least one of arsenic, antimony, bismuth, tin, lead, selenium, tellurium, platinum, iridium, ruthenium, and rhodium.
  • the target material is an oxyanion.
  • the target material is an oxyanion of at least one of tellurium, selenium, bismuth, antimony and arsenic.
  • the insoluble fixing agent is a finely divided solid having a surface area from about 25 m 2 /g to about 500 m 2 /g.
  • the process further comprises contacting the target material-loaded insoluble fixing agent with a stripping solution to dissolve, solublize, or otherwise displace most of the target material in the target material-loaded insoluble fixing agent to form a loaded stripping solution and barren insoluble fixing agent.
  • the stripping solution is one of a strong base, an oxalate, ethanedioate, a strongly absorbing exchange oxyanion, a reductant or reducing agent, and oxidant or oxidizing agent.
  • the process further comprises cycling the barren insoluble fixing agent to contacting step (b), wherein the barren insoluble fixing agent is contacted with the electrolytic side stream to form the target material- loaded insoluble fixing agent.
  • the process further comprises removing at least most of the dissolved target material from the loaded stripping solution.
  • first and second fixing agents are used.
  • the electrolyte side stream comprises a target material- bearing stream, having a first concentration of target material.
  • the electrolyte side stream is contacted with an insoluble first fixing agent, such as an adsorbent or absorbent, to produce a target material-bearing first fixing agent.
  • the first contacting step removes most, if not all, of the target material from the electrolyte side steam.
  • the target material-bearing first fixing agent is contacted with an alkaline stripping solution ("release agent") to produce an intermediate target material-rich solution having a second concentration of the target material.
  • release agent alkaline stripping solution
  • the second concentration of target material may exceed the first concentration of target material.
  • the alkaline stripping solution can be or include, for example, a leaching agent.
  • the second concentration of target material is a concentration about equal to the solubility limit of the target material (at the process conditions of the second step). More commonly the second concentration of the target material is between about 0.1 and about 2,500 g/L, even more commonly between about 0.1 and about 1,000 g/L, and even more commonly between about 0.25 g/L and about 500 g/L.
  • a soluble or dissolved second fixing agent is contacted with the intermediate target material-rich solution in an amount sufficient to precipitate most, if not all, of the target material as a target material-bearing solid.
  • the target material-bearing solid may be separated from the intermediate target material-rich solution by any suitable solid/liquid separation technique to produce a separated solid for disposal and/or recovery of the target material and a stripping solution for recycle to the second contracting step.
  • the insoluble fixing agent including the first fixing agent, is commonly a particulate solid.
  • the insoluble fixing agent (including the first fixing agent) is preferably an insoluble rare earth metal compound, more preferably an insoluble rare earth oxide comprising an insoluble rare earth compound, such as hydrous or anhydrous rare earth oxides, fluorides, carbonates, fluorocarbonates, silicates, and the like.
  • a particularly preferred insoluble fixing agent is CeO 2 .
  • the fixing agent is particularly effective in removing arsenic having an oxidation state of +3 or +5.
  • the soluble or dissolved second fixing agent typically has an oxidation state lower than the oxidation state of the insoluble (first) fixing agent.
  • the oxidation state of the second fixing agent is one of +3 or +4.
  • the soluble fixing agent preferably is a soluble rare earth metal compound and more preferably includes salts comprising rare earth compounds, such as bromides, nitrates, phosphites, chlorides, chlorites, chlorates, nitrates, and the like. More preferably, the soluble fixing agent is a rare earth (III) chloride.
  • the intermediate solution can include a valuable product.
  • the valuable product is commonly any metal of interest, more commonly includes one or more of the transition metals and even more commonly includes a metal selected from the group of metals consisting of copper, nickel, cobalt, lead, precious metals, and mixtures thereof. All or a portion of the residual valuable product may be recovered from the intermediate solution.
  • the fixing agent is a non-rare earth salt additive.
  • the non-rare earth salt additive is a non-rare earth metal having a +3 oxidation and is substantially free of a rare earth.
  • the insoluble composition is a precipitate formed between the target material and the non-rare earth salt additive.
  • the non- rare earth salt additive comprises one of boron, aluminum, gallium, indium, thallium and a transition metal.
  • the rare earth-containing fixing agent is a rare earth salt additive.
  • the rare earth salt additive is a rare earth having a +3 oxidation state and a non-rare metal having a +3 oxidation state.
  • the insoluble composition is a precipitate formed between the target material and at least one of the rare earth and the non-rare earth.
  • the non-rare earth metal comprises one of boron, aluminum, gallium, indium, thallium and a transition metal.
  • the fixing agent is a rare earth, preferably a soluble rare earth.
  • the insoluble composition is an insoluble target material- containing composition formed by the contacting of the target material and the soluble rare earth.
  • the electrolytic side stream contains a valuable metal. At least most, if not all, of the valuable metal within the electrolytic side stream is cycled to the electrolytic cell.
  • the electrolytic side stream contains copper. At least most, if not all, of the copper within the electrolytic side stream is cycled to the electrolytic cell by the purified electrolytic stream.
  • electrolytic side stream comprising a target material and dissolved copper, wherein electrolytic side stream has a first target material concentration
  • the process preferably further comprises:
  • the target material-loaded insoluble fixing agent comprises at least one of a strong base, an oxalate, ethanedioate, a strongly absorbing exchange oxyanion, a reductant or reducing agent, and oxidant or oxidizing agent.
  • the process further comprises:
  • the barren insoluble fixing agent is contacted with the electrolytic side stream to form the target material-loaded insoluble fixing agent.
  • the target material will be present in a reduced oxidation state and this condition might be undesirable.
  • an oxidant may be contacted with the electrolyte feed stream to increase the target material oxidation state.
  • arsenic as an example, the presence of arsenite might favor the use of an oxidant before the fixing agent is applied.
  • the insoluble target material-containing composition is typically in the form of precipitate that can be removed as a solid.
  • the insoluble target material-containing composition has at least about 0.01 wt. %, even more preferably at least about 0.1 wt. %, and even more preferably ranges from about 5 to about 50 wt. % of the target material.
  • the target material is commonly in the form of an oxygen-containing anion with an oxyanion being illustrative.
  • the target material is one or more of arsenic, antimony, bismuth, selenium, tellurium, tin, platinum, ruthenium, rhodium, and iridium.
  • the soluble fixing agent, or precipitant can be supported by a suitable carrier or can be unsupported.
  • a method includes the steps of:
  • a rare earth salt additive comprising a rare earth in the +3 oxidation state and a non-rare metal in the +3 oxidation state
  • a non-rare earth salt additive comprising a non-rare earth metal in the +3 oxidation state and being substantially free of a rare earth; and forming a precipitate between the target material and at least one of the rare earth and non-rare earth salt additives.
  • the non-rare earth metal can be any non-rare earth metal in the +3 oxidation state, with transition metals, boron, aluminum, gallium, indium, and thallium being preferred, and the transition metals and aluminum being particularly preferred.
  • Preferred transition metals include the elements having atomic numbers 22-29, 40- 45, 47, 72-77, and 79.
  • the rare earth salt additive is, in one formation, a bimetallic, lanthanide-based salt solution.
  • the non-rare earth salt additive in a preferred formulation, contains aluminum in the +3 oxidation state.
  • the rare earth salt additive includes cerium in the +3 oxidation state and the non-rare earth slat additive includes aluminum in the +3 oxidation state.
  • a method includes the steps: (a) providing an electrolytic stream comprising a dissolved target material and dissolved valuable product, the target material being in the form of an oxyanion and the valuable product being at least one of a transition metal;
  • the present invention can include a number of advantages depending on the particular configuration.
  • the process of the present invention can remove variable amounts of target materials as needed to comply with application and process requirements.
  • the target material removal process can remove high concentrations of target materials to produce a treated electrolytic stream having no more than about 500 ppm, in some cases no more than about 100 ppm, in other cases no more than about 50 ppm.
  • the target material removal process can produce a treated electrolytic stream having no more than about 20 ppb, and in still other cases no more than about 1 ppb target material.
  • the insoluble rare earth/target material product can be qualified as non-hazardous waste.
  • the target material removal process can be relatively insensitive to pH.
  • the disclosed process can effectively fix target materials, particularly arsenic, antimony and/or bismuth, from electrolytic streams over a wide range of pH levels, as well as at extremely high and low pH values.
  • target materials particularly arsenic, antimony and/or bismuth
  • the capability of the present invention to treat electrolytic streams over a wide range of pH values can eliminate the need to alter and/or maintain the pH of the solution within a narrow range when removing the target material.
  • the electrolytic stream is a copper elector fining stream
  • the stream can be flexibly treated without significant concern for the pH of electrolytic stream.
  • significant cost advantages can be achieved by eliminating the need to adjust and maintain pH while fixing the target materials contained within the electrolytic stream.
  • the target material removal process can also be relatively insensitive to target material concentration.
  • the process can remove relatively low and/or high levels of target materials, particularly arsenic, antimony and bismuth from electrolytic streams.
  • the process can be a robust and/or versatile process.
  • the term “a” or “an” entity refers to one or more of that entity.
  • the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein. It is also to be noted that the terms “comprising”, “including”, and “having” can be used interchangeably.
  • absorption refers to the penetration of one substance into the inner structure of another, as distinguished from adsorption.
  • adsorption refers to the adherence of atoms, ions, molecules, polyatomic ions, or other substances of a gas or liquid to the surface of another substance, called the adsorbent.
  • the attractive force for adsorption can be, for example, ionic forces such as covalent, or electrostatic forces, such as van der Waals and/or London's forces.
  • each of the expressions “at least one of A, B and C”, “at least one of A, B, or C”, “one or more of A, B, and C", “one or more of A, B, or C" and "A, B, and/or C” means A alone, B alone, C alone, A and B together, A and C together, B and C together, or A, B and C together.
  • composition refers to one or more chemical units composed of one or more atoms, such as a molecule, polyatomic ion, chemical compound, coordination complex, coordination compound, and the like.
  • bonds and/or forces such as covalent bonds, metallic bonds, coordination bonds, ionic bonds, hydrogen bonds, electrostatic forces (e.g., van der Waal's forces and London's forces), and the like.
  • insoluble refers to materials that are intended to be and/or remain as solids in water and are able to be retained in a device, such as a column, or be readily recovered from a batch reaction using physical means, such as filtration. Insoluble materials should be capable of prolonged exposure to water, over weeks or months, with little ( ⁇ 5%) loss of mass.
  • oxyanion or oxoanion is a chemical compound with the generic formula A x O/- (where A represents a chemical element other than oxygen and O represents an oxygen atom).
  • A represents metal, metalloid, and/or Se (which is a non-metal), atoms.
  • metal-based oxyanions examples include chromate, tungstate, molybdate, aluminates, zirconate, bismuthate, etc.
  • metalloid-based oxyanions include arsenate, arsenite, antimonate, germanate, bismuthate, silicate, etc.
  • particle refers to a solid or microencapsulated liquid having a size that ranges from less than one micron to greater than 100 microns, with no limitation in shape.
  • precipitation refers not only to the removal of target material-containing ions in the form of insoluble species but also to the immobilization of contaminant-containing ions on or in insoluble particles.
  • precipitation includes processes, such as adsorption and absorption.
  • rare earth refers to one or more of yttrium, scandium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium erbium, thulium, ytterbium, and lutetium.
  • lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium erbium, thulium, ytterbium, and lutetium are known as lanthanoids.
  • soluble refers to materials that readily dissolve in water. For purposes of this invention, it is anticipated that the dissolution of a soluble compound would necessarily occur on a time scale of minutes rather than days. For the compound to be considered to be soluble, it is necessary that it has a significantly high solubility product such that upwards of 5 g/L of the compound will be stable in solution.
  • sorb refers to adsorption and/or absorption.
  • Fig. 1 depicts a process according to an embodiment of the present invention
  • Fig. 2 depicts an electrolysis cell according to an embodiment of the present invention.
  • Fig. 3 depicts another process according to another embodiment of the present invention.
  • the electrolytic solution comprises an aqueous solution.
  • the fixing agent whether soluble or insoluble, preferably includes a rare earth.
  • Specific examples of such materials for removing target materials include lanthanum (III) compounds, soluble lanthanum metal salts, lanthanum oxide, cerium dioxide, and soluble cerium salts, which have been described in U.S. Patent Application No. 12/616,653 with a filing date of November 11, 2009, the contents of which is incorporated herein in its entirety by this reference.
  • the electrolytic solution can be a rich electrolytic solution formed in unit operation 301 (Fig. 1) and/or an electrolyzed-electrolytic solution formed in an electrolysis cell 303.
  • the rich electrolytic solution is substantially pregnant with a valuable metal to be electrodeposited on an electrode of the electrolysis cell 303.
  • the electrolyzed-electrolytic solution can be one of an electrolytic solution substantially depleted of the valuable metal (which was electrodeposited on an electrode, such as in an electrowinning process) or substantially laden with contaminants generated within the electrolysis cell (such as in an electrorefining process).
  • the unit operation comprises forming an electrolytic solution rich in the valuable metal to electrodeposited on an electrode in the electrolysis cell 303.
  • the unit operation 301 may comprise one or more of resin-in leach, carbon-in leach, resin-in pulp, carbon-in pulp, stripping, leaching, ion-exchange, hydrometallurgy and combinations thereof.
  • the electrolytic solution can be formed in leaching process, such as, an acid leach, bio-leach, pressure oxidation leach, or other leaching process know to one of ordinary skill in the art.
  • the leaching process can include a resin or carbon source to concentrate and/or capture the valuable metal during the leaching process, including pulp leaching processes.
  • the electrolytic solution can be formed in an ion-exchange process, wherein the valuable metal is captured and/or concentrated on an ion- exchange resin, followed by elution to form a concentrated solution containing the valuable metal.
  • the electrolytic solution can be formed by a stripping and/or extraction process, such as, with a complexing and/or phase transfer agent to selectively extract and concentration the valuable metal in solution.
  • a target material contained with the electrolytic solution is removed contacting the electrolytic solution with a rare earth-containing fixing agent to form a target material-loaded insoluble fixing agent (process 302).
  • the target material contained with the electrolytic solution can be from one or both of the unit operation 301 or the electrolysis cell 303.
  • at least most, if not all, of the target material is removed from the electrolytic solution by the contacting of the electrolytic solution with the rare earth-containing fixing agent.
  • the target material- loaded insoluble fixing agent is separated from at least one of the rich feed stream and the electrolyzed stream to form a purified stream.
  • the purified stream forms at least some of the electrolytic solution comprising the electrolytic cell 303.
  • the process 302 can further include separating the target material from the target material-loaded insoluble fixing agent to form a target material product 304.
  • the particular target materials removed depend on whether the fixing agent is insoluble or soluble in the aqueous solution, particularly under standard conditions (e.g., Standard Temperature and Pressure "STP").
  • insoluble cerium fixing agents effectively remove arsenic, when arsenic is part of a complex multi-atomic unit having an oxidation state preferably of +3 or higher and even more preferably a oxidation state from +3 to +5, while soluble cerium fixing agents remove effectively arsenic, when arsenic is part of a complex multi-atomic unit and has an oxidation state of +5.
  • Target materials preferably includes not only arsenic but also elements having an atomic number selected from the group of consisting of atomic numbers 5, 9, 13, 14, 22 to 25, 31, 32, 33, 34, 35, 40 to 42, 44, 45, 49 to 53, 72 to 75, 77, 78, 80, 81, 82, 83, 85, 92, 94, 95, and 96 and more preferably from the group consisting of atomic numbers 13, 14, 33, 34, 40 to 42, 44, 45, 50, 51, 52, 77, 78, 80, 81, 82, 83, 92, 94, 95, and 96.
  • atomic numbers include the elements of arsenic, aluminum, astatine, bromine, boron, fluorine, iodine, silicon, titanium, vanadium, chromium, manganese, gallium, thallium, germanium, selenium, mercury, zirconium, niobium, molybdenum, ruthenium, rhodium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, iridium, platinum, lead, uranium, plutonium, americium, curium, and bismuth.
  • target materials amenable to removal and stabilization by the insoluble fixing agent include, without limitation, target materials in the form of complex anions, such as metal, metalloid, and selenium oxyanions.
  • the target material removed comprises one of tellurium, selenium, lead, bismuth, antimony, tin, arsenic, platinum, iridium, ruthenium, and rhodium. In a more preferred embodiment, the target material removed comprises one of tellurium, selenium, lead, tin, antimony, bismuth and arsenic.
  • the fixing agent reacts with the target material contained in electrolytic solution to form a purified electrolytic solution.
  • the target material comprises an oxyanion.
  • the fixing agent can comprise a mixture of fixing agents, the mixture comprising soluble or insoluble fixing agents. The fixing agent reacts with the target material to form an insoluble species with the fixing agent. The insoluble species is immobilized, for example, by precipitation, thereby yielding a treated and substantially purified electrolytic solution.
  • the electrolytic solution further comprises an aqueous solution of the dissolved cations of the valuable metal undergoing electrorefining. More over, the electrolytic solution comprises a mineral acid conjugate base, such as, but not limited to sulfate CSO 4 2 ), hydrogen sulfate (HSO 4 1 -), nitrate (NO 3 1 ), chloride (Cl 1 -), and bromide (Br 1 -).
  • the electrolytic can comprise a sulfamate solution, such as, in some configurations for electrorefining of nickel.
  • Fig. 2 depicts an electrolysis cell 100 for electrorefining of a valuable-metal.
  • the electrolysis cell 100 comprises an anode 102, a cathode 104, an electrolytic solution 106, an external current path 108 and a power source 110.
  • the anode 102 comprises a contaminant-containing valuable- metal.
  • the cathode 104 preferably comprises one of a substantially contaminant- free valuable-metal or a metal substantially non-reactive with the valuable-metal upon which the valuable-metal is electrodeposited.
  • the external current path 108 comprises an electrically conductive path, such as, a wire typically used within an electrical circuit.
  • the power source 110 is any electric power source, such as, an electrical generator, an electrical power sub-station, or a battery.
  • the electrolytic solution 106 comprises an electrolyte solution, preferably an aqueous electrolyte solution.
  • An electrolyte solution means a solution comprising a solvent (such as, water) and ionically dissociated components, where the ionically dissociated components comprise cations and anions that conduct electricity and can be separated from the solution by an electrically charged electrode.
  • the electrolytic solution 106 comprises the valuable-metal in a dissolved state as cation, such as M n+ , where n is an integer greater than zero.
  • the electrolyte solution 106 preferably, further comprises a mineral acid or the conjugate base of a mineral acid.
  • Preferred mineral acids comprise, without limitation, hydrochloric, hydrobromic, sulfuric, and nitric acids.
  • the mineral acid comprises sulfuric acid (H2SO 4 ) and/or the conjugate bases of sulfuric acid (HSO 4 1- and/or SO 4 2- ).
  • the anode 102 has a positive charge (that is, the anode accepts electrons in an oxidative process) and the cathode 104 has a negative charge (that is, the cathode releases electrons in a reductive process).
  • the electrochemical process at the anode 102 comprises dissolving the valuable-metal at the anode 102. That is, electrons are withdrawn and/or taken away from the anode 102 by the power source 110 and the oxidized species of the valuable-metal and contaminants are generated.
  • the electrochemical reactions of the anode 102 can be expressed by the following chemical reactions:
  • K 0 -> K m+ + m e- (4)
  • M represents the valuable-metal
  • K represents the one or more contaminants contained within the anode 102
  • n and m are integers greater than zero.
  • the oxidized species M n+ and K m+ are dissolved in the electrolytic solution 106 as soluble components of the electrolytic solution 106.
  • the oxidized species K m+ comprises contaminants substantially having electrochemical oxidation potentials (that is, for electrochemical potentials for the given electrolysis cell 100) about equal or more reactive (that is, less noble] than the valuable-metal.
  • the oxidized contaminant K is in the form of an oxyanion.
  • the oxyanion comprises K x O/ " (where K represents a chemical element other than oxygen and O represents an oxygen atom).
  • Contaminants more noble that is having an electrochemical oxidation potential greater than the valuable-metal, form little, if any, dissolved cationic species.
  • the more noble contaminants form a solid, substantially insoluble slime 112 within the electrolysis cell 110.
  • the slime 112 comprises one or more precious metal contaminants.
  • the cathode 104 At the cathode 104 one or both of the valuable-metal cation M n+ and the one or more contaminant cations K m+ , respectively, accept n and m electrons and are electrodeposited at the cathode 104 as reduced species, preferably, M 0 and K 0 . At least most of the valuable-metal M is deposited at the cathode 104 and little, if any, of the one or more contaminants K are deposited at the cathode 104.
  • the ability and/or extent that the valuable metal cation M n+ and the one or more contaminant cations K m+ are respectively deposited at the cathode are influenced by the reductive potentials for the valuable-metal and the one or more contaminants in the electrolytic solution 106 and the conditions under which the electrolysis cell 100 is operated.
  • the valuable-metal can be any metal.
  • the valuable-metal is a transition metal.
  • the valuable metal is one of copper, nickel or cobalt.
  • the anode 102 comprises copper.
  • the copper anode has a copper purity level of at least about 95%. More preferably, the copper purity level of the anode 102 is at least about 99%, more preferably at least about 99.9%.
  • the copper anode further comprises one or more contaminants.
  • the one or contaminant comprise arsenic, antimony, bismuth, nickel, cobalt, tin, zinc, iron, tellurium, selenium, lead, silver, gold, and platinum group metals.
  • the platinum group metals are platinum, osmium, iridium, ruthenium, rhodium and palladium.
  • the slime 112 comprises the one or more contaminants more noble than copper such as silver, gold, platinum, osmium, iridium, ruthenium, rhodium, palladium, nickel, lead (typically as insoluble lead sulfate) and mixtures thereof being non-limiting examples.
  • the one or more contaminants having an oxidation potential about equal to and/or less noble than copper comprise arsenic, antimony, bismuth, nickel, iron, cobalt, tin, zinc, tellurium, selenium, and lead.
  • the electrolytic solution 106 preferably, comprises an aqueous copper solution. More preferably, the electrolytic solution 106 comprises copper sulfate, more specifically, copper (II) sulfate.
  • the electrolytic solution 106 has a copper sulfate concentration from about 20 to about 300 grams copper sulfate per liter. Preferably, the copper sulfate concentration of the electrolytic solution is from about 100 to about 200 grams copper sulfate per liter. More preferably, the electrolytic solution 106 copper sulfate concentration is from about 30 grams/liter to about 60 grams/liter.
  • the electrolytic solution 106 further comprises sulfuric acid. Preferably, the sulfuric acid of the electrolytic solution 106 has a concentration from about 100 to about 500 grams H2SO4 per liter, more preferably from about 150 to about 250 grams H2SO4 per liter.
  • the electrolytic solution 106 comprises one or more contaminants.
  • the one or more contaminants comprise arsenic, tin, zinc, antimony, bismuth, nickel, iron, cobalt, tellurium, selenium and lead.
  • the lead and nickel can be present in the electrorefining cell in one or both of the electrolytic solution 106 as a cationic species (that is, Pb 2+ and Ni 2+ ) and the slime 112 (as insoluble lead sulfate and as nickel metal).
  • the cationic Pb 2+ is typically low due to the formation of a substantially insoluble PbSO 4 precipitate.
  • the iron and cobalt are substantially present within the electrolytic solution 106 as cationic species, that is, respectively, as one or more of Fe 2+ , Fe 3+ , Co 2+ , and Co 3+ .
  • the cobalt and nickel comprising the electrolytic solution have a +2 oxidation state.
  • the arsenic, antimony, bismuth, tellurium and selenium are, preferably, present in the electrolytic solution 106 as ionic species. That is, arsenic is preferably present in the electrolytic solution 106 as one or both of arsenite, AsO 2 1 ", and arsentate, AsO 4 3 ", oxyanions. Preferably, at least most of the arsenic is present as arsentate.
  • the arsenic comprising the electrolytic solution 106 comprises arsentate.
  • the antimony comprising the electrolytic solution 106 can comprise one or more Of Sb(OH) 4 1 ", SbO 2 1 ", Sb(OH) 6 1 " and SbO 3 1 ", oxyanions.
  • the antimony comprises antimony having one of a +5 or +3 oxidation state.
  • the electrolytic solution 106 can comprise one or more of the following ionic species of bismuth Bi(H 2 O) 6 3+ , Bi(H 2 O) 5 (OH) 2+ , Bi(H 2 O) 4 (OH) 2 1+ , Bi(H 2 O) 3 (OH) 3 , Bi(H 2 O) 2 (OH) 4 1 ", BiO 3 1 ", BiO 2 1 ", BiO 3 3 ", and BiO 1+ .
  • the bismuth comprises bismuth having one of a +5 or +3 oxidation state.
  • the electrolytic solution can comprise one or more of the following tellurium and selenium species: TeO 3 2 ", TeO 4 2 ", TeO 6 6 “, SeO 4 2 " and SeO 3 2 ".
  • the electrolytic solution 106 comprises silver having a +1 oxidation state.
  • the one or more contaminants dissolved in the electrolytic solution 106 increase in concentration as copper dissolved in the electrolyte 106 is electrodeposited on the cathode 104 and as further copper and contaminants are dissolved at the anode 102.
  • concentration of the contaminants increase, the electrodeposition of the contaminants at the cathode 104 can substantially increase.
  • the contaminants can destabilize the electrolytic solution 106.
  • high levels of arsenic within the electrolytic solution can form precipitates and/or complex ionic species with other contaminants within the electrolytic solution 106 (such as, but not limited to antimony, bismuth, selenium and tellurium).
  • the contaminants having a reduction potential, at its concentration in the electrolytic solution 106, about equal to or less noble than copper can be electrodeposited with the copper at the cathode 104.
  • the electrodeposition of at least some of the contaminants the cathode 104 can affect electrodeposited copper quality and purity.
  • the contaminants can affect grain structure of the electrodeposited copper.
  • the concentration of the contaminants can vary in the electrolyte solution 106. While not wanting to be limited by example, the nickel concentration can be as large as about 150 g/L or greater. Preferably, the nickel concentration in the electrolyte solution 106 is from about 0 g/L to about 40 g/L. More preferably, the electrolyte solution 106 nickel concentration is from about 0 g/L to about 20 g/L.
  • the arsenic concentration in the electrolyte solution 106 can be as large as about 60 g/L or greater. Preferably, the arsenic concentration in the electrolyte solution 106 is from about 0.1 g/L to about 25 g/L.
  • the electrolyte 106 arsenic concentration is from about 1 g/L to about 25 g/L.
  • the iron concentration in the electrolyte solution 106 can be as large as about 25 g/L or greater.
  • the iron concentration in the electrolyte solution 106 is from about 0.1 g/L to about 15 g/L.
  • the electrolyte iron concentration is from about 3 g/L to about 5 g/L.
  • the electrolyte solution antimony concentration can be as large as 2 g/L or greater.
  • the antimony concentration in the electrolyte solution 106 is from about 0.1 g/L to about 1.5 g/L.
  • the electrolyte antimony concentration is from about 0.8 g/L to about 1.0 g/L.
  • the electrolyte solution bismuth concentration can be as large as about 1.5 g/L or greater.
  • the bismuth concentration in the electrolyte solution 106 is from about 0.05 g/L to about 0.7 g/L. More preferably, the electrolyte solution bismuth concentration is from about 0.1 g/L to about 0.5 g/L.
  • the electrolytic solution 106 can comprise one or more of: cobalt having a solution concentration from about 0 g/L to about 3 g/L; tin having a solution concentration from about 0 g/L to about 1 g/L; zinc having a solution concentration from about 0 g/L to about 1 g/L; tellurium having a solution concentration from about 0 mg/L to about 10 mg/L; and selenium having a solution concentration from about 0 mg/L to about 10 mg/L.
  • the electrodeposited cathode 104 comprises copper.
  • the electrodeposited cathode 104 comprises at least about 99% copper.
  • at least about 99.9% of the electrodeposited cathode 104 comprises copper.
  • the electrodeposited cathode 104 comprises at least about 99.99% copper.
  • at least about 99.999% of the electrodeposited cathode 104 comprises copper.
  • Fig. 3 depicts a process 200 for treating the electrolytic solution 106 having a target material and a valuable metal.
  • the target material may comprise materials for disposal and/or recoverable materials of value.
  • a side stream 125 of the electrolytic solution 106 is removed from the electrolysis cell 100.
  • the side stream 125 may be a substantially continuously generated side stream, such as, a bleed stream, or may be an intermediately removed stream in the form of a batch volume side stream. It can be appreciated that the side stream 125 contains the target material contained within the electrolytic solution 106.
  • the side stream 125 comprises a volume percent of electrolytic solution 106 total volume, the volume percent of the side stream 125 is presented by the following formula:
  • Volume % side stream 100 * volume of side stream / total volume of electrolyte solution in process (7)
  • the volume percent of the side stream 125 is no greater than about 25% of the total volume of the electrolyte solution 106. More preferably, the volume percent of the side stream 125 is no greater than about 3%. Even more preferably, the volume percent of the side stream 125 is no greater than about 1% of the total of the electrolyte solution 106. In some configurations, the volume percent of the side stream 125 is from about 0.001% to about 0.1% of the total of the electrolyte solution 106. It can be appreciated, that the side stream 125 volume can vary depending on one or more of the level of contaminants contained within the anode, the level of contaminants dissolved in the electrolytic solution 106, and desired level of contaminants to which can be suitably maintained within the electrolytic solutions 106.
  • the side stream 125 is contacted with a fixing agent.
  • the fixing agent may be a soluble or insoluble fixing agent. While not wanting to be bound by any theory, it is believed that soluble and insoluble rare earth fixing agents commonly do not remove metal and metalloid dissociated cations from solution. This can permit metal and metalloid oxyanions to be removed selectively form a solution containing both metal and metalloid oxyanions and dissociated cations.
  • the side stream 125 is contacted with the insoluble fixing agent to form a target material-loaded insoluble fixing agent and a purified side stream 195.
  • the side stream 125 has an initial concentration of the target material within the side stream 125.
  • the fixing agent may comprise an adsorbent or absorbent.
  • the contacting of the fixing agent with the side stream 125 having the target material within the side stream 125 removes most, if not all, of the target material from the side steam 125 to form the purified side stream 195.
  • the purified side stream 195 has a purified concentration of the target material contained within the purified side stream 195.
  • the initial concentration is at least greater than the purified concentration. Preferably, most, more preferably about 75% or more, and even more preferably about 95% or more of the target material in the side stream 125 is loaded onto the insoluble fixing agent.
  • the purified side stream 195 has an arsenic concentration less than about 15 g/1 dissolved arsenic, more preferably less than about 10 g/L dissolved arsenic. Even more preferably, the dissolved arsenic concentration in the purified side stream is less than about 1 g/L.
  • the dissolved antimony concentration in the purified side stream 195 is preferably less than about 300 mg/L, more preferably less than about 200 mg/L. Even more preferably, the purified side stream 195 has a dissolved antimony concentration less than about 100 mg/L.
  • the dissolved bismuth concentration in the purified side stream 195 is preferably less than about 300 mg/L, more preferably less than about 200 mg/L.
  • the purified side stream 195 has a dissolved bismuth concentration less than about 100 mg/L.
  • the purified side stream 195 has a tellurium concentration less than about 1 mg/1 dissolved tellurium, more preferably less than about 0.5 mg/L dissolved tellurium. Even more preferably, the dissolved tellurium concentration in the purified side stream is less than about 0.1 mg/L.
  • the purified side stream 195 has a selenium concentration less than about 1 mg/1 dissolved selenium, more preferably less than about 0.5 mg/L dissolved selenium. Even more preferably, the dissolved selenium concentration in the purified side stream is less than about 0.1 mg/L.
  • the insoluble fixing agent comprises one of yttrium, scandium and a lanthanoid.
  • the insoluble fixing agent is preferably a particulate solid.
  • the insoluble fixing agent is preferably is an insoluble rare earth compound comprising an insoluble rare earth oxide, such as hydrous or anhydrous rare earth oxides, or a rare earth fluoride, carbonate, fluorocarbonate, silicate, and the like.
  • the insoluble fixing agent is particularly effective in removing arsenic have an oxidation state of +3 or +5.
  • the insoluble fixing agent comprises cerium.
  • the insoluble fixing agent comprises cerium oxide.
  • a particularly preferred insoluble fixing agent is CeO 2 .
  • the insoluble fixing agent is preferably a finely divided solid having an average surface area of between about 25 m 2 /g and about 500 m 2 /g, more preferably between about 70 m 2 /g and about 400 m z /g, and even more preferably between about 90 m 2 /g and about 300 m z /g.
  • the insoluble fixing agent may be derived from precipitation of a rare earth metal salt or from thermal decomposition of, for example, a rare earth metal carbonate or oxalate at a temperature preferably between about 100 to about 700 and even more preferably between about 180 and 350 0 C in a furnace in the presence of an oxidant, such as air. Formation of the insoluble fixing agent is further discussed in copending U.S. Application Serial No. 11/932,837, filed October 31, 2007, which is incorporated herein by this reference.
  • the preferred insoluble fixing agent comprises a rare earth compound
  • other fixing agents may be employed. Any fixing agent, whether solid, liquid, gaseous, or gel, that is effective at fixing the target material in solution through precipitation, ion exchange, or some other mechanism may be used. Examples of other fixing agents include at least those set forth above.
  • the insoluble fixing agent is an aggregated particulate having a mean surface area of at least about 1 m 2 /g.
  • the aggregated particulates can have a surface area of at least about 5 m 2 /g; in other cases, more than about 10 m 2 /g; and, in still other cases, more than about 25 m 2 /g.
  • the particulates can have a surface area of more than about 70 m 2 /g; in other cases, more than about 85 m 2 /g; in still other cases, more than about 115 m 2 /g; and, in still other cases, more than about 160 m 2 /g.
  • the aggregated particulates can include a polymer binder, such as thermosetting polymers, thermoplastic polymers, elastomeric polymers, cellulosic polymers, and glasses, to at least one of bind, affix, and/or attract the insoluble fixing agent constituents into particulates having one or more of desired size, structure, density, porosity, and fluid properties.
  • a polymer binder such as thermosetting polymers, thermoplastic polymers, elastomeric polymers, cellulosic polymers, and glasses, to at least one of bind, affix, and/or attract the insoluble fixing agent constituents into particulates having one or more of desired size, structure, density, porosity, and fluid properties.
  • the insoluble fixing agent can include one or more flow aids, with or without a binder.
  • Flow aids can improve the fluid dynamics of a fluid over and/or through the insoluble fixing agent to prevent separation of slurry components, prevent the settling of fines, and, in some cases, hold the fixing agent and other components in place.
  • the insoluble fixing agent can be blended with or include other components, such as ion-exchange materials (e.g., synthetic ion exchange resins), porous carbon such as activated carbon, metal oxides [e.g., alumina, silica, silica-alumina, gamma- alumina, activated alumina, acidified alumina, and titania), metal oxides containing labile metal anions (such as aluminum oxychloride), non-oxide refractories (e.g., titanium nitride, silicon nitride, and silicon carbide), diatomaceous earth, mullite, porous polymeric materials, crystalline aluminosilicates such as zeolites (synthetic or naturally occurring), amorphous silica-alumina, minerals and clays [e.g., bentonite, smectite, kaolin, dolomite, montmorillinite, and their derivatives), ion exchange resins, por
  • the target material-loaded insoluble fixing agent comprises most of the target material in the side stream 125.
  • the insoluble fixing agent and the target material form a substantially insoluble target material-loaded fixing agent.
  • most, and even more preferably about 75% or more, of the target material is loaded on the insoluble fixing agent.
  • the affinity of the insoluble fixing agent for specific target materials is believed to be a function of pH and/or target material concentration.
  • the insoluble fixing agent is commonly used as a particulate in a fixed or fluidized bed and, in certain configurations, may be desirable for use in a stirred tank reactor.
  • the insoluble fixing agent includes a flocculent and/or dispersing agent, as discussed herein, to maintain a substantially uniform particle distribution in the bed.
  • the target material will be present in a reduced oxidation state and this condition might be undesirable.
  • an oxidant may be contacted with the side stream 125 to increase the oxidation state of target material. That is, the contacting step 130 may be preceded by an oxidation step to oxidize the target material for better target material removal efficiency and/or affinity of the target material for the insoluble fixing agent.
  • the presence of arsenite might favor the use of an oxidant before the fixing agent is applied.
  • the process 200 operational conditions should be controlled.
  • arsenic is the target material, for example, the insoluble fixing agent
  • the insoluble fixing agent selectively removes at least most of the arsenic while leaving at least most of the valuable product as dissolved (cationic) species in the side stream 125.
  • the pH of the side stream 125 preferably is no more than about pH 6 and even more preferably is no more than about pH 2 to adsorb both arsenic (V) and arsenic (III).
  • Arsenic (III) sorbs onto the insoluble fixing agent over a broad pH range while arsenic (V) is preferably sorbed by the insoluble fixing agent at lower pH levels.
  • the purified side stream 195 is separated from the target material-loaded insoluble fixing agent.
  • the separation process may be any method known to one of skill in art for separating a liquid stream from a solid, such as, but not limited to, centrifugation, cyclonic (including hydrocycloning), decantation (including counter-current decantation), filtration (including screening), sedimentation (including gravity separating techniques) and combinations and/or variations thereof.
  • the insoluble fixing agent can be supported and/or configured for the side stream 125 to flow through the insoluble fixing agent.
  • the target material-loaded insoluble fixing agent is formed on the support and/or configured for the purified side stream 195 to flow through the insoluble fixing agent.
  • the target material-loaded fixing agent is contacted, in step 150, with a stripping solution, or release agent, to unload, or dissolve, preferably most and even more preferably about 95% or more of the target material from the target material- loaded fixing agent and form a barren fixing agent 160 (which is recycled to step 130) and one or both of a separated product 185 and a valuable product 175.
  • a stripping solution, or release agent to unload, or dissolve, preferably most and even more preferably about 95% or more of the target material from the target material- loaded fixing agent and form a barren fixing agent 160 (which is recycled to step 130) and one or both of a separated product 185 and a valuable product 175.
  • Any acidic, neutral, or basic stripping solution or release agent may be employed.
  • the desorption process of the target material-loaded fixing agent is believed to be a result of a one or more of: 1) a stronger affinity by the rare earth comprising the fixing agent for the release agent than the sorbed target material or its composition and 2) an upward or downward adjustment of the oxidation state of the rare earth comprising the surface of the fixing agent and/or of the sorbed target material and/or the sorbed target material-containing oxyanion.
  • the stripping solution is alkaline and comprises a strong base.
  • the stripping solution comprises at least one of an alkali metal hydroxide and group I salt of ammonia, an amide, and an amine (such as a primary, secondary, tertiary, or quaternary amine) and mixtures thereof.
  • the stripping solution comprises an alkali metal hydroxide. While not wishing to be bound by any theory, it is believed that, at high concentrations, hydroxide ions compete with, and displace, oxyanions from the surface of the insoluble fixing agent.
  • the stripping solution includes a caustic compound in an amount preferably ranging from about 1 to about 15 wt. %, even more preferably from about 1 to about 10 wt. %, and even more preferably from about 2.5 to about 7.5 wt. %, with about 5 wt. % being even more preferred.
  • the preferred pH of the stripping solution is preferably greater (e.g., more basic) than the pH at which the target material was loaded onto the fixing agent.
  • the stripping solution pH is preferably at least about pH 10, even more preferably at least about pH 12, and even more preferably at least about pH 14.
  • the (first) stripping solution comprises an oxalate or ethanedioate, which, relative to target material-containing oxyanions, is preferentially sorbed, over a broad pH range, by the insoluble fixing agent.
  • the insoluble fixing agent is contacted with a second stripping solution having a preferred pH of at least about pH 9 and even more preferably of at least about pH 11 to desorb oxalate and/or ethanedioate ions in favor of hydroxide ions.
  • a strong base is preferred for the second stripping solution.
  • the sorbed oxalate and/or ethanedioate anions can be heated to a preferred temperature of at least about 500 degrees Celsius to thermally decompose the sorbed oxalate and/or ethanedioate ions and remove them from the insoluble fixing agent.
  • the [first] stripping solution includes a strongly adsorbing exchange oxyanion, such as phosphate, carbonate, silicate, vanadium oxide, or fluoride, to displace the sorbed target material-containing oxyanion.
  • the first stripping solution has a relatively high concentration of the exchange oxyanion.
  • Desorption of the exchange oxyanion is at done at a different (higher) pH and/or exchange oxyanion concentration than the first stripping solution.
  • desorption can be by a second stripping solution which includes a strong base and has a lower concentration of the exchange oxyanion than the oxyanion concentration in the first stripping solution.
  • the exchange oxyanion can be thermally decomposed to regenerate the insoluble fixing agent.
  • the exchange oxyanion can be desorbed by oxidation or reduction of the insoluble fixing agent or exchange oxyanion.
  • the stripping solution includes a reductant or reducing agent, such as ferrous ion, lithium aluminum hydride, nascent hydrogen, sodium amalgam, sodium borohydride, stannous ion, sulfite compounds, hydrazine (Wolff- Kishner reduction), zinc-mercury amalgam, diisobutylaluminum hydride, lindlar catalyst, oxalic acid, formic acid, and a carboxylic acid (e.g., a sugar acid, such as ascorbic acid), to reduce the rare earth, sorbed target material, and/or sorbed target material-containing oxyanion.
  • a reductant or reducing agent such as ferrous ion, lithium aluminum hydride, nascent hydrogen, sodium amalgam, sodium borohydride, stannous ion, sulfite compounds, hydrazine (Wolff- Kishner reduction), zinc-mercury amalgam, diisobutylaluminum hydride
  • surface reduction of the insoluble fixing agent will reduce cerium [IV) to cerium (III), which may interact less strongly with target materials and oxyanions.
  • the pH is increased to desorb the sorbed target material or its oxyanion.
  • the stripping solution includes an oxidant or oxidizing agent, e.g., peroxygen compounds (e.g., peroxide, permanganate, persulfate, etc.), ozone, chlorine, hypochlorite, Fenton's reagent, molecular oxygen, phosphate, sulfur dioxide, and the like, that oxidizes the sorbed target material and/or its oxyanion to a higher oxidation state, e.g., arsenic (III) to arsenic (V); followed by a pH adjustment and a desorption process.
  • Desorption of arsenic (V) from insoluble rare earth compounds typically occurs at a pH of at least about pH 12 and even more typically at least about pH 14.
  • a first concentration of the target material in the side stream 125 is typically less than a second concentration of the target material in one or both of the separated-product 185 and the valuable product 175.
  • the first concentration of the target material is no more than about 75% of the second concentration and even more commonly no more than about 50% of the second concentration.
  • a first concentration of the arsenic is between about 0.1 mg/L to about 5 g/L
  • the second concentration of arsenic is between about 0.25 g/L and about 7.5 g/L.
  • the target material is removed from one or both of the separated product 185 and the valuable product 175 by a suitable technique to form a target material and a barren stripping solution (which may be recycled to step 150).
  • Removal may be effected by any suitable technique including precipitation (such as using a sulfide (for transition metals), an alkaline earth metal carbonate (for fluoride), and a rare earth or iron salt (for arsenic)), adsorption, absorption, electrolysis, cementation, amalgamation, and the like.
  • the target material is precipitated using a soluble rare earth fixing agent as noted above.
  • the second concentration of the target material is a about equal to the solubility limit (concentrations) of the target material (at the given process conditions). More preferably, the second concentration of the target material is between about 0.1 and about 2,500 g/L, even more commonly between about 0.1 and about 1,000 g/L, and even more commonly between about 0.25 g/L and about 500 g/L.
  • a soluble or dissolved second fixing agent is contacted with one or both of the separated-product 185 and valuable product 175 in an amount sufficient to precipitate most, if not all, of the target material as a target material-bearing solid.
  • the target material-bearing solid may be separated from the intermediate solution by any suitable solid/liquid separation technique to produce a stripping solution for recycle and a separated solid for disposal or recover a valuable solid (not shown).
  • the valuable product 175 and valuable solid may be any metal of interest.
  • metals of interest include, without limitation, one or more of the transition metals.
  • the metals of interest include a metal selected from the group of metals consisting of copper, nickel, cobalt, lead, precious metals, and mixtures thereof. All or a portion of the valuable product from the side stream 125 may be recovered.
  • the soluble second fixing agent typically has an oxidation state lower than the oxidation state of the first fixing agent.
  • the oxidation state of the second fixing agent is one of +3 or +4.
  • the soluble fixing agent preferably is a soluble rare earth metal compound and more preferably includes salts comprising rare earth compounds, such as bromides, nitrates, phosphites, chlorides, chlorites, chlorates, nitrates, and the like. More preferably, the soluble fixing agent is a rare earth (III) chloride.
  • the concentration of the target material in the side stream 125 may be increased by any suitable technique, such as through water removal.
  • Water may be removed, for example, by evaporation, distillation, and/or filtration techniques (such as, membrane filtration).
  • Other techniques include precipitation and re-dissolution, absorption or adsorption followed by stripping, ion exchange followed by stripping, and the like of the target material.
  • the separated purified side stream 195 is recycled to the electrolysis cell 100.
  • the purified side stream 195 has, relative to the side stream 125, a reduced concentration of the target material.
  • the purified stream 195 preferably has no more than about 1,000 ppm, even more preferably no more than about 500 ppm, even more preferably no more than about 50 ppm, and yet even more preferably no more than about 1 ppm of the target material.
  • the purified stream 195 has no more than about 50 ppb, even more preferably no more than about 5 ppb of the target material.
  • the fixing agent comprises a soluble fixing agent
  • the soluble fixing is contacted with the side stream 125 to form an insoluble target material-containing composition and a purified side stream 195.
  • the target material comprises the one or more contaminants contained within the side stream 125.
  • the soluble fixing agent comprises a rare earth. More preferably, the soluble fixing agent comprises a rare earth-containing composition having one or more rare earths.
  • the insoluble target material-containing composition comprises the rare earth-containing composition having one or more rare earths.
  • the insoluble target material-containing composition is typically in the form of precipitate that can be removed as a solid.
  • the insoluble target material-containing composition has at least about 0.01 wt. %, even more preferably at least about 0.1 wt. %, and even more preferably ranges from about 5 to about 50 wt. % of the target material.
  • the soluble fixing agent, or precipitant can be supported by a suitable carrier or can be unsupported.
  • the ability to form the insoluble target material-containing composition in the form of a solid comprising a relatively high concentration of the target material can greatly reduce the volume of the insoluble target material- containing composition requiring disposal, thereby reducing disposal costs.
  • the target material or a composition incorporating the target material combines, with the soluble fixing agent to form the insoluble target material-containing composition.
  • the soluble fixing agent is preferably one or more of scandium, yttrium, and a lanthanoid and is in a form that is soluble in water and/or the side stream 125.
  • the soluble fixing agent comprises cerium
  • the cerium preferably has an oxidation state of +4 or less.
  • the soluble fixing agent may be, without limitation, a salt comprising a bromide, nitrate, phosphite, chloride, chlorite, chlorate, and like of scandium, yttrium, or lanthanoid, with a chloride of cerium (III), cerium (IV] or a mixture thereof being preferred. While not wishing to be bound by any theory, it is believed that soluble forms of cerium (IV) can form nonocrystalline cerium dioxide, which then sorbs target materials or a composition incorporating the target material.
  • the soluble fixing agent is added, commonly as a separate aqueous solution, to the side stream 125.
  • soluble fixing agent is added to the side stream 125 in an amount to produce an average molar ratio of the fixing agent to the target material in solution of less than about 8:1 and preferably ranging from about 0.5:1 to about 5:1.
  • the pH of the side stream is adjusted to maintain at least some, if not at least most, of the soluble fixing dissolved in the side stream 125. That is, the pH of the side stream 125 is adjusted to form little, if any, rare earth sulfate, carbonate, and/or hydroxide precipitate.
  • a chelating agent may be added to the soluble fixing agent aqueous solution and/or the side stream 125 to increase the solubility of the fixing agent in one or both of the fixing agent aqueous solution and/or side stream 125.
  • a typical chelating agent is a chemical compound containing at least two nonmetal entities capable of binding to a metal atom and/or ion. While not wishing to be bound by any theory, chelating agents function by making several chemical bonds with metal ions.
  • Exemplary chelating agents include ethylene diamine tetra acetic acid (EDTA), dimercaprol (BAL), dimercaptosuccinic acid (DMSA), 2,3- dimercapto-1-propanesulfonic acid (DMPS), and alpha lipoic acid (ALA), aminophenoxyethane-tetraacetic acid (BAPTA), deferasirox, deferiprone, deferoxamine, diethylene triamine pentaacetic acid (DTPA), dimercapto-propane sulfonate (DMPS), ethylenediamine tetraacetic acid (calcium disodium versante) (CaNa 2 -EDTA), ethylene glycol tetraacetic acid (EGTA), D-penicillamine, methanesulfonic acid, methanephosphonic acid, and mixtures thereof.
  • EDTA ethylene diamine tetra acetic acid
  • BAL dimercaprol
  • DMSA dimercaptosuccin
  • the soluble fixing agent may further include one or both of an organic or inorganic additive.
  • the additive is one or more of a flocculent, coagulant, and thickener, to induce flocculation, settling, and/or formation of the precipitated solids.
  • a flocculent coagulant, and thickener
  • examples of such additives include lime, alum, ferric chloride, ferric sulfate, ferrous sulfate, aluminum sulfate, sodium aluminate, polyaluminum chloride, aluminum trichloride, polyelectrolytes, polyacrylamides, polyacrylate, and the like.
  • the insoluble target material-containing composition is separated from a purified side of stream 195.
  • the insoluble target material-containing composition may be further processed to form one or more of a separated product 185, valuable product 175, valuable solid and/or separated solid.
  • the contacting of the fixing agent with the side stream 125 comprises forming a precipitate between a target material and at least one of rare earth and non-rare earth salt additives and a purified side stream 195.
  • the target material comprises the one or more contaminants contained within the side stream 125.
  • the rare earth salt additive comprises a rare earth in the +3 oxidation state.
  • the rare earth salt additive comprises a bimetallic, lanthanide-based salt solution.
  • the non-rare earth salt additive comprises aluminum in the +3 oxidation state.
  • the rare earth salt additive comprises cerium in the +3 oxidation state.
  • the non-rare earth salt additive comprises a non-rare earth metal in the +3 oxidation stat and is substantially free of a rare earth.
  • the non-rare earth metal can be any non-rare earth metal in the +3 oxidation state, with transition metals, boron, aluminum, gallium, indium, and thallium being preferred, and the transition metals and aluminum being particularly preferred.
  • the non-rare earth salt additive particularly provides a significant reduction in the amount of rare earth needed to remove arsenic from the side stream 106.
  • Preferred transition metals include the elements having atomic numbers 22-29, 40-45, 47, 72-77, and 79.
  • the preferred transition metals comprise the transition metals titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium, iridium, and gold.
  • the rare earth and the non-rare earth salt additives are combined to form a mixed salt additive.
  • the soluble fixing agent(s) are combined with one or more non-rare earths having a +3 oxidation state, particularly a transition metal or metal from Group 13 of the Periodic Table of the Elements, with aluminum or iron in the +3 oxidation state being preferred.
  • the soluble fixing agent is a rare earth metal in the +3 oxidation state, and the soluble fixing agent and non-rare-earth metal are each in the form of water dissociable salts.
  • a double salt mixture is formed by mixing cerium [III) chloride with aluminum (III) chloride.
  • the double salt mixture is formed by mixing lanthanum (III) chloride with aluminum (III) chloride. In another example, the double salt mixture is formed by mixing lanthanum (III) chloride with iron (III) chloride.
  • at least one mole of the non-rare-earth is present for each mole of the rare earth soluble fixing agent. In a more preferred formulation, at least 3 moles of the non-rare-earth are present for each mole of the rare earth soluble fixing agent. In an even more preferred formulation, at least one mole of the non-rare-earth having an oxidation state of +3 is present for each mole of the rare earth soluble fixing agent having an oxidation state of +3.
  • a solution comprising the mixed salt additive can have any pH; that is, the mixed salt solution can have an acidic, neutral, or basic pH.
  • the mixed salt additive which is typically a bimetallic lanthanide-based salt solution, is contacted with the side stream 125 at standard or higher temperature.
  • the mixed salt solution can be contacted with the side stream 125 over a wide temperature range, preferably from about the freezing point of the side stream 125 to about the boiling point of the side stream 125.
  • the side stream 125 has a pH value.
  • the pH value of the side stream 125, before and after mixed salt addition, can range from a pH of about pH 0 or less to a pH of about pH 14 or greater.
  • the pH of the side stream 125 has a pH of less than about pH 8, prior to and after the contacting of the side stream 125 with the mixed salt solution. More preferably, the pH of the side stream after contacting the mixed salt solution is less than about pH 2.
  • the contacting of the rare earth and non-rare earth salt additives with the side stream 125 forms the precipitate. In another configuration, the contacting of the non-rare earth salt additive with the side stream 125 forms the precipitate.
  • the rare earth salt additive comprises cerium in the +3 oxidation state and the non-rare earth salt additive includes aluminum in the +3 oxidation state. The non-rare earth salt additive can provides significant reductions in the amount of rare earths required to remove the selected one or more contaminants from the side stream 106.
  • step 140 the purified side stream 195 is separated from the precipitate.
  • the precipitate may be further processed to form one or more of a separated product 185, valuable product 175, valuable solid and/or separated solid.
  • the contacting of the side stream 125 with the fixing agent further comprises providing a side stream having one or more dissolved contaminants and one or more dissolved valuable products and providing a fixing agent comprising a rare earth.
  • at least one of the one or more contaminants is in the form of any oxyanion.
  • at least one of the one or more dissolved valuable products is a transition metal.
  • the contacting of the side stream 125 and the fixing agent precipitates at least most of the dissolved target material as a target-material containing precipitate and leaves at least most of the valuable product dissolved in a purified side stream 195.
  • the purified side stream 195 is separated from the target-material containing precipitate.
  • the target-material containing precipitate may be further processed to form one or more of a separated product 185, valuable product 175, valuable solid and/or separated solid.
  • Residual soluble fixing may be removed by precipitation or other suitable separation methods known to one of skill within the art.
  • the residual soluble fixing agent may be removed by forming an insoluble rare earth composition within the purified side stream 195.
  • the insoluble rare earth composition may be formed by adjusting the pH and/or by adding a precipitating forming composition to the purified side stream 195.
  • the precipitating forming composition contains one or more entities form a precipitate when contacted with the rare earth contained within the purified side stream 195.
  • any solublilized and/or dissolved rare earth composition may be removed from the purified side stream 195 by contacting with one an oxalate and/or carbonate, carbonates being preferred for purified side streams having a pH greater than about pH 7.
  • the insoluble rare earth fixing agent can be added to the electrolytic solution contained within the electrolytic cell to remove one or more of the target contaminants. That is, the insoluble rare earth-containing fixing agent can be contacted with the electrolytic solution contained within the electrolytic cell to form a target material-loaded insoluble fixing agent.
  • the target material-loaded insoluble fixing agent can be separated from the electrolytic solution by any solid liquid separation process. The separated target material-loaded insoluble fixing agent can be contacted with a stripping agent as described.
  • an electrolytic stream is contacted with the rare earth fixing agent to remove one or more of the target contaminants.
  • the electrolytic stream can be rich or lean in the valuable metal. That is, the electrolytic stream can comprise an electrolytic stream before, after or during the electrodepositing of the valuable metal contained within the electrolytic stream.
  • the present invention in various embodiments, configurations, or aspects, includes components, methods, processes, systems and/or apparatus substantially as depicted and described herein, including various embodiments, configurations, aspects, subcombinations, and subsets thereof. Those of skill in the art will understand how to make and use the present invention after understanding the present disclosure.
  • the present invention in various embodiments, configurations, and aspects, includes providing devices and processes in the absence of items not depicted and/or described herein or in various embodiments, configurations, or aspects hereof, including in the absence of such items as may have been used in previous devices or processes, e.g., for improving performance, achieving ease and/or reducing cost of implementation.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

L'invention porte globalement sur un procédé pour retirer un ou plusieurs contaminants à partir d'une solution électrolytique, et, plus particulièrement, sur un procédé pour retirer le ou les contaminants contenus dans une solution d'électroaffinage à l'aide de métaux de terre rare.
PCT/US2010/030599 2009-04-09 2010-04-09 Utilisation d'une terre rare pour le retrait d'antimoine et de bismuth WO2010118368A1 (fr)

Priority Applications (4)

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EA201171231A EA201171231A1 (ru) 2009-04-09 2010-04-09 Использование редкоземельного элемента для удаления сурьмы и висмута
AU2010233100A AU2010233100A1 (en) 2009-04-09 2010-04-09 Use of a rare earth for the removal of antimony and bismuth
CA2757853A CA2757853A1 (fr) 2009-04-09 2010-04-09 Utilisation d'une terre rare pour le retrait d'antimoine et de bismuth
MX2011010666A MX2011010666A (es) 2009-04-09 2010-04-09 Uso de una tierra rara para la remocion de antimonio y bismuto.

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US16809709P 2009-04-09 2009-04-09
US61/168,097 2009-04-09

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US (1) US20100258448A1 (fr)
AR (1) AR076275A1 (fr)
AU (1) AU2010233100A1 (fr)
CA (1) CA2757853A1 (fr)
CL (1) CL2011002508A1 (fr)
EA (1) EA201171231A1 (fr)
MX (1) MX2011010666A (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108026650A (zh) * 2015-09-25 2018-05-11 阿克苏诺贝尔化学品国际有限公司 电极
CN108249704A (zh) * 2018-02-01 2018-07-06 无锡深南电路有限公司 一种印制pcb电路板所产生棕化废液的处理工艺

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8349764B2 (en) 2007-10-31 2013-01-08 Molycorp Minerals, Llc Composition for treating a fluid
US20180251383A9 (en) * 2010-04-13 2018-09-06 Molycorp Minerals, Llc Non-metal-containing oxyanion removal from waters using rare earths
JP6295393B2 (ja) * 2011-04-13 2018-03-20 セキュア ナチュラル リソーシズ エルエルシーＳｅｃｕｒｅ Ｎａｔｕｒａｌ Ｒｅｓｏｕｒｃｅｓ Ｌｌｃ 希土類元素含有添加物による鉛化合物の除去方法
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species
KR101426422B1 (ko) 2012-05-10 2014-08-06 한국원자력연구원 안질환 또는 암 치료용 아이오딘 씨드의 제조방법 및 이에 의하여 제조되는 아이오딘 씨드
WO2014004610A1 (fr) * 2012-06-27 2014-01-03 Arizona Board Of Regents, A Body Corporate Of The State Of Arizona, Acting For And On Behalf Of Arizona State University Système et procédé pour l'électroraffinage de silicium
US20140286857A1 (en) * 2013-03-21 2014-09-25 Basf Corporation Methods of preparing metal containing inorganic ion exchangers
US10711358B2 (en) * 2014-02-20 2020-07-14 Jx Nippon Mining & Metals Corporation Method of producing low alpha-ray emitting bismuth, and low alpha-ray emitting bismuth
AU2015226889B2 (en) 2014-03-07 2019-09-19 Secure Natural Resources Llc Cerium (IV) oxide with exceptional arsenic removal properties
WO2019036711A1 (fr) * 2017-08-18 2019-02-21 Chemtreat, Inc. Compositions et procédés destinés à l'élimination du sélénium
RU2758043C1 (ru) * 2021-02-25 2021-10-25 Акционерное общество "Аксион-Редкие и Драгоценные металлы" Способ извлечения платины и палладия из серебряных электролитов

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5133948A (en) * 1991-07-11 1992-07-28 Asarco Incorporated Process for the removal of bismuth from copper refining electrolyte by using lead oxide
US5248398A (en) * 1990-11-16 1993-09-28 Macdermid, Incorporated Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath
US6800204B2 (en) * 2002-02-15 2004-10-05 Clear Water Filtration Systems Composition and process for removing arsenic and selenium from aqueous solution
US20080156734A1 (en) * 2006-12-28 2008-07-03 Chevron U.S.A. Inc. Apparatus for treating a flow of an aqueous solution containing arsenic

Family Cites Families (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2872286A (en) * 1945-08-31 1959-02-03 Theron G Finzel Bismuth phosphate carrier process for pu recovery
US3635797A (en) * 1968-11-18 1972-01-18 Nevada Enzymes Inc Enzymatic composition
US3865728A (en) * 1971-11-12 1975-02-11 Dow Corning Algicidal surface
US4001375A (en) * 1974-08-21 1977-01-04 Exxon Research And Engineering Company Process for the desulfurization of flue gas
DE2526053C2 (de) * 1975-06-11 1983-03-03 Chemische Fabrik Uetikon, 8707 Uetikon Verfahren zur selektiven Entfernung von Phosphaten
US4078058A (en) * 1976-07-13 1978-03-07 Research Corporation Cerium sulfadiazine for treating burns
US4145282A (en) * 1977-01-24 1979-03-20 Andco Industries, Inc. Process for purifying waste water containing fluoride ion
IT1157390B (it) * 1978-10-27 1987-02-11 Cnen Procedimento ed impianto per la depurazione continua di fluidi contaminati e per il condizionamento dei concentrati da cio' risultanti
US4251496A (en) * 1979-03-22 1981-02-17 Exxon Research & Engineering Co. Process for the removal of SOx and NOx from gaseous mixture containing the same
US4313925A (en) * 1980-04-24 1982-02-02 The United States Of America As Represented By The United States Department Of Energy Thermochemical cyclic system for decomposing H2 O and/or CO2 by means of cerium-titanium-sodium-oxygen compounds
US4433196A (en) * 1982-06-25 1984-02-21 Conoco Inc. Color precursor removal from detergent range alkyl benzenes
US4507206A (en) * 1982-07-19 1985-03-26 Hughes Geoffrey F Method for restoring and maintaining eutrophied natural bodies of waters
US4636289A (en) * 1983-05-02 1987-01-13 Allied Corporation Solution mining of sodium minerals with acids generated by electrodialytic water splitting
US4498706A (en) * 1983-08-15 1985-02-12 Intermountain Research & Development Corp. Solution mining of trona or nahcolite ore with aqueous NaOH and HCl solvents
SE452307B (sv) * 1983-09-12 1987-11-23 Boliden Ab Forfarande for rening av fororenade vattenlosningar innehallande arsenik och/eller fosfor
US5080926A (en) * 1984-02-09 1992-01-14 Julian Porter Anti-fouling coating process
AU579647B2 (en) * 1985-02-21 1988-12-01 Asahi Kasei Kogyo Kabushiki Kaisha Process for adsorption treatment of dissolved fluorine
US4652054A (en) * 1985-04-16 1987-03-24 Intermountain Research & Development Corporation Solution mining of trona or nahcolite ore with electrodialytically-produced aqueous sodium hydroxide
EP0265906B1 (fr) * 1986-10-31 1995-04-19 Nippon Zeon Co., Ltd. Pansement
DE3864932D1 (de) * 1987-06-29 1991-10-24 Rhone Poulenc Chimie Verfahren zur gewinnung eines ceriumoxids.
US4902426A (en) * 1987-06-30 1990-02-20 Pedro B. Macedo Ion exchange compositions
US4814152A (en) * 1987-10-13 1989-03-21 Mobil Oil Corporation Process for removing mercury vapor and chemisorbent composition therefor
US4891067A (en) * 1988-05-13 1990-01-02 Kennecott Utah Copper Corporation Processes for the treatment of smelter flue dust
US5192452A (en) * 1988-07-12 1993-03-09 Nippon Shokubai Kagaku Kogyo, Co., Ltd. Catalyst for water treatment
US5082570A (en) * 1989-02-28 1992-01-21 Csa Division Of Lake Industries, Inc. Regenerable inorganic media for the selective removal of contaminants from water sources
US5711930A (en) * 1989-03-10 1998-01-27 Thiele Kaolin Company Process for improving the phyiscal properties of formed particles
ES2063194T3 (es) * 1989-05-26 1995-01-01 Kao Corp Procedimiento de produccion de acido fosfatidico.
US4999174A (en) * 1990-06-22 1991-03-12 Gas Desulfurization Corporation Use of cerium oxide for removal of chlorine from fuel gases
ZA928157B (en) * 1991-10-25 1993-06-09 Sasox Processing Pty Ltd Extraction or recovery of metal values.
GEP20002074B (en) * 1992-05-19 2000-05-10 Westaim Tech Inc Ca Modified Material and Method for its Production
US5178768A (en) * 1992-08-20 1993-01-12 Pall Corporation Mixed filter bed composition and method of use
FR2699524B1 (fr) * 1992-12-21 1995-02-10 Rhone Poulenc Chimie Composition à base d'un oxyde mixte de cérium et de zirconium, préparation et utilisation.
US5281253A (en) * 1993-01-06 1994-01-25 Praxair Technology, Inc. Multistage membrane control system and process
US5500131A (en) * 1994-04-05 1996-03-19 Metz; Jean-Paul Compositions and methods for water treatment
US5712219A (en) * 1994-04-08 1998-01-27 Kansas State University Research Foundation Iron oxide magnesium oxide composites and method for destruction of cholrinated hydrocarbon using such composites
US5603838A (en) * 1995-05-26 1997-02-18 Board Of Regents Of The University And Community College Systems Of Nevada Process for removal of selenium and arsenic from aqueous streams
AUPN585795A0 (en) * 1995-10-06 1995-11-02 Tox Free Systems Inc. Volatile materials treatment system
US5859064A (en) * 1996-03-13 1999-01-12 The United States Of America As Represented By The Secretary Of The Navy Chemical warfare agent decontamination solution
US5707508A (en) * 1996-04-18 1998-01-13 Battelle Memorial Institute Apparatus and method for oxidizing organic materials
US6030537A (en) * 1996-08-02 2000-02-29 Engelhard Corporation Method for removing arsenic from aqueous systems containing competing ions
AUPO589697A0 (en) * 1997-03-26 1997-04-24 Commonwealth Scientific And Industrial Research Organisation Sediment remediation process
FR2764399A1 (fr) * 1997-06-05 1998-12-11 Eastman Kodak Co Depollution d'un effluent photographique par traitement avec un alumino-silicate polymere fibreux
US6613234B2 (en) * 1998-04-06 2003-09-02 Ciphergen Biosystems, Inc. Large pore volume composite mineral oxide beads, their preparation and their applications for adsorption and chromatography
US6843617B2 (en) * 1998-06-18 2005-01-18 Rmt, Inc. Stabilization of toxic metals in a waste matrix and pore water
US6653519B2 (en) * 1998-09-15 2003-11-25 Nanoscale Materials, Inc. Reactive nanoparticles as destructive adsorbents for biological and chemical contamination
AU1717600A (en) * 1998-11-10 2000-05-29 Biocrystal Limited Methods for identification and verification
WO2001004058A1 (fr) * 1999-07-08 2001-01-18 Heinig Charles F Jr Nouveaux materiaux et procedes pour purifier de l'eau
US6187192B1 (en) * 1999-08-25 2001-02-13 Watervisions International, Inc. Microbiological water filter
US7173474B1 (en) * 1999-09-15 2007-02-06 Linear Technology Corporation Load-generated drive, no quiescent current, techniques and circuits for high speed switching of transistors
US6177015B1 (en) * 1999-10-18 2001-01-23 Inco Limited Process for reducing the concentration of dissolved metals and metalloids in an aqueous solution
US6342163B1 (en) * 1999-11-12 2002-01-29 United States Filter Corporation Apparatus and method for sanitizing and cleaning a filter system
FR2801299B1 (fr) * 1999-11-23 2002-06-07 Rhodia Terres Rares Dispersion colloidale aqueuse a base d'au moins un compose d'un lanthanide et d'un complexant, procede de preparation et utilisation
US7179849B2 (en) * 1999-12-15 2007-02-20 C. R. Bard, Inc. Antimicrobial compositions containing colloids of oligodynamic metals
US7329359B2 (en) * 1999-12-20 2008-02-12 Eltron Research, Inc. Application of catalysts for destruction of organic compounds in liquid media
US6338800B1 (en) * 2000-02-22 2002-01-15 Natural Chemistry, Inc. Methods and compositions using lanthanum for removing phosphates from water
US6852903B1 (en) * 2000-05-31 2005-02-08 The United States Of America As Represented By The Secretary Of The Army Decontamination of chemical warfare agents using a reactive sorbent
US20020003116A1 (en) * 2000-07-07 2002-01-10 Golden Josh H. System and method for removal of arsenic from aqueous solutions
FR2812201B1 (fr) * 2000-07-31 2003-08-01 Hightech Business Agency Hba Methode de traitement bactericide, fongicide, virucide et insecticide de l'air ambiant
JP3960914B2 (ja) * 2000-10-02 2007-08-15 三井金属鉱業株式会社 セリウム系研摩材及びセリウム系研摩材の製造方法
US6986798B2 (en) * 2000-11-30 2006-01-17 Showa Denko K.K. Cerium-based abrasive, production process thereof
DE10060099A1 (de) * 2000-12-04 2002-06-06 Basf Ag Regenerierung eines Dehydrierkatalysators
EP1383502A4 (fr) * 2001-03-06 2007-07-25 Strakan Int Ltd Composes et procedes pour le traitement de desordres urogenitaux
CA2442541A1 (fr) * 2001-04-02 2002-10-17 Japan Science And Technology Corporation Compose de manganese et d'oxygene adsorbeur d'arsenic, adsorbeur d'arsenic, et procede d'elimination par adsorption d'arsenic de solutions aqueuses
DE10117435B4 (de) * 2001-04-03 2006-01-12 Msa Auer Gmbh Verfahren zur Herstellung eines Filterkörpers
US7387719B2 (en) * 2001-04-24 2008-06-17 Scimist, Inc. Mediated electrochemical oxidation of biological waste materials
AU2002300062B8 (en) * 2001-07-16 2010-04-15 Dudley Mills Pty Ltd Removal of Phosphate from Water
US6858147B2 (en) * 2001-08-03 2005-02-22 Dispersion Technology, Inc. Method for the removal of heavy metals from aqueous solution by means of silica as an adsorbent in counter-flow selective dialysis
KR20040035712A (ko) * 2001-08-03 2004-04-29 몰튼 피터 수성 처리 용액으로부터 금속 이온을 제거하는데 사용되는조성물 및 그것의 이용 방법
US7476311B2 (en) * 2001-09-26 2009-01-13 Wrt International Llc Arsenic removal from aqueous media using chemically treated zeolite materials
JP4236857B2 (ja) * 2002-03-22 2009-03-11 三井金属鉱業株式会社 セリウム系研摩材およびその製造方法
US7183235B2 (en) * 2002-06-21 2007-02-27 Ada Technologies, Inc. High capacity regenerable sorbent for removing arsenic and other toxic ions from drinking water
US6843919B2 (en) * 2002-10-04 2005-01-18 Kansas State University Research Foundation Carbon-coated metal oxide nanoparticles
US6849187B2 (en) * 2002-12-10 2005-02-01 Engelhard Corporation Arsenic removal media
US6863825B2 (en) * 2003-01-29 2005-03-08 Union Oil Company Of California Process for removing arsenic from aqueous streams
EP1632284A4 (fr) * 2003-05-02 2009-12-16 Japan Techno Co Ltd Eau antiseptique active ou fluide de systeme d'eau antiseptique active, et procede et dispositif de production de ceux-ci
AR045347A1 (es) * 2003-08-08 2005-10-26 Rovcal Inc Celda alcalina de alta capacidad
US6855665B1 (en) * 2003-09-23 2005-02-15 Alexander Blake Compositions to remove radioactive isotopes and heavy metals from wastewater
US7783883B2 (en) * 2004-06-25 2010-08-24 Emc Corporation System and method for validating e-mail messages
US8167141B2 (en) * 2004-06-30 2012-05-01 Brita Lp Gravity flow filter
US20060000763A1 (en) * 2004-06-30 2006-01-05 Rinker Edward B Gravity flow carbon block filter
DE102004035905A1 (de) * 2004-07-20 2006-02-16 Biotronik Vi Patent Ag Magnesiumhaltiges Wundauflagematerial
US7276640B2 (en) * 2004-10-18 2007-10-02 Nanoscale Corporation Metal oxide nanoparticles for smoke clearing and fire suppression
US7329356B2 (en) * 2004-12-21 2008-02-12 Aquagems Laboratories, Llc Flocculating agent for clarifying the water of man-made static water bodies
US20090286678A1 (en) * 2005-05-02 2009-11-19 Symyx Technologies, Inc. High Surface Area Metal And Metal Oxide Materials and Methods of Making the Same
US7491335B2 (en) * 2005-05-13 2009-02-17 The Board Of Regents Of The University Of Texas System Removal of arsenic from water with oxidized metal coated pumice
US7344643B2 (en) * 2005-06-30 2008-03-18 Siemens Water Technologies Holding Corp. Process to enhance phosphorus removal for activated sludge wastewater treatment systems
US20070012631A1 (en) * 2005-07-15 2007-01-18 Coffey Richard T Methods for controlling pH in water sanitized by chemical or electrolytic chlorination
US7156994B1 (en) * 2005-09-30 2007-01-02 Archer Virgil L Drinking water filter used with tap water and other water sources
US7481939B2 (en) * 2005-11-07 2009-01-27 Patrick Haley Method for removal of phosphate from bodies of water by topical application of phosphate scavenging compositions with a hand held, hose end sprayer
JP2008050348A (ja) * 2006-07-27 2008-03-06 Fujitsu Ltd 植物の防疫剤、植物の防疫方法及び植物の防疫システム、並びに、植物及び植物の栽培方法
US20090012204A1 (en) * 2007-07-06 2009-01-08 Lynntech, Inc. Functionalization of polymers with reactive species having bond-stabilized decontamination activity
US8084392B2 (en) * 2007-07-06 2011-12-27 Ep Minerals, Llc Crystalline silica-free diatomaceous earth filter aids and methods of manufacturing the same
US20100042206A1 (en) * 2008-03-04 2010-02-18 Icon Medical Corp. Bioabsorbable coatings for medical devices
US8119555B2 (en) * 2008-11-20 2012-02-21 R. J. Reynolds Tobacco Company Carbonaceous material having modified pore structure
EP2216010A1 (fr) * 2009-02-05 2010-08-11 Rhodia Opérations Composition aqueuse convenant en tant que shampoing

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5248398A (en) * 1990-11-16 1993-09-28 Macdermid, Incorporated Process for direct electrolytic regeneration of chloride-based ammoniacal copper etchant bath
US5133948A (en) * 1991-07-11 1992-07-28 Asarco Incorporated Process for the removal of bismuth from copper refining electrolyte by using lead oxide
US6800204B2 (en) * 2002-02-15 2004-10-05 Clear Water Filtration Systems Composition and process for removing arsenic and selenium from aqueous solution
US20080156734A1 (en) * 2006-12-28 2008-07-03 Chevron U.S.A. Inc. Apparatus for treating a flow of an aqueous solution containing arsenic

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108026650A (zh) * 2015-09-25 2018-05-11 阿克苏诺贝尔化学品国际有限公司 电极
CN108026650B (zh) * 2015-09-25 2020-12-11 阿克苏诺贝尔化学品国际有限公司 电极
CN108249704A (zh) * 2018-02-01 2018-07-06 无锡深南电路有限公司 一种印制pcb电路板所产生棕化废液的处理工艺

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