EP0002009A1 - Einrichtung und Verfahren zur Elektrolyse unter Verwendung einer halbdurchlässigen kationischen Membrane und Turbulenz erzeugende Hilfsmittel - Google Patents

Einrichtung und Verfahren zur Elektrolyse unter Verwendung einer halbdurchlässigen kationischen Membrane und Turbulenz erzeugende Hilfsmittel Download PDF

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Publication number
EP0002009A1
EP0002009A1 EP78101296A EP78101296A EP0002009A1 EP 0002009 A1 EP0002009 A1 EP 0002009A1 EP 78101296 A EP78101296 A EP 78101296A EP 78101296 A EP78101296 A EP 78101296A EP 0002009 A1 EP0002009 A1 EP 0002009A1
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Prior art keywords
cathode
cell
cation
permselective membrane
membrane
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EP78101296A
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English (en)
French (fr)
Inventor
Edward Dunnington Creamer
Michael Krumpelt
Jacob Jorné
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BASF Corp
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BASF Wyandotte Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm cells

Definitions

  • the present invention relates to electrolytic cells and particularly to the electrolysis of brine utilizing a cation-permselective membrane.
  • German Offen. 2,419,204 an increase in efficiency of the electrodes in a diaphragm cell for the electrolysis of brine is obtained where inclined plates are positioned at the electrodes functioning to guide the gas evolved thereon toward the middle of the electrode chamber for release.
  • a similar design is disclosed in British 1,460,357 and U.S. 3,930,151.
  • U.S. 3,930,981 a diaphragm cell for the electrolysis of brine is disclosed having perforated metal anodes and baffles to direct anode gases away from the inter-electrodic gap in order to protect the diaphragm against erosion.
  • a vertical electrode electrolytic cell apparatus and a process for electrolysis, particularly the electrolysis of an alkali metal chloride such as brine to produce sodium hydroxide, chlorine and hydrogen wherein improved current efficiency is obtained by reducing the hydroxyl ion -polarization on the surface of a cation-permselective membrane utilized in said electrolytic cell. Said polarization is effectively overcome by inducing turbulence in the catholyte liquor between the cathode and said cation-permselective membrane.
  • the process of the invention provides at any given weight concentration of sodium hydroxide in the catholyte, a means of reducing the amount of anion (hydroxyl ion) passing through the membrane by reducing the weight concentration of the hydroxyl ion on the surface of the membrane. Since the weight concentration of sodium hydroxide in the catholyte is directly proportional to the extent of back-migration of hydroxyl ion through the permselective membrane and thus the electrolysis efficiency of the cell, the process of the invention provides increased current efficiency in the cell.
  • Both single cell and multicell arrangements having a plurality of anodes, cathodes, anolyte and catholyte compartments separated by a plurality of cation-permselective membranes are contemplated. Where multicell arrangements are utilized, said cells are preferably connected in series.
  • the turbulence which is induced in the catholyte at the surface of said membrane is preferably achieved by utilizing a gas-directing cathode wherein the gas evolved upon the cathode is directed toward or away from said membrane.
  • Said cathode is preferably an expanded metal sheet having an open mesh network of interconnected webs or filaments, said webs being positioned at an angle of about 20° to about 70° to the plane of said sheet.
  • Other means of inducing turbulence in the catholyte include but are not limited to recirculation of the catholyte, for instance, by pumping and agitation of the catholyte by mechanical means, for instance, by stirring.
  • Figure 1 is a perspective view of a portion of one embodiment of the electrode utilized in the novel process of this invention.
  • Figure 2 shows a cross-section taken along line 2-2 of Figure 1.
  • Figure 3 is a schematic diagram of a two- compartment electrolytic cell for the electrolysis of brine utilizing a cation permselective membrane and a gas directing cathode.
  • the process of the present invention is preferably practiced using an apparatus comprising a combination of a gas-directing cathode and a cation-permselective membrane in an electrolysis cell, particularly a chlor-alkali cell for the electrolysis of an alkali metal chloride such as brine to produce sodium hydroxide, chlorine and hydrogen.
  • the process is also generally adapted for use in the electrolysis of other materials, organic and inorganic.
  • membrane cells generally an enclosure is provided which is divided into two compartments by said membrane. In one compartment thereof, the catholyte compartment, there is disposed a cathode having a particular structure, as will be described hereinafter.
  • the anolyte compartment there is disposed solid or flattened or unflattened expanded metal anode composed of a conductive electrolytically active material such as graphite or more desirably an anode known in the prior art as a dimensionally stable anode, for instance, a titanium substrate bearing a coating of a precious metal, precious metal oxide or other electrolytically active, corrosion resistant material.
  • Said anode can be in the form of a gas-directing, turbulence-inducing anode.
  • the present invention is preferably practiced using a hydrolyzed 1 cation-permselective membrane made of a copolymer of tetrafluoroethylene and a fluorosulfonated perfluorovinyl ether such as a copolymer of tetrafluoroethylene and sulfonyl fluoride perfluorovinyl ether.
  • a hydrolyzed 1 cation-permselective membrane made of a copolymer of tetrafluoroethylene and a fluorosulfonated perfluorovinyl ether such as a copolymer of tetrafluoroethylene and sulfonyl fluoride perfluorovinyl ether.
  • Such membrane materials are sold for use in chlor-alkali cells under the trademark "Nafion”.
  • the membranes ordinarily have a thickness-ori the order of 0.1 to 0.4 millimeter.
  • a direct current is passed between the electrodes causing the generation of chlorine at the anode and the selective transport of hydrated sodium anions across said membrane into the catholyte compartment.
  • These sodium ions combine with hydroxide ions formed at the cathode by the electrolysis of water to produce sodium hydroxide; hydrogen gas also being liberated at the cathode.
  • the cation-permselective membrane is not a perfect barrier to anions, and therefore, allows a certain number of anions to pass in the opposite direction.
  • the amount of anion (hydroxyl ion) passing through said membrane determines the hydrolysis efficiency or the amount of electrical energy required to produce a given quantity of chlorine and caustic.
  • the concentration of hydroxide ion in the cathode compartment of the cell which is related to the extent of back-migration of the hydroxyl ions through the cation-permselective membrane, results in a certain number of hydroxyl ions passing through the membrane thus allowing the formation L of oxygen and other less valuable products in the anolyte, thereby reducing the current efficiency of the cell.
  • a gas-directing cathode 10 utilized in the process of this invention which comprises an unflattened, expanded-metal.
  • an electrode is used as a cathode 10 it is generally made of nickel coated steel or nickel (coating not shown in the drawing) wherein the nickel coating exists at least on the face or front of the cathode 10 which is directed toward the cation-permselective membrane 24.
  • the coated face of each cathode 10 is mounted opposite an anode 23 in the electrolysis cell as illustrated in Figure 3.
  • the anode 23 can be either solid or flattened or unflattened expanded metal and is generally made of a corrosion resistant metal such as titanium having a coating of a precious metal oxide.
  • the cathode 10 shown is provided with diamond-shaped openings 11 in which the top half section consisting of sides 12 and 13 of each diamond is pushed forwardly of the vertical center plane of the cathode 10 and the bottom half section consisting of sides 14 and 15 of each diamond-shaped opening 11 is pushed rearwardly of the vertical center plane of the cathode 10.
  • the corners of each diamond-shaped opening situated between sides 12 and 13, and the corresponding sides 14 and 15 lie approximately in the vertical plane of the cathode.
  • each diamond-shaped opening 11 is tilted or pushed toward the back of the cathode 10 (the side not facing the cation-permselective membrane 24) while the top half section, consisting of sides 12 and 13, of each diamond-shaped opening 11 is tilted or pushed toward the front of the cathode 10 so that gas which is released on both halves of the diamond-shaped opening 11 pass through said opening to the back of the cathode 10 and are deflected rearwardly by the tilted top half of the cathode 10 and into the electrolyte space between the cathode 10 and the cell wall 20 as indicated in Figure 3.
  • an electrolytic cell of the invention comprising a cell wall 20, a flattened, expanded metal anode 23, a gas-directing expanded metal cathode 10 and a cation- L permselective membrane 24.
  • Conductive means for connecting the anode and cathode to sources of positive and negative electrical potentials, respectively, are not shown.
  • An aqueous solution of alkali metal chloride, preferably acidic, is fed through line 22 and exits from line 21. Water is fed in through line 25 and sodium hydroxide solution is obtained through line 26.
  • chlorine gas is removed through line 28 and hydrogen gas is correspondingly removed through line 27.
  • the electrolysis is conducted at high caustic current efficiency by maintaining the gas-directing, expanded metal cathode 10 in relation to the' cation-permselective membrane 24 such that the hydrogen gas evolved on the cathode 10 is directed rearwardly (as shown) or forwardly toward the cation-permselective membrane 24 so as to induce turbulent flow between said membrane 24 and said cathode 10.
  • a high concentration sodium hydroxide solution can be obtained through line 26 while at the same time maintaining high caustic current efficiency.
  • any cation-permselective membrane which is electrolytically conductive in the hydrated state, which exists under electrolytic cell conditions can be utilized in the process of the invention.
  • the preferred membrane material is sold under the trademark "Nafion”. Said material is a copolymer having structural units of the formula:
  • This copolymer generally has an equivalent weight of from about 900 to about 1600, preferably from about 1100 to about 1500.
  • Such copolymers are prepared as disclosed in U.S. Patent No. 3,282,875, incorporated herein by reference, by reacting at a temperature below about 110°C. a perfluorovinyl ether with tetrafluoroethylene in an aqueous liquid phase, preferably at a pH below 8 in the presence of a free radical initiator such as ammonium persulfate. Subsequently, the acyl fluoride groups of the copolymer are hydrolyzed to the free acid or salt form using conventional means.
  • ion exchange membranes can be used which are resistant to the heat and corrosive conditions exhibited in such cells.
  • these membranes are utilized in the form of a thin film which can be deposited on an inert support such-as a cloth woven of polytetrafluoroethylene, or the like or can have a thickness which can be varied over a considerable range, generally thicknesses of from about 0.1 to about 0.4 millimeter being typical.
  • the membrane is a composite structure composed of a 0.038 millimeter coating of said copolymer having an equivalent weight of about 1500 on one side of said woven polytetrafluoroethylene cloth and a 0.1 millimeter to 0.13 millimeter coating of said copolymer having an equivalent weight of about 1100 on the opposite side of said woven cloth.
  • the membrane can be fabricated in any desired shape.
  • the copolymer sold under the trademark "Nafion" is preferably fabricated to the desired dimension in the form of the sulfonyl fluoride. In this non-acid form, the copolymer is soft and pliable and can be heat- sealed to form strong bonds.
  • the material is hydrolyzed.
  • the sulfonyl fluoride groups are converted to free sulfonic acid or sodium sulfonate groups. Hydrolysis can be effected by boiling the membrane in water or alternatively in caustic alkali solution.
  • the cell membrane is desirably subjected to a heat treatment at 100°C. to 275°C. for a period of several hours to 4 minutes so as to provide improved selectivity and higher current efficiency, i.e., lower energy consumption per unit of product obtained from the chlor-alkali cell.
  • the aqueous alkali metal hydroxide solution is obtained having a lower salt concentration when the membrane is treated in this manner.
  • the treatment can consist of placing the membrane between electrically heated flat plates or in an oven where said membrane is suitably protected by placing slightly larger thin sheets of polytetrafluoroethylene, for instance, on either side of the membrane.
  • the anodes can be solid, flattened expanded metal or gas-directing anodes such as unflattened, expanded metal anodes. They can be made of materials having surface coatings of noble metal, noble metal alloys or noble metal oxides, for instance, ruthenium oxide and mixtures thereof with titanium dioxide on a substrate which is conductive such as titanium. Platinum is an especially useful coating on a titanium anode. Preferably, dimensionally stable anodes are utilized as exemplified by a ruthenium oxide- titanium dioxide coating on a titanium substrate.
  • Bipolar electrodes can also be employed. Those having skill in the art will know the variations in structure that will be made to accommodate bipolar rather than monopolar electrodes in such cells and, therefore, these changes in structure need not be described in detail. Of course, as is known in the art, pluralities of individual cells can be employed in multicell units having common feed and product manifolds and being housed in unitary structures. Such constructions are also known in the art and need not be discussed herein.
  • the expanded metal, gas-directing cathodes generally can be made of any electrically conductive material which will resist the attack of the contents of the cell.
  • Such materials are, for instance, nickel, steel and iron. 1 Titanium or noble metal coatings on steel or other conductive substrate as well as metals such as platinum, iridium, ruthenium or rhodium are especially useful as coatings. Nickel and the noble metals can be deposited as surface coatings by plasma or flame spraying, electrodeposition or electroless coating on suitable conductive substrates, for instance, copper, silver, steel and iron.
  • the cathodes are preferably nickel coated, steel cathodes which can be prepared in accordance with procedures known to those skilled in the art or with procedures disclosed in copending, commonly assigned application Serial No. 658,538, filed February 17, 1976 in the U.S. Patent Office and incorporated herein by reference.
  • a steel cathode can be coated with a dense, non-porous, electroless nickel coating by immersing said steel cathode in a bath at a suitable temperature; the bath containing a suitable nickel salt, water, a complexing agent and a reducing agent.
  • the preferred nickel coated, steel cathodes can also be prepared in accordance with copending, commonly assigned application Serial No. 611,030, filed September 8, 1975 in the U.S. Patent Office and incorporated herein by reference.
  • a steel cathode can be coated with nickel by either flame-spraying or plasma-spraying the powdered metal onto the steel cathode surface.
  • the expanded metal, gas-directing cathodes include means for directing the gas evolved from the cathode during electrolysis toward or away from the cation-permselective membrane of the cell. Utilizing these cathodes, the evolved gas is deflected from its natural upward path between the cathode and the cation-permselective membrane thus causing turbulent flow of the catholyte to occur in the area between the cathode and said membrane.
  • the expanded metal, gas-directing cathode is formed of a sheet of metal which is characterized as a continuous fabric mesh having an open mesh network of interconnected webs or filaments enclosing openings of diamond shape, although oval or other shaped openings can be used.
  • the webs are, in general, flat in cross-section and are positioned at an angle of about 20° to about 70°, preferably about 35° to about 55° to the plane of the original sheet from which they are formed.
  • Such sheets of expanded metal are known to those skilled in the art for use as electrodes in chlor-alkali electrolysis cell technology and are shown in Figures 1, 2 and 3 of the drawings herein and further described in the prior art, for instance, in U.S. 3,598,715 and U.S. 3,930,981, which are hereby incorporated by reference.
  • the size of the openings in said cathodes can be, for instance, from about 3/16 inch x 1/2 inch to about 3/8 inch x 1-1/4 inch (height and width of the opening, respectively).
  • the electrolysis process of the invention is generally adapted for use in the electrolysis of organic as well as inorganic materials.
  • the electrolysis 1 solution contains chloride ions and is a water solution of at least one alkali metal chloride such as sodium chloride.
  • alkali metal chloride such as sodium chloride.
  • Other soluble or partially soluble salts or hydroxides are useful in aqueous solution.
  • sodium sulfates, sulfites or phosphates can also be utilized, at least in part.
  • sodium hydroxide and potassium hydroxide can be used.
  • Sodium chloride is the preferred alkali metal chloride for the production of chlorine and caustic since sodium chloride, as well as potassium chloride, do not form insoluble salts or precipitates and produce stable hydroxides.
  • the concentration of sodium chloride in a brine which is charged to the anolyte compartment of the cell will usually be as high as feasible, generally at least about 200 to about 340 grams per liter of sodium chloride and about 200 to about 360 grams per liter of potassium chloride with intermediate figures for mixtures.
  • the anolyte can be neutral or acidified to a pH in the range of about 1 to about 6, preferably about 2 to about 4, and most preferably about 3 to about 4, acidification normally being effected by utilizing a suitable acid such as hydrochloric acid.
  • the anolyte is desirably acid to effect neutralization of any hydroxyl ions entering the anode compartment from the catholyte thus preventing the formation of oxygen.
  • the temperature of the electrolyte is generally maintained at less than 105°C., preferably between about 20°C. to about 95°C., and most preferably about 65°C. to 'about 95°C.
  • the temperature of the electrolyte can be increased by recirculation of portions thereof and by the proper regulation of the proportion of feed to the anolyte.
  • cooling of the electrolyte can be effected by exposure of the anolyte liquid to ambient conditions before entry or re-entry of such liquid into the anolyte of the cell.
  • the weight percent of salt conversion in the anolyte of the cell is determined by dividing the weight concentration of the alkali metal chloride in the anolyte effluent by the weight concentration of the alkali metal chloride in the solution which is continuously added to the anolyte, correcting for the water of hydration transported across the membrane and multiplying by 100.
  • the weight percent salt conversion is about 50% to about 85%, preferably about 65% to about 75%.
  • an alkali metal chloride brine containing about 300 to about 340 grams per liter is continuously added to the anode compartment of the cell and the depleted brine removed.
  • the concentration by weight of the caustic solution made in the cell is from about 10% to about 40% and is free of chloride or essentially free thereof, often containing as low as 0.1 to 10 grams per liter of chloride and usually about 1 gram or less per liter.
  • the caustic concentration can be further increased by evaporation of water and because of the unusually high concentration of caustic obtained directly from the cell very little additional energy in the form of heat is required to raise the concentration to a desirable, marketable concentration of about 50% by weight.
  • the electrical operating conditions of the cell can vary over a wide range.
  • Cell voltages are generally about 2.9 to about 5 volts, and current density is generally about 0.75 to about 3 amperes per square inch.
  • current density is generally about 0.75 to about 3 amperes per square inch.
  • the walls of the electrolytic cells utilized in the process disclosed herein can be formed of any suitable electrically non-conductive material having resistance to chlorine, hydrochloric acid and sodium hydroxide at the temperatures at which the cell is operated.
  • suitable materials have been found to be coated metals, chlorinated polyvinyl chloride, polypropylene containing up to 40% of an inert, fibrous filler such as asbestos or talc, chlorendic acid-based polyester resins, phenol-formaldehyde resins and the like.
  • the materials of construction have sufficient rigidity to be self-supporting.
  • FIG. 3 This example illustrates the use of the electrolytic cell of the invention in the electrochemical conversion of an aqueous solution of sodium chloride to sodium hydroxide and chlorine.
  • An electrolytic cell body was constructed of chlorinated polyvinyl chloride plastic containing 20 percent by weight of asbestos based upon the total weight of said filled plastic.
  • the cell is schematically shown in Figure 3 and contained a cathode assembly as schematically shown in Figure 2.
  • the cell contained a flattened expanded metal anode made of ruthenium oxide-coated titanium and a cathode made of nickel coated steel.
  • the electrodes communicate with current sources by means of steel members.
  • the cathode was shaped into a turbulence inducing form by expanding a metal sheet by stamping out openings between the remaining webs or filaments of the mesh which measure 3/8 inch high by 1-1/4 inches wide; the remaining metal filaments being about 2 millimeters in thickness.
  • the electrodes were mounted in the cell on either side of a cation-permselective membrane so as to provide an electrode spading of 0.1 inch with the cathode installed so as to direct cathodic gases away from the membrane.
  • the membrane was manufactured by E. I. du Pont de Nemours & Company, Inc., and sold under the trademark "Nafion", type 313.
  • the membrane was joined to a backing or supporting layer network of polytetrafluoroethylene filaments woven into a cloth having an area percentage of openings i rtherein of about 22% by volume.
  • the membranes which were initially flat are fused onto the polytetrafluoroethylene cloth under conditions of high temperature and pressure with some of the membrane'portions actually being caused to flow around the filaments of the cloth during the fusing so that the membrane and cloth become an integral unit.
  • the membrane was hydrolyzed by boiling in water.
  • the cation-permselective membrane utilized was in two layers each bonded together and consisting of a hydrolyzed copolymer of a perfluorinated hydrocarbon and a fluorosulfonated perfluorovinyl ether; the outer layer being 2 mil in thickness and having an equivalent weight of about 1350 and the inner layer being 4 mil in thickness and having an equivalent weight of about 1100.
  • Ruthenium oxide coated titanium anodes were used which were prepared by coating a titanium mesh having about 2 millimeter thickness filaments with about 50% by volume open area with ruthenium oxide to a thickness of about 10 -3 millimeters.
  • the cell was operated under the following conditions:
  • the cell was operated continuously for a period of 10 days.
  • Example 1 is repeated except that said turbulence inducing cathode is positioned so as to direct cathodic gases toward said membrane.
  • An average value for current efficiency of the cell is comparable to results obtained in ,the cell of Example 1.
  • a cell forming no part of this invention was operated in accordance with the above procedure with the exception that the expanded-metal cathode utilized was a flattened, expanded-metal cathode so that turbulence on the surface of the cation-permselective membrane is not induced by directing the evolving cathodic gases toward or away from said membrane.
  • a flattened, expanded-metal cathode having openings measuring 3/16 inch in height by 1/2 inch in width . was utilized in addition to a flattened, expanded metal electrode having larger 3/8 inch high by 1-1/4 inch wide openings.
  • Current efficiencies obtained utilizing said cells having flattened, expanded-metal electrodes present as cathodes indicate a current efficiency average of 77%.
  • Examples 1 and 2 are repeated except that the anode used is an expanded metal anode shaped into a turbulence inducing form by expanding a metal sheet of ruthenium oxide-coated titanium by stamping out openings between the remaining webs of filaments of the mesh which measure 3/8 inch high by 1-1/4 inches wide.
  • the anode is positioned in the cell so as to direct evolving gases away from the cell membrane. Average values for current efficiency is L comparable to the results obtained in the cell of Example 1.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
EP78101296A 1977-11-10 1978-11-03 Einrichtung und Verfahren zur Elektrolyse unter Verwendung einer halbdurchlässigen kationischen Membrane und Turbulenz erzeugende Hilfsmittel Withdrawn EP0002009A1 (de)

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US850344 1977-11-10
US05/850,344 US4142950A (en) 1977-11-10 1977-11-10 Apparatus and process for electrolysis using a cation-permselective membrane and turbulence inducing means

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Cited By (4)

* Cited by examiner, † Cited by third party
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EP0039171A2 (de) * 1980-04-15 1981-11-04 Asahi Kasei Kogyo Kabushiki Kaisha Elektrolyse einer wässrigen Alkalichloridlösung und electrolytische Zelle dafür
DE3219704A1 (de) * 1982-05-26 1983-12-01 Uhde Gmbh, 4600 Dortmund Membran-elektrolysezelle
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Families Citing this family (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE30864E (en) * 1977-06-27 1982-02-09 Olin Corporation Process for electrolysis in a membrane cell employing pressure actuated uniform spacing
JPS5948872B2 (ja) * 1978-02-20 1984-11-29 クロリンエンジニアズ株式会社 電解用陰極及びその製造法
DE2821982A1 (de) * 1978-05-19 1979-11-22 Hooker Chemicals Plastics Corp Trennwand mit einer membran fuer filterpressenartig angeordnete elektrolysezellen
IT1113412B (it) * 1979-02-15 1986-01-20 Oronzio De Nora Impianti Procedimento eletttrolitico ed apparecchiatura per la preparazione di ipoalogenito di metallo alcalino
US4401530A (en) * 1981-09-28 1983-08-30 Diamond Shamrock Corporation Electrode
DE3228884A1 (de) * 1982-08-03 1984-02-09 Metallgesellschaft Ag, 6000 Frankfurt Vertikal angeordnete plattenelektrode fuer gasbildende elektrolyseure
JPS59190379A (ja) * 1983-04-12 1984-10-29 Kanegafuchi Chem Ind Co Ltd 縦型電解槽及びそれを用いる電解方法
US4507183A (en) * 1983-06-03 1985-03-26 The Dow Chemical Company Ruthenium coated electrodes
US4652345A (en) * 1983-12-19 1987-03-24 International Business Machines Corporation Method of depositing a metal from an electroless plating solution
US5041197A (en) * 1987-05-05 1991-08-20 Physical Sciences, Inc. H2 /C12 fuel cells for power and HCl production - chemical cogeneration
US5445746A (en) * 1992-08-28 1995-08-29 Cer-Wat Corporation Method for dewatering a porous wet web
US5256288A (en) * 1992-08-28 1993-10-26 Cer-Wat, Inc. Filtration medium including substrate-supported porous membrane and method for the manufacture thereof
JPH08129103A (ja) * 1994-10-31 1996-05-21 Shinto Paint Co Ltd カラーフィルター製造用金網状電極及び同電極を用いたカラーフィルターの製造方法
DE4444114C2 (de) * 1994-12-12 1997-01-23 Bayer Ag Elektrochemische Halbzelle mit Druckkompensation
US6368472B1 (en) 1998-11-04 2002-04-09 Mcguire Byron Duvon Electrolytic chemical generator
US6368474B1 (en) 2000-05-16 2002-04-09 Electromechanical Research Laboratories, Inc. Chlorine generator
US6942766B2 (en) * 2003-01-16 2005-09-13 Chris Alan Lemke Chlorine generator
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US8427979B1 (en) 2006-07-27 2013-04-23 Mobitrum Corporation Method and system for dynamic information exchange on location aware mesh network devices
US7801058B2 (en) * 2006-07-27 2010-09-21 Mobitrum Corporation Method and system for dynamic information exchange on mesh network devices
US20090189739A1 (en) * 2008-01-25 2009-07-30 Mobitrum Corporation Passive voice enabled rfid devices
WO2010096504A1 (en) * 2009-02-17 2010-08-26 Mcalister Technologies, Llc Apparatus and method for controlling nucleation during electrolysis
MY187664A (en) 2009-02-17 2021-10-08 Mcalister Tech Llc Apparatus and method for gas capture during electrolysis
US9040012B2 (en) 2009-02-17 2015-05-26 Mcalister Technologies, Llc System and method for renewable resource production, for example, hydrogen production by microbial electrolysis, fermentation, and/or photosynthesis
US8075750B2 (en) 2009-02-17 2011-12-13 Mcalister Technologies, Llc Electrolytic cell and method of use thereof
RU2484182C2 (ru) * 2009-02-17 2013-06-10 МАКЭЛИСТЭР ТЕКНОЛОДЖИЗ, ЭлЭлСи Электролитическая ячейка и способ ее применения
US9034294B1 (en) 2009-04-24 2015-05-19 Simbol, Inc. Preparation of lithium carbonate from lithium chloride containing brines
US8741256B1 (en) 2009-04-24 2014-06-03 Simbol Inc. Preparation of lithium carbonate from lithium chloride containing brines
US8637428B1 (en) 2009-12-18 2014-01-28 Simbol Inc. Lithium extraction composition and method of preparation thereof
US10190030B2 (en) 2009-04-24 2019-01-29 Alger Alternative Energy, Llc Treated geothermal brine compositions with reduced concentrations of silica, iron and lithium
US9051827B1 (en) 2009-09-02 2015-06-09 Simbol Mining Corporation Selective removal of silica from silica containing brines
US10935006B2 (en) 2009-06-24 2021-03-02 Terralithium Llc Process for producing geothermal power, selective removal of silica and iron from brines, and improved injectivity of treated brines
ES2750527T3 (es) 2010-02-17 2020-03-26 All American Lithium LLC Procedimientos de preparación de carbonato de litio altamente puro y de otros compuestos que contienen litio altamente puro
US9127244B2 (en) 2013-03-14 2015-09-08 Mcalister Technologies, Llc Digester assembly for providing renewable resources and associated systems, apparatuses, and methods
US9909223B1 (en) 2014-08-04 2018-03-06 Byron Duvon McGuire Expanded metal with unified margins and applications thereof
US10604414B2 (en) 2017-06-15 2020-03-31 Energysource Minerals Llc System and process for recovery of lithium from a geothermal brine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2070757A1 (de) * 1969-12-06 1971-09-17 Nippon Soda Co
FR2263034A1 (de) * 1974-03-09 1975-10-03 Asahi Chemical Ind
JPS52114571A (en) * 1976-03-24 1977-09-26 Tokuyama Soda Co Ltd Electrolysis

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2925371A (en) * 1956-06-01 1960-02-16 Carwin Company Electrolytic cell
GB1196631A (en) * 1966-05-31 1970-07-01 Monsanto Co Electrolytic Diaphragm Cell
US3598715A (en) * 1968-02-28 1971-08-10 American Potash & Chem Corp Electrolytic cell
US3770612A (en) * 1970-08-24 1973-11-06 Allied Chem Apparatus for electrolytic oxidation or reduction, concentration, and separation of elements in solution
US3989615A (en) * 1971-07-06 1976-11-02 Nippon Soda Company Limited Diaphragm process electrolytic cell
US3910827A (en) * 1971-07-07 1975-10-07 Ppg Industries Inc Diaphragm cell
BE790369A (fr) * 1971-10-21 1973-04-20 Diamond Shamrock Corp Procede et appareil pour la preparation d'hydroxydes de metaux alcalins de haute purete dans une cuve electrolytique.
IT989421B (it) * 1973-06-25 1975-05-20 Oronzio De Nora Impiantielettr Cella di elettrolisi con elettrodi di forma particolare e deflettori atti ad allontanare i gas che si sviluppano agli elettrodi fuori dal lo spazio interelettrodico
US4065376A (en) * 1976-05-04 1977-12-27 Diamond Shamrock Corporation Electrolytic cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2070757A1 (de) * 1969-12-06 1971-09-17 Nippon Soda Co
FR2263034A1 (de) * 1974-03-09 1975-10-03 Asahi Chemical Ind
JPS52114571A (en) * 1976-03-24 1977-09-26 Tokuyama Soda Co Ltd Electrolysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 88, 1978, page 329, ref. 67260v, Columbus, Ohio, (USA) NISHIMURA: "Cathode design for diaphragm cell used in brine electrolysis"; & JP-A-52 114 571 (TOKUYAMA SODA KK.) published 26-09-1977 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0039171A2 (de) * 1980-04-15 1981-11-04 Asahi Kasei Kogyo Kabushiki Kaisha Elektrolyse einer wässrigen Alkalichloridlösung und electrolytische Zelle dafür
EP0039171B1 (de) * 1980-04-15 1984-11-21 Asahi Kasei Kogyo Kabushiki Kaisha Elektrolyse einer wässrigen Alkalichloridlösung und electrolytische Zelle dafür
DE3219704A1 (de) * 1982-05-26 1983-12-01 Uhde Gmbh, 4600 Dortmund Membran-elektrolysezelle
EP3537603A1 (de) 2017-12-28 2019-09-11 Renesas Electronics Corporation Leistungsumwandlungsvorrichtung und halbleiterbauelement
IT202100006248A1 (it) 2021-03-16 2022-09-16 Ingenio S R L Elettrolizzatore per l’elettrolisi dell’acqua e metodo per la produzione di idrogeno

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