US3337433A - Electrolytic process - Google Patents

Electrolytic process Download PDF

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Publication number
US3337433A
US3337433A US262498A US26249863A US3337433A US 3337433 A US3337433 A US 3337433A US 262498 A US262498 A US 262498A US 26249863 A US26249863 A US 26249863A US 3337433 A US3337433 A US 3337433A
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US
United States
Prior art keywords
cathode
diaphragm
reactive material
cell
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US262498A
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English (en)
Inventor
George T Miller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Occidental Chemical Corp
Original Assignee
Hooker Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to GB26293/59A priority Critical patent/GB889639A/en
Priority to US45567A priority patent/US3109787A/en
Priority claimed from US45669A external-priority patent/US3109795A/en
Priority to FR834368A priority patent/FR1270717A/fr
Priority to DEA35249A priority patent/DE1112722B/de
Application filed by Hooker Chemical Corp filed Critical Hooker Chemical Corp
Priority claimed from US262497A external-priority patent/US3251756A/en
Priority to US262498A priority patent/US3337433A/en
Priority to US262496A priority patent/US3312610A/en
Priority to FR965830A priority patent/FR85416E/fr
Priority to FR965832A priority patent/FR85418E/fr
Priority to FR965831A priority patent/FR85417E/fr
Priority to GB9213/64A priority patent/GB1042392A/en
Priority to DEH51938A priority patent/DE1210425B/de
Priority to GB9214/64A priority patent/GB1042393A/en
Priority to DEH51937A priority patent/DE1210424B/de
Priority to GB9212/64A priority patent/GB1042391A/en
Priority to DE1964H0051939 priority patent/DE1210426C2/de
Priority to BE694669D priority patent/BE694669A/xx
Priority to BE694671D priority patent/BE694671A/xx
Priority to BE694670D priority patent/BE694670A/xx
Publication of US3337433A publication Critical patent/US3337433A/en
Application granted granted Critical
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE APRIL 1, 1982. Assignors: HOOKER CHEMICALS & PLASTICS CORP.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • 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
    • 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
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • This invention relates to an electrolytic cell and more particularly to a diaphragm in an electrolytic cell.
  • a reactive material present in the cell reacts with one of the products being produced at either the anode or the cathode of the cell to produce an end product. It has been found that in certain cells of this type a shut-down of the cell for cleaning of the diaphragm becomes desirable when the reactive material included in the cell Wets or builds up on the diaphragm. Build-up of the reactive material on the diaphragm, if it does not cause the cell to malfunction, causes at least a decrease in the efficiency of the cell and a corresponding decrease in the yield of the desired end product. The build-up of the reactive material on the diaphragm may also cause an increase in the electrical power needed for operation of the cell, thus increasing the cost of operating the cell and adding to the electrical load of the installation.
  • Another object of the invention is to prevent the wetting of a diaphragm by a reactive material contained within an electrolytic cell, thereby increasing cell life and efficiency.
  • Another object is to protect a diaphragm in an electrolytic cell which is wetted by a reactive material contained within the cell.
  • a further object is to inhibit wetting of a diaphragm by molten phosphorus in an electrolytic cell producing phosphine.
  • the invention has particular application to uses in which the reactive material is phosphorus and a product of the cell is phosphine.
  • Another aspect of the invention which is of importance is the structure of the covered or sheathed diaphragm and the materials thereof.
  • an electrolytic cell will be of increased efliciency when it comprises anodic and cathodic electrodes, a diaphragm separating anode and cathode, an electrolyte in contact with the electrodes and the diaphragm, from which electrolyte a product of electrolysis is formed at an electrode when an electric current flows between the electrodes through the electrolyte, and a reactive material 3,337,433 Patented Aug. 22, 1967 14, cathode compartment 16, and cathode 18.
  • a porous or permeable diaphragm 20 separates anode and cathode compartments and separates the electrolyte into anolyte 17 and catholyte 19 sections.
  • a reactive material 24 e.g., phosphorus, in liquid state.
  • Diaphragm 20 is covered, coated, or protected in such a manner that the side thereof facing the reactive material, where it may otherwise contact that material, is coated with a coating, cover or sheath 22 against which the reactive material then does not adhere or wet the coating, which action is evidenced by convex meniscus 21.
  • Ports 26 and 28 permit the addition and removal of anolyte from the anode section 12.
  • Ports 30 and 32 permit the addition and removal of catholyte from the cathode section 16.
  • Port 34 permits the addition and removal of the reactive material from cathode section 16.
  • Suflicient reactive material 24 is added to the cathode compartment 16 to contact the portion or edge of cathode 18, permitting contact of the reactive material with a greater surface of the cathode by a wetting action.
  • Anolyte gas discharge port 36 is provided in the top of the anode section to remove analyte gas from the electrolytic cell.
  • Catholytic gas discharge port 38 is provided on the top of the cathode section 16 to remove catholyte gas. Gas-liquid interfaces are indicated at 15.
  • Electrolyzing current to the electrodes is transmitted by anode electrical connector 40 and cathode electrical connector 42 joining the anode and cathode to the positive and negative poles, respectively, of a source of direct current 44.
  • a heating or cooling means such as a constant temperature hath, not shown, may be employed to maintain the cell at or near a desired temperature.
  • Cell vessel 10 may be constructed of a material capable of resisting corrosion by the electrolyte and other materials employed in the cell.
  • suitable materials of construction of cell vessel 10 include glass, glazed ceramic, tantalum, titanium, hard rubber, polyethylene, polyurethane, rigid materials coated with phenolformaldehyde resin, and the like.
  • Diaphragm 20 which separates the anode section 12 from the cathode section 16 may be semipermeable or permeable material resistant to the cell contents and capable of maintaining the anode and cathode gases separate.
  • suitable materials for use as a diaphragm include: porous alundum, porous porcelain,
  • FIGURE 1 is a central vertical sectional view of apparatus of this invention along 1-1
  • FIGURE 2 is a horizontal sectional view along 22.
  • Cell vessel 10 contains anode compartment 12, anode of the types which may be normally employed in lead storage batteries.
  • Cover, coating or surface 22 is a material which does not become wetted by the reactive material. Such lack of wetting effect is indicated by formation of a convex meniscus when the surface is in contact with a reactive material contained in the cell. The surface, in essence, prevents the reactive material from wetting the diaphragm.
  • glass fabric is the material which is non-wettable by phosphorous.
  • non-wettable materials suitable for the practice of this invention are vinylidene polymers, polypropylene, polyurethane, chlorinated polyether, acrylonitrile resins, polyethylene, fluorinated hydrocarbon resins, polyester resins, polyvinyl chloride resins, graphite, phenolformaldehyde resins, natural gum rubber and chloroprene resins. It is preferred that the above resins be fabrics thereof, but it is to be understood that the resins themselves in their thermosetting or thermoplastic forms may also be utilized in the invention in accordance with the description herein. These sheathing materials also should be permeable, non-resistance to electrochemical flow and stable in the electrolyte media which may be utilized.
  • the cover material may be applied to the diaphragm by any suitable method, as by spraying, fusing, adhering, wrapping about the diaphragm, mechanically fastening, depositing, and integrally forming with the diaphragm. lt is preferred, however, to form a fabric material into the shape of the diaphragm, but slightly larger and then to insert the diaphragm into the preformed sheath. Alternately, one may wrap the fabric around the diaphragm and fasten it so that it will remain in place. The diaphragm is then placed into and connected to the cell vessel 10. It is to be understood that one or both sides of the diaphragm may be coated, usually depending on which surface or surfaces may come into contact with the reactive material.
  • cathodic materials include lead, amalgamated lead, cadmium, tin, aluminum, nickel, alloys of nickel, such as Mumetal (an alloy containing 77.2 percent nickel, 4.8 percent copper, 1.5 percent chromium, and 14.9 percent iron), Monel, copper, silver, bismuth, and alloys thereof.
  • lead-tin, lead-bismuth, and tin-bismuth alloys may be employed.
  • Various shapes of cathodes may be employed, e.g., the cathode may be cylindrical as illustrated, or may be of plate or other shape.
  • Mats of metallic wool and porous metallic sheaths may also be employed, if desired. Essentially the reactive material will wet such materials and rise to cover the cathode surface thinly, promoting reaction with the product of electrolysis generated at the cathode surface.
  • Suitable anode materials include lead, platinum, lead peroxide, graphite and other materials of construction capable of conducting current and resisting corrosion under the conditions of electrolysis employed.
  • the electrolyte may be a salt or other organic or inorganic electrolyte which is itself nonreactive with the reactive material utilized and which is capable of forming a product, e.g., hydrogen gas or ion, under electrolytic conditions employed which will react with the reactive material.
  • a product e.g., hydrogen gas or ion
  • suitable compounds in aqueous solution include hydrochloric acid, sodium chloride, lithium chloride, potassium chloride, sodium sulfate, potassium sulfate, monosodium phosphate, disodium phosphate, acetice acid, ammonium hydroxide, phosphoric acid, sulfuric acid and mixtures thereof.
  • the concentration of a compound in an aqueous electrolyte may vary from about 1 to about 95 percent, but is usually between about 5 and about 80 percent, preferably between about and about 50 percent.
  • suitable concentrations of metal ions may be between 0.01 percent and 5 percent by weight of electrolyte, however, between about 0.02 percent and 3 percent by weight of electrolyte may also be utilized. Preferably though between about 0.02 percent and 0.5 percent by weight of electrolyte may be utilized.
  • metallic ions which may be utilized are antimony, bismuth, lead, tin, cadmium, mercury, silver, zinc, cobalt, calcium, barium, and mixtures thereof.
  • the metal ions may be placed in the electrolyte by employing a consumable anode of the desired metal or metals, such as a lead anode, whereby the metal ions are formed in the electrolyte and transferred to the area adjacent to the cathode.
  • Salts or other compounds of the metals such as chlorides, phosphates, acetates, and the like, also may be dissolved in the electrolyte if desired.
  • finely divided metal in elemental form is added to the electrolyte.
  • the diaphragm protected in the manner illustrated and described herein is preferably utilized in the electrolytic production of phosphine.
  • the temperature of the catholyte and anolyte should be maintained above the melting point of phosphorus (about 44 degrees centigrade), and below the boiling point of the electrolyte. Temperatures between about 60 degress centigrade and 110 degrees centigrade are satisfactory, but optimum yields of phosphine are obtained at temperatures between about 70 degrees centigrade and 100 degrees centigrade.
  • an electric current is passed through the cell, molten phosphorus on the surface of the cathode is consumed in the formation of a catholyte gas in the cathode section.
  • the catholyte gas is predominantly phosphine, but contains some hydrogen.
  • the anolyte gas depends on the over-voltages of the anions in the anolyte, with reference to the anode material.
  • the anolyte gas predominates in oxygen if sulfuric acid or phosphoric acid is used with a platinum anode, whereas for the same anode, chlorine predominates if hydrochloric acid is used as anolyte.
  • the coproduction of anodic oxidation products may be carried out in the anode compartment of the cell of this invention without departing from the spirit of the invention.
  • the current density on the cathode may be controlled so that the phosphorus is consumed at a rate at which it is replenished on the cathode surface from the molten pool of phosphorus.
  • the cathode current density may be set by the operator and is dependent on which density gives the best results, the cell design and the construction of the cathode.
  • the optimum cathodic current density appears to be between about 6 and 12 amperes per square foot.
  • other current densities consistent with the economic production of phosphine may be employed.
  • the phosphine containing gas produced at the cathode has a relatively high concentration of phosphine, usually more than 60 percent, and it may be as high as percent phosphine by volume or higher.
  • the catholyte gas is substantially free from other phosphorus hydrides.
  • a lead plate is employed as the cathode
  • a graphite rod is employed as the anode with an alundum diaphragm coated with glass fabric to keep the phosphorus from the diaphragm, separating the anode from the cathode.
  • the wicking action becomes more rapid. It was further observed that the rate of the wicking action was faster for some metals than others, and that the thickness of the phosphorus layer on the metal surfaces was thicker on some metals than on others. Further, in the utilization of the invented apparatus for phosphine production when phosphorus is the reactive material, it has been found that the non-wetting materials, sheathing the diaphragm prevents the diaphragm from building up a layer of phosphorus on its surface, which otherwise would cause a decrease in the efliciency of the cell.
  • Suitable reactive materials which may be utilized in the apparatus of the invention are sulfur, the alkali metals and their salts, e.g., potassium, sodium lithium, rubidium, cesium, sodium chloride, etc., alkaline earth metals, e.g., beryllium,
  • the porosity or openings of the coating material may be between 0.5 micron and A of an inch, as desired, to block the flow of reactive material through the protective coating of the diaphragm.
  • Example I To an electrolytic cell containing a graphite anode and lead cathode were added 2,330 parts of 10 percent hydrogen chloride solution containing 1 gram per liter of lead chloride. A porous alundum diaphragm in a glass cloth sleeve with openings about 764 Of an inch, separated the anode and cathode so as to form anodic and cathodic compartments. 266 parts of phosphorus were added to the cathodic chamber. The cell was maintained at 95 degrees centigrade. An electric potential was applied to the electrodes to cause flow of a current of about 4.6 amperes.
  • Example 2 Example 1 was repeated, except for the omission of the glass fabric sleeve. The cell was operated forabout 66 days. The voltage during this period had to be increased from 4.2 to 5.3 volts. At the time of shut down, 70 percent of the porous diaphragm area was coated with phosphorus and was blocked by it.
  • Examples 3 to 14 These examples illustrate the various nonwettable materials which may be utilized in place of glass cloth to sheath or cover the diaphragm of the electrolytic cell of Example 1, and thereby to increase the efliciency of the cell by preventing the deposition of a reactive material on its surface to block openings therein. Elemental phosphorus under concentrated hydrochloric acid was heated to cell temperature, between about 70 and 80 degrees centigrade. The following fabrics were then tested:
  • Polyester (Dacron (R)) Polyvinyl chloride (Tygon(R)) Graphite (rod and fabric) Phenoliormaldehyde resins Natural gum iubber Polymer of chloroprene (N eoprene (R)).
  • a process for producing chemicals which comprises contacting anodic and cathodic electrodes with an contact with a material reactive with a product of electrolysis produced there, said reactive material being selected from the group consisting of phosphorus, sulfur, alkali metals, alkaline earth metals, magnesium, germanium, and lead, maintaining a thin layer of the reactive material on the surface of said electrode, separating the anode and cathode with a diaphragm having its side facing the electrode which contacts the reactive material covered with a material covered with a material against which the reactive material is non-Wetting, and passing an electric current between the anode and the cathode through the electrolyte to produce a compound of the reactive material and the product of electrolysis of the electrode in contact therewith.
  • a process for producing phosphine' which comprises contacting anodic and cathodic electrodes with an electrolyte, the lower portion of the cathodic electrode being in contact with phosphorus, maintaining a thin layer of phosphorus on the surface of said cathode electrode, sepa rating the anode and cathode with a diaphragm having its side facing the cathode covered with a material against which phosphorus is nonwetting, and passing an electric current between the anode and the cathode through the electrolyte to produce phosphine.
  • nonwettable material is a glass fabric.
  • a process for producing phosphine which comprises contacting anodic and cathodic electrodes with an electrolyte, the lower portion of a cathodic electrode being in contact with phosphorus which is reactive with a product of electrolysis produced there, to produce phosphine, maintaining a thin layer of phosphorus on the surface of said electrode, separating the anode and cathode with a diaphragm having a side facing the cathodic electrode covered with a material selected from the group consisting of glass fabric, vinyldene polymers, polypropylene, polyurethane, chlorinated polyether, acrylonitrile resins, polyethylene, fluorinated hydrocarbon resins, polyester resins, polyvinyl chloride resins, graphite, phenolformaldehyde resins, natural gum rubber and chloroprene resins, against which the reactive material is nonwetting, and passing an electric current between the anode and the cathode through the electrolyte.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Glass Compositions (AREA)
US262498A 1959-07-31 1963-03-04 Electrolytic process Expired - Lifetime US3337433A (en)

Priority Applications (18)

Application Number Priority Date Filing Date Title
GB26293/59A GB889639A (en) 1959-07-31 1959-07-31 Improvements in or relating to the production of phosphine
US45567A US3109787A (en) 1959-07-31 1960-07-27 Production of phosphine
FR834368A FR1270717A (fr) 1959-07-31 1960-07-29 Procédé de production de la phosphine par voie électrolytique
DEA35249A DE1112722B (de) 1959-07-31 1960-08-01 Verfahren zur elektrolytischen Herstellung von Phosphin
US262498A US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process
US262496A US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine
FR965830A FR85416E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
FR965832A FR85418E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
FR965831A FR85417E (fr) 1959-07-31 1964-03-03 Procédé de production de la phosphine par voie électrolytique
DE1964H0051939 DE1210426C2 (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
GB9213/64A GB1042392A (en) 1959-07-31 1964-03-04 Electrolytic cell, and process for producing phosphine therewith
DEH51938A DE1210425B (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
GB9214/64A GB1042393A (en) 1959-07-31 1964-03-04 Process and apparatus for producing phosphine
DEH51937A DE1210424B (de) 1959-07-31 1964-03-04 Verfahren zur elektrolytischen Herstellung von Phosphin
GB9212/64A GB1042391A (en) 1959-07-31 1964-03-04 Electrolytic cell, and process for producing phosphine therewith
BE694670D BE694670A (US07816562-20101019-C00012.png) 1959-07-31 1967-02-27
BE694671D BE694671A (US07816562-20101019-C00012.png) 1959-07-31 1967-02-27
BE694669D BE694669A (US07816562-20101019-C00012.png) 1959-07-31 1967-02-27

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB26293/59A GB889639A (en) 1959-07-31 1959-07-31 Improvements in or relating to the production of phosphine
US45669A US3109795A (en) 1960-07-27 1960-07-27 Method of preparing phosphine
US29249663A 1963-03-04 1963-03-04
US262497A US3251756A (en) 1963-03-04 1963-03-04 Electrolytic process for making phosphine
US262498A US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process
US262496A US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine

Publications (1)

Publication Number Publication Date
US3337433A true US3337433A (en) 1967-08-22

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Application Number Title Priority Date Filing Date
US262496A Expired - Lifetime US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine
US262498A Expired - Lifetime US3337433A (en) 1959-07-31 1963-03-04 Electrolytic process

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Application Number Title Priority Date Filing Date
US262496A Expired - Lifetime US3312610A (en) 1959-07-31 1963-03-04 Electrolytic process for producing phosphine

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US (2) US3312610A (US07816562-20101019-C00012.png)
BE (3) BE694671A (US07816562-20101019-C00012.png)
DE (4) DE1112722B (US07816562-20101019-C00012.png)
GB (4) GB889639A (US07816562-20101019-C00012.png)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009010203A1 (de) 2007-07-18 2009-01-22 Monopharm Handelsgesellschaft Mbh Diaphragmalyse-verfahren und verwendung der nach dem verfahren erhaltenen produkte
EP2592053A3 (de) * 2011-11-09 2013-07-03 Monopharm Beratungs- Und Handelsgesellschaft Mbh Verfahren zur Herstellung eines Katholyts und dessen Verwendung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404076A (en) * 1965-04-15 1968-10-01 Shell Oil Co Electrolytic preparation of hydrides
CN112703274A (zh) * 2018-11-28 2021-04-23 阿耶尔斯集团有限责任公司 用于高效节能地电化学生产氢化物气体的方法和设备

Citations (6)

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US1094315A (en) * 1912-11-16 1914-04-21 Hood Rubber Co Inc PROCESS FOR PRODUCING 1.3-GLYCOLS, (β-GLYCOLS.)
US2688594A (en) * 1948-12-27 1954-09-07 American Enka Corp Mercury cell
US2944956A (en) * 1956-11-16 1960-07-12 Dow Chemical Co Chlorine cell having protected diaphragm
US3017338A (en) * 1958-03-03 1962-01-16 Diamond Alkali Co Electrolytic process and apparatus
US3109795A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Method of preparing phosphine
US3109788A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Electrolytic production of phosphine

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1926837A (en) * 1931-07-10 1933-09-12 Martin E Cupery Electrolytic reduction of organic nitro compounds
US2780593A (en) * 1951-09-01 1957-02-05 New Jersey Zinc Co Production of metallic titanium
US2719822A (en) * 1952-01-10 1955-10-04 Universal Oil Prod Co Production of chlorine from hydrogen chloride

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1094315A (en) * 1912-11-16 1914-04-21 Hood Rubber Co Inc PROCESS FOR PRODUCING 1.3-GLYCOLS, (β-GLYCOLS.)
US2688594A (en) * 1948-12-27 1954-09-07 American Enka Corp Mercury cell
US2944956A (en) * 1956-11-16 1960-07-12 Dow Chemical Co Chlorine cell having protected diaphragm
US3017338A (en) * 1958-03-03 1962-01-16 Diamond Alkali Co Electrolytic process and apparatus
US3109795A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Method of preparing phosphine
US3109788A (en) * 1960-07-27 1963-11-05 Hooker Chemical Corp Electrolytic production of phosphine

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009010203A1 (de) 2007-07-18 2009-01-22 Monopharm Handelsgesellschaft Mbh Diaphragmalyse-verfahren und verwendung der nach dem verfahren erhaltenen produkte
US20110059028A1 (en) * 2007-07-18 2011-03-10 Burkhard Ponitz Method for membrane electrolysis and the use of the products obtained by it
CN101808947B (zh) * 2007-07-18 2012-12-12 莫纳制药贸易有限公司 用于膜电解的方法和由其获得的产物的用途
AU2008278002B2 (en) * 2007-07-18 2013-01-17 Monopharm Handelsgesellschaft Mbh Diaphragm analysis method and use of products obtained using the method
EP2592053A3 (de) * 2011-11-09 2013-07-03 Monopharm Beratungs- Und Handelsgesellschaft Mbh Verfahren zur Herstellung eines Katholyts und dessen Verwendung

Also Published As

Publication number Publication date
DE1210426B (de) 1966-02-10
US3312610A (en) 1967-04-04
BE694670A (US07816562-20101019-C00012.png) 1967-07-31
DE1210426C2 (de) 1966-09-22
DE1112722B (de) 1961-08-17
GB1042391A (en) 1966-09-14
BE694669A (US07816562-20101019-C00012.png) 1967-07-31
BE694671A (US07816562-20101019-C00012.png) 1967-07-31
DE1210425B (de) 1966-02-10
GB889639A (en) 1962-02-21
DE1210424B (de) 1966-02-10
GB1042392A (en) 1966-09-14
GB1042393A (en) 1966-09-14

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