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WO1999022045A1 - Electrode de bain electrolytique pour la production de fluor et bloc carbone isotrope utilise dans cette electrode - Google Patents

Electrode de bain electrolytique pour la production de fluor et bloc carbone isotrope utilise dans cette electrode Download PDF

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Publication number
WO1999022045A1
WO1999022045A1 PCT/JP1998/004859 JP9804859W WO9922045A1 WO 1999022045 A1 WO1999022045 A1 WO 1999022045A1 JP 9804859 W JP9804859 W JP 9804859W WO 9922045 A1 WO9922045 A1 WO 9922045A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
electrolytic bath
fluorine
anode
carbonaceous material
Prior art date
Application number
PCT/JP1998/004859
Other languages
English (en)
Japanese (ja)
Inventor
Tetsuro Tojo
Jiro Hiraiwa
Nobuatsu Watanabe
Masahide Sangawa
Original Assignee
Toyo Tanso Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Tanso Co., Ltd. filed Critical Toyo Tanso Co., Ltd.
Publication of WO1999022045A1 publication Critical patent/WO1999022045A1/fr

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Classifications

    • 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
    • C25B1/245—Fluorine; 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
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene

Definitions

  • the anode of the electrolytic bath for fluorine generation which is inexpensive, has a longer life, and has excellent electrode characteristics, is significantly reduced by greatly reducing the costs required for machining and the former stage of molding and improving the ability to suppress the anode effect.
  • An isotropic carbonaceous block can be provided.
  • the inventors of the present invention first pointed out that the problem remaining in the previously developed isotropic carbonaceous block, that is, the problem that the cost required for molding and In order to find a solution near the limit, we believe that the mechanical strength of the block can be solved if it can be positively weakened to the point where self-damage can be avoided and good electrode characteristics can be maintained. Various experimental studies were repeated.
  • the reaction between fluorine generated on the anode made of a carbonaceous electrode and the carbon electrode during electrolysis generates fluorinated graphite having extremely low surface energy.
  • the wettability between the anode and the bath becomes poor, and the portion becomes electrochemically inactive.
  • the effective area of the anode decreases with increasing coverage of the anode surface with fluorinated graphite, and the current density increases. This is the main cause of anode overvoltage in fluorine electrolysis.
  • the coverage of graphite fluoride exceeds about 20 ° / 0 , the voltage rises sharply and power cannot be supplied. This phenomenon is the anodic effect.
  • the heat treatment temperature is usually from 1000 ° C to 1500 ° C, preferably from 1000 ° C to 1200 ° C.
  • the isotropic carbonaceous block obtained in this way has a characteristic structure that is much more dense but moderately porous compared to the carbon material blocked by so-called extrusion molding. Has become.
  • the raw material such as altered pitch @ mesocarbon microbeads, should be a monolithic material with a nearly spherical
  • the anisotropy of the specific resistance in the vertical and horizontal directions can be equal to or less than 1.2 even in mold molding.
  • the average pore radius is 0.5 / im or more
  • the cumulative pore volume is 80 mm 3 / g or more
  • the gas permeability is 0.1 cm 2 / s
  • Such an isotropic carbon block prevents bubbles of fluorine gas generated on the electrode surface while preventing the electrolytic bath from penetrating into the electrode, and has a high current density as a fluorine electrolysis electrode. It can be used more stably up to electrolysis conditions.
  • 5 in the figure is a bus bar
  • 6 is an insulating material
  • 7 is an electrolytic cell lid made of metal
  • 8 is a cathode gas outlet
  • 9 is an anode gas outlet
  • 10 is a bolt for mounting the anode 2
  • 11 indicates a holding plate
  • 12 indicates a metal-coated surface.
  • the anode 2 made of a carbonaceous block is an L-shaped bus bar 5 made of metal.
  • a holding plate 11 and a supporting member such as a bolt 10 which can be electrically connected to the apparatus main body.
  • the obtained raw material was molded by four methods using both the CIP molding and the die molding while changing the pressure so as to obtain a product having dimensions of 340 XI 70 X thickness 70 (mm).
  • the carbonaceous block for the anode as a sample was fired by firing nine types (for Experimental Examples 1 to 4, for Experimental Examples 5 to 8 and for Experimental Example 9) at 100 ° C.
  • the test pieces were prepared, and five test pieces each of 10 ⁇ 10 ⁇ 10 mm and 10 ⁇ 10 ⁇ 60 mm were prepared, and each physical property was measured.
  • the flexural strength is 10 X 10 X 60 mm for the test piece (however, the dimensional tolerance is 10 ⁇ 0.02, 5 ⁇ 0.02, 60 ⁇ 0.1), between the fulcrums
  • the distance shall be 40 mm and measured with a universal material testing machine.
  • the radius of curvature of the fulcrum at the fulcrum is 1.5 mm
  • the angle of the press wedge is 60 °
  • the radius of curvature at the tip is 3 mm.
  • Place the test piece horizontally on the abutment apply a vertical load at the uniform speed in the center of the test piece, and measure the maximum load when the test piece breaks. Read on.
  • the bending strength of the test piece is calculated by the following formula and rounded to one decimal place.
  • PB pressure of second chamber 135 at time
  • VB volume of second chamber 135 (cm 3 )
  • samples 8 carbonaceous blocks of (bulk density in molding pressure 900 k gZcm 2 is 1. e gZcin 3, the bending strength 1 129 kgf Zcm 2)
  • a critical current density of about 1 OAZdm 2 when using a carbon material by conventional extrusion molding for the anode is obtained, and the lower the molding pressure becomes, the lower the bulk density and bending strength become. It can be seen that the current density has increased and the ability to suppress the anodic effect has increased.
  • the bulk density molding pressure was obtained at 1 00 kg / cm 2 1. 33 g / cm 3, in the case of bending strength 334 kgf / cm 2 Sample 5, until the current density up to 40 A / dm 2 Even when the voltage was applied, no anodic effect occurred during electrolysis.
  • the carbonaceous Proc the properties l OO e OO k gZcm 2 about, preferably forming is carried out in conditions of a 100 to 300k g cm 2 about a relatively low pressure. Therefore, not only can a small-scale CIP molding apparatus be used, but also a general-purpose mold molding apparatus can be used, so that the molding cost can be reduced as compared with the case where the conventional large-scale CIP apparatus needs to be used. The number of birds can be reduced.
  • the electrode of the electrolytic bath for generating fluorine of the present invention and the isotropic carbonaceous block used for the electrode are constituted as described above, and are inexpensive but exhibit excellent electrode characteristics while exhibiting excellent electrode characteristics. Are suitable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

L'invention se rapporte à un bloc carboné destiné à une électrode positive, qui, bien que peu coûteux, possède une longue durée de vie et d'excellentes caractéristiques d'électrode. L'invention concerne également une électrode comportant un tel bloc carboné. Ce bloc carboné isotrope est utilisé en tant qu'électrode positive dans un bain électrolytique contenant un sel fondu à base de fluorure d'hydrogène et permettant la production de fluor. Ce bloc carboné isotrope possède une masse volumique apparente inférieure à 1,6 g/cm3, une résistance à la flexion supérieure à 200 kgf/cm2, un rayon moyen de porosité supérieur à 0,5 νm, un volume cumulé de porosité supérieur à 80 mm3/g et une perméabilité aux gaz supérieure à 0,1 cm2/s.
PCT/JP1998/004859 1997-10-28 1998-10-27 Electrode de bain electrolytique pour la production de fluor et bloc carbone isotrope utilise dans cette electrode WO1999022045A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP9/295463 1997-10-28
JP29546397 1997-10-28

Publications (1)

Publication Number Publication Date
WO1999022045A1 true WO1999022045A1 (fr) 1999-05-06

Family

ID=17820923

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/004859 WO1999022045A1 (fr) 1997-10-28 1998-10-27 Electrode de bain electrolytique pour la production de fluor et bloc carbone isotrope utilise dans cette electrode

Country Status (1)

Country Link
WO (1) WO1999022045A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6428569B1 (en) 1999-11-09 2002-08-06 Scimed Life Systems Inc. Micro structure stent configurations
JP2006170298A (ja) * 2004-12-15 2006-06-29 Aisin Chem Co Ltd クラッチフェーシング
US7226475B2 (en) 1999-11-09 2007-06-05 Boston Scientific Scimed, Inc. Stent with variable properties

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60221591A (ja) * 1984-04-17 1985-11-06 Central Glass Co Ltd フツ素の製造方法
JPH0132162B2 (fr) * 1984-11-16 1989-06-29 Kogyo Gijutsu Incho
JPH0353090A (ja) * 1989-07-18 1991-03-07 Asahi Glass Co Ltd フッ素の製造方法
JPH055194A (ja) * 1990-02-06 1993-01-14 Toyo Tanso Kk 炭素電極ならびにそれを用いるｈｆ含有溶融塩の電解方法及び装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60221591A (ja) * 1984-04-17 1985-11-06 Central Glass Co Ltd フツ素の製造方法
JPH0132162B2 (fr) * 1984-11-16 1989-06-29 Kogyo Gijutsu Incho
JPH0353090A (ja) * 1989-07-18 1991-03-07 Asahi Glass Co Ltd フッ素の製造方法
JPH055194A (ja) * 1990-02-06 1993-01-14 Toyo Tanso Kk 炭素電極ならびにそれを用いるｈｆ含有溶融塩の電解方法及び装置

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6428569B1 (en) 1999-11-09 2002-08-06 Scimed Life Systems Inc. Micro structure stent configurations
US7226475B2 (en) 1999-11-09 2007-06-05 Boston Scientific Scimed, Inc. Stent with variable properties
US7879082B2 (en) 1999-11-09 2011-02-01 Boston Scientific Scimed, Inc. Micro structure stent configurations
JP2006170298A (ja) * 2004-12-15 2006-06-29 Aisin Chem Co Ltd クラッチフェーシング

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