EP1061158B1 - Parallel Betrieb von Amalgamelektrolyseuren und Membranelektrolyseuren - Google Patents

Parallel Betrieb von Amalgamelektrolyseuren und Membranelektrolyseuren Download PDF

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Publication number
EP1061158B1
EP1061158B1 EP00111000A EP00111000A EP1061158B1 EP 1061158 B1 EP1061158 B1 EP 1061158B1 EP 00111000 A EP00111000 A EP 00111000A EP 00111000 A EP00111000 A EP 00111000A EP 1061158 B1 EP1061158 B1 EP 1061158B1
Authority
EP
European Patent Office
Prior art keywords
brine
electrolysis
amalgam
station
stream
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
EP00111000A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1061158A2 (de
EP1061158A3 (de
Inventor
Fritz Dr. Gestermann
Hans-Dieter Pinter
Helmut Ziegler
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1061158A2 publication Critical patent/EP1061158A2/de
Publication of EP1061158A3 publication Critical patent/EP1061158A3/de
Application granted granted Critical
Publication of EP1061158B1 publication Critical patent/EP1061158B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/36Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in mercury cathode cells
    • C25B1/42Decomposition of amalgams
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/34Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/02Process control or regulation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the invention relates to a method for the parallel operation of amalgam electrolyzers and membrane electrolysers with a common brine circuit below Use of an oxygen consumption cathode resistant to mercury in the Membrane electrolyzer.
  • the oxygen consumable cathode for use in NaCl electrolysis is from the literature basically known. For their operation e.g. in a pressure-compensated arrangement, as described in DE 19622744 Cl, brine is of the usual membrane cell quality used. This brine is mercury-free to protect the cathode activation held.
  • the mercury contamination for chloralkali electrolysis using the amalgam process known NaCl brine is typically from about 10 mg / l to 400 mg / l in normal operation or as a peak value after the system has come to a standstill.
  • Another aspect is the gradual changeover from amalgam electrolysis on membrane processes play an important role: if the energetically less favorable, Mercury-resistant cathode activation during the parallel operation of amalgam and membrane processes should be used, with the aim of being more complete Conversion to the optimal cathode activation, which is sensitive to mercury the entire brine and alkali cycle must be completely changed mercury-free, which causes enormous problems, especially in the Alkaline cycle that mercury can be partially in metallic form.
  • the task is therefore to provide an electrolysis process in which an amalgam electrolysis and a Membrane electrolysis, preferably using an oxygen consumable cathode, can be operated in parallel with the same brine circuit.
  • the procedure is said to Have advantages of known methods with oxygen consumption cathodes.
  • the object is achieved through the use of oxygen consumption cathodes solved in a membrane electrolysis process that against the effects of Mercury are resistant.
  • the task is also accomplished through the use of a Ca / Mg ion exchanger dissolved, the Ca / Mg content even with mercury Brine lowers to ⁇ 20 ppb, which is necessary to ensure the full life of the membranes to ensure.
  • the catalyst matrix is sintered or pressed with the support.
  • the carbon components (soot) can also be dispensed with if the catalyst density and / or the rendered hydrophobic support are set such that the majority of the catalyst particles are also contacted electrically.
  • the carbon soot can be omitted from the oxygen depletion cathode so that the electrode matrix consists only of Teflon and silver, whereby the silver takes on the function of the catalyst as well as that of electron conduction and accordingly such a high Ag loading is necessary that the particles separate touch and form conductive bridges with each other.
  • the wire mesh, a fine expanded metal as known from battery technology, as also a felt made of silver, silver-plated nickel or silver-plated alkali-resistant material, e.g. Inconnel steel. It is essential that the silver catalyst is stable behaves towards mercury.
  • sulfate content at ⁇ 5 g / l is achieved by appropriate operation, for example continuous or discontinuous discharge of the sulfate by means of precipitation or partial flow precipitation, for example with addition of CaCO 3 , BaCl 2 or BaCO 3 , or in particular in the case of very low-sulfate salts, can be adjusted by discharging a partial stream of the depleted brine.
  • Another possibility is the nanofiltration of the brine or a partial flow of the brine by means of ion-selective membranes in the feed upstream of the membrane electrolyser, or another separation process, for example by means of ion exchangers. It is important that only the partial flow to the membrane electrolyzer has to be set to the sulfate ion concentration mentioned, with the side effect that the main flow also gradually adjusts to a lower content in the circuit.
  • the SiO 2 content in the NaCl brine can easily be kept at ⁇ 5 ppm by avoiding free concrete areas in the salt store (brine bunker).
  • Peak mercury levels with a concentration of up to 400 mg Hg / l in the brine are from the oxygen consumption cathode operated behind the membrane in the sodium hydroxide solution survived easily.
  • the usual concentration of 150-200 mg / l mercury at normal peaks and ⁇ 10 mg / l mercury in normal operation is for the operation of the oxygen consumption cathode no barrier.

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)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Secondary Cells (AREA)
EP00111000A 1999-06-12 2000-05-30 Parallel Betrieb von Amalgamelektrolyseuren und Membranelektrolyseuren Expired - Lifetime EP1061158B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19926887A DE19926887A1 (de) 1999-06-12 1999-06-12 Elektrolyseverfahren
DE19926887 1999-06-12

Publications (3)

Publication Number Publication Date
EP1061158A2 EP1061158A2 (de) 2000-12-20
EP1061158A3 EP1061158A3 (de) 2000-12-27
EP1061158B1 true EP1061158B1 (de) 2004-04-14

Family

ID=7911060

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00111000A Expired - Lifetime EP1061158B1 (de) 1999-06-12 2000-05-30 Parallel Betrieb von Amalgamelektrolyseuren und Membranelektrolyseuren

Country Status (14)

Country Link
US (1) US6224740B1 (ko)
EP (1) EP1061158B1 (ko)
JP (1) JP2001029956A (ko)
KR (1) KR20010049521A (ko)
CN (1) CN1277269A (ko)
AT (1) ATE264412T1 (ko)
BR (1) BR0002624A (ko)
CA (1) CA2311042A1 (ko)
DE (2) DE19926887A1 (ko)
ES (1) ES2219223T3 (ko)
NO (1) NO20002992L (ko)
SG (1) SG87894A1 (ko)
TW (1) TW539774B (ko)
ZA (1) ZA200002914B (ko)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106216360A (zh) * 2016-08-16 2016-12-14 南京格洛特环境工程股份有限公司 一种副产品盐的精制及资源化利用方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10149779A1 (de) 2001-10-09 2003-04-10 Bayer Ag Verfahren zur Rückführung von Prozessgas in elektrochemischen Prozessen
CA2543958C (en) * 2003-10-31 2012-04-10 Metal Alloy Reclaimers, Inc Ii Process for reduction of inorganic contaminants from waste streams
EP1640060A1 (en) 2004-09-22 2006-03-29 3M Espe Ag Mixer for multi-component pastes, kit, and method of mixing paste components
EP1802385B1 (en) * 2004-09-22 2008-01-23 3M Espe AG Mixer for multi-component pastes, kit, and method of mixing paste components
JP2008223115A (ja) * 2007-03-15 2008-09-25 Asahi Kasei Chemicals Corp 塩水の処理方法
US8569205B2 (en) * 2009-07-06 2013-10-29 MAR Systems, Inc. Media for removal of contaminants from fluid streams and method of making same

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3037818C2 (de) * 1980-10-07 1985-08-14 Hoechst Ag, 6230 Frankfurt Verfahren zur Herstellung von Natriumbisulfat
DE3543379A1 (de) * 1985-12-07 1987-06-11 Metallgesellschaft Ag Verfahren zur elektrolytischen herstellung von alkalimetallhydroxid, chlor und wasserstoff
US5028302A (en) * 1989-11-16 1991-07-02 Texas Brine Corporation Purification of chlor-alkali membrane cell brine
JPH08283978A (ja) * 1995-04-10 1996-10-29 Permelec Electrode Ltd ガス拡散電極の製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106216360A (zh) * 2016-08-16 2016-12-14 南京格洛特环境工程股份有限公司 一种副产品盐的精制及资源化利用方法

Also Published As

Publication number Publication date
SG87894A1 (en) 2002-04-16
ES2219223T3 (es) 2004-12-01
JP2001029956A (ja) 2001-02-06
DE50006039D1 (de) 2004-05-19
CN1277269A (zh) 2000-12-20
BR0002624A (pt) 2001-01-02
KR20010049521A (ko) 2001-06-15
NO20002992D0 (no) 2000-06-09
ATE264412T1 (de) 2004-04-15
CA2311042A1 (en) 2000-12-12
EP1061158A2 (de) 2000-12-20
ZA200002914B (en) 2000-12-12
US6224740B1 (en) 2001-05-01
EP1061158A3 (de) 2000-12-27
TW539774B (en) 2003-07-01
NO20002992L (no) 2000-12-13
DE19926887A1 (de) 2000-12-14

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