EP0150018B1 - Verfahren zum Elektrolysieren von flüssigen Elektrolyten - Google Patents

Verfahren zum Elektrolysieren von flüssigen Elektrolyten Download PDF

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Publication number
EP0150018B1
EP0150018B1 EP85100185A EP85100185A EP0150018B1 EP 0150018 B1 EP0150018 B1 EP 0150018B1 EP 85100185 A EP85100185 A EP 85100185A EP 85100185 A EP85100185 A EP 85100185A EP 0150018 B1 EP0150018 B1 EP 0150018B1
Authority
EP
European Patent Office
Prior art keywords
electrolyte
electrode
flow
electrodes
gas
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
Application number
EP85100185A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0150018A1 (de
Inventor
Karl-Heinz Dr. Tetzlaff
Dieter Dr. Schmid
Jürgen Dr. Russow
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.)
ThyssenKrupp Industrial Solutions AG
Original Assignee
Hoechst AG
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Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to AT85100185T priority Critical patent/ATE45191T1/de
Publication of EP0150018A1 publication Critical patent/EP0150018A1/de
Application granted granted Critical
Publication of EP0150018B1 publication Critical patent/EP0150018B1/de
Expired legal-status Critical Current

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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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • 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
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

Definitions

  • the invention relates to a method for the electrolysis of liquid electrolytes with gas bubbles in the electrolyte in undivided or divided by at least one partition electrolysis cells, in which at least one electrode is broken.
  • the two-phase flow affects not only the electrochemical conditions, but also the strength and service life of the components.
  • the object of the invention is to eliminate the hydrostatic and hydrodynamic effects, to reduce the influence of the height on the gas bubble content of the electrolyte and to reduce the space behind the electrode.
  • a method is therefore proposed in which at least one perforated electrode is used and which is characterized in that the electrolyte is allowed to flow through the electrolysis cell using gravity in such a way that a gas space is formed to the side of the main flow direction of the electrolyte and the gas space formed in the electrolyte Gas bubbles are released into these.
  • the electrolyte is allowed to flow in such a way that both electrodes, the perforated electrode and a partition, or the partition walls are wetted.
  • the electrolyte can also be partially deflected in a meandering manner.
  • a perforated electrode is to be understood as an electrode which has openings which are larger than the diameter of the resulting gas bubbles, so that the openings cannot be blocked by individual gas bubbles.
  • Suitable electrodes are, for example, perforated sheets, expanded metals, wire mesh, electrodes made from individual rods or sheet strips, so-called spaghetti electrodes. Electrodes with recesses in which the gas can be drawn off are also suitable.
  • the perforated structure of the electrodes can also be designed such that the electrolyte flowing down is accumulated several times.
  • the electrodes can also be made of porous material.
  • Electrodes with a closed or openwork structure can be used as the counter electrode. Gas diffusion electrodes are also suitable. Diaphragms or ion exchange membranes can be used as partitions. The partitions can be constructed in several layers. The electrolysis cells can also be divided into several chambers by partitions.
  • both sides can be operated according to the proposed method, or only one side, the other side being able to be operated according to the prior art.
  • the electrodes can be flat or curved.
  • the electrodes should be closer to the counter electrode or to the partition have or ran more or less completely on the partition. You can also be mechanically connected to this.
  • Known spacers can be used to fix the distance between the electrode and counterelectrode or electrode and partition. A too large distance from the counter electrode or the partition would lead to an unnecessarily large electrolyte throughput, because an ion-conducting connection of the electrode and counter electrode or electrode and partition must of course be achieved. All or part of the electrolyte may flow on the back of the electrode. The resulting gas bubbles release their gas content in the gas space adjacent to the main flow direction by bursting at the phase boundary. In the case of plate-shaped electrodes, this is the rear space behind the electrode.
  • electrolyte droplets which may be entrained when the bubbles burst open can be returned to the electrode again, for example, by obliquely arranged metal sheets which can also serve to supply the current. Electrolyte and gas can be removed individually as they are largely separated. The electrolyte should run across the entire width of the electrode. The facilities required for this, such as distribution channels, are known per se.
  • the electrolyte can also flow between the partitions, and in special cases also within the partitions.
  • a diaphragm can be arranged between the two. Ion exchange membrane, diaphragm and electrode can lie close together. If the electrolyte throughput is greater, however, it may be expedient to leave a gap between the ion exchange membrane and the diaphragm in which the electrolyte can flow. The electrolyte thus remains largely free of bubbles.
  • electrolysis cells with several chambers, such as for example in the electrodialysis of sea water, in which cation and anion exchange membranes are arranged alternately, the electrolyte can also flow between these partition walls.
  • spacers or electrodes can also ensure that the electrolyte flows down in several channels.
  • electrodes and partition walls must be arranged in such a way that a certain slope, characterized by the angle ⁇ , is created with respect to the horizontal.
  • the angle a must be greater than 0 and less than 180 °.
  • An a greater than 90 ° should mean that the electrolyte flows at the bottom of the broken electrode.
  • the ion-conducting connection to the counterelectrode or to the partition must then be secured by capillary forces. This means that hydrophilic surfaces must be present. If a gap is desired between the electrode and the partition, it must be small. The permissible electrolyte throughput is also limited in this case.
  • an angle ⁇ between 0 and 90 °.
  • an angle ⁇ of about 90 ° is to be preferred, especially if the electrolytic cell is to be operated on the anode and cathode side using the method according to the invention.
  • the method according to the invention can be used in divided and undivided electrolysis cells.
  • the proposed method is also suitable for secondary reactions within the electrolytic cell, for example for the production of propylene oxide from propylene via the halogen intermediate known per se.
  • Fig. 1 two perforated electrodes 3 and 4 are shown, which are fixed by disc-shaped spacers 5. Nets and threads are also suitable as spacers 5.
  • the electrolyte 1 is applied to the upper edge of the electrodes and flows downward, with both electrodes being wetted. Part of the electrolyte 1 can also flow down the back of the electrodes 3 and 4.
  • FIGS. 2 and 3 largely correspond to FIG. 1.
  • the electrode 4 has a closed structure.
  • the electrode 4 consists of a gas diffusion electrode.
  • Fig. 4 shows an arrangement divided by a partition 6. Electrolyte 1a and 1b therefore flows in separate rooms, one electrode and the partition 6 each being wetted.
  • the spacing of the components 3, 4 and 6 can be fixed by means of spacers similar to FIG. 1. 5, the electrodes 3 and 4 lie directly on the partition 6. In this case one speaks of the zero distance.
  • the electrode 3 is shown here as a wire mesh.
  • the largely flowing on the back of the electrodes electrolyte 1a and 1 is constantly mixed due to the broken structure of the electrodes 3 and 4 and conveys the resulting gas bubbles to the boundary of the gas space.
  • the electrode 3 is mechanically connected directly to the partition.
  • the electrolyte 1b flows here completely on the back of the electrode 3.
  • FIG. 7 shows an arrangement with two partition walls 6 and 2.
  • the electrolyte 1b preferably flows between the partition walls 6 and 2, which can expediently be fixed by means of spacers similar to FIG. 1. It should be noted here that the free amount of electrolyte is determined by the geometry and the material properties. This fact has to be taken into account, for example, by creating overflows at the electrolyte application point.
  • the electrolyte 1b is in contact with the electrode 3 through the partition 2 designed as a diaphragm. The mass transfer takes place largely through diffusion.
  • the gas bubbles arise at the point of contact of the electrode 3 with the electrolyte-filled diaphragm 2 and can release their gas content to the gas space adjoining on the side.
  • Fig. 8 shows an arrangement with partition 6, which is designed so that the electrolyte 1 flows at least partially through the partition 6.
  • the electrodes 3 and 4 rest on the partition 6.
  • the arrangement is before, preferably suitable for low electrolyte requirements, such as in water electrolysis.
  • Fig. 9 shows an arrangement for a divided electrolytic cell, in which the electrolyte 1a and 1b is at least partially jammed several times.
  • the electrode 3 consists of sheet metal strips which are arranged in a region so close to the partition 6 that a throttle point is created. This forces some of the electrolyte to flow over the top edge of the sheet metal strips. A similar effect is achieved by the horizontally arranged wires from which the electrode 4 is constructed. The effect of the throttle point can be adjusted by the spacer 5.
  • FIG. 10 and 11 show an electrode in which the openings are not led through to the rear.
  • Fig. 10 shows a vertical section
  • Fig. 11 shows a horizontal section of the same arrangement.
  • the electrolyte 1b flows downwards in channels, wetting the partition 6 and part of the electrode 3.
  • the partial wetting can be achieved in that the regions of the electrode 3 adjoining the partition 6 are made hydrophilic and the more distant regions are hydrophobic.
  • Another possibility is to operate the arrangement with an angle a ⁇ 90 °.
  • the gas space adjoining the main flow direction of the electrolyte is enclosed here by the electrode 3 itself.
  • This type of electrode can also serve as a bipolar partition.
  • Fig. 12 shows a horizontal section of an arrangement in which the electrolyte 1b also flows down channels.
  • the electrode 3 is made of wires here. As shown, the electrode 3 can be partially wetted or even completely.
  • the electrode 3 consists of porous material and is arranged next to one another in strips. The individual strips leave gaps through which the gas bubbles can release their gas content into the gas space adjacent to the side. Part of the gas formed can pass through the pores the electrode 3 get into this gas space.
  • FIG. 14 shows an undivided arrangement in which the electrodes 3 and 4 made up of many wires are inserted into one another like a comb.
  • the electrode and counter electrode are therefore not next to each other but one below the other.
  • the anode is marked with "+” and the cathode with "-”.
  • the electrolyte 1 flows across the wires.
  • the electrolyte 1 can also be made to flow parallel to the wires.
  • Fig. 15 differs from Fig. 14 only in that a different profile is shown instead of the wires.
  • FIG. 16 shows an arrangement of electrode 3 and counterelectrode 4 divided by a partition 6, in which the individual wires of the electrodes are likewise inserted into one another like a comb.
  • the flow direction of the electrolytes 1a and 1b can also be parallel to the wires.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Fuel Cell (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)
EP85100185A 1984-01-19 1985-01-10 Verfahren zum Elektrolysieren von flüssigen Elektrolyten Expired EP0150018B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85100185T ATE45191T1 (de) 1984-01-19 1985-01-10 Verfahren zum elektrolysieren von fluessigen elektrolyten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843401637 DE3401637A1 (de) 1984-01-19 1984-01-19 Verfahren zum elektrolysieren von fluessigen elektrolyten
DE3401637 1984-01-19

Publications (2)

Publication Number Publication Date
EP0150018A1 EP0150018A1 (de) 1985-07-31
EP0150018B1 true EP0150018B1 (de) 1989-08-02

Family

ID=6225281

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85100185A Expired EP0150018B1 (de) 1984-01-19 1985-01-10 Verfahren zum Elektrolysieren von flüssigen Elektrolyten

Country Status (9)

Country Link
US (1) US4627897A (enrdf_load_stackoverflow)
EP (1) EP0150018B1 (enrdf_load_stackoverflow)
JP (1) JPS60159186A (enrdf_load_stackoverflow)
AT (1) ATE45191T1 (enrdf_load_stackoverflow)
CA (1) CA1289506C (enrdf_load_stackoverflow)
DE (2) DE3401637A1 (enrdf_load_stackoverflow)
IN (1) IN163785B (enrdf_load_stackoverflow)
NO (1) NO167470C (enrdf_load_stackoverflow)
ZA (1) ZA85416B (enrdf_load_stackoverflow)

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US4767511A (en) * 1987-03-18 1988-08-30 Aragon Pedro J Chlorination and pH control system
US4875988A (en) * 1988-08-05 1989-10-24 Aragon Pedro J Electrolytic cell
DE4120679C2 (de) * 1991-06-22 1995-11-09 Grimma Masch Anlagen Gmbh Elektrolyseverfahren und Elektrolysezelle für gasentwickelnde oder gasverbrauchende elektrolytische Prozesse
SE505714C2 (sv) * 1991-09-19 1997-09-29 Permascand Ab Elektrod med kanalbildande trådar, sätt att tillverka elektroden, elektrolyscell försedd med elektroden samt sätt vid elektrolys
US5348664A (en) * 1992-10-28 1994-09-20 Stranco, Inc. Process for disinfecting water by controlling oxidation/reduction potential
DE4306889C1 (de) * 1993-03-05 1994-08-18 Heraeus Elektrochemie Elektrodenanordnung für gasbildende elektrolytische Prozesse in Membran-Zellen und deren Verwendung
NO931689L (no) * 1993-05-10 1994-11-11 Sigurd Fongen Anordning for elektrokjemisk syntese for "in-line" og "off-line" bleking, oksidasjon og desinfeksjon av organiske stoffer i væsker.
DE69602383T2 (de) * 1995-01-30 1999-09-16 First Ocean Co., Ltd. Vorrichtung einer zusammengesetzten Elektrode für die Elektrolyse von Wasser
US5626327A (en) * 1995-04-27 1997-05-06 Borg-Warner Automotive, Inc. Solenoid-driven valve having a roller bearing
WO2000062828A1 (en) * 1996-04-30 2000-10-26 Medtronic, Inc. Autologous fibrin sealant and method for making the same
CA2349508C (en) 2001-06-04 2004-06-29 Global Tech Environmental Products Inc. Electrolysis cell and internal combustion engine kit comprising the same
DE10234806A1 (de) * 2002-07-31 2004-02-19 Bayer Ag Elektrochemische Zelle
US7390399B2 (en) * 2004-12-21 2008-06-24 Siemens Water Technologies Holding Corp. Water treatment control systems and methods of use
US20060169646A1 (en) * 2005-02-03 2006-08-03 Usfilter Corporation Method and system for treating water
US7905245B2 (en) * 2005-09-30 2011-03-15 Siemens Water Technologies Corp. Dosing control system and method
DE102010021833A1 (de) * 2010-05-28 2011-12-01 Uhde Gmbh Elektrode für Elektrolysezelle
US8882972B2 (en) 2011-07-19 2014-11-11 Ecolab Usa Inc Support of ion exchange membranes
US8562810B2 (en) 2011-07-26 2013-10-22 Ecolab Usa Inc. On site generation of alkalinity boost for ware washing applications
DE102012204040A1 (de) * 2012-03-15 2013-09-19 Bayer Materialscience Aktiengesellschaft Verfahren zur Elektrolyse von Alkalichloriden mit Sauerstoffverzehrelektroden
WO2014001964A2 (en) 2012-06-27 2014-01-03 Koninklijke Philips N.V. An apparatus and a method of generating bubbles and foams
US9222178B2 (en) 2013-01-22 2015-12-29 GTA, Inc. Electrolyzer
US8808512B2 (en) * 2013-01-22 2014-08-19 GTA, Inc. Electrolyzer apparatus and method of making it
JP6187861B2 (ja) * 2013-07-11 2017-08-30 パナソニックＩｐマネジメント株式会社 電解電極デバイスおよび当該電解電極デバイスを備える電解水生成装置
DE102015111103A1 (de) 2014-07-23 2016-01-28 Innovatec Gerätetechnik Gmbh Elektrolysezelle und Verfahren zum Betreiben einer Elektrolysezelle
JP6371854B2 (ja) * 2014-09-29 2018-08-08 富士フイルム株式会社 人工光合成モジュール
US10844494B2 (en) 2015-09-18 2020-11-24 The Trustees Of Columbia University In The City Of New York Membraneless electrochemical flow-through reactor

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Also Published As

Publication number Publication date
IN163785B (enrdf_load_stackoverflow) 1988-11-12
JPS60159186A (ja) 1985-08-20
CA1289506C (en) 1991-09-24
NO850236L (no) 1985-07-22
US4627897A (en) 1986-12-09
EP0150018A1 (de) 1985-07-31
DE3572012D1 (en) 1989-09-07
NO167470C (no) 1991-11-06
DE3401637A1 (de) 1985-07-25
ATE45191T1 (de) 1989-08-15
ZA85416B (en) 1985-09-25
NO167470B (no) 1991-07-29

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