EP0579910A1 - Dispositif pour le traitement électrolytique de liquides dans un compartiment anodique et cathodique - Google Patents

Dispositif pour le traitement électrolytique de liquides dans un compartiment anodique et cathodique Download PDF

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Publication number
EP0579910A1
EP0579910A1 EP93107034A EP93107034A EP0579910A1 EP 0579910 A1 EP0579910 A1 EP 0579910A1 EP 93107034 A EP93107034 A EP 93107034A EP 93107034 A EP93107034 A EP 93107034A EP 0579910 A1 EP0579910 A1 EP 0579910A1
Authority
EP
European Patent Office
Prior art keywords
chamber
separating
partition plate
membrane
plate
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.)
Granted
Application number
EP93107034A
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German (de)
English (en)
Other versions
EP0579910B1 (fr
Inventor
Karl-Heinz Dulle
Benno Dr. Lüke
Jochen Prasser
Wolfgang Dr. Strewe
Joachim Dr. Schulze
Martin Wollny
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
Uhde GmbH
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 Uhde GmbH filed Critical Uhde GmbH
Publication of EP0579910A1 publication Critical patent/EP0579910A1/fr
Application granted granted Critical
Publication of EP0579910B1 publication Critical patent/EP0579910B1/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
    • 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

  • the invention is directed to a device for the electrolytic treatment of liquids, of the type specified in the preamble of claim 1.
  • Such a metal electrolysis cell is known for example from the applicant's EP-0 095 039.
  • Such membrane cells have great advantages over other cell designs. They are used in particular for the production of chlorine, sodium hydroxide solution and hydrogen, and they have advantages over conventional mercury and diaphragm cells in both ecological and energy terms. In the standard fields of application, such cells are also used for the electrolytic cleaning or regeneration of waste water, thin acids and the like.
  • the membranes effectively separate the anodic NaCl solution from the cathodic NaOH solution and separate the gaseous products chlorine and hydrogen.
  • they have the special task of controlling the electrolysis process in such a way that only cations can pass through the membranes, while the passage of the anions is almost completely prevented becomes. This ensures that the hydroxyl ions of the NaOH solution which are pushing in the direction of the anode are largely retained by the membrane and cannot be discharged at the anode with the formation of oxygen and other by-products.
  • Modern ion exchange membranes have a current efficiency of 95-98% related to NaOH production, ie only a few percent of the hydroxyl ions can pass through the membrane with the formation of about 1.5-2% oxygen in chlorine gas.
  • the electrolyte For the electrolysis process to function properly inside the electrode chambers, the electrolyte must be distributed as evenly as possible over the entire height and width of the chamber, i.e. the best possible mixing of the liquids in the chambers is desirable. This fluid mixing is particularly important in the anolyte chambers of the chlor-alkali cells, since the ion exchange membranes only work optimally in a relatively narrow range of chloride concentration, temperature and pH.
  • the electrolysis cell is operated in such a way that the inlet concentration of the anolyte of chloride is 300 g / l and the outlet concentration is approximately 200 g / l, it cannot be ruled out that stagnation of the anolyte in regions of the anode chamber where the flow is unfavorable chloride depletion to well below 200 g / l can occur, which would lead to local membrane damage in a short time.
  • the anolyte is strongly acidified to reduce the oxygen content in the chlorine gas before entering the anolyte chambers by adding hydrochloric acid to pH values of 1 and below.
  • the membranes only have sufficient chemical resistance at pH values above about 1.5 to 2, it is imperative to mix the anolyte so well immediately after entering the anolyte chamber that the electrolysis effect, in particular by reaction with the If the membrane contains hydroxyl ions in the anolyte, the pH value above 1.5 is also secured in the inlet area of the anolyte chamber.
  • the average flow rate in the anolyte chamber in the horizontal direction is very low at a few centimeters per minute. In the vertical direction, however, it is larger, especially in the upper chamber area, due to the buoyancy of the chlorine gas. As a result, a certain natural liquid mixing occurs in the vertical direction in the anolyte chamber, the intensity of which essentially depends on the amount of chlorine gas produced, ie on the cell load. The natural mixing is in the horizontal direction in the lower chamber area on the other hand, very small and the worse the wider the cell, the worse.
  • DE-30 17 006-C2 serves to improve the gas bubble extraction in mercury cells with horizontal electrodes in order to prevent gas cushions between the electrodes. It can only be used with horizontally arranged electrodes.
  • An electrolyte cell without a separator is shown in DE-20 03 885-B2, while EP-0 121 608-A2 discloses a plate-shaped cathode without perforation and with a fine perforated counter anode for better current distribution and voltage gain.
  • the object of the invention is to provide a solution with which, without external aids, better liquid mixing in the respective electrolysis chambers of membrane electrolysis cells is achieved with as uniform a membrane loading as possible while avoiding foam formation in the membrane area, with a strongly acidified anolyte solution being able to be fed to the membrane cell as a starting material without the ion exchange membrane becoming ineffective prematurely.
  • this object is achieved in accordance with the invention in that at least one separating element with flow around the area is provided in each primary anode chamber and / or cathode chamber to form a defined mixing flow.
  • the invention makes use of the knowledge of using the gas bubbles formed on the electrodes as a kind of conveying aid, by preventing the gas bubbles from being distributed over the entire chamber space.
  • An upward flow is generated by the gas bubbles which only form on one side of the separating element in the region of the electrode. Since the separating element can be flushed around, there is a natural vertical circulation in the chambers.
  • the invention represents a significant improvement of the known ion exchange membrane cells, since it makes it possible to produce chlorine gas with a high concentration and low oxygen content without the aid of external pump devices and without adverse effects on the membrane behavior.
  • the object stated at the outset can be achieved in terms of the method according to the invention by using a method using the device described, such a method being characterized in that a natural soleplate is generated at least in the anode chamber via a separating element.
  • the device for electrolytic treatment of liquids shown in simplified form in FIG. 1 is generally designated 1 and is formed by an anode chamber 2 and a cathode chamber 3, which are separated from one another in the center by an ion exchange membrane 4.
  • inlet openings 5 for the supply of fresh electrolytes or fresh brine and upper outlet openings 6 for the removal of the respective electrolyte product.
  • Electrode plate 7 Shown in dashed lines on both sides of the ion exchange membrane 4 is an electrode plate 7 with the electrical ones Connections 8 and 9, which in turn are only indicated symbolically.
  • Essential to the invention is a separating plate, designated 10, in the anode and / or in the cathode chamber, only one separating plate being shown in FIG. 1.
  • a bubble formation is indicated by dots, the left half of the figure in FIG. 1 without the partition plate indicating the undisturbed distribution of the bubbles in the chamber 3, while a directional bubble formation in the electrolyte is indicated by the partition plate.
  • FIG. 2 shows the side view of a separating plate 10a, which is equipped with guide webs 12 that are essentially vertical, but inclined against the direction of gravity, the direction of inclination being different on the front and rear. It can be seen from such a configuration that there is a kind of helical flow around the separating plate, as indicated by the arrows, the rear separating webs are indicated by dashed lines and with 12 ' referred to and which causes the horizontal throughput of the electrolyte in the chamber.
  • FIGS. 3a and 3b Another embodiment is shown in FIGS. 3a and 3b, here the separating plate 10b is formed from individual segments which alternately have a lower underflow weir 13 and upper overflow weirs 14, the partial plates denoted by 10 ′ being able to be arranged in a zigzag shape, as can be seen from Fig. 3b.
  • FIG. 4 shows a further modified exemplary embodiment in the representation corresponding to FIG. 1.
  • An inflow weir 15 is provided in the area of the lower fresh brine supply 5c, which forces the fresh brine to first carry out the flow deflection indicated by the arrows 11c.

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)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
EP93107034A 1992-07-24 1993-04-30 Dispositif pour le traitement électrolytique de liquides dans un compartiment anodique et cathodique Expired - Lifetime EP0579910B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4224492A DE4224492C1 (de) 1992-07-24 1992-07-24 Vorrichtung zum elektrolytischen Behandeln von Flüssigkeiten mit einer Anoden- und einer Kathodenkammer sowie deren Verwendung
DE4224492 1992-07-24

Publications (2)

Publication Number Publication Date
EP0579910A1 true EP0579910A1 (fr) 1994-01-26
EP0579910B1 EP0579910B1 (fr) 1996-10-09

Family

ID=6464018

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93107034A Expired - Lifetime EP0579910B1 (fr) 1992-07-24 1993-04-30 Dispositif pour le traitement électrolytique de liquides dans un compartiment anodique et cathodique

Country Status (4)

Country Link
EP (1) EP0579910B1 (fr)
AT (1) ATE144006T1 (fr)
DE (2) DE4224492C1 (fr)
ES (1) ES2093311T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014402A1 (fr) * 1997-09-16 1999-03-25 Krupp Uhde Gmbh Appareil pour electrolyse
US6596136B1 (en) 1998-10-30 2003-07-22 Uhdenora Technologies S.R.L. Membrane electrolytic cell with active gas/liquid separation
DE102008007605A1 (de) 2008-02-04 2009-08-06 Uhde Gmbh Modifiziertes Nickel

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19607667C2 (de) * 1996-02-29 2000-11-02 Krupp Uhde Gmbh Verfahren zur Verwertung von Abfallsalzsäure
DE102017217361A1 (de) 2017-09-29 2019-04-04 Thyssenkrupp Uhde Chlorine Engineers Gmbh Elektrolysevorrichtung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH242830A (de) * 1946-12-13 1946-06-15 Oerlikon Maschf Bipolar-Elektrolyseur.
US4138295A (en) * 1976-12-23 1979-02-06 Diamond Shamrock Technologies S.A. Process and apparatus for downward recycling of the electrolyte in diaphragm cells

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA928245A (en) * 1969-01-30 1973-06-12 Ppg Industries, Inc. Electrolytic cell
IT1165047B (it) * 1979-05-03 1987-04-22 Oronzio De Nora Impianti Procedimento per migliorare il trasporto di materia ad un elettrodo e mezzi idrodinamici relativi
DE3219704A1 (de) * 1982-05-26 1983-12-01 Uhde Gmbh, 4600 Dortmund Membran-elektrolysezelle
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH242830A (de) * 1946-12-13 1946-06-15 Oerlikon Maschf Bipolar-Elektrolyseur.
US4138295A (en) * 1976-12-23 1979-02-06 Diamond Shamrock Technologies S.A. Process and apparatus for downward recycling of the electrolyte in diaphragm cells

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999014402A1 (fr) * 1997-09-16 1999-03-25 Krupp Uhde Gmbh Appareil pour electrolyse
US6596136B1 (en) 1998-10-30 2003-07-22 Uhdenora Technologies S.R.L. Membrane electrolytic cell with active gas/liquid separation
DE102008007605A1 (de) 2008-02-04 2009-08-06 Uhde Gmbh Modifiziertes Nickel
WO2009097962A1 (fr) 2008-02-04 2009-08-13 Uhde Gmbh Alliage de nickel et électrode en nickel à gradient de concentration dans la zone périphérique

Also Published As

Publication number Publication date
DE4224492C1 (de) 1993-12-09
ES2093311T3 (es) 1996-12-16
ATE144006T1 (de) 1996-10-15
EP0579910B1 (fr) 1996-10-09
DE59304090D1 (de) 1996-11-14

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