EP0252172B1 - Electrolysis process - Google Patents

Electrolysis process Download PDF

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Publication number
EP0252172B1
EP0252172B1 EP86109265A EP86109265A EP0252172B1 EP 0252172 B1 EP0252172 B1 EP 0252172B1 EP 86109265 A EP86109265 A EP 86109265A EP 86109265 A EP86109265 A EP 86109265A EP 0252172 B1 EP0252172 B1 EP 0252172B1
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EP
European Patent Office
Prior art keywords
cell
process according
electrolyte
material transport
transport coefficient
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EP86109265A
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German (de)
French (fr)
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EP0252172A1 (en
Inventor
Dieter Bruun
Wolfgang Dietz
Klaus-Jürgen Dr. Müller
Conrad Hans Hendrik Reynvaan
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Enviro-Cell Umwelttechnik Te Oberursel Bonds GmbH
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Deutsche Carbone AG
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Priority to AT86109265T priority Critical patent/ATE40720T1/en
Priority to DE8686109265T priority patent/DE3662060D1/en
Priority to EP86109265A priority patent/EP0252172B1/en
Priority to DE8619501U priority patent/DE8619501U1/en
Priority to JP62021910A priority patent/JPS6314884A/en
Priority to US07/020,357 priority patent/US4806224A/en
Priority to PT85218A priority patent/PT85218B/en
Priority to ES8701977A priority patent/ES2007633A6/en
Publication of EP0252172A1 publication Critical patent/EP0252172A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells

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  • the invention relates to an electrolysis process, wherein an electrolyte is passed through an electrolysis cell and the mass transfer coefficient is increased by introducing mechanical energy.
  • electrochemical cells For electrochemical reactions, e.g. To achieve in aqueous solutions, the most varied versions of electrochemical cells are used, e.g. Cells with a fixed bed made of graphite granules, metal wool or metal foam, or stacks of expanded metals. Plate cells are generally used at higher concentrations. It is also known that the mode of action of a cell, especially a plate cell, can be improved by increasing the stream transport coefficient. This is e.g. in that the medium to be treated is circulated at high speed through the cell and the batched liquid is then carried on in batches or a small volume flow is metered into the system in front of the cell and a corresponding small volume flow is branched off after the cell.
  • the mass transfer coefficient is increased by the introduction of mechanical energy, but in the prior art the entire electrolytic cell has been exposed to mechanical vibrations or other means for increasing the mass transfer coefficient, without making a differentiation according to the electrolyte flow in the electrolysis cell .
  • the change in the electrode overvoltages can be very disruptive because this leads to an area at the cell outlet in which undesired side reactions take place at the electrode. In most cases this is on the cathode e.g. the production of hydrogen.
  • the invention is therefore based on the object of proposing an electrolysis process of the type mentioned at the outset, in which the current density at the cell outlet is appreciably increased, without the occurrence of undesirable side reactions.
  • the invention is characterized in that the increase in the mass transfer coefficient increases along the direction of the electrolyte flow.
  • the idea on which the invention is based is therefore to increase the current density at the cell outlet by increasing the mass transfer coefficient there compared to the cell outlet, for example by exposing the electrolyte to pressure waves whose intensity at the cell outlet is stronger than at the cell inlet. It is obvious that in one liquid-filled, open-topped container, the housing of which is caused to vibrate, for example by blows, the amplitude of the vibration is greater in the upper region than in the lower region, in which the side plates are held together by a base. For example, if an electrochemical cell consists of a rectangular box in which the electrodes are suspended as plates, and if this box is vibrated from the outside by vibrators, the amplitude of the vibration in the upper area of the box is greater than in the lower area. If one now places the cell inlet downwards in the box and the cell outlet upwards, the stream transport coefficient along the direction of the electrolyte flow can be influenced in this way, and this essentially increases. The gas bubbles at the cell outlet can then be reduced or avoided.
  • FIG. 1 shows a vessel 1 of an electrolysis cell, in which an electrolyte 2 is located.
  • An anode 3, which is surrounded by a diaphragm 4, and several cathodes 5 are immersed in the electrolyte.
  • the electrolyte is continuously introduced into the vessel 1 via a side inlet 8 in the direction of arrow 9. It leaves the vessel via an overflow at the upper edge of the vessel or via holes or the like provided there.
  • a distributor tube not shown and laid over the bottom of the vessel, ensures a uniform distribution of the electrolyte, the direction of flow of which is indicated in the cell by arrows 10 .
  • Fig. 1 also shows that the vibrator 6 Schwin conditions in the direction of arrow 7, which are essentially perpendicular to the plane of the plates 3, 5.
  • FIG. 2 shows a diagram as a further explanation, the direction of the electrolyte flow 10 being indicated as the abscissa x.
  • the ordinates y are the amplitudes of the mechanical vibrations with which the electrolysis cell is subjected. It also follows from this that a smaller amplitude acts on the electrolyte at the inlet 16 of the electrolytic cell than at the outlet 17. This is shown by the curve 18.

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  • 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)
  • Electrolytic Production Of Metals (AREA)

Abstract

An electroltytic process is described by which in order to increase the depletion factory, the material coefficient of the electrolyte passing through an electrolytic cell is increased along the direction of the electrolytic flow.

Description

Die Erfindung betrifft ein Elektrolyseverfahren, wobei man einen Elektrolyten durch eine Elektrolysezelle hindurchleitet und dabei den Stofftransportkoeffizienten durch Einbringen mechanischer Energie erhöht.The invention relates to an electrolysis process, wherein an electrolyte is passed through an electrolysis cell and the mass transfer coefficient is increased by introducing mechanical energy.

Um elektrochemische Umsetzungen, z.B. in wäßrigen Lösungen, zu erreichen, werden die verschiedensten Ausführungen von elektrochemischen Zellen verwendet, bei kleineren Konzentrationen z.B. Zellen mit einem Festbett aus Graphitgranulat, Metallwolle oder Metallschaum oder Stapeln von Streckmetallen. Bei größeren Konzentrationen verwendet man im allgemeinen Plattenzellen. Es ist ebenfalls bekannt, daß die Wirkungsweise einer Zelle, besonders einer Plattenzelle, durch Erhöhung des Strofftransportkoeffizienten zu verbessern ist. Dies wird z.B. dadurch erreicht, daß man das zu behandelnde Medium mit hoher Geschwindigkeit im Kreise durch die Zelle fährt und die behandelte Flüssigkeit dann chargenweise weiterführt oder dem System vor der Zelle einen kleinen Volumenstrom zudosiert und einen entsprechenden kleinen Volumenstrom nach der Zelle abzweigt. Andere Methoden zur Erhöhung des Stofftransportkoeffizienten sind das mechanische Rühren oder Einführen von Gas in die Zelle. Die aufsteigenden Gasblasen erhöhen ebenfalls den Stofftransportkoeffizienten. Auch wird oft die Elektrode bewegt, um so eine höhere Relativbewegung von Elektrolyt und Elektrode zu erhalten. Dies kann geschehen durch eine Vibration der Elektrode, durch ein Verwirbeln eines Festbettes oder durch rotierende Elektroden. Ebenfalls ist es bekannt, die Grenzschicht in einer Plattenzelle durch mechanische Bewegung von Teilchen oder anderen Körpern zu stören und aufzubrechen und so den Stofftransportkoeffizienten zu erhöhen.For electrochemical reactions, e.g. To achieve in aqueous solutions, the most varied versions of electrochemical cells are used, e.g. Cells with a fixed bed made of graphite granules, metal wool or metal foam, or stacks of expanded metals. Plate cells are generally used at higher concentrations. It is also known that the mode of action of a cell, especially a plate cell, can be improved by increasing the stream transport coefficient. This is e.g. in that the medium to be treated is circulated at high speed through the cell and the batched liquid is then carried on in batches or a small volume flow is metered into the system in front of the cell and a corresponding small volume flow is branched off after the cell. Other methods of increasing the mass transfer coefficient are mechanical stirring or the introduction of gas into the cell. The rising gas bubbles also increase the mass transfer coefficient. The electrode is also often moved in order to obtain a higher relative movement of the electrolyte and the electrode. This can be done by vibrating the electrode, by swirling a fixed bed or by rotating electrodes. It is also known to disrupt and break up the boundary layer in a plate cell by mechanical movement of particles or other bodies and thus to increase the mass transfer coefficient.

Ebenfalls bekannt ist die Verwendung von Ultraschall. Es ist auch bekannt, daß diese letzte Methode nicht nur den Vorteil des erhöhten Stofftransportkoeffizienten hat, sondern zusätzlich die Gasblasenbelegung der Elektrodenoberfläche reduziert dadurch, daß die Gasblasen besser von den Oberflächen abgelöst werden.The use of ultrasound is also known. It is also known that this last method not only has the advantage of the increased mass transfer coefficient, but additionally reduces the gas bubble coverage of the electrode surface in that the gas bubbles are detached better from the surfaces.

Eine gute Übersicht über die hierbei anstehende Problematik mit Lösungsvorschlägen, beruhend auf verschiedenen Bewegungsprinzipien beschreibt ein Aufsatz, der in der Zeitschrift "Neue Hütte", September 1982, Seite 317-322 erschienen ist. Einen ins Detail gehenden Lösungsvorschlag beschreibt ein anderer Aufsatz, der in der Zeitschrift "Erzmetall", 1974, Seite 107-114, erschienen ist. Hier ist ein Elektrolyseverfahren beschrieben, bei dem man den Elektrolyten durch die Elektrolysezelle hindurchleitet. Von diesem Stand der Technik geht die Erfindung aus.A good overview of the pending problems with proposed solutions, based on various principles of movement, is described in an article that appeared in the journal "Neue Hütte", September 1982, pages 317-322. Another article, which appeared in the journal "Erzmetall", 1974, pages 107-114, describes a detailed solution. An electrolysis process is described here in which the electrolyte is passed through the electrolysis cell. The invention is based on this prior art.

Hingewiesen werden soll auch noch auf einen zusammenfassenden Aufsatz, erschienen in "Quarterly Reviews" 7 (1953), Seiten 84-101.Attention should also be drawn to a summary article, published in "Quarterly Reviews" 7 (1953), pages 84-101.

In den beiden erstgenannten Veröffentlichungen wird zwar der Stofftransportkoeffizient durch Einbringen mechanischer Energie erhöht, jedoch hat man beim Stand der Technik die gesamte Elektrolysezelle den mechanischen Schwingungen oder sonstigen Mitteln zur Erhöhung des Stofftransportkoeffizienten ausgesetzt, und zwar ohne hierbei eine Differenzierung entsprechend dem Elektrolytfluß in der Elektrolysezelle vorzunehmen.In the first two publications, the mass transfer coefficient is increased by the introduction of mechanical energy, but in the prior art the entire electrolytic cell has been exposed to mechanical vibrations or other means for increasing the mass transfer coefficient, without making a differentiation according to the electrolyte flow in the electrolysis cell .

Bei Festbettzellen und auch bei Plattenzellen besteht aber unabhängig vom Stofftransportkoeffizienten das Problem, daß die kathodische und anodische Überspannung vom Zelleinlauf zum Zellauslauf nicht konstant bleiben. (Wir bezeichnen nun mit einer elektrochemischen Zelle eine Einheit, bei der Kathode und Anode aus jeweils einem Stück sind und nicht in Richtung des Elektrolytflusses segmentiert, so daß damit verschiedene Potentiale eingestellt werden können.)With fixed bed cells and also with plate cells, there is the problem regardless of the mass transfer coefficient that the cathodic and anodic overvoltage from the cell inlet to the cell outlet do not remain constant. (We now refer to an electrochemical cell as a unit in which the cathode and anode are each made of one piece and are not segmented in the direction of the electrolyte flow, so that different potentials can be set.)

Die Verschiebung der kathodischen und anodischen Überspannung rührt daher, daß die Zellspannung ja am Zelleinlauf und Zellauslauf gleich ist, die Stromdichte aber im allgemeinen am Zellauslauf wesentlich geringer. Bleibt nun der Widerstand der behandelten Lösung vom Zelleinlauf zum Zellauslauf im wesentlichen gleich, wie das im allgemeinen der Fall ist, so verändert sich mit der geringer werdenden Stromdichte auch der Anteil des ohmschen Spannungsabfalls. Dadurch, daß die Zellspannung konstant ist, müssen notwendig die Überspannungen steigen. Dies wird beschrieben durch die GleichungThe shift in the cathodic and anodic overvoltage stems from the fact that the cell voltage is the same at the cell inlet and cell outlet, but the current density is generally much lower at the cell outlet. If the resistance of the treated solution from the cell inlet to the cell outlet remains essentially the same as is generally the case, the proportion of the ohmic voltage drop also changes with the decreasing current density. Because the cell voltage is constant, the overvoltages must necessarily increase. This is described by the equation

Zellspannung = kathodische Überspannung + anodische Überspannung + lokaler Zellwiderstand x lokalem StromCell voltage = cathodic overvoltage + anodic overvoltage + local cell resistance x local current

Die Änderung der Elektrodenüberspannungen kann sehr störend sein, weil man dadurch am Zellauslauf in einen Bereich kommt, in dem unerwünschte Nebenreaktionen an der Elektrode stattfinden. In den meisten Fällen ist das an der Kathode z.B. die Produktion von Wasserstoff.The change in the electrode overvoltages can be very disruptive because this leads to an area at the cell outlet in which undesired side reactions take place at the electrode. In most cases this is on the cathode e.g. the production of hydrogen.

Es ist bekannt, daß man bei der Verwendung von Festbettzellen dieses Problem dadurch entschärfen kann, daß beim Zellauslauf ein größeres Festbettvolumen angeboten wird oder die Packungsdichte auf eine andere Weise erhöht wird, z.B. durch kleinere Körnung des verwendeten Granulats oder eine stärkere Komprimierung einer Füllung mit Metallwolle oder Metallschaum. Auf diese Weise kann dann der dort lokal fließende Strom gesteigert werden, und der Beitrag des ohmschen Spannungsabfalls wird wieder etwas größer. (Siehe z.B. die DE-PS 2 622 497 oder 3 532 573.)It is known that when using fixed bed cells this problem can be alleviated by offering a larger fixed bed volume at the cell outlet or by increasing the packing density in another way, e.g. through smaller granulation of the granulate used or a stronger compression of a filling with metal wool or metal foam. In this way, the local current flowing there can then be increased, and the contribution of the ohmic voltage drop becomes somewhat larger again. (See e.g. DE-PS 2 622 497 or 3 532 573.)

Der Erfindung liegt daher die Aufgabe zugrunde, ein Elektrolyseverfahren der eingangs genannten Art vorzuschlagen, bei dem die Stromdichte am Zellauslauf fühlbar erhöht wird, und zwar ohne das Auftreten unerwünschter Nebenreaktionen.The invention is therefore based on the object of proposing an electrolysis process of the type mentioned at the outset, in which the current density at the cell outlet is appreciably increased, without the occurrence of undesirable side reactions.

Zur Lösung dieser Aufgabe ist die Erfindung dadurch gekennzeichnet, daß die Erhöhung des Stofftransportkoeffizienten entlang der Richtung des Elektrolytflusses zunimmt.To achieve this object, the invention is characterized in that the increase in the mass transfer coefficient increases along the direction of the electrolyte flow.

Der der Erfindung zugrundeliegende Gedanke ist es also, die Stromdichte am Zellauslauf dadurch zu erhöhen, daß dort der Stofftransportkoeffizient im Vergleich zum Zellauslauf erhöht wird, z.B. dadurch, daß man den Elektrolyten Druckwellen aussetzt, deren Intensität am Zellauslauf stärker ist als am Zelleinlauf. Es ist offensichtlich, daß in einem flüssigkeitsgefüllten, oben offenen Behälter, dessen Gehäuse man z.B. durch Schläge in Schwingungen versetzt, die Amplitude der Schwingung im oberen Bereich größer ist als im unteren Bereich, bei dem die Seitenplatten durch einen Boden zusammengehalten werden. Besteht eine elektrochemische Zelle also z.B. aus einem rechteckigen Kasten, in den die Elektroden als Platten eingehängt sind, und wird dieser Kasten von außen durch Vibratoren in Schwingung versetzt, so ist die Amplitude der Schwingung im oberen Bereich des Kastens größer als im unteren. Legt man nun den Zelleinlauf nach unten in den Kasten und den Zellauslauf nach oben, so läßt sich auf diese Weise der Strofftransportkoeffizient entlang der Richtung des Elektrolytflusses beeinflussen, und zwar nimmt dieser im wesentlichen zu. Dadurch kann dann die Gasblasenbildung am Zellauslauf verringert oder vermieden werden.The idea on which the invention is based is therefore to increase the current density at the cell outlet by increasing the mass transfer coefficient there compared to the cell outlet, for example by exposing the electrolyte to pressure waves whose intensity at the cell outlet is stronger than at the cell inlet. It is obvious that in one liquid-filled, open-topped container, the housing of which is caused to vibrate, for example by blows, the amplitude of the vibration is greater in the upper region than in the lower region, in which the side plates are held together by a base. For example, if an electrochemical cell consists of a rectangular box in which the electrodes are suspended as plates, and if this box is vibrated from the outside by vibrators, the amplitude of the vibration in the upper area of the box is greater than in the lower area. If one now places the cell inlet downwards in the box and the cell outlet upwards, the stream transport coefficient along the direction of the electrolyte flow can be influenced in this way, and this essentially increases. The gas bubbles at the cell outlet can then be reduced or avoided.

Damit ist es nun möglich, einen größeren Abreicherungsfaktor in einer einzigen Zelle zu erreichen, ohne daß an den Elektroden eine Gasentwicklung auftritt. Es können damit dann die unerwünschten Nebenreaktionen vermieden werden. Bei vielen Reaktionen kann man davon ausgehen, daß bei beginnender Gasblasenbelegung der Elektrodenoberfläche die elektrochemische Umsetzung nahezu vollständig zum Stillstand kommt.It is now possible to achieve a larger depletion factor in a single cell without gas developing at the electrodes. The undesirable side reactions can then be avoided. In many reactions, it can be assumed that the electrochemical conversion almost completely comes to a standstill when gas bubbles begin to cover the electrode surface.

Das erreichbare Abreichungsverhältnis (= Einlaufkonzentration durch Auslaufkonzentration) ist dann im wesentlichen davon bestimmt, bis zu welcher Konzentration man in einer Zelle die Entwicklung von Gasblasen durch eine Nebenreaktion vermeiden kann. Mit dem angegebenen Verfahren kann man dabei einen beträchtlichen Vorteil erzielen, wie an folgender Rechnung klargemacht werden soll.The achievable depletion ratio (= inlet concentration by outlet concentration) is then essentially determined by the concentration up to which the development of gas bubbles in a cell can be avoided by a side reaction. With the given method one can achieve a considerable advantage, as will be made clear on the following calculation.

Die Gasblasenentwicklung tritt also ein, wenn die Differenz der Stromdichte an Zelleinlauf und Zellauslauf einen gewissen Wert G überschreitet. Diese Stromdichte ist proportional dem Produkt aus Stofftransportkoeffizient und Konzentration. Bezeichnen wir mit dem Index 0 die Werte für den Zellleinlauf, mit dem Index 1 die Werte für den Zellauslauf, mit K den Stofftransportkoeffizienten und mit C die Konzentration, so muß also folgende Ungleichung erfüllt sein, damit keine unerwünschte Nebenreaktion auftritt.

  • G>KOxCO-KixCi
The gas bubble development therefore occurs when the difference in the current density at the cell inlet and cell outlet exceeds a certain value G. This current density is proportional to the product of mass transfer coefficient and concentration. If we designate the values for the cell run-in with the index 0, the values for the cell run-out with the index 1, the mass transfer coefficient with K and the concentration with C, then the following inequality must be satisfied so that no undesirable side reaction occurs.
  • G> KOxCO-KixCi

Kann man es nun erreichen, daß das Verhältnis von K 0 : K 1 = 1 : 2, so wird das mögliche C 1, die Auslaufkonzentration, offenbar halb so groß sein wie in dem Fall, daß K 0 = K 1. Das bedeutet, man kann die erreichbare Endkonzentration noch einmal halbieren. Die Änderung des Stofftransportkoeffizienten kann ohne weiteres auch sehr viel größer sein und eine entsprechend stärkere Verringerung der Auslaufkonzentration ist dann möglich.If one can now achieve that the ratio of K 0: K 1 = 1: 2, the possible C 1, the outlet concentration, will obviously be half as large as in the case where K 0 = K 1. That means you can halve the achievable final concentration again. The change in the mass transfer coefficient can easily be much larger and a correspondingly greater reduction in the outlet concentration is then possible.

Die Erfindung wird im folgenden anhand eines Ausführungsbeispieles näher erläutert, aus dem sich weitere wichtige Merkmale ergeben. Es zeigt:

  • Fig. 1 schematisch in einer Ansicht eine Elektrolysezelle zur Erläuterung des Prinzips des erfindungsgemäßen Elektrolyseverfahrens;
  • Fig. 2 ein Diagramm, wobei als Beispiel über der Länge der Elektrolysezelle in Richtung des Elektrolytflusses (entsprechend der Höhe der Elektrolysezelle in Fig. 1) die Amplitude der hierbei angewendeten Druckwellen aufgetragen ist.
The invention is explained in more detail below on the basis of an exemplary embodiment from which further important features result. It shows:
  • 1 shows a schematic view of an electrolysis cell to explain the principle of the electrolysis process according to the invention;
  • FIG. 2 shows a diagram, the amplitude of the pressure waves used being plotted as an example over the length of the electrolytic cell in the direction of the electrolyte flow (corresponding to the height of the electrolytic cell in FIG. 1).

Fig. 1 zeigt ein Gefäß 1 einer Elektrolysezelle, in dem sich ein Elektrolyt 2 befindet. In den Elektrolyten tauchen ein eine Anode 3, die von einem Diaphragma 4 umgeben ist, sowie mehrere Kathoden 5. Der Elektrolyt wird über einen seitlichen Einlaß 8 in Richtung des Pfeiles 9 in das Gefäß 1 kontinuierlich eingeführt. Er verläßt das Gefäß über einen Überlauf am oberen Rand des Gefäßes oder über dort vorgesehene Löcher oder dergl. Ein nicht gezeigtes und über dem Boden des Gefäßes verlegtes Verteilerrohr sorgt für eine gleichmäßige Verteilung des Elektrolyten, dessen Strömungsrichtung in der Zelle durch die Pfeile 10 angedeutet ist.1 shows a vessel 1 of an electrolysis cell, in which an electrolyte 2 is located. An anode 3, which is surrounded by a diaphragm 4, and several cathodes 5 are immersed in the electrolyte. The electrolyte is continuously introduced into the vessel 1 via a side inlet 8 in the direction of arrow 9. It leaves the vessel via an overflow at the upper edge of the vessel or via holes or the like provided there. A distributor tube, not shown and laid over the bottom of the vessel, ensures a uniform distribution of the electrolyte, the direction of flow of which is indicated in the cell by arrows 10 .

Links in Fig. 1 ist zur Erläuterung des Prinzips des erfindungsgemäßen Verfahrens angedeutet, daß sich in Richtung des Elektrolytflusses 10 hintereinander mehrere Quirle 11, 12, 13, 14, 15 befinden. Der unterste Quirl 11, der sich also in der Nähe des Elektrolyteneinlaufs befindet, wird mit geringer Drehzahl angetrieben, während der oberste Quirl 15, der sich in der Nähe des Auslasses befindet, mit der höchsten Drehzahl angetrieben wird. Die dazwischen befindlichen Quirle 12, 13, 14 werden mit einer mittleren Drehzahl angetrieben derart, daß die von den Quirlen hervorgerufene Verwirbelung des Elektrolyten in Richtung des Elektrolytflusses 10 zunimmt.On the left in FIG. 1, to explain the principle of the method according to the invention, it is indicated that several whorls 11, 12, 13, 14, 15 are located one behind the other in the direction of the electrolyte flow 10. The lowest whisk 11, which is therefore in the vicinity of the electrolyte inlet, is driven at a low speed, while the uppermost whisk 15, which is in the vicinity of the outlet, is driven at the highest speed. The whorls 12, 13, 14 located between them are driven at a medium speed such that the swirling of the electrolyte caused by the whorls increases in the direction of the electrolyte flow 10.

Diese Darstellung soll nur das Prinzip des erfindungsgemäßen Verfahrens verdeutlichen; in der Praxis wird man die hierdurch bewirkte Erhöhung des Stofftransportkoeffizienten auf andere Art und Weise durchführen, bevorzugt durch einen Vibrator 6. Dieser ist an der Wand des Gefäßes 1 befestigt, und zwar bevorzugt im oberen Bereich der Wand, so daß die von ihm ausgehenden Schallwellen ihre größte Amplitude im Auslaßbereich des Gefäßes haben. Man könnte auch übereinander mehrere der Vibratoren 6 an der Wand des Gefäßes befestigen, wobei man dann den obersten Vibrator mit einer größeren Amplitude beaufschlagt als den untersten der Vibratoren.This representation is only intended to illustrate the principle of the method according to the invention; in practice, the increase in the mass transfer coefficient caused thereby will be carried out in another way, preferably by means of a vibrator 6. This is attached to the wall of the vessel 1, preferably in the upper region of the wall, so that the sound waves emanating from it have their greatest amplitude in the outlet region of the vessel. One could also fasten several of the vibrators 6 one above the other on the wall of the vessel, in which case the top vibrator is then subjected to a greater amplitude than the bottom one of the vibrators.

Versuche haben gezeigt, daß die Anregung wenigstens einer der Wände des Gefäßes 1 mit diesen Vibratoren oder mit wenigstens einem der Vibratoren für den gewünschten Effekt ausreicht. Man muß also nicht das gesamte Elektrolysegefäß in Schwingungen versetzen, wie dies beim Stand der Technik der Fall war, ganz abgesehen davon, daß man bei diesem Verfahren den Stofftransportkoeffizienten nicht in Richtung des Elektrolytflusses beeinflussen kann.Experiments have shown that the excitation of at least one of the walls of the vessel 1 with these vibrators or with at least one of the vibrators is sufficient for the desired effect. It is therefore not necessary to vibrate the entire electrolysis vessel, as was the case in the prior art, quite apart from the fact that with this method the mass transfer coefficient cannot be influenced in the direction of the electrolyte flow.

Auf andere Lösungswege wurde in den Patentansprüchen bereits hingewiesen, beispielsweise darauf, daß man auch die Elektroden 3 und/oder 5 zu den Schwingungen anregen kann usw. Allen Prinzipien ist es gemeinsam, daß die hierbei in das Bad eingeführte Schwingungsenergie im Bereich des Auslaufs größer ist als im Bereich des Einlaufs.Other solutions have already been pointed out in the patent claims, for example that electrodes 3 and / or 5 can also be excited to vibrate, etc. It is common to all principles that the vibration energy introduced into the bath is greater in the area of the outlet than in the area of the enema.

Fig. 1 zeigt auch noch, daß der Vibrator 6 Schwingungen in Richtung des Pfeiles 7 aussendet, die also im wesentlichen senkrecht zur Ebene der Platten 3, 5 verlaufen.Fig. 1 also shows that the vibrator 6 Schwin conditions in the direction of arrow 7, which are essentially perpendicular to the plane of the plates 3, 5.

Fig. 2 zeigt als weitere Erläuterung ein Diagramm, wobei die Richtung des Elektrolytflusses 10 als Abszisse x angegeben ist. Als Ordinate y sind die Amplituden der mechanischen Schwingungen aufgetragen, mit denen die Elektrolysezelle beaufschlagt wird. Auch hieraus ergibt sich, daß am Einlaß 16 der Elektrolysezelle eine geringere Amplitude auf den Elektrolyten einwirkt als am Auslaß 17. Dies ist durch die Kurve 18 dargestellt.2 shows a diagram as a further explanation, the direction of the electrolyte flow 10 being indicated as the abscissa x. The ordinates y are the amplitudes of the mechanical vibrations with which the electrolysis cell is subjected. It also follows from this that a smaller amplitude acts on the electrolyte at the inlet 16 of the electrolytic cell than at the outlet 17. This is shown by the curve 18.

Claims (8)

1. An electrolysis process in which an electrolyte (2) is passed through an electrolysis cell (1) thus increasing the material transport coefficient by introducing mechanical energy, characterized in that the increase of the material transport coefficient is increasing along the direction (10) of the electrolytic flow.
2. A process according to claim 1, characterized in that the increase of the material transport coefficient is obtained by a relative movement of electrodes and electrolyte.
3. A process according to claim 1, characterized in that the increase of the material transport coefficient is obtained by the electrolyte being subjected to pressure waves substantially expanding vertically to the electrodes planes extending parallel to each other.
4. A process according to claim 3, characterized in that the difference in the material transport coefficient along the direction of the electrolytic flow is obtained by change of the amplitude of the pressure wave.
5. A process according to claim 4, characterized in that the amplitude of the pressure wave in the area of the cell outlet is larger by at least the factor 4 as compared to the area of the cell inlet.
6. A process according to claim 4 or 5, characterized in that the pressure wave is generated by one or several vibrators secured to the housing of the electro-chemical cell.
7. A process according to claim 6, characterized in that the change of the amplitude of the pressure wave along the direction of the electrolytic flow is obtained by the provision of the vibrators and/or the structural arrangement of the cell housing.
8. A process according to any of the foregoing claims, characterized in that the electro-chemical reaction is taking place on a solid bed electrode.
EP86109265A 1986-07-07 1986-07-07 Electrolysis process Expired EP0252172B1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AT86109265T ATE40720T1 (en) 1986-07-07 1986-07-07 ELECTROLYSIS PROCESS.
DE8686109265T DE3662060D1 (en) 1986-07-07 1986-07-07 Electrolysis process
EP86109265A EP0252172B1 (en) 1986-07-07 1986-07-07 Electrolysis process
DE8619501U DE8619501U1 (en) 1986-07-07 1986-07-19 Electrolytic cell
JP62021910A JPS6314884A (en) 1986-07-07 1987-02-03 Electrolytic method
US07/020,357 US4806224A (en) 1986-07-07 1987-03-02 Electrolytic process
PT85218A PT85218B (en) 1986-07-07 1987-06-30 ELECTROLYSIS PROCESS
ES8701977A ES2007633A6 (en) 1986-07-07 1987-07-06 Electrolysis process.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP86109265A EP0252172B1 (en) 1986-07-07 1986-07-07 Electrolysis process

Publications (2)

Publication Number Publication Date
EP0252172A1 EP0252172A1 (en) 1988-01-13
EP0252172B1 true EP0252172B1 (en) 1989-02-08

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EP86109265A Expired EP0252172B1 (en) 1986-07-07 1986-07-07 Electrolysis process

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US (1) US4806224A (en)
EP (1) EP0252172B1 (en)
JP (1) JPS6314884A (en)
AT (1) ATE40720T1 (en)
DE (2) DE3662060D1 (en)
ES (1) ES2007633A6 (en)
PT (1) PT85218B (en)

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FR2681079B1 (en) * 1991-09-06 1994-09-09 Kodak Pathe DEVICE AND METHOD FOR ELECTROLYSIS WITH POROUS AND AGITATED ELECTRODE.
US5312532A (en) * 1993-01-15 1994-05-17 International Business Machines Corporation Multi-compartment eletroplating system
US5310486A (en) * 1993-05-25 1994-05-10 Harrison Western Environmental Services, Inc. Multi-stage water treatment system and method for operating the same
US5419823A (en) * 1993-11-09 1995-05-30 Hardwood Line Manufacturing Co. Electroplating device and process
US6454918B1 (en) * 1999-03-23 2002-09-24 Electroplating Engineers Of Japan Limited Cup type plating apparatus
EP1460149B1 (en) * 2001-12-03 2010-09-08 Japan Techno Co., Ltd Hydrogen-oxygen gas generator and hydrogen-oxygen gas generating method using the generator
CA2606190A1 (en) * 2005-04-27 2006-11-02 Hw Process Technologies, Inc. Treating produced waters
JP4732833B2 (en) * 2005-08-22 2011-07-27 樫山工業株式会社 Screw rotor and vacuum pump
US7365258B1 (en) 2006-08-02 2008-04-29 Drum Workshop, Inc. Sound box with external and internal impact surfaces
US20080069748A1 (en) * 2006-09-20 2008-03-20 Hw Advanced Technologies, Inc. Multivalent iron ion separation in metal recovery circuits
US20080128354A1 (en) * 2006-11-30 2008-06-05 Hw Advanced Technologies, Inc. Method for washing filtration membranes

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US3351539A (en) * 1965-04-06 1967-11-07 Branson Instr Sonic agitating method and apparatus
DE1263768B (en) * 1965-07-09 1968-03-21 Basf Ag Device for carrying out electrochemical reactions of organic compounds with flowing electrolytes
US3699014A (en) * 1970-12-29 1972-10-17 Norton Co Vibratory process
BG22251A1 (en) * 1974-10-04 1979-12-12 Petrov Method and installation for non-ferros elektrolysis
US4049512A (en) * 1975-10-31 1977-09-20 Tolle Jr Albert E Cathode structure for electrolytic apparatus employing impellers
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EP0171647A1 (en) * 1984-07-25 1986-02-19 Deutsche Carbone AG Process for the electrolytic deposition of metals from an electrolysis bath
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Also Published As

Publication number Publication date
US4806224A (en) 1989-02-21
JPS6314884A (en) 1988-01-22
DE8619501U1 (en) 1986-11-06
DE3662060D1 (en) 1989-03-16
ES2007633A6 (en) 1989-07-01
ATE40720T1 (en) 1989-02-15
EP0252172A1 (en) 1988-01-13
PT85218A (en) 1988-07-29
PT85218B (en) 1993-07-30

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