EP0084519B1 - Vessel containing an unstable solution of a metal salt or complex, and process for sealing such a vessel - Google Patents

Vessel containing an unstable solution of a metal salt or complex, and process for sealing such a vessel Download PDF

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Publication number
EP0084519B1
EP0084519B1 EP83810011A EP83810011A EP0084519B1 EP 0084519 B1 EP0084519 B1 EP 0084519B1 EP 83810011 A EP83810011 A EP 83810011A EP 83810011 A EP83810011 A EP 83810011A EP 0084519 B1 EP0084519 B1 EP 0084519B1
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Prior art keywords
container
sealing
vessel
seal
solution
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EP83810011A
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German (de)
French (fr)
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EP0084519A2 (en
EP0084519A3 (en
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Colin Charles Blake
Paul Anthony Bacon
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Novartis AG
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Ciba Geigy AG
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/005Anodic protection
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06Operating or servicing

Definitions

  • the invention relates to a container for a pressurized, unstable solution of a metal salt or complex according to the preamble of patent claim 1.
  • metal salt or complex solutions are unstable because, under certain conditions, the salt or complex decomposes and the metal precipitates out of the solution.
  • Silver and copper salt or complex solutions in particular are particularly unstable.
  • Pressurized containers inside which a reciprocating or rotatable shaft is provided, which can be used to mix or stir the contents of the container, require e.g. sealant surrounding the shaft, which prevents the contents of the container from escaping where the shaft enters the container.
  • sealant surrounding the shaft, which prevents the contents of the container from escaping where the shaft enters the container.
  • Various methods have been developed to achieve such a seal, such as the use of stuffing boxes and in particular lip seals and mechanical surface seals. However, all of these sealing methods require close contact between two surfaces, one of which rotates or reciprocates with respect to the other.
  • a lip seal these are the surfaces of the lip seal itself and that of the shaft.
  • a mechanical surface seal these are the surfaces of the two components of the seal, one of which is fixed and the other rotates with the shaft.
  • Such sealing systems basically require the presence of a thin liquid film of the trapped liquid between the two surfaces, which film is an effective sealing medium.
  • US-A-3 910 833 describes an electrolytic silver recovery device in which the shaft of the rotating electrode is guided through the vessel wall by means of a special liquid sealing system. A space surrounding the shaft in the area of the wall bushing is filled with a special sealing liquid. This is kept under such a high pressure that some sealing fluid constantly escapes through the mechanical seal between the shaft and the wall of the vessel, thereby lubricating this seal on the one hand and preventing the penetration of corrosive solutions into the lip seal.
  • This known liquid sealing system is relatively complicated and complex and therefore correspondingly expensive.
  • the present invention is now intended to eliminate the sealing problem in the case of pressurized, unstable solutions of metal salts or complexes in a container with a shaft, and accordingly to improve a container of the type defined at the outset in such a way that its seal has a longer service life.
  • the electrolytic recovery device comprises a container V made of PVC.
  • a rotatably mounted cathode C made of stainless steel is provided in the container V.
  • the cathode C sits on a drive shaft S, which is mounted in a bearing B in the housing wall of the container V.
  • a drive roller P is firmly seated on the shaft S and is connected to drive means (not shown) located outside the device.
  • the cathode C is electrically connected via the shaft S.
  • the drive means rotate the cathode C in the container V.
  • the shaft S is sealed in the container V by means of a mechanical sealing system X, which consists of a rotating surface sealing element X, which is fastened on the shaft S by means of a rubber bellows Be.
  • the surface sealing element X is in sealing contact with the counter surface sealing element X 2 , which is attached to the upper housing part of the container V by means of an O-ring O.
  • a graphite anode A is concentrically attached to the inner wall of the container V with the latter.
  • a solution inlet Q leads from a solution reservoir (not shown) via a pump into the interior of the container V, and an outlet pipe R leads out of the container V.
  • An electrical connecting line W connects the mating surface seal X 2 to the anode A.
  • an aqueous solution containing metal ions is passed through the inlet Q into the interior of the container V ge during neutral operation pumps while the cathode C and the anode A are connected to a current source U via the electrical connection terminals U 1 and U 2 , forming an electrical cell.
  • the cathode C is rotated and the metal from the aqueous solution is deposited on the cathode.
  • the aqueous solution is continuously pumped slowly into the container V through the inlet Q and leaves it again through the outlet R, so that the solution in the container V is constantly under pressure.
  • a liquid-tight seal must be provided around the shaft S. If this is not the case, liquid creeps along the shaft and exits at the top of the container. This causes corrosion of the bearing B in contact with the solution, and also contamination, since the solution is pressed out of the upper end of the container around the shaft in an uncontrollable manner. It is therefore necessary that the sealing elements X, and X 2 together form a so-called «liquid seal».
  • the rotating surface seal element X consisted of ceramic material and the stationary counter-face seal element X 2 made of graphite.
  • the cell was not connected to a power source, but water was let through the container V at a pressure of 1.01 bar and the cathode C was rotated at a speed of 1000 rpm. After 48 hours of continuous operation, no fluid loss from the container was found.
  • the cell was also not connected to the power source, but a saline solution (100 g NaCl per liter) was pumped continuously through the container under a pressure of 1.01 bar and the cathode was again rotated at 1000 rpm . Again, no loss of liquid was found in the container after 48 hours of continuous operation, because sodium chloride forms a stable salt solution.
  • a saline solution 100 g NaCl per liter
  • the cell was again not connected to the power source, but the fixing solution was pumped through the container under a pressure of 1.01 bar and the cathode was rotated at 1000 rpm. After three hours of operation, it was observed that liquid escaped from the container at the point of entry of the shaft S. The operation was interrupted and the sealing elements X, and X 2 were examined. It was found that metallic silver had deposited on both elements, causing a gap between the sealing surfaces and thus breaking the liquid seal.
  • the same fixing solution was pumped through the same container under the same conditions and the cell was connected to the power source, but here the line W was connected to the anode A and to the electrically conductive mating surface sealing element X 2 .
  • the experiment was then interrupted and the container opened. Again a deposit of silver in powder form was found on the cathode, but no deposit of silver metal or any other deposit on the surfaces of the two sealing elements X, and X 2 .
  • the potential between the counter surface sealing element X 2 and the shaft was 1.5 V.
  • Stainless steel is suitable as a further electrically conductive material for the fixed counter surface sealing element X 2 .
  • the rotatable counter surface sealing element X can also consist of graphite or stainless steel.
  • Other suitable manufacturing materials are tungsten carbide and polytetrafluoroethylene. The preferred combination is graphite-graphite.
  • the container is an electrolytic cell, and the current generated by the potential difference between the counter surface sealing element X 2 and the cathode causes some silver metal to be deposited on the cathode.
  • the invention is used to protect seals in other pressurized containers in which a shaft rotates or moves back and forth, the dimensions of the cathode and, if necessary, the current flow through the electrically conductive seal, if necessary, can also be reduced formed cell are limited to a minimum. This also keeps the amount of metal deposited on the cathode and any side effects on the solution in the container equally low.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Secondary Cells (AREA)
  • Sealing Devices (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Sealing Using Fluids, Sealing Without Contact, And Removal Of Oil (AREA)

Description

Die Erfindung betrifft ein Behältnis für eine unter Druck stehende instabile Lösung eines Metallsalzes oder -komplexes gemäss dem Oberbegriff des Patentanspruchs 1.The invention relates to a container for a pressurized, unstable solution of a metal salt or complex according to the preamble of patent claim 1.

Viele Metallsalz- oder komplexlösungen sind instabil, da sich unter gewissen Bedingungen das Salz oder der Komplex zersetzt und das Metall aus der Lösung ausfällt. Vor allem Silber- und Kupfersalz- oder -komplexlösungen sind besonders instabil.Many metal salt or complex solutions are unstable because, under certain conditions, the salt or complex decomposes and the metal precipitates out of the solution. Silver and copper salt or complex solutions in particular are particularly unstable.

Unter Druck stehende Behältnisse, in deren Innerem eine hin und her bewegbare oder drehbare Welle vorgesehen ist, die zum Mischen oder Rühren des Behältnisinhalts dienen kann, erfordern z.B. die Welle umgebende Dichtungsmittel, die verhindern, dass der Behältnisinhalt dort, wo die Welle in das Behältnis eintritt, entweichen kann. Zur Erzielung einer solchen Abdichtung wurden verschiedene Verfahren entwickelt, wie die Verwendung von Stopfbuchsen und insbesondere von Lippendichtungen und mechanischen Flächendichtungen. Jedoch erfordern alle diese Abdichtungsmethoden eine enge Berührung von zwei Flächen, von denen die eine sich gegenüber der anderen dreht oder hin und her bewegt. Im Falle einer Lippendichtung sind dies die Oberflächen der Lippendichtung selbst und diejenige der Welle. Im Falle einer mechanischen Flächendichtung sind dies die Oberflächen der beiden Komponenten der Dichtung, von denen die eine fest steht und die andere sich mit der Welle dreht.Pressurized containers, inside which a reciprocating or rotatable shaft is provided, which can be used to mix or stir the contents of the container, require e.g. sealant surrounding the shaft, which prevents the contents of the container from escaping where the shaft enters the container. Various methods have been developed to achieve such a seal, such as the use of stuffing boxes and in particular lip seals and mechanical surface seals. However, all of these sealing methods require close contact between two surfaces, one of which rotates or reciprocates with respect to the other. In the case of a lip seal, these are the surfaces of the lip seal itself and that of the shaft. In the case of a mechanical surface seal, these are the surfaces of the two components of the seal, one of which is fixed and the other rotates with the shaft.

Solche Dichtungssysteme erfordern grundsätzlich das Vorhandensein eines dünnen Flüssigkeitsfilms der eingeschlossenen Flüssigkeit zwischen den beiden Oberflächen, wobei dieser Film ein wirkungsvolles Dichtungsmedium darstellt.Such sealing systems basically require the presence of a thin liquid film of the trapped liquid between the two surfaces, which film is an effective sealing medium.

Werden solche Dichtungssysteme bei Behältnissen verwendet, welche instabile Lösungen von Metallsalzen oder-komplexen enthalten, so wurde festgestellt, dass zwischen den dichtenden Flächen eine Zersetzung des Flüssigkeitsfilms stattfindet, die zum Niederschlag von Metall auf den Dichtungsflächen und damit zu starken Verlusten durch Entweichen von Lösung aus dem Behältnis führt.If such sealing systems are used in containers which contain unstable solutions of metal salts or complexes, it has been found that a decomposition of the liquid film takes place between the sealing surfaces, which leads to the precipitation of metal on the sealing surfaces and thus to severe losses due to the escape of solution leads to the container.

Das Auftreten der beschriebenen Undichtigkeit fällt besonders schwer ins Gewicht, wenn wässerige Lösungen von Silbersalzen oder Silberkomplexen verwendet werden.The occurrence of the described leak is particularly difficult if aqueous solutions of silver salts or silver complexes are used.

In US-A-3 910 833 ist ein elektrolytisches Silberwiedergewinnungsgerät beschrieben, bei dem die Welle der rotierenden Elektrode mittels eines speziellen Flüssigkeitsdichtungssystems durch die Gefässwand geführt ist. Dabei ist ein die Welle im Bereich der Wanddurchführung umschliessender Raum mit einer speziellen Dichtflüssigkeit gefüllt. Diese ist unter einem so hohen Druck gehalten, dass ständig etwas Dichtflüssigkeit durch die mechanische Dichtung zwischen Welle und Gefässwand austritt und dadurch einerseits diese Dichtung schmiert und andererseits das Eindringen von korrosiver Lösung in die Lippendichtung verhindert. Dieses bekannte Flüssigkeitsdichtungssystem ist relativ kompliziert und aufwendig und daher entsprechend kostspielig.US-A-3 910 833 describes an electrolytic silver recovery device in which the shaft of the rotating electrode is guided through the vessel wall by means of a special liquid sealing system. A space surrounding the shaft in the area of the wall bushing is filled with a special sealing liquid. This is kept under such a high pressure that some sealing fluid constantly escapes through the mechanical seal between the shaft and the wall of the vessel, thereby lubricating this seal on the one hand and preventing the penetration of corrosive solutions into the lip seal. This known liquid sealing system is relatively complicated and complex and therefore correspondingly expensive.

Aus GB-A-1 224 047 ist es bekannt, metallische Teile in chemischen Apparaten durch anodische Beschaltung gegenüber Korrosion und unerwünschter Beschichtung zu schützen. Diese Druckschrift beschäftigt sich ausschliesslich mit dem Schutz eines metallenen Nickel-Plattierungstanks, gibt jedoch keinerlei Anregungen in bezug auf das der Erfindung zugrundeliegende Problem bei Dichtungen in Silberwiedergewinnungsgeräten. Ausserdem ist das dort beschriebene Verfahren, bei dem Nickel mittels einer alkalischen Lösung und einer porösen Trennwand daran gehindert werden soll, sich in unerwünschten Bereichen des Vernickelungstanks niederzuschlagen, für Silberwiedergewinnungszellen, in denen eine saure Lösung elektrolysiert wird, nicht geeignet.From GB-A-1 224 047 it is known to protect metallic parts in chemical apparatus against corrosion and undesired coating by anodic wiring. This document deals exclusively with the protection of a metal nickel plating tank, but does not give any suggestions regarding the problem on which the invention is based in the case of seals in silver recovery devices. In addition, the method described therein, in which nickel is to be prevented by means of an alkaline solution and a porous partition, from being deposited in undesired areas of the nickel-plating tank, is not suitable for silver recovery cells in which an acidic solution is electrolyzed.

Durch die vorliegende Erfindung soll nun das Dichtungsproblem bei unter Druck stehenden instabilen Lösungen von Metallsalzen oder -komplexen in einem Behältnis mit Welle beseitigt und dementsprechend ein Behältnis der eingangs definierten Art dahingehend verbessert werden, dass seine Dichtung höhere Standzeiten aufweist.The present invention is now intended to eliminate the sealing problem in the case of pressurized, unstable solutions of metal salts or complexes in a container with a shaft, and accordingly to improve a container of the type defined at the outset in such a way that its seal has a longer service life.

Das erfindungsgemässe Behältnis ist im kennzeichnenden Teil von Patentanspruch 1 beschrieben. Bevorzugte und besonders zweckmässige Weiterbildungen ergeben sich aus den abhängigen Ansprüchen.The container according to the invention is described in the characterizing part of claim 1. Preferred and particularly expedient further developments result from the dependent claims.

Im folgenden wird die Erfindung anhand der Zeichnung näher erläutert. Die einzige Zeichnungsfigur zeigt einen Längsschnitt durch ein elektrolytisches Metallwiedergewinnungsbehältnis mit rotierender Kathode gemäss der Erfindung.The invention is explained in more detail below with reference to the drawing. The only drawing figure shows a longitudinal section through an electrolytic metal recovery container with a rotating cathode according to the invention.

Das elektrolytische Wiedergewinnungsgerät umfasst ein aus PVC bestehendes Behältnis V. Im Behältnis V ist eine drehbar gelagerte Kathode C aus nichtrostendem Stahl vorgesehen. Die Kathode C sitzt auf einer Antriebswelle S, die in einem Lager B in der Gehäusewandung des Behältnisses V gelagert ist. Auf der Welle S sitzt eine Antriebsrolle P fest auf, die mit ausserhalb des Geräts gelegenen (nicht gezeigten) Antriebsmitteln verbunden ist.The electrolytic recovery device comprises a container V made of PVC. In the container V, a rotatably mounted cathode C made of stainless steel is provided. The cathode C sits on a drive shaft S, which is mounted in a bearing B in the housing wall of the container V. A drive roller P is firmly seated on the shaft S and is connected to drive means (not shown) located outside the device.

Der elektrische Anschluss der Kathode C erfolgt über die Welle S. Die Antriebsmittel setzen die Kathode C im Behältnis V in Drehung. Die Welle S ist im Behältnis V mittels eines mechanischen Dichtungssystems X abgedichtet, welches aus einem rotierenden Oberflächendichtungselement X, besteht, das auf der Welle S mittels eines Gummibalges Be befestigt ist. Das Oberflächendichtungselement X, steht in dichtender Berührung mit dem Gegenflächendichtungselement X2, das am oberen Gehäuseteil des Behältnisse V mittels eines O-Ringes O befestigt ist.The cathode C is electrically connected via the shaft S. The drive means rotate the cathode C in the container V. The shaft S is sealed in the container V by means of a mechanical sealing system X, which consists of a rotating surface sealing element X, which is fastened on the shaft S by means of a rubber bellows Be. The surface sealing element X is in sealing contact with the counter surface sealing element X 2 , which is attached to the upper housing part of the container V by means of an O-ring O.

An der Innenwand des Behältnisse V ist mit diesem konzentrisch eine Graphitanode A befestigt.A graphite anode A is concentrically attached to the inner wall of the container V with the latter.

Ein Lösungseinlass Q führt von einem Lösungsvorratsbehälter (nicht gezeigt) über eine Pumpe in das Innere des Behältnisse V, und ein Auslassrohr R führt aus dem Behältnis V heraus.
Eine elektrische Verbindungsleitung W verbindet die Gegenflächendichtung X2 mit der Anode A.
A solution inlet Q leads from a solution reservoir (not shown) via a pump into the interior of the container V, and an outlet pipe R leads out of the container V.
An electrical connecting line W connects the mating surface seal X 2 to the anode A.

Weiter unten wird das Material, aus welchem die Dichtungselemente X, und X2 bestehen, noch weiter beschrieben.The material from which the sealing elements X and X 2 are made is described further below.

Ohne zunächst auf die elektrische Verbindungsleitung W einzugehen, wird bei neutralem Betrieb eine wässerige, Metallionen enthaltende Lösung durch den Einlass Q in das Innere des Behältnisse V gepumpt, während die Kathode C und die Anode A über die elektrischen Anschlussklemmen U1 und U2 unter Bildung einer elektrischen Zelle an eine Stromquelle U angeschlossen sind. Die Kathode C wird in Drehung versetzt und das Metall aus der wässerigen Lösung auf der Kathode abgelagert. Die wässerige Lösung wird kontinuierlich langsam in das Behältnis V durch den Einlass Q hineingepumpt und verlässt ihn wieder durch den Auslass R, so dass die Lösung im Behältnis V ständig unter Druck steht.Without first going into the electrical connection line W, an aqueous solution containing metal ions is passed through the inlet Q into the interior of the container V ge during neutral operation pumps while the cathode C and the anode A are connected to a current source U via the electrical connection terminals U 1 and U 2 , forming an electrical cell. The cathode C is rotated and the metal from the aqueous solution is deposited on the cathode. The aqueous solution is continuously pumped slowly into the container V through the inlet Q and leaves it again through the outlet R, so that the solution in the container V is constantly under pressure.

Um die Welle S herum muss eine flüssigkeitsdichte Abdichtung vorgesehen sein. Ist dies nicht der Fall, so kriecht Flüssigkeit längs der Welle und tritt am oberen Ende des Behältnisses aus. Dies verursacht eine Korrosion des mit der Lösung in Kontakt kommenden Lagers B, und ausserdem eine Verschmutzung, da die Lösung aus dem oberen Ende des Behälters um den Schaft herum in unkontrollierbarer Weise herausgedrückt wird. Es ist daher erforderlich, dass die Dichtungselemente X, und X2 zusammen eine sogenannte «Flüssigkeitsdichtung» bilden.A liquid-tight seal must be provided around the shaft S. If this is not the case, liquid creeps along the shaft and exits at the top of the container. This causes corrosion of the bearing B in contact with the solution, and also contamination, since the solution is pressed out of the upper end of the container around the shaft in an uncontrollable manner. It is therefore necessary that the sealing elements X, and X 2 together form a so-called «liquid seal».

Hierbei bildet, während das auf der rotierenden Welle festsitzende Oberflächendichtungselement X, in enger Berührung mit dem Gegenflächendichtungselement X2 rotiert, ein dünner Flüssigkeitsfilm eine Flüssigkeitsdichtung zwischen den beiden Elementen, welche eine direkte Berührung zwischen den beiden Dichtungselementen verhindert und als Schmiermittel zwischen ihnen wirkt.Here, while the surface sealing element X stuck on the rotating shaft rotates in close contact with the counter surface sealing element X 2 , a thin liquid film forms a liquid seal between the two elements, which prevents direct contact between the two sealing elements and acts as a lubricant between them.

Ist jedoch eine instabile Lösung eines Metallsalzes oder -komplexes im Behältnis vorhanden, so wurde festgestellt, dass diese Lösung dazu neigt, sich an der Stelle des Flüssigkeitsdichtung zu zersetzen, so dass Metall auf den Oberflächen der beiden Dichtungselemente X, und X2 abgelagert wird.However, if an unstable solution of a metal salt or complex is present in the container, it was found that this solution tends to decompose at the location of the liquid seal, so that metal is deposited on the surfaces of the two sealing elements X, and X 2 .

Dies verursacht eine Vergrösserung des Abstandes zwischen den Dichtungsflächen der beiden Elemente und gestattet den Zutritt von mehr Lösung an die Dichtungsstelle, was zur Folge hat, dass nun mehr Metall auf den Dichtungsflächen der beiden Elemente abgelagert wird, bis sie schliesslich so weit auseinanderklaffen, dass keine Flüssigkeitsdichtung mehr bewirkt wird und die Flüssigkeit an der Welle entlang fliessen kann.This causes the distance between the sealing surfaces of the two elements to increase and allows more solution to enter the sealing location, with the result that more metal is now deposited on the sealing surfaces of the two elements until they finally diverge so far that none Liquid seal is more effected and the liquid can flow along the shaft.

Bei einem Vergleichsversuch bestand das rotierende Oberflächendichtungselement X, aus keramischem Material und das feststehende Gegenflächendichtungselement X2 aus Graphit.In a comparison experiment, the rotating surface seal element X consisted of ceramic material and the stationary counter-face seal element X 2 made of graphite.

Bei einem Vorversuch wurde die Zelle nicht mit einer Stromquelle verbunden, jedoch Wasser durch das Behältnis V mit einem Druck von 1,01 bar durchgelassen und die Kathode C mit einer Drehzahl von 1000 U/min in Drehung versetzt. Nach 48 Stunden kontinuierlichem Betrieb wurden keine Flüssigkeitsverluste aus dem Behältnis festgestellt.In a preliminary test, the cell was not connected to a power source, but water was let through the container V at a pressure of 1.01 bar and the cathode C was rotated at a speed of 1000 rpm. After 48 hours of continuous operation, no fluid loss from the container was found.

Bei einem zweiten Versuch wurde die Zelle ebenfalls nicht mit der Stromquelle verbunden, jedoch wurde eine Kochsalzlösung (100 g NaCI je Liter) kontinuierlich unter einem Druck von 1,01 bar durch das Behältnis gepumpt und die Kathode wiederum mit 1000 U/min in Drehung versetzt. Wiederum wurde beim Behältnis nach 48 Stunden kontinuierlichem Betrieb kein Flüssigkeitsverlust festgestellt, denn Natriumchlorid bildet eine stabile Salzlösung.In a second experiment, the cell was also not connected to the power source, but a saline solution (100 g NaCl per liter) was pumped continuously through the container under a pressure of 1.01 bar and the cathode was again rotated at 1000 rpm . Again, no loss of liquid was found in the container after 48 hours of continuous operation, because sodium chloride forms a stable salt solution.

In einem dritten Versuch wurde eine Lösung eingesetzt, deren Zusammensetzung ungefähr derjenigen einer photographischen Fixierlösung entsprach und die je Liter:

  • 0,5 mol Ammoniumthiosulfat
  • 0,1 mol Natriumsulfit
  • 0,2 mol Essigsäure und
  • 0,3 mol Silberbromid

enthielt. Tatsächlich bildet das Silberbromid mit dem Thiosulfiteinen instabilen wasserlöslichen Komplex, so dass eine instabile wässerige Silbersalzlösung gebildet wird.In a third experiment, a solution was used whose composition approximately corresponded to that of a photographic fixing solution and which per liter:
  • 0.5 mol ammonium thiosulfate
  • 0.1 mol sodium sulfite
  • 0.2 mol of acetic acid and
  • 0.3 mol of silver bromide

contained. In fact, the silver bromide forms an unstable water-soluble complex with the thiosulfite, so that an unstable aqueous silver salt solution is formed.

Die Zelle wurde wiederum nicht an die Stromquelle angeschlossen, jedoch die Fixierlösung unter 1,01 bar Druck durch das Behältnis gepumpt und die Kathode mit 1000 U/min rotiert. Nach drei Stunden Betrieb wurde beobachtet, dass Flüssigkeit aus dem Behältnis an der Eintrittsstelle der Welle S in diesen austrat. Der Betrieb wurde unterbrochen und die Dichtungselemente X, und X2 untersucht. Es wurde gefunden, dass auf beiden Elementen Ablagerung von metallischem Silber stattgefunden hatte, welche einen Spalt zwischen den Dichtungsflächen verursachte und damit die Flüssigkeitsdichtung aufgehoben hatte.The cell was again not connected to the power source, but the fixing solution was pumped through the container under a pressure of 1.01 bar and the cathode was rotated at 1000 rpm. After three hours of operation, it was observed that liquid escaped from the container at the point of entry of the shaft S. The operation was interrupted and the sealing elements X, and X 2 were examined. It was found that metallic silver had deposited on both elements, causing a gap between the sealing surfaces and thus breaking the liquid seal.

Bei einem vierten Versuch wurde die gleiche Fixierlösung unter den gleichen Bedinungen durch das gleiche Behältnis gepumpt, jedoch in diesem Falle die Zelle an eine Stromquelle angeschlossen, wobei jedoch die Leitung W nicht mit dem Gegenflächendichtungselement X2 verbunden war. Das Behältnis arbeitete dann als eine Elektrolytzelle mit einer Stromdichte von 0,2 A' cm-2. Jedoch wurde nach zwei Stunden der Austritt von Flüssigkeit aus dem Behältnis um die Welle S herum beobachtet. Der Versuch wurde dann unterbrochen und das Behältnis geöffnet. Es wurde gefunden, dass sich metallisches Silber auf der Kathode C in Pulverform abgesetzt hatte. Auch wurden Ablagerungen von Silvermetall auf den Dichtungsflächen der beiden Dichtungselemente X, und X2 festgestellt.In a fourth experiment, the same fixing solution was pumped through the same container under the same conditions, but in this case the cell was connected to a power source, but the line W was not connected to the counter surface sealing element X 2 . The container then worked as an electrolyte cell with a current density of 0.2 A 'cm- 2. However, after two hours, the leakage of liquid from the container around the S wave was observed. The experiment was then interrupted and the container opened. It was found that metallic silver had deposited on the cathode C in powder form. Deposits of silver metal were also found on the sealing surfaces of the two sealing elements X and X 2 .

Beim fünften Versuch wurde die gleiche Fixierlösung unter den gleichen Bedinungen durch das gleiche Behältnis gepumpt und die Zelle an die Stromquelle angeschlossen, aber hierbei die Leitung W mit der Anode A und mit dem elektrisch leitenden Gegenflächendichtungselement X2 verbunden. In diesem Falle konnte sogar nach 48 Stunden ununterbrochenem Betrieb kein Flüssigkeitsverlust aus dem Behältnis beobachtet werden. Der Versuch wurde dann unterbrochen und das Behältnis geöffnet. Wiederum wurde auf der Kathode eine Ablagerung von Silber in Pulverform festgestellt, jedoch kein Niederschlag von Silbermetall oder irgendeiner anderen Ablagerung auf den Flächen der beiden Dichtungselemente X, und X2. In diesem Falle betrug das Potential zwischen dem Gegenflächendichtungselement X2 und der Welle 1,5 V.In the fifth experiment, the same fixing solution was pumped through the same container under the same conditions and the cell was connected to the power source, but here the line W was connected to the anode A and to the electrically conductive mating surface sealing element X 2 . In this case, no liquid loss from the container was observed even after 48 hours of uninterrupted operation. The experiment was then interrupted and the container opened. Again a deposit of silver in powder form was found on the cathode, but no deposit of silver metal or any other deposit on the surfaces of the two sealing elements X, and X 2 . In this case the potential between the counter surface sealing element X 2 and the shaft was 1.5 V.

Als weiteres elektrisch leitendes Material für das feststehende Gegenflächendichtungselement X2 ist nichtrostender Stahl geeignet. Das drehbare Gegenflächendichtungselement X, kann ebenfalls aus Graphit oder nichtrostendem Stahl bestehen. Andere geeignete Herstellungsmaterialien sind Wolframkarbid und Polytetrafluoräthylen. Die bevorzugte Kombination ist Graphit-Graphit.Stainless steel is suitable as a further electrically conductive material for the fixed counter surface sealing element X 2 . The rotatable counter surface sealing element X can also consist of graphite or stainless steel. Other suitable manufacturing materials are tungsten carbide and polytetrafluoroethylene. The preferred combination is graphite-graphite.

In dem zuletzt beschriebenen Versuch stellt das Behältnis eine elektrolytische Zelle dar, und der durch die Potentialdifferenz zwischen dem Gegenflächendichtungselement X2 und der Kathode erzeugte Strom verursacht, dass sich etwas Silbermetall auf der Kathode ablagert. Wird jedoch die Erfindung zum Schutze von Dichtungen in anderen unter Druck stehenden Behältnissen verwendet, in welchen eine Welle sich dreht oder sich hin und her bewegt, so können die Abmessungen der Kathode und erforderlichenfalls durch elektrische Abschirmung der elektrisch leitenden Dichtung auch der Stromfluss durch die so gebildete Zelle auf ein Mindestmass beschränkt werden. Hierdurch wird auch die Menge des auf der Kathode abgesetzten Metalls sowie etwaige Nebenwirkungen auf die Lösung im Behältnis gleichermassen niedrig gehalten.In the experiment described last, the container is an electrolytic cell, and the current generated by the potential difference between the counter surface sealing element X 2 and the cathode causes some silver metal to be deposited on the cathode. However, if the invention is used to protect seals in other pressurized containers in which a shaft rotates or moves back and forth, the dimensions of the cathode and, if necessary, the current flow through the electrically conductive seal, if necessary, can also be reduced formed cell are limited to a minimum. This also keeps the amount of metal deposited on the cathode and any side effects on the solution in the container equally low.

Claims (3)

1. A vessel for a pressurised unstable solution of a metal salt or complex, wherein a moving shaft (S) extends liquid-tight through a wall of the vessel (V) by means of a sealing system (X) comprising a stationary counter-face seal (X2) and a face seal (X,) which moves with the shaft (S), with a least the stationary counter-face seal (X2) of the sealing system (X) consisting of electro-conductive material, characterised in that said vessel (V) is equipped with a cathode (C), with electrical terminals (Ui, U2) being provided for applying a voltage between the counter-face seal (X2) and the cathode (C).
2. A vessel according to claim 1, characterised in that the counter-face seal (X2) consists of graphite.
3. A vessel according to either of claims 1 or 2, characterised in that the sealing system (X) is in the form of a lip seal, the seal lip of which consists of the electro-conductive material.
EP83810011A 1982-01-19 1983-01-13 Vessel containing an unstable solution of a metal salt or complex, and process for sealing such a vessel Expired EP0084519B1 (en)

Applications Claiming Priority (2)

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GB8201366 1982-01-19
GB8201366 1982-01-19

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EP0084519A2 EP0084519A2 (en) 1983-07-27
EP0084519A3 EP0084519A3 (en) 1983-08-03
EP0084519B1 true EP0084519B1 (en) 1985-12-18

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EP (1) EP0084519B1 (en)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4889608A (en) * 1987-02-10 1989-12-26 Pine Instrument Company Electrode system
FR2639961A1 (en) * 1988-11-28 1990-06-08 Lobry Andre Device for protecting surfaces in contact with liquid against scaling or corrosion
FR2657089A1 (en) * 1990-01-16 1991-07-19 Lobry Andre Protection against scaling and corrosion of surfaces in contact with liquids
US7481922B2 (en) * 2004-01-05 2009-01-27 Edward Horton Madden Fluid treatment apparatus

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3240685A (en) * 1962-02-23 1966-03-15 Ibm Method and device for selective anodization
NL297569A (en) * 1962-09-06
US3169504A (en) * 1963-12-16 1965-02-16 Wankesha Bearings Corp Cathodic system
US3429799A (en) * 1966-05-31 1969-02-25 Monsanto Co Fluid-tight electrical connections for electrolytic cells
US3486999A (en) * 1967-11-02 1969-12-30 Leonard F Craft Apparatus for preventing scale formation in water systems
GB1224047A (en) * 1968-12-10 1971-03-03 Tsniitmash Method of inhibiting the formation of a coating on chemical equipment
US3910833A (en) * 1974-09-26 1975-10-07 David R Knighton Apparatus for recovering silver from photographic film processing liquids
US3985634A (en) * 1975-01-27 1976-10-12 Larson Kay R Electrolytic silver recovery apparatus
FR2327326A1 (en) * 1975-10-08 1977-05-06 Solvay PROCESS FOR THE HANDLING OF AQUEOUS SOLUTIONS OF ALKALINE METAL HYDROXIDES CONCENTRATED IN ALKALINE METAL HALOGENIDES
US4113600A (en) * 1977-04-21 1978-09-12 A. O. Smith Corporation Flue pipe anode ring for water heater

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DE3361502D1 (en) 1986-01-30
US4545873A (en) 1985-10-08
JPS58128138A (en) 1983-07-30
EP0084519A2 (en) 1983-07-27
EP0084519A3 (en) 1983-08-03

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