DE2251442C3 - Process for the electrolytic detoxification of cyanide - Google Patents

Process for the electrolytic detoxification of cyanide

Info

Publication number
DE2251442C3
DE2251442C3 DE19722251442 DE2251442A DE2251442C3 DE 2251442 C3 DE2251442 C3 DE 2251442C3 DE 19722251442 DE19722251442 DE 19722251442 DE 2251442 A DE2251442 A DE 2251442A DE 2251442 C3 DE2251442 C3 DE 2251442C3
Authority
DE
Germany
Prior art keywords
cyanide
anodes
steel
detoxification
electrolytic
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
DE19722251442
Other languages
German (de)
Other versions
DE2251442A1 (en
DE2251442B2 (en
Inventor
Helmut Dr.Rer.Nat. 5419 Dierdorf Reuther
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.)
Keramchemie GmbH
Original Assignee
Gewerkschaft Keramchemie, 5433 Siershahn
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 Gewerkschaft Keramchemie, 5433 Siershahn filed Critical Gewerkschaft Keramchemie, 5433 Siershahn
Priority to DE19722251442 priority Critical patent/DE2251442C3/en
Publication of DE2251442A1 publication Critical patent/DE2251442A1/en
Publication of DE2251442B2 publication Critical patent/DE2251442B2/en
Application granted granted Critical
Publication of DE2251442C3 publication Critical patent/DE2251442C3/en
Expired legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/10Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
    • A62D3/11Electrochemical processes, e.g. electrodialysis
    • A62D3/115Electrolytic degradation or conversion
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20Organic substances
    • A62D2101/26Organic substances containing nitrogen or phosphorus
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40Inorganic substances
    • A62D2101/45Inorganic substances containing nitrogen or phosphorus
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • C02F2101/18Cyanides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Electrolytic Production Of Metals (AREA)

Description

Die Erfindung bezieht sich auf ein Verfahren zur elektrolytischen Entgiftung von Cyanid im Durchlaufoder Standverfahren, wobei Anoden aus Stahl verwendet und dem Elektrolyten Kupfersalze zugesetzt werden.The invention relates to a process for the electrolytic detoxification of cyanide in a continuous or Stand-up process, in which anodes made of steel are used and copper salts are added to the electrolyte will.

Aus dem Buch »Die Abwässer in der Metallindustrie«, von Dr. R. Weiner, 1965, Seiten 178/179, ist es bekannt, daß in stärker konzentrierten Cyanid-Lösungen die Zerstörung des Cyanids durch Elektrolyse erfolgen kann, wobei diese Zerstörung durch Oxidation an unlöslichen Anoden geschieht. Gleich- ω zeitig in der Lösung vorhandene Schwermetalle, z. B. Kupfer, werden in metallischer Form an der Kathode abgeschieden. Dabei werden Stahlbleche als unlösliche Anoden verwendet. Diese Stahlblech-Anoden sind jedoch nur in solchen Lösungen beständig, die J5 keine lösenden Anionen, wie Chlorid oder Sulfat, in größerer Menge enthalten.From the book "Die Abwässer in der Metallindustrie", by Dr. R. Weiner, 1965, pages 178/179, it is known that in more concentrated cyanide solutions the destruction of the cyanide by electrolysis can take place, this destruction occurring through oxidation on insoluble anodes. Equal- ω Heavy metals present early in the solution, e.g. B. copper, are in metallic form at the cathode deposited. Steel sheets are used as insoluble anodes. These sheet steel anodes however, they are only stable in solutions that include J5 does not contain large quantities of dissolving anions such as chloride or sulphate.

Gemäß einem nicht zum Stand der Technik gehörenden Vorschlag wurden bei einem Verfahren zur elektrolytischen Entgiftung von Cyanid die Stahlblech-Anoden durch VA-Stahl-Anoden ersetzt. Obwohl VA-Stahl in chemischer Hinsicht ein hochresistenter Werkstoff ist, wurden dennoch die Anoden aus VA-Stahl in verhältnismäßig kurzer Zeit zerstört. Dabei ist die Zerstörung der Anoden ebenfalls darauf 4-> zurückzuführen, daß die zu entgiftende Cyanid-Lösung lösende Anionen, wahrscheinlich Chlorid, in größerer Menge enthielt.According to a proposal not belonging to the prior art, a method for electrolytic decontamination of cyanide replaces the sheet steel anodes with VA steel anodes. Even though VA steel is a highly resistant material from a chemical point of view, the anodes were nonetheless made of VA steel destroyed in a relatively short time. The destruction of the anodes is also on it 4-> attributed to the fact that the cyanide solution to be detoxified has dissolving anions, probably chloride, in contained a larger amount.

Der Erfindung liegt daher die Aufgabe zugrunde, ein Verfahren gemäß dem Oberbegriff des Anspruches 1 so weiterzubilden, daß sich die Anwesenheit von lösenden Anionen in der zu entgiftenden Cyanid-Lösung nicht nachteilig bzw. zerstörend auf die Anoden auswirkt. Zur Lösung dieser Aufgabe wird bei einem Verfahren gemäß dem Oberbegriff des Anspruches 1 vorgeschlagen, daß als Anodenmaterial VA-Stahl verwendet wird und dem Elektrolyten Kupfersalze in Mengen von 50-150 mg Cu2+Zl zugesetzt werden.The invention is therefore based on the object of developing a method according to the preamble of claim 1 so that the presence of dissolving anions in the cyanide solution to be detoxified does not have a disadvantageous or destructive effect on the anodes. To solve this problem it is proposed in a method according to the preamble of claim 1 that VA steel is used as the anode material and that copper salts in amounts of 50-150 mg Cu 2+ Zl are added to the electrolyte.

Bei diesem Verfahren zeigen die VA-Anoden keinerlei Gewichtsabnahme, auch über längere Zeiträume hinweg nicht, d. h., durch das erfindungsgemäße Verfahren wird der oxidative Angriff auf die Anode verhindert, und die Anode ist somit unbegrenzt haltbar. Durch die Zugabe von Kupfersalzen zum Elektroylten wird eine Passivierung der Anode bewirkt, d. h., es bildet sich an der Anode ein verhältnismäßig dünner Belag aus feinpulverigem Kupfer. Dieser pulverige Belag bildet jedoch an der Anode keine unlösliche, nichtleitende Sperrschicht, sondern verhindert nur die Oxidation der Anode. Das abgeschiedene, feinpulverige Kupfer geht wieder in Lösung und wird wieder abgeschieden.With this method, the VA anodes show no weight loss whatsoever, even over long periods of time not away, d. That is, by the method according to the invention, the oxidative attack on the Prevents anode, and the anode is therefore indefinitely durable. By adding copper salts a passivation of the anode is effected for the electroylte, d. that is, a proportionately formed at the anode thin coating of fine-powdered copper. However, this powdery coating forms on the anode no insoluble, non-conductive barrier layer, but only prevents oxidation of the anode. The secluded, fine-powdered copper goes back into solution and is deposited again.

Das erfindungsgemäße Verfahren kann mit einer bei der elektrolytischen Oxidation üblichen Stromausbeute von 65 % bis zu einem Restgehait von 0,5 g/l CN" durchgeführt werden. Daran kann sich eine chemische Restentgiftung anschließen.The process according to the invention can be carried out with a current yield that is customary in electrolytic oxidation of 65% to a residual content of 0.5 g / l CN "can be carried out. A chemical Connect residual detoxification.

Das erfindungsgemäße Verfahren ist besonders vorteilhaft, wenn der Elektrolyt 100 mg Cu2+/! enthält. The method according to the invention is particularly advantageous if the electrolyte contains 100 mg Cu 2+ /! contains.

Bei einem Ausfuhrungsbeispiel wurden 22,5 1 einer Lösung mit 10 g/l CN" im Standverfahren bis auf einen Restgehalt von 180 mg/1 CN" entgiftet. Es wurden 393 mg Kupfersulfat/l zu entgiftender Lösung zugesetzt, was einer Konzentration von ca. 100 mg/I Cu2+ entspricht. Die Gesamtmenge an oxidiertem Cyanid betrug 221 g.In one exemplary embodiment, 22.5 l of a solution with 10 g / l CN "were detoxified in the standing process down to a residual content of 180 mg / 1 CN". 393 mg copper sulfate / l solution to be detoxified were added, which corresponds to a concentration of approx. 100 mg / l Cu 2+ . The total amount of oxidized cyanide was 221 g.

Elektrolysedaten:Electrolysis data: 2,3 V2.3V Zellenspannung:Cell voltage: 100 A100 A Stromstärke:Amperage: 6 Std. 40 Min6 hours 40 minutes Elektrolysedauer:Electrolysis time: 27 mm27 mm Elektrodenabstand:Electrode distance:

Hieraus ergibt sich für die Entgiftung von 1 kg Cyanid ein Leistungsbedarf von 6,8 kW.This results in a power requirement of 6.8 kW for the detoxification of 1 kg of cyanide.

Claims (2)

Patentansprüche:Patent claims: 1. Verfahren zur elektrolytischen Entgiftung · von Cyanid im Durchlauf- oder Standverfahren, wobei Anoden aus Stahl verwendet und dem Elektrolyten Kupfersalze zugesetzt werden, dadurch gekennzeichnet, daß als Anodenmaterial VA-Stahl verwendet wird und dem Elektrolyten Kupfersalze in Mengen von 50—150 mg Cu2+/1 zugesetzt werden.1. Process for electrolytic detoxification of cyanide in a continuous or standing process, using anodes made of steel and adding copper salts to the electrolyte, characterized in that VA steel is used as the anode material and copper salts in quantities of 50-150 mg Cu are used for the electrolyte 2+ / 1 can be added. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß dem Elektrolyten 100 mg Cu2+/1 zugesetzt werden.2. The method according to claim 1, characterized in that the electrolyte 100 mg Cu 2+ / 1 are added. 1515th
DE19722251442 1972-10-20 1972-10-20 Process for the electrolytic detoxification of cyanide Expired DE2251442C3 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19722251442 DE2251442C3 (en) 1972-10-20 1972-10-20 Process for the electrolytic detoxification of cyanide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19722251442 DE2251442C3 (en) 1972-10-20 1972-10-20 Process for the electrolytic detoxification of cyanide

Publications (3)

Publication Number Publication Date
DE2251442A1 DE2251442A1 (en) 1974-04-25
DE2251442B2 DE2251442B2 (en) 1979-05-17
DE2251442C3 true DE2251442C3 (en) 1980-01-10

Family

ID=5859558

Family Applications (1)

Application Number Title Priority Date Filing Date
DE19722251442 Expired DE2251442C3 (en) 1972-10-20 1972-10-20 Process for the electrolytic detoxification of cyanide

Country Status (1)

Country Link
DE (1) DE2251442C3 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3429156A1 (en) * 1984-08-08 1986-02-20 Alfred Teves Gmbh, 6000 Frankfurt METHOD AND CIRCUIT FOR MONITORING AND CONTROLLING A SLIP-CONTROLLED BRAKE SYSTEM

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4218916C2 (en) * 1992-06-10 1996-03-21 Heraeus Elektrochemie Use of a grid anode for electrolytic detoxification or regeneration of an aqueous solution containing cyanide
DE102011081805A1 (en) 2011-08-30 2013-02-28 Akretia Gmbh Electrolytic refining of metals from solid starting material containing metal to be refined, comprises contacting starting material with cyanide-containing leaching solution, electrolytically depositing metal, and partially reacting cyanide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3429156A1 (en) * 1984-08-08 1986-02-20 Alfred Teves Gmbh, 6000 Frankfurt METHOD AND CIRCUIT FOR MONITORING AND CONTROLLING A SLIP-CONTROLLED BRAKE SYSTEM
DE3429156C2 (en) * 1984-08-08 1994-06-23 Teves Gmbh Alfred Circuit arrangement for monitoring and controlling an anti-lock brake system

Also Published As

Publication number Publication date
DE2251442A1 (en) 1974-04-25
DE2251442B2 (en) 1979-05-17

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Legal Events

Date Code Title Description
OD Request for examination
C3 Grant after two publication steps (3rd publication)
8327 Change in the person/name/address of the patent owner

Owner name: KERAMCHEMIE GMBH, 5433 SIERSHAHN, DE

8339 Ceased/non-payment of the annual fee