EP0581093A1 - Process and agent for the oxidative destruction of azides - Google Patents

Process and agent for the oxidative destruction of azides Download PDF

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Publication number
EP0581093A1
EP0581093A1 EP93111094A EP93111094A EP0581093A1 EP 0581093 A1 EP0581093 A1 EP 0581093A1 EP 93111094 A EP93111094 A EP 93111094A EP 93111094 A EP93111094 A EP 93111094A EP 0581093 A1 EP0581093 A1 EP 0581093A1
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EP
European Patent Office
Prior art keywords
iodine
azides
azide
iodide
solution
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
EP93111094A
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German (de)
French (fr)
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EP0581093B1 (en
Inventor
Arnulf Dr. Heubner
Michael Dr. Schwarz
Bernd Dr. Reckmann
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Merck Patent GmbH
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Merck Patent GmbH
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Priority to DE4224114A priority patent/DE4224114A1/en
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    • 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
    • A62D3/30Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/903Nitrogenous

Abstract

Die Erfindung betrifft Verfahren und Mittel zur oxidativen Zerstörung von Aziden. Das Verfahren ist dadurch gekennzeichnet, daß die zu entsorgenden Azid enthaltenden Lösungen mit einer Jod/Jodid-Lösung in Gegenwart von Thiosulfat behandelt werden. Vorzugsweise wird das Mittel in Form von Tabletten eingesetzt.The invention relates to methods and agents for the oxidative destruction of azides. The process is characterized in that the azide-containing solutions to be disposed of are treated with an iodine / iodide solution in the presence of thiosulfate. The agent is preferably used in the form of tablets.

Description

Die Erfindung betrifft Verfahren und Mittel zur oxidativen Zerstörung von Aziden, insbesondere zur Entsorgung von Azid enthaltenden Lösungen aus dem Bereich der klinischen Chemie, wie sie z.B. im Rahmen der Diagnostik im Laboratorium anfallen.The invention relates to methods and agents for the oxidative destruction of azides, in particular for the disposal of azide-containing solutions from the field of clinical chemistry, as described e.g. in the context of diagnostics in the laboratory.

Zum Konservieren von wäßrigen Lösungen in diagnostischen Testsätzen wird fast ausschließlich Natriumazid verwendet. Auf die Problematik der Vernichtung von Aziden aus Abfällen wird in der Literatur hingewiesen; es sind jedoch keine brauchbaren Lösungen für dieses Problem aus dem Stand der Technik bekannt. In US 3,768,865 wird vorgeschlagen, mit Azid belastete Salzlösungen in unterirdischen Kavernen zu lagern, bis sie im wesentlichen frei von Azid sind, und die Lösungen dann wieder an die Erdoberfläche zu pumpen. In J. Chem. Educ. 62, 93 (1985) wird ausgeführt, daß die Oxidation mit Cer(IV)-ammoniumsulfat eine häufig beschriebene Methode zur Vernichtung anorganischer Azide ist, die Reaktion jedoch extrem langsam abläuft und nicht befriedigend ist.Sodium azide is used almost exclusively to preserve aqueous solutions in diagnostic test kits. The literature points to the problem of the destruction of azides from waste; however, no viable solutions to this problem are known in the art. No. 3,768,865 proposes to store salt solutions contaminated with azide in underground caverns until they are essentially free of azide, and then to pump the solutions back to the surface of the earth. In J. Chem. Educ. 62 , 93 (1985) states that oxidation with cerium (IV) ammonium sulfate is a frequently described method for the destruction of inorganic azides, but the reaction proceeds extremely slowly and is unsatisfactory.

Es gibt bisher keine geeignete Methode zur Entsorgung von Azid in Abfällen. Der Erfindung liegt deshalb die Aufgabe zugrunde, Mittel und Verfahren zur Verfügung zu stellen, die die beschriebenen Nachteile vermeiden und eine die Umwelt schonende Zerstörung von Aziden erlauben, d.h. die keine schädlichen Abbauprodukte liefern.So far, there is no suitable method for disposing of azide in waste. The invention is therefore based on the object of making available means and methods which avoid the disadvantages described and which permit environmentally friendly destruction of azides, ie which do not provide any harmful degradation products.

Gegenstand der Erfindung ist ein Verfahren zu oxidativen Zerstörung von Aziden, das dadurch gekennzeichnet ist, daß die zu entsorgenden Azid enthaltenden Lösungen mit einer Jod/Jodid-Lösung in Gegenwart von Thiosulfat behandelt werden.The invention relates to a process for the oxidative destruction of azides, which is characterized in that the azide-containing solutions to be disposed of are treated with an iodine / iodide solution in the presence of thiosulfate.

Ein weiterer Gegenstand der Erfindung ist ein Mittel zur oxidativen Zerstörung von Aziden, gekennzeichnet durch Jod/Jodid- und Thiosulfat enthaltende Tabletten, sowie dessen Verwendung zur Entsorgung von Aziden, vorzugsweise in Lösungen aus dem Bereich der klinischen Chemie.Another object of the invention is an agent for the oxidative destruction of azides, characterized by tablets containing iodine / iodide and thiosulfate, and its use for the disposal of azides, preferably in solutions from the field of clinical chemistry.

Die Oxidation von Stickstoffwasserstoffsäure mit Jod in Gegenwart von etwas Thiosulfat als Katalysator führt die Säure quantitativ in Stickstoff über. Diese Reaktion war bisher zur Analyse von Stickstoffwasserstoffsäure bekannt. Sie hat jedoch keinen Eingang gefunden in das seit langem bestehende Bedürfnis der unschädlichen Entsorgung von Aziden.The oxidation of hydrochloric acid with iodine in the presence of some thiosulfate as a catalyst converts the acid quantitatively into nitrogen. This reaction was previously known for the analysis of hydrochloric acid. However, it has found no entry in the long-standing need for the harmless disposal of azides.

Überraschenderweise hat sich gezeigt, daß das erfindungsgemäße Verfahren auch bei äußerst geringen Konzentrationen von Azid im Überschuß von Serumbestandteilen und Puffersubstanzen wirksam ist. Das läßt darauf schließen, daß das Azid sehr schnell reagiert, noch bevor das Jod durch andere oxidierbare Serumbestandteile aufgebraucht ist.Surprisingly, it has been shown that the process according to the invention is effective even at extremely low concentrations of azide in excess of serum components and buffer substances. This suggests that the azide reacts very quickly before the iodine is used up by other oxidizable serum components.

Das Verfahren nach der Erfindung wird so durchgeführt, daß man zur Azid enthaltenden Abfallösung zunächst eine katalytische Menge Natriumthiosulfat und anschließend eine Jodlösung bis zur dauerhaften Färbung hinzugibt.The process according to the invention is carried out by first adding a catalytic amount of sodium thiosulfate to the waste solution containing azide and then adding an iodine solution until permanent coloring.

Überschüssiges Jod kann nach einer bestimmten Einwirkungszeit mit Thiosulfat oder anderen Reduktionsmitteln wie Metabisulfit, Dithionit, Ascorbinsäure, in Jodid überführt werden. Die Oxidation mit Jod ist völlig unabhängig vom pH-Wert, sie wird jedoch vorzugsweise in gepufferten Systemen durchgeführt. Der pH-Wert der zu entsorgenden Lösungen liegt vorzugsweise im Bereich von pH 6 bis pH 9.Excess iodine can be converted into iodide after a certain exposure time with thiosulfate or other reducing agents such as metabisulfite, dithionite, ascorbic acid. Oxidation with iodine is completely independent of the pH value, but is preferably carried out in buffered systems. The pH of the solutions to be disposed of is preferably in the range from pH 6 to pH 9.

Als Jodlösung wird eine wäßrige Lösung von Jod und Kaliumjodid im Gewichtsverhältnis von etwa 2:1 eingesetzt. Dieses Verhältnis ist jedoch nicht kritisch und kann in einem weiten Bereich variiert werden. Die einzusetzende Jodkonzentration ist abhängig vom Gehalt an oxidierbaren Substanzen in der Abfallösung. Da zur Vernichtung von einem Mol Natriumazid 0,5 Mol Jod (J₂ ) verbraucht werden, sind 126,9 g Jod die minimale Konzentration, die dazu erforderlich ist. Die Azidkonzentrationen im Abfall bewegen sich in der Regel in der Größenordnung von wenigen mmol, so daß entsprechend geringe Mengen an Jod erforderlich sind.An aqueous solution of iodine and potassium iodide in a weight ratio of about 2: 1 is used as the iodine solution. However, this ratio is not critical and can be varied over a wide range. The iodine concentration to be used depends on the content of oxidizable substances in the waste solution. Since 0.5 mol of iodine (J₂) is consumed to destroy one mole of sodium azide, 126.9 g of iodine are the minimum concentration required for this. The azide concentrations in the waste are generally of the order of magnitude of a few mmol, so that correspondingly small amounts of iodine are required.

Jod/Kaliumjodid als auch Natriumthiosulfat werden vorzugsweise in Form von Tabletten eingesetzt. Eine Jod/Kaliumjodid-Tablette zur Entsorgung von 1 l Azid enthaltendem Abfall enthält z.B. 1 g Jod und 0,5 g Kaliumjodid neben üblichen Tablettierhilfsmittelen wie Polyethylenglykol, Magnesiumsulfat, Magnesiumcarbonat, Mannit, Sorbit, Methylzellulose, Calciumstearat usw. Die Natriumthiosulfatkonzentration liegt bei etwa 0,1 bis 1 Gew.-% der Jodkonzentration. Es ist auch möglich, Jodid zusammen mit Thiosulfat zu verpressen.Iodine / potassium iodide and sodium thiosulfate are preferably used in the form of tablets. An iodine / potassium iodide tablet for the disposal of waste containing 1 l of azide contains, for example, 1 g of iodine and 0.5 g of potassium iodide in addition to conventional tabletting aids such as polyethylene glycol, magnesium sulfate, magnesium carbonate, mannitol, sorbitol, methyl cellulose, calcium stearate, etc. The sodium thiosulfate concentration is around 0 , 1 to 1 wt .-% of the iodine concentration. It is also possible to inject iodide together with thiosulfate.

Aufgrund der Tatsache, daß Jod antiseptisch, bakterizid, sporizid, fungizid und viruzid wirkt und in der Hauptsache Abfälle von Körperflüssigkeiten entsorgt werden müssen, ergibt sich der zusätzliche Vorteil, daß mit dem erfindungsgemäßen Mittel nicht nur das Azid zerstört wird, sondern auch alle Keime abgetötet werden.Due to the fact that iodine has an antiseptic, bactericidal, sporicidal, fungicidal and virucidal effect and that waste from body fluids has to be disposed of, there is the additional advantage that the agent according to the invention not only destroys the azide but also kills off all germs will.

Beispiel 1example 1

Die Abfallösung aus einem Analysengerät enthält 4,89 mmol/l Natriumazid. Zu einem ml dieser Lösung werden 200 µl einer 0,1%igen wäßrigen Natriumthiosulfatlösung und 1 ml einer 0,2%igen wäßrigen Lösung aus Jod (7,88 mmol/l) und Kaliumjodid (7,88 mmol/l) hinzugegeben.The waste solution from an analyzer contains 4.89 mmol / l sodium azide. 200 ml of a 0.1% aqueous sodium thiosulfate solution and 1 ml of a 0.2% aqueous solution of iodine (7.88 mmol / l) and potassium iodide (7.88 mmol / l) are added to one ml of this solution.

Nach einer Inkubationszeit von 15 Minuten wird Natriumthiosulfatlösung bis zur vollständigen Entfärbung der Lösung hinzugegeben. Die anschließende Messung der Natriumazidkonzentration zeigt, daß noch 1,5 µmol Natriumazid intakt sind.After an incubation period of 15 minutes, sodium thiosulfate solution is added until the solution is completely decolorized. The subsequent measurement of the sodium azide concentration shows that 1.5 µmol sodium azide are still intact.

Beispiel 2Example 2

Zur gleichen Abfallösung wie in Beispiel 1 werden 20 µl der wäßrigen 0,1%igen Natriumthiosulfatlösung und 1 ml einer 0,4%igen wäßrigen Lösung aus Jod und Kaliumjodid hinzugegeben.20 μl of the aqueous 0.1% sodium thiosulfate solution and 1 ml of a 0.4% aqueous solution of iodine and potassium iodide are added to the same waste solution as in Example 1.

Nach einer Inkubationszeit von 15 Minuten und der anschließenden Entfärbung der Lösung ist kein Natriumazid mehr nachweisbar. Wenn anstelle der Natriumthiosulfatlösung eine Lösung von Natriummetabisulfit, Natriumdithionit oder Ascorbinsäure zur Entfärbung eingesetzt wird, ändert das nichts am Ergebnis.After an incubation period of 15 minutes and the subsequent decolorization of the solution, sodium azide can no longer be detected. If a solution of sodium metabisulfite, sodium dithionite or ascorbic acid is used for decolorization instead of the sodium thiosulfate solution, this does not change the result.

Beispiel 3Example 3

Zu einer Natriumazid enthaltenden Abfallösung werden folgende Tabletten hinzugegeben:
Die 1. Tablette enthält
8,00 % Kaliumjodid
0,09 % Natriumthiosulfat
48,81 % basisches Magnesiumcarbonat
40,00 % Magnesiumsulfat
0,10 % Calciumstearat
3,00 % Talcum
Die 2.Tablette enthält
52,7 g Polyethylenglykol 400
8,3 g Polyethylenglykol 4000
16,9 g Polyethylenglykol 6000
10,0 g Jod
10,0 g Wasser
Nach einer Inkubationszeit von ca. 15 Minuten wird gegebenenfalls mit einer Natriumthiosulfatlösung oder einer Tablette die im wesentlichen Natriumthiosulfat enthält, entfärbt.
The following tablets are added to a waste solution containing sodium azide:
The 1st tablet contains
8.00% potassium iodide
0.09% sodium thiosulfate
48.81% basic magnesium carbonate
40.00% magnesium sulfate
0.10% calcium stearate
3.00% talc
The 2nd tablet contains
52.7 g polyethylene glycol 400
8.3 g polyethylene glycol 4000
16.9 g polyethylene glycol 6000
10.0 g iodine
10.0 g water
After an incubation period of about 15 minutes, decolorization is carried out with a sodium thiosulfate solution or a tablet which essentially contains sodium thiosulfate.

Beispiel 4Example 4

Analog Beispiel 3 werden folgende Tabletten eingesetzt:
Die 1. Tablette enthält
0,09 % Natriumthiosulfat
52,81 % basisches Magnesiumcarbonat
44,00 % Magnesiumsulfat
0,10 % Calciumstearat
3,00 % Talcum
Die 2. Tablette enthält
52,7 g Polyethylenglykol 400
8,3 g Polyethylenglykol 4000
16,9 g Polyethylenglykol 6000
10,0 g Jod
5,0 g Kaliumjodid
10,0 g Wasser
The following tablets are used as in Example 3:
The 1st tablet contains
0.09% sodium thiosulfate
52.81% basic magnesium carbonate
44.00% magnesium sulfate
0.10% calcium stearate
3.00% talc
The 2nd tablet contains
52.7 g polyethylene glycol 400
8.3 g polyethylene glycol 4000
16.9 g polyethylene glycol 6000
10.0 g iodine
5.0 g potassium iodide
10.0 g water

Claims (5)

Verfahren zur oxidativen Zerstörung von Aziden, dadurch gekennzeichnet, daß die zu entsorgenden Azid enthaltenden Lösungen mit einer Jod/Jodid-Lösung in Gegenwart von Thiosulfat behandelt werden.Process for the oxidative destruction of azides, characterized in that the solutions containing azide to be disposed of are treated with an iodine / iodide solution in the presence of thiosulfate. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Azid enthaltenden Lösungen mit Jod/Jodid- und mit Thiosulfat-enthaltenden Tabletten versetzt werden.Process according to Claim 1, characterized in that the solutions containing azide are mixed with tablets containing iodine / iodide and thiosulphate. Mittel zur oxidativen Zerstörung von Aziden, gekennzeichnet durch Jod/Jodid- und Thiosulfat enthaltende Tabletten.Agent for the oxidative destruction of azides, characterized by tablets containing iodine / iodide and thiosulfate. Mittel nach Anspruch 3, dadurch gekennzeichnet, daß die Jod/Jodid enthaltende Tablette Jod und Kaliumjodid im Gewichtsverhältnis 2:1 enthält.Agent according to claim 3, characterized in that the tablet containing iodine / iodide contains iodine and potassium iodide in a weight ratio of 2: 1. Verwendung des Mittels nach den Ansprüchen 3 und 4 zur Entsorgung von Aziden in Lösungen aus dem Bereich der klinischen Chemie.Use of the agent according to claims 3 and 4 for the disposal of azides in solutions from the field of clinical chemistry.
EP93111094A 1992-07-22 1993-07-10 Process and agent for the oxidative destruction of azides Expired - Lifetime EP0581093B1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE4224114 1992-07-22
DE4224114A DE4224114A1 (en) 1992-07-22 1992-07-22 Process and agent for the oxidative destruction of azides

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EP0581093A1 true EP0581093A1 (en) 1994-02-02
EP0581093B1 EP0581093B1 (en) 1998-01-21

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US (1) US5457265A (en)
EP (1) EP0581093B1 (en)
JP (1) JPH06206082A (en)
CA (1) CA2100922A1 (en)
CZ (1) CZ144693A3 (en)
DE (2) DE4224114A1 (en)
ES (1) ES2112358T3 (en)
IL (1) IL106422D0 (en)
ZA (1) ZA935285B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6024860A (en) * 1997-08-15 2000-02-15 American Pacific Corporation System for electrochemical decomposition of sodium azide
DE19859783C2 (en) * 1998-12-23 2002-05-23 Gmbu Ges Zur Foerderung Von Me Airbag recycling method and apparatus
US7338540B1 (en) * 2002-08-06 2008-03-04 Ultramet Incorporated Decomposition of organic azides
CZ301150B6 (en) * 2007-06-13 2009-11-18 Austin Detonator S.R.O. Method of disposing wastewater from manufacture of explosives
HU0700440A2 (en) * 2007-06-27 2009-06-29 Sanofi Aventis Chemical process
WO2009131615A2 (en) * 2008-04-23 2009-10-29 Siemens Water Technologies Corp. Process for decontamination of inorganic hazardous components from a waste stream
GB201913242D0 (en) * 2019-09-13 2019-10-30 Vws Uk Ltd Method and apparatus for treatment of wastewater containing azide ions

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5073273A (en) * 1991-05-22 1991-12-17 Trw Vehicle Safety Systems, Inc. Treatment of azide containing waste

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3768865A (en) * 1972-07-13 1973-10-30 Ppg Industries Inc Process for the disposal of salt solutions contaminated with azide

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5073273A (en) * 1991-05-22 1991-12-17 Trw Vehicle Safety Systems, Inc. Treatment of azide containing waste

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 111, no. 26 Columbus, Ohio, US; abstract no. 239274q, 'Determination of chemical oxygen demand in water' *
HOLLEMAN-WIBERG 'Lehrbuch der anorganischen chemie' , WALTER DE GRUYTER , BERLIN-NEW YORK 1985 *

Also Published As

Publication number Publication date
ES2112358T3 (en) 1998-04-01
US5457265A (en) 1995-10-10
ZA935285B (en) 1994-04-20
DE4224114A1 (en) 1994-01-27
CA2100922A1 (en) 1994-01-23
DE59308018D1 (en) 1998-02-26
IL106422D0 (en) 1993-11-15
JPH06206082A (en) 1994-07-26
EP0581093B1 (en) 1998-01-21
CZ144693A3 (en) 1994-02-16

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