EP1005899A2 - Method for producing a water-in-oil emulsion used for decontamination - Google Patents

Method for producing a water-in-oil emulsion used for decontamination Download PDF

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Publication number
EP1005899A2
EP1005899A2 EP99120765A EP99120765A EP1005899A2 EP 1005899 A2 EP1005899 A2 EP 1005899A2 EP 99120765 A EP99120765 A EP 99120765A EP 99120765 A EP99120765 A EP 99120765A EP 1005899 A2 EP1005899 A2 EP 1005899A2
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EP
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Prior art keywords
emulsion
water
venturi nozzle
solution
detoxification
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Granted
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EP99120765A
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German (de)
French (fr)
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EP1005899A3 (en
EP1005899B1 (en
Inventor
Jürgen Dr. Steinwandel
Thomas Hug
Michael Vetter
Wolfgang Wagner
Willo Westermayer
Heiner Koch
Ingo Dr. Kitzmann
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Airbus Defence and Space GmbH
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Dornier GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/49—Mixing systems, i.e. flow charts or diagrams

Definitions

  • the invention relates to a method for producing a water-in-oil emulsion for detoxification of chemically or biologically contaminated surfaces.
  • DE 36 38 625 C2 contains a detoxification liquid for military applications known that the above Always takes requirements into account. This is what it is about is a water-in-oil emulsion with the special feature that the proportion of Water phase far exceeds that of the oil phase. Oxidation active compounds to destroy the warfare agents are usually water-soluble chlorine-containing compounds. Alternatively, the use of water-soluble peroxo compounds possible. Very good detoxification properties are e.g. with chlorinated hydrocarbons or xylene as an oil phase.
  • DE 36 07 424 A1 describes a method for producing a detoxification emulsion described in the case of a pressurized water flow the individual Emulsion starting materials can be added in several mixing sections. Subsequently is the mixture in an emulsion accelerator under high hydraulic Pressure mixed further and applied via a discharge lance.
  • DE 196 38 018 C1 describes a method for producing a water-based Detoxifying foam disclosed. Water and decontaminant concentrate are mixed in a mixer and in a decontamination foam using a Venturi nozzle converted.
  • a continuous mixing is a Water-in-oil emulsion possible.
  • the time for mixing the emulsion is significantly reduced.
  • the two emulsion starting solutions pre-mixed on a static mixer element before being fed into the Venturi nozzle.
  • the emulsion starting solutions of the Venturi nozzle are advantageous under increased Pressure supplied.
  • a high pressure pump can be used.
  • the venturi nozzle Leaving water-in-oil emulsion directly on a surface to be detoxified upset.
  • the emulsion continuously mixed in the Venturi nozzle can thus applied directly for decontamination without any additional intermediate steps become.
  • the process according to the invention can in particular be carried out using xylene, diesel fuel or Kerosene can be used as an oil phase.
  • An oxidizing agent such as calcium hypochlorite, Trichloroisocyanuric acid, sodium percarbonate, sodium peroxodisulfate, Magnesium monoperoxophthalate or phthalimidoperoxocaproic acid or mixtures be used from it.
  • Suitable emulsifiers for use in the process according to the invention for example dodecylbenzenesulfonic acid or Genapol UD - 050 (Hoechst AG).
  • the aqueous emulsion starting solution can additionally contain emulsion and dispersion auxiliaries be added.
  • positions 1-3 are successively in water (position 4, table 1) solved.
  • the two emulsifiers positions 5, 6, table 1) first dissolved in isopropanol (position 7, table 1) and then this solution Xylene (position 8, table 1) added.
  • isopropanol another can lower alcohol with up to four carbon atoms (C1 to C4) for the solution of the Emulsifiers are used.
  • the emulsion starting solutions are initially a static mixing element M (turbulence mixer) and then one High pressure pump HP supplied to build up pressure.
  • the well premixed liquid is relaxed in a Venturi nozzle V, in the primary relaxation area Compressed air from a mechanical compressor K is fed.
  • Compressed air is necessary because the natural suction of the Venturi nozzle V is not sufficient for producing the desired emulsion.
  • the foam-like water-in-oil emulsion produced in the Venturi nozzle V can over a spray lance, not shown here, are applied.
  • the successful production of the desired water in oil emulsion is first checked by determining the electrical conductivity.
  • the conductivity of all emulsions produced according to the test procedure described was around 1 microsiemens and thus corresponds to the conductivity that also results from the conventional stirring method.
  • the formation of emulsions takes place by orders of magnitude faster.
  • the decontamination effect of the continuously produced and applied emulsion was determined as follows. Lacquered (Bw standard lacquers) sheet metal samples which had previously been exposed to a warfare agent simili (in the present case methyl salicylate as S-Lost Simili) are exposed to the emulsion produced by the method according to the invention at different angles of inclination (0 °, 45 °, 90 °) . After an exposure time of the order of 5 minutes. sheets are rinsed with water. The behavior of real objects can be simulated with a sufficiently high degree of certainty using the differently inclined painted sheet metal samples. Decisive for decontamination success is good emulsion adhesion, especially for vertically oriented surfaces. The residual coating remaining after decontamination (mainly simulated warfare agents diffused into the paint) of the sheet metal samples is converted into a selective adsorber by pressure extraction and, after desorption, subjected to a quantitative analysis by gas chromatography.
  • a warfare agent simili in the present case methyl salicylate as S-Lost Simili
  • the degrees of decontamination determined are shown in FIG. 2, differentiated according to the individual surface inclination angles.
  • the left column group on the left shows the decontamination rates in% for the emulsion produced by the conventional stirring method, which was applied manually to a surface.
  • the angles of inclination of the surface were 0 ° (left column), 45 ° (middle column) and 90 ° (right column).
  • the emulsion starting solutions be prepared so that the dissolved in isopropanol Emulsifiers are added to the aqueous phase (this is due to the water solubility of the emulsifier system is possible without any problems), so the desired one is not Obtained water-in-oil emulsion, but at best an oil-in-water emulsion. This is based on the resulting electrical conductivities in the Millisiemens range (approx. 0.15 mS) easily understandable.

Abstract

The process involves (a) producing an emulsion starting solution by using a decontamination active substance in water, (b) producing a second emulsion starting solution by using one or several emulsifiers in a low alcohol and subsequent addition of the produced solution in the oil phase and (c) passing both emulsion starting solutions into a venturi nozzle (V) into which pressurized air compressed by a compressor (K) is feed via a radial opening.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer Wasser-in-Öl-Emulsion für die Entgiftung chemisch oder biologisch kontaminierter Oberflächen.The invention relates to a method for producing a water-in-oil emulsion for detoxification of chemically or biologically contaminated surfaces.

Die Reinigung von mit chemischen und biologischen Giftstoffen kontaminierten Oberflächen ist sowohl im militärischen, als auch im zivilen Bereich von Bedeutung. Im militärischen Bereich werden derartige Kontaminationen durch den Einsatz entsprechender B-und C-Waffen hervorgerufen. Dabei handelt es sich entweder um hochtoxische Substanzen (B und C) oder um stark ätzende Stoffe (C). Aufgrund des momentanen Bedrohungsszenarios steht eine potentielle Anwendung von B- und C-Waffen im Vordergrund, insbesondere beim Einsatz der Streitkräfte in ausländischen Krisengebieten. Im Vergleich zur Herstellung von Atomwaffen gestaltet sich die Produktion von B-und C- Waffen ungleich einfacher und darüber hinaus wesentlich kostengünstiger und es kann daher davon ausgegangen werden, daß praktisch alle Schwellenländer in Krisengebieten über entsprechende Technologien verfügen.The cleaning of contaminated with chemical and biological toxins Surfaces are important both in the military and in the civilian area. In the military field, such contaminations are caused by the use corresponding B and C weapons. This is either highly toxic substances (B and C) or strongly corrosive substances (C). Because of the Current threat scenarios indicate a potential use of B and C weapons in the foreground, especially when deploying the armed forces in foreign countries Crisis areas. In comparison to the production of nuclear weapons, the Production of B and C weapons is much easier and moreover essential cheaper and it can therefore be assumed that practically all Emerging markets in crisis areas have the appropriate technologies.

Im militärischen Bereich besteht hinsichtlich B-und C-Kontamination bei Geräten und Personenschutzanzügen die Anforderung zum einen in einer wirkungsvollen Reinigung der kontaminierten Oberflächen, ggf. auch mit Tiefenwirkung (Lacke, Kunststoffe, Gummi u.a. Substanzen, die eine Eindiffusion der Giftstoffe zulassen), zum anderen in einer so gut wie möglich gleichzeitigen Zerstörung der Giftstoffe bereits an der Oberfläche. Eine Entgiftung von Geräten im weitesten Sinn (Schiffe, Flugzeuge/Hubschrauber, Rad- und Kettenfahrzeuge, mobile Bodenanlagen, Waffen, personengebundene Ausrüstung) muß deren uneingeschränkte Wiederverwendbarkeit durch das Bedienungspersonal ohne ABC-Vollschutz ermöglichen. Dazu ist es von ganz wesentlicher Bedeutung, daß entsprechende Entgiftungsverfahren auch die oben erwähnte Tiefenwirkung aufweisen, da für bestimmte, insbesondere chemische Kampfstoffe des Typs Phosphorsäureester (Nervenkampfstoffe) sehr geringe Schwellwerte bezüglich gesundheitlicher Beeinträchtigung gegeben sind und drüber hinaus bekannt ist, daß diese Substanzen in gewisse Oberflächen (z.B. Kunstharzlacke u.ä.) nicht unbeträchtlich eindiffundieren.In the military field there is contamination of devices and B and C Personal protective suits, on the one hand, require effective cleaning the contaminated surfaces, possibly with a depth effect (paints, plastics, Rubber etc. Substances that allow the diffusion of toxins) to others already in as much as possible simultaneous destruction of the toxins on the surface. Detoxification of devices in the broadest sense (ships, planes / helicopters, Wheeled and tracked vehicles, mobile floor systems, weapons, personal equipment) must be fully reusable by the operating personnel without full ABC protection. It is for that It is essential that appropriate detoxification procedures also include have the above-mentioned depth effect, since for certain, especially chemical Weapons of the type phosphoric acid ester (nerve agents) very low Thresholds regarding health impairment are given and above it is also known that these substances can be found in certain surfaces (e.g. synthetic resin paints etc.) do not diffuse insignificantly.

Für militärische Anwendungen ist in der DE 36 38 625 C2 eine Entgiftungsflüssigkeit bekannt, die den o.a. Anforderungen grundsätzlich Rechnung trägt. Dabei handelt es sich um eine Wasser-in-Öl-Emulsion mit der Besonderheit, daß der Anteil der Wasserphase den der Ölphase bei weitem übertrifft. Oxidationsaktive Verbindungen zur Zerstörung der Kampfstoffe sind i.d.R. wasserlösliche chlorhaltige Verbindungen. Alternativ dazu ist die Verwendung von wasserlöslichen Peroxoverbindungen möglich. Sehr gute Entgiftungseigenschaften werden z.B. mit chlorierten Kohlenwasserstoffen oder Xylol als Ölphase erzielt.DE 36 38 625 C2 contains a detoxification liquid for military applications known that the above Always takes requirements into account. This is what it is about is a water-in-oil emulsion with the special feature that the proportion of Water phase far exceeds that of the oil phase. Oxidation active compounds to destroy the warfare agents are usually water-soluble chlorine-containing compounds. Alternatively, the use of water-soluble peroxo compounds possible. Very good detoxification properties are e.g. with chlorinated hydrocarbons or xylene as an oil phase.

Eine Vielzahl weiterer möglicher Stoffe für die Ölphase in Emulsionen ist in der EP 0 095 045 A1 genannt. Diese sind jedoch entweder aufgrund ihrer Wassermischbarkeit (z.B. niedere bis mittlere aliphatische Alkohole wie Methanol, Äthanol, Propanol/Isopropanol und Butanol) zur Herstellung der besonders wirksamen Wasser-in-Öl-Emulsionen nicht geeignet, oder sie sind aus sicherheitstechnischen Gründen, z.B. aufgrund des niederen Entflammungspunktes trotz sonstiger brauchbarer Eigenschaften nicht einsetzbar (z.B. Ottokraftstoffe oder andere Leichtbenzinfraktionen, oder aliphatische Kohlenwasserstoffe bis ca. C9). Demgegenüber ist die Verwendung von Dieselfraktionen oder Kerosinfraktionen als Ölphase, die ebenfalls in der EP 0 095 045 genannt werden, möglich, jedoch mit schlechteren Dekontaminationsergebnissen als bei der Verwendung von Xylol.A large number of other possible substances for the oil phase in emulsions is in the EP 0 095 045 A1 called. However, these are either due to their water miscibility (e.g. low to medium aliphatic alcohols such as methanol, ethanol, Propanol / isopropanol and butanol) for the production of the particularly effective Water-in-oil emulsions are not suitable, or they are for safety reasons Reasons, e.g. due to the low flash point despite usable Properties cannot be used (e.g. petrol or other light petroleum fractions, or aliphatic hydrocarbons up to approx. C9). In contrast is the Use of diesel fractions or kerosene fractions as an oil phase, too be mentioned in EP 0 095 045, possible, but with poorer decontamination results than when using xylene.

Das Anmischen einer geeigneten Wasser-in-Öl-Entgiftungsemulsion (kontrollierbar durch Messung der elektrischen Leitfähigkeit; diese beträgt um ca. 1 Mikrosiemens) unter Verwendung spezifischer Emulgatoren ist ein arbeits- und zeitintensiver Vorgang. Dazu kommt, daß die Emulsionen nur bedingt lagerfähig sind, zum einen aufgrund natürlicher Entmischung infolge verschiedener Umwelteinflüsse, zum anderen aufgrund nachlassender Oxidationsfähigkeit der Aktivkomponenten durch chemischen Zerfalls in Abhängigkeit von mehrfachen Parametern wie z.B Temperatur, Konzentration in der Wasserphase, pH-Wert sowie Verteilungsgrad der Emulsion. Die Wasser-in-Öl-Emulsion bildet sich in keinem Fall spontan durch bloßes Zusammenschütten geeigneter Ausgangslösungen. Vielmehr ist ein intensiver Rührprozess unter Lufteintrag zur Emulsionsbildung erforderlich. Der Lufteintrag erfolgt dabei unmittelbar durch das Ansaugen von Umgebungsluft aufgrund der Bewegung des Rührers in der Flüssigkeit. Die besten Resultate hinsichtlich Emulsionsbildung sowie korrespondierender Bildungszeit werden derzeit unter Verwendung von Turborührern erzielt. Dabei werden Rührzeiten im Bereich von einer Stunde benötigt, bevor die Emulsion überhaupt ausgebracht werden kann.Mixing a suitable water-in-oil detoxification emulsion (controllable by measuring electrical conductivity; this is around 1 microsiemens) using specific emulsifiers is a labor and time intensive Process. In addition, the emulsions can only be stored to a limited extent, on the one hand due to natural segregation due to various environmental influences, to others due to a decrease in the oxidizing ability of the active components chemical decay depending on multiple parameters such as temperature, Concentration in the water phase, pH value and degree of distribution of the emulsion. The water-in-oil emulsion never forms spontaneously by simply spilling it together suitable starting solutions. Rather, it is an intensive stirring process with air entry required for emulsion formation. The air is introduced directly by sucking in ambient air due to the movement of the Stirrer in the liquid. The best results regarding emulsion formation as well Corresponding educational time are currently using turbo stirrers achieved. Mixing times in the range of one hour are required before the Emulsion can be applied at all.

Es ist offensichtlich, daß ein solches Verfahren hinsichtlich der Verfügbarkeit der Emulsion im Einsatzfall große Schwächen aufweist.It is obvious that such a method is available in terms of the availability of the Emulsion has great weaknesses when used.

Um ein kontinuierliches und rasches Anmischen der Entgiftungsemulsion zu erreichen, erfolgt in dem Verfahren gemäß der DE 39 35 677 C2 die Zusammenführung von wäßriger Phase und Ölphase und die Bildung der Emulsion in einer Mischstrekke, die sich in einem Strahlrohr zum Ausbringen der Emulsion befindet.In order to achieve a continuous and rapid mixing of the detoxification emulsion, in the process according to DE 39 35 677 C2 the merging takes place of aqueous phase and oil phase and the formation of the emulsion in a mixing section, which is located in a jet pipe for spreading the emulsion.

In der DE 36 07 424 A1 ist ein Verfahren zur Erzeugung einer Entgiftungsemulsion beschrieben, bei dem einem unter Druck stehenden Wasserstrom die einzelnen Emulsionsausgangsstoffe in mehreren Mischstrecken zudosiert werden. Anschließend wird die Mischung in einem Emulsionsbeschleuniger unter hohem hydraulischen Druck weiter vermischt und über eine Ausbringlanze ausgebracht.DE 36 07 424 A1 describes a method for producing a detoxification emulsion described in the case of a pressurized water flow the individual Emulsion starting materials can be added in several mixing sections. Subsequently is the mixture in an emulsion accelerator under high hydraulic Pressure mixed further and applied via a discharge lance.

In der DE 196 38 018 C1 ist ein Verfahren zur Herstellung eines wasserbasierten Entgiftungsschaums offenbart. Wasser und Dekontaminationsmittelkonzentrat werden in einem Mischer vermischt und mittels einer Venturidüse in Dekontaminationsschaum umgewandelt.DE 196 38 018 C1 describes a method for producing a water-based Detoxifying foam disclosed. Water and decontaminant concentrate are mixed in a mixer and in a decontamination foam using a Venturi nozzle converted.

Es ist Aufgabe der Erfindung, ein Verfahren zu schaffen, mit dem ein kontinuierliches und rasches Anmischen einer für ein gutes Dekontaminationsergebnis besonders vorteilhaften Wasser-in-Öl-Emulsion erreicht wird, wobei auch bei Emulsionen, bei denen der Anteil der Wasserphase den der Ölphase bei weitem übertrifft, eine stabile Wasser-in-Öl-Emulsion erreicht wird.It is an object of the invention to provide a method with which a continuous and quick mixing, especially for a good decontamination result advantageous water-in-oil emulsion is achieved, with emulsions, too where the proportion of the water phase far exceeds that of the oil phase, a stable one Water-in-oil emulsion is achieved.

Diese Aufgabe wird mit dem Gegenstand des Patentanspruch 1 gelöst. Vorteilhafte Ausbildungen des erfindungsgemäßen Verfahrens sind Gegenstand weiterer Ansprüche.This object is achieved with the subject matter of claim 1. Beneficial Developments of the method according to the invention are the subject of further claims.

Gemäß der Erfindung wird die Wasser-in-Öl-Emulsion für die Entgiftung chemisch oder biologisch kontaminierter Oberflächen auf folgende Weise angemischt:

  • eine wässrige Emulsionsausgangslösung wird durch Lösung einer entgiftungsaktiven Substanz in Wasser hergestellt,
  • eine ölhaltige Emulsionsausgangslösung wird durch Lösung eines oder mehrerer Emulgatoren in einem niederen Alkohol und anschließender Zugabe der entstandenen Lösung in die Ölphase hergestellt,
  • die beiden Emulsionsausgangslösungen werden einer Venturidüse zugeführt, in die über eine radiale Öffnung von einem Kompressor verdichtete Druckluft zugeführt wird.
According to the invention, the water-in-oil emulsion for detoxifying chemically or biologically contaminated surfaces is mixed in the following way:
  • an aqueous emulsion starting solution is prepared by dissolving a detoxifying substance in water,
  • an oil-containing emulsion starting solution is prepared by dissolving one or more emulsifiers in a lower alcohol and then adding the resulting solution to the oil phase,
  • the two emulsion starting solutions are fed to a Venturi nozzle, into which compressed air is fed via a radial opening from a compressor.

Mit dem erfindungsgemäßen Verfahren ist ein kontinuierliches Anmischen einer Wasser-in-Öl-Emulsion möglich. Die Zeitdauer für das Anmischen der Emulsion wird wesentlich verringert.With the method according to the invention a continuous mixing is a Water-in-oil emulsion possible. The time for mixing the emulsion is significantly reduced.

In einer vorteilhaften Ausführung werden die beiden Emulsionsausgangslösungen vor der Zufuhr in die Venturidüse an einem statischen Mischerelement vorgemischt.In an advantageous embodiment, the two emulsion starting solutions pre-mixed on a static mixer element before being fed into the Venturi nozzle.

Vorteilhaft werden die Emulsionsausgangslösungen der Venturidüse unter erhöhtem Druck zugeführt. Hierzu kann z.B. eine Hochdruckpumpe eingesetzt werden.The emulsion starting solutions of the Venturi nozzle are advantageous under increased Pressure supplied. For this, e.g. a high pressure pump can be used.

In einer besonders vorteilhaften Ausführung der Erfindung wird die die Venturidüse verlassende Wasser-in-Öl-Emulsion unmittelbar auf eine zu entgiftende Oberfläche aufgebracht. Die in der Venturidüse kontinuierlich angemischte Emulsion kann somit ohne weitere Zwischenschritte direkt für den Dekontaminationseinsatz ausgebracht werden. In a particularly advantageous embodiment of the invention, the venturi nozzle Leaving water-in-oil emulsion directly on a surface to be detoxified upset. The emulsion continuously mixed in the Venturi nozzle can thus applied directly for decontamination without any additional intermediate steps become.

Das erfindungsgemäße Verfahren kann insbesondere mit Xylol, Dieselkraftstoff oder Kerosin als Ölphase angewandt werden.The process according to the invention can in particular be carried out using xylene, diesel fuel or Kerosene can be used as an oil phase.

Als entgiftungsaktive Substanz kann vorteilhaft ein Oxidationsmittel wie Calcium-Hypochlorit, Trichlorisocyanursäure, Natrium-Percarbonat, Natrium-Peroxodisulfat, Magnesium-Monoperoxophtalat oder Phtalimidoperoxocapronsäure oder Mischungen daraus verwendet werden.An oxidizing agent such as calcium hypochlorite, Trichloroisocyanuric acid, sodium percarbonate, sodium peroxodisulfate, Magnesium monoperoxophthalate or phthalimidoperoxocaproic acid or mixtures be used from it.

Als Emulgatoren für den Einsatz in dem erfindungsgemäßen Verfahren eignen sich zum Beispiel Dodecylbenzolsulfonsäure oder Genapol UD - 050 (Hoechst AG).Suitable emulsifiers for use in the process according to the invention for example dodecylbenzenesulfonic acid or Genapol UD - 050 (Hoechst AG).

Der wässrigen Emulsionsausgangslösung können zusätzlich Emulsions- und Dispergierhilfsstoffe zugegeben werden.The aqueous emulsion starting solution can additionally contain emulsion and dispersion auxiliaries be added.

Die Erfindung wird anhand eines Ausführungsbeispiels unter Bezugnahme auf Zeichnungen näher erläutert. Es zeigen:

Fig. 1
ein Aufbau zur Durchführung des erfindungsgemäßen Verfahrens;
Fig. 2
ein Diagramm zur Wirksamkeit der mit dem erfindungsgemäßen Verfahren hergestellten Wasser-in-Öl-Emulsion (Munsteremulsion).
The invention is explained in more detail using an exemplary embodiment with reference to drawings. Show it:
Fig. 1
a structure for performing the method according to the invention;
Fig. 2
a diagram of the effectiveness of the water-in-oil emulsion (Munster emulsion) produced with the method according to the invention.

Der Ablauf des erfindungsgemäßen Verfahrens wird anhand der Fig. 1 anhand einer vorteilhaften Ausführung näher erläutert. Beispielhaft wurde eine Entgiftungsemulsion der prozentualen Zusammensetzung nach Tabelle 1 hergestellt. Die Funktion der einzelnen Substanzen ist in Klammer jeweils hinzugefügt. Position Stoff Menge (Gramm) Menge Gew.% 1 Natriumchlorid (Emulsionshilfsstoff) 1.000,00 9, 9 2 Dichlorisocyanursäure (Na-Salz) (Entgiftungsaktive Substanz) 100,00 1, 0 3 Talk (talcum purum 325 mesh) (Dispergierhilfsstoff) 200, 00 2, 0 4 Wasser (Leitungsqualität) 7. 600, 00 75, 5 5 Dodecylbenzolsulfonsäure (Na-Salz) (Emulagtor) 40, 00 0, 4 6 Genapol UD -050 (Hoechst AG) (Emulgator) 10, 00 0, 1 7 2- Propanol (Isopropanol) (Lösungsvermittler für Emulgatoren) 120, 00 1, 2 8 Xylol (Isomerengemisch ) (Ölphase) 1000, 00 9, 9 Σ 10. 070, 00 Σ 100, 0 The sequence of the method according to the invention is explained in more detail with reference to FIG. 1 using an advantageous embodiment. As an example, a detoxification emulsion of the percentage composition according to Table 1 was produced. The function of the individual substances is added in brackets. position material Quantity (grams) Quantity weight% 1 Sodium chloride (emulsion aid) 1,000.00 9, 9 2nd Dichloroisocyanuric acid (Na salt) (detoxifying substance) 100.00 1, 0 3rd Talcum (talcum purum 325 mesh) (dispersing agent) 200.00 2, 0 4th Water (pipe quality) 7,600.00 75, 5th 5 Dodecylbenzenesulfonic acid (Na salt) (Emulagtor) 40, 00 0, 4 6 Genapol UD -050 (Hoechst AG) (emulsifier) 10, 00 0.1 7 2- propanol (isopropanol) (solubilizer for emulsifiers) 120.00 1, 2 8th Xylene (mixture of isomers) (oil phase) 1000, 00 9, 9 Σ 10,070.00 Σ 100, 0

Gemäß der hier betrachteten Ausführung des erfindungsgemäßen Verfahrens zur kontinuierlichen Anmischung und Ausbringung einer Entgiftungsemulsion werden zwei Emulsionsausgangslösungen in den Behältern E1,E2 separat hergestellt. Dabei werden die Positionen 1-3 (Tabelle 1) nacheinander in Wasser (Position 4, Tabelle 1) gelöst. Parallel dazu werden die beiden Emulgatoren (Positionen 5, 6 Tabelle 1) zunächst in Isopropanol (Position 7, Tabelle 1) gelöst und danach diese Lösung dem Xylol (Position 8, Tabelle 1) zugegeben. Anstatt Isopropanol kann ein anderer niederer Alkohol mit bis zu vier Kohlenstoffatomen (C1 bis C4) für die Lösung der Emulgatoren eingesetzt werden.According to the embodiment of the inventive method for continuous mixing and application of a detoxification emulsion two emulsion starting solutions in the containers E1, E2 prepared separately. Here positions 1-3 (table 1) are successively in water (position 4, table 1) solved. In parallel, the two emulsifiers (positions 5, 6, table 1) first dissolved in isopropanol (position 7, table 1) and then this solution Xylene (position 8, table 1) added. Instead of isopropanol another can lower alcohol with up to four carbon atoms (C1 to C4) for the solution of the Emulsifiers are used.

Mittels der Dosierpumpen P1,P2 werden die Emulsionsausgangslösungen zunächst einem statischen Mischelement M (Turbulenzmischer) und daran anschließend einer Hochdruckpumpe HP zum Druckaufbau zugeführt. Die gut vorgemischte Flüssigkeit wird in einer Venturidüse V entspannt, wobei im primären Entspannungsbereich Druckluft aus einem mechanischen Kompressor K eingespeist wird. Der Einsatz von Druckluft ist notwendig, da die natürliche Ansaugung der Venturidüse V nicht ausreichend für Herstellung der gewünschten Emulsion ist.Using the metering pumps P1, P2, the emulsion starting solutions are initially a static mixing element M (turbulence mixer) and then one High pressure pump HP supplied to build up pressure. The well premixed liquid is relaxed in a Venturi nozzle V, in the primary relaxation area Compressed air from a mechanical compressor K is fed. The use of Compressed air is necessary because the natural suction of the Venturi nozzle V is not sufficient for producing the desired emulsion.

Die in der Venturidüse V erzeugte, schaumartige Wasser-in-Öl-Emulsion kann über eine hier nicht dargestellte Sprühlanze ausgebracht werden. The foam-like water-in-oil emulsion produced in the Venturi nozzle V can over a spray lance, not shown here, are applied.

Das erfolgreiche Herstellen der gewünschten Wasser in Öl-Emulsion wird zunächst anhand der Bestimmung der elektrischen Leitfähigkeit kontrolliert.
Die Leitfähigkeit betrug bei allen gemäß dem beschriebenen Versuchsablauf hergestellten Emulsionen um 1 Mikrosiemens und entspricht damit der Leitfähigkeit, wie sie sich auch beim konventionellen Rührverfahren ergibt. Allerdings erfolgt bei dem erfindungsgemässen Verfahren die Emulsionsbildung um Zeitgrössenordnungen schneller.The successful production of the desired water in oil emulsion is first checked by determining the electrical conductivity.
The conductivity of all emulsions produced according to the test procedure described was around 1 microsiemens and thus corresponds to the conductivity that also results from the conventional stirring method. However, in the method according to the invention, the formation of emulsions takes place by orders of magnitude faster.

Die Dekontaminationswirkung der kontinuierlich hergestellten und ausgebrachten Emulsion wurde wie folgt ermittelt.
Lackierte (Bw-Standardlacke) Blechproben, die vorher mit einem Kampfstoffsimili (im vorliegenden Fall Methylsalicylat als S-Lost Simili) beaufschlagt wurden, werden in unterschiedlichen Neigungswinkeln (0°, 45°, 90°) mit der nach dem erfindungsgemäßen Verfahren erzeugten Emulsion beaufschlagt. Nach einer Einwirkzeit der Größenordnung 5 min. werden Bleche mit Wasser abgespült. Mit den unterschiedlich geneigten lackierten Blechproben kann mit ausreichend hoher Sicherheit das Verhalten bei realen Obiekten simuliert werden. Entscheidend für den Dekontaminationserfolg ist eine gute Emulsionshaftung insbesondere bei senkrecht orientierten Flächen.
Die nach der Dekontamination verbleibende Restbelegung (in der Hauptsache in den Lack eindiffundierter Kampfstoffsimili) der Blechproben wird mittels Druckextraktion in einen selektiven Adsorber überführt und nach Desorption einer gaschromatographischen quantitativen Analyse unterzogen.The decontamination effect of the continuously produced and applied emulsion was determined as follows.
Lacquered (Bw standard lacquers) sheet metal samples which had previously been exposed to a warfare agent simili (in the present case methyl salicylate as S-Lost Simili) are exposed to the emulsion produced by the method according to the invention at different angles of inclination (0 °, 45 °, 90 °) . After an exposure time of the order of 5 minutes. sheets are rinsed with water. The behavior of real objects can be simulated with a sufficiently high degree of certainty using the differently inclined painted sheet metal samples. Decisive for decontamination success is good emulsion adhesion, especially for vertically oriented surfaces.
The residual coating remaining after decontamination (mainly simulated warfare agents diffused into the paint) of the sheet metal samples is converted into a selective adsorber by pressure extraction and, after desorption, subjected to a quantitative analysis by gas chromatography.

Die ermittelten Dekontaminationsgrade sind in Fig. 2, unterschieden nach den einzelnen Oberflächenneigungswinkeln, dargestellt.
In der linken Säulengruppe links sind die Dekontaminationsraten in % für die nach dem herkömmlichen Rührverfahren hergestellten Emulsion dargestellt, die manuell auf eine Oberfläche aufgetragen wurde. Die Neigungswinkel der Oberfläche betrugen 0° (linke Säule), 45° (mittlere Säule) und 90° (rechte Säule). The degrees of decontamination determined are shown in FIG. 2, differentiated according to the individual surface inclination angles.
The left column group on the left shows the decontamination rates in% for the emulsion produced by the conventional stirring method, which was applied manually to a surface. The angles of inclination of the surface were 0 ° (left column), 45 ° (middle column) and 90 ° (right column).

In der mittleren Säulengruppe sind für die entsprechenden Oberflächenneigungswinkel die Dekontaminationsraten für die nach dem erfindungsgemäßen Verfahren hergestellten Emulsion dargestellt. Die Emulsion wurde auf die Oberfläche aufgespüht. Man erkennt, daß mit der nach dem erfindungsgemäßen Verfahren hergestellten Emulsion eine annähernd identische Wirksamkeit erreicht werden kann.In the middle column group are for the corresponding surface inclination angles the decontamination rates for those according to the inventive method prepared emulsion shown. The emulsion was sprayed onto the surface. It can be seen that with the manufactured by the inventive method Emulsion an almost identical effectiveness can be achieved.

Wird nicht nach der erfindungsgemäßen Verfahren vorgegangen, indem die Emulsionsausgangslösungen derart hergestellt werden, daß die in Isopropanol gelösten Emulgatoren der wässrigen Phase zugegeben werden (dies ist aufgrund der Wasserlöslichkeit des Emulgatorsystems problemlos möglich), so wird nicht die gewünschte Wasser-in-Öl-Emulsion erhalten, sondern allenfalls eine Öl-in-Wasser-Emulsion. Dies ist anhand der sich ergebenden elektrischen Leitfähigkeiten im Millisiemensbereich (ca. 0,15 mS) ohne weiteres nachvollziehbar. Da darüber hinaus die Viskosität dieser Emulsion deutlich geringer ist als diejenige der Wasser-in-Öl-Emulsion, ist auch die Haftung auf geneigten Proben schlechter, was in einem wesentlich schlechteren Dekontaminationsergebnis resultiert. Die zugehörigen Dekontaminationsraten sind in Fig. 2, rechte Säulengruppe, dargestellt.Is not proceeded according to the inventive method by the emulsion starting solutions be prepared so that the dissolved in isopropanol Emulsifiers are added to the aqueous phase (this is due to the water solubility of the emulsifier system is possible without any problems), so the desired one is not Obtained water-in-oil emulsion, but at best an oil-in-water emulsion. This is based on the resulting electrical conductivities in the Millisiemens range (approx. 0.15 mS) easily understandable. Because beyond that the viscosity of this emulsion is significantly lower than that of the water-in-oil emulsion, adhesion to inclined samples is also worse, which results in a much worse decontamination result results. The associated Decontamination rates are shown in Fig. 2, right column group.

Claims (8)

Verfahren zum kontinuierlichen Anmischen einer schaumartigen Wasser-in-Öl-Emulsion für die Entgiftung chemisch oder biologisch kontaminierter Oberflächen, wobei eine erste Emulsionsausgangslösung durch Lösung einer entgiftungsaktiven Substanz in Wasser hergestellt wird, eine zweite Emulsionsausgangslösung durch Lösung eines oder mehrerer Emulgatoren in einem niederen Alkohol und anschließender Zugabe der entstandenen Lösung in die Ölphase hergestellt wird, die beiden Emulsionsausgangslösungen einer Venturidüse (V) zugeführt werden, in die über eine radiale Öffnung zusätzlich durch einen Kompressor (K) verdichtete Druckluft zugeführt wird. Process for the continuous mixing of a foam-like water-in-oil emulsion for the detoxification of chemically or biologically contaminated surfaces, whereby a first emulsion starting solution is prepared by dissolving a detoxification-active substance in water, a second emulsion starting solution is prepared by dissolving one or more emulsifiers in a lower alcohol and then adding the resulting solution to the oil phase, the two emulsion starting solutions are fed to a Venturi nozzle (V) into which compressed air is additionally fed via a radial opening by a compressor (K). Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der niedere Alkohol für die Lösung der Emulgatoren 1 bis 4 Kohlenstoffatome enthält.A method according to claim 1, characterized in that the lower alcohol contains 1 to 4 carbon atoms for the solution of the emulsifiers. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die entgiftungsaktive Substanz ein Oxidationsmittel wie Calcium-Hypochlorit, Trichlorisocyanursäure, Natrium-Percarbonat, Natrium-Peroxodisulfat, Magnesium-Monoperoxophtalat oder Phtalimidoperoxocapronsäure oder Mischungen daraus ist.A method according to claim 1 or 2, characterized in that the detoxification-active Substance an oxidizing agent such as calcium hypochlorite, trichloroisocyanuric acid, Sodium percarbonate, sodium peroxodisulfate, magnesium monoperoxophthalate or phthalimidoperoxocaproic acid or mixtures thereof is. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Ölphase Xylol, Dieselkraftstoff oder Kerosin ist.Method according to one of the preceding claims, characterized in that that the oil phase is xylene, diesel fuel or kerosene. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der ersten Emulsionsausgangslösung Emulsions- und Dispergierhilfsstoffe zugegeben werden.Method according to one of the preceding claims, characterized in that that the first emulsion starting solution emulsion and dispersion aids be added. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Emulsionsausgangslösungen vor der Zufuhr in die Venturidüse an einem statischen Mischerelement (M) vorgemischt werden. Method according to one of the preceding claims, characterized in that that the emulsion starting solutions at one point before being fed into the Venturi nozzle static mixer element (M) are premixed. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die Emulsionsausgangslösungen der Venturidüse (V) unter erhöhtem Druck zugeführt werden.Method according to one of the preceding claims, characterized in that that the emulsion starting solutions of the Venturi nozzle (V) under increased pressure be fed. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß die die Venturidüse (V) verlassende Wasser-in-Öl-Emulsion unmittelbar auf eine zu entgiftende Oberfläche aufgebracht wird.Method according to one of the preceding claims, characterized in that that the water-in-oil emulsion leaving the Venturi nozzle (V) immediately on a surface to be detoxified is applied.
EP99120765A 1998-12-03 1999-10-20 Method for producing a water-in-oil emulsion used for decontamination Expired - Lifetime EP1005899B1 (en)

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DE19855800A DE19855800C2 (en) 1998-12-03 1998-12-03 Production of a water-in-oil emulsion for decontamination purposes
DE19855800 1998-12-03

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DE4114560A1 (en) * 1991-05-04 1992-11-05 Lettko Herbert Aerochem Thixotropic bleaching powder dispersion prodn. for decontamination of chemical warfare agents - involves dispersing bleaching powder in colloidal alumina and silica, and copolymer resin in water
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CZ306632B6 (en) * 2008-02-21 2017-04-12 Vop Cz, S.P. A method of continuous production of an emulsion decontamination mixture in the form of inverse emulsion and a device for implementing this method

Also Published As

Publication number Publication date
EP1005899A3 (en) 2003-01-02
ATE300997T1 (en) 2005-08-15
EP1005899B1 (en) 2005-08-03
DE19855800A1 (en) 2000-06-08
DE19855800C2 (en) 2001-01-25
DE59912354D1 (en) 2005-09-08

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