DE3638625A1 - Detoxifying emulsion and process, apparatus and check on results for preparation of the emulsion - Google Patents

Abstract

The invention proposes novel and effective further-developed emulsions, based on the known "Munster emulsion" for the decontamination of equipment and people. Furthermore, a process for the preparation of these emulsions in a continuous procedure is presented. Moreover, two apparatuses for carrying out the process are described. These include, in the final stage, monitoring of the production of the emulsion, which is suitable for detoxification and active, and is released for use under control according to this.

Description

The invention relates to detoxification emulsions, as well as methods, pre directions and success control for the production of the emulsion.

Suitable detoxification to protect against chemical warfare agents medium used. Hereby the toxins, the buildings, Have contaminated material, equipment and people, made harmless will. Detoxification means loosening and chemical degradation of chemical warfare agents, warfare agent mixtures and warfare agents with Plastic thickeners. This procedure must be respectful of people and Take material. Therefore, aggressive chemicals hardly come into this Consider. Furthermore, the detoxification agent should be used universally be and if possible work against all warfare agents. Also penetrate chemical warfare agents in the surface of materials such as B. of paint, rubber and plastic. No superficial is sufficient here Decontamination but the detox must be able be sticky to the surface and into the surface like that to be able to penetrate deeply like the chemical warfare agent in order to detoxify. Since penetrated warfare agent again after detoxification diffuses back to the surface, otherwise there is a risk of subsequent poisoning.

An emulsion fulfills the requirements of a detoxification agent optimally. Such emulsions are known (e.g. as "Munsteremulsion") and have already been published in the prospectus the company Kärcher GmbH & Co "material and terrain decontamination Module C-8 DADS ".

The object of the invention is to provide a detoxification emulsion in this way improve that the efficiency of the detoxification process is increased. It should be easy to understand that a detoxification emulsion, depending on whether it is used for device or personal decontamination should have a different composition.  

The present invention is not only concerned with particular suitable and effective emulsions, but also shows beneficial Methods and devices for producing the invention Emulsions, as well as a performance check to achieve the specified aspired to emulsification.

The object of the invention is the beginning of emulsions described type by the characterizing features of claims 1 and 4 solved.

Through the use of active ingredients, which consist of inorganic or consist of organic active ingredients and in particular by The addition of dispersible solids is a highly active water-in-oil Emulsion with a suspended solid content generated. The suspension fine-grained particulate matter within the emulsion phase has an accelerating effect, depending on its quantitative share and stabilizing for emulsion formation. It also works a solid content present within certain limits is favorable reaching the required viscosity range. About that the proportion of solvents also determines the viscosity out. With higher proportions of solvents, mechanical influences Energy the viscosity only slightly.

The solvent must be suitable as an extractant and also in be able to keep plastics in solution. The fact that the detoxification emulsion introduced is a water-in-oil Emulsion acts, explains the good detoxification achieved with it Results. As a continuous phase, perchlorethylene has instant Contact with the contaminated device surface and acts as Extractant. Because it's a water-in-oil emulsion, can be assumed that the corrosion on sensitive Devices is negligible. Not the one due to hypochlorite and other salt ion corrosive aqueous phase has contact with the device, but the perchlorethylene phase. After the Decontamination of sensitive devices only with perchlor ethylene be washed off. If the device is not sensitive, it may be missing Risk of corrosion can even be rinsed with water.  

That as a detoxification emulsion for material decontamination he agent according to the invention described in claim 1 is therefore from the In terms of structure, an emulsion / suspension.

The emulsion known as "Munster emulsion" essentially covers Lichen the preamble of the present invention, which from 0.5 to 7.5 percent by weight active and / or oxidizing Substances, preferably calcium hypochlorite, from 15 to 30 weight percent solvent, preferably chlorinated hydrocarbon substances, 1 to 2 percent by weight emulsifier, preferably calcium sulfonate exists. In addition there are 7.5 to 0.5 percent by weight Electrolyte, for example table salt, in reverse addition to calcium hypochlorite. The rest is water.

This emulsion becomes a part according to the present invention added to solids. The solid can also be used together with the calcium hypochlorite. The emulsion is optimally stabilized when a solids content of 1.2 to 1.5 percent by weight is present. This can be calcium hydroxide be that already in the production of calcium hypochlorite can arise. When using larger amounts of calcium hydroxide the emulsion can still be produced at temperatures down to + 3 ° C will. However, other dispersible solids can also be used active areas on their surface, such as magnesium oxide, aerosil (Silica dust), calcium carbonate, bentonite, insoluble metal hydroxides, fuller earth or diatomaceous earth for the formation of suspensions be used.

In addition to calcium hypochlorite, other active substances can also be used Chlorine carriers such as sodium hypochlorite and organic chlorine carriers such as Chloramine and trichloroisocyanuric acid, oxidizing agents and hydroxides are used will.  

In addition to table salt, the following other substances can also be used as electrolytes can be used:

Sodium hydrogen carbonate, sodium hydroxide, trisodium phosphate, Calcium chloride, sodium hydrogen sulfate, calcium hypochlorite with and without calcium hydroxide, ferric chloride, sodium sulfate and. a. m.

The addition of electrolyte leads to the area of unstable ent Poisoning emulsion in an oil-in-water emulsion by phase reversal in the area of stable water-in-oil emulsion. Since the Effects of electrolytes on phase reversal can add up the individual shares at economically favorable yet Emulsion-forming combinations can be substituted.

The formation of the emulsion according to claims 1 and 2 can Addition of the agents of claim 3 in their mode of operation still ge be increased. It has been shown that when the emulsion is acidified, d. H. when the pH is reduced to 4 to 9 and when monohydric lower alcohols emulsification much better and runs faster. Acidification can be done by introducing Carbon dioxide in the emulsion and / or the aqueous phase, either from the bottle or can also be caused by using combustion exhaust gases. As Adding alcohol is particularly suitable for isopropanol.

The emulsion for personal detoxification according to claim 4 has in the Basic composition also like the "Munster emulsion" active ingredient, a solvent, emulsifier and water, however, the basic proportions are 1 to 10 percent by weight of active ingredient, 40 percent by weight of solvent and 20 percent by weight Emulsifier. The active ingredient consists of organic active substances and is dissolved in alcohol before the detoxification.  

The organic substances contain active chlorine. Such chlorine carriers are z. B. chloramine-B, chloramine-T, chlorohydantion or trichloriso cyanuric acid.

Here, too, chlorinated hydrocarbons are preferred as solvents wise perchlorethylene, use. Calcium sulfonate also serves as Emulsifier. With this emulsion, too, an improvement and loading acceleration of the reactions of the emulsion by acidifying the emulsion, preferably by carbon dioxide or an acid salt and by adding alcohols, preferably isopropanol.

The responsiveness and viscosity, as well as the structure of the Ent poison emulsion, and thus their reaction time can be determined by the choice of the isopropanol concentration between 1 and 50 weight percentages on the one hand and by lowering the pH to values from 4 to 9, on the other hand, vary within wide limits.

By lowering the pH value, is formed in the aqueous phase chlorine acid. This reacts with chloride ions to form free chlorine. The latter enters the organic phase extractively and is in here Contact with contaminations implemented on site in a decontaminating manner.

To prepare the emulsion according to claims 1 to 3 is Invention proposed according to the following method (claim 6). The single ones characteristic steps are given below in the prescribed Order listed:

• - the introduction of water into a tank
• - The formation of an aqueous solution of active substance, preferably Calcium hypochlorite, neutral salt, preferably table salt and solid, preferably calcium hydroxide
• - The withdrawal of the aqueous solution from the tank and the introduction of Carbon dioxide or adding acidic salt to the aqueous solution to achieve a given pH value
• - the return of the acidified solution to the water tank
• - withdrawing the solution from the tank and guiding the aqueous solution in the circuit to the pump, dry mixer and carbon dioxide stations addition or addition of acidic salt and return to the tank  
• - The withdrawal of the aqueous solution after 15 minutes of circulation business
• - The admixture of perchlorethylene, emulsifier and isopropanol
• - The stabilization of the emulsion until ready for use as Detoxifier.

As a suitable device for producing emulsions according to claims 1 to 3 and for carrying out the method according to claim 6, the device shown in FIG. 1 is first proposed according to claim 7. It consists of the following components:

• - A water inlet ( 1 ) operated by a pump ( 2 )
• - a tank ( 3 ) with a pH regulator ( 8 )
• - A pump ( 4 ) for withdrawing the aqueous solution
• - a dry mixer ( 5 )
• - a carbon dioxide bottle ( 7 ) with a solenoid valve ( 6 )
• - a back-mixing chamber ( 9 )
• - A reservoir ( 12 ) and a downstream metering pump ( 11 )
• - A pump ( 10 ) for withdrawing the emulsion from the chamber ( 9 )
• - An electrochemical success control ( 13 ) on the stabilization of the emulsion
• - A spray lance ( 14 ) for spraying the emulsion.

As a further suitable device in accordance with the object of claims 1 to 3 and 6, the device presented in FIG. 2 is described in claim 8, which is characterized by the following characteristic features:

• - A water inlet ( 1 ) operated by a pump ( 2 )
• - a tank ( 3 ) with a pH controller ( 8 )
• - A pump ( 4 ) for withdrawing the aqueous solution
• - a dry mixer ( 5 )
• - a carbon dioxide bottle ( 7 ) with a solenoid valve ( 6 )
• - A reservoir ( 12 ) and a downstream metering pump ( 11 )
• - two mixers ( 15, 16 )
• - An electrochemical success control ( 13 ) on the stabilization of the emulsion
• - A spray lance ( 14 ) for spraying the emulsion.

While the device according to claim 7 is intended for a one-step emulsion production with backmixing of partial emulsion amounts, the device according to claim 8 works in a two-step production process. The mixing takes place in the single-stage device in a funnel-shaped chamber which opens into a static mixer at the bottom. In contrast to this, the device according to claim 8 works with two static mixing chambers arranged one behind the other. The emulsion concentrate formed in the mixer 15 only forms the dischargeable emulsion in the mixer 16 . The mixture is returned to the suction side of pump 4 until the emulsion is finally finished.

To produce the emulsion according to claims 4 to 5, Invention proposed according to the following method (claim 9), the  perform typical steps in the order listed are:

• - The formation of an aqueous, transportable and storable solution Solvent (chlorinated hydrocarbon) and emulsifier (calcium sulfonate) in a container
• - the formation of a solution of alcohol and chloramine (active ingredient) in another container by breaking one of the chloramines containing glass ampoule
• - the combination of both solutions in one container
• - The acidification of the solution by introducing carbon dioxide up to achieve a given pH value
• - The stabilization of the emulsion until ready for use as Ent poisoner.

According to claim 10, the finished detoxification emulsion can be reached by measuring the electrical conductivity of the emulsion precisely to be controlled. If the electrical conductivity drops to values of  10 µSi / cm drops, is a highly active water-in-oil Emulsion emerged. The values can be measured according to claim 11 value converters can be used, electrical, optical or acoustic Generate signals that are used to control a valve, which, when the stable emulsion is reached, becomes part of the emulsion releases for detoxification while the other part releases to the circle running operation is returned.

The invention is illustrated below with reference to the drawings presented embodiments explained in more detail. It shows

Fig. 1 shows the apparatus schematically shown for the production of the emulsion according to claim 7,

Fig. 2 shows the apparatus schematically shown for the production of the emulsion according to claim 8.

The related numbers are in the list of reference symbols in detail guided.

Using the device for the one-step manufacturing process described in FIG. 1, an exemplary composition of the emulsion, the process according to claim 6 itself and the success control over the end point of the emulsion are to be shown.

Via the pump 2 , water is filled into the tank 3 from the water inlet 1 . The pump 4 conveys the water from the tank 3 into a circuit. In the dry mixers station 5 , calcium hypochlorite as an active substance, containing calcium hydroxide as a dispersible solid and sodium chloride as an electrolyte, are added and dissolved in the water.

This aqueous solution is acidified by adding carbon dioxide from a bottle 7 using a solenoid valve 6 and returned to the tank 3 . There, the pH controller 8 measures the pH. The solution is then circulated for about 15 minutes, during which time it is brought to a pH of 4 to 9 by means of a controlled acidification. The premixed solution is then discharged from the circuit and introduced into the upper part of a cylindrical or conical backmixing chamber 9 . In this case, a mixture of perchlorethylene (solvent), calcium sulfonate (emulsifier) and isopropanol is drawn from the reservoir 12 via the metering pump 11 . For better emulsion formation, a portion of the emulsion is withdrawn from the lower region of the mixer 9 at the same time via the pump 10 and returned to the upper region of the chamber 9 for backmixing. Behind the pump 10 is the electrochemical success control 13 , which determines the end point of the emulsification by measuring the electrical conductivity. If values of less than or equal to 10 microsiemens per cm are found during this measurement, an optimally effective water-in-oil emulsion has formed. This can then be used for decontamination using, for example, a spray lance. Such an emulsion suitable for device decontamination then consists, for example, in accordance with claims 1 to 3:

15% perchlorethylene (solvent) 1% calcium sulfonate (emulsifier) 7.5% calcium hypochlorite (active substance) 1.5% calcium hydroxide (dispersion solid) 1.0% table salt (electrolyte) 10.0% isopropanol (to promote emulsion)

The rest is water.  

In Fig. 2, an apparatus for a two-stage manufacturing process is shown. The premix consisting of an aqueous solution with calcium hypochlorite, calcium hydroxide and common salt is formed as in device 1. When a pH of 4 to 9 is reached by acidification of the solution, this solution is derived from the circuit. On the way, the mixture of perchlorethylene, calcium sulfonate and isopropanol drawn off from the storage container 12 via the metering pump 11 is added before the mixture reaches the mixer 15 . The mixture then passes into the mixer 16 . After removal from the mixer 16 , the emulsion is checked for its usability by measuring the electrical conductivity with the electrochemical success control 13 . The finished and effective emulsion is then fed to the intended use, while the not yet completed emulsion is returned to the mixer 16 .

There is a ready-made emulsion suitable for staff detoxification according to claims 4 to 5, for example from:

40% perchlorethylene (solvent) 20% calcium sulfonate (emulsifier) 5% chloramine (active organic ingredient) 10% isopropanol (solvent for chloramine).

The rest is water. This emulsion is used in typesetting produced. It becomes part 2 according to the method in claim 9 solutions completed shortly before detoxification.  

Detoxification emulsion, as well as method, device and success control for the preparation of the emulsion

• Reference list 1 water inlet
  2 pump
  3 tank
  4 pump
  5 dry mixers
  6 solenoid valve
  7 carbon dioxide bottle
  8 pH controllers
  9 back- mixing chamber
  10 pump
  11 dosing pump
  12 storage containers
  13 Electrochemical success monitoring
  14 spray lance
  15 mixers
  16 mixers

Claims (11)

1. Emulsion for the decontamination of combat poisoned Mate rialien consisting of an active ingredient, a neutral set, a solvent, an emulsifier and water, characterized in that the active ingredient consists of inorganic or organic active substances and that the emulsion contains a proportion of dispersible solids is added. 2. Emulsion according to claim 1, consisting of 0.5 to 7.5 weight percent active and / or oxidizing substances, preferred wise calcium hypochlorite, 7.5 to 0.5 percent by weight electro lyt, for example table salt, 15 to 30 percent by weight of solution medium, preferably chlorinated hydrocarbons, 1 to 2 Weight percentages calcium sulfonate and water, characterized, that the emulsion is 1.2 to 1.5 percent by weight on dispersing solids, preferably fine-grained Metal hydroxides is added.   3. emulsion according to claim 1 and 2, characterized, that the emulsion is acidified to a pH of 4 to 9 is, preferably by carbon dioxide, and that the emulsion monohydric lower alcohols, preferably isopropanol in one Amount of 1 to 50 percent by weight is added. 4. Emulsion for personal detoxification and decontamination of Combat poisoned materials, especially personal equipment, consisting of an active Active ingredient, a solvent, an emulsifier and water, characterized, that the active ingredient consists of organic active substances and that the active ingredient in alcohol before detoxification is solved. 5. Emulsion according to claim 4, consisting of 1 to 10 weights percent dissolved organic active ingredient, 40 Ge weight percent chlorinated hydrocarbon, preferably Perchlorethylene, 20 weight percent emulsifier and water, characterized, that the emulsion is acidified to a pH of 4 to 9 is, preferably by carbon dioxide or an acid salt and that the organic active ingredient in 10 to 20 wt Zenten alcohol, preferably isopropanol is dissolved.   6. A method for producing a detoxification emulsion according to claims 1 to 3, characterized by

• - the introduction of water into a tank
• - The formation of an aqueous solution of active substance, preferably calcium hypochlorite, neutral salt, preferably table salt and solid, preferably calcium hydroxide
• - The withdrawal of the aqueous solution from the tank and the introduction of carbon dioxide or addition of acidic salt into the aqueous solution until a predetermined pH is reached
• - the return of the acidified solution to the water tank
• - The withdrawal of the solution from the tank and guidance of the aqueous solution in the circuit to the pump, dry mixer, carbon dioxide addition or addition of acidic salt and return to the tank
• - The withdrawal of the aqueous solution after 15 minutes of operation
• - The admixture of perchlorethylene, emulsifier and Isopro panol
• - The stabilization of the emulsion until it can be used as a detoxifier.

7. Device for producing a detoxification emulsion according to claims 1 to 3 and 6, characterized by

• - A water inlet ( 1 ) operated by a pump ( 2 )
• - a tank ( 3 ) with a pH controller ( 8 )
• - A pump ( 4 ) for withdrawing the aqueous solution
• - a dry mixer ( 5 )
• - a carbon dioxide bottle ( 7 ) with a solenoid valve ( 6 )
• - a back-mixing chamber ( 9 )
• - A reservoir ( 12 ) and a downstream metering pump ( 11 )
• - A pump ( 10 ) for withdrawing the emulsion from the chamber ( 9 )
• - An electrochemical success control ( 13 ) on the stabilization of the emulsion
• - A spray lance ( 14 ) for spraying the emulsion.

8. A device for producing a detoxification emulsion according to claims 1 to 3, 4 to 5 and 6, characterized by

• - A water inlet ( 1 ) operated by a pump ( 2 )
• - a tank ( 3 ) with a pH controller ( 8 )
• - A pump ( 4 ) for withdrawing the aqueous solution
• - a dry mixer ( 5 )
• - a carbon dioxide bottle ( 7 ) with a solenoid valve ( 6 )
• - A storage container ( 12 ) and a downstream metering pump ( 11 )
• - two mixers ( 15, 16 )
• - An electrochemical success control ( 13 ) on the stabilization of the emulsion
• - A spray lance ( 14 ) for spraying the emulsion.

9. A method for producing a detoxification emulsion according to claims 4 to 5, characterized by

• - The formation of an aqueous, transportable and storable solution from solvent (chlorinated hydrocarbon) and emulsifier (calcium sulfonate) in a container
• - The formation of a solution of alcohol and chloramine (active ingredient) in another container by breaking a glass ampoule containing the chloramine
• - the combination of both solutions in one container
• - Acidification of the solution by introducing carbon dioxide until a predetermined pH value is reached
• - The stabilization of the emulsion until it can be used as a detoxifier.

10. Method for controlling the emulsion stabilization according to the Claims 6 and 9, characterized, that electrical conductivity for electrochemical determination the end point of the emulsification is used. 11. The method according to claim 10, characterized, that when an electrical conductivity of 10 micro Siemens per cm and less the values of the conductivity measurement a transducer electrical, optical or acoustic signals  generate, with the help of which a valve is controlled, which at Reaching the stable emulsion part of the emulsion for Ent Poison release releases while the other part goes to the cycle operation is returned.