DE1223701B - Process for the production of additives for fire extinguishing water containing organic gelling agents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

A62d

German class: 61 b - 2

Number: ί 223 701

File number: A 46010 VIb / 61b

Filing date: May 9, 1964

Opening day: August 25, 1966

The invention relates to a process for the production of organic gelling agents containing Additives for the production of gelled fire extinguishing water, if necessary in the presence of a Wetting agent.

If the viscosity of the water is increased by dissolving a thickener or gelling agent in it, it is found to be more effective than pure water because it drains less rapidly from the surfaces to which it is applied. Suitable gelling agents are soluble alginates and soluble Cellul'oseverbindungen as Natriumcarboxymethylcellulosfe, wherein a Vqrteil the application of these materials is that very small amounts of them fÖY ¹ the generation of the desired thickening is required.

In practice, a solution containing gelling agents is first prepared in a container or kettle, and the thickened or gelled water is then through a pipe or a hose Fire fed. However, there is a difficulty in mixing such thickening bodies or gelling agents with water in such a way that they are in an effective solution as quickly as possible, because "the time for fire-fighting operations is essential and important, and the substances listed difficult to enter into an easy and effortless solution.

It is known to use a system of pipes and pumps which the thickener in Entrain powder form and result in a solution by means of vigorous circulation. These operations however, if carried out well, they inevitably require several minutes and require that Presence of a special device. "It is the production of a fire extinguishing foam which consists of a suspension of a soluble alginate in a salt solution together with a foam-forming material, and the addition of this suspension to water for fire extinguishing is suggested been. Such a suspension can be introduced into a water stream so that a very rapid solution is obtained without the need to use a kettle or container; however, it only enables alginate quantities of the order of 7% to be taken up in them Dimensions. This means that for every part of sodium alginate 14 parts of other materials are carried along, this is then permissible and expedient if the other materials have a useful effect exercise during foam formation. However, this can also be a serious disadvantage when e.g. B.

Process for the production of

Additives for fire extinguishing water containing organic gelling agents

Applicant:

Alginate Industries Limited, London

Representative:

Dr. E. Wiegand and Dipl.-Ing. W. Niemann,

Patent Attorneys, Munich 15, Nussbaumstr. 10

Named as inventor:
Robert Ralph Merton,
Richard Henry McDowell, London

Claimed priority:
Great Britain 10 May 1963 (18 710),
dated June 17, 1963 (24 092)

only the effect of the alginate is desired, which is the case when water is to be thickened.

There is also a frost-proof fire extinguishing agent known, which consists of a liquid emulsion of halogenated, preferably brominated hydrocarbons and that to achieve the necessary Frost protection electrolytes for the water content as well as a certain amount of cellulose derivatives or Cellulose derivatives are added. This fire extinguishing agent with halogenated hydrocarbons and electrolytes in the water, the cellulose derivatives or cellulose derivatives are used for Avoidance of a normally occurring salting out of the emulsifiers by the intended Electrolytes. This is known for the production of thickened or gelled fire extinguishing water Fire extinguishing agents not suitable.

Finally, a process for the preparation of an aqueous gel solution for fire extinguishing purposes is known, which involves mixing water with a gelling agent which is a surface active ingredient contains, and the aqueous solution contains an oil, ζ. Β. a light or heavy hydrocarbon oil, is added. The object of the invention is in particular to create additives containing organic gelling agents for the production of gelatinized fire extinguishing water, which is easily mixed with water

609 657/237

the one that is to be aimed at a fire or fire, and preferably a good one Have shelf life.

The method according to the invention is characterized in that the gelling agent prior to addition to the water in a liquid, non-aqueous, but water-miscible medium that contains the gelling agent does not dissolve or swell to a perceptible extent, is stably suspended.

The suspending liquid may consist of a glycol, e.g. B. ethylene glycol or dipropylene glycol, and the gelling agent to be suspended therein can be present in any desired amount which the suspension remains flowable so that it is easily introduced into and dispersed in a stream of water can be. Preferably the amount of thickener or gelling agent exceeds about 15%> of the total weight of the suspension.

The preferred gelling agent consists of a water soluble alginate, e.g. B. sodium alginate, though Sodium carboxymethyl cellulose can also be used. It should preferably be fine be divided to obtain rapid dissolution after dispersing in the water. It can be seen that when a gelling agent is introduced in dry form in such a finely divided state in Water, it would clump together and dissolve more slowly than in a less finely divided state.

The alginate used does not need to be of high purity. Raw alginate that contains naturally occurring components of seaweed or seaweed, provides solutions in many cases of sufficiently high viscosity.

It is also not essential that the suspension be stable when standing or stored, as it can with Can be produced or managed as needed to keep the solids in suspension. On the other hand is the avoidance of the settling of the colloid is desirable, and it is particularly expedient and beneficial is to keep the colloid permanently and permanently in suspension. Accordingly, the invention encompasses the addition of a substance to the mixture that delays settling.

In an expedient and advantageous manner, a suspension for use in water thickening has the following properties:

a) it should contain as high a proportion as possible of the colloidal thickener;

b) «it should mix easily with water and quickly cause the water to thicken;

c) the settling of the colloid during storage should take place as slowly as possible.

The type and amount of ingredients used in the mixture changes may have on these properties opposite effects, and these are appropriately selected to give zn the optimal Überemstimmung for the conditions to be under which the product is used. For example, if the mixture is to be drawn up through a side pipe by means of suction, the suction force being provided by passing a stream of water through a suction constriction or nozzle, the viscosity of the mixture must be kept low enough to allow the flow of a sufficient amount of liquid .Allow, however, this may limit the proportion of solids in the mixture. On the other hand, when the mixture is pressed into a stream of water by means of a pump which can process or pass a paste, the viscosity is limited only by the ease with which the mixture is dispersed in the water. In practice, it has been found that the viscosity of the suspension after it has been stirred is not more than 30,000 to 80,000 cP

ίο should.

Essential properties of the liquid to be used to suspend the colloid are that it should not cause swelling of the colloid and that it should be miscible with water. More desired Properties of the liquid are that it should have a high density to reduce the settling rate of the colloid and for should be suitable for use or application with suspending agents; furthermore it should not burn

ao bar or have a high flash point. A preferred liquid for use with sodium alginate is ethylene glycol, but any other liquid (e.g. diethylene glycol or propylene or dipropylene glycol or 2-ethoxyethanol) which has the above essential characteristics can be used; ethylene glycol cannot be used with sodium carboxymethyl cellulose as it causes swelling, but all other liquids mentioned above can be used with this colloid. Both the sodium alginate and the ethylene glycol used in the mixture must be essentially dry, since increasing amounts of water cause the alginate to swell, which means that more space is taken up within the suspending liquid. at a lower concentration to obtain a suspension of acceptable viscosity, it has been found in practice that with a moisture content of up to 10% in the sodium alginate and up to 1% moisture in the ethylene glycol is satisfactory Results are obtained: There is limited swelling of the alginate at these levels of moisture, and although this causes some increase in the viscosity of the suspension, it also delays settling.
The finer the sodium alginate is divided in this suspension, the faster the particles dissolve after they are well dispersed in water. Furthermore, there is a corresponding advantage that fine particles settle more slowly in a suspension than coarser particles, so that for these two reasons it is advantageous to use such a finely ground alginate as is practical. On the other hand, for a given ratio of sodium alginate to ethylene glycol, the more finely divided alginate gives a suspension of higher viscosity.

To achieve suspensions that are sufficiently flowable to mix easily with water, 1 part by weight of sodium alginate ground so finely that 95% of the particles are smaller Greater than 100 microns in diameter, with about 2 parts by weight of ethylene glycol used. Alternatively, 1 part by weight of alginate so finely ground that 95% of the particles have a diameter less than 35 microns with

5 6

about 3 parts by weight of ethylene glycol for use, mix with water if a suitable one is obtained, forming salt is incorporated into the suspension. That

The preferred method for lowering the gel-forming salt is to avoid inclination in the suspending medium of the colloid for separation, the sus- soluble and finely divided, so that it quickly with the Pendulum fluid is the introduction of a material that reacts 5 sodium alginate when the suspension is in which of the suspension a high viscosity at low water is introduced.

The invention therefore encompasses the incorporation

fcosity granted at high shear dimensions. Ideally a soluble alginate in a suspension in a

a thixotropic gel is formed; however, every non-aqueous, but water-miscible sus-

Increase the effect of lowering the pendulum liquid, in which the alginate is not

of the colloid for deposition. It has also been resolved, or quiut, to a substantial degree

considered to delay the deposition of salt, which is not depending on the suspension liquid

in that a substance dissolves in the suspension material, but this does so when the suspension is mixed

is dissolved, which its density in the vicinity of those water a gelation of the alginate after its

brings the alginate, but does not cause the dispersion 15 dissolution.

The mixture and the dissolution of the alginate, if necessary, can be anionic or non-water disturbs. On the other hand, the deposition of ionic wetting agent in any of the suspensions can be prevented by adding inert insoluble according to the invention, so that Material in which mixed hunt includes (bulk material). the introduction of air as well as the suspension in

The deposition of the colloid in the suspending water results in a thickened foam which, by changing the viscosity, comprises substances which can be used for extinguishing, e.g. B. some amine salts of burning liquids and especially of long-chain polycarboxylic acids which are soluble in water, such as alcohol, the suspending liquid and acetone, methyl ethyl ketone or the like, which are a gel. In the suspension of sodium alginate in 25 have an educational effect on the alginate, is suitable. Ethylene glycol are the triamanolamine salts of Die Luft can be obtained by means of a special pump or alginic acid and a carboxyvinyl polymer, which can be obtained from a Sang system or by other means under the designation "Carbopol 934" in the "early" after the suspension of the thickening hamdel (Carbopol , a registered means to be introduced in an expedient manner.
Trademarks of BF Goodrich Company)., 30 The invention will hereinafter become particularly effective with reference to. The salts of other amines examples explained in more detail,
can be preferred in other suspending liquids. .
will. example 1

Other substances that make up the suspension of triethanolamine ginate in ethyl

Aigdnats in Ethylene Glycol are alkali 35 Lenglycol was first made by turning in

sate «of fatty acids, e.g. B. sodium stearate or oleate about 136 kg ethylene glycol about 0.748 kg alginic acid

or a mixture of the two. The organic substance with a dry solids content of 90% suspen-

toierte Beatonit, which under the name of dated and about 0.68 kg of triethanolamine with stirring

"Bentone 27" is commercially available ("Bentone", the mixture with a device which a

a registered trademark that gives National Lead 40 high shear. The stirring

Company), also improved the suspension in was continued until the alginate was complete

same mixes. was dissolved with the formation of triethanolamine ginate,

Another benefit of using with which took several hours. Approximately

Sodium alginate thickened water for fire- 45.4 kg sodium alginate with a dry solids-

Combat purposes consists in the fact that by the content of 90 ⁰ Zo and such a fineness that

guiding a salt of a polyvalent metal the 95 percent by weight of the powder on a particle

Solution can be converted into a gel. In size with a diameter less than

Compared to a thickened water remains that were 35 microns were then gradually brought down

water present in gel form is added to the solution for a long time, the stirring continuing

Renewed time in place and in thicker layers on the 50 was set. The product consisted of a thick one

Objects, which are protected from fire, suspension with a density of 1.33 g / cm ³

should, whereby to a lesser extent a penetration which no separation after three months of exposure

takes place in porous materials. These influences have been observed. You could! By means of a

in some cases in the prevention of fire pressurized current pump to be pumped; at introduction

settling more effectively, and there is a lower 55 in a water stream flowing through a hose

Risk of property damage from water. a place which is about 15 m above the end of the

Recently the manufacture of gel-shaped tubing was removed to an extent of about

like water by mixing together solutions 9 1 suspension per 4541 water flowed, that was

of sodium alginate and of a calcium salt, water to a viscosity of 150 cP during the

which have been made separately in advance, 60 time during which it leaves the hose

z «n point in time. of use. A solution of had thickened.

Naifarium algimate (prepared from a suspension Example 2

according to the invention) can with a solution of a "

Calium salt can be gelled in this way; However, a solution of triethanolamine ginate in ethyl

the use of a suspension of 65 lenglycol was granted in a corresponding manner as in

Sodium alginate described in a water-miscible FlMs- Example 1, prepared. To about 90.7 kg

Liquid also a means of making one of these solutions was about 45.4 kg of sodium alginate

complete mixture by putting them in simpler with a dry matter content of 90 ⁰ Zo that on

such a fineness was ground that 95 percent by weight of the powder was ground to a particle size of finer than 100 microns in diameter was added and mixed well. The mix had one Consistency similar to that of the mixture of Example 1 and when introduced into water corresponding results were obtained at a level of about 6.75 liters per 454 liters of water.

Example 3

About 0.34 kg of the carboxyvinyl polymer available commercially under the name "Carbopol 934" were dispersed in about 136 kg of ethylene glycol. While stirring the mixture vigorously, were about 0.34 kg of triethanolamine was added. After the carboxyvinyl polymer was completely dissolved, were approximately 45.4 kg of sodium alginate with a particle size less than 35 microns in diameter, as described in Example 1, stirred in. The suspension showed no noticeable separation on storage for several weeks. When introduced into a stream of water to thicken the water results similar to those of Example 1 were obtained.

Example 4

About 0.454 kg of sodium oleate and about 0.454 kg of sodium stearate became about 90.7 kg of ethylene glycol heated to 60 ° C. About 45.4 kg of sodium alginate with a dry solids content of 90%, which is so was finely ground that 95 percent by weight of the material was particles with a diameter of passed less than 100 microns, then added and mixed well. After 5 days of storage the product was mixed again, and then after storage for several weeks no noticeable separation observed. When introduced into a stream of water to the extent of about 6,751 per 4541 water gave similar results, as in Example 1 obtained.

Example 5

For the preparation of a suspension of sodium carboxymethyl cellulose dipropylene glycol was used as the suspending medium. A settling or deposition was made by using a carboxyvinyl polymer (Carbopol 934) and the amine "Ethomeen C-25" (Ethomeen, registered trademark of Armor & Co.) prevented. Approximately 0.476 kg of carboxyvinyl polymer (Carbopol 934) were in about 136 kg of dipropylene glycol at a Temperature of 60 ° C dispersed. About 1.02 kg of the amine "Ethomeen-C-25" was added, and the mixture was stirred for 2 hours, in which time the carboxyvinyl polymer was complete has been resolved. About 45.4 kg of high viscosity sodium carboxymethyl cellulose, which through A sieve with a mesh size of about 0.104 mm was then stirred in. The product consisted of a suspension with little tendency to settle. 2 parts of this suspension were mixed with 100 parts of water to form a solution having a viscosity of about 200 cP.

Example 6

About 22.7 kg of sodium alginate with a dry solids content of 90%, which is ground so finely was that 95 weight percent of the material was particles less than 35 microns in diameter passed, were in the dry state with about 2.27 kg of a sodium lauryl sulfate from technical Mixed quality. This mixture then became about 90.7 kg of a solution of triethanolamine alginate added in ethylene glycol, which, as described in Example 1, was prepared. the Suspension could through a side pipe attached to a foam formation nozzle, which was used for fire extinguishing purposes and fire fighting is applied. A standard nozzle was modified to have an approximately 9.52 mm side tube in the main pipe entered without restriction, but with a control valve inserted in the side pipe was. Water was pumped through the nozzle at a rate of about 454 l / min, the Flow rate of the suspension of alginate and wetting agent to a rate of about 22.5 l / min.

ao. was adjusted. A stable foam consisting of 3 parts air to 1 part liquid was produced. In contrast to the common fire foam extinguishing agents (fire foams), the Contact with water-miscible liquids did not destroy and was intended to extinguish burning Methanol, ethanol, acetone and methylethylene ketone and other burning liquids are suitable.

An example of the method of making a

Suspension for the formation of gel-like water

30. is brought below.

Example 7

Dipropylene glycol was used as the suspending medium. The deposition was due to the use avoided by a carboxyvinyl polymer (Carbopol 934) and the amine Ethomeen C-25. About 0.476 kg of the carboxyvinyl polymer (Carbopol 934) were added to about 136 kg of dipropylene glycol at a temperature of 60 ° C. About 1.02 kg of the amine Ethomeen C-25 was added and the mixture was stirred for 2 hours, the carboxyvinyl polymer being completely dissolved became. About 45.4 kg of sodium alginate, which through a sieve with a mesh size of about 0.074 mm had been sieved and about 11.3 kg calcium sulfate dihydrate was then stirred in. That Product consisted of a suspension with little tendency to settle or separate out. If those Suspension introduced into a stream of water in the ratio of 2 parts of suspension to 100 parts of water a liquid which could be directed onto a fire was obtained, which was quickly solidified into a gel upon reaching its destination.

Other materials can be included to delay or accelerate the salt formed will. For example, the sodium alginate in the wet state can be mixed with sodium citrate before drying and grinding to a fine powder for inclusion be mixed into the suspension. This ensures complete dissolution of the alginate in the Water before a calcium salt causes gelation.

Although it is desirable that the colloidal thickening material, which is the fire-extinguishing compound according to the invention, on an ongoing basis is to remain suspended, it is not essential for the purpose of the invention. To a deposition

or to prevent deposition, the containers in which the suspension is stored can be used with a device for stirring the mixture prior to immediate use. the Ingestion of a suspending agent in sufficient quantity to produce a complete suspension, Nonetheless, the solids separation can result in a hard mass, which is difficult to achieve stir is avoid.

Claims (6)

Claims: ίο 1. Process for the preparation of additives containing organic gelling agents for the production of gelled fire extinguishing water, optionally in the presence of a wetting agent, thereby characterized in that the gel former in a liquid, non-aqueous, but water-miscible medium that does not dissolve or swell the gel former to any noticeable extent, stable is suspended. 2. The method according to claim 1, characterized in that the finely divided gel former, in particular Sodium alginate or carboxymethyl cellulose, in a glycol, especially in ethylene or propylene glycol is suspended. 10 3. The method according to claim 1 or 2, characterized in that the gel former before the suspension is comminuted to a particle size which is 95% below 100 microns and especially below 35 microns. 4. The method according to any one of claims 1 to 3, characterized in that the suspension of the gel compound an amine salt to prevent deposition of the colloid formed a long-chain polycarboxylic acid, a triethanolamine salt of alginic acid or an alkali salt a fatty acid is added. 5. The method according to any one of claims 1 to 4, characterized in that the suspension a water-soluble salt of a polyvalent metal and / or one which promotes foaming known wetting agent is added. 6. The method according to any one of claims 1 to 5, characterized in that in the Suspending medium at least 15 * / o of the gel former are suspended. Considered publications:
German Patent No. 965184;
French patent specification No. 1307121.