DE2814033A1 - PROCESS FOR THE PRODUCTION OF FLAME EXTINGUISH POWDER MIXTURES - Google Patents

Description

22.672 / SsE patent attorneys

Dr. Walter Kraus η Dr AnnekäteWeisert

"'Irmgardsfr. 15, 8000 Munich

1855

1) Elzett Müvek
Budapest, Hungary

2) Magyar Nephadsereg Haditechnikai Intezet Budapest, Hungary

Process for the production of flame-extinguishing powder mixtures

The invention relates to a method of manufacture of flame-extinguishing powder mixtures.

In. The fire fighting practice are called fire extinguishing agents powder mixtures of various types have long been used. The most widely shipped powdered meats can be grouped based on their active ingredients in the following way?

1. alkali metal hydrogen carbonates,

2. alkali metal hydrogen carbonate adducts,

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3. Alkali Metal Halides, 2814033

4. Phosphate geriiische,

5. Mixtures of ∆ lka lime tall sulphates and forests.

From the above groups are the substances of the groups 1 and 2 "special agents for flame extinguishing powder, the Group 5 substances are also used to extinguish light metal fires suitable and the substances of groups 4 and 5 are active ingredients of Glutlösehpulver. The flame extinguishing powder can In addition to the active ingredients, also substances to ensure hydrophobicity and volatility and, if necessary, others as well Supplements included. Today the most modern contain extinguishing powder as active ingredient the adducts of group 2 · Such flame-releasing powders are, for example, * in the following patents described «GB-PS 1 118 215, GB-PS 1 168 092, GB-PS 1 190 152 and BiE-P? 2,258,256.

The dissolving effect of these powders is three to five times as great, like those of the extinguishing powder, the alkali metal hydrogen carbonates keep eating. The adducts are stable and inert. Their disadvantages are the relatively small grain size required for deletion, which limits the reject distance is, as well as the high cost of producing the Active ingredients.

The mechanism of dissolving flan-in-powder is as follows. The basic extinguishing property of the E ¹ lamb extinguishing powder is the inhibition of the radical chain reaction of the combustion. -The inhibition takes place in a heterogeneous or in a homogeneous phase. In the first case it works

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Powder particles that got into the Flarmazone as an "elementary wall", while in the ixeakfcion, which takes place in a homogeneous phase, the alkali metal particle evaporated from the surface of the powder and in a vapor state the milk that continues the combustion process recombined. The effect of the inhibition depends on the ifatur of the in the course of the thermal decomposition from the powder resulting particles, the particle size - with the exit parameters the residence time of the powder particle determined in the flame zone - as well as the size of the particle surface from where the size of the 'particle surface the heterogeneous combination, as well as the evaporated zone the secondary, homogeneous jxecorabinization influence When checking the inhibition mechanism it has been found that it is beneficial if im all of the selected active ingredient type Surface of the powder particle and the residence time of the Particle in the flame zone can be raised, lifting the basic inhibition mechanism of the fire extinguishing effect the oxygen displacement also occurs arising from the thermal decomposition of the solvent Inert gases as a secondary dissolving effect. Therefore, the fire extinguishing powders are mostly substances from which when extinguishing a large amount of inert gases (mostly COg »ϊίΗχ) is exempt of a fire extinguishing powder are in addition to the good extinguishing effect, the suitable flowability, good stability and small hydrophobicity. It's a very serious problem

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gate extinguishing effect and suitable flowability at the same time au secure because from the point of view of the extinguishing effect the small and, of the fluidity, the large grain size the advantageous size is. By means of aggregates the flowability of the small particles can be increased, but with it the residence time in the lamb zone for a given one The value and the clearance distance remain proportionate is small. -

According to the aforementioned CT-PS 2 258 2> G, alkali metal hydrogen carbonate adducts can be produced by spray drying. The active ingredient content of the products manufactured using the process described there is, however, quite low, on average 55-70 %. Through an eluid bed treatment, which is very time-consuming (1-1.5 hours), the active ingredient content of the products can only be on average 80-84 ⁰ C.

The aim of the invention is to develop a process for the production of Flarnmlösehpulvergemischen, to eliminate the disadvantages mentioned above,

According to the invention they are produced by spray drying Solution to be processed Carriers of great specificity Superficial and appropriately selected quality and TrorngrolenDistribution added and the reaction next the starting materials will be carried out on the surface of these carriers. By means of this on this A wise catalyzed reaction can produce such products in a shorter residence time, in which the active ingredient content is much higher (average

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borrowed 88-92 %) than that of the products manufactured according to the above PS. Another advantage of the products prepared according to the invention is that they contain only a small amount (less than 1% by weight) of unreacted amino or iminov compounds and do not require any aftertreatment. The high degree of conversion is also promoted by adding ammonium hydrogen carbonate or ammonium carbonate to the starting material to be processed. The thermal decomposition of these compounds creates a sea vapor atmosphere in the spray chamber that contains GOp and NEW.

3 ^? Another advantage of the method according to the invention is that the discharge distance of the Flaramlösehpulver - under similar conditions - by iodification of the carrier substance, for example. whose average grain size and grain size distribution can be varied over a wide range. Another advantage is that the dividing of the fuel baw. whose use for extinguishing is much more economical than in the case of a powder that does not contain a carrier.According to the invention, the reactions of the following substances are used to produce the active substance of the fire extinguishing powder:

a) reactive amino or imino compounds which contain at least one NHo " ^bBW · ¹ ^" ^grade PP ^e , such as urea, guanidine, dicyandiamide, thiourea, melamine, semicarbazide, etc.

b) Alkali metal carbonates, bicarbonates, alkali metal hydroxides un <ä

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ο) /.PiirionitLcib.yärogenkDrbonrt or ammonium carbonate "or their mixtures of carriers with a large surface and carried out -.- according to the agitated torn size distribution.

As carrier substances from a large surface, z.ß. the clays "{aluminum oxide ?, ! s aluminum oxide hydrates"), perlites, natural and synthetic zeolites, bentonites, asbestos into consideration.

In an advantageous ^embodiment. Ihruiigsforr "of the method eus is the mixtures of corresponding '■ olverhültniP'-ene (0.7-1.2: 1-2) of the TTonnonenten a) uaä b) with -10 wt .- ^ ^ of the ponfente o) a saturated aqueous solution is prepared. In this saturated aqueous solution, the carrier is first introduced in a range of 0.5-90% based on the introduced tropical substance, and for the production of a (! Methvloellulose example, Carboxvraethy cellulose) stable Fuspension 0.5-2% cellulose ziogegeben the suspension prepared in this way is used in the fuel atrockner the best parameters of Ppritatrockners are the following:.. inlet temperature of air: 200-500 ⁰ C. Exit temperature of L »ffc: 100-180 ⁰ C, dwell time: 2-25

The suspension used in the fuel dryer decomposes into small particles in the outlet nozzle, under the action of the hot air introduced into the dryer

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AO

evaporates des Nasser and the ^ eaktiou runs along the Surface of the carrier material it and in smaller iv-a ^ e to the Partial amounts resulting from the solution. The relationship The two operations depend on the quality of the one used Reaction components, quality, grain size and iVienge of the carrier material used, as well as of the operation spsrame tern, the fuel drying off. By, their corresponding Attitude it can be achieved that the The reaction that takes place on the carrier fish is the decisive reaction.

The reaction takes place between components a) and b), and adducts are formed. The component c) nitrates no part of the rupture, it decomposes and thus sicriert a CO ₂ and NH ^ containing water vapor atmosphere in the reaction space, which promotes the formation of a high conversion (over 85 ⁰ C). Under the circumstances of Soritztrooknens in the duct-forming reaction, which takes place on the carrier granules in a favorable gas atmosphere, contains an active ingredient mostly formed on carrier granules. Its grain size and ballistic consistency can be regulated by modifying the properties of the carrier grains. In the course of extinguishing, the alkali ions evaporating from the surface of the carrier substance develop an effective inhibition.

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holding Lösohstoffe no significant change in-7er "tillu / is to the erase power of his, ara fluid bed NACU-bebunrdelten Δ-Jdukte The erfind prepared ungsgeuiLiß -'ulve ^r-r Oenöti;.. t no ilachuehandlung since the 'Conversion is so high that the unreacted starting materials in such small;.. Änge the Loschvprgang riiaiil influence '3EI the erf induügsgemässeii producing PeuerlösGhpulvergewiiTCheri is the aggregate wall because of the JIie ^r 5barkeit enhancing additive is not necessary to lower or uax- a small amount of it is needed.

Jureh the VerwenJung of ex'findungsger / iu ^ s method, it is possible that the active ingredients can I'igenschaften th after the appli (5ungsi "jethoden au vary" In the case of "small V'oa Hendgex-ö by Yerniinderung the ^r J ] rir'-g only off korugrü3e and by reducing the carrier substance .. \ e.age a powder can be produced which has the appropriate extinguishing and ballistic properties or Fahraeugen are suitable, larger carrier material size and a larger end of carrier material will be used. '

The invention is illustrated in more detail by the following examples.

In the examples that appear together in Table 1. are collected, the specified amounts of the components a) _t b) and c) are measured and a saturated aqueous solution is prepared, then the carrier is added and

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the suspension stabilized with 1-2 ^ "Meth.ylcellalose. ITech the injection molding machine the particle size distribution of the product obtained and r.?;ch the addition of the additives substances the Löschliraft and the Aufwandskemtzeinhen certainly. Are the examples given in the table a variant de? F-substances 1, in which no substance c) and no carrier was used; this substance served as a comparative substance. This comparative substance was treated after its production on a PIu Id bed to increase its active ingredient gen * Its,

For testing the extinguishing power, a postponed model of the standard fire described in various forms, the pale B, is used, which consists of an air nozzle to secure an air flow of 2 liters / min. a ßegelbank for setting the nozzle and 5 disc-shaped Ietalischlassel (diameter: 3 _f 5, 7 _t 9, 11 13 cm) consists.

Water up to a TTche O _f 5 era in the bowl of 1 cm height, then poured on 0.4 om gasoline layer. 1 g of powder mixture is placed in the powder bowl of the nozzle. The gasoline poured into the bowl used for the test is ignited, after 10 seconds of pre-burning the air flow is applied to the nozzle and the powder is brewed into the PlaramBone. In the course of the test, the diameter of the bowl is gradually increased and the test is continued until the measured substance is no longer usable, cum extinguishing the fire.

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is hig. The strength is determined by the diameter de »characterizes the greatest extinguished fire. To the Fire extinguishing test are the extinguishing powders of the following composition used?

Active ingredient $ ?, 5%

he hydrophobize Btoff

(Potassium stearate or silicone) 2.0%

Mica powder 0.5 &

The results of the fire extinguishing tests are in summarized in Table 2.

From the information it can be seen that the extinguishing power with the comparison substance after-treated on the fluid bed is almost identical. These results were with the Manual tests confirmed.

Example B.

The experiment described above works with the difference repeats that as substance C-) instead of ammonium carbonate, an equivalent amount of ammonium hydrogen carbonate is used or the mixture of 0.25 moles of ammonium hydrogen carbonate and 0.25 moles of ammonium carbonate are used. the modified in this way means that the fabrics 14 and 14 show, in the fire extinguishing tests described above, a release effect that is similar to that shown in FIG Table 2 is equivalent to the results given.

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Example G

The preparation of the active ingredients 7 and 8 of Table 1 is repeated with the harvest rs ο hied that one as Substance b) an equivalent iv: tightness of fCalium carbonate resp. Sodium hydroxide and the mixture of 0.5 iViol sodium hydrogen carbonate and 0.7 AlO 1 potassium hydroxide is used. The substances modified in this way show an extinguishing effect in the fire extinguishing tests described above, which is equivalent to the results given in Table 2.

Example D

The preparation of the active ingredient 7 of Table 1 is repeated with the difference that as substance a) an equivalent amount of guanidine, thiourea or Pemicarbazide and the 1: 1 Geraisch of urea and Peraikarbazid or the 2: 1 mixture of urea and Dicyandiamide used. The substances modified on this "'' iron beige in the fire extinguishing versions described above an extinguishing effect which is equivalent to the results given in Table 2.

The flame-releasing powder mixtures prepared by using the active ingredients produced according to the invention can also contain other substances, a, B _# the following: substances that ensure hydrophobicity (e.g. potassium stearate, silicone oil, silicone produced on a grain surface), additives that reduce the grain

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(ί.Β. graphite, mica, etc.), other inert substances that do not react with the components, E.B. Talc, tricalcium phosphate, Bariam sulfate, silica gel. We give them following examples of «

Example I.

Active ingredient of the example Example IV 1 92 % Potassium stearate Active ingredient of the example 2% mica Silicone oil 1.5 % Tricalaium phosphate Barium sulfate 2.5 % Silica gel Example V 3% Example II Active ingredient of the example Active ingredient of the example Potassium stearate 1 87 % Mmethyldichlorosilane Tricalbium phosphate 2% graphite Mica 8 0 9 8 4 2 / 1 % Barium sulfate 10% Example III Active ingredient of the example 2 91 % Silicone oil 2% Tricalcium phosphate 3% Talk 4% 3 88 % 2% 10% 10 94 % 2% 3% 0723 1 %

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Table 1

Manufacture of the active ingredients

= i-xveaktionteilneaiacr carrier parameters

Diel a J b) c) of the fuel

iai- ClLoIJ (l _t 2A.ol) (0.5 hxol) dryer

Grain size of

T. TT, ν Proein from (see) _duk; _

tes (/ u J

1 Hair
material KHGO ₃ 2 urine
material KHGO ₃ 3 urine
material KHGO, 4th urine
material KHGO ₃ 5 urine
material KHCO ^ 5 urine
material NaHCO ₃ 7th Urine--.
material NaHCO ₃ 8th Dicyan
diamid KHCO ₃ Q
j Dicyan
diamid SHCO ₅ LO Hair
a ϊ off KHGO, Ll urine
material SHCO, 12th urine
material IHCO ,; 12- -Urine
material KHCO ₅

(NH ₄ I ₂ CO
(NH ₄ J ₂ GO clay from 5-20 / u

30th

(NH ₄ J ₂ CO ₃ (NH ₄ J ₂ CO ₃

(NH ₄ J ₂ GO ₃ (NH ₄ J ₂ GO ₃

(NH ₄ J ₂ CO ₃ clay from 20-50 / u 40

Clay from 50-100 / U 50

AlZSiO ₂ of 10-20 / ΐλ 35

from

10-20 / u 40

Clay from 5-20 / α 30

AlZSiO ₂ from

10-20 / u 40 r

Clay from 5-20 / u 50

AlZSiO ₂ from 10-20 / ii 40

Alumina from 5-20 / α 35

AlZSiO ₀ from 10-20 / U 30 8 % B & ntonite

Clay voa 5-20 / U. 50 5 % perlite + 5 % bentonite

AlZSiO ₅ from 18-20 / U 50 5 % perlite + 5 % bentonite

360 140 20 10-40

370 130 15 30-70

360 120 10 80-140

375 135 15 15-40

375 135 15 20-50

380 140 20 15-45

375 135 15-20-55

470 175 15 10-50

490 185 15 15-35

380 135 20 20-50

380 135 20 30-70

380 135 18 15-45

380 135 18 25-65

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(Continuation of Table 1)

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Bei- Heaictions participant

game a) b) o)

Nam- (1 mole) (1.2 moles) (0.5J "ol)

Impurities

Parameter grain spray size dryer des

14 urine * SaHCO material

15 Urinary NaHGO material

(NH _A ) _o C0-z alumina from ± *? _νοα 20-50 / U 40%

5% perlite 5% bentonite (NH ₄ ) «CO, clay from

* ^ 20-50 / U 40 #

8? 5 bentonite 130 15 45-90

130.. 15 50-100

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Table 2 The results of the fire extinguishing attempts

sample Extent of success
richly erased
Fire Amount of to
Use delete
the substance
(S) Comparison subscans 9 1 1 9 r-l 2 9 r-l 3 7th 1 A. 9 1 3 7th 1 6th 7th 1 IO 9 1 11 7th 1 Comparative Substance 5 0.5 1 5 0.5

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Claims (12)

/ Iy process for the production of extinguishing powder adducts, characterized in that one passes through on carrier particles with a large specific surface Spraying process a reaction of the following substances a) reactive amino - bsw. Imino compounds, which contain at least one ML or HH group, such as urea, guanidine, dicyandiamide, thiourea, melamine, Remicarbazide or mixtures thereof and b) Alkali metal icarbonates and / or alkali metal hydrogen carbonates and / or alkali metal hydroxides in the presence of ammonium hydrogen carbonate and / or ammonium carbonate performs. ■ 2. The method according to claim 1, characterized in that that the carrier material used is alumina (aluminum oxide), Aluminum oxyhydrate, natural and synthetic zeolites, Perlite, bentonite or asbestos are used. 3 · The method of claim 1 or 2, characterized in that mentioned under b as point) Alkaliraetallverbindung uses a ITatrium- or Kaliumsal ζ. 4 »Method according to one of claims 1 to 3, characterized in that the process is carried out in a spray dryer at an inlet temperature of 2 ^ 0-5 ^ 0 ⁰ C, an outlet temperature of 100-180 ⁰ O and a Vervseilzeit of 5-25 sec performs. 5 · method naoh one of claims 1 to 4 _f characterized by the fact that the solvent used is water used. 809842/0723
ORIGINAL INSPECTED 6. Method n; -ch one of the speeches 1 to 5, thereby Kekei ^ aeiccriet, dal nan the starting to / f eia FatelysatortrLt ^ eiCtofi'pulver u It a middle "" ornpröRe under 200 / U in one. iuge of 0, ^ - 90 wt .- ^ indicates. 7. Ycrfauren uach a: ^{1 of} the speeches 1 to 6, characterized in that one uses one-nlysf; tortr-.f? Rstof powder with a rittleren grain size of 10-120 / rev. 8. "Increase n ^ oti a '' ier claims 1 to ^ 7, the
characterized in that the total weight of the "opponents a) and b) and UIH ₁ HGO; and / or (NHi) ₉ CO _{71 is} 10-50 ^ of the weight of the Henktionsgepisch. 9. The method according to any one of claims 1 to B, characterized in that the components a) and b) in. ", ίο! ratios of 0.7-1.2: 1.2 are used. 10. Fire extinguishing powder mixture, especially znm TS— see fires of the pale A, B, G, D or E, characterized in that it is an adduct according to one of claims 1 to 6 in a range of 70-97 &, aggregates, awecttiiossiß materials which ensure hydrophobicity, compatibility with extinguishing foams or flowability, contain lubricants, surface-active agents, coloring agents in a range of 3 ~ 30 % and, if desired, indexes, conventional fire-releasing ingredients. 11. Fire extinguishing powder mixture according to claim 10, characterized in that it is an adduct according to one of claims 1 to 9 in an amount of 5 ~ 95 ^, other conventional fire extinguishing substances in a? 'Close of 5 ~ 95 ¹ ^ 809842/0723
BAD ORIGINAL * ■ " 28U033 and an ooei -lehxere ZasoaUrstoff in one> eye from 0-50 & contains. 12. üeaerlüeciipalvc-r / ieiräsch ηεοη foEDiucb. IO or 11, characterized, ciaS es -3ie / iddakte d-er claims 1 to 9 "eberiSo as Jic -aperen herkö ^ ilicheo. E 'contained in a n.ei-gL · from J0-7C V- . 8 O 9 8 4 2/0723
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