DE2025758C3 - Flowable mixture and its use to combat fog or to remove fog - Google Patents

Description

It is known that worldwide civil air traffic is handled in the autumn and winter months in many places on earth through unity; so fog is sensitively disturbed. Trot / With highly developed radio localization, it is very often the case in fog that airplanes can be safely transported into has moved the proximity of the runway by radio beam, turn around and the next fog-free Have to go to the airport, because the μΐη beginning d_-r The light markings set on the runway cannot be seen from a height of 30 ni (standard value of landing category II) are. Redirects to ID cards. Delays, even cancellations, but flights very detrimental to air passengers and airlines impact are the regular consequences of this Nebe !. Abseil down this economical one !! Points of view ss Jen created additional dangers through fog. Finally, it is to be determined that also outside of air traffic. / B in the street. Railways and ships play an addicting role in effective fog removal

2 "is due.

It is also known that one of different Side striving. Develop procedures and means for fogging runways on airfields / u, whereby the problem is principally autohemical. electrical, physical, mechanical and was attacked chemically. For example, the warming and Elimination of the mist from misty air dure '· Combustion -.On gasoline powered. Or it was misty air with electrically charged particles electric fields. Visual fields. Dry ice, l-ice particles, cold water as well as hygio ~ kop see substances (CaCl ... NaCl) zn eliminate s, i seeks. Furthermore, a mechanical method with rotating screens has become known.

None of these suggestions could be found in the Praxifesten Gain a foothold.

The thermal process of combustion son Gasoline is far too expensive from the fuel side.

the electrical and physical processes are too expensive in terms of their installation and operating costs. NaCl and CaCl., Cause severe corrosion. Dry ice is only limited, namely in the case of "supercooled" Fogging, effective, and the mechanical method of the rotating sieves defogging only inadequately small air spaces.

Other chemical compounds, such as SiI-beriodide, were also used to combat the mist or surfactants. However, silver iodide is on the one hand too expensive and on the other hand only for combating effective from "supercooled" mists. Also with surfactants like those in the German patent 956 278 and in U.S. Patent 2,962,450 (long-chain alkyl sulfates and -sulfonate), the problem of fog dissolution could not be solved.

The variety of requirements for chemical mist control agents, of which above all the effect also compared to that in practice many times over more occurring "warm" fog, which is non-corrosive compared to the ones used in aircraft construction Metal alloys and the nontoxicity to the biological environment are in the foreground is known to be met by urea.

What remains unsolved, however, is how to convert urea into the required stable and atomizable fine distribution. Urea has a very strong tendency to stick together, so that any spraying in the form of dust is impossible

• becomes emaclil. Without the solution de- · l'nibLir.s der stable and atomizable Feinveneiiii-iL is therefore (ji'e successful participation in the fog mi; H .-. mstolI m futile in practice.

The other extensive! ';Iici;::; ii "jun known about artificial fertilizers and also! L ι ·;> - u 111 iiiriassenden manifold additions / .e / in I"■> ■. ": R, _. _ η ■. ■ ι ιοί conditioning ^{smcl / llr} HerMc'hm · .: li; · ..:: uivlvirksatnen urinary stool combination nu; iiüb.-medi- «end wiiksam. The demand on the t>: ·.! ■ ;! .n: e; ien J-Jarnsti'lipartikel, in the shortest line m ;; ...: ■ \\ _; ...._ _: - jröpfclu-: ¹ · of the nebula in Weehseiwin, · ..- ··. - ;; ..: ^ _; / u niiissen. sets the principle under .. _: , \ .;,, οϋ, μ different: !! "!! ^ related problem de; γ · .ι ·. \ '.! Μ · .-- renation of urea for the Landv. > n ^{^:;;} ,, ι ·. _ir . · _Λ1 ) a certain Hydropi-.obierungsgiad er ·, · ..;: - .. i · ,; is and is strived for.

[^ it was now found that water! .- 1 ·

tigc Kiuidensatioiisprodukt. ·; nc: ·. Compounds and formaldehyde ;. ι. releasing substances that. :,!

• Even a good efficacy

- ^ - -ι ·>! ι> pi.no- ri _; .rm-;! .c.urm he · .k- tie-

eiii-K!

jeiÜ., τ ■ \ on possess fog. auLVroidcn-l ·.:, mim the accumulation of urea \, -:!: tkL; n and therefore: nsbes..ndere zur Nebelbekamp; jn- - ,.! .. inet are i) a the agglutinations: the leiiun ll.-M.riotT-partl'-dn by adding the erlindunii- ^ mii !; an-ievnn-ii condensation products completely lost - "\ ird. can f.:stc products bi- / ·. 11 which can be discharged into the foggy air with high levels of condensation and which do not bead lumpy even during long storage periods. Another advantage is that the components prevent a collapse. that these J _5, thanks to their specific interaction to Harnsö.i -ovvohl as solids with the Harnstotlcranalicn m a mill, preferably an air-jet mill may be added to Harnstofi and so direct the finished flowable mixture of urine Stofl and provide condensation product. But preferably also mis a Aqueous solution of both components by spray drying and - if appropriate - _T ui, L - subsequent grinding one obtains extremely effective urea formulations.

'The present invention therefore relates to flow, ähigp Mixtures consisting of Ma'nlagiTcgate are considered. The air jet mill suitable sicli besoudei- »ut. there is an excellent one Oispergiereffeki. a narrow grain spectrum At the same time, ensure a wide range of variation in the range of parts and particularly cool grinding. This device can also be used advantageously : n / units used for fog control. such as aircraft.

the instantization process can also be used to produce the flowable mixtures; into consideration come.

The component used according to the invention: i) is made from mononuclear phenols containing sulpho groups or from the corresponding mononuclear phenols containing sulpho groups or from the corresponding sulpho group-containing mono- or bifunctional phenols and formaldehyde or formaldehyde-releasing substances. Formaldehyde or formaldehyde-releasing substances and sulfites are produced in such a way that the molar ratio of phenolic component to formaldehyde is preferably about 1: 1 to 1: 3.5. The condensation products to be used according to the invention are fermentable by reacting the phenolic components with formaldehyde and alkali hydrogen sulphide in the alkaline range (e.g. according to Fiat Final Report 1 (113) or by reacting the phenolic components which are sulfonated on the nucleus with formaldehyde (H ο u be η -. Wc \ I. Met'.ioden organic Chemistry, Volume 14 2. S. 264) instead of formaldehyde or formaldehyde-donating compounds and alkali sulfite can also be an alkali metal salt of Hydroxymethansulfonsüure ve ^r be spent.

The alkali sulphides are preferably Ka Hum sulphides, especially sodium sulphides. -hydrogen sulfites and disulfites into consideration.

According to the invention, formalin is used as the formaldehyde-releasing substances. Paraformaldehyde. Trioxane and formals, especially those with low molecular weight alcohols, for use. Mononuclear phenols are, for example, o-cresol. m-cresol or technical \ halophenols, such as o-chlorophenol. O-sec-butylphenol, o-tert-butylphenol and xylenols called.

Alkylphenols are preferably used, their Total alkyl groups less than 4 carbon

a) one or more water-soluble sulfo-group-containing condensation products from phenolic compounds and formaldehyde or formaldehyde-releasing compounds _and d '"

b) urea, component a) advantageously in a proportion of 1 to 50 percent by weight is present and in their composition a molar ratio of the phenolic compound Formaldehyde from about 1: 1 to 1; 3.5 and wherein the flowable mixtures are advantageous

have a particle size of 1 to 30 ". ^^

The present invention further relates to a based phenols such as W

Process for the production of this flowable diphenyl sulfone 22 - -and4

mix by adding solutions of the two components a) wah *> ^ "^ ™ £

and b) in common to spray drying and gegc- 6 ₅ not sation zu_ w

also subjected to a subsequent grinding- Ah ^ f

or in a mixture of different Linzel components

₅₀ can be used.

An example of the use of different phenols is the use of about 3 to about 30 percent by weight substituted by alkyl or aryl radicals Phenols, ζ B Pf ^ "^^^" Ι

55 nylphenol, i ^ "* ¹ - ¹ : ^^

made from phenol and styrene) in Gernisch, with ζ Β Knaolcn or Ch orpheno en .m ^ nsaton approach. Be. der Mt ^^ ⁿ ^ Jf _en ^VO J _a J je kem.gen phenols f £ <? ± zuj £ ^ aM

60 ^^^^ f

> _the . leads.

in

In practice, commercially available Ah ^ fon.erte J ^ sulfonic acid amides, creso.su.fonsauren

6-sulfonic acid and the like can be used. The sulfonated For you, phenols are substances that leave with formaldehyde or formaldehyde alone condensable or as a mixture with the phenols mentioned above or in a mixture with phenols. Formaldehyde or formaldehyde-releasing substances and alkali sulfuene.

The condensation time can be about 2 to about 15 hours, but usually it will be with a reaction time of about 5 to about 11 hours at a temperature of about 90 His about 120 ° C get well effective products.

Component a) to be used according to the invention is further distinguished by the fact that it non-corrosive to the metal alloys used in vehicle and, above all, aircraft construction works and is non-toxic.

The following describes the production and properties of the component used according to the invention a) and their application are explained in more detail.

Component a) I

From cresol, 2-naphthol-6-sulfonic acid, formaldehyde and sodium sulfite, according to Fiat Final Report 1013 a powdery phenol-formaldehyde condensation product containing sulfone groups a particle size of about 10 to 20 u obtained, which is added directly to the urea.

Component a) 2

A mixture of 302 parts of a technical cresol cut with a proportion of about 40 ⁰ O m-cresol, 16 parts of tripropylenephenol (made from phenol and tripropylene), 528 parts of crystallized sodium sulfite and 500 parts of 30 ° oigem formalin in 300 parts of water is for 6 hours 102 to 105 ° C condensed. It is then cooled to 80 ° C., diluted with 645 parts of water, neutralized with sulfuric acid at room temperature and finally the solution is converted into a fine powder by spray drying. The particle size of the particles used to condition the urea ranged from about 1 to 100 microns.

Component a) 3

120 parts of a technical cresoi cut (with about 40% m-Krcsol), 39 parts of 2,2'-dihydroxydiphynyl, 264 parts of crystallized sodium sulfite and 20 (1 part of 30% formalin in 155 parts of water are condensed at 102 to 105 "C for 11 hours. After condensation with 100 parts of water at 80 Γ and diluted with sulfuric acid neutralized product is spray-dried and as a powder with a particle size of 10 to 20 μ as Conditioning agent added to the urea.

Component a) 4

200 parts of water, 159 parts of m-cresol, 132 parts of sodium sulfite and 200 parts of 3O "/ o formaldehyde solution are heated with stirring for 11 hours at 102 to 105 ⁰ C, then at 70 to 8O ⁰ C with 186 parts of water are added, then neutralized with sulfuric acid at room temperature and the resulting confluence product is subjected to spray drying.To condition the urea, the powder with a separated particle size of 5 to 20 n is used.

Component a) 5

A mixture of 186 parts of water, 264 parts of crystallized sodium sulfite, 180 parts of a teehnisciien Nylenol mixture and 200 parts of 30 ″ formalin is stirred for 1 hour at 102 to 105 ° C. After condensation, this is diluted with 100 parts of water at 80 ° C. and neutralized with sulfuric acid Condensate is spray-dried and used as a powder with a particle size of 10 to 2U ₁ , / for conditioning the urea.

Component a) 6

189 parts of o-chlorophenoI. 132 parts of sodium III!,;

and 200 parts of a 3 ()% formaldehyde solution: are heated in 150 parts of water to give the condensate ■■■ 11 hours at 102 to 105 ° C. Then ⁷ is diluted with 282 parts of water at 80 C and neutralized with sulfuric acid. That is how it is made.

Condensate is sprühge 'icknet and the powder v. a particle size of : '.) to 30 μ used as a conditioning agent for urea.

The amount of added component a) / u Urea can be used within wide limits, namely from etv ..

Ij 1 to about 50 percent by weight, based on the total weight, can be varied. Since · ■ also ncbelwirksam component., The amount of grain poncntc a) is at the top in itself no limit μι-sets. In practice - in particular; _; .

economic reasons - quantities of about 5! ■>:> about 20 "g of the total weight as particularly favorable. proven.

The effective concentration of component; · ί depends on the other hand on the desired end part

size of the conditioned urea, so that an addition of component a) of about 10% of the total weight is sufficient to provide urea particles> 30μ.

In the following, the inventive flow -

capable mixtures described in more detail:

Flowable mixture 1

10 parts by weight of component a) I were completely dissolved in water with 90 parts by weight of urea and as a 40 "aqueous solution with the aid of a spray dryer at 90 ° C into a fine powder, particle size essentially 5 to 30 μ, transferred. Then the powder turned into waterproof paper Containers (packs) of 15 kg each and packed for 30 days, five containers stacked on top of each other, themselves left to yourself. After the elapsed time of 30 days, there were no agglomerations of the Product in the containers (packs) Pure urea, sprayed on its own, already accumulated during the Spraying process.

Flowable mixture 2

20 parts by weight of component a) 2 were mixed with 80 parts by weight of urea in an air jet mill (Micronizer type) with a throughput of 15 kg urea / hour so that a product from 10 to 20 μ particle size resulted. The product then became the same. Test and under exposed to the same conditions as in the case of mixture 1, without any agglomeration of the property was ascertainable. Pure urea, wedded alone, balled up immediately afterwards the meal presentation.

Flowable mixtures 3 bis (p

In a manner analogous to that described for mixture 2, using components a) 3 to receive 6 corresponding conditioned ureas.

The loading of the fog chamber with the urea conditioned according to the invention for fogging can be varied within relatively wide limits from about 1 mg / m ^{: 1} to 100 mg / m ³ . However, the actual load required must understandably be dependent on weather-related parameters, e.g. B. the wind speed, can be determined on a case-by-case basis.

Various types of equipment can be used for defogging. For this purpose, for example, one or more helicopters or small aircraft can inject the flowable mixtures according to the invention into the mist, or the particles can be brought or shot into the mist in a directed manner from the ground, for example with large ventilators or fans. Finally, compressed gases, such as, for example, compressed air, CO ₂ , N ₂ or fluorocarbons, can also serve as propellants for the mixtures according to the invention. S.

example

In a natural fog in which marked poles were attached along an axis and

ίο a visibility of 3 m (fog density 2 to 3 & / m ^{; 1} ) and a temperature of 10 ⁰ C prevailed, was from a height of 10 m from the first pole in the direction of the axis of the poles with the help of a spray device, such as it is used in the spraying of pesticides in agriculture, 5 g of the conditioned urea de: mixture 2 introduced. Within about 10 minutes there was an improvement in visibility in the Nebe up to about 18 m.

ao The mixtures also gave in an analogous manner
and 3 to 6 similarly good effects.

Claims (10)

Patent claims: 1. Flowable mixture, consisting of a) one or more water-soluble sulfo-containing Condensation products from phenolic compounds and formaldehyde or formaldehyde-releasing compounds and b) urea. 2. Mixture according to claim i, consisting of components a) and b) with a proportion of component a) about 1 to 50, in particular 5 to 20 percent by weight. 3. Mixture according to claim I and 2. consisting of components a) and b) with a Particle size around 1 to 30, in particular 10 to 20 μm. 4. Mixture according to claim 1 to 3, consisting of components a) and b) with a mol ratio of component a) from phenolic compound to formaldehyde from about 1: i to 1: 3.5. 5. Mixture according to claim 1 to 4. consisting of components a) and b), wherein the Component a) consists essentially of a condensation product consisting of mononuclear sulfo-group-free phenols and formaldehyde or Formaldehyde-giving compounds and sulfites have been produced in an alkaline medium. 6. Mixture according to claim 1 to 5, consisting of components a) and b), wherein the Component a) consists essentially of a condensation product which consists of a mononuclear sulfo-group-free alkylphenol, formaldehyde or Formaldehyde-releasing substances and sulfites, the alkyl groups of the phenol have up to 4 carbon atoms ^. 7. Mixture according to claim 1 to ft, consisting of components a) and b), wherein the component a) emitting a mixed condensate of mononuclear phenols, formaldehyde or formaldehyde Substances and sulfites with up to 30 percent by weight of zsveikernigen condensed and'or phenols containing non-condensed sulfo groups or free from sulfo groups Represents connections. 8. Process for the preparation of mixtures according to Claim 1 to 7, characterized in that that the solutions of components a) and b) together with a spray drying and optionally subjected to a subsequent grinding. °. Method according to claim 8, characterized in that that one makes the grinding with the help of an air jet mill. 10. Use.eines mixture according to claim I to 7 from components a) and b) with a particle size of etsva 1 to 30 u as Fog control agent or for fog removal