CS244012B1 - Process for preparing a foaming agent by hydrolysis of keratin in an alkaline environment - Google Patents

Abstract

The method relates to the field of preparation of a foaming agent, specifically an air-mechanical foam, intended for extinguishing flammable liquids immiscible with water. The aim is to increase the amount of the product by 4 to 15%, to achieve a multiple increase in the stability of the foam, to reduce the amount of the stabilizing solution FeSO. by one third and to reduce the formation of secondary sludge by approximately 35%. The stated purpose is achieved by preparing the foaming agent by hydrolysis of keratins in an alkaline environment in the presence of cationic or non-ionic surfactants in an amount of 0.1 to 10 parts by weight of the active component of the surfactant per 100 parts by weight of organic material.

Description

The invention relates to a method of producing a foaming agent, specifically a pneumatic foam, intended for heating flammable liquids that are not extinguishable with water.

Partially hydrolyzed keratins of animal origin, such as horn meal, feathers or degraded proteins of various wastes that are left over from the processing of agricultural crops, such as soybeans, cotton and the like, are used as a foaming agent for air-mechanical foam intended for extinguishing flammable liquids immiscible with water.

It is known from the literature that keratins are degraded enzymatically or by acid or alkaline hydrolysis. Enzymatic degradation uses enzymes such as papain, trypsin, pepsins, proteinases, etc. This method of degradation is significant, expensive and is used for food purposes.

In acid hydrolysis, sulfuric, nitric or phosphoric acid is used. The product obtained is useful as a protective colloid, but does not have very good foaming properties. In addition, the hydrolysis requires the use of acid-resistant apparatus.

The most commonly used is alkaline hydrolysis, the course of which is controlled to ensure that it proceeds to the optimum degree. The properties of the obtained product are most influenced by the hydrolyzing agent used. Calcium hydroxide is considered the most preferred hydrolyzing agent, which has the advantage of low price and lower corrosiveness compared to other agents.

The resulting product gives a better foam than hydrolysis with other agents, such as potassium or sodium hydroxide or ammonium hydroxide solution. The disadvantage is too deep degradation leading to amino acids with poor foaming properties and the formation of secondary sludge. The reaction time depends on the temperature and ranges from 6 to 30 hours.

The above-mentioned disadvantages are eliminated by the method of preparing foaming preparations according to the invention. The method of preparing a foaming preparation by hydrolysis of keratins carried out in an alkaline environment according to the invention consists in the hydrolysis being carried out in the presence of cationic or nonionic surfactants in an amount of 0.1 to 10 parts by weight of surfactant per 1.00 parts by weight of organic material.

For the most advantageous surfactants, the concentration was optimized at a constant reaction time of ⁰ hours. It was found that when comparing the preparation of the foaming preparation by alkaline hydrolysis without a catalyst with the process according to the invention, when surfactants are present as micellar catalysts, the reaction time at the room temperature of the reaction mixture is shortened from 6 hours to 2 hours.

When using the most powerful catalysts, the amount of product increases by 4 to 15% and a product is obtained that exhibits a several-fold increase in foam stability, which allows the amount of stabilizing 'FeSO^ solution to be reduced by one third. The iron content in the product is thus reduced from 1% by weight to 0.6% by weight and the possibility of secondary sludge formation is reduced by approximately 35%.

Comparison of foaming, yields for products made from 200 g of feathers and nitrogen utilization in % for two-hour hydrolysis is shown in the following table:

and use of Ca(OH)2

a. 8: the catalyst according to the invention is presented in Table 3

Table:

Catalyst foaming (ml) lifetime (min.) weight of a product made from 200 g of feathers (g) %N Ca(OH) ₂ 700 20 248 46.5 hexadecyltrimethylammonium bromide 750 30 326 61 hexadecylbis(2-hydroxyethyl) methylammonium bromide 780 30 335 62 N-lauryl-N,N-dimethyl-N-benzyl- ammonium chloride (ORTHOSAN - MB) 800 30 375 69

polymer-N,N-dimethy1-N-(2-hydroxy-

propyl)-ammonium chloride 720 30 341 63 (DEXTROSIL DE) CH, | ^{3 θ} η ^Η 2η + ^°· ^(0Η 2 ^θΗ 2 ^θ ν° ^Η 2·γ· ^σΗ 2^~^ ^Η 2 ^0ΐθ OH CH,CH, V OH n - 12 : 15 (SYNTAMIN SF) condensate of stearic acid with alkyl amines 640 30 339 63 (SYNTAMIN J) condensate of stearic acid with quaternary alkylolamines or with diethylenetriamine 730 30 350 66 (SYNTAMINE OG) octadecyldimethyl-(2-hydroxy-3- 700 30 329 61 -chloropropyl)ammonium chloride nonylphenol polyglycol ether with approximately 5 oxyethylene groups 720 30 331 61 (SLOVAFOL 905) 770 30 237 28,'

According to the valid PND δ. 39-823-71, the foaming should be 600 ml, the foam life 20 minutes. The foaming and life were greatly exceeded in all cases.

Example

To 800 ml of water, 0.2 parts by weight of hexadecyltrimethylammonium bromide, 40 parts by weight of calcium hydroxide are added and 200 parts by weight of feathers are dosed in 20 minutes. At the same time, 40 parts by weight of sodium carbonate are added in three doses.

After two hours of boiling, the reaction mixture is set aside and the undissolved keratin residues together with the formed limestone are sedimented for 24 hours. The clear solution is separated from the settled sludge, acidified with 10 to 12% hydrochloric acid to pH 5 and the precipitate is separated. Hydrogen sulfide is boiled out of the clear hydrolysate and such a quantity of water is distilled off that the density of the product is at least 1.160 g/cm^ at 20 °C.

The crude product is stabilized with a stabilizing solution composed of 340 parts by weight of ferrous sulfate heptahydrate and 1,000 parts by weight of water, which is adjusted by adding such an amount of saturated sodium carbonate solution that the pH of the stabilizing solution is 6.5.

The stabilizing solution is dosed to the raw product in an amount of 9 parts by weight of stabilizing solution per 100 parts by weight of raw product. 0.4 parts by weight of sodium persulfite and 0.02 parts by weight of indicator, disodium salt of 2,3-dihydroxy-1,5-benzenedisulfonic acid (TIRON), dissolved in 2 parts by weight of hot water are further added to the raw product.

The mixture of the stabilizing solution and the crude product is boiled for 20 minutes, then the pH is adjusted with a saturated sodium carbonate solution to 6.5 to 6.8 and the resulting sludge is sedimented. After separation of the feathers, a clear final product is obtained in an amount of 326 parts by weight with a density of 1.166 g/cm . The amount of nitrogen transferred from the feathers to the final product, i.e. the nitrogen utilization, is 61%.

Example 2

The working procedure is the same as in Example 1, with the difference that 1.7 parts by weight of hexadecylbis-(2-hydroxyethyl)methylammonium bromide is used as the catalyst. The reaction yield is 335 parts by weight of product with a density of 1.175 g/cm. The nitrogen utilization is 62%.

Example 3

The working procedure is the same as in example 1, with the difference that 0.83 parts by weight of N-lauryl-N,N-dimethyl-N-benzylammonium chloride, i.e. the active ingredient of OETHOSAN MB, is used as the catalyst. The reaction yield is 375 parts by weight of a product with a density of 1.173 g/cm^, the nitrogen utilization is 69%.

Example 4

The working procedure is the same as in Example 3 with the difference that the amount of N-lauryl-N, N-dimethyl-N-benzylammonium chloride (OHTHOSAN MB) is 1.33 parts by weight as the active ingredient and the hydrolysis time is shortened to 1 hour. The reaction yield is 339 parts by weight of a product with a density of 1.169 g/cm², the nitrogen utilization is 63%.

Example 5

The working procedure is the same as in example 1 with the difference that 3.5 parts by weight of the polymer-N,N-dimethyl-N-(2-hydroxypropyl)-ammonium chloride, the active ingredient of DEXTHOSIL DE, is used as the catalyst. The reaction yield is 341 parts by weight of the product with a density of 1.176 g/cm³, the nitrogen utilization is 63%.

Attached

The working procedure is the same as in example 1, with the difference that 1.55 parts by weight of the active ingredient SYNTAMIN SF is used as the catalyst, i.e.

p ^C n ^H 2n+1° ^(CH 2 ^CH 2° ⁵ 5 -CHg-CH-CH-jN-CHg-CHg-OH Cl.

OH CH ₃

The reaction yield is 339 parts by weight of product with a density of 1.169 g/cm\ the nitrogen utilization is

».

Example 7

The working procedure is the same as in example 1, with the difference that 10 parts by weight of the active ingredient SYNTAMIN J, i.e. a condensate of stearic acid with alkylolamines, is used as the catalyst. The reaction yield is 350 parts by weight of a product with a density of 1.175 g/cm^, the nitrogen utilization is 66%.

Example 8

The working procedure is the same as in example 1, with the difference that 1.7 parts by weight of a condensate of stearic acid with quaternary alkylolamines or with diethylenetriamine, i.e. the active ingredient of SYNTAMIN OC, is used as a catalyst. The reaction yield is 329 parts by weight of a product with a density of 1.174 g/cm^, the nitrogen utilization is 61%.

Example 9

The working procedure is the same as in Example 1 with the difference that 1.7 parts by weight of the active ingredient octadecyldimethyl(2-hydroxy-3-chloropropyl)-ammonium chloride is used as the catalyst. The reaction yield is 331 parts of a product with a density of 1.182 g/cm\ the nitrogen utilization is 61%.

Example

The working procedure is the same as in example 1, with the difference that 2.7 parts by weight of nonylphenol polyglycol ether with approximately 5 oxyethylene groups, i.e. with the active ingredient SLOVAFOL 905, is used as the catalyst. The reaction yield is 237 parts by weight of a product with a density of 1.183 g/cm^i and the nitrogen yield is 28.7%.

Claims (1)

A process for the production of a foaming agent by hydrolysis of keratin in an alkaline medium, characterized in that the hydrolysis is carried out in the presence of cationic or nonionic surfactants in an amount of 0.1 to 10% by weight. parts of the active ingredient surfactant in an amount of 0.1 to 10 wt. parts by weight of the active ingredient surfactant per 100 wt. parts of organic material containing keratin.