RU2673048C2 - Anti-icing composition - Google Patents

Abstract

FIELD: construction.

SUBSTANCE: invention relates to an anti-icing composition for various surfaces, such as asphalt, concrete, metal, alloy, glass, glass, ceramics. Anti-icing composition includes, by weight. %: 20–60 potassium acetate or eutonic mixture of potassium acetate and sodium acetate in a mass ratio of 3.1/1.0, 3–10 two- or trihydric alcohols: ethylene glycol, propylene glycol, glycerin, and 0.01–0.1 fullerenols – individual fullerenol – C₆₀(OH)₂₄ or mixtures of fullerenols (C₆₀(OH)_14–28 + C₇₀(OH)_10–22), water – the rest is up to 100.

EFFECT: technical result is the provision of anti-icing composition having anti-corrosion, bactericidal, anti-fungal properties, environmental safety and convenient to use.

1 cl, 16 ex, 3 tbl

Description

The invention relates to liquid anti-icing compositions and can be used for protection against icing for many industrial and economic purposes, in particular for pavements, street stairs, runways based on asphalt, concrete, roof surfaces, gutters, pipes, external parts of aircraft , automobiles based on metals and alloys, automobile glasses, transparent building constructions based on glasses, ceramic, ceramics.

The range of liquid de-icing agents is very diverse, but not all of these are environmentally friendly.

Known anti-icing fluid for surface treatment of aircraft equipment to remove snow and ice deposits and prevent re-icing, which contains glycol, a surfactant - ethoxylated higher fatty alcohols fraction C ₁₂ -C ₁₈ with the number of oxyethylation equal to 7-10, inhibitor corrosion - 1,2,3-benzotriazole or tolyltriazole and the pH regulator is alkali metal hydroxide [RU 2336290, C09K 3/18, published on 20.10.2008]. This anti-icing fluid is not safe for the environment due to its 1,2,3-benzotriazole or tolyltriazole.

Known anti-icing liquid, including 50-55% alkylene polyol, 0.3-0.4% benzenesulfonate methyldiethylaminomethyl derivatives of diethylene glycol esters of fatty alcohols, 0.1-0.2% stearic acid, 0.15-0.2% quaternary methyl sulfate, product condensation of stearic acid with diethanolamine, 0.3-0.4% of a technical mixture of polyethylene glycol ethers of monoalkylphenols based on propylene trimers of the following composition: C ₉ H ₁₉ C ₆ H ₄ O (C ₂ H ₄ O) _n H, where n is the average number moles of ethylene oxide attached to one mole of alkyl phenols, n = 9-12, as e corrosion inhibitor 0.5-1.5% of sodium tetraborate and the remainder water [RU 2235748, C09K 3/18, published 10.09.2004]. Known anti-icing liquid is used to remove ice deposits from the surface of aircraft, as well as to prevent re-ground icing of aircraft at the stage of their preparation for take-off. The main disadvantage is the use in a known composition of diatomic glycols, which are known to be quite toxic.

Known environmentally friendly anti-icing liquid for ground handling of aircraft before take-off with a density at 20 ° C of 1.27-1.32 g / cm ³ and a boiling point of 119-124 ° C, including propylene glycol, corrosion inhibitors, an aqueous solution of potassium formate or a mixture of water solutions of formate and potassium acetate, glycerin, surfactant, thickener, if necessary [RU 2475512, C09K 3/18, published 02.20.2013]. Salts of phosphoric acid, sodium nitrite, sodium benzoate, water glass, benzotriazole, triethanolamine are used as a corrosion inhibitor; as a surfactant - neonol, shampoo, etc .; as thickeners are sulfocell, acrylic resin, etc. The components of the known anti-icing liquid are in the following ratios (g / kg): propylene glycol 50-300, glycerin 10-80, corrosion inhibitors 12.3-41.1, thickener 0.0- 12.0, an aqueous solution of potassium formate with γ = 1.1-1.4 or a mixture of potassium formate with potassium acetate γ = 1.32-1.37 the rest.

The specified analogue in terms of features is the closest to the claimed composition and is selected as a prototype. The common features of the known composition and the claimed composition is the presence of the following four components: potassium acetate, propylene glycol, glycerin and water.

The disadvantages of the prototype:

- environmental friendliness of known composition: propylene glycol in a concentration of up to 30 mass. % and at the same time glycerin in a concentration of up to 8 mass. % toxic enough. Liquid glass does not recycle over time and can salinize the soil, increase pH and, as a result, inhibit vegetation and serve as the basis for the development of bacterial, fungal and viral flora. Inhibiting anticorrosive agents (nitrite and sodium benzoate, benzotriazole) are environmentally hazardous, create an additional burden on wastewater and soil;

- not wide enough the temperature range of application of the known composition (from 0 to -35 ° C), due to the use of sufficiently dilute solutions of formate or potassium acetate.

The objective of the invention is to provide an anti-icing composition, which would simultaneously have anti-icing properties for various surfaces would have anti-corrosion, bactericidal, antifungal properties, would be environmentally friendly and convenient to use.

The task is achieved in that the anti-icing composition includes, mass. %:

potassium acetate or a eutonic mixture of potassium acetate and acetate sodium in a mass ratio of 3.1 / 1.0 20-60 di- or trihydric alcohols selected from ethylene glycol, propylene glycol glycerin 3-10 individual fullerenol C ₆₀ (OH) ₂₄ or a mixture of fullerenols (C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 ) with a mass ratio of 3/1 0.01-0.1 water  - the rest is up to 100.

Potassium acetate (CH ₃ COOK) or a eutonic mixture of potassium acetate and sodium acetate (CH ₃ COOK + CH ₃ COONa) serve as a melting agent, di- or trihydric alcohols - ethylene glycol (CH ₂ OH-CH ₂ OH), propylene glycol (CH ₂ OH-CH ₂ -CH ₂ OH), glycerin (CH ₂ OH-CHOH-CH ₂ OH) - as a fixing and adhesive agent.

Fullerenols, in other words, polyhydroxylated fullerenes - individual C ₆₀ (OH) ₂₄ fullerenol, a mixture of fullerenols (C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 ), are water-soluble nanoclusters based on light ₆₀ C fullerene derivatives or a standard fullerene mixture (C ₆₀ + C ₇₀ + C _{n> 70} ).

Individual fullerenol C ₆₀ (OH) ₂₄ can be obtained in two ways [KN Semenov, NA Charykov, VN Postnov, VV Sharoyko, IV Vorotyntsev, MM Galagudza, IV Murin. Fullerenols: Physicochemical properties and applications. Progress in Solid State Chemistry 2016.V. 44 (2). P. 59-74]:

1. direct heterogeneous oxidation of fullerene C ₆₀ dissolved in an aromatic solvent (toluene, xylenes, etc.), alkali (mainly NaOH, H ₂ O ₂ , etc.) in the presence of an interphase catalyst or without the participation of the latter;

2. hydrolysis of C ₆₀ Br ₂₄ , which, in turn, can be obtained by direct heterogeneous-catalytic synthesis of fullerene C ₆₀ with Br ₂ [K.N. Semenov, V.A. Keskinov, A.K. Pärtman, V.V. Yakovlev, O.V. Arapov. Solubility C ₆₀ Br _n (n = 6, 8, 24) in organic solvents. Journal of Physical Chemistry. 2009.V. 83. No. 11. S. 2124-2129].

The synthesis of a mixture of fullerenols (C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 ) with a mass ratio of 3/1 is carried out by the heterogeneous-catalytic method. To fullerene soot obtained in our case by the Kretschmer method, o-xylene is added to dissolve the fullerene mixture, as well as a solution of NaOH in water and an interphase catalyst - n-tetrabutylammonium hydroxide. Then the mixture is mechanically mixed for several days, then the fullerene black is filtered off, the aqueous phase is separated from the organic separation funnel, the fullerenol mixture is salted out from the aqueous phase with methanol and recrystallized three times from water to methanol. Finally, the sodium forms are removed from the preparation by washing in a Soxhlet apparatus (the solvent is methanol saturated with hydrochloric acid). In the obtained mixture of fullerenols, the ratio of C ₆₀ (OH) _14-28 and C ₇₀ (OH) _10-22 in mole numbers corresponds approximately to the content of C ₆₀ and C ₇₀ fullerenes contained in fullerene soot obtained by the Kretschmer method, i.e. about 3/1. The mass ratio of C ₆₀ (OH) _14-28 and C ₇₀ (OH) _{10-22 is} approximately the same, because the average molecular weights of both forms are very close. The presence of heavier fullerenes in the resulting mixture of fullerenols is possible only in trace amounts, since the total content of heavy fullerenes (C _{n> 70} ) in fullerene soot is usually less than 2 mass. %

The advantages of the claimed composition:

- environmental friendliness: the natural oxidation of the main anti-icing agents to: CH ₃ COOK to KHCO ₃ (fertilizer), CH ₃ COONa to NaHCO ₃ (soil alkalizing agent), polyhydric alcohols CH ₂ OH-CH ₂ OH, CH ₂ OH-CH ₂ - CH ₂ OH, CH ₂ OH-CHOH-CH ₂ OH is not oxidized in air;

- additional environmental friendliness of the composition is achieved through the use of water-soluble nanoclusters that do not oxidize in air, stimulate the growth of the root system of plants and increase stress resistance of the latter;

- additional operational properties of the anti-icing composition - bactericidal activity, antifungal and antiviral properties, high adhesion to various surfaces, are manifested due to the presence of water-soluble nanoclusters in the formulation;

- a sufficiently wide temperature range for the use of the composition (from 0 to -60 ° C) is a consequence of using a saturated solution of potassium acetate or a eutonic solution of sodium and potassium acetates, which allows to maximize the cryometric effect.

Due to the presence of water-soluble nanoclusters, the anti-icing composition has the following additional operational properties: low vapor pressure, lack of odor, bactericidal activity, antiviral properties, antifungal properties, high adhesion to various surfaces, corrosion inhibition, environmental friendliness [D.P. Tyurin, K.N. Semenov, N.A. Charykov, I.A. Cherepkova, B.A. Keskinov, M.Yu. Matuzenko, N.A. Kulenova, Z.M. Akhmetvalieva. Electro-chemical and corrosion properties of some water soluble derivatives of light fullerenes C ₆₀ and C ₇₀ . Materials of the XII International Scientific Conference "Advanced Technologies, Equipment and Analytical Systems for Materials Science and Nanomaterials". Volume 4. Ust-Kamenogorsk: BRANCH of RSE "NTs KPMS RK" VNIITSVETMET. 2015. C. 429-432; GG Panova, IN Ktitorova, OV Skobeleva, NG Sinjavina, NA Charykov, KN Semenov. Impact of polyhydroxy fullerene (fullerol or fullerenol) on growth and biophysical characteristics of barley seedlings in favored and stressful conditions. Plant Growth Regulation. 2016. V. 79 (3). P. 309-318; KN Semenov, NA Charykov, VN Postnov, VV Sharoyko, IV Vorotyntsev, MM Galagudza, IV Murin. Fullerenols: Physicochemical properties and applications. Progress in Solid State Chemistry 2016.V. 44 (2). P. 59-74; L.M. Anikina, BB Yakushev, N.G. Sinyavina, G.G. Panova, N.A. Charykov, V.A. Keskinov, M.V. Keskinova, K.N. Semenov. Integrated microfertilizer and method for its production. Patent RU 2541405, published 02/10/2015].

The use of salt formulations (salt solutions or in dry form) to combat glaciation is associated with the existence of a cryoscopic effect. The cryoscopic effect is a decrease in the freezing point of the solvent (in our case, water) compared with a pure solvent when a non-volatile substance (or non-volatile substances) is introduced into a liquid solution. If the freezing point of an aqueous solution is lower than the ambient temperature (air), then such a solution will begin to dissolve ice, gradually diluting during dissolution until its freezing temperature equals the temperature of the medium. For example, a saturated solution of sodium chloride (26.4 wt.% NaCl) will dissolve ice up to a temperature of T = -21.2 ° C.

It should be noted that carbon nanoclusters have an additional and incredibly strong cryoscopic effect [M.Yu. Matuzenko, DP Tyurin, OS Manyakina, KN Semenov, NA Charykov, KV Ivanova, VA Keskinov. Cryometry and excess functions of fullerenols and trismalonates of light fullerenes - C ₆₀ (OH) _{24 ± 2} and C ₇₀ [= C (COOH) ₂ ] ₃ , aqueous solutions. NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2015, V.6. No. 5. P. 704-714; M.Yu. Matuzenko, AA Shestopalova, KN Semenov, NA Charykov, VA Keskinov. Cryometry and excess functions of the adduct of light fullerene C ₆₀ and arginine-C ₆₀ (C ₆ H ₁₂ NAN ₄ O ₂ ) ₈ H ₈ aqueous solutions. NANOSYSTEMS: PHYSICS, CHEMISTRY, MATHEMATICS, 2015, V. 6. No. 5. P. 715-725].

Table 1 shows the dependence of the crystallization temperature of ice and the concentration of saturated solutions at the points of invariant equilibrium (eutonics) for some binary water-salt systems. The temperature of the invariant point (T-nonv., C) is the minimum during joint crystallization with ice, in other words, the minimum melting temperature of ice in this binary system. The singular points (eutonic, peritonic, checkpoints, with the participation of wedge compounds) and their properties in water-salt systems are described in [N.A. Charykov, A.V. Rumyantsev, M.V. Charykova, B.A. Shakhmatkin, S.V. Ruzaev. Invariant points and monovariant lines on the phase diagrams of binary, triple and quadruple systems // Zh. physical Chem. 2000.V. 74. No. 5. S. 793-800; ON. Charykov, B.A. Shakhmatkin, M.V. Charykova, S.V. Ruzayev. Triangular and pyramidal regions in the diagrams of fusibility and solubility of multicomponent systems // Zh. physical Chem. 2000.V. 74. No. 9. S. 1562-1569].

As can be clearly seen from table 1, potassium acetate shows the best results in lowering the freezing temperature of water or melting ice.

It is noticeably more beneficial to use triple systems: two salts and water [N.A. Charykov, A.V. Rumyantsev, M.V. Charykova. Extremes of solvent activity in multicomponent systems // Zh. physical Chem. 1998.V. 72. No. 1. S. 39-44; ON. Charykov, A.V. Rumyantsev, M.V. Charykova. Topological isomorphism of solubility and fusibility diagrams. The course of biphasic equilibrium curves // Zh. physical Chem. 1998.V. 72. No. 2. S. 277-280].

Table 2 shows the physicochemical characteristics of some of the most promising for cryometric applications of water-salt systems containing two salts with a common ion. Type of crystallization: eutonic - separate crystallization of salts and ice (with an invariant point of the eutonic type without the formation of compounds); compound - a ternary compound crystallizes in the system; solid solution - salts or their crystalline hydrates form a solid solution. The expected cryometric effect at special points is the minimum melting temperature of ice in this binary system. Technological prospects: “possible” - the system is possibly promising; "high" - the system is promising with a fairly high degree of probability, "maximum" - the system is the most promising.

As can be clearly seen from table 2, the eutonic mixture of potassium and sodium acetates shows the best results in lowering the freezing point of water or ice melting and even surpasses individual acetates.

As you know, the melting ability (kg of ice / kg of dry reagent) is very strong and non-linear, almost exponentially dependent on temperature. The melting ability decreases sharply with decreasing temperature and for the vast majority of compositions it drops to almost zero at temperatures ≤ -20 ° C.

Table 3 shows the melting ability (kg of ice / kg of dry reagent) of various compounds at temperatures from -5 to -25 ÷ -35 ° C.

From table 3 it is clearly seen that potassium acetate and a eutonic mixture of sodium and potassium acetates undoubtedly have a maximum melting ability compared to other salt formulations.

De-icing Test Examples

To obtain an anti-icing composition, the calculated amounts of potassium acetate or a eutonic mixture of potassium acetate and sodium acetate in a mass ratio of 3.1 / 1.0, individual fullerenol C ₆₀ (OH) ₂₄ or a mixture of fullerenols (C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 ) with a mass ratio of 3/1 was dissolved in distilled water with mechanical stirring and room temperature. Then, a polyhydric alcohol, which was also dissolved in it, was added to the formed aqueous solution with mechanical stirring and at room temperature.

A method for determining liquidus temperatures — the onset of crystallization of ice from a solution upon cooling — a complex thermal analysis — DTA and TA curves. Device: Calve Cooling Scanning Calorimeter (designed by KEP Technologies). From the liquidus temperatures, the melting ability is uniquely determined.

Example 1

Composition: CH ₃ COOK - 20 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, N ₂ About - addition to 100 mass. % (here and everywhere further).

Freezing point (liquidus) - T _c = -18 ± 0.5 ° C.

Example 2

Composition: CH ₃ COOK - 40 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _s = -48 ± 1 ° C.

Example 3

Composition: CH ₃ COOK - 50 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, N ₂ About - addition to 100 mass. %

Freezing point (liquidus) - T _c = -64 ± 1 ° C.

Example 4

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 20 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -22 ± 1 ° C.

Example 5

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 40 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, N ₂ About - addition to 100 mass. %

Freezing point (liquidus) - T _c = -54 ± 1 ° C.

Example 6

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 60 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, N ₂ About - addition to 100 mass. %

Freezing point (liquidus) - T _c = -77 ± 1 ° C.

Example 7

Composition: CH ₃ COOK - 20 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -24 ± 0.5 ° C.

Example 8

Composition: CH ₃ COOK - 40 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, N ₂ About - addition to 100 mass. %

Freezing point (liquidus) - T _c = -53 ± 1 ° C.

Example 9

Composition: CH ₃ COOK - 50 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -67 ± 1 ° C.

Example 10

Composition: CH ₃ COOK - 20 mass. %, CH ₂ OH — CH ₂ —CH ₂ OH — 10 wt. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -22 ± 0.5 ° C.

Example 11

Composition: CH ₃ COOK - 40 mass. %, CH ₂ OH-CHOH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.01 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -51 ± 1 ° C.

Example 12

Composition: CH ₃ COOK - 50 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) ₂₄ - 0.1 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -65 ± 1 ° C.

Example 13

Composition: CH ₃ COOK - 50 mass. %, CH ₂ OH-CH ₂ OH - 3 mass. %, C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 - 0.1 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -66 ± 1 ° C.

Example 14

Optimum extremely low-temperature anti-icing composition:

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 60 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 - 0.1 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -87 ± 1 ° C.

Melting capacity (kg of ice / kg of dry reagent) at temperatures, ° C: -10 (12); -20 (6.3); -30 (4.0); -40 (2.1); -50 (1.1); -60 (0.27).

Example 15

Optimum medium temperature anti-icing composition:

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 40 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 - 0.1 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _c = -53 ± 1 ° C.

Melting capacity (kg of ice / kg of dry reagent) at temperatures, ° C: -10 (7.1); -20 (3.3); -30 (1.9); -40 (0.47).

Example 16

Optimum anti-icing composition:

Composition: CH ₃ COOK + CH ₃ COONa (eutonic mixture with a mass ratio of salts of 3.1 / 1.0) - 20 mass. %, CH ₂ OH-CH ₂ OH - 10 mass. %, C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 - 0.1 mass. %, H ₂ O - addition to 100 mass. %

Freezing point (liquidus) - T _s = -25 ± 1 ° С.

Melting capacity (kg of ice / kg of dry reagent) at temperatures, ° C: -10 (2.8); -20 (0.91).

Claims (2)

Anti-icing composition, including, by weight. %: potassium acetate or a eutonic mixture of potassium acetate and acetate sodium in a mass ratio of 3.1 / 1.0 20-60 di- or trihydric alcohols selected from ethylene glycol, propylene glycol glycerin 3-10 individual fullerenol C ₆₀ (OH) ₂₄ or a mixture of fullerenols (C ₆₀ (OH) _14-28 + C ₇₀ (OH) _10-22 ) 0.01-0.1 water the rest is up to 100