RU2550186C1 - Oil anti-freeze and anti-sticking and granular material anti-dust agent (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: agent against freezing and sticking in oil and dust-formation of moist granular materials, containing an alkaline runoff from caprolactam production and an additive in the form of glycerine. Also disclosed are versions of said agent, where the additives used are acetic acid and/or low-molecular weight acids from the wood chemical industry or glycerine and acetic acid and/or low-molecular weight acids from the wood chemical industry.

EFFECT: high effectiveness of the antifreeze agent owing to higher strength, flexibility and service life of films formed on metal surfaces, faster and higher degree of wetting carbon and high-strength hydrophobic materials while preserving quality factors of the antifreeze agent, such as low chilling point and homogeneity of the composition.

6 cl, 3 tbl, 12 ex

Description

The invention relates to antifreeze reagents for coating metal surfaces of dump cars, open wagons and other mining and transport equipment against freezing and sticking of overburden, coal, iron ore, non-ferrous metal ores, limestone, clay, chalk, marl and other wet bulk materials, as well as to prevent dust formation on quarry technological roads during opencast mining of suitable rocks, as well as blowing, dusting, freezing and freezing in bulk transported about cargo at ambient temperature up to minus 50 ° C.

Antifreeze reagents for these purposes are widely known in the art.

For example, the antifreeze reagent is known, described in USSR author's certificate No. 1113568, which includes an aqueous solution of sodium salts of adipic acid - a waste in the process of producing cyclohexanone by oxidation of cyclohexane (alkaline runoff of caprolactam production). Also known is the composition (USSR author's certificate No. 1373713), which includes an aqueous solution of sodium salts of adipic acid — waste in the process of producing cyclohexanone by oxidation of cyclohexane (alkaline stock of caprolactam production) and an aqueous solution of sodium salts of hydrochloric, sulfuric, thiosulfuric acids - a by-product of the synthesis of isopropylphenylpaphenylenediamine - diaphragm "FP". The composition described in USSR author's certificate No. 1680750 is obtained by mixing an aqueous solution of sodium salts of adipic acid — waste in the process of producing cyclohexanone by oxidation of cyclohexane (alkaline effluent from caprolactam production) and an aqueous-acidic effluent from cyclohexanone based on mono- and dicarboxylic acids. However, the described compositions are not resistant to delamination - at an ambient temperature below minus 10-15 ° C, sedimentation begins, in addition, the pour point is not lower than minus 30 ° C, which is not enough to process wet bulk materials in the winter.

Closest to the claimed solution is the antifreeze reagent described in RF patent No. 2486223, which includes an aqueous solution of sodium salts of carboxylic acids - an alkaline stock of caprolactam production and an additive that lowers the pour point and prevents delamination, which can be used as ethyl alcohol, isopropyl alcohol, head fraction of ethyl alcohol, methanol-ether-aldehyde fraction (MAEF), methyl alcohol, 2-methyl-propanol, iso-amyl alcohol, ethylene glycol, diethylene glycol, triethyl anglycol, propylene glycol, diethylene glycol monoethyl ether, potassium acetate, sodium acetate, potassium formate, sodium formate, calcium chloride, magnesium chloride, sodium chloride. This invention solves the problem of separation of the composition at low temperatures and allows to obtain an antifreeze reagent with a pour point below minus 50 ° C.

However, the described composition does not allow to create a uniform and flexible film on the metal surfaces of cars that prevents freezing of the transported cargo, capable of maintaining the integrity of the structure when exposed to bulk cargo weighing up to 60-66 tons. Also, the described composition is not characterized by a high degree of wetting of coal and other hydrophobic materials, which leads to a low uniformity of the created film and an increase in the consumption of antifreeze reagent.

In addition, to obtain a non-delaminating composition with a pour point below minus 50 ° C, it is necessary to introduce an additive that reduces the pour point and prevents delamination, in an amount up to 50%, which leads to a significant increase in the price of the finished antifreeze reagent.

Accordingly, the problem and the technical result of this invention is to increase the efficiency of the antifreeze reagent by increasing the strength, flexibility and service life of the film formed on the metal surfaces, increasing the speed and degree of wetting of coal and other hydrophobic materials while maintaining the quality of the antifreeze reagent, such as low pour point and uniformity of composition. The concentration of the additive is also reduced, the raw material base is expanding. In the production of antifreeze reagent, large-tonnage production waste is used.

Three options for solving the problem are proposed.

This problem is solved in that the antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials, containing the alkaline runoff of caprolactam production (SHCHSPK) and the additive, differs in that it contains glycerin, wt.%:

ShchSPK 85-99 glycerol 1-15.

Preferably, the antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials is a mixture of SCHPK from 90 to 95 wt.% And glycerin from 5 to 10 wt.%, Since the combination of qualitative characteristics provides the best technical result of the product obtained by this formula.

This problem is also solved by the fact that the antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials, containing alkaline stock of caprolactam production and an additive, is characterized in that as an additive it contains acetic acid and / or low molecular weight forest chemical acids in the following ratio components, wt.%:

ShchSPK 95-99 acetic acid and / or low molecular weight acids 1-5.

Preferably, the antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials is a mixture of alkali-alkali polycarbonate from 97 to 99 wt.% And acetic acid and / or low molecular weight forest chemical acids from 1 to 3 wt.%, Since the combination of qualitative characteristics provides the best technical result of the product obtained by this formula.

This problem is also solved by the fact that the antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials, containing alkaline stock of caprolactam production and an additive, is characterized in that as an additive it contains glycerin and acetic acid and / or low molecular weight forest chemical when the following ratio of components, wt.%:

ShchSPK 80-98 glycerol 1-15 acetic acid and / or low molecular weight acids 1-5.

Preferably, the antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials is a mixture of alkali polypropylene powder from 87 to 94 wt.%, Glycerol from 5 to 10 wt.% And acetic acid and / or low molecular weight forest chemical acids from 1 to 3 wt. .%, since the combination of qualitative characteristics provides the best technical result of the product obtained by this formula.

Alkaline runoff of caprolactam production (ShchSPK) is a by-product of caprolactam production obtained in the process of cyclohexane oxidation formed at the following enterprises: KuibyshevAzot OJSC, Kemerovo Azot OJSC, Shchekinoazot OKHK, GrodnoAzot OJSC and others, including located outside of Russia and the Republic of Belarus. ShchSPK is an aqueous solution of sodium salts of acidic by-products of air oxidation of cyclohexane, including wt.%:

Dry matter 25-65 Sodium salts of organic acids (in terms of sodium adipate) 18-30 Cyclohexanol 0.7-0.8 Cyclohexanone 0.1-0.2 Resin 8-10 Water rest solution pH 10-13.

Any glycerin from the range can be used as glycerin: distilled glycerin, crude glycerin obtained from fats and oils by hydrolysis, or transesterification, or synthetically from propylene and by other methods known to specialists (GOST 6259-75, GOST 6823-2000, GOST 6824 -96, GOST 7482-96 and others).

As the glycerin-containing product, for example, the glycerol phase (a by-product of the production of fatty acid esters from vegetable oils) and glyceric water, which is a by-product of the production of fatty acids, can be used.

The glycerin phase is a by-product of the production of fatty acid esters (biodiesel) from vegetable oils such as rapeseed, soybean and others. The composition of the glycerol phase, wt.%:

Glycerol 60-70 Soaps 15-20 Methanol 10-15 Potassium hydroxide 2-5 Water 1-2

Glycerin water is a large-tonnage waste product for the production of fatty acids and glycerin from natural vegetable and animal fats. Glycerin water contains glycerin 15-20 wt.%.

Any acetic acid (technical, food, forest chemical, synthetic or regenerated) can be used. Under the products containing acetic acid, understand the large-tonnage production waste, in which the content of acetic acid is not less than 50 wt.%, For example, low molecular weight acids, forest chemical. Also, the acid can be arbitrarily selected from a number of organic and inorganic acids that are readily soluble in water, the sodium salts of which are also readily soluble in water.

Low molecular weight wood-chemical acids are obtained in the process of processing black acid into technical acetic acid and rectification of technical acetic acid in the production of edible acetic acid. Low molecular weight forest chemical acids consist of acetic, formic, propionic and other low molecular weight acids, the mass fraction of acids in terms of acetic acid is not less than 80 wt.%.

Laboratory and pilot studies have shown that the introduction of 1 wt.% Glycerol and / or glycerin-containing product into the antifreeze reagent allows you to create a strong and flexible film on the metal surface, which does not deteriorate when exposed to bulk cargo, and leads to an increase in the degree of wetting of coal and other hydrophobic materials to a satisfactory level. Increasing the concentration of glycerol and / or glycerol-containing product leads to an increase in coating strength, degree of wetting and lowering pour point, however, exceeding the concentration of more than 30 wt.% Does not lead to changes in the quality indicators of the finished antifreeze reagent.

The introduction of 1 wt.% Acetic acid and / or a product containing acetic acid and / or acid from a number of organic and inorganic acids, readily soluble in water, the sodium salts of which are also readily soluble in water, into the antifreeze reagent allows you to create a durable and flexible film on the metal surface, which does not deteriorate when exposed to bulk cargo, and leads to an increase in the degree of wetting of coal and other hydrophobic materials to a satisfactory level. An increase in the concentration of acetic acid and / or product containing acetic acid leads to an increase in coating strength, degree of wetting and lowering pour point, however, exceeding the concentration of more than 20 wt.% Does not lead to changes in the quality indicators of the finished antifreeze reagent, in addition, the pH value decreases below 8, which negatively affects the corrosion activity of the antifreeze reagent.

The alkaline runoff of caprolactam production is a by-product of a complex and variable composition, the dry matter content varies from 25 to 65 wt.%, The content of sodium salts of organic acids from 18 to 30 wt.%, And therefore the pour point of this product is not constant. The pour point of SCHSPK depending on the composition varies from minus 25 ° C to minus 37 ° C, which is not enough for work in the winter.

The research results showed that the introduction to the described composition of glycerol and / or glycerin-containing product from 1 to 30 wt.% (According to the first embodiment), acetic acid and / or products containing, for example, acetic acid from 1 to 20 wt.% (By the second option), or a mixture of glycerol and / or glycerin-containing product from 1 to 20 wt.% and acetic acid and / or products containing acetic acid and / or acid from a number of organic and inorganic acids, readily soluble in water, the sodium salts of which also highly soluble in water, from 1 to 20 m wt.% (according to the third option) leads to a decrease in the pour point of the finished product to minus 65 ° C.

The pour points of aqueous solutions of glycerol and acetic acid are shown in tables 1 and 2, respectively. A 10 wt.% Aqueous solution of glycerol solidifies at a temperature of minus 1.6 ° C, while the addition of 10% glycerol to alkaline superconcentrated alloys leads to a sharp unpredictable decrease in pour point to minus 50-56 ° C depending on the composition of alkaline runoff.

An aqueous solution of acetic acid with a concentration of 11.85 wt.% Freezes at a temperature of minus 3.91, while the addition of 5% acetic acid to alkali-carbon dioxide leads to a decrease in the pour point to minus 51-56 ° C, depending on the composition of the alkaline runoff.

Thus, a mixture of alkali polystyrene and glycerol, alkali polystyrene and acid or alkali polystyrene, glycerol and acid is characterized by a pour point much lower than the pour point of alkaline runoff, aqueous solutions of glycerol or acetic acid separately, i.e. there is a temperature depression not described for the products used in the mixture. EFFECT: invention makes it possible to obtain an antifreeze reagent with a low freezing temperature up to minus 65 ° C at a low mass content of glycerin and / or acetic acid, due to which an economic effect is achieved.

To assess the strength of the film formed on the metal surface, studies were conducted on a four-ball friction machine CMT-1 GOST 9490-75 with measurement of the values of the welding load and the diameter of the wear spot. Studies of antifreeze reagents obtained according to the recipe described in examples No. 1-12 were carried out according to GOST 6953 in comparison with the prototype and are shown in table 3.

To assess the speed and degree of wetting of coal, the contact angle was determined from the profile of a drop of antifreeze reagent located on the flat surface of a solid body - coal, by tangent to the point of three-phase contact. Studies of antifreeze obtained according to the recipe described in examples No. 1-12, in comparison with the prototype, alkali alcohol complex, aqueous solutions of glycerol and acetic acid, are shown in table 3.

As the obtained experimental data (pour point, wear spot diameter, welding load and contact angle of contact) show, any mixture of these components gives positive results.

Examples of the production of antifreeze reagent.

Example No. 1

Antifreeze reagent is obtained by mixing 85 wt.% Alkaline runoff of caprolactam production and 15 wt.% Distilled technical glycerin.

Example No. 2

Antifreeze reagent is obtained by mixing 90 wt.% Alkaline runoff of caprolactam production and 10 wt.% Glycerin.

Example No. 3

Antifreeze reagent is obtained by mixing 99 wt.% Alkaline runoff of caprolactam production and 1 wt.% Glycerol.

Example No. 4

Antifreeze reagent is obtained by mixing 84 wt.% Alkaline runoff of caprolactam production, 8 wt.% Distilled industrial glycerin and 8 wt.% Glycerin water, which is a by-product of the production of fatty acids.

Example No. 5

Antifreeze reagent is obtained by mixing 95 wt.% Alkaline runoff of caprolactam production and 5 wt.% Acetic acid.

Example No. 6

Antifreeze reagent is obtained by mixing 99 wt.% Alkaline runoff of caprolactam production and 1 wt.% Low molecular weight forest chemical acids.

Example No. 7

Antifreeze reagent is obtained by mixing 96 wt.% Alkaline runoff of caprolactam production, 2 wt.% Acetic acid and 2 wt.% Low molecular weight forest chemical acids.

Example No. 8

Antifreeze reagent is obtained by mixing 95 wt.% Alkaline runoff of caprolactam production and 5 wt.% Formic acid.

Example No. 9

Antifreeze reagent is obtained by mixing 93 wt.% Alkaline runoff of caprolactam production and 7 wt.% Nitric acid.

Example No. 10

Antifreeze reagent is obtained by mixing 90.5 wt.% Alkaline runoff of caprolactam production, 8 wt.% Glycerol and 1.5 wt.% Acetic acid.

Example No. 11

Antifreeze reagent is obtained by mixing 88 wt.% Alkaline runoff of caprolactam production, 10 wt.% Industrial distilled glycerin and 2 wt.% Low molecular weight wood chemical acids.

Example No. 12

Antifreeze reagent is obtained by mixing 80 wt.% Alkaline runoff of caprolactam production, 15 wt.% Glycerol and 5 wt.% Acetic acid.

Comparison of the quality of the product obtained in the above examples with the antifreeze reagent prepared according to the prototype (RF patent for the invention 2486223), SchSPK, aqueous solutions of glycerol and acetic acid is presented in table 3. As a prototype, a composition with obviously better quality characteristics was chosen, representing 85 wt.% a mixture of alkaline runoff production of caprolactam and 15 wt.% ethylene glycol.

The resulting antifreeze reagent is an easily moving dark brown liquid without mechanical impurities, having a pour point from minus 50 ° C to minus 65 ° C, stability and uniformity of composition, low viscosity at low temperatures. The described composition allows to obtain a durable flexible film on the metal surface, not prone to destruction and tearing during transportation of bulk cargo weighing up to 60-66 tons, which significantly increases the service life of the antifreeze reagent. Also, the antifreeze reagent is characterized by a high speed and degree of wetting of coal and other hydrophobic materials, which leads to a decrease in consumption and expansion of the scope.

Claims (6)

1. The antifreeze reagent against freezing, sticking, freezing in mass and dust formation of moist granular materials, containing an alkaline stock of caprolactam production (SCSPK), which is a by-product of caprolactam production and is an aqueous solution of sodium salts of acidic by-products of cyclohexane air oxidation, and an additive that differs the fact that as an additive contains glycerin in the following ratio of components, wt.%:
ShchSPK 85-99 glycerol 1-15 2. The antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials according to claim 1, characterized in that it is a mixture of SCHPK from 90 to 95 wt.% And glycerin from 5 to 10 wt.%. 3. The antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials, containing the alkaline stock of caprolactam production (SHPSPK), which is a by-product of caprolactam production and is an aqueous solution of sodium salts of acidic by-products of cyclohexane air oxidation, and an additive that differs the fact that as an additive contains acetic acid and / or low molecular weight acids, chemical in the following ratio of components, wt.%:
ShchSPK 95-99 acetic acid and / or low molecular weight acids, forest chemical 1-5 4. The antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials according to claim 3, characterized in that it is a mixture of alkali-polypropylene oxide from 97 to 99 wt.% And acetic acid and / or low molecular weight forest chemical acids from 1 to 3 wt.%. 5. The antifreeze reagent against freezing, sticking, freezing in mass and dust formation of moist granular materials, containing alkaline stock of caprolactam production (SCSPK), which is a by-product of caprolactam production and is an aqueous solution of sodium salts of acidic by-products of air oxidation of cyclohexane, and an additive that differs the fact that as an additive it contains glycerin and acetic acid and / or low molecular weight forest chemical acids in the following ratio of components, wt.%:
ShchSPK 80-98 glycerol 1-15 acetic acid and / or low molecular weight acids, forest chemical 1-5 6. The antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials according to claim 5, characterized in that it is a mixture of alkali-polypropylene oxide from 87 to 94 wt.%, Glycerol from 5 to 10 wt.% And acetic acid and / or low molecular weight forest chemical acids from 1 to 3 wt.%.