WO2015187055A1 - Réactif antigel contre le gel, l'agrégation, la congélation en masse et la formation de poussières de matériaux en vrac (variantes) - Google Patents

Réactif antigel contre le gel, l'agrégation, la congélation en masse et la formation de poussières de matériaux en vrac (variantes) Download PDF

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Publication number
WO2015187055A1
WO2015187055A1 PCT/RU2015/000261 RU2015000261W WO2015187055A1 WO 2015187055 A1 WO2015187055 A1 WO 2015187055A1 RU 2015000261 W RU2015000261 W RU 2015000261W WO 2015187055 A1 WO2015187055 A1 WO 2015187055A1
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WO
WIPO (PCT)
Prior art keywords
freezing
antifreeze
sticking
acetic acid
low molecular
Prior art date
Application number
PCT/RU2015/000261
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English (en)
Russian (ru)
Inventor
Дмитрий Георгиевич СЕМЕНОВ
Алексей Витальевич ТРУШКОВ
Лейла Рустамовна КУТУШЕВА
Original Assignee
Дмитрий Георгиевич СЕМЕНОВ
Алексей Витальевич ТРУШКОВ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Дмитрий Георгиевич СЕМЕНОВ, Алексей Витальевич ТРУШКОВ filed Critical Дмитрий Георгиевич СЕМЕНОВ
Publication of WO2015187055A1 publication Critical patent/WO2015187055A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

Definitions

  • the invention relates to antifreeze reagents for coating the metal surfaces of dump cars, open wagons and other mining 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, as well as blowing, dusting, freezing and freezing in bulk imogo cargo at the temperature ambient to minus 50 ° C.
  • Antifreeze reagents for these purposes are widely known in the art.
  • the antifreeze reagent is known (USSR author's certificate l 1 13568, IPC E21 F5 / 20, published September 15, 1984), which includes an aqueous solution of sodium salts of adipic acid - a waste in the process of obtaining cyclohexanone by oxidation of cyclohexane (alkaline runoff - of caprolactam).
  • composition of the antifreeze reagent (USSR author's certificate JY21373713, IPC ⁇ 09 ⁇ / 22, E21F5 / 20, published February 16, 1988), which includes an aqueous solution of sodium salts of adipic acid - a waste in the process of producing cyclohexanone by oxidation of cyclohexane (alkaline caprolactam production effluent) and an aqueous solution of sodium salts of hydrochloric, sulfuric, and thiosulfuric acids are a by-product of the synthesis of isopropylphenylpaphenylenediamine - FP diafen.
  • composition is known (USSR copyright certificate 680750, IPC S09KZ / 22, published September 30, 1991), which is obtained by mixing an aqueous solution of sodium salts of carboxylic acids - waste in the process of obtaining cyclohexanone by oxidation of cyclohexane (alkaline stock production of caprolactam ) and aqueous acidic effluent from the production of cyclohexanone based on mono- and dicarboxylic acids.
  • the described compositions are not resistant to delamination - at an ambient temperature below minus 10-15 ° C, sedimentation begins, in addition, their pour point is not lower than minus 30 ° C, which is not enough for processing wet bulk materials in the winter.
  • the antifreeze reagent (RF patent JY "2486223, IPC ⁇ 09 ⁇ / 18, publ. 06/27/2013), which includes an aqueous solution of sodium salts of carboxylic acids - alkaline stock production of caprolactam, and an additive that reduces freezing point and preventing delamination, which can be used as ethanol, isopropyl alcohol, head fraction of ethyl alcohol, methanol-ether-aldehyde fraction (MAEF), methyl alcohol, 2-methyl-propanol, iso-amyl alcohol ethylene glycol, diethyl nglycol, triethylene glycol, 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.
  • the known tool does not allow creating 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.
  • it does not provide the required 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.
  • the disadvantage of this tool is the need to introduce additives that lower the pour point below minus 50 ° C and prevent delamination, in an amount up to 50%, which leads to a significant increase in the cost of antifreeze reagent.
  • the objective of the proposed invention is to increase the effectiveness of the antifreeze reagent while reducing operating costs.
  • the technical result of the invention is to improve the performance of antifreeze reagent, such as low pour point and uniformity of composition, as well as to reduce the concentration of the additive and expand the raw material base in connection with the use of large-tonnage production wastes.
  • the antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials, containing the alkaline runoff of caprolactam production (ALB) and an additive is characterized in that it contains glycerin as an additive in the following ratio of components , wt.%:
  • the antifreeze reagent against freezing, adhering, freezing in mass and dusting of wet bulk materials is a mixture of alkali polystyrene alcohol from 90 to 95 wt.% And glycerol from 5 to 10 wt.%.
  • the antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials containing the alkaline stock of caprolactam production (ALB) and the additive, is characterized in that it contains acetic acid and / or low molecular weight wood-chemical acids in the following ratio of components, wt.%:
  • the antifreeze reagent against freezing, sticking, freezing in mass and dusting of wet bulk materials is preferable. 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.%.
  • the antifreeze reagent against freezing, sticking, freezing in the mass and dust formation of wet bulk materials, containing the alkaline runoff of caprolactam production (SCHSPK) and the additive is characterized in that it contains a mixture of two components as an additive, one of which glycerol is, and the other is acetic acid and / or low molecular weight forest chemical acids in the following ratio of components, wt.%:
  • the antifreeze reagent against freezing, sticking, freezing in mass and dust formation of wet bulk materials is a mixture of alkali-polypropylene oxide from 87 to 94 wt.% And glycerol from 5 to 10 wt.%, And acetic acid and / or low molecular weight forest chemical acids from 1 up to 3 wt.%.
  • the alkaline effluent of caprolactam production is a by-product of caprolactam production, which is formed during the neutralization of acidic products of the process of liquid-phase oxidation of cyclohexane.
  • ShchSPK is formed at the following enterprises: Kuibyshev Azot OJSC, Kemerovo Azot OJSC, Shchekinoazot OHK, GrodnoAzot OJSC and others, including those located outside Russia and the Republic of Belarus.
  • ALB is a water solution of mono- and dibasic carboxylic sodium salts, which also contains sodium carbonate, cyclohexanone, cyclohexanol and other impurities.
  • glycerin from the series can be used as glycerin: distilled glycerin, crude glycerin - glycerol, glycerol content of at least 60 wt.%, Obtained from fats and vegetable oils hydrolysis, transesterification or saponification during the production of fatty acids, their sodium and potassium salts, fatty alcohols or fatty acid esters (biodiesel) or synthetically from propylene and other methods known to specialists, or a mixture of them in any combination with each other .
  • any acetic acid technical, food, forest chemical, synthetic or regenerated
  • a product known as low molecular weight wood chemical can also be used.
  • Low molecular weight forest 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 food acetic acid.
  • Low molecular weight forest chemical acids consist of acetic, formic, propionic and other low molecular acids; the mass fraction of acids in terms of acetic acid is not less than 80 wt.%.
  • Acetic acid and / or low molecular weight wood chemical acids into the composition of 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 hydrophobic materials to a satisfactory level.
  • An increase in the concentration of acetic acid and / or low molecular weight forest chemical acids leads to an increase in coating strength, degree of wetting, and lowering of the pour point, however, exceeding a concentration of more than 5 wt.% Does not lead to changes in the quality parameters 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.%, In connection with which the pour point of this product is not is a constant value.
  • the pour point of SCHSPK depending on the composition varies from minus 25 ° ⁇ to minus 37 ° ⁇ , which is not enough for work in the winter period.
  • glycerol into the described composition is from May 1 to May 15. % (according to the first embodiment), acetic acid and / or low molecular weight forest chemical acids from 1 to 5 wt.% (second option) or a mixture of glycerol from 1 to 15 wt.% and acetic acid and / or low molecular weight wood chemical from 1 to 5 wt.% (according to the third embodiment) - leads to a decrease in the pour point of the finished product to minus 65 ° C.
  • 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 previously described for used in the mixture of products.
  • the invention allows to obtain an antifreeze reagent with a low freezing point up to minus 65 ° C at a low mass content of the additive in the form of glycerol and / or acetic acid, thereby achieving the technical result indicated in the invention.
  • Antifreeze reagent is obtained by mixing 85 wt.% Alkaline runoff of caprolactam production and 15 wt.% Distilled technical glycerin.
  • Antifreeze reagent is obtained by mixing on May 90. % alkaline runoff of caprolactam production and 10% by weight of glycerol formed during the preparation of fatty acid methyl esters from rapeseed oil.
  • Antifreeze reagent is obtained by mixing 86 wt.% Alkaline runoff of caprolactam production and 14 wt.% Glycerol obtained in the production of fatty acids from vegetable oil.
  • Antifreeze reagent is obtained by mixing 92 wt.% Alkaline runoff of caprolactam production, 4 wt.% Of distilled industrial glycerin and 4 wt.% Glycerol, which is formed during the preparation of fatty acid methyl esters from rapeseed oil.
  • Example 5
  • Antifreeze reagent is obtained by mixing 96 wt.% Alkaline runoff production of caprolactam and 4 wt.% About acetic acid.
  • Antifreeze reagent is obtained by mixing 97 wt.% Alkaline runoff of caprolactam production and 3 wt.% Low molecular weight forest chemical acids.
  • Antifreeze reagent is obtained by mixing 96 wt.%> Alkaline runoff production of caprolactam, May 2. % acetic acid and 2 wt.% low molecular weight wood-chemical acids.
  • Antifreeze reagent is obtained by mixing 90.5% by weight of alkaline runoff of caprolactam production, 8% by weight of glycerin, which is formed upon receipt of methyl esters of fatty acids from rapeseed oil and on May 1.5. % acetic acid.
  • Antifreeze reagent is obtained by mixing 88 wt.% Alkaline runoff of caprolactam production, 10 wt.% Industrial distilled glycerin and 2 wt.% Low molecular weight forest chemical acids.
  • Antifreeze reagent is obtained by mixing 92.5 wt.% Alkaline waste of caprolactam production, 5 wt.% Glycerol, formed during the production of fatty acid methyl esters from rapeseed oil and 2.5 wt.% Low molecular weight forest chemical acids.
  • 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.
  • the antifreeze reagent obtained according to the invention is a dark brown mobile 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 proposed 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.
  • 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.
  • the invention allows to increase the efficiency of the antifreeze reagent and reduce operating costs.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des réactifs antigel pour le revêtement de surfaces métalliques de wagons et de wagons basculants, de wagons gondoles et autres équipements de transport minier et de transport contre le gel et l'agrégation sur ces derniers de mort-terrain, de charbon, de minerai de fer, de minerais non ferreux, de calcaire, d'argile, de craie, de marne et autres matériaux en vrac humides. Le but et le résultat technique de la présente invention consistent en une augmentation de l'efficacité du réactif antigel grâce une augmentation de la résistance, de la flexibilité et de la durée de vie du film formé sur les surfaces métalliques, en une augmentation de la vitesse et du niveau de mouillage du charbon et autres matériaux hydrophobes tout en conservant les indices de qualité du réactif antigel comme une faible température de solidification et l'uniformité de la composition. Le réactif antigel contre le gel, l'agrégation, la congélation en masse et la formation de poussières de matériaux en vrac humides comprend un flux alcalin issu de la production de caprolactame et consistant en un produit secondaire de la production de caprolactame, lequel se présente sous forme d'une solution aqueuse de sels de sodium de produits secondaires acides résultant de l'oxydation dans l'air de cyclohexane, ainsi qu'un additif en qualité duquel on utilise de la glycérine ou de l'acide acétique et/ou des acides de faible poids moléculaire issus de l'industrie chimique du bois.
PCT/RU2015/000261 2014-06-05 2015-04-23 Réactif antigel contre le gel, l'agrégation, la congélation en masse et la formation de poussières de matériaux en vrac (variantes) WO2015187055A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2014123011 2014-06-05
RU2014123011/05A RU2550186C1 (ru) 2014-06-05 2014-06-05 Реагент антифриз против примерзания, прилипания, смерзания в массе и пыления сыпучих материалов (варианты)

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Publication number Priority date Publication date Assignee Title
RU2618010C1 (ru) * 2016-07-12 2017-05-02 Валерий Викторович Жмаев Антиобледенительная жидкость для обработки стенок и днищ горно-транспортного оборудования от примерзания и смерзания угля в массе и при транспортировке сыпучего груза
RU2635266C1 (ru) * 2016-11-07 2017-11-09 Общество с ограниченной ответственностью "КемСнаб" (ООО "КемСнаб") Антигололедный реагент для транспортного оборудования

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002026910A1 (fr) * 2000-09-29 2002-04-04 Mli Associates, Llc Fluides antigivrage ou de degivrage sans danger pour l'environnement
RU2280666C1 (ru) * 2005-03-10 2006-07-27 Закрытое акционерное общество "НИИКерамзит" научно-исследовательский институт по керамзиту Средство для борьбы с гололедом на дорожном покрытии
RU2486223C1 (ru) * 2011-12-01 2013-06-27 Алексей Витальевич Трушков Профилактическое средство против примерзания, прилипания и пыления сыпучих материалов

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SU1680750A1 (ru) * 1989-06-23 1991-09-30 Украинский научно-исследовательский и проектно-конструкторский институт по обогащению и брикетированию углей Профилактическое средство от выдувани и смерзани твердых топлив при транспортировании

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002026910A1 (fr) * 2000-09-29 2002-04-04 Mli Associates, Llc Fluides antigivrage ou de degivrage sans danger pour l'environnement
RU2280666C1 (ru) * 2005-03-10 2006-07-27 Закрытое акционерное общество "НИИКерамзит" научно-исследовательский институт по керамзиту Средство для борьбы с гололедом на дорожном покрытии
RU2486223C1 (ru) * 2011-12-01 2013-06-27 Алексей Витальевич Трушков Профилактическое средство против примерзания, прилипания и пыления сыпучих материалов

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