FR2998300A1 - Salt comprising biphasic grains consisting of a core of first water-insoluble phase and a shell of a second water soluble phase, useful for snow clearance on roads, where dissolution of grains in water is lower than freezing point of water - Google Patents

Salt comprising biphasic grains consisting of a core of first water-insoluble phase and a shell of a second water soluble phase, useful for snow clearance on roads, where dissolution of grains in water is lower than freezing point of water Download PDF

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Publication number
FR2998300A1
FR2998300A1 FR1203067A FR1203067A FR2998300A1 FR 2998300 A1 FR2998300 A1 FR 2998300A1 FR 1203067 A FR1203067 A FR 1203067A FR 1203067 A FR1203067 A FR 1203067A FR 2998300 A1 FR2998300 A1 FR 2998300A1
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water
shell
grains
phase
grain
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French (fr)
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Guy Baret
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Individual
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/18Materials 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
    • C09K3/185Thawing materials

Abstract

Salt for snow clearance comprising biphasic grains consisting of a core of a first water-insoluble phase and a shell of a second water soluble phase, is claimed. The dissolution of grains in water is lower than a freezing point of water.

Description

SEL DE DENEIGEMENT Domaine technique de l'invention L'invention est relative à un sel de déneigement non polluant pour l'environnement, les sols et les nappes phréatiques. État de la technique Le sel de déneigement routier également appelé fondant routier est constitué essentiellement de chlorure de sodium NaCI d'origine marine ou en provenance de carrières. Il peut contenir différentes proportions de chlorure de calcium CaCl2. Il représente un tonnage annuel de l'ordre de un million de tonnes pour la France et de l'ordre de deux millions de tonnes pour l'Allemagne. Lorsqu'il est dissous dans l'eau, ce sel de déneigement routier possède le défaut de libérer des ions chlorures. Or les ions chlorures entraînent une corrosion rapide de l'ensemble des infrastructures et des objets métalliques. C'est par exemple le cas des ouvrages d'art métalliques des infrastructures routières qui seraient corrodés de manière inacceptable. Ces mêmes ions chlorures entraînent également une pollution des sols proches des axes routiers, des nappes phréatiques et des lacs.TECHNICAL FIELD OF THE INVENTION The invention relates to a non-polluting de-icing salt for the environment, soils and groundwater. STATE OF THE ART Road salt removal, also called road salt, consists mainly of sodium chloride NaCI of marine origin or coming from quarries. It can contain different proportions of CaCl2 calcium chloride. It represents an annual tonnage of about one million tonnes for France and about two million tonnes for Germany. When dissolved in water, this road-clearing salt has the defect of releasing chloride ions. But chloride ions cause rapid corrosion of all infrastructure and metal objects. This is for example the case of metal structures of road infrastructures that would be corroded in an unacceptable way. These same chloride ions also cause pollution of soils close to roads, groundwater and lakes.

Par ailleurs, l'ion sodium libéré lors de la dissolution du chlorure de sodium accroît de manière très importante la dégradation des bétons. D'autres sels de déneigement sont connus et exploités. Il s'agit des acétates ou des formiates de sodium ou de potassium qui sont utilisés en solution liquide partiellement alcoolique pour le déglaçage des pistes d'aéroports. 1 Il est également connu d'utiliser des mélanges de granules de chlorure de sodium et de graviers fins pour apporter à la fois un effet fondant dû au chlorure de sodium et une accroche mécanique grâce aux graviers. Un tel mélange présente cependant la difficulté de se séparer en raison de la différence de densité apparente des deux phases chlorure de sodium et gravier. Il doit donc être préparé juste avant utilisation ce qui n'est pas toujours possible. Résumé de l'invention L'invention vise un sel de déneigement n'ayant pas de caractère corrosif et n'étant pas polluant pour l'environnement, les nappes phréatiques et les lacs. Plus particulièrement, l'invention vise un sel de déneigement ne contenant ni ions sodium ni ions chlorure. Selon l'invention, on tend vers cet objectif à l'aide un sel de déneigement formé de grains bi-phasiques constitués d'un coeur en une première phase insoluble dans l'eau et d'une coque en une seconde phase soluble dans l'eau et dont la dissolution dans l'eau abaisse le point de congélation de l'eau. Selon un développement de l'invention, la première phase formant le coeur d'un grain du sel de déneigement est un carbonate d'au moins un élément alcalino-terreux choisi parmi le magnésium, le calcium et le strontium.Moreover, the sodium ion released during the dissolution of sodium chloride greatly increases the degradation of the concretes. Other de-icing salts are known and exploited. These are acetates or formates of sodium or potassium which are used in partially alcoholic liquid solution for the de-icing of airport runways. It is also known to use mixtures of granules of sodium chloride and fine gravel to provide both a melting effect due to sodium chloride and a mechanical grip thanks to the gravel. Such a mixture however has the difficulty of separating due to the apparent density difference of the two sodium chloride and gravel phases. It must be prepared just before use, which is not always possible. SUMMARY OF THE INVENTION The invention relates to a salt of snow removal having no corrosive nature and not being polluting for the environment, groundwater and lakes. More particularly, the invention relates to a snow removal salt containing neither sodium ions nor chloride ions. According to the invention, this objective is attained by means of a de-icing salt formed from bi-phasic grains consisting of a core in a first phase insoluble in water and a shell in a second phase soluble in water. water and whose dissolution in water lowers the freezing point of water. According to a development of the invention, the first phase forming the core of a grain of the de-icing salt is a carbonate of at least one alkaline earth element selected from magnesium, calcium and strontium.

Selon un autre développement de l'invention, la seconde phase soluble dans l'eau formant la coque d'un grain du sel de déneigement contient au moins un composé choisi parmi les formiates et les acétates des éléments alcalino-terreux.According to another development of the invention, the second water-soluble phase forming the shell of a grain of the de-icing salt contains at least one compound chosen from the formates and acetates of the alkaline-earth elements.

Description sommaire des dessins D'autres avantages et caractéristiques ressortiront plus clairement de la description qui va suivre de modes particuliers de réalisation donnés à titre 2 d'exemples non limitatifs et illustrés à l'aide des dessins annexés, dans lesquels : la figure 1 représente un grain de sel de déneigement selon l'invention dans lequel la phase soluble dans l'eau formant la coque du grain recouvre de manière continue le coeur du grain insoluble. la figure 2 représente un grain de sel de déneigement selon l'invention dans lequel la phase soluble dans l'eau formant la coque du grain recouvre partiellement la surface du coeur du grain insoluble.BRIEF DESCRIPTION OF THE DRAWINGS Other advantages and features will emerge more clearly from the following description of particular embodiments given by way of nonlimiting example and illustrated with the aid of the appended drawings, in which: FIG. a salt-de-icing salt according to the invention wherein the water-soluble phase forming the shell of the grain continuously covers the heart of the insoluble grain. FIG. 2 represents a snow removal salt grain according to the invention in which the water-soluble phase forming the shell of the grain partially covers the surface of the core of the insoluble grain.

Description de modes particuliers de réalisation de l'invention Selon un premier mode préférentiel de réalisation de l'invention selon la figure 1, un grain du sel de déneigement possède un coeur 1 dont la composition est formée à plus de 80% en masse de carbonate de calcium CaCO3. Ce coeur en carbonate de calcium est produit par extraction en carrière et broyage. La granulométrie moyenne de ces particules de CaCO3 est comprise entre 0,5 et 6 mm, plus typiquement entre 2 mm et 4 mm. Ce grain du sel de déneigement possède une coque 2 dont la composition est un acétate de calcium à plus de 80%. Cette coque recouvre de façon continue toute la surface de la particule du coeur en CaCO3. Cette coque est produite par action chimique d'acide acétique à 80% sur la couche de surface de la particule de carbonate de calcium dont la partie interne forme le coeur du grain de sel de déneigement. Après dissolution de la coque au contact de la neige ou de la glace à faire fondre, le coeur insoluble dans l'eau assure une accroche mécanique.DESCRIPTION OF PARTICULAR EMBODIMENTS OF THE INVENTION According to a first preferred embodiment of the invention according to FIG. 1, a grain of the de-icing salt has a core 1 whose composition is formed at more than 80% by mass of carbonate. Calcium CaCO3. This calcium carbonate core is produced by quarrying and grinding. The average particle size of these CaCO3 particles is between 0.5 and 6 mm, more typically between 2 mm and 4 mm. This grain of the de-icing salt has a shell 2 whose composition is more than 80% calcium acetate. This shell continuously covers the entire surface of the CaCO3 core particle. This shell is produced by the chemical action of 80% acetic acid on the surface layer of the calcium carbonate particle, the inner part of which forms the heart of the salt grain of snow removal. After dissolution of the shell in contact with the snow or ice to melt, the insoluble heart in the water ensures a mechanical grip.

Selon un deuxième mode préférentiel de réalisation de l'invention, un grain du sel de déneigement possède un coeur dont la composition est formée à plus de 80% en masse d'un mélange de carbonate mixte de calcium et de magnésium (Cal..x,Mgx)CO3. Ce coeur est produit par extraction en carrière et broyage. La granulométrie moyenne de ces particules de carbonate mixte de calcium et de 3 magnésium est comprise entre 0.5 et 5 mm, plus typiquement entre 2 mm et 3 mm. Ce grain du sel de déneigement possède une coque dont la composition est un acétate mixte de calcium et de magnésium (Ca1_x,Mgx)(CH3C00)2 à plus de 80%. Cette coque recouvre de façon continue toute la surface de la particule du coeur en (Cai_x,Mgx)CO3. Cette coque est produite par action chimique d'acide acétique concentré à 70% sur la couche de surface de la particule de carbonate mixte de calcium et de magnésium dont la partie interne forme le coeur du grain de sel de déneigement. Le ratio magnésium sur calcium dans le coeur est donc identique au ratio magnésium sur calcium dans la coque. Ce ratio est typiquement compris entre 0.05 et 0.30. Après dissolution de la coque au contact de la neige ou de la glace à faire fondre, le coeur insoluble dans l'eau assure une accroche mécanique. Selon un troisième mode préférentiel de réalisation de l'invention selon la figure 2, un grain du sel de déneigement possède un coeur 1 dont la composition est formée à plus de 80% en masse de carbonate de calcium CaCO3. Ce coeur en carbonate de calcium est produit par extraction en carrière et broyage. La granulométrie moyenne de ces particules de CaCO3 est comprise entre 0.5 et 5 mm, plus typiquement entre 2 mm et 3 mm. Ce grain du sel de déneigement possède une coque 3 dont la composition est un formiate de calcium à plus de 80%. Cette coque est produite par dispersion des particules formant le coeur du grain dans une solution aqueuse d'acétate de calcium, puis séchage de la solution. Cette coque recouvre par ilots la surface de la particule du coeur.According to a second preferred embodiment of the invention, a grain of the de-icing salt has a core whose composition is formed to more than 80% by weight of a mixture of mixed carbonate of calcium and magnesium (Cal..x , Mgx) CO3. This heart is produced by quarrying and grinding. The average particle size of these particles of mixed carbonate of calcium and magnesium is between 0.5 and 5 mm, more typically between 2 mm and 3 mm. This grain of the de-icing salt has a shell whose composition is a mixed acetate of calcium and magnesium (Ca1_x, Mgx) (CH3C00) 2 to more than 80%. This shell continuously covers the entire surface of the particle of the heart in (Cai_x, Mgx) CO3. This shell is produced by chemical action of acetic acid concentrated to 70% on the surface layer of the particle of mixed carbonate of calcium and magnesium whose inner part forms the heart of the grain of salt of clearing of snow. The ratio of magnesium to calcium in the heart is therefore identical to the ratio of magnesium to calcium in the shell. This ratio is typically between 0.05 and 0.30. After dissolution of the shell in contact with the snow or ice to melt, the insoluble heart in the water ensures a mechanical grip. According to a third preferred embodiment of the invention according to FIG. 2, a grain of the snow removal salt has a core 1 whose composition is formed at more than 80% by weight of calcium carbonate CaCO3. This calcium carbonate core is produced by quarrying and grinding. The average particle size of these CaCO3 particles is between 0.5 and 5 mm, more typically between 2 mm and 3 mm. This grain of the de-icing salt has a shell 3 whose composition is more than 80% calcium formate. This shell is produced by dispersing the particles forming the heart of the grain in an aqueous solution of calcium acetate, and then drying the solution. This shell covers by islets the surface of the particle of the heart.

L'invention n'est pas limitée aux modes particuliers de réalisation décrits ci- dessus. En particulier le sel de déneigement pourra être mélangé : à une phase inerte, notamment du gravier, pour augmenter l'accroche sur le sol traité à une phase fondante totalement soluble dans l'eau, notamment un acétate de calcium ou un acétate mixte de calcium et de magnésium. 4The invention is not limited to the particular embodiments described above. In particular, the de-icing salt may be mixed with: an inert phase, in particular gravel, to increase the adhesion on the treated soil to a totally water-soluble melting phase, in particular a calcium acetate or a mixed calcium acetate and magnesium. 4

Claims (6)

REVENDICATIONS1. Sel de déneigement formé de grains caractérisé en ce que les grains sont bi-phasiques et constitués d'un coeur en une première phase insoluble dans l'eau et d'une coque en une seconde phase soluble dans l'eau et dont la dissolution dans l'eau abaisse le point de congélation de l'eau.REVENDICATIONS1. De-icing salt formed from grains characterized in that the grains are bi-phasic and consist of a core in a first phase insoluble in water and a shell in a second phase soluble in water and whose dissolution in the water lowers the freezing point of the water. 2. Sel de déneigement selon la revendication 1 caractérisé en ce que la première phase formant le coeur d'un grain est un carbonate d'au moins un élément alcalino-terreux choisi parmi le magnésium, le calcium et le strontium.2. de-icing salt according to claim 1 characterized in that the first phase forming the core of a grain is a carbonate of at least one alkaline earth element selected from magnesium, calcium and strontium. 3. Sel de déneigement selon les revendications 1 ou 2 caractérisé en ce que la seconde phase soluble dans l'eau formant la coque d'un grain contient au moins un composé choisi parmi les formiates des éléments alcalino-terreux.3. de-icing salt according to claim 1 or 2 characterized in that the second water-soluble phase forming the shell of a grain contains at least one compound selected from the formates of the alkaline earth elements. 4. Sel de déneigement selon les revendications 1 ou 2 caractérisé en ce que la seconde phase soluble dans l'eau formant la coque d'un grain contient au moins un composé choisi parmi les acétates des éléments alcalino-terreux.4. de-icing salt according to claim 1 or 2 characterized in that the second water-soluble phase forming the shell of a grain contains at least one compound selected from acetates alkaline earth elements. 5. Sel de déneigement selon l'une quelconque des revendications 1 à 4 caractérisé en ce que la première phase formant le coeur d'un grain est formée à plus de 80% de carbonate de calcium et que la seconde phase soluble dans l'eau formant la coque d'un grain est formée à plus de 80% un acétate de calcium.5. snow removal salt according to any one of claims 1 to 4 characterized in that the first phase forming the core of a grain is formed to more than 80% of calcium carbonate and the second phase soluble in water forming the shell of a grain is formed more than 80% calcium acetate. 6. Sel de déneigement selon l'une quelconque des revendications 1 à 4 caractérisé en ce que la première phase formant le coeur d'un grain est formée à plus de 80% d'un carbonate double de calcium et de magnésium et que la seconde phase soluble dans l'eau formant la coque d'un grain est formée à plus de 80% d'un acétate double de calcium et de magnésium. 5. Sel de déneigement selon l'une quelconque des revendications 1 à 6 caractérisé en ce que la granulométrie moyenne des grains formant le sel de déneigement est comprise entre 0.5 et 6 mm. 8. Sel de déneigement selon l'une quelconque des revendications 1 à 6 caractérisé en ce que la granulométrie moyenne des grains formant le sel de déneigement est comprise entre 2 et 4 mm. 66. de-icing salt according to any one of claims 1 to 4 characterized in that the first phase forming the core of a grain is formed to more than 80% of a double carbonate of calcium and magnesium and the second Water-soluble phase forming the shell of a grain is formed to more than 80% of a double acetate of calcium and magnesium. 5. de-icing salt according to any one of claims 1 to 6 characterized in that the average particle size of grains forming the de-icing salt is between 0.5 and 6 mm. 8. de-icing salt according to any one of claims 1 to 6 characterized in that the average grain size of grains forming the de-icing salt is between 2 and 4 mm. 6
FR1203067A 2012-11-16 2012-11-16 Salt comprising biphasic grains consisting of a core of first water-insoluble phase and a shell of a second water soluble phase, useful for snow clearance on roads, where dissolution of grains in water is lower than freezing point of water Pending FR2998300A1 (en)

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FR1203067A FR2998300A1 (en) 2012-11-16 2012-11-16 Salt comprising biphasic grains consisting of a core of first water-insoluble phase and a shell of a second water soluble phase, useful for snow clearance on roads, where dissolution of grains in water is lower than freezing point of water

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FR1203067A FR2998300A1 (en) 2012-11-16 2012-11-16 Salt comprising biphasic grains consisting of a core of first water-insoluble phase and a shell of a second water soluble phase, useful for snow clearance on roads, where dissolution of grains in water is lower than freezing point of water

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108774493A (en) * 2018-07-10 2018-11-09 大连海洋大学 Anti-skidding increasing resistance composite environment-friendly deicing salt of one kind and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444672A (en) * 1981-12-21 1984-04-24 Gancy Alan B Process of making calcium acetate deicing agents and product
US4606836A (en) * 1985-01-22 1986-08-19 Gancy Alan B Continuous process for the manufacture of calcium magnesium acetate deicer
US4913831A (en) * 1987-01-14 1990-04-03 Chevron Research Company Deicing compositions comprising calcium magnesium acetate double salt and processes for their production
US5132035A (en) * 1989-03-06 1992-07-21 General Atomics International Services Corporation Deicing compositions comprising calcium magnesium acetate and chelating agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444672A (en) * 1981-12-21 1984-04-24 Gancy Alan B Process of making calcium acetate deicing agents and product
US4606836A (en) * 1985-01-22 1986-08-19 Gancy Alan B Continuous process for the manufacture of calcium magnesium acetate deicer
US4913831A (en) * 1987-01-14 1990-04-03 Chevron Research Company Deicing compositions comprising calcium magnesium acetate double salt and processes for their production
US5132035A (en) * 1989-03-06 1992-07-21 General Atomics International Services Corporation Deicing compositions comprising calcium magnesium acetate and chelating agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108774493A (en) * 2018-07-10 2018-11-09 大连海洋大学 Anti-skidding increasing resistance composite environment-friendly deicing salt of one kind and preparation method thereof

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