EP1490452A2 - Self-heating composition based on orthophosphoric acid impregnated into a highly porous mineral oxide, method for the production thereof and use of the same - Google Patents

Self-heating composition based on orthophosphoric acid impregnated into a highly porous mineral oxide, method for the production thereof and use of the same

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Publication number
EP1490452A2
EP1490452A2 EP03738213A EP03738213A EP1490452A2 EP 1490452 A2 EP1490452 A2 EP 1490452A2 EP 03738213 A EP03738213 A EP 03738213A EP 03738213 A EP03738213 A EP 03738213A EP 1490452 A2 EP1490452 A2 EP 1490452A2
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European Patent Office
Prior art keywords
composition according
mineral oxide
orthophosphoric acid
oxide
composition
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EP03738213A
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German (de)
French (fr)
Inventor
Lorraine Leite
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Solvay Solutions UK Ltd
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Rhodia Consumer Specialties Ltd
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Publication of EP1490452A2 publication Critical patent/EP1490452A2/en
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    • 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
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions

Definitions

  • Self-heating composition based on orthophosphoric acid impregnated on a mineral oxide of high porosity, its preparation process and its use
  • the present invention relates to a self-heating composition based on orthophosphoric acid impregnated on a mineral oxide of high porosity, its preparation process and its use for heating various drinks and foods without the addition of an external energy source.
  • the present invention also relates to a heat source which can be used in a portable heater for heating food or drink.
  • the heat sources used in such a device are self-heating compositions which can be stored for long periods and which are activated by the addition of an aqueous solution such as for example water.
  • This heat source must not present any danger to the user during storage, transport or during activation.
  • US 5,935,486 describes the use of an acid anhydride and in particular of P 2 O 5 and an anhydride base and in particular of CaO which produce heat by their hydration reaction on the one hand and by the neutralization reaction between the hydrated products obtained on the other hand.
  • a self-heating composition comprising a mixture of a powder obtained by the dry impregnation of a mineral oxide of great porosity with a sufficient amount of orthophosphoric acid (H 3 PO4) followed by drying with a basic anhydride powder.
  • basic anhydride in the sense of the present invention partially hydrated basic oxides such as for example calcium oxide of commercial grade (CaO) well known for containing calcium hydroxides.
  • Other examples of basic anhydrides are, for example, metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, strontium, and barium. Mention may in particular be made, among these oxides LjO 2 , Na 2 O, K 2 O, Rb 2 O, Cs 2 O, MgO, CaO, SrO and BaO.
  • Calcium oxide (CaO) is the preferred basic anhydride.
  • Heat is produced by the hydration of basic anhydride and by the neutralization reaction between the hydrated basic product obtained and the orthophosphoric acid used.
  • proportions such as H3PO4 and basic anhydride starting are used that the neutralization reaction is carried out as completely as possible, that is to say in amounts close to the stoichiometric amounts. This in fact makes it possible to obtain a greater amount of heat on the one hand and a substantially neutral final product on the other hand.
  • substantially neutral is meant a final product whose pH is between about 4 and about 10, and even more preferably between about 6 and about 8.
  • the mineral oxide can be chosen from silica, alumina, silica-alumina, zirconia or titanium oxide.
  • silica is used. This can be a precipitation silica or a combustion silica.
  • the mineral oxide must be of high porosity. This means that its pore volume must be at least 1 ml / g and preferably at least 3ml / g.
  • the mineral oxide may for example be a Tixosil 38A, Tixosil 38D, Tixosil 38X, or Tixosil 365 silica from the company RHODIA.
  • the sufficient quantity of orthophosphoric acid to be used for the impregnation preferably corresponds to the maximum quantity which it is possible to impregnate on the mineral oxide, that is to say the volume for which the mineral oxide is more able to absorb liquid orthophosphoric acid.
  • the impregnation is carried out dry, that is to say that the concentrated orthophosphoric acid is added with a burette in doses of 25 ml drop by drop.
  • the drying is carried out for example in an oven at atmospheric pressure at a temperature between 100 and 200 ° C for at least 3 hours.
  • the quantities of CaO and of acid impregnated on the high porosity mineral oxide used during mixing are such that the Ca / P molar ratio is between 0 , 5 and 2 and preferably about 1, 5.
  • This product from the mixing stage is obtained in the form of a powder, which it is possible to shape (extruded, pellets, etc.) according to the shaping processes commonly used in industry.
  • the self-heating composition of the invention is activated by contacting with an activation solution which is an aqueous solution.
  • an activation solution which is an aqueous solution.
  • Water is preferred.
  • the activation solution is preferably used in an amount such that the amount of water is sufficient to allow complete hydration of the basic anhydride. An excess of water could possibly make it possible to regulate a heating temperature obtained which is too high by evaporation of the water.
  • the temperature at within the composition can reach a temperature in the region of 100 ° C. in a few minutes.
  • the present invention thus also relates to the use of the composition obtained for the heating of solid or liquid food without external input energy.
  • This use can be done in a device provided for this purpose as described for example in document US 5,935,486 incorporated by reference.
  • an antifreeze substance such as calcium chloride or prolpylene glycol can be added to the water or to the aqueous solution used. This can be very advantageous when the self-heating device is used under very low temperature conditions.
  • This means of generating water can include in particular the heating of a hydrate which releases water or the release of water obtained by breaking an oil-in-water or water-in-oil emulsion.
  • Example 1 Example of preparation of a mixture between high porosity silica impregnated with concentrated phosphoric acid and quicklime (CaO) according to the invention
  • the high porosity silica used is a silica called Tixosil 38A from the company RHODIA having a pore volume of 3.2 ml / g.
  • the sufficient amount of concentrated orthophosphoric acid to be used for the impregnation preferably corresponds to the maximum amount that it is possible to impregnate on the silica, that is to say the volume for which the saturation of the silica is obtained.
  • the impregnated silica is dried in an oven at atmospheric pressure at 150 ° C overnight.
  • this curve allows us to access the maximum temperature reached by the self-heating system (in this case this maximum temperature is 97.3 ° C), as well as the rate of temperature rise ( here the temperature rise speed is 2.3 ° C / second).

Abstract

The invention relates to a self-heating composition based on orthophosphoric acid which is impregnated into a highly porous mineral oxide. The invention also relates to a method for producing said composition and to the use of the same for heating drinks and various foods without using an external energy source.

Description

Composition auto-chauffante à base d'acide orthophosphorique imprégné sur un oxyde minéral de grande porosité, son procédé de préparation et son utilisation Self-heating composition based on orthophosphoric acid impregnated on a mineral oxide of high porosity, its preparation process and its use
La présente invention concerne une composition auto-chauffante à base d'acide orthophosphorique imprégné sur un oxyde minéral de grande porosité, son procédé de préparation et son utilisation pour chauffer des boissons et des aliments divers sans apport d'une source d'énergie extérieure.The present invention relates to a self-heating composition based on orthophosphoric acid impregnated on a mineral oxide of high porosity, its preparation process and its use for heating various drinks and foods without the addition of an external energy source.
La présente invention concerne également une source de chaleur qui peut être utilisée dans un dispositif chauffant portable pour chauffer de la nourriture ou des boissons.The present invention also relates to a heat source which can be used in a portable heater for heating food or drink.
Les sources de chaleur employées dans un tel dispositif sont des compositions auto-chauffantes qui peuvent être stockées pour de longues périodes et qui sont activées par l'ajout d'une solution aqueuse comme par exemple de l'eau.The heat sources used in such a device are self-heating compositions which can be stored for long periods and which are activated by the addition of an aqueous solution such as for example water.
Cette source de chaleur ne doit pas présenter de danger pour l'utilisateur au cours de son stockage, de son transport ou pendant son activation.This heat source must not present any danger to the user during storage, transport or during activation.
Elle doit être pratique à utiliser, avoir un poids et un volume le plus petit possible tout en générant suffisamment de chaleur pour les différentes applications pour lesquelles elle est prévue.It must be practical to use, have the smallest possible weight and volume while generating enough heat for the various applications for which it is intended.
Un nombre considérable de sources de chaleur aptes au transport et en particulier pour des applications concernant la nourriture sont connues.A considerable number of heat sources suitable for transport and in particular for applications relating to food are known.
Cependant, les matériaux utilisés jusqu'ici présentent des inconvénients tels que la formation de produits inflammables et/ou toxiques qui sont potentiellement dangereux et qui nécessitent donc des précautions particulières pour leur mise en oeuvre, ou bien une insuffisance d'efficacité qui nécessite l'utilisation d'un volume et d'un poids de matériau plus important. Ainsi, US 3,079,911 décrit l'utilisation d'une composition exothermique activée par addition d'eau comprenant un mélange de sulfate de cuivre, aluminium, chlorure de potassium et sulfate de calcium. Cependant la réaction de ce mélange conduit à la production de gaz qui peuvent être inflammables ou corrosifs.However, the materials used hitherto have drawbacks such as the formation of flammable and / or toxic products which are potentially dangerous and which therefore require special precautions for their implementation, or else an insufficient efficiency which requires the use of a larger volume and weight of material. Thus, US 3,079,911 describes the use of an exothermic composition activated by the addition of water comprising a mixture of copper sulphate, aluminum, potassium chloride and calcium sulphate. However, the reaction of this mixture leads to the production of gases which can be flammable or corrosive.
US 4,809,673 décrit l'hydratation de l'oxyde de calcium pour générer de la chaleur. L'inconvénient de ce système et le manque d'efficacité dans la production de chaleur et la faible densité de cette poudre qui nécessite donc l'utilisation d'un grand volume d'oxyde de calcium.US 4,809,673 describes the hydration of calcium oxide to generate heat. The disadvantage of this system and the lack of efficiency in the production of heat and the low density of this powder which therefore requires the use of a large volume of calcium oxide.
US 4,753,085 décrit l'utilisation de soude et d'acide chlorhydrique qui produit une grande quantité de chaleur mais qui nécessite la manipulation dangereuse d'acide chlorhydrique qui est un acide fort.US 4,753,085 describes the use of soda and hydrochloric acid which produces a large amount of heat but which requires the dangerous handling of hydrochloric acid which is a strong acid.
US 5,935,486 décrit l'utilisation d'un anhydride d'acide et en particulier de P2O5 et d'une base anhydride et en particulier de CaO qui produisent de la chaleur par leur réaction d'hydratation d'une part et par la réaction de neutralisation entre les produits hydratés obtenus d'autre part.US 5,935,486 describes the use of an acid anhydride and in particular of P 2 O 5 and an anhydride base and in particular of CaO which produce heat by their hydration reaction on the one hand and by the neutralization reaction between the hydrated products obtained on the other hand.
Cependant l'utilisation d'un anhydride d'acide et en particulier de P205 qui est décrit comme préféré présente des inconvénients. En effet, ce produit est très sensible aux traces d'humidité et nécessite lors de sa mise en œuvre des précautions particulières tel qu'un enrobage des particules de P2Os dans de l'huile, ce qui complique la préparation du système auto-chauffant d'une part, et qui nuit à l'efficacité du matériau car les réactions d'hydratation de P2O5 et la réaction de neutralisation des produits hydratés de P2O avec les produits basiques hydratés ne seront pas totales en raison de la difficulté d'accès du P2O5 enrobé.However, the use of an acid anhydride and in particular of P 2 0 5 which is described as preferred has drawbacks. Indeed, this product is very sensitive to traces of humidity and requires during its implementation special precautions such as coating the particles of P 2 Os in oil, which complicates the preparation of the auto-system. heating on the one hand, and which affects the effectiveness of the material because the hydration reactions of P 2 O 5 and the neutralization reaction of the hydrated products of P 2 O with the hydrated basic products will not be total due to difficulty in accessing the coated P 2 O 5 .
Le besoin existait de trouver un matériau auto-chauffant efficace, plus facile à mettre en oeuvre et qui ne génère pas de produits toxiques ou néfastes pour l'environnement.There was a need to find an effective self-heating material, easier to use and which does not generate toxic or harmful products for the environment.
Ce besoin et d'autres sont satisfaits par la presention invention qui a en effet pour objet une composition auto-chauffante comprenant un mélange d'une poudre obtenue par l'imprégnation à sec d'un oxyde minéral de grande porosité par une quantité suffisante d'acide orthophosphorique (H3PO4) suivie d'un séchage avec une poudre d'anhydride basique.This need and others are satisfied by the presention invention which in fact relates to a self-heating composition comprising a mixture of a powder obtained by the dry impregnation of a mineral oxide of great porosity with a sufficient amount of orthophosphoric acid (H 3 PO4) followed by drying with a basic anhydride powder.
Par anhydride basique on entend au sens de la présente invention des oxydes basiques partiellement hydratés comme par exemple l'oxyde de calcium au grade commercial (CaO) bien connu pour contenir des hydroxydes de calcium. D'autres exemples d'anhydrides basiques sont par exemple des oxydes de métaux tels que le lithium, sodium, potassium, rubidium, césium, magnésium, strontium, et barium. On peut citer en particulier parmi ces oxydes LjO2, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO et BaO.By basic anhydride is meant in the sense of the present invention partially hydrated basic oxides such as for example calcium oxide of commercial grade (CaO) well known for containing calcium hydroxides. Other examples of basic anhydrides are, for example, metal oxides such as lithium, sodium, potassium, rubidium, cesium, magnesium, strontium, and barium. Mention may in particular be made, among these oxides LjO 2 , Na 2 O, K 2 O, Rb 2 O, Cs 2 O, MgO, CaO, SrO and BaO.
L'oxyde de calcium (CaO) est l'anhydride basique préféré.Calcium oxide (CaO) is the preferred basic anhydride.
La chaleur est produite par l'hydratation de l'anhydride basique et par la réaction de neutralisation entre le produit basique hydraté obtenu et l'acide orthophosphorique utilisé.Heat is produced by the hydration of basic anhydride and by the neutralization reaction between the hydrated basic product obtained and the orthophosphoric acid used.
De manière préférentielle, on utilise des proportions telles en H3PO4 et en anhydride basique de départ que la réaction de neutralisation s'effectue de manière la plus complète possible, c'est à dire dans des quantités proches des quantités stoechiométriques. Ceci permet en effet d'obtenir une plus grande quantité de chaleur d'une part et un produit final substanciellement neutre d'autre part.Preferably, proportions such as H3PO4 and basic anhydride starting are used that the neutralization reaction is carried out as completely as possible, that is to say in amounts close to the stoichiometric amounts. This in fact makes it possible to obtain a greater amount of heat on the one hand and a substantially neutral final product on the other hand.
Par substanciellement neutre, on entend un produit final dont le pH est compris entre environ 4 et environ 10, et de manière encore plus préférentielle entre environ 6 et environ 8.By substantially neutral is meant a final product whose pH is between about 4 and about 10, and even more preferably between about 6 and about 8.
L'imprégnation de l'acide orthophosphorique sur l'oxyde minéral de grande porosité peut être effectuée de la manière décrite dans la demande de brevet FR 0200929 déposée en France le 25 janvier 2002.The impregnation of orthophosphoric acid on the high porosity mineral oxide can be carried out as described in patent application FR 0200929 filed in France on January 25, 2002.
L'oxyde minéral peut être choisi parmi la silice, l'alumine, la silice-alumine, la zircone ou l'oxyde de titane. De préférence on utilise la silice. Celle-ci peut être une silice de précipitation ou une silice de combustion.The mineral oxide can be chosen from silica, alumina, silica-alumina, zirconia or titanium oxide. Preferably, silica is used. This can be a precipitation silica or a combustion silica.
L'oxyde minéral doit être de grande porosité. Ceci signifie que son volume poreux doit être d'au moins 1ml/g et de préférence d'au moins 3ml/g. Lorsque l'oxyde de minéral est de la silice, il peut s'agir par exemple d'une silice Tixosil 38A, Tixosil 38D, Tixosil 38X, ou Tixosil 365 de la société RHODIA.The mineral oxide must be of high porosity. This means that its pore volume must be at least 1 ml / g and preferably at least 3ml / g. When the mineral oxide is silica, it may for example be a Tixosil 38A, Tixosil 38D, Tixosil 38X, or Tixosil 365 silica from the company RHODIA.
La quantité suffisante d'acide orthophosphorique à utiliser pour l'imprégnation correspond de préférence à la quantité maximale qu'il est possible d'imprégner sur l'oxyde minéral, c'est à dire le volume pour lequel l'oxyde minéral n'est plus capable d'absorber l'acide orthophosphorique liquide.The sufficient quantity of orthophosphoric acid to be used for the impregnation preferably corresponds to the maximum quantity which it is possible to impregnate on the mineral oxide, that is to say the volume for which the mineral oxide is more able to absorb liquid orthophosphoric acid.
L'imprégnation se fait à sec, c'est à dire que l'on ajoute l'acide orthophosphorique concentré avec une burette par doses de 25 ml au goutte à goutte.The impregnation is carried out dry, that is to say that the concentrated orthophosphoric acid is added with a burette in doses of 25 ml drop by drop.
Le séchage est effectué par exemple dans une étuve à la pression atmosphérique à une température comprise entre 100 et 200°C pendant au moins 3 heures.The drying is carried out for example in an oven at atmospheric pressure at a temperature between 100 and 200 ° C for at least 3 hours.
Le produit issu de cette étape d'imprégnation est ensuite mélangé à l'anhydride basique.The product resulting from this impregnation step is then mixed with basic anhydride.
Lorsque l'anhydride basique est de la chaux vive (CaO), les quantités de CaO et d'acide imprégné sur l'oxyde minéral de grande porosité mises en œuvre lors du mélage sont telles que le rapport molaire Ca/P est compris entre 0,5 et 2 et de préférence d'environ 1 ,5.When the basic anhydride is quicklime (CaO), the quantities of CaO and of acid impregnated on the high porosity mineral oxide used during mixing are such that the Ca / P molar ratio is between 0 , 5 and 2 and preferably about 1, 5.
Ce produit issu de l'étape de mélange est obtenu sous la forme d'une poudre, qu'il est possible de mettre en forme (extrudés, pastilles...) suivant les procédés de mise en forme couramment utilisés dans l'industrie.This product from the mixing stage is obtained in the form of a powder, which it is possible to shape (extruded, pellets, etc.) according to the shaping processes commonly used in industry.
II est possible d'ajouter également à la composition auto-chauffante un ou plusieurs matériaux inertes pour réguler, typiquement retarder le taux de production de chaleur, ou simplement renforcer mécaniquement les pastilles ou granules utilisés. La composition auto-chauffante de l'invention est activée par mise en contact avec une solution d'activation qui est une solution aqueuse. L'eau est préférée. La solution d'activation est utilisée de préférence dans une quantité telle que la quantité d'eau soit suffisante pour permettre l'hydratation complète de l'anhydride basique. Un excès d'eau pourrait éventuellement permettre de réguler une température de chauffage obtenue trop forte par évaporation de l'eau.It is also possible to add to the self-heating composition one or more inert materials to regulate, typically delay the rate of heat production, or simply mechanically reinforce the pellets or granules used. The self-heating composition of the invention is activated by contacting with an activation solution which is an aqueous solution. Water is preferred. The activation solution is preferably used in an amount such that the amount of water is sufficient to allow complete hydration of the basic anhydride. An excess of water could possibly make it possible to regulate a heating temperature obtained which is too high by evaporation of the water.
Sans vouloir limiter l'invention à une théorie scientifique, il est probable que les réactions exothermiques mises en jeu lors de la mise en contact de cette composition auto-chauffante avec l'eau soient les suivantes dans le cas où l'anhydride basique est l'oxyde de calcium et l'oxyde minéral de grande porosité imprégné par l'acide orthophosphorique est une silice :Without wishing to limit the invention to a scientific theory, it is probable that the exothermic reactions brought into play when this self-heating composition is brought into contact with water are the following in the case where the basic anhydride is calcium oxide and mineral oxide of high porosity impregnated with orthophosphoric acid is silica:
Hydratation de la chaux vive : CaO (s) + H20 (I) → Ca(OH)2 (s)Hydration of quicklime: CaO (s) + H 2 0 (I) → Ca (OH) 2 (s)
ΔH = -15,6 kcal/mole CaO(s) Relarguage de l'acide : H3PO4/SiO2 (s) + H2O (I) → H3PO4 (I) + SiO2 (s)ΔH = -15.6 kcal / mole CaO (s) Acid release: H 3 PO 4 / SiO 2 (s) + H 2 O (I) → H 3 PO 4 (I) + SiO 2 (s)
ΔH = -5, 15 kcal/mole H3P04 Neutralisation : 2 H3PO4 (I) + 3 Ca(OH)2 (s)→ Ca3(PO4)2 (s) + 6ΔH = -5.15 kcal / mole H 3 P0 4 Neutralization: 2 H 3 PO 4 (I) + 3 Ca (OH) 2 (s) → Ca 3 (PO 4 ) 2 (s) + 6
H2OH 2 O
ΔH = -77, 1 kcal/mole Ca3(P04)2 (s) D'où la réaction globale : 3 CaO + 2H3PO4/SiO2 → Ca3(PO4)2 + SiO2 ΔH = -77, 1 kcal / mole Ca 3 (P0 4 ) 2 (s) Hence the overall reaction: 3 CaO + 2H 3 PO 4 / SiO 2 → Ca 3 (PO 4 ) 2 + SiO 2
ΔH = -134,2 kcal/mole Ca3(P04)2 (s)ΔH = -134.2 kcal / mole Ca 3 (P0 4 ) 2 (s)
Ainsi, lorsque l'on ajoute de l'eau à la composition auto-chauffante de l'invention selon un rapport composition/eau compris entre 0.5 et 2 et de préférence d'environ 1 , dans une enceinte isolante et fermée, la température au sein de la composition peut atteindre une température voisine de 100°C en quelques minutes.Thus, when water is added to the self-heating composition of the invention according to a composition / water ratio of between 0.5 and 2 and preferably about 1, in an insulating and closed enclosure, the temperature at within the composition can reach a temperature in the region of 100 ° C. in a few minutes.
La présente invention a ainsi-également pour objet l'utilisation de la composition obtenue pour le chauffage d'aliments solides ou liquides sans apport extérieur d'énergie. Cette utilisation peut se faire dans un dispositif prévu à cet effet tel que décrit par exemple dans le document US 5,935,486 incorporé par référence.The present invention thus also relates to the use of the composition obtained for the heating of solid or liquid food without external input energy. This use can be done in a device provided for this purpose as described for example in document US 5,935,486 incorporated by reference.
En outre, on peut ajouter à l'eau ou à la solution aqueuse utilisée une substance antigel comme par exemple du chorure de calcium ou du prolpylène glycol. Ceci peut être très avantageux dans le cas d'utilisation du dispositif auto-chauffant dans des conditions de températures très basses.In addition, an antifreeze substance such as calcium chloride or prolpylene glycol can be added to the water or to the aqueous solution used. This can be very advantageous when the self-heating device is used under very low temperature conditions.
Il est possible également d'utiliser un moyen de générer de l'eau pour obtenir la solution d'activation. Ce moyen de générer de l'eau peut inclure notamment le chauffage d'un hydrate qui relargue de l'eau ou le relarguage d'eau obtenu en cassant une émulsion huile-dans-eau ou eau-dans-huile.It is also possible to use a means of generating water to obtain the activation solution. This means of generating water can include in particular the heating of a hydrate which releases water or the release of water obtained by breaking an oil-in-water or water-in-oil emulsion.
D'autres aspects et avantages des produits objets de l'invention apparaîtront à la lumière des exemples qui sont présentés ci-dessous à titre illustratif et nullement limitatif.Other aspects and advantages of the products which are the subject of the invention will appear in the light of the examples which are presented below by way of illustration and in no way limitative.
Exemple 1 : Exemple de préparation d'un mélange entre silice de grande porosité imprégnée par de l'acide phosphorique concentré et une chaux vive (CaO) selon l'inventionExample 1: Example of preparation of a mixture between high porosity silica impregnated with concentrated phosphoric acid and quicklime (CaO) according to the invention
La silice de grande porosité utilisée est une silice appelée Tixosil 38A de la société RHODIA ayant un volume poreux de 3,2 ml/g. L'acide orthophosphorique utilisé est H3PO4 à 85% normapur de marque Prolabo réf. 20624295 (MH3PO4 = 98 g/mol, d = 1 ,7g/ml). La quantité suffisante d'acide orthophosphorique concentré à utiliser pour l'imprégnation correspond de préférence à la quantité maximale qu'il est possible d'imprégner sur la silice c'est à dire le volume pour lequel on obtient la saturation de la silice.The high porosity silica used is a silica called Tixosil 38A from the company RHODIA having a pore volume of 3.2 ml / g. The orthophosphoric acid used is H 3 PO 4 at 85% normapur of the Prolabo brand ref. 20624295 (MH3PO4 = 98 g / mol, d = 1.7 g / ml). The sufficient amount of concentrated orthophosphoric acid to be used for the impregnation preferably corresponds to the maximum amount that it is possible to impregnate on the silica, that is to say the volume for which the saturation of the silica is obtained.
Pour une masse de silice de 50g on devra utiliser en théorie 3,2 x 50 = 160 ml de H3PO4 à 85% soit, 1 ,7x160 = 272g de H3PO4 à 85% (ou 231 ,2g de H3PO4 pur). L'imprégnation se fait à sec, c'est à dire que l'on ajoute l'acide concentré avec une burette par doses de 25 ml au goutte à goutte. Le volume maximum atteint imprégné est de 134ml. La différence entre les 160ml théoriquement utilisables et les 134ml utilisés en pratique provient de la viscosité de l'acide qui est plus importante que celle de l'eau.For a mass of silica of 50g, 3.2 x 50 = 160 ml of H 3 PO 4 at 85% should be used in theory, i.e. 1.7x160 = 272g of H 3 PO 4 at 85% (or 231.2g of H 3 PO 4 pure). The impregnation is carried out dry, that is to say that the concentrated acid is added with a burette in doses of 25 ml drop by drop. The maximum volume reached impregnated is 134 ml. The difference between the theoretically usable 160ml and the 134ml used in practice comes from the viscosity of the acid which is greater than that of water.
Ensuite on procède au séchage de la silice imprégnée dans une étuve à pression atmosphérique à 150°C pendant une nuit.Then the impregnated silica is dried in an oven at atmospheric pressure at 150 ° C overnight.
La chaux vive utilisée est une chaux CaO à 92% de Prolabo, M = 56 g. mol"1, réf. 22.645.360.The quicklime used is CaO lime at 92% from Prolabo, M = 56 g. mol "1 , ref. 22.645.360.
On pèse 2.43 g de CaO et 3.57 g de silice imprégnée par l'acide. Le mélange physique des deux poudres est effectué dans un mortier.2.43 g of CaO and 3.57 g of acid impregnated silica are weighed. The physical mixing of the two powders is carried out in a mortar.
Exemple 2 :Exemple de testExample 2: Test example
6 grammes de la poudre autochauffante sont placés dans le fond d'un DEWAR. Un thermocouple relié à un système d'acquisition est placé au cœur de la poudre. Après 10 minutes nécessaire à la stabilisation de la température, on déclenche l'arrivée de 3 g d'eau sur la poudre et on enregistre une courbe Température = f(temps).6 grams of the self-heating powder are placed in the bottom of a DEWAR. A thermocouple connected to an acquisition system is placed at the heart of the powder. After 10 minutes necessary for the temperature to stabilize, 3 g of water are triggered on the powder and a Temperature = f (time) curve is recorded.
L'exploitation de cette courbe nous permet d'accéder à la température maximale atteinte par le système auto-chauffant ( dans le cas présent cette température maximale est de 97,3 °C ), ainsi qu'à la vitesse de montée en température (ici la vitesse de montée en température est de 2,3 °C/seconde).Using this curve allows us to access the maximum temperature reached by the self-heating system (in this case this maximum temperature is 97.3 ° C), as well as the rate of temperature rise ( here the temperature rise speed is 2.3 ° C / second).
Ces résultats mettent en évidence la grande efficacité de la composition selon l'invention. These results demonstrate the high effectiveness of the composition according to the invention.

Claims

Revendications claims
1- Composition auto-chauffante comprenant un mélange d'une poudre d'un oxyde minéral de grande porosité imprégné par une quantité suffisante d'acide orthophosphorique (H3PO4) avec une poudre d'anhydride basique.1- Self-heating composition comprising a mixture of a powder of a mineral oxide of high porosity impregnated with a sufficient amount of orthophosphoric acid (H 3 PO 4 ) with a powder of basic anhydride.
2- Composition selon la revendication 1 , caractérisée en ce que l'anhydride basique est un oxyde basique partiellement hydraté de métaux choisi parmi2- Composition according to claim 1, characterized in that the basic anhydride is a partially hydrated basic metal oxide chosen from
LiO2, Na2O, K2O, Rb2O, Cs2O, MgO, CaO, SrO, BaO ou leurs mélanges.LiO 2 , Na 2 O, K 2 O, Rb 2 O, Cs 2 O, MgO, CaO, SrO, BaO or their mixtures.
3- Composition selon la revendication 2, caractérisée en ce que l'anhydride basique est de l'oxyde de calcium (CaO).3- Composition according to claim 2, characterized in that the basic anhydride is calcium oxide (CaO).
4- Composition selon l'une quelconques des revendications 1 à 3, caractérisée en ce que les proportions de H3PO4 et d'anhydride basique sont proches des quantités stoechiométriques de la réaction de neutralisation4- Composition according to any one of claims 1 to 3, characterized in that the proportions of H 3 PO4 and basic anhydride are close to the stoichiometric amounts of the neutralization reaction
5- Composition selon la revendication 3 et 4, caractérisée en ce que les quantités de CaO et d'acide orthophosphorique imprégné sur l'oxyde minéral de grande porosité mises en œuvre lors du mélange sont telles que le rapport molaire Ca/P est compris entre 0,5 et 2.5- Composition according to claim 3 and 4, characterized in that the amounts of CaO and orthophosphoric acid impregnated on the mineral oxide of high porosity used during mixing are such that the molar ratio Ca / P is between 0.5 and 2.
6- Composition selon la 5, caractérisée en ce que les quantités de CaO et d'acide orthophosphorique imprégné sur l'oxyde minéral de grande porosité mises en œuvre lors du mélange sont telles que le rapport molaire Ca/P est d'environ 1 ,5.6- Composition according to 5, characterized in that the amounts of CaO and orthophosphoric acid impregnated on the mineral oxide of high porosity used during mixing are such that the Ca / P molar ratio is approximately 1, 5.
7- Composition selon l'une quelconques des revendications 1 à 6, caractérisée en ce que l'imprégnation de l'acide orthophosphorique sur l'oxyde minéral de grande porosité est effectuée à sec et suivie d'un séchage7- Composition according to any one of claims 1 to 6, characterized in that the impregnation of orthophosphoric acid on the mineral oxide of high porosity is carried out dry and followed by drying
8- Composition selon l'une quelconque des revendications 1 à 7, caractérisée en ce que l'oxyde minéral a un volume poreux d'au moins 1ml/g et de préférence d'au moins 3ml/g. 9- Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce que l'oxyde minéral peut être choisi parmi la silice, l'alumine, la silice- alumine, la zircone ou l'oxyde de titane.8- Composition according to any one of claims 1 to 7, characterized in that the mineral oxide has a pore volume of at least 1ml / g and preferably at least 3ml / g. 9- Composition according to any one of claims 1 to 8, characterized in that the mineral oxide can be chosen from silica, alumina, silica-alumina, zirconia or titanium oxide.
10- Composition selon la revendication 9, caractérisée en ce que l'oxyde minéral est de la silice.10- Composition according to claim 9, characterized in that the mineral oxide is silica.
11- Composition selon l'une quelconque des revendications 1 à 10, caractérisée en ce que la quantité suffisante d'acide orthophosphorique à utiliser pour l'imprégnation correspond à la quantité maximale qu'il est possible d'imprégner sur l'oxyde minéral, c'est à dire le volume pour lequel l'oxyde minéral n'est plus capable d'absorber l'acide orthophosphorique liquide.11- Composition according to any one of claims 1 to 10, characterized in that the sufficient amount of orthophosphoric acid to be used for the impregnation corresponds to the maximum amount that it is possible to impregnate on the mineral oxide, that is to say the volume for which the mineral oxide is no longer capable of absorbing liquid orthophosphoric acid.
12- Utilisation de la composition selon l'une quelconques des revendications 1 à 11 pour le chauffage d'aliments solides ou liquides.12- Use of the composition according to any one of claims 1 to 11 for the heating of solid or liquid food.
13- Utilisation de la composition selon la revendication 12, caractérisée en ce qu'on ajoute de l'eau à ce produit selon un rapport composition/eau compris entre 0.5 et 2.13- Use of the composition according to claim 12, characterized in that water is added to this product according to a composition / water ratio between 0.5 and 2.
14- Utilisation selon la revendication 13, caractérisée en ce qu'on ajoute de l'eau à ce produit selon un rapport composition/eau d'environ 1. 14- Use according to claim 13, characterized in that water is added to this product according to a composition / water ratio of about 1.
EP03738213A 2002-04-02 2003-03-31 Self-heating composition based on orthophosphoric acid impregnated into a highly porous mineral oxide, method for the production thereof and use of the same Withdrawn EP1490452A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0204071A FR2837830B1 (en) 2002-04-02 2002-04-02 SELF-HEATING COMPOSITION BASED ON ORTHOPHOSPHORIC ACID IMPREGNATED ON A LARGE POROSITY MINERAL OXIDE, PREPARATION METHOD AND USE THEREOF
FR0204071 2002-04-02
PCT/FR2003/000994 WO2003083007A2 (en) 2002-04-02 2003-03-31 Self-heating composition based on orthophosphoric acid impregnated into a highly porous mineral oxide, method for the production thereof and use of the same

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US10036574B2 (en) 2013-06-28 2018-07-31 British American Tobacco (Investments) Limited Devices comprising a heat source material and activation chambers for the same
US10542777B2 (en) 2014-06-27 2020-01-28 British American Tobacco (Investments) Limited Apparatus for heating or cooling a material contained therein
US11064725B2 (en) 2015-08-31 2021-07-20 British American Tobacco (Investments) Limited Material for use with apparatus for heating smokable material
US11241042B2 (en) 2012-09-25 2022-02-08 Nicoventures Trading Limited Heating smokeable material
US11452313B2 (en) 2015-10-30 2022-09-27 Nicoventures Trading Limited Apparatus for heating smokable material
US11659863B2 (en) 2015-08-31 2023-05-30 Nicoventures Trading Limited Article for use with apparatus for heating smokable material
US11672279B2 (en) 2011-09-06 2023-06-13 Nicoventures Trading Limited Heating smokeable material
US11825870B2 (en) 2015-10-30 2023-11-28 Nicoventures Trading Limited Article for use with apparatus for heating smokable material
US11924930B2 (en) 2015-08-31 2024-03-05 Nicoventures Trading Limited Article for use with apparatus for heating smokable material

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US11672279B2 (en) 2011-09-06 2023-06-13 Nicoventures Trading Limited Heating smokeable material
US11241042B2 (en) 2012-09-25 2022-02-08 Nicoventures Trading Limited Heating smokeable material
US10036574B2 (en) 2013-06-28 2018-07-31 British American Tobacco (Investments) Limited Devices comprising a heat source material and activation chambers for the same
US10542777B2 (en) 2014-06-27 2020-01-28 British American Tobacco (Investments) Limited Apparatus for heating or cooling a material contained therein
US11064725B2 (en) 2015-08-31 2021-07-20 British American Tobacco (Investments) Limited Material for use with apparatus for heating smokable material
US11659863B2 (en) 2015-08-31 2023-05-30 Nicoventures Trading Limited Article for use with apparatus for heating smokable material
US11924930B2 (en) 2015-08-31 2024-03-05 Nicoventures Trading Limited Article for use with apparatus for heating smokable material
US11452313B2 (en) 2015-10-30 2022-09-27 Nicoventures Trading Limited Apparatus for heating smokable material
US11825870B2 (en) 2015-10-30 2023-11-28 Nicoventures Trading Limited Article for use with apparatus for heating smokable material

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CN1656192A (en) 2005-08-17
AU2003244729A8 (en) 2003-10-13
FR2837830B1 (en) 2004-05-21
CA2481526A1 (en) 2003-10-09
WO2003083007A3 (en) 2004-04-15
WO2003083007A2 (en) 2003-10-09

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