WO2016071143A1 - Preparation of nanoparticles by treatment of a solution in a hydrothermal medium - Google Patents
Preparation of nanoparticles by treatment of a solution in a hydrothermal medium Download PDFInfo
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- WO2016071143A1 WO2016071143A1 PCT/EP2015/074777 EP2015074777W WO2016071143A1 WO 2016071143 A1 WO2016071143 A1 WO 2016071143A1 EP 2015074777 W EP2015074777 W EP 2015074777W WO 2016071143 A1 WO2016071143 A1 WO 2016071143A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
- B01J3/008—Processes carried out under supercritical conditions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
- B01J4/002—Nozzle-type elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00119—Heat exchange inside a feeding nozzle or nozzle reactor
Definitions
- the invention relates to a method for producing nanoparticles by continuously treating a salt solution under high pressure and temperature conditions to modify the composition thereof.
- hydrothermal conditions has been studied for many years for mineral synthesis operations from dissolved salts in aqueous solution.
- the conditions employed are subcritical conditions, with in particular a treatment temperature below the critical temperature of 375 ° C.
- the syntheses being carried out in a closed medium, at constant volume, the pressure is equal to the autogenous pressure, ie the saturation vapor pressure of the water at the temperature in question, generally below the critical pressure of the water, ie 221 bar .
- the feed tubing of the saline solution is in contact with supercritical water over a similarly reduced length. It follows a strong heating of the saline solution upstream of its contact with the supercritical water. Heating above 150 ° C to 180 ° C induces transformation of the saline solution, sometimes undesired partial precipitation of dissolved salts in particulate form. This heating also partly explains the formation of the deposit on the walls of the inlet tubing of the saline solution at the point of contact with the superheated water.
- the object of the invention is to remedy these drawbacks and relates to a process for producing nanoparticles by continuous treatment of a saline solution under conditions of high pressure and high temperature.
- the invention consists in providing, in a mixing device, a hot aqueous salt solution and a cold water solution in a stream of superheated water at a temperature above 250 ° C. and characterized in that the pipe of The aqueous saline solution is surrounded by the supply line for the cold water solution and the temperature difference between the cold water solution and the saline solution is at least 50 ° C.
- a thin cold water jacket provides a barrier to exchanges between the saline solution and the superheated water due to temperature differences between, on the one hand, saline solution and cold water and, on the other hand, between the solution of superheated water and cold water.
- the cold water supply line that surrounds the saline supply line is at least as long as this line for supplying the saline solution inside the mixing device. .
- the cold water supply pipe is longer than the saline supply pipe of a length at least equal to the diameter of the water supply. the supply line of the saline solution.
- the temperature of the cold water at the inlet of the mixing device is between 0 ° C. and 60 ° C. and typically more typically between 10 ° C. and 30 ° C.
- the temperature of the saline solution at the inlet of the mixing device is between 50 ° C. and 120 ° C. and typically more typically between 80 ° C. and 120 ° C.
- the cold water is supplemented with a pH-modifying compound chosen from organic acids, ammonia, amines and urea.
- cold water is added with a fuel compound in superheated water and selected from alcohols and ketones. Description of particular embodiments.
- An installation for treating an aqueous saline solution in a hydrothermal medium according to the invention contains:
- a pump for raising the pressure of the main flow of the water solution to a value P1 e greater than 50 bar
- a heater intended to raise the temperature of this main stream of the pressurized water solution to a temperature greater than 250 ° C.
- a pump for raising the pressure of the secondary flow of the water solution to a value P2 water greater than the pressure P1 e at
- a pump for raising the pressure of the aqueous salt solution to a value P3 SO i greater than the pressure P2 water
- the pressure and temperature values of the superheated water 1 can be chosen respectively between 50 bar and 1000 bar and 250 ° C and 700 ° C, the pressure always being chosen higher than the autogenous pressure of the water at the temperature considered.
- the pressure and temperature values of the superheated water may be chosen beyond the critical point of water, with a pressure P e u greater than 221 bar and a higher temperature 375 ° C.
- the pressure P2 of the water of the secondary stream 3 of the water solution will be chosen to be at least 5 bars higher and at least 25 bars above the pressure P1 water of the flow of the superheated water solution.
- the pressure P3 of the flow of the aqueous saline solution 2 will be chosen to be greater than at least 5 bars and typically at least 25 bars at the pressure P2 water of the secondary stream of the water solution.
- the mass flow rate of the secondary stream of water 3 is between 3% and 20% of the mass flow rate of the superheated water stream, typically between 5% and 10% of the mass flow rate of the superheated water stream.
- the mass flow rate of the saline aqueous solution 2 is typically between 0.1% and 10% of the mass flow rate of the superheated water flow.
- the pipe 13 for supplying cold water and the pipe 12 for supplying the saline solution are concentric.
- the difference in temperature between the saline solution 2 and the cold water 3 on the one hand, and the cold water 3 and the superheated water 1 on the other hand causes the formation of a cold water jacket 4 which spreads in the middle after the end of the cold water supply pipe.
- supply lines 12 of saline solution and 13 of cold water No contact takes place between these pipes 12 and 13 is the reaction medium consisting of the mixture of the saline solution and the superheated water before reaction between them to form the nanoparticles, and no deposit is formed on the end of these pipes12 and 13.
- the reaction between the saline solution 2 and the superheated water 1 is modified by introducing into the stream of cold water 3 at least one pH-modifying compound chosen from ammonia amines of formula R-NH 2, urea and organic acids, and in particular acetic acid, lactic acid and oxalic acid.
- at least one pH-modifying compound chosen from ammonia amines of formula R-NH 2, urea and organic acids, and in particular acetic acid, lactic acid and oxalic acid.
- cold water 3 is added with a fuel compound in superheated water and chosen from alcohols and ketones.
- This fuel compound is oxidized on contact between the flow of cold water 3 and superheated water 1, carbon dioxide form CO2 in a highly exothermic reaction which causes an increase in the temperature of the reaction medium.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Préparation de nanoparticules par traitement Preparation of nanoparticles by treatment
d'une solution en milieu hydrothermal a solution in a hydrothermal medium
Domaine technique de l'invention Technical field of the invention
L'invention concerne un procédé de production de nanoparticules par traitement en continu d'une solution saline dans des conditions de pression et de température élevées pour en modifier la composition. The invention relates to a method for producing nanoparticles by continuously treating a salt solution under high pressure and temperature conditions to modify the composition thereof.
État de la technique State of the art
L'utilisation de conditions hydrothermales est étudiée depuis de nombreuses années pour des opérations de synthèse de minéraux à partir de sels dissous en solution aqueuse. Les conditions employées sont des conditions sous- critiques, avec en particulier une température de traitement inférieure à la température critique de l'eau de 375°C. Les synthèses étant réalisées en milieu fermé, à volume constant, la pression est égale à la pression autogène, soit la pression de vapeur saturante de l'eau à la température considérée, généralement inférieure à la pression critique de l'eau, soit 221 bars. The use of hydrothermal conditions has been studied for many years for mineral synthesis operations from dissolved salts in aqueous solution. The conditions employed are subcritical conditions, with in particular a treatment temperature below the critical temperature of 375 ° C. The syntheses being carried out in a closed medium, at constant volume, the pressure is equal to the autogenous pressure, ie the saturation vapor pressure of the water at the temperature in question, generally below the critical pressure of the water, ie 221 bar .
Parallèlement, des procédés utilisant du CO2 en phase supercritique ont été développés pour l'extraction de principes aromatiques ou de molécules spécifiques à partir d'un composé naturel. In parallel, processes using supercritical phase CO2 have been developed for the extraction of aromatic principles or specific molecules from a natural compound.
Depuis une vingtaine d'années, plusieurs équipes de recherche ont développé des réacteurs en continu pour effectuer des synthèses de composés minéraux sous forme de particules très fines, notamment de nanoparticules dans des conditions hydrothermales. Ces conditions correspondent à des conditions de pression-température sous-critiques (inférieures à la pression et la température du point critique de l'eau 221 bars, 375°C) ou des conditions supercritiques, au- delà du point critique. Ces synthèses hydrothermales consistent à mélanger une solution des sels précurseurs avec de l'eau surchauffée près du point critique. Les espèces oxydantes présentes dans l'eau supercritique provoquent alors la précipitation de composés oxydes correspondant aux sels précurseurs. Le mélange est effectué en continu dans un dispositif de mélange qui est généralement un dispositif en forme de T. For twenty years, several research teams have developed continuous reactors to synthesize mineral compounds in the form of very fine particles, particularly nanoparticles under hydrothermal conditions. These conditions correspond to subcritical pressure-temperature conditions (below the pressure and the critical point temperature of the water 221 bar, 375 ° C) or supercritical conditions, beyond the critical point. These hydrothermal syntheses consist of mixing a solution of the precursor salts with superheated water near the critical point. The oxidizing species present in the supercritical water then cause the precipitation of oxide compounds corresponding to the precursor salts. The mixing is carried out continuously in a mixing device which is generally a T-shaped device.
La synthèse de particules en continu en phase eau sous-critique ou supercritique présente une difficulté technique majeure. La réaction de précipitation des sels précurseurs dissous avec les espèces oxydantes présentes dans l'eau supercritique est très rapide et elle conduit à la formation de dépôts minéraux sur les parois du dispositif utilisé pour le mélange. En particulier, le dispositif en T souvent utilisé et schématisé en figure 1 dans lequel l'eau supercritique 1 entre en contact avec la solution de sels 2 est rapidement obstrué par un dépôt 20 qui empêche alors le fonctionnement correct de l'installation. Le brevet WO20081 14755 décrit un « micromixer » en forme de T dont la section des tubulures favorise le mélange et limite la formation d'un dépôt. Continuous particle synthesis in the subcritical or supercritical water phase presents a major technical difficulty. The precipitation reaction of the dissolved precursor salts with the oxidizing species present in the supercritical water is very rapid and leads to the formation of mineral deposits on the walls of the device used for mixing. In particular, the T-device often used and schematized in FIG. 1 in which the supercritical water 1 comes into contact with the salt solution 2 is rapidly blocked by a deposit 20 which then prevents the correct operation of the installation. Patent WO2008114755 describes a T-shaped "micromixer" whose section of the tubes promotes mixing and limits the formation of a deposit.
Des solutions de mélangeurs ont été proposées et certaines brevetées pour limiter le phénomène d'obstruction des tubulures par des produits de la réaction. Par exemple un dispositif développé à l'University Collège London concerne un dispositif appelé « Confined jet mixer » et schématisé en figure 2. Il consiste en deux tubes concentriques, le tube intérieur convoyant la solution des précurseurs et le tube extérieur fournissant le flux d'eau supercritique. Les brevets WO2005/077505 de Nottingham University FR-09 55023 de l'Université de Bourgogne décrivent un mélangeur, schématisé en figure 3, à contre-courant entre la solution des précurseurs et l'eau supercritique. Mixer solutions have been proposed and some patented to limit the phenomenon of obstruction of tubing by reaction products. For example, a device developed at University College London relates to a device called "Confined jet mixer" and shown schematically in Figure 2. It consists of two concentric tubes, the inner tube conveying the solution of the precursors and the outer tube providing the flow of supercritical water. Patent WO2005 / 077505 of Nottingham University FR-09 55023 from the University of Burgundy describe a mixer, schematized in Figure 3, against the current between the solution of precursors and supercritical water.
Toutes les solutions proposées ont en commun qu'elles n'évitent pas le contact entre la solution saline des précurseurs et l'eau supercritique à proximité d'une paroi. La tubulure d'amenée de la solution saline constitue souvent cette paroi, et la formation d'un dépôt obstrue la tubulure d'amenée de la solution saline sur de longues durées d'utilisation dans des conditions industrielles. All the proposed solutions have in common that they do not prevent the contact between the precursor saline solution and the supercritical water near a wall. The tubing of supply of the saline solution often constitutes this wall, and the formation of a deposit obstructs the supply tubing of the saline solution over long periods of use under industrial conditions.
Par ailleurs la tubulure d'amenée de la solution saline est en contact avec l'eau supercritique sur une longueur même réduite. Il s'en suit un fort échauffement de la solution saline en amont de son contact avec l'eau supercritique. Un échauffement au-delà de 150°C à 180°C induit une transformation de la solution saline, parfois une précipitation partielle non désirée des sels dissous sous forme de particules. Cet échauffement explique également en partie la formation du dépôt sur les parois de la tubulure d'amenée de la solution saline au point de contact avec l'eau surchauffée. In addition, the feed tubing of the saline solution is in contact with supercritical water over a similarly reduced length. It follows a strong heating of the saline solution upstream of its contact with the supercritical water. Heating above 150 ° C to 180 ° C induces transformation of the saline solution, sometimes undesired partial precipitation of dissolved salts in particulate form. This heating also partly explains the formation of the deposit on the walls of the inlet tubing of the saline solution at the point of contact with the superheated water.
Enfin l'addition d'un troisième réactant souvent nécessaire pour orienter la réaction entre la solution saline et l'eau supercritique est difficile à maîtriser car les conditions d'un mélange homogène dans le volume réactionnel ne sont pas réunies en raison de la vitesse très élevée de réaction dans les conditions supercritiques. Finally, the addition of a third reactant often necessary to guide the reaction between the saline solution and the supercritical water is difficult to control because the conditions of a homogeneous mixture in the reaction volume are not met because of the very high speed. high reaction rate under supercritical conditions.
Objet de l'invention L'invention a pour but de remédier à ces inconvénients et concerne un procédé de production de nanoparticules par traitement en continu d'une solution saline dans des conditions de pression et de température élevées. OBJECT OF THE INVENTION The object of the invention is to remedy these drawbacks and relates to a process for producing nanoparticles by continuous treatment of a saline solution under conditions of high pressure and high temperature.
L'invention consiste à apporter conjointement, dans un dispositif de mélange, une solution saline aqueuse chaude et une solution d'eau froide dans un flux d'eau surchauffée à une température supérieure à 250°C et caractérisé en ce que la canalisation d'amenée de la solution saline aqueuse est entourée par la canalisation d'amenée de la solution d'eau froide et que l'écart de température entre la solution d'eau froide et la solution saline est au moins de 50°C. En effet l'auteur a découvert qu'une mince gaine d'eau froide assure une barrière aux échanges entre la solution saline et l'eau surchauffée du fait des écarts de température entre, d'une part la solution saline et l'eau froide et, d'autre part, entre la solution d'eau surchauffée et l'eau froide. The invention consists in providing, in a mixing device, a hot aqueous salt solution and a cold water solution in a stream of superheated water at a temperature above 250 ° C. and characterized in that the pipe of The aqueous saline solution is surrounded by the supply line for the cold water solution and the temperature difference between the cold water solution and the saline solution is at least 50 ° C. Indeed the author discovered that a thin cold water jacket provides a barrier to exchanges between the saline solution and the superheated water due to temperature differences between, on the one hand, saline solution and cold water and, on the other hand, between the solution of superheated water and cold water.
Selon, l'invention, la canalisation d'amenée de l'eau froide qui entoure la canalisation d'amenée de la solution saline est au moins aussi longue que cette canalisation d'amenée de la solution saline à l'intérieur du dispositif de mélange. According to the invention, the cold water supply line that surrounds the saline supply line is at least as long as this line for supplying the saline solution inside the mixing device. .
Selon un développement de l'invention, à l'intérieur du dispositif de mélange, la canalisation d'amenée de l'eau froide est plus longue que la canalisation d'amenée de la solution saline d'une longueur au moins égale au diamètre de la canalisation d'amenée de la solution saline. According to a development of the invention, inside the mixing device, the cold water supply pipe is longer than the saline supply pipe of a length at least equal to the diameter of the water supply. the supply line of the saline solution.
Selon l'invention, la température de l'eau froide à l'entrée du dispositif de mélange est comprise entre 0°C et 60°C et typiquement plus typiquement comprise entre 10°C et 30°C. According to the invention, the temperature of the cold water at the inlet of the mixing device is between 0 ° C. and 60 ° C. and typically more typically between 10 ° C. and 30 ° C.
Selon, l'invention, la température de la solution saline à l'entrée du dispositif de mélange est comprise entre 50°C et 120°C et typiquement plus typiquement comprise entre 80°C et 120°C. Selon un autre développement de l'invention, l'eau froide est additionnée d'un composé modificateur de pH choisi parmi les acides organiques, l'ammoniac, les aminés et l'urée. According to the invention, the temperature of the saline solution at the inlet of the mixing device is between 50 ° C. and 120 ° C. and typically more typically between 80 ° C. and 120 ° C. According to another embodiment of the invention, the cold water is supplemented with a pH-modifying compound chosen from organic acids, ammonia, amines and urea.
Selon un autre développement de l'invention, l'eau froide est additionnée d'un composé carburant dans l'eau surchauffée et choisi parmi les alcools et les cétones. Description de modes particuliers de réalisation. According to another development of the invention, cold water is added with a fuel compound in superheated water and selected from alcohols and ketones. Description of particular embodiments.
D'autres avantages et caractéristiques ressortiront plus clairement de la description qui va suivre de modes particuliers de réalisation de l'invention donnés à titre d'exemples non limitatifs. Other advantages and features will emerge more clearly from the following description of particular embodiments of the invention given as non-limiting examples.
Une installation de traitement d'une solution aqueuse saline en milieu hydrothermal selon l'invention contient : An installation for treating an aqueous saline solution in a hydrothermal medium according to the invention contains:
- une source d'eau froide - a source of cold water
- une pompe pour élever la pression du flux principal de la solution d'eau à une valeur P1 eau supérieure à 50 bars a pump for raising the pressure of the main flow of the water solution to a value P1 e greater than 50 bar
- un réchauffeur destiné à porter la température de ce flux principal de la solution d'eau pressurisée à une température supérieure 250°C a heater intended to raise the temperature of this main stream of the pressurized water solution to a temperature greater than 250 ° C.
- une pompe pour élever la pression du flux secondaire de la solution d'eau à une valeur P2eau supérieure à la pression P1 eau a pump for raising the pressure of the secondary flow of the water solution to a value P2 water greater than the pressure P1 e at
- une source d'une solution aqueuse saline a source of a saline aqueous solution
- une pompe pour élever la pression de la solution aqueuse saline à une valeur P3SOi supérieure à la pression P2eau a pump for raising the pressure of the aqueous salt solution to a value P3 SO i greater than the pressure P2 water
- un dispositif de mélange du flux principal de la solution d'eau surchauffée avec la solution aqueuse saline, dispositif dans lequel le flux d'eau secondaire retarde le contact entre le du flux principal de la solution d'eau surchauffée et la solution aqueuse saline à la sortie de la canalisation d'amenée de la solution aqueuse saline a device for mixing the main flow of the superheated water solution with the saline aqueous solution, in which the secondary water flow retards contact between the main flow of the superheated water solution and the saline aqueous solution; at the outlet of the supply line of the aqueous saline solution
- et un dispositif permettant le refroidissement et la détente du mélange après réaction. and a device for cooling and relaxing the mixture after reaction.
Les valeurs de pression et de température de l'eau surchauffée 1 pourront être choisies respectivement entre 50 bars et 1000 bars et 250°C et 700°C, la pression étant toujours choisie supérieure à la pression autogène de l'eau à la température considérée. En particulier, les valeurs de pression et de température de l'eau surchauffée pourront être choisies au-delà du point critique de l'eau, avec une pression Peau supérieure à 221 bars et une température supérieure 375°C. The pressure and temperature values of the superheated water 1 can be chosen respectively between 50 bar and 1000 bar and 250 ° C and 700 ° C, the pressure always being chosen higher than the autogenous pressure of the water at the temperature considered. In particular, the pressure and temperature values of the superheated water may be chosen beyond the critical point of water, with a pressure P e u greater than 221 bar and a higher temperature 375 ° C.
La pression P2eau du flux secondaire 3 de la solution d'eau sera choisie supérieure d'au moins 5 bars et typiquement d'au moins 25 bars à la pression P1 eau du flux de la solution d'eau surchauffée. La pression P3 du flux de la solution aqueuse saline 2 sera choisie supérieure d'au moins 5 bars et typiquement d'au moins 25 bars à la pression P2eau du flux secondaire de la solution d'eau. The pressure P2 of the water of the secondary stream 3 of the water solution will be chosen to be at least 5 bars higher and at least 25 bars above the pressure P1 water of the flow of the superheated water solution. The pressure P3 of the flow of the aqueous saline solution 2 will be chosen to be greater than at least 5 bars and typically at least 25 bars at the pressure P2 water of the secondary stream of the water solution.
Le débit massique du flux secondaire d'eau 3 est compris entre 3% et 20% du débit massique du flux d'eau surchauffée, typiquement entre 5% et 10% du débit massique du flux d'eau surchauffée. The mass flow rate of the secondary stream of water 3 is between 3% and 20% of the mass flow rate of the superheated water stream, typically between 5% and 10% of the mass flow rate of the superheated water stream.
Le débit massique de la solution aqueuse saline 2 est typiquement compris entre 0.1 % et 10% du débit massique du flux d'eau surchauffée. The mass flow rate of the saline aqueous solution 2 is typically between 0.1% and 10% of the mass flow rate of the superheated water flow.
Selon un mode préférentiel de réalisation de l'invention, la canalisation 13 d'amenée de l'eau froide et la canalisation 12 d'amenée de la solution saline sont concentriques. L'écart de température entre la solution saline 2 et l'eau froide 3 d'une part, et l'eau froide 3 et l'eau surchauffée 1 d'autre part entraine la formation d'une gaine d'eau froide 4 qui se propage dans le milieu après l'extrémité de la canalisation d'amenée d'eau froide. De ce fait, le contact entre la solution saline 2 et l'eau surchauffée 1 a lieu dans le dispositif de mélange après l'extrémité des canalisations d'amenée 12 de la solution saline et 13 de l'eau froide. Aucun contact n'a lieu entre ces canalisations 12 et 13 est le milieu réactionnel 5 constitué du mélange de la solution saline et de l'eau surchauffée avant réaction entre elles pour former les nanoparticules, et aucun dépôt ne se forme sur l'extrémité de ces canalisations12 et 13. According to a preferred embodiment of the invention, the pipe 13 for supplying cold water and the pipe 12 for supplying the saline solution are concentric. The difference in temperature between the saline solution 2 and the cold water 3 on the one hand, and the cold water 3 and the superheated water 1 on the other hand causes the formation of a cold water jacket 4 which spreads in the middle after the end of the cold water supply pipe. As a result, the contact between the saline solution 2 and the superheated water 1 takes place in the mixing device after the end. supply lines 12 of saline solution and 13 of cold water. No contact takes place between these pipes 12 and 13 is the reaction medium consisting of the mixture of the saline solution and the superheated water before reaction between them to form the nanoparticles, and no deposit is formed on the end of these pipes12 and 13.
Dans un autre développement de l'invention, la réaction entre la solution saline 2 et l'eau surchauffée 1 est modifiée par l'introduction dans le flux d'eau froide 3 d'au moins un composé modificateur de pH choisi parmi l'ammoniac, les aminés de formule R-NH2, l'urée et les acides organiques, et notamment l'acide acétique, l'acide lactique et l'acide oxalique. In another development of the invention, the reaction between the saline solution 2 and the superheated water 1 is modified by introducing into the stream of cold water 3 at least one pH-modifying compound chosen from ammonia amines of formula R-NH 2, urea and organic acids, and in particular acetic acid, lactic acid and oxalic acid.
Selon un autre développement de l'invention, l'eau froide 3 est additionnée d'un composé carburant dans l'eau surchauffée et choisi parmi les alcools et les cétones. Ce composé carburant est oxydé au contact entre le flux d'eau froide 3 et l'eau surchauffée 1 , forme du dioxyde de carbone CO2 dans une réaction fortement exothermique qui entraine une augmentation de la température du milieu réactionnel. According to another development of the invention, cold water 3 is added with a fuel compound in superheated water and chosen from alcohols and ketones. This fuel compound is oxidized on contact between the flow of cold water 3 and superheated water 1, carbon dioxide form CO2 in a highly exothermic reaction which causes an increase in the temperature of the reaction medium.
Claims
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15790864.1A EP3215263A1 (en) | 2014-11-03 | 2015-10-26 | Preparation of nanoparticles by treatment of a solution in a hydrothermal medium |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1402496A FR3027822A1 (en) | 2014-11-03 | 2014-11-03 | PREPARATION OF NANOPARTICLES BY TREATING A SOLUTION IN A HYDROTHERMAL ENVIRONMENT |
| FRFR1402496 | 2014-11-03 |
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| Publication Number | Publication Date |
|---|---|
| WO2016071143A1 true WO2016071143A1 (en) | 2016-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2015/074777 Ceased WO2016071143A1 (en) | 2014-11-03 | 2015-10-26 | Preparation of nanoparticles by treatment of a solution in a hydrothermal medium |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3215263A1 (en) |
| FR (1) | FR3027822A1 (en) |
| WO (1) | WO2016071143A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997029050A1 (en) * | 1996-02-08 | 1997-08-14 | Aerojet-General Corporation | Injector for scwo reactor |
| WO2004037753A1 (en) * | 2002-10-21 | 2004-05-06 | Exxonmobil Chemical Patents Inc. | Method and system for reducing decomposition byproducts in a methanol to olefin reactor system |
| WO2005077505A2 (en) * | 2004-02-11 | 2005-08-25 | The University Of Nottingham | Counter current mixing reactor |
| FR2948034A1 (en) * | 2009-07-20 | 2011-01-21 | Centre Nat Rech Scient | PARTICLE SYNTHESIS THERMOHYDROLYSIS OF MINERAL PRECURSORS |
| US20120055285A1 (en) * | 2010-09-01 | 2012-03-08 | Directa Plus S.R.L. | Multiple feeder reactor for the production of nano-particles of metal |
-
2014
- 2014-11-03 FR FR1402496A patent/FR3027822A1/en not_active Withdrawn
-
2015
- 2015-10-26 WO PCT/EP2015/074777 patent/WO2016071143A1/en not_active Ceased
- 2015-10-26 EP EP15790864.1A patent/EP3215263A1/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997029050A1 (en) * | 1996-02-08 | 1997-08-14 | Aerojet-General Corporation | Injector for scwo reactor |
| WO2004037753A1 (en) * | 2002-10-21 | 2004-05-06 | Exxonmobil Chemical Patents Inc. | Method and system for reducing decomposition byproducts in a methanol to olefin reactor system |
| WO2005077505A2 (en) * | 2004-02-11 | 2005-08-25 | The University Of Nottingham | Counter current mixing reactor |
| FR2948034A1 (en) * | 2009-07-20 | 2011-01-21 | Centre Nat Rech Scient | PARTICLE SYNTHESIS THERMOHYDROLYSIS OF MINERAL PRECURSORS |
| US20120055285A1 (en) * | 2010-09-01 | 2012-03-08 | Directa Plus S.R.L. | Multiple feeder reactor for the production of nano-particles of metal |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3215263A1 (en) | 2017-09-13 |
| FR3027822A1 (en) | 2016-05-06 |
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