EP0155876A1 - Method and installation for obtaining solutions with a high percentage of dissolved gas; solutions obtained - Google Patents

Method and installation for obtaining solutions with a high percentage of dissolved gas; solutions obtained Download PDF

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EP0155876A1
EP0155876A1 EP85400353A EP85400353A EP0155876A1 EP 0155876 A1 EP0155876 A1 EP 0155876A1 EP 85400353 A EP85400353 A EP 85400353A EP 85400353 A EP85400353 A EP 85400353A EP 0155876 A1 EP0155876 A1 EP 0155876A1
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Prior art keywords
pressure
gas
temperature
under
dissolution
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EP85400353A
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German (de)
French (fr)
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EP0155876B1 (en
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Jean-Louis Pean
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20—Mixing gases with liquids
    • B01F23/29—Mixing systems, i.e. flow charts or diagrams

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  • the present invention relates to a process for obtaining solutions with a high content of dissolved gas, the solutions obtained by this process and an installation for implementation,
  • a process has been found which makes it possible to obtain a regular oroduction of a solvent / carbon dioxide mixture which can reach high concentrations of 25 to 30% by weight, at a temperature in the region of 20 ° C. and at a pressure lower than the vapor pressure of carbon dioxide at the same temperature.
  • hydrochlorofluorinated hydrocarbon mixture with a high concentration of carbon dioxide is compressed under high pressure for their subsequent use.
  • chlorofluorocarbons suitable for carrying out the process are the products known under the trademark "Freon”, in particular “dichlorodifluoroinethane CCl 2 F 2 ", designated under the trademark "Freon 12".
  • the compressed “Freon” is sub-cooled in the cold exchanger called the cooler exchanger (5) on the inlet pipe to "Freon” (4).
  • the inlet temperature varies between - 10 ° C and + 50 ° C, and the minimum outlet temperature is - 10 ° C; the instantaneous flow being 500 kg / hour.
  • the cold exchanger on the pipe is bathed in a thermostatically controlled bath (6) of a refrigeration unit (7) which can lower the temperature down to - 10 ° C.
  • the temperature of the thermostatically controlled bath is controlled and regulated by means of the temperature regulator (8).
  • the sub-cooled “Freon” circulates inside the insulated pipe (9), crosses the valve (10) controlled by the level regulator (11), liquid hydrocarbon in the dissolution zone, then always under insulated pipe is routed to the spray nozzle (12 A), located at the top of the saturator (13).
  • This spray nozzle can be of any suitable type, such as the swirl type with full cone and impact diameter of 15 to 50 cm, with a high flow rate of 500 kg / hour under a differential pressure of 10 bars.
  • the saturator body (13), the volume of which is a function of the desired flow rate, can be of cylindrical shape, for example 2 meters high and 200 millimeters in diameter, resistant to a test pressure of 50 bars.
  • the saturator is: fitted with pressure control means via the display manometer and low and high pressure alarm pressure switch (16) and the purge valve and safety valve (17), calibrated at 35 bars, both located at the top of the saturator (13). It is also provided with means for controlling the temperature of the liquid in the saturator, by means of the temperature probe (18); as well as means for controlling and regulating the level of the "Freon", in the saturator, by means of the level regulator (11).
  • the saturator is surrounded by thermal insulation (13a).
  • Carbon dioxide circulates in line (23), fitted with a non-return valve or a high anti-siphon point, shown in (24), the two means being able to be associated.
  • This pipe (24) penetrates to the lower part of the saturator body (13) where it is extended by a perforated ramp (25) intended for the boiling under pressure of carbon dioxide in the liquid “Freon” (26).
  • the temperature of the "Freon” solution containing C0 2 is + 10 ° C.
  • This solution with a high concentration of dissolved C0 2 is drawn off by the heat-insulated pipe (27), at the bottom of the saturator (13).

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The solution-saturation (13,26) is produced in a countercurrent manner under low pressure of the gas (19) in a chlorofluorohydrocarbon (1) which is sprayed (12A,12B), previously compressed (3), and supercooled (5) to a temperature in the neighborhood of or lower than the temperature chosen for the chlorofluorohydrocarbon dissolved gas mixture at the outlet (30), the first gas-liquid chlorofluorohydrocarbon contact being effected by a bubbling (25) under pressure of the gas in the chlorofluorohydrocarbon (26) under conditions of temperature and pressure lower than the critical conditions, with a strict thermal regulation (31) throughout the dissolving stage so as to effect it below the critical conditions, thereafter the chlorofluorohydrocarbon mixture having a high content of dissolved gas is compressed (28A,28B) under high pressure. Application in the chlorofluorohydrocarbon solutions and in particular dichlorodifluoromethane having a high content of carbon dioxide.

Description

La présente invention concerne un procédé d'obtention de solutions à forte teneur en gaz dissous, les solutions obtenues par ce procédé et une installation de mise en oeuvre,The present invention relates to a process for obtaining solutions with a high content of dissolved gas, the solutions obtained by this process and an installation for implementation,

Depuis très longtemps on a tenté de mettre au point une technique sûre et efficace permettant l'emmagasinage de la quantité maximale d'un gaz dans un liquide ; en vue d'une production régulière du mélange solvant-gaz à forte concentration de celui-ci, à une température voisine de l'ambiante et à une pression inférieure à la tension de vapeur du gaz à cette même température.For a very long time, attempts have been made to develop a safe and effective technique allowing the storage of the maximum quantity of a gas in a liquid; for regular production of the solvent-gas mixture at a high concentration thereof, at a temperature close to ambient and at a pressure below the vapor pressure of the gas at this same temperature.

Parmi les produits caractérisés par une forte solubilité et une forte réaction exothermique, ou ceux répondant à la deuxième caractéristique, on peut citer l'anhydride carbonique et le protoxyde d'azote.Among the products characterized by high solubility and a strong exothermic reaction, or those meeting the second characteristic, there may be mentioned carbon dioxide and nitrous oxide.

En vue de la dissolution de l'anhydride carbonique à forte concentration, on a proposé la compression de ce gaz sous haute température, c'est-à-dire sous 150 bars entre 150 à 200° C, dans un solvant du type hydrocarburechlorofluoré, désigné commercialement sous la marque " Fréon " . Le mélange anhydride carbonique dans le Fréon est réglé par débitmètre piloté, cependant dans ces conditions dites en supercritique,la densité de l'anhydride carbonique évolue très rapidement en fonction de la pression et les contrôles par pression en sont d'autant plus imprécis.With a view to dissolving carbon dioxide at high concentration, it has been proposed to compress this gas under high temperature, that is to say under 150 bars between 150 and 200 ° C., in a solvent of the hydrochlorofluorocarbon type, commercially designated under the brand name "Freon". The carbon dioxide mixture in the Freon is regulated by a controlled flow meter, however under these conditions known as supercritical, the density of carbon dioxide changes very quickly as a function of the pressure and the pressure controls are all the more imprecise.

Aussi, on a recherché la réalisation du mélange solvant/ anhydride carbonique, tel "Tréon"/anhydride carbonique en conservant toujours de l'anhydride carbonique gaz détendu à partir de sa tension de vapeur saturante, donc inférieure aux conditions critiques.Also, we sought the realization of the solvent / carbon dioxide mixture, such as "Treon" / carbon dioxide by always retaining carbon dioxide gas expanded from its saturated vapor pressure, therefore below critical conditions.

Selon la technique antérieure, la concentration des solutions en CO2 ne dépasse pas en général une quinzaine de pourcents .According to the prior art, the concentration of CO2 solutions does not generally exceed fifteen percent.

Il a été trouvé un procédé permettant d'obtenir une oroduc- tion régulière d'un mélange solvant/anhydride carbonique pouvant at- teindre de fortes concentrations de 25 à 30 % en poids, à une température voisine de 20°C et à une pression inférieure à la tension de vapeur de l'anhydride carbonique à cette même température.A process has been found which makes it possible to obtain a regular oroduction of a solvent / carbon dioxide mixture which can reach high concentrations of 25 to 30% by weight, at a temperature in the region of 20 ° C. and at a pressure lower than the vapor pressure of carbon dioxide at the same temperature.

Selon ce procédé, on réalise la saturation sous pression suboritique de l'anhydride carbonique dans un hydrocarburechlorofluoré par pulvérisation de l'hydrocarburechlorcfluoré comprimé, sous-refroidi à une température voisine ou inférieure à celle choisie pour le mélange CO2-/hydrocarburechlorofluoré en sortie, à contre-courant de l'anhydride carbonique, le premier contact gaz-liquide étant réalisé par dëbullage sous pression subcritique de l'anhydride carbonique dans l'hydrocarbure chlorofluoré, dans des conditions de température et pression inférieures sur conditions critiques, avec régulation thermique rigoureuse pendant toute la phase de dissolution, de manière à l'effectuer en dessous des conditions critiques.According to this process, the carbon dioxide anhydride is saturated under suboritic pressure in a chlorofluorocarbon by spraying compressed compressed hydrocarbon-lorcfluorinated, sub-cooled to a temperature close to or lower than that chosen for the CO 2 - / chlorofluorocarbon mixture at the outlet, against the flow of carbon dioxide, the first gas-liquid contact being made by boiling under subcritical pressure of carbon dioxide in the chlorofluorocarbon, under conditions of temperature and pressure lower on critical conditions, with rigorous thermal regulation during all the phase of dissolution, so as to carry out it under critical conditions .

Ensuite le mélange hydrocarburechlorofluoré à forte concentration en anhydride carbonique est comprimé sous haute-pression en vue de leur utilisation ultérieure.Then the hydrochlorofluorinated hydrocarbon mixture with a high concentration of carbon dioxide is compressed under high pressure for their subsequent use.

La pulvérisation donne une très grande surface liquide- gaz pour le contact liquide/gaz.Spraying gives a very large liquid-gas surface for liquid / gas contact.

L'hydrocarburechlorofluoré comprimé est sous-refroidi par rapport à la pression environnante, bien en dessous de la température d'équilibre. Il apparait avantageux de cormprimer le dit hydrocarbure

Figure imgb0001
The compressed chlorofluorocarbon is sub-cooled relative to the surrounding pressure, well below the equilibrium temperature. It seems advantageous to cormpress the said hydrocarbon
Figure imgb0001

Les hydrocarburechlorofluorés convenant à la mise en oeuvre du procédé, sont les produits connus sous la marque commerciale "Fréon", en particulier le "dichlorodifluoroinéthane CCl2F2", désigné sous la marque "Fréon 12".The chlorofluorocarbons suitable for carrying out the process are the products known under the trademark "Freon", in particular "dichlorodifluoroinethane CCl 2 F 2 ", designated under the trademark "Freon 12".

Afin d'accroître le taux de saturation du "Fréon" en anhydride carbonique, il est apparu avantageux de recycler une fraction de "Fréon" contenant de l'anhydride carbonique dissous vers la pulvérisation. après compression et maintien en température dans des conditions identiques à celles de la pulvérisation de l'hydrocarburechlorofluoré pur.In order to increase the saturation rate of "Freon" with carbon dioxide, it has appeared advantageous to recycle a fraction of "Freon" containing dissolved carbon dioxide towards the spray. after compression and temperature maintenance under conditions identical to those of the spraying of pure chlorofluorocarbon.

Le débullage ascendant de l'anhydride carbonique, réalisé dans la partie inférieure de la phase de saturation, est effectué sous une pression subcritique de préférence proche de la pression critique.The upward boiling of carbon dioxide, carried out in the lower part of the saturation phase, is carried out under a subcritical pressure preferably close to the critical pressure.

Au cours de la phase de saturation, la tempéraure est fixée entre -10 -20°C de préférence inférieure à la température ambiante, et

Figure imgb0002
circuit-fermé, le débit de circulation du fluide caloporteur à l'intérieur de la zone de dissolution-saturation étant régulé par la température de la dite zone.During the saturation phase, the temperature is fixed between -10 -20 ° C, preferably lower than room temperature, and
Figure imgb0002
circuit closed, circulation of the coolant flow rate within the dissolution-saturation zone being regulated by the temperature of said zone.

La réaction exothermique de dissolution étant très importante et la température du vrac dichlorodifluorométhane pouvant at- teindre + 50°C, on comprend la nécessité du refroidissement de l'hydrocarbure, de manière à l'introduire dans la zone de saturation à température voisine ou inférieure à celle fixée pour le mélange à sa sortie de la zone de dissolution-saturation.As the exothermic dissolution reaction is very important and the temperature of the bulk dichlorodifluoromethane can reach + 50 ° C, we understand the necessity of cooling the hydrocarbon, so as to introduce it into the saturation zone at neighboring or lower temperature. to that fixed for the mixture at its exit from the dissolution-saturation zone.

Les solutions à très forte concentration en anhydride carbonique, de 25 à 30 % en poids, sont particulièrement appréciées dans de nombreux domaines d'application, notamment dans celui dit du foisonnement des mousses plastiques, de la fabrication des plastiques expansés et du caoutchouc mousse où elles conduisent à d'excellents résultats; également dans le domaine technique des aérosols, dans la surpressurisation d'un liquide à faible tension de vapeur, et dans le domaine des mélanges liquide-gaz : carbonatation, flottation etc..Solutions with a very high concentration of carbon dioxide, from 25 to 30% by weight, are particularly appreciated in many fields of application, in particular in the so-called expansion of plastic foams, the manufacture of expanded plastics and foam rubber where they lead to excellent results; also in the technical field of aerosols, in the overpressurization of a liquid with low vapor pressure, and in the field of liquid-gas mixtures: carbonation, flotation etc.

Le procédé de l'invention est avantageusement mis en oeuvre dans une installation du type représenté sur la figure du dessin annexé, les températures et pressions indiquées sont représentatives du "Fréon 12".The process of the invention is advantageously implemented in an installation of the type shown in the figure of the appended drawing, the temperatures and pressures indicated are representative of "Freon 12".

L'installation comprend essentiellement deux échangeurs froids; un échangeur refroidisseur en amont du saturateur et un échangeur-régulateur interne au saturateur.The installation essentially comprises two cold exchangers; a cooling exchanger upstream of the saturator and an internal exchanger-regulator in the saturator.

Le "Fréon" est stocké, en vrac à température ambiante, dans le réservoir de stockage (1), il traverse une pompe (2) avec clapet à décharge sous 15 bars, il est ensuite repris par la pompe-de surpression (3) double effet à piston. Cette pompe peut fonctionner en débitant 500 kg/heure, soit 375 litres/heure de "Fréson 12" (densité F 12 = 1,32 à 20°C), avec une pression de refoulement de 40 bars.The "Freon" is stored, in bulk at room temperature, in the storage tank (1), it passes through a pump (2) with relief valve under 15 bars, it is then taken up by the booster pump (3) double piston effect. This pump can operate by delivering 500 kg / hour, or 375 liters / hour of "Fréson 12" (density F 12 = 1.32 at 20 ° C), with a discharge pressure of 40 bar.

Le ."Fréon" comprimé est sous-refroidi dans l'échangeur froid dit échangeur refroidisseur (5) sur la canalisation d'arrivée dn "Fréon" (4). La température d'entrée varie entre - 10° C et + 50° C, et la température de sortie minimale est de - 10°C ; le débit instantané étant de 500 kg/heure. L'échangeur froid sur canalisation baigne dans un bain thermostaté (6) d'un groupe frigorifique (7) pouvant abaisser la température jusqu'à - 10°C. La température du bain thermostaté est contrôlée et régulée par l'intermédiaire du régulateur de température (8).The compressed "Freon" is sub-cooled in the cold exchanger called the cooler exchanger (5) on the inlet pipe to "Freon" (4). The inlet temperature varies between - 10 ° C and + 50 ° C, and the minimum outlet temperature is - 10 ° C; the instantaneous flow being 500 kg / hour. The cold exchanger on the pipe is bathed in a thermostatically controlled bath (6) of a refrigeration unit (7) which can lower the temperature down to - 10 ° C. The temperature of the thermostatically controlled bath is controlled and regulated by means of the temperature regulator (8).

Le "Fréon" sous-refroidi circule à l'intérieur de la canalisation calorifugée (9), traverse la vanne (10) commandée par le régulateur de niveau (11), de l'hydrocarbure liquide dans la zone de dissolution, puis toujours sous canalisation calorifugée est acheminé vers la buse de pulvérisation (12 A), située à la partie supérieure du saturateur (13). Cette buse de pulvérisation peut être de tout type convenable, tel du type tourbillonnaire à cône plein et à impact de diamètre de 15 à 50 cm, d'un débit élevé de 500 kg/heure sous une pression différentielle de 10 bars.The sub-cooled "Freon" circulates inside the insulated pipe (9), crosses the valve (10) controlled by the level regulator (11), liquid hydrocarbon in the dissolution zone, then always under insulated pipe is routed to the spray nozzle (12 A), located at the top of the saturator (13). This spray nozzle can be of any suitable type, such as the swirl type with full cone and impact diameter of 15 to 50 cm, with a high flow rate of 500 kg / hour under a differential pressure of 10 bars.

Le "Fréon" recyclé est recomprimé dans la pompe de recyclage (14) donnant une pression différentielle de 10 bars et un débit de 500 kg/heure, puis il est remonté dans la canalisation calorifugée (15) vers la buse de pulvérisation (12B) du même type que la buse de pulvérisation (12 A) et également située à la partie supérieure du corps du saturateur (13).The recycled "Freon" is recompressed in the recycling pump (14) giving a differential pressure of 10 bars and a flow rate of 500 kg / hour, then it is reassembled in the heat-insulated pipe (15) towards the spray nozzle (12B) of the same type as the spray nozzle (12 A) and also located at the upper part of the saturator body (13).

La corps du saturateur (13) dont le volume est fonction du débit désiré, peut être de forme cylindrique, par exemple de hauteur 2 mètres et diamètre 200 millimètres, résistant à une pression d'épreuve de 50 bars. Le saturateur est: muni des moyens de contrôle de pression par l'intermédiaire du manomètre de visualisation et pressostat d'alarme basse et haute pression (16) et de la vanne de purge et soupape de sécurité (17), tarée à 35 bars, situés l'un et l'autre à la partie supérieure du saturateur (13). Il est également muni des moyens de contrôle de la température du liquide du saturateur, par l'intermédiaire de la sonde de température (18) ; ainsi que des moyens de contrôle et régulation du niveau du "Fréon", dans le saturateur, par l'intermédiaire du régulateur-de niveau(11) . Le saturateur est entouré par le calorifugeage (13a).The saturator body (13), the volume of which is a function of the desired flow rate, can be of cylindrical shape, for example 2 meters high and 200 millimeters in diameter, resistant to a test pressure of 50 bars. The saturator is: fitted with pressure control means via the display manometer and low and high pressure alarm pressure switch (16) and the purge valve and safety valve (17), calibrated at 35 bars, both located at the top of the saturator (13). It is also provided with means for controlling the temperature of the liquid in the saturator, by means of the temperature probe (18); as well as means for controlling and regulating the level of the "Freon", in the saturator, by means of the level regulator (11). The saturator is surrounded by thermal insulation (13a).

L'anhydride carbonique est stocké en vrac dans le réservoir de stockage hante pression (19), maintenu sous 40 bars au minimum. 0°C la pression est de 40 bars, à-5°C elle se situe à 30 bars, il est donc prévu un réchauffage par température négative en hiver, par l'intermédiaire de l'épingle chauffante (20). L'anhydride carbonique délivré sous une pression d'au moins 40 bars passe à travers le réchauffeur anti-givrage (21) du détendeur C02 (22). La pression de l'anhydride carbonique en amont du détendeur est au moins de 40 bars et en aval de 30 bars ± 0,5 bar, le détendeur (22) fonctionne à débit instantané de 120 kg/heure (60 m3/heure). L'anhydride carbonique circule dans la canalisation (23), munie d'un clapet anti-retour ou d'un point haut anti-siphon, figuré en (24), les deux moyens pouvant âtre associés. Cette canalisation (24) pénètre à la partie inférieure du corps du saturateur (13) où elle se prolonge par une rampe perforée (25)destinée au débullage sous-pression de l'anhydride carbonique dans le "Fréon" liquide (26). La température de la solution de "Fréon" contenant du C02 est de + 10°C. Catte solution à forte concentration en C02 dissous est soutirée par la canalisation calorifugée (27), à la la partie inférieure du saturateur (13). Une fraction de cette solution saturée en CO2 est prélevée vers le recyclage via la pompe (14), et l'autre fraction destinée à l'utilisation est comprimée par les deux pompes de reprise en parallèle (28A) et (283), ayant chacune un débit minimum de 150 kg/heure, sous une pression élevée de refoulement, ajustée selon la demande de l'utilisateur par exemple de 150 bars, et sur la conduite d'utilisation (30), véhiculant le mélange vers l'utilisation maintenant le CO2 en phase dissoute, on a intercalé un accumulateur anti-coup de bélier (29).The carbon dioxide is stored in bulk in the haunted pressure storage tank (19), maintained at a minimum of 40 bars. 0 ° C the pressure is 40 bars, at -5 ° C it is located at 30 bars, it is therefore planned to reheat by negative temperature in winter, by means of the heating pin (20). The carbon dioxide delivered under a pressure of at least 40 bars passes through the anti-icing heater (21) of the C0 2 regulator (22). The carbon dioxide pressure upstream of the regulator is at least 40 bars and downstream of 30 bars ± 0.5 bar, the regulator (22) operates at an instantaneous flow rate of 120 kg / hour (60 m3 / hour). Carbon dioxide circulates in line (23), fitted with a non-return valve or a high anti-siphon point, shown in (24), the two means being able to be associated. This pipe (24) penetrates to the lower part of the saturator body (13) where it is extended by a perforated ramp (25) intended for the boiling under pressure of carbon dioxide in the liquid "Freon" (26). The temperature of the "Freon" solution containing C0 2 is + 10 ° C. This solution with a high concentration of dissolved C0 2 is drawn off by the heat-insulated pipe (27), at the bottom of the saturator (13). A fraction of this saturated CO 2 solution is taken for recycling via the pump (14), and the other fraction intended for use is compressed by the two parallel recovery pumps (28A) and (283), having each a minimum flow rate of 150 kg / hour, under a high discharge pressure, adjusted according to user demand for example 150 bars, and on the use line (30), conveying the mixture to use now CO 2 in dissolved phase, an anti-water hammer accumulator (29) was inserted.

Le saturateur est en outre équipé d'un échangeur interne dit échangeur+régulateur (31) en vue de compenser la réaction exothermique de dissolution du C02 dans le "Fréon" ; Cet échangeur interne étant situé pour sa partie inférieure au-dessus de la rampe de débullage du C02 (25) et pour sa partie supérieure en dessous du niveau liquide maintenu par le régulateur (11).The saturator is also equipped with an internal exchanger known as an exchanger + regulator (31) in order to compensate for the exothermic reaction of dissolution of C0 2 in the "Freon"; This internal exchanger being located for its lower part above the ramp for boiling the C0 2 (25) and for its upper part below the liquid level maintained by the regulator (11).

L'échange calorifique se fait par l'intermédiaire du fluide caloporteur constituant le bain thermostaté (6), maintenu à - 10°C par le groupe frigorifique (7). Le courant de fluide caloporteur circulant en circuit fermé calorifugé entre le groupe frigorifique et le saturateur, quitte le bain thermostaté par la canalisation (32) calc- rifugée jusqu'à son raccordement à la partie inférieure de l'échangeur interne (31) situé au-dessus de la rampe de débullage du CO, (25). Après un échange calorifique dans le sens ascendant, le fluide caloporteur après circulation dans la conduite (33), passage dans le système vanne-triple (34) est relancé par les pompes de circulation (35A) et (35B) en vue de son recyclage par la canalisation calorifugée (36) au bain thermostaté (6). Le débit de circulation du fluide caloporteur à l'intérieur de l'échangeur interne (31) est régulé par la température du milieu liquide dans le saturateur, indiquée par la sonde de température (18) et au moyen du régulateur (37) .The heat exchange takes place via the heat transfer fluid constituting the thermostatically controlled bath (6), maintained at -10 ° C by the refrigeration unit (7). The current of heat transfer fluid circulating in a closed circuit insulated between the refrigeration unit and the saturator, leaves the thermostated bath through the calcified pipe (32) until it is connected to the lower part of the internal exchanger (31) located at -above the CO bubble, (25). After a heat exchange in the upward direction, the heat transfer fluid after circulation in the line (33), passage in the valve-triple system (34) is restarted by the circulation pumps (35A) and (35B) for recycling by the thermally insulated pipe (36) to the thermostatically controlled bath (6). The circulation rate of the heat transfer fluid inside the internal exchanger (31) is regulated by the temperature of the liquid medium in the saturator, indicated by the temperature probe (18) and by means of the regulator (37).

Claims (10)

1. Procédé d'obtention de solutions du type hydrocarburechlorofluoré à forte teneur en gaz dissous, caractérisé en ce qu'on réalise la dissolution-saturation à contre-courant, sous pression subcritique du gaz dans un hydrocarburechlorofluoré, préalablement comprimé sous pression, et sous-refroidi à une température voisine ou inférieure à celle choisie pour le mélange gaz dissous-hydrocarbure chlorofluoré en sortie, l'hydracarburechlorofluoré étant pulvérisé dans la zone de dissolution maintenue sous pression du gaz, le premier contact du gaz avec l'hydrocarbure liquide étant réalisé par débullage sous pression subcritique du gaz dans l'hydrocarburechlorofluoré, dans des conditions de température et pression inférieures aux conditions critiques, avec régulation thermique rigoureuse pendant toute la phase dissolution-saturation, de manière à ce qu'elle soit effectuée en dessous des conditions critiques.1. A process for obtaining solutions of the hydrochlorofluorinated hydrocarbon type with a high content of dissolved gas, characterized in that the dissolution-saturation is carried out against the current, under subcritical pressure of the gas in a hydrochlorofluorinated hydrocarbon, previously compressed under pressure, and under -chilled to a temperature close to or lower than that chosen for the dissolved gas-chlorofluorinated hydrocarbon mixture at the outlet, the hydroacarburechlorofluorinated being sprayed into the dissolution zone maintained under gas pressure, the first contact of the gas with the liquid hydrocarbon being produced by bubbling under subcritical pressure of the gas in chlorofluorocarbon, under temperature and pressure conditions below the critical conditions, with rigorous thermal regulation throughout the dissolution-saturation phase, so that it is carried out below the critical conditions . 2. Procédé d'obtention de solutions à forte teneur en gaz dissous, selon la revendication 1, caractérisé en ce que le gaz soluble est l'anhydride carbonique et l'hydrocarburechlorofluoré le dichlorodifluorométhane.2. Method for obtaining solutions with a high content of dissolved gas, according to claim 1, characterized in that the soluble gas is carbon dioxide and the hydrochlorofluorocarbon dichlorodifluoromethane. 3.Procédé d'obtention de solutions à forte teneur en gaz dissous selon la revendication 2, caractérisé en ce que le dichlorodifluorométhane est préalablement comprimé pour le pulvériser sous une pression supérieure d'environ 10 bars à celle régnant dans la zone haute de dissolution-saturation, et en le sous-refroidissant à une température inférieure de 10 à 20°C par rapport à la température de la solution saturée en sortie de la dite zone de dissolution-saturation, l'anhydride carbonique étant débullé dans la zone inférieure de dissolution-saturation sous une pression subcritique, de préférence proche de la pression critique, la température étant maintenue, au cours de la phase de dissolution de l'anhydride carbonique dans le dichlorodifluorométhane, en subcritique de préférence inférieure à la température ambiante par l'intermédiaire d'une régulation thermique interne au moins de l'ordre du degré,au moyen d'un fluide caloporteur, 3. Process for obtaining solutions with a high content of dissolved gas according to claim 2, characterized in that the dichlorodifluoromethane is previously compressed to spray it under a higher pressure of about 10 bars than that prevailing in the high dissolution zone - saturation, and by sub-cooling it to a temperature 10 to 20 ° C lower than the temperature of the saturated solution leaving the said dissolution-saturation zone, the carbon dioxide being bubbled into the lower dissolution zone -saturation under a subcritical pressure, preferably close to the critical pressure, the temperature being maintained, during the phase of dissolution of carbon dioxide in dichlorodifluoromethane, in subcritical preferably below room temperature via d '' internal thermal regulation at least of the order of a degree, by means of a heat transfer fluid, 4. Procédé d'obtention de solutions à forte teneur en gaz dissous selon une quelconque des revendications 1 à 3, caractérisé en ce qu'une fraction du mélange solvant-hydrocarburechlorofluoré contenant du gaz dissous est recyclé, après compression et renvoyé à la pulvérisation dans des conditions identiques à la pulvérisation de l'hydrocarburechlorofluoré.4. Method for obtaining solutions with a high content of dissolved gas according to any one of claims 1 to 3, characterized in that a fraction of the solvent-hydrocarbon-chlorofluorinated mixture containing dissolved gas is recycled, after compression and returned to spraying in conditions identical to the spraying of chlorofluorocarbon. 5. Procédé d'obtention de solutions à forte teneur en gaz dissous selon une quelconque des revendications 1 à 4, caractérisé en ce que le sous-refroidissement de l'hydrocarburechlorofluoré et la régulation de la température au cours de la phase de dissolution du gaz sont assurés par l'intermédiaire d'un même fluide caloporteur, circulant en circuit fermé, le débit de circulation du fluide caloporteur à l'intérieur de la zone de dissolution-saturation étant régulé par la température dans la dite zone.5. Method for obtaining solutions with a high dissolved gas content according to any one of claims 1 to 4, characterized in that the sub-cooling of the chlorofluorocarbon and the regulation of the temperature during the phase of dissolution of the gas are provided by means of the same heat transfer fluid, circulating in a closed circuit, the flow rate of circulation of the heat transfer fluid inside the dissolution-saturation zone being regulated by the temperature in said zone. 6. Procédé d'obtention de solutions à forte teneur en gaz dissous selon une quelconque des revendications 1 à 5, caractérisé en ce que les solutions mélange hydrocarburechlorofluoré à forte teneur en gaz dissous sont comprimées sous haute pression.6. Method for obtaining solutions with a high content of dissolved gas according to any one of claims 1 to 5, characterized in that the solutions of hydrocarbon-chlorofluoric mixture with a high content of dissolved gas are compressed under high pressure. 7. Procédé d'obtention de solutions à forte teneur en gaz dissous selon une quelconque des revendications 1 à 6, caractérisé en ce que le procédé est continu.7. Method for obtaining solutions with a high content of dissolved gas according to any one of claims 1 to 6, characterized in that the process is continuous. 8. Installation de mise en oeuvre du procédé selon une quelconque des revendications 1 à 7, caractérisée par deux échangeurs froids, un échangeur-refroidisseur (5) en amont du saturateur (13) et un échangeur-régulateur (31), avec les moyens de régulation thermique interne (18) au saturateur (13).8. Installation for implementing the method according to any one of claims 1 to 7, characterized by two cold exchangers, an exchanger-cooler (5) upstream of the saturator (13) and an exchanger-regulator (31), with the means internal thermal regulation (18) to the saturator (13). 9. Installation de mise en oeuvre du procédé selon la re- vendication 8, caractérisée en ce qu'elle comprend une pompe de surpression de l'hydrecarburechlorofluoré (3), un échangeur froid (5) sur la canalisation d'arrivée de l'hydrocarbure (4), d'un saturateur calorifugé (13), muni à sa partie supérieure de buses de pulvérisation de l'hydrocarbure (12A) (123), des moyens de contrôle de pression (16) et de sécurité (17), des moyens de contrôle de la température de la phase liquide de dissolution (18) et de niveau de celle-ci (11), d'un échangeur-régulateur interne (31), puis. à sa partie inférieure d'une rampe de débullage du gaz (25), et de la canalisation de soutirage (27) avec les pompes de reprise haute-pression (28A)(28B) vers l'utilisation et la pompe de recyclage (14) vers la buse de pulvérisation (123), en outre, elle comprend le circuit fermé de circulation du fluide caloporteur entre le bain thermostaté (6) muni d'un régulateur de température (8),inclus dans le groupe frigorifique (7) et l'échangeur-régulateur interne (31), ce circuit étant muni des moyens de circulation (34) (35a) (35b) et de régulation de débit (37).9. Installation for implementing the method according to resend ication 8, characterized in that it comprises a booster pump of the hydrecarburechlorofluoré (3), a cold exchanger (5) on the inlet pipe of the hydrocarbon (4), a heat-insulated saturator (13), provided at its upper part with nozzles for spraying the hydrocarbon (12A) (123), pressure control (16) and safety (17) means ), means for controlling the temperature of the liquid dissolution phase (18) and its level (11), an internal exchanger-regulator (31), then. at its lower part of a gas boiling ramp (25), and of the draw-off line (27) with the high-pressure recovery pumps (28A) (28B) towards the use and the recycling pump (14 ) towards the spray nozzle (123), in addition, it comprises the closed circuit for circulation of the heat transfer fluid between the thermostatic bath (6) provided with a temperature regulator (8), included in the refrigeration unit (7) and the internal exchanger-regulator (31), this circuit being provided with circulation means (34) (35a) (35b) and flow regulation (37). 10. Solutions obtenues par un procédé selon-une quelconque des revendications 1 à 7, utilisables dans le domaine des mousses plastiques, des plastiques erpansés et du caoutchouc mousse, dans le domaine technique des aérosols : surpressurisation d'un liquide à faible tension de vapeur, et dans le domaine .des mélanges liquide- gaz :carbonatation, flottation.10. Solutions obtained by a process according to any one of claims 1 to 7, usable in the field of foams plastics, expanded plastics and foam rubber, in the aerosol technical field: overpressurization of a liquid with low vapor pressure, and in the field of liquid-gas mixtures: carbonation, flotation.
EP85400353A 1984-02-29 1985-02-26 Method and installation for obtaining solutions with a high percentage of dissolved gas; solutions obtained Expired EP0155876B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85400353T ATE29678T1 (en) 1984-02-29 1985-02-26 METHOD AND EQUIPMENT FOR PREPARING SOLUTIONS WITH A HIGH PERCENTAGE OF DISSOLVED GAS; SO OBTAINED SOLUTIONS.

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FR8403130 1984-02-29
FR8403130A FR2560064A1 (en) 1984-02-29 1984-02-29 PROCESS FOR OBTAINING SOLUTIONS WITH HIGH GAS CONTENT, SOLUTIONS OBTAINED AND INSTALLATION FOR IMPLEMENTATION

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EP0155876B1 EP0155876B1 (en) 1987-09-16

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EP (1) EP0155876B1 (en)
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AT (1) ATE29678T1 (en)
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DE (1) DE3560616D1 (en)
ES (1) ES8604236A1 (en)
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FR2642986A1 (en) * 1989-02-15 1990-08-17 Carboxyque Francaise Process and plant for producing a mixture of "freon" and carbon dioxide
FR2651151A1 (en) * 1989-02-15 1991-03-01 Carboxyque Francaise Process for the development and storage of a mixture of freon and carbon dioxide
WO1996014354A3 (en) * 1994-11-02 1997-02-13 Solvay Fluor & Derivate Foaming agents containing liquid carbon dioxide

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JPH0611512B2 (en) * 1986-06-19 1994-02-16 三井東圧化学株式会社 Method and apparatus for continuously producing foam sheet
US5112525A (en) * 1987-12-10 1992-05-12 Colgate-Palmolive Company Method for making a post-foaming gel
DE19754686A1 (en) * 1997-12-10 1999-06-17 Messer Griesheim Gmbh Method and device for introducing gas into a liquid
US6135433A (en) * 1998-02-27 2000-10-24 Air Liquide America Corporation Continuous gas saturation system and method
GB2541753A (en) * 2015-08-25 2017-03-01 Linde Ag A method of cryogenic chilling or cryogenic freezing of a product
CN112850973B (en) * 2021-03-05 2024-08-20 郑州大学 Modularized multi-stage area mineralization metallurgy system and treatment method
CN117983027B (en) * 2024-04-03 2024-06-11 潍坊欣泽希化工有限公司 Dynamic absorption device for hydrogen bromide acetic acid solution production and control method thereof

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FR2642986A1 (en) * 1989-02-15 1990-08-17 Carboxyque Francaise Process and plant for producing a mixture of "freon" and carbon dioxide
FR2651151A1 (en) * 1989-02-15 1991-03-01 Carboxyque Francaise Process for the development and storage of a mixture of freon and carbon dioxide
WO1996014354A3 (en) * 1994-11-02 1997-02-13 Solvay Fluor & Derivate Foaming agents containing liquid carbon dioxide
US6303667B1 (en) 1994-11-02 2001-10-16 Solvay Fluor Und Derivate Foaming agents containing liquid carbon dioxide

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DE3560616D1 (en) 1987-10-22
US4626376A (en) 1986-12-02
FR2560064A1 (en) 1985-08-30
ES540730A0 (en) 1986-01-16
JPS60210693A (en) 1985-10-23
EP0155876B1 (en) 1987-09-16
AU3908485A (en) 1985-09-05
ATE29678T1 (en) 1987-10-15
ES8604236A1 (en) 1986-01-16
AU573490B2 (en) 1988-06-09
CA1270745A (en) 1990-06-26

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