EP0921730A1 - Process and system of carbonation of liquids - Google Patents

Process and system of carbonation of liquids

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Publication number
EP0921730A1
EP0921730A1 EP97937553A EP97937553A EP0921730A1 EP 0921730 A1 EP0921730 A1 EP 0921730A1 EP 97937553 A EP97937553 A EP 97937553A EP 97937553 A EP97937553 A EP 97937553A EP 0921730 A1 EP0921730 A1 EP 0921730A1
Authority
EP
European Patent Office
Prior art keywords
liquid
carbonation
carbonator
stage
valve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97937553A
Other languages
German (de)
French (fr)
Inventor
Fernando Jorge Nunes De Almeida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP0921730A1 publication Critical patent/EP0921730A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L2/00Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
    • A23L2/52Adding ingredients
    • A23L2/54Mixing with gases

Definitions

  • the present invention relates to a new process of carbonation.
  • the invention also includes a suitable system for carrying out the new process, denoted by the term carbonator.
  • Carbonation is a process by means of which carbon dioxide, Co 2 , is incorporated into a product, usually in an aqueous liquid. It is used especially for the production of carbonated beverages, a general designation which includes carbonated waters, carbonated fruit juices, colas and carbonated cooling drinks in general, as well as carbonated wines.
  • the carbonated products may be for example water, mineral waters, aqueous solutions containing extracts of fruits or other vegetable extracts, especially of cola, tea or coffee, sugar or other sweeteners, caramel, citric acid, ascorbic acid, colorants and, generally in small concentrations, inorganic anions and cations such as bicarbonate, chloride, fluoride, sodium, calcium, potassium, magnesium, etc. They may also contain alcohol, in the case of wines, flavourings, colorants, thickeners, dispersants and solid products in suspension, normally vegetable fibres and fruit pulps or others. Naturally, for the preparation of beverages, all of the above-mentioned components or additives should be of alimentary grade.
  • carbonation may also be applied in other fields, for example for pH adjustment in liquids or others.
  • Carbonation is a complex process which comprises the physical phenomena of dispersal and dissolution of C0 2 in the liquid medium together with chemical phenomena of interaction of C0 2 first with the water, forming unstable carbonic acid, and subsequently with other components of the medium to be carbonated, giving rise to carbonates and other compounds which play a part in the fixation of C0 2 .
  • Carbonation processes are known at the present time and are very widely diffused in industry, principally in the food-industry sector and especially in the industry for the preparation of non-alcoholic beverages.
  • Saturators are devices in which a C0 diffuser is located in a reactor, generally of tubular form, into which a liquid to be carbonated is passed in a continuous manner. This diffusion is effected by causing gaseous C0 to pass under slight pressure through the diffuser, dispersing it throughout the liquid to be carbonated.
  • Diffusers are normally devices which have, in their terminal part in contact with the liquid, a porous plate which can be made from various materials, such as for example porous porcelain, porous metal plates, etc.
  • Porous tubes can also be used as diffusers, for example metal tubes which are inserted inside the saturator, normally of concentric tubular form.
  • the pressure of C0 2 should be sufficient to provide an adequate flow of C0 2 to overcome the resistance of the porous diffuser and the pressure of the particular fluid to be carbonated.
  • the saturator is of Venturi type and the C0 is introduced immediately upstream of the constriction or at the entry to it, thereby obtaining a more rapid incorporation owing to the variation in pressure caused by the Venturi effect.
  • a pressure vessel is used. In accordance with this technique, the vessel is charged with gaseous C0 up to a high pressure,
  • the liquid to be carbonated is introduced into the vessel by means of calibrated perforations which produce fine jets.
  • the intimate contact thus effected between the C0 present within the vessel and the liquid introduced promotes the incorporation of the C0 2 into the liquid.
  • J60087837 describes a system for the carbonation of liquids, especially beverages, in which gaseous C0 2 is atomized within a liquid under reduced pressure, a high efficiency of carbonation being claimed.
  • DE 4319526 describes an apparatus for carbonation which allows a uniform and controllable level of carbonation by using a control unit when C0 2 is introduced.
  • WO 9415489 describes a process of carbonation of mineral water in which, after a conventional carbonation with gaseous C0 2 , PET bottles are filled with the cooled water and a specific quantity of solid C0 2 is added to each bottle, these being closed as rapidly as possible. Clearly, this process is not suitable for industrial use.
  • DE 3634814 describes a method of carbonation of liquids, especially non-alcoholic beverages, in which gaseous C0 is added in a zone of low pressure from an injector.
  • DE 3431906 describes a system for the saturation of liquids with a gas, especially C0 , which makes use of a porous membrane.
  • EP-145918 describes a process for rapid carbonation of water by means of a controlled flow of gaseous C0 2 .
  • DD-211489 describes a system for the carbonation of liquids, for example lemonade, in which the C0 2 /air mixture is recycled, allowing an saving in the use of C0 .
  • WO 8400671 describes an automatic system for the carbonation of liquids for beverages, in which the introduction of gaseous C0 into the carbonation chamber is effected via a valve controlled automatically.
  • DE 3132706 describes a system for the carbonation of beverages in which the liquid for carbonation and the C0 are made to pass in contraflow through a series of storage tanks.
  • the production of sparkling wines by carbonation is the subject of processes described, for example, in SU 1082803 and SU 1124019, gaseous C0 being used in both cases.
  • Obtaining carbonated beverages for immediate use in restaurants or for domestic consumption is the subject for example of WO 9015011, EP-296570, GB 2186265, GB 2137894, BE- 898455, WO 8204243, GB 2097274, EP-59534, BE-878003, BE-877855 and EP-33157. All of these systems utilize gaseous C0 2 , introduced by various means and under different conditions into a stream of the liquid for carbonation when the latter is tapped from a storage reservoir into a receptacle for immediate consumption, for example into a glass.
  • the process of carbonation is influenced especially by the operating pressure, by the temperature and also by the pH in particular and by the composition in general of the liquid medium.
  • the pressure and temperature at which the carbonated product is going to be stored until the moment of use must also be taken into account, bearing in mind that this storage is normally effected in plastic, glass or metal, generally aluminium, containers.
  • These containers are sealed by crown pressure caps, by screw caps or, in the case of so-called cans, they are punched and equipped with devices for easy opening formed by a tear-away groove with a ringpull for the action of opening.
  • the greater part of the C0 2 is found in the carbonated product in equilibrium at a certain pressure, but can be easily liberated once this equilibrium is disturbed, usually by a reduction in the pressure, which may occur simply as a result of opening the container in which the carbonated product is stored under a slight pressure and of placing the liquid at atmospheric pressure.
  • the material of the container is partially permeable to C0 , as is the case with certain plastic materials used for bottles for beverages, there may be a tendency for a gradual loss of C0 over time.
  • All of the known industrial processes for carbonation of liquids have in common the fact that they are carried out in a single operation and make use of gaseous carbon dioxide. In general, to obtain an acceptable degree of carbon- ation the pressure of C0 2 should be elevated.
  • the improved processes referred to above cite pressures of 0.22 to 5.2 MPa or refer to "high pressure".
  • C0 2 defective fixation of C0 2 also represents an major disadvantage at the time of consumption.
  • the C0 2 tends to be released in the form of bubbles, which contributes to the flavour of the product.
  • the release is in general too rapid, which has the result that a beverage which is not consumed quickly does not ultimately give the same degree of satisfaction.
  • the subject of the present invention is a new process of carbonation which differs completely from the conventional processes described in terms of implementation and results.
  • a further subject of the invention is a suitable apparatus for implementing the new process, denoted by the term carbonator, and a system for industrial use in which the apparatus of the invention is linked to auxiliary devices which enable all of the operations to obtain carbonated liquids, especially carbonated beverages, to be carried out.
  • the new process of carbonation of the present invention may be used for all the cases in which use has been made hitherto of the conventional carbonation techniques described, especially for the production of carbonated beverages in general, carbonated waters, carbonated fruit juices, colas and other carbonated cooling drinks, as well as carbonated wines.
  • the use of the process of the present invention is not necessarily limited to the field of beverages .
  • the process of the present invention is characterized in that it comprises at least one stage of carbonation or of prior carbonation in which use is made not of gaseous carbon dioxide but of carbon dioxide in liquid form, thereby promoting dissolution of C0 throughout the liquid which it is intended to carbonate at a moderate pressure by means of the intimate contact of the liquid carbon dioxide with the liquid for carbonation atomized into fine droplets.
  • the liquid for carbonation and the liquid C0 2 are simultaneously atomized in a closed container which has suitable devices for the atomization of the liquid for carbonation and of the liquid
  • This container is termed a carbonator.
  • the process of the present invention can be carried out in two stages, a pre-carbonation and a subsequent post-carbonation, utilizing, in the pre-carbonation stage, carbon dioxide in liquid form as described above.
  • the liquid may then be subjected to a conventional post-carbonation, to complete the process.
  • the first stage of pre-carbonation is carried out in a container such as that described, in this case termed pre-carbonator, and the subsequent stage is carried out in a conventional post-carbonator .
  • This particular two-stage case is preferred when preparing carbonated beverages whose composition includes syrups, these being introduced for example in a mixer inserted between the pre-carbonator and the post-carbonator.
  • the new process of carbonation consists in the incorporation of C0 2 into a liquid for carbonation in a carbonation chamber, use being made, for this purpose, of liquid C0 2 which is brought into intimate contact with the aforementioned liquid at moderate pressure.
  • the C0 is atomized inside the chamber in which the liquid for carbonation is also atomized, so that the paths of the two fluids intersect.
  • the new process of carbonation consists in the incorporation of C0 2 into the liquid for carbonation in two consecutive stages carried out in two different chambers, namely pre-carbonation and final post-carbonation, liquid C0 2 being utilized in the first stage in the pre-carbonator in which it is brought into contact with the liquid for carbonation, preferably in such a manner that the streams of the two fluids intersect, as described.
  • the subsequent stage of final post- carbonation may be carried out in accordance with the conventional techniques of carbonation, except that the liquid for carbonation, which has previously been subjected to pre-carbonation, contains, already incorporated, an appreciable quantity of carbon dioxide, as a result of which the operation is in general more rapid and less critical than conventional carbonation.
  • the carbonator or pre-carbonator in accordance with the technique of the present invention is formed by a chamber or container in which there are different nozzles for injecting liquid C0 2 , on the one hand, and the liquid for carbonation on the other.
  • the liquid for carbonation is atomized by means of injectors in sufficient number for the volume which it is intended to treat. This atomization converges in the centre of the chamber.
  • a stream of liquid C0 2 which, under the working conditions of temperature and pressure, is ultimately converted into dry ice, i.e. into solid C0 2 in subdivided form and, in this case, finely divided form.
  • the stream of C0 2 intercepts the various atomizations of the liquid, cooling it and combining with it.
  • a constant injection of liquid C0 2 is created via the atomization apertures so as to form a vertical downward stream of C0 2 .
  • the C0 is converted immediately into dry ice even before coming into contact with the liquid for carbonation.
  • the liquid intended for carbonation is injected via the injectors arranged in several rows placed at various heights so as to form in the interior of the carbonator or of the pre- carbonator jets whose paths are initially horizontal, in such a way as also to atomize the liquid.
  • the jets of C0 2 and of the liquid for carbonation intersect, resulting in a fine dispersion or incorporation of the carbon dioxide into the liquid.
  • the entire process may be carried out in an atmosphere with controllable pressure and temperature, thus permitting various degrees of incorporation of C0 into the liquid.
  • the usual pressure of the process is only from approximately 200 to approximately 4000 hPa (relative pressure) , a moderate pressure when compared with the pressures generally necessary for conventional carbonation.
  • the introduction of the liquid C0 is preferably effected from a cryogenic reservoir at a pressure of 1.5 to 2.5 MPa, and the diameter of the inlet apertures is a function of the volume to be treated and of the pressure. Moreover, the diameter of the injection apertures for the liquid for carbonation is also a function of the volume to be treated and of the nature of the liquid.
  • the temperature of carbonation of the process of the present invention is preferably a temperature below the ambient temperature, suitable temperatures being between approximately 4°C and approximately 15 °C. Normally it is possible to attain a suitable temperature for the process without having recourse to refrigerating units for cooling the carbonator and the liquid for carbonation, taking advantage only of the cooling arising out of the use of cryogenic C0 2 and its expansion during the process.
  • the liquid may be subjected to a conventional post-carbonation to complete the process, augmenting the quantity of dissolved C0 .
  • the liquid to be treated in the stage of carbonation in accordance with the present invention or in pre-carbonation in the particular case of two stages should be free of solid particles or of dissolved components which could interfere with the process, for example by raising its viscosity, which could be the case with sweetners or others. If it is intended that a beverage should contain solids, be these fruit fibres or pulps, etc., or constituents such as those referred to, these must be added subsequently to the pre-carbonated liquid, between the stage of pre-carbonation and that of the final post-carbonation, for which a mixer may be inserted in the system of carbonation. This mixing may be effected by conventional techniques.
  • the liquid may be routed to a post-carbonator in which a conventional carbonation is carried out by dissolving C0 2 under customary conditions of pressure and temperature, different from those utilized in stage 1.
  • a further subject of the present invention is a suitable apparatus for carrying out the carbonation, comprising a carbonator as described below.
  • a subject of the present invention is an appropriate system for carrying out a carbonation in at least two stages, comprising a pre-carbonator, a mixer if required, and a post-carbonator similar to a conventional carbonator.
  • the carbonator in accordance with the present invention or the pre-carbonator in the particular two-stage case comprises a reservoir made from suitable material which has sufficient separate inlet ports for the introduction of liquid C0 and of the liquid for carbonation and injectors for the atomization of these in a geometrical arrangement such that the jets intersect as described.
  • the carbonator or pre-carbonator can be of any form.
  • a cylindrical form is suitable, the height being conveniently greater than the diameter.
  • the bottoms may be flat, conical or domed, in accordance with usual practice in the case of the low-pressure reservoirs used in the food industry and in the chemical industry.
  • the form may also be prismatic, it being possible for the bottoms in this case to be flat or pyramidal.
  • the carbonator or pre-carbonator can be of any material compatible with the liquid to be treated and with the standards of cleanliness customary in the food industry.
  • stainless steel is employed, although other materials may be employed, such as carbon steel, enamelled steel, polymeric materials, etc.
  • the pre-carbonator has external thermal insulation, which contributes to the economy of the process.
  • the carbonator or pre-carbonator may advantageously be equipped with control, monitoring or safety instruments, such as, for example, controlled valves, for example pneumatic valves or electrovalves, for regulating the inlet and outlet of fluids, level detectors, pressure and temperature gauges, inspection ports, safety valves, valves for the withdrawal of samples, etc.
  • the pressure and temperature gauges may be of appropriate form, equipped with local indicators and/or signal transmitters for remote indicators and/or regulators, for example in a synoptic panel or control robot.
  • Figure 1 shows a carbonator or pre-carbonator in a non- limiting preferred embodiment.
  • the numerals denote the following:
  • 1 - steel tank preferably of stainless steel
  • Figure 2 shows an example of a system comprising a pre- carbonator, a mixer and a conventional post-carbonator. This figure shows the following:
  • V12 -inlet valve to mixer for precarbonated liquid.
  • system is computerized and has appropriate programs for each product.
  • the automated or computerized system may, for example, consist of a system similar to that represented in Figure 1 in which the valves 4, 5, 6, 7, 11 and 12 are controlled electrically or pneumatically by means of signals received from a robot, which in turn receives instructions derived from the measuring instruments 8, 9 and 13.
  • the automated or computerized system may, for example, consist of a system in which the valves VI and V12 and the pumps Bl and B2 are controlled electrically or pneumatically by means of signals received from a robot, which in turn receives instructions derived from the measuring instruments PI to P4, TI and Nl to N3.
  • the process of the present invention offers numerous advantages over the conventional process of carbonation, of which the following are notable:
  • Another advantage of the process of the present invention is the slower release of gas after the packaging has been opened, which allows enjoyment of the beverage without an adverse effect on the taste for a longer period of time, even after it has been poured out into the glass.
  • a further advantage of the process of the present invention is the moderate pressure at which it can be carried out, which allows the utilization of more economical equipment.
  • An additional advantage of the present invention is the optional availability of a totally automated system in which all of the operations can be carried out in sequence with previously established parameters for an operation under optimal conditions. The system may be controlled by computer with previously designed programs suitable for each product.
  • Example 1 Preparation of carbonated water 100 of drinking water and 85 g of liquid C0 2 were introduced simultaneously into a carbonator similar to that shown in Figure 1, previously filled with gaseous C0 2 and cooled to about 7°C, via the respective valves and in such a manner that the jets of the atomized fluids intersected inside the apparatus.
  • the C0 was derived from a cryogenic reservoir at about -20°C and 2.0 MPa. The flows were adjusted in such a manner that the temperature during the process inside the carbonator was maintained at around 6.5°c and the pressure reached around 0.12 MPa. During atomization of the C0 2 , the latter was converted to dry ice by expansion, having cooled to around -76°C. The introduction lasted about 1 minute.
  • Example 2 Preparation of cola soft drink 100 L of drinking water and 100 g of liquid C0 2 were introduced simultaneously into a pre-carbonator of a two- stage carbonation system, similar to that shown in Figure 2, previously filled with gaseous C0 2 and cooled to around 6°C, via the respective valves and in such a manner that the jets of the atomized fluids intersected inside the apparatus.
  • the C0 was derived from a cryogenic reservoir at about -20°C and 2.0 MPa.
  • the flows were adjusted in such a manner that the temperature during the process inside the pre-carbonator was maintained at about 6°C and the pressure reached about 0.08 MPa.
  • the latter was converted to dry ice by expansion, having cooled to around -76°C.
  • the introduction lasted about 1 minute.
  • the discharge valve of the pre- carbonator was opened and the pre-carbonated water passed into the mixer where it was mixed with a syrup consisting of vegetable extracts and sugar, with the usual composition of a cola syrup.
  • the mixture passed immediately to the post-carbonator where a classical carbonation was carried out at 0.6 MPa.
  • the final product contained 6 g/L of C0 2 .
  • the cola soft drink obtained was packed in PET bottles and kept under perfect conditions for a storage period of 1 year.
  • organoleptic qualities were evaluated by tasters and compared with a cola soft drink obtained using the conventional process, and it was shown that these qualities were maintained to a much higher degree.
  • Example 2 the pre-carbonated water passed as in Example 2 to the mixer, being mixed therein with a syrup consisting of an extract of lime-lemon and sugar.
  • Example 2 a lime-lemon carbonated beverage being obtained with excellent organoleptic properties and optimal fixation of C0 in the liquid, as evaluated by tasting and conservation tests.

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  • Health & Medical Sciences (AREA)
  • Nutrition Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Non-Alcoholic Beverages (AREA)
  • Devices For Dispensing Beverages (AREA)

Abstract

The invention relates to a process and system for carbonation of a liquid, comprising at least one stage of incorporation of carbon dioxide into the liquid to be carbonated, carbon dioxide being used in liquid state and brought into closed contact with the liquid to be carbonated at a moderate pressure. The stage of incorporation of carbon dioxide into the liquid to be carbonated is advantageously carried out in a chamber into which both the liquid carbon dioxide and the liquid to be carbonated are atomized, in a manner that the paths of the two fluids intersect inside the chamber. Application for the preparation of carbonated beverages.

Description

PROCESS AND SYSTEM OF CARBONATION OF LIQUIDS
The present invention relates to a new process of carbonation. The invention also includes a suitable system for carrying out the new process, denoted by the term carbonator. Carbonation is a process by means of which carbon dioxide, Co2 , is incorporated into a product, usually in an aqueous liquid. It is used especially for the production of carbonated beverages, a general designation which includes carbonated waters, carbonated fruit juices, colas and carbonated cooling drinks in general, as well as carbonated wines.
The carbonated products may be for example water, mineral waters, aqueous solutions containing extracts of fruits or other vegetable extracts, especially of cola, tea or coffee, sugar or other sweeteners, caramel, citric acid, ascorbic acid, colorants and, generally in small concentrations, inorganic anions and cations such as bicarbonate, chloride, fluoride, sodium, calcium, potassium, magnesium, etc. They may also contain alcohol, in the case of wines, flavourings, colorants, thickeners, dispersants and solid products in suspension, normally vegetable fibres and fruit pulps or others. Naturally, for the preparation of beverages, all of the above-mentioned components or additives should be of alimentary grade.
In addition to the case of the preparation of beverages, carbonation may also be applied in other fields, for example for pH adjustment in liquids or others. Carbonation is a complex process which comprises the physical phenomena of dispersal and dissolution of C02 in the liquid medium together with chemical phenomena of interaction of C02 first with the water, forming unstable carbonic acid, and subsequently with other components of the medium to be carbonated, giving rise to carbonates and other compounds which play a part in the fixation of C02.
Carbonation processes are known at the present time and are very widely diffused in industry, principally in the food-industry sector and especially in the industry for the preparation of non-alcoholic beverages.
These known carbonation processes can be classified generally as two technical variants: 1) carbonation in saturators; and
2) carbonation in pressure vessels
In the technique (1) of carbonation in saturators, diffusion of gaseous carbon dioxide throughout the liquid to be carbonated is promoted. Saturators are devices in which a C0 diffuser is located in a reactor, generally of tubular form, into which a liquid to be carbonated is passed in a continuous manner. This diffusion is effected by causing gaseous C0 to pass under slight pressure through the diffuser, dispersing it throughout the liquid to be carbonated. Diffusers are normally devices which have, in their terminal part in contact with the liquid, a porous plate which can be made from various materials, such as for example porous porcelain, porous metal plates, etc. Porous tubes can also be used as diffusers, for example metal tubes which are inserted inside the saturator, normally of concentric tubular form. The pressure of C02 should be sufficient to provide an adequate flow of C02 to overcome the resistance of the porous diffuser and the pressure of the particular fluid to be carbonated. In a technical variant, the saturator is of Venturi type and the C0 is introduced immediately upstream of the constriction or at the entry to it, thereby obtaining a more rapid incorporation owing to the variation in pressure caused by the Venturi effect. In another known technique of carbonation (2) , a pressure vessel is used. In accordance with this technique, the vessel is charged with gaseous C0 up to a high pressure,
5 which may usually be from 5 to 6 10 Pa. Then the liquid to be carbonated is introduced into the vessel by means of calibrated perforations which produce fine jets. The intimate contact thus effected between the C0 present within the vessel and the liquid introduced promotes the incorporation of the C02 into the liquid. In order to maintain the efficiency of the process it is usual to replace the C02 consumed to keep pace with its absorption by the liquid, in such a way as to maintain the working pressure.
Some improvements have been introduced into the above- mentioned carbonation processes, but in general these improvements do not substantially change the essential nature of the processes and relate, above all, to matters of detail.
J60087837 describes a system for the carbonation of liquids, especially beverages, in which gaseous C02 is atomized within a liquid under reduced pressure, a high efficiency of carbonation being claimed.
DE 4319526 describes an apparatus for carbonation which allows a uniform and controllable level of carbonation by using a control unit when C02 is introduced. WO 9415489 describes a process of carbonation of mineral water in which, after a conventional carbonation with gaseous C02, PET bottles are filled with the cooled water and a specific quantity of solid C02 is added to each bottle, these being closed as rapidly as possible. Clearly, this process is not suitable for industrial use.
DE 3634814 describes a method of carbonation of liquids, especially non-alcoholic beverages, in which gaseous C0 is added in a zone of low pressure from an injector.
DE 3431906 describes a system for the saturation of liquids with a gas, especially C0 , which makes use of a porous membrane.
EP-145918 describes a process for rapid carbonation of water by means of a controlled flow of gaseous C02.
DD-211489 describes a system for the carbonation of liquids, for example lemonade, in which the C02/air mixture is recycled, allowing an saving in the use of C0 .
WO 8400671 describes an automatic system for the carbonation of liquids for beverages, in which the introduction of gaseous C0 into the carbonation chamber is effected via a valve controlled automatically.
DE 3132706 describes a system for the carbonation of beverages in which the liquid for carbonation and the C0 are made to pass in contraflow through a series of storage tanks. The production of sparkling wines by carbonation is the subject of processes described, for example, in SU 1082803 and SU 1124019, gaseous C0 being used in both cases.
Obtaining carbonated beverages for immediate use in restaurants or for domestic consumption is the subject for example of WO 9015011, EP-296570, GB 2186265, GB 2137894, BE- 898455, WO 8204243, GB 2097274, EP-59534, BE-878003, BE-877855 and EP-33157. All of these systems utilize gaseous C02, introduced by various means and under different conditions into a stream of the liquid for carbonation when the latter is tapped from a storage reservoir into a receptacle for immediate consumption, for example into a glass.
The process of carbonation is influenced especially by the operating pressure, by the temperature and also by the pH in particular and by the composition in general of the liquid medium. The pressure and temperature at which the carbonated product is going to be stored until the moment of use must also be taken into account, bearing in mind that this storage is normally effected in plastic, glass or metal, generally aluminium, containers. These containers are sealed by crown pressure caps, by screw caps or, in the case of so-called cans, they are punched and equipped with devices for easy opening formed by a tear-away groove with a ringpull for the action of opening.
In any case, the greater part of the C02, whether dissolved or combined, is found in the carbonated product in equilibrium at a certain pressure, but can be easily liberated once this equilibrium is disturbed, usually by a reduction in the pressure, which may occur simply as a result of opening the container in which the carbonated product is stored under a slight pressure and of placing the liquid at atmospheric pressure. If the material of the container is partially permeable to C0 , as is the case with certain plastic materials used for bottles for beverages, there may be a tendency for a gradual loss of C0 over time. All of the known industrial processes for carbonation of liquids have in common the fact that they are carried out in a single operation and make use of gaseous carbon dioxide. In general, to obtain an acceptable degree of carbon- ation the pressure of C02 should be elevated. The improved processes referred to above cite pressures of 0.22 to 5.2 MPa or refer to "high pressure".
Usually, the incorporation of C02 is facilitated by using a low temperature, to which the liquid is in general cooled by means of refrigerating units or heat exchangers, which involves considerable investments.
On the other hand, because the provision of C02 to industry in appreciable quantities is usually made in cryogenic storage tanks in which the C02 is present in the liquid state, these processes also involve the existence of gas atomizers which are normally atmospheric heat exchangers provided with coils of flanged tubes, which also raises the cost of the system. The alternative of utilizing gaseous C0 provided in pressurized metal cylinders has the disadvantages of being more expensive and of requiring more labour for transporting, positioning and connecting the cylinders and for activating the individual valves, which is unacceptable since it is unsuitable for domestic use or use in restaurants or even in small trials on a laboratory scale. Beverages carbonated by the conventional processes exhibit a reduced degree of fixation of C0 in the liquid, which presents two principal disadvantages. In the first place, in the case of beverages or other liquids packaged in materials partially permeable to C02, a gradual loss of gas through the wall of the container occurs, which reduces the shelf life of the product, with very deleterious economic consequences. This gradual loss is very appreciable, especially in the case of PET bottles. Nevertheless PET is tending to become ever more prevalent as the material of choice for the packaging of gasified beverages, its use for this purpose having experienced a spectacular increase of 80% between 1992 and 1995 in the European market. In the US market, owing to restrictions on the use of PVC, the use of PET has become general and in the Japanese market the trend is in the same direction. The disadvantage, however, of the permeability of PET to gases, and especially to C0 , has led to research into the development of mixed packaging or of alternative materials such as polyethylene naphthalate (PEN) , which is, however, ten times as expensive.
On the other hand, defective fixation of C02 also represents an major disadvantage at the time of consumption. Once the packaging is opened, the C02 tends to be released in the form of bubbles, which contributes to the flavour of the product. However, the release is in general too rapid, which has the result that a beverage which is not consumed quickly does not ultimately give the same degree of satisfaction. The subject of the present invention is a new process of carbonation which differs completely from the conventional processes described in terms of implementation and results.
A further subject of the invention is a suitable apparatus for implementing the new process, denoted by the term carbonator, and a system for industrial use in which the apparatus of the invention is linked to auxiliary devices which enable all of the operations to obtain carbonated liquids, especially carbonated beverages, to be carried out. The new process of carbonation of the present invention may be used for all the cases in which use has been made hitherto of the conventional carbonation techniques described, especially for the production of carbonated beverages in general, carbonated waters, carbonated fruit juices, colas and other carbonated cooling drinks, as well as carbonated wines. However, the use of the process of the present invention is not necessarily limited to the field of beverages .
The process of the present invention is characterized in that it comprises at least one stage of carbonation or of prior carbonation in which use is made not of gaseous carbon dioxide but of carbon dioxide in liquid form, thereby promoting dissolution of C0 throughout the liquid which it is intended to carbonate at a moderate pressure by means of the intimate contact of the liquid carbon dioxide with the liquid for carbonation atomized into fine droplets.
Preferably, for this purpose, the liquid for carbonation and the liquid C02 are simultaneously atomized in a closed container which has suitable devices for the atomization of the liquid for carbonation and of the liquid
C0 . This container is termed a carbonator.
In a particular case of special interest, the process of the present invention can be carried out in two stages, a pre-carbonation and a subsequent post-carbonation, utilizing, in the pre-carbonation stage, carbon dioxide in liquid form as described above. The liquid may then be subjected to a conventional post-carbonation, to complete the process. In this particular case, the first stage of pre-carbonation is carried out in a container such as that described, in this case termed pre-carbonator, and the subsequent stage is carried out in a conventional post-carbonator .
This particular two-stage case is preferred when preparing carbonated beverages whose composition includes syrups, these being introduced for example in a mixer inserted between the pre-carbonator and the post-carbonator.
The new process of carbonation consists in the incorporation of C02 into a liquid for carbonation in a carbonation chamber, use being made, for this purpose, of liquid C02 which is brought into intimate contact with the aforementioned liquid at moderate pressure.
Preferably, the C0 is atomized inside the chamber in which the liquid for carbonation is also atomized, so that the paths of the two fluids intersect. In accordance with the particular two-stage case, the new process of carbonation consists in the incorporation of C02 into the liquid for carbonation in two consecutive stages carried out in two different chambers, namely pre-carbonation and final post-carbonation, liquid C02 being utilized in the first stage in the pre-carbonator in which it is brought into contact with the liquid for carbonation, preferably in such a manner that the streams of the two fluids intersect, as described. In turn, the subsequent stage of final post- carbonation may be carried out in accordance with the conventional techniques of carbonation, except that the liquid for carbonation, which has previously been subjected to pre-carbonation, contains, already incorporated, an appreciable quantity of carbon dioxide, as a result of which the operation is in general more rapid and less critical than conventional carbonation.
The carbonator or pre-carbonator in accordance with the technique of the present invention is formed by a chamber or container in which there are different nozzles for injecting liquid C02 , on the one hand, and the liquid for carbonation on the other. In this chamber, the liquid for carbonation is atomized by means of injectors in sufficient number for the volume which it is intended to treat. This atomization converges in the centre of the chamber. Meanwhile there is introduced into the chamber a stream of liquid C02 which, under the working conditions of temperature and pressure, is ultimately converted into dry ice, i.e. into solid C02 in subdivided form and, in this case, finely divided form. The stream of C02 intercepts the various atomizations of the liquid, cooling it and combining with it.
In accordance with a preferred embodiment of the process of the present invention, a constant injection of liquid C02 is created via the atomization apertures so as to form a vertical downward stream of C02. The C0 is converted immediately into dry ice even before coming into contact with the liquid for carbonation. At the same time, the liquid intended for carbonation is injected via the injectors arranged in several rows placed at various heights so as to form in the interior of the carbonator or of the pre- carbonator jets whose paths are initially horizontal, in such a way as also to atomize the liquid. The jets of C02 and of the liquid for carbonation intersect, resulting in a fine dispersion or incorporation of the carbon dioxide into the liquid.
The entire process may be carried out in an atmosphere with controllable pressure and temperature, thus permitting various degrees of incorporation of C0 into the liquid. The usual pressure of the process is only from approximately 200 to approximately 4000 hPa (relative pressure) , a moderate pressure when compared with the pressures generally necessary for conventional carbonation. The introduction of the liquid C0 is preferably effected from a cryogenic reservoir at a pressure of 1.5 to 2.5 MPa, and the diameter of the inlet apertures is a function of the volume to be treated and of the pressure. Moreover, the diameter of the injection apertures for the liquid for carbonation is also a function of the volume to be treated and of the nature of the liquid.
The temperature of carbonation of the process of the present invention is preferably a temperature below the ambient temperature, suitable temperatures being between approximately 4°C and approximately 15 °C. Normally it is possible to attain a suitable temperature for the process without having recourse to refrigerating units for cooling the carbonator and the liquid for carbonation, taking advantage only of the cooling arising out of the use of cryogenic C02 and its expansion during the process.
After the pre-carbonation the liquid may be subjected to a conventional post-carbonation to complete the process, augmenting the quantity of dissolved C0 .
In any case, the liquid to be treated in the stage of carbonation in accordance with the present invention or in pre-carbonation in the particular case of two stages should be free of solid particles or of dissolved components which could interfere with the process, for example by raising its viscosity, which could be the case with sweetners or others. If it is intended that a beverage should contain solids, be these fruit fibres or pulps, etc., or constituents such as those referred to, these must be added subsequently to the pre-carbonated liquid, between the stage of pre-carbonation and that of the final post-carbonation, for which a mixer may be inserted in the system of carbonation. This mixing may be effected by conventional techniques.
After the pre-carbonation and the optional mixing of the above-mentioned components, the liquid may be routed to a post-carbonator in which a conventional carbonation is carried out by dissolving C02 under customary conditions of pressure and temperature, different from those utilized in stage 1. A further subject of the present invention is a suitable apparatus for carrying out the carbonation, comprising a carbonator as described below.
In particular a subject of the present invention is an appropriate system for carrying out a carbonation in at least two stages, comprising a pre-carbonator, a mixer if required, and a post-carbonator similar to a conventional carbonator.
The carbonator in accordance with the present invention or the pre-carbonator in the particular two-stage case comprises a reservoir made from suitable material which has sufficient separate inlet ports for the introduction of liquid C0 and of the liquid for carbonation and injectors for the atomization of these in a geometrical arrangement such that the jets intersect as described.
The carbonator or pre-carbonator can be of any form. A cylindrical form is suitable, the height being conveniently greater than the diameter. The bottoms may be flat, conical or domed, in accordance with usual practice in the case of the low-pressure reservoirs used in the food industry and in the chemical industry. Alternatively the form may also be prismatic, it being possible for the bottoms in this case to be flat or pyramidal.
The carbonator or pre-carbonator can be of any material compatible with the liquid to be treated and with the standards of cleanliness customary in the food industry. Preferably stainless steel is employed, although other materials may be employed, such as carbon steel, enamelled steel, polymeric materials, etc.
Preferably the pre-carbonator has external thermal insulation, which contributes to the economy of the process. The carbonator or pre-carbonator may advantageously be equipped with control, monitoring or safety instruments, such as, for example, controlled valves, for example pneumatic valves or electrovalves, for regulating the inlet and outlet of fluids, level detectors, pressure and temperature gauges, inspection ports, safety valves, valves for the withdrawal of samples, etc. The pressure and temperature gauges may be of appropriate form, equipped with local indicators and/or signal transmitters for remote indicators and/or regulators, for example in a synoptic panel or control robot.
The mixer and the conventional post-carbonator, when present, may have the usual characteristics of these items of equipment. Figure 1 shows a carbonator or pre-carbonator in a non- limiting preferred embodiment. In this figure, the numerals denote the following:
1 - steel tank, preferably of stainless steel
2 - distribution cage for the liquid for carbonation 3 - liquid injectors
4 - pneumatically activated valves for decompression
5 - electrovalves for C02 in liquid phase
6 - electrovalves for C02 in liquid phase
7 - pneumatically activated valve for liquid inlet 8 - pressure transducer
9 - temperature transducer
10 - injectors for C02 in liquid phase
11 - pneumatically activated valve for liquid outlet
12 - electrovalve for withdrawal of liquid samples 13 - maximum level detector
14 - safety valve
15 - thermal insulation
Figure 2 shows an example of a system comprising a pre- carbonator, a mixer and a conventional post-carbonator. This figure shows the following:
PI, P2, P3 and P4 - pressure stats TI - temperature probe Nl, N2 and N3 - level probes Bl and B2 - pressurization pumps VI - valve for injection of liquid for carbonation V2 - valve for injection of liquid C02 V3 - decompression valve for the pre-carbonator V4 - outlet valve for liquid V5 - by-pass valve to mixer
V6 - outlet valve for mixer
V7 - outlet valve for filling
V8 - outlet valve for post-carbonator V9 - inlet valve for gaseous C02
V10 -pressurization valve for post-carbonator
Vll - inlet valve for syrup
VS1 and VS2 - safety valves
V12 -inlet valve to mixer for precarbonated liquid. In an especially preferred embodiment of the system of the present invention, there is an automatic or computerized control in which the optimal parameters for each utilization have been previously established.
In an especially preferred embodiment, the system is computerized and has appropriate programs for each product.
The automated or computerized system may, for example, consist of a system similar to that represented in Figure 1 in which the valves 4, 5, 6, 7, 11 and 12 are controlled electrically or pneumatically by means of signals received from a robot, which in turn receives instructions derived from the measuring instruments 8, 9 and 13.
In the same way, in the case of the example of Figure 2, the automated or computerized system may, for example, consist of a system in which the valves VI and V12 and the pumps Bl and B2 are controlled electrically or pneumatically by means of signals received from a robot, which in turn receives instructions derived from the measuring instruments PI to P4, TI and Nl to N3.
The process of the present invention offers numerous advantages over the conventional process of carbonation, of which the following are notable:
There is a better fixation of the C0 in the liquid; Simultaneously with the carbonation, air is removed from the liquid, which also allows a better fixation of C0 ; As a consequence of this better fixation, the keeping- quality of the product during storage is improved and the shelf life of the carbonated products in accordance with the process of the present invention may be increased. Also owing to this effect, packaging beverages carbonated by the present process, in PET, does not present the problem of rapid progressive loss such as occurs with beverages produced by the conventional process. In the particular case of the two-stage process, there are better conditions for absorption of C02 by virtue of the stage of pre-carbonation;
Another advantage of the process of the present invention, also related to the better fixation of the C02 in the liquid, is the slower release of gas after the packaging has been opened, which allows enjoyment of the beverage without an adverse effect on the taste for a longer period of time, even after it has been poured out into the glass.
From an industrial point of view it should also be emphasized that this process eliminates the need for refrigerating units for cooling the liquid, inasmuch as the sole cooling is effected by the liquid C02 itself introduced into the process. Moreover, the utilization of cryogenic C02 does not presuppose the existence of evaporators. In this way the investment required is considerably reduced.
A further advantage of the process of the present invention is the moderate pressure at which it can be carried out, which allows the utilization of more economical equipment. An additional advantage of the present invention is the optional availability of a totally automated system in which all of the operations can be carried out in sequence with previously established parameters for an operation under optimal conditions. The system may be controlled by computer with previously designed programs suitable for each product.
The examples which follow are intended to illustrate the invention without, however, restricting its scope in any way.
Example 1: Preparation of carbonated water 100 of drinking water and 85 g of liquid C02 were introduced simultaneously into a carbonator similar to that shown in Figure 1, previously filled with gaseous C02 and cooled to about 7°C, via the respective valves and in such a manner that the jets of the atomized fluids intersected inside the apparatus. The C0 was derived from a cryogenic reservoir at about -20°C and 2.0 MPa. The flows were adjusted in such a manner that the temperature during the process inside the carbonator was maintained at around 6.5°c and the pressure reached around 0.12 MPa. During atomization of the C02, the latter was converted to dry ice by expansion, having cooled to around -76°C. The introduction lasted about 1 minute. At the end of the operation, the carbonated water was discharged via the discharge valve and immediately bottled. Example 2 : Preparation of cola soft drink 100 L of drinking water and 100 g of liquid C02 were introduced simultaneously into a pre-carbonator of a two- stage carbonation system, similar to that shown in Figure 2, previously filled with gaseous C02 and cooled to around 6°C, via the respective valves and in such a manner that the jets of the atomized fluids intersected inside the apparatus. The C0 was derived from a cryogenic reservoir at about -20°C and 2.0 MPa. The flows were adjusted in such a manner that the temperature during the process inside the pre-carbonator was maintained at about 6°C and the pressure reached about 0.08 MPa. During atomization of the C02, the latter was converted to dry ice by expansion, having cooled to around -76°C. The introduction lasted about 1 minute.
After this operation, the discharge valve of the pre- carbonator was opened and the pre-carbonated water passed into the mixer where it was mixed with a syrup consisting of vegetable extracts and sugar, with the usual composition of a cola syrup.
The mixture passed immediately to the post-carbonator where a classical carbonation was carried out at 0.6 MPa. The final product contained 6 g/L of C02.
In tests carried out at the Centre de Recherches Claude Delorme (Air Liquide, Paris) , it was shown that both in the glass as well as in sampling (tasting) its performance was clearly superior to that obtained with a classical carbonation . It was shown in particular that the product from a bottle open for several days maintains a sufficient quantity of dissolved C0 .
The cola soft drink obtained was packed in PET bottles and kept under perfect conditions for a storage period of 1 year.
After this period, the organoleptic qualities were evaluated by tasters and compared with a cola soft drink obtained using the conventional process, and it was shown that these qualities were maintained to a much higher degree.
Example 3 : Preparation of lime and lemon soft drink
100 L of water and 80 g of liquid C02 were introduced simultaneously into a pre-carbonator of a two-stage carbonation system, similar to that shown in Figure 2, previously filled with gaseous C02 and cooled to about 6°C, via the respective valves and in such a manner that the jets of the atomized fluids intersected inside the apparatus, proceeding in a manner identical to that indicated in Example
2. The pressure inside the chamber reached approximately 0.15 MPa during this operation.
After this operation, the pre-carbonated water passed as in Example 2 to the mixer, being mixed therein with a syrup consisting of an extract of lime-lemon and sugar.
Immediately afterwards, a conventional post-carbonation was carried out as in Example 2, a lime-lemon carbonated beverage being obtained with excellent organoleptic properties and optimal fixation of C0 in the liquid, as evaluated by tasting and conservation tests.

Claims

1. Process for carbonation of a liquid, characterized in that it comprises at least one stage of incorporation of carbon dioxide into the liquid for carbonation in which the carbon dioxide in the liquid state is brought into intimate contact with the said liquid at a moderate pressure.
2. Process according to Claim 1, characterized in that the stage of incorporation of carbon dioxide into the liquid for carbonation is carried out in a chamber or container into which the atomized liquid carbon dioxide and the liquid for carbonation, also atomized, are introduced simultaneously in such a manner that the paths of the two fluids intersect inside the said chamber or container.
3. Process according to either of Claims 1 or 2, characterized in that C02 is incorporated into the liquid for carbonation in at least two consecutive stages effected in two different chambers, the pre-carbonation and the final post-carbonation, atomized liquid C0 being used in the first stage in a device termed pre-carbonator in which the liquid for carbonation is atomized in such a manner that the paths of the two fluids intersect inside the first chamber and afterwards, in a subsequent phase, a post-carbonation using gaseous C02 is carried out in the second chamber.
4. Process according to any of Claims 1 to 3 , characterized in that the single stage of carbonation or the first stage of pre-carbonation is carried out in a chamber or container in which there are different nozzles for injecting liquid C02 , on the one hand, and the liquid for carbonation on the other and in which the liquid for carbonation is atomized by means of injectors in sufficient number for the volume which it is intended to treat, this atomization converging in the centre of the chamber and a stream of liquid C02 being introduced into the chamber in the meantime in such a manner as to intercept the various atomizations of the liquid, cooling it and combining with it.
5. Process according to any of Claims l to 4, characterized in that in the single stage of carbonation or in the first stage of pre-carbonation a constant injection of liquid C02 is created via the atomization apertures so as to form a vertical downward stream of C02 and simultaneously to inject the liquid intended for carbonation via the injectors arranged in several rows placed at various heights so as also to atomize the liquid and so that the jets of C02 and of the liquid for carbonation intersect, resulting in a fine dispersion and in incorporation of the carbon dioxide into the liquid.
6. Process according to any of Claims 1 to 5 , characterized in that the single stage of carbonation or the first stage of pre-carbonation is carried out in an atmosphere with controllable pressure and temperature, thus permitting various degrees of incorporation of C0 into the liquid.
7. Process according to any of Claims 1 to 6, characterized in that the single stage of carbonation or the first stage of pre-carbonation is carried out at a mean process pressure of approximately 200 to approximately 4000 hPa (relative pressure) and at a mean process temperature of between approximately 4°C and approximately 15°C.
8. Process according to any of Claims 1 to 6, characterized in that the introduction of liquid C0 is effected from a reservoir of cryogenic C02 at a pressure of 1.5 to 2.5 MPa.
9. Process according to any of Claims 1 to 8, characterized in that after the pre-carbonation stage the liquid is subjected to a conventional post-carbonation stage.
10. Process according to any of Claims 1 to 9, characterized in that the components of the liquid for carbonation which contain solids or which alter the viscosity of the liquid are added to the pre-carbonated liquid between the pre-carbonation stage and the final post-carbonation stage.
11. Utilization of the process according to any of Claims 1 to 10 for the preparation of carbonated beverages.
12. carbonator for carrying out carbonation according to either of Claims 1 or 2, characterized in that it comprises a container made from a material resistant to the liquid for carbonation and to the working pressure containing devices for the simultaneous atomization in its interior of the liquid C02 and of the liquid for carbonation arranged in such a manner that the paths of the two fluids intersect.
13. Carbonator according to Claim 12, characterized in that it is equipped with control, monitoring and safety instruments, such as, for example, controlled valves for regulating the inlet and outlet of fluids, level detectors, pressure and temperature gauges, inspection ports, safety valves and valves for the withdrawal of samples, the pressure and temperature gauges being of appropriate form, equipped with local indicators and/or signal transmitters for remote indicators and/or regulators.
14. Carbonator according to either of Claims 12 or 13 , characterized in that it comprises: a tank made of suitable material, preferably stainless steel, and having at least some of the following components : a distribution cage for the liquid for carbonation, liquid injectors, a decompression valve, valves for C02 in liquid phase, valves for C02 in liquid phase, - valve for liquid inlet, a pressure transducer, a temperature transducer, injectors for C02 in liquid phase a valve for liquid outlet, a valve for withdrawal of liquid samples, a maximum level detector, a safety valve, thermal insulation.
15. Carbonator according to Claim 14, characterized in that it is equipped with an automatic or computerized control in which the optimum parameters for each utilization have been previously established.
16. Carbonator according to Claim 15, characterized in that it is equipped with a computerized control and has appropriate programs for each product.
17. System for carrying out a carbonation according to any of Claims 1 to 10, characterized in that it comprises a pre-carbonator according to any of Claims 12 to 16, optionally an intermediate mixer, and a pre-carbonator interconnected with each other by means of suitable tubing.
18. System of carbonation according to Claim 17, characterized in that it is equipped with at least some of the following components: pressure stats, temperature probe, level probes, - pressurization pumps, valve for injection of the liquid for carbonation, valve for injection of liquid C02 decompression valve for the pre-carbonator, - outlet valve for liquid, by-pass valve to mixer, outlet valve for mixer, outlet valve for filling, outlet valve for post-carbonator, - inlet valve for gaseous C0 , pressurization valve for post-carbonator, inlet valve for syrup, safety valves, inlet valve to mixer for pre-carbonated liquid.
19. System of carbonation according to either of Claims 17 or 18, characterized in that it is equipped with an automatic or computerized control in which the optimum parameters for each utilization have been previously established.
20. System of carbonation according to Claim 19, characterized in that it is equipped with a computerized control and has appropriate programs for each product.
EP97937553A 1996-08-14 1997-08-02 Process and system of carbonation of liquids Withdrawn EP0921730A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PT10190596A PT101905B (en) 1996-08-14 1996-08-14 NEW CARBONATING PROCESS AND SYSTEM
PT10190596 1996-08-14
PCT/EP1997/004274 WO1998006280A1 (en) 1996-08-14 1997-08-02 Process and system of carbonation of liquids

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DE102004041816B4 (en) * 2004-08-30 2008-01-03 Kwc Ag Device for carbonating and cooling drinks
ITGE20060076A1 (en) * 2006-07-28 2008-01-29 Asset S R L DEVICE FOR THE TREATMENT AND DISTRIBUTION OF BEVERAGES, IN PARTICULAR WATER.
RU2597387C1 (en) * 2015-05-21 2016-09-10 Федеральное государственное бюджетное образовательное учреждение высшего образования "Уфимский государственный нефтяной технический университет" Method of purifying water and device therefor

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US4022119A (en) * 1975-12-22 1977-05-10 Shasta Beverages Division Of Consolidated Food Corporation Liquid carbon dioxide carbonation apparatus
SU1124019A1 (en) * 1983-05-26 1984-11-15 Краснодарский ордена Трудового Красного Знамени политехнический институт Method for producing gas-saturated wine
AT389034B (en) * 1984-06-15 1989-10-10 Gyoergy Dr Timar METHOD FOR PRODUCING CARTRIDGES FOR PREPARING CARBONATED BEVERAGES
RU1773465C (en) * 1990-06-05 1992-11-07 Армянский Научно-Исследовательский Институт Виноградства, Виноделия И Плодоводства Device for manufacturing gassed beverages
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RU2008340C1 (en) * 1991-03-19 1994-02-28 Краснодарский научно-исследовательский центр хранения и переработки сельскохозяйственной продукции Method of producing carbonated beverages or wines

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PT101905A (en) 1998-03-31

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