CA1160893A - Process for preparing carbonated liquids with activated charcoal - Google Patents
Process for preparing carbonated liquids with activated charcoalInfo
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- CA1160893A CA1160893A CA000360978A CA360978A CA1160893A CA 1160893 A CA1160893 A CA 1160893A CA 000360978 A CA000360978 A CA 000360978A CA 360978 A CA360978 A CA 360978A CA 1160893 A CA1160893 A CA 1160893A
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- carbon dioxide
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Abstract
PROCESS FOR PREPARING CARBONATED LIQUIDS
WITH ACTIVATED CHARCOAL
ABSTRACT
Carbonated water and/or beverages are prepared by contacting water with activated charcoal having carbon dioxide adsorbed thereon in an amount OF at least 20 cm3 per gram of charcoal. In a preferred embodiment, the carbonation is conducted in a closed vessel under superatmospheric pressure.
WITH ACTIVATED CHARCOAL
ABSTRACT
Carbonated water and/or beverages are prepared by contacting water with activated charcoal having carbon dioxide adsorbed thereon in an amount OF at least 20 cm3 per gram of charcoal. In a preferred embodiment, the carbonation is conducted in a closed vessel under superatmospheric pressure.
Description
~8g~3 DESCRIPTION
.
PROCESS FOR PREPARING CARBONATED
LIQUIDS WITH ACTIVATED CHARCOAL
. _ Technical Field . _ _ .
05 This invention relates to carbonated beverages. More particularly, it relates to consumer or "at home" prepara-tion of carbonated beverages having substantially the same palatabili-ty and effervescence of bottled or canned carbonated beverages.
This invention especially relates -to the preparation of carbonated beverages from activated charcoal which contains adsorbed carbon dioxide.
Background of the Invention Attempts to commercialize point of consump-tion or at home preparation of carbonated beverages have not met with any lasting success over the years. The principal shortcoming of the several techniques has been that the consumer-prepared carbonated beverage has been significantly inferior in one or more aspects to the bottled or canned carbonated beverages available in s-tores and super-markets. The most common complaints leveled at the carbonated beverage prepared by the consumer is that , 3`
the quality and the guantity o~ the carbonation, the bubble size and the duration of the effervescence does not compare favorably with the commercially available bottled carbonated beverage.
05 On the other hand, there are si~nificant advantages to consumer preparation of carbonated beverages vis-a-vis packaged liquid carbonated beverages. Thus, the use of glass, metal or other bulky containers is avoided, the necessity of bottling, shipping and storing carbonated beverages consisting o~ a ma3or percentage of water is eliminated and the utility in terms of portability by the user is greatly enhanced. Thus, campers, packpackers, hun-ters, fishermen, outdoor spectators, housewives and travellers can enjoy a carbonated beverage without having to transport bulky and heavy quantities o~
the canned or bottled variety. Further, disposable and returnable cans and bottles would no longer be of major concern to environmentalists who have been ~0 seeking ways to conserve both the country's natuxal resources and natural beauty.
U.S. Patent No. 2,073,273 to We-ts-tein discloses a means to prepare a carbonated beverage wherein water plus sweetener and flavor is placed in a small pressure vessel and a metal cartridge contain-ing carbon dioxide is inserted into the sealed vessel where movement of the cartridge causes a piercing o~ the cartridge thereby injecting the carbon dioxide into the water to form the carbonated beverage. The carbon dioxide also pressurizes the vapor space above the liquid causing the carbonated beverage to pass out o~ -the vessel through a serving nozzle when an external valve is opened. This de~ice met wi-th some measure o~ success in preparing un~lavored and unsweetened carbonated water for home use, but the carbonation volume was lower than bottled club soda.
The prior art includes a significant number of dry compositions for use in preparing 05 carbonated beverages at home. In most of these a source of carbsnate and acid, kno~n in the art as a chemical "couple", are combined with sweeteners and a source of flavor so that upon addition of the composition to a glass of water, the "couple" reacts to yield carbon dioxide and at least some measure of carbonation to the beverage. U.S. Patent No. 2,603,569 to Alther discloses the carbonation of a citric acid-sucrose complex with a sodium bicarbonate-sucrose complex. U.S. Patent No. 2,742,363 to Hughes claims a combination of an alkali metal bicarbonate and a sulfonic acid ion exchange resin in i-ts hydrogen form. ~n U.S. Patent Nos. 2,851,359 and 2,953,459 to Diller a highly soluble phosphate and a slowly soluble phosphate are combinecl with an alkali metal or ammonium carbonate or bicarbonate to prolong the ebullition of the beverage. U.S. Patent No. 3,241,977 to Mitchell et al. discloses c:hemical carbonation with citric, adipic or tartaric acid in finely divided ~orm and which is saicl to approximate the carbonation sensation of cola-type beverages sold in air-tight bottles or cans which are produced by a satura-ted solution containing several volumes of carbon dioxide. U.S. Patent No. 3,~11,417 to Feldman et al. discloses a dry beverage composition adapted to be reconstituted with water to an effervescent beverage which includes as an essential carbona-ting ingredient, an organic compound having a carbonic acid anhydride group, capable of controlled hydrolysis in water to releas~ carbon dioxide at a substantially uniform rate. U.S. Patent No. 3,667,962 to Fritzberg et al. discloses a carbonation composition utilizing two distinct bodies formed from an a~ueous solution of a saccharide, one contains an edible food acid and -the other an edible bicarbonate. Upon addition 05 to water the two t.able-ts dissolve quickly and react to evolve carbon dioxide.
Many of the dry powder chemical couples have a common and acknowledged defect, an unpleasant taste in the beverage directly resulting from the components of the powder. U.S. Patent No. 2,742,363 to Hughes and U.S. Patent No. 3,476,520 to Hovey addressed this problem by placing the chemicals in a container which is pervious to gas and water but impervious to solid reactants and by-products. U.S.
Patent No. 2,975,603 to Barnes et al. takes another approach by utilizing carbonated ice containing at least 25 milliliters of carbon di.oxide per gram of ice as the source of carbonation.
U.S. Patent No. 2,882,244 to Milton discloses the preparation and composition of zeolite X.
Milton teaches that zeolite X adsorbs water more strongly than carbon dioxide and that a more strongly held adsorbate, such as water, will displace a less strongly held adsorbate, such as carbon dioxide.
Further, comparison data are presented which show that at low pressures, ziolite X has a higher adsorptive capacity for water and carbon dioxide than does charcoal. However, the data presented for charcoal are inconclusive on its relative adsorptive capacity for water and carbon dioxide since they were not measured at the same pressure. Further, the physical properties and nature of the charcoal are not presen-ted.
Milton also teaches that common adsorbents such as, charcoal and silica gel, behave differently from ziolite X and do not ~xhibit its molecular sieve action. Rather than showing preference for polar, polarizable lmsaturated molecules as does ziolite X, charcoal and silica gel are said to show a main preference based on volatility of the adsorbate.
05 U.S. Patent Nos. 3,888,998 to Sampson et al., 3,992,493 and 4,025,655 to Whyte et al. and 4,007,134, 4,110,255 and 4,147,808 to Liepa et al.
disclose carbonation methods, compositions and devices whereby carbon dioxide containing molecular sieves a~e used to carbonate aqueous solutions.
Sampson et al. and Whyte et al. teach the use of molecular sieves having at least 5 weight percent adsorbed carbon dioxide for effectin~ the carbonation of aqueous liquids. Molecular sieves having larger pore openings (greater than 6 Angstroms) were found to release carbon dioxide to aqueous liquids at a high rate but this rate is not sustained over a long period. Molecula:r sieves having small pore openings (3-5 Angstroms, particularly 3-4 Angstroms), on the other hand, released carbon dioxide to aqueous liquids at a slower rate but for a long period of time. In addition, the large pore sieves adsorbed suhstan-tially more C02 per unit weight than the 3-5A sieves. Liepa et al. disclose carbonation devices composed of molecular sieves formed into a rigid body having a specific surface area to mass ratio which may be achieved by providing vertical channels throu~h the rigid body. These patentees found that when carbon dioxide is adsorbed into these discs, it will be released when the disc is contacted with water. They also teach that common adsorbents, such as charcoal and silica gel, do not have the adsorptive capacity necessary to carbonate a beverage at the point of consumption.
The use of molecular sieves for carbonating li~uids may lead to the inefficient use of carbon dioxide. Rapid release rates of carbon dioxide into the liquid to be carbonated can result in the loss 05 of a major portion of the carbon dioxide from the liquid to the surrounding atmosphere. Carbonation processes which more efficiently utilize carbon dioxide are therefore highly desirable.
Thus, it is an object of this invention to provide a simple process for point of consumption preparation of carbonated beverages which increases the efficient use of carbon dioxide, i.e., substan-tially reduces the amount of carbon dioxide escaping from the beverage during the carbonation process, while producing a carbonated beverage having substan-tially the same taste and effervescence of the commercially available product.
Summary of the Invention In accordance with the present invention, it has been found that carbonated water and/or beverages can be prepared by c:ontacting water with activated charcoal having carbon dioxide adsorbed therein. More particularly, this invention is directed to a method of carbonating an aqueous liguid which comprises contacting an aqueous liquid with an effective amount of activated charcoal having adsorbed -therein at least 2C cm3 of carbon dioxide per gram of charcoal. In a preferred embodi~
ment, the carbonation is conducted in a closed vessel under superatmospheric pressure.
Brief Descriptlon of the Drawings The present invention will be more readily understood by reference to -the accompanying drawings.
Figure 1 is a graph of the volume of carbon dioxide adsorbed on two activated coconut charcoals versus adsorption pressure.
Figure 2 is a graph of the volume of 05 carbon dioxide adsorbed on two activated coconut charcoals versus the time after pressure on the charcoals was vented.
Figure 3 and 4 are graphs of the volumes of carbonation produced in water by various quantities of coconut charcoal and zeolite 13X versus the time of carbonation.
Description of the Preferred Embodiments Beverage carbonation with activated charcoal having carbon dioxide adsorbed thereon provides a system which makes more efficient use of the carbon dioxld~ than is obtained with a process which utilizes zeolites containing adsorbed carbon dioxide. Although zeolites adsorb more carbon dioxide per uni-t weight, under ambient conditions, than does activated charcoal, when the sieves are i.mmersed in water, the initial rate of CO2 releases from the! sieves is much higher than ~rom the activated charcoal. Conse~uently, the activated charcoal provides a higher Co2 retention efficiency in the beverage compared to molecular sieves. The fact that the charcoal surfaces are mostly hydrophobic in nature may explain why the activated charcoal exhibits a more controlled initial rate of CO2 release on immersion ln water, compared with the highly hydrophilic ~ionic) molecular sieves.
Activated charcoals are prepared by the destructiv~ pyrolysis of natural and syn-thetic organic materials. Among the widely used natural produc-ts are coal, petroleum, polysaccharides, such as sugars and starches and cellulosics. such as woody ~ 3 by-products, coconut shells, hard and soft woods, fruit pits and corncobs. Synthetic polymeric materials such as saran, polyfurfuryl alcohol and polystyrene-divinyl benzene copolymers, can be used 05 to prepare activated charcoals with very uniform mocroporous structures. These starting materials are converted to activated charcoals by first carbon-izing at 400-500C to eliminate the bulk of the volatile matter and then oxidizing (activating) with gas at ~00-1000C to develop the porosity and surface area. Not all activated charcoals may be employed in the sùbject invention. The activated charcoal must have an adsorptive capacity for carbon dioxide at ambient conditions and the adsorbed carbon dioxide must be released when the charcoal is contacted with wa-ter. Only activated charcoals having pores in -the r~nge of about 4 to about 20 Angstroms can adsorb C2 at ambient temperature and pressure. However, charcoals having pores as wide as about 50 Agstroms can be filled with adsorbed carbon dioxide at sub-ambient temperatures and/or pressures about 1 atmos-phere. Thus, activated charcoal having pore sizes of about 4 to about 50 Angstroms and having the ability to adsorb C02 and desorb it when contacted with water may usefully be employed in the subject invention, with activated charcoal prepared from natural products being preferred and activated charcoal prepared from coconut shells being parti-cularly preferred.
Carbon dioxide is adsorbed onto the activated charcoal by contacting the charcoal with gaseous or liquid carbon dioxide. Since water displaces the C2 from the charcoal, the adsorption ~or loading) should be conducted under anhydrous conditions. The charcoal should be dehydrated before being loaded with CO2 by such means as subjecting it to dry heat to reduce its adsorbed moisture conten-t. One conven-ient method of preparing the co2 loaded charcoal is 05 in a column packed with the activated charcoal. A
stream of heated dry gas, such as carbon dioxide, air or nitrogen, is passed through the column -to reduce the moisture content of the charcoal and then gaseous or liquid carbon dioxide is passed through the column to load the activated charcoal. The adsorption can be conducted at ambient or slightly above ambient temperature and substantially atmospheric pressure, i.e., just enough positive pressure to ensure a flow of carbon dioxide through the column.
Where hiyher loading of the activated charcoal is desired or where the subsequent carbonation is to be conducted in a closed vessel at superatmospheric pressure, -the CO2 adsorption onto the charcoal is conducted at sub-ambient tempexature or super-atmospheric pressure or, for maxirnum loading, acombination of both. Any sub-ambient temperature is useful with a practical limit being the sublimation temperature of dry ice at 1 atmosphere, minus 78.5C.
Elevated pressures of up to several hundred pounds, usually about 80 psig, preferclbly up to about 50 psig, can be usefully employed. To summariæe, -the C2 loading conditions include a temperature of about 35 to minus 78C and a pressure of 0 to about 80 psig.
To be usefully employed in the subject carbonation process, the activated charcoal should contain at least 20 cm3 to CO2 per gram of charcoal, preferably 40 cm3/gram. As used herein the volume of adsorbed CO2 is measured at standard conditions of temperature and pressure, OC and 1 atmosphere.
This minimum level is readily obtained at ambient conditions. Where lower temperatures and/or higher pressures are employed the adsorptive capacity of the useful activated charcoals is 400 cm3 of CO2/gram 05 or higher.
The loaded charcoal is a stable product and can be stored until it is desired to prepare carbonated beverages. However, since water will displace the adsorbed carbon dioxide from the activated charcoal, it is important that appropria-te storage conditions be used. Efficient storage may be provided by storing the charcoal under substan-tially anhydrous conditions. Where elevated pressures were used for the CO2 adsorption, the adsorption level may he maintained by storing the charcoal at substantially the same pressure employed for the adsorptio~ or at a storage pressure slightly above--the adsorption pressure. Similarly, where lower temperatures are employed to increase the CO2 adsorp-tion over that obtained at ambient or slightly aboveambient temperatures, the storage temperature should be no more than the adsorp-tion temperature to maintain the CO2 loading. The ac-tivated charcoal can be packaged under anhydrous conditions in sealed packages which can then be stored at a required temperature, for example, in a refrigerator or a freezer. Where elevated storage pressures are required, the storage vessel obviously must be capable of maintaining that pressure during the storage period. Since s-torage pressures of 80 psig are contemplated by this inven-tion, a soft drink can or similar metal container can safely serve as a storage vessel. By providing the proper storage containers or packages and the necessary storage temperature and/or pressure, activated charcoal containing adsorbed carbon dioxide can be stored essentially indefinitely. A shelf life of several months and usually substantially longer, can be readily achieved.
The water employed to prepare carbonated 05 beverages according to this invention may be any type of drinking water available to the user.
Household tap water, bottled water, fresh drinking water from a campsite stream, etc., are examples of water available at point of consumption preparation of these carbonated beverages.
In accordance with the practice of this invention water and activated charcoal containing at least 20 cm3 of adsorbed carbon dioxide per gram of charcoal are contacted in a vessel, Vi2 . drinking glass, pitcher, pressure vessel, etc. The water - displaces the carbon dioxide releasing it to the body of water where it is dissolved to produce carbonated water. In a preferred embodiment, color-ing, flavorin~ and sweetener are added to or dissolved in the water so as to produce a carbonated beverage.
The coloring, flavoring and swee-tener can conveniently be provided in a syrup form~ available commercially, or in a dry mix, also available commercially. In this Eashion, such familiar beverayes as carbonated cola, carbonated root beer, carbonated lemon-lime soda, carbonated cream soda, etc., can be prepared at home. Only the ingenuity of the user, the availa-bility of flavored syrup or dry mix and the individual tastes of the consumers limit the variety of carbonated beverages which may be prepared by the process of this invention.
The carbonation achieved by the prac-tice of this inven-tion under normal conditions of temper-ature and pressure generally exceeds 1 volume and generally is in the range of 1.3 - 1.5. C'arbonation in the soft drink beverage industry is expressed as "volumes of carbonation" or "volumes of C02" and is defined as -the volume of C02 (measured at standard conditions of 0C and 1 atmosphere) dissolved per 05 volume of carbonated liquid.
Where higher volumes of carbonation are desired, i.e., from 1.5 to about 4.0, the carbonation must be conducted, in accordance with the present invention, in a closed vessel at superatmospheric pressure of up to about 80 psig. In achieving these higher carbonation levels, it is preferred to use activated charcoal having higher loadings of C02, e.g., above about 80 cc/g, preferably about 100 cc/g. These levels may be achieved at loading conditions of reduced temperature and/or elevated - pressure. Since the upper limit of loading pressure is about 80 psig there is an inherent safety aspect in this superatmospheric carbonation, the maximum pressure that is developed in the closed vessel is that which was employed in preparing the loaded charcoal. Although it is preferred that a head space be provided above the li~uid in the closed carbonation vessel, this is not cri-tical when activa-ted charcoal is the source of the carbonation since this material releases the carbon dioxide at such a slow rate that it is rapidly taken up by the liquid being carbonated.
Thereore closed vessel carbonation with activated charcoal can be conducted without an appreciable head space. This is not the situation where molecular sieves are the carbonation medium. The rapid release of the carbon dioxide from molecular sieves requires that an appreciable head space (vapor space) be provided above the liquid where the carbonation is conducted in a closed vessel. Even where a head space is provided, the carbon dioxide released from molecular sieves may develop an undesirable high pressure.
The relative quantities of activated charcoal and water to be employed in practicing this 05 invention so as to prepare carbonated liquids depend, obviously, on a number of factors, such as, the volume of carbonation desired in the beverage, the quantity of carbonated beverage being prepared, the amount of carbon dioxide which escapes from the surface of the liquid and the quantity of carbon dioxide adsorbed on the charcoal. Generally, about 0.2 to about 12 grams of activated charcoal loaded with carbon dioxide will be reguixed to prepare one fluid ounce of carbonated beverage. This range provides for a carbonation volume of from 1.3 to - about 4~0, a C02 loading of 20 to 400 cm3/gram and a --C2 utilization of about 50%. Those skille~ in the art can appreciate that the necessary amoun~ is readily calculable or can be determined by a few sample preparations.
Carbonaton is usually achieved in accor-dance with the present invention by placing the C02 loaded activated charcoal in a vessel and adding the liquid to be carbonated so that it covers the charcoal, Since the charcoal remains in the vessel following carbonation, the carbonated liquid and the charcoal must be separa~ed by, for example, decanting, filtration or straining of the carbonated liquid.
Alternatively, the charcoal can be confined in a chamber in the vessel having a surface which is pervious to gas and liquid but impervious to solids.
In a similar fashion the loaded activated charcoal can be contained in an envelope or bag having a surface which permits the passage of CO2 and water but retains the solid charcoal within its interior.
When carbonation is conducted at super-atmospheric pressure, a closed vessel or assembly, capable of withstanding pressure of up to abou-t 80 psig can be employed. In one embodiment, a rigid 05 receptacle in the shape of a wide-mouth bottle serves as -the container for the liquid to be carbonated. A domed cover adap-ted to be affixed to the container serves as the receptacle for the charcoal. This domed cover is provided with a hinged screen which extends across the open end of the cover. When the cover is affixed to the container, the screen partitions off the inside of the cover from the lower containPr. The openings in the screen are sized to permit free passage of gas and liquid while preventing the passage of the activated charcoal in the form it is being employed. In use,-the domed cover is removed from the lower container, and tap water is placed in -the lower container.
Optionally, a flavored syrup or dry mix containing coloring, flavoring, and sweetener is admixed with the water in the lower container. The screened portion of the cover is swung back, the necessary quantity of CO2 loaded activated charcoal is placed inside the domed cover, the sc:reen is placed back into position and retained the:re by fastening means provided for -that purpose. The cover is then affixed to the lower container and the entire assembly is placed in an inverted position so as to bring the water and activated charcoal into contact. Following a sufficient period of time for the water to displace the carbon dioxide and effect carbonation of the liguid, the apparatus is returned to its upright position. A spring loaded, manually operated valve, provided in the domed cover for the purpose, is depressed -to relieve the pressure within the closed vessel. The cover is then removed to dispense the carbonated beverage into serving glasses.
In another embodiment, the charcoal and water are both placed in the same portion of the apparatus 05 and the cover is affixed. Following sufficient time for the carbonation, the cover is removed and the beverage is poured through a screen to separate the charcoal from the beverage.
The activated charcoal may usefully be employed in a variety of shapes and forms. Granules, powder or pellets are readily available forms of activated charcoal which may be employed. By combining these forms of charcoal with appropriate, inert binders, such as clay, etc. discs o activated charcoal may be prepared which can be employed in practicing this inventio~.
In a preferred embodiment, activated charcoal in the form of discs, is loaded with C02 at an elevatecl pressure of up to about 50 psig or up to about 80 psig and, optionally, a low temperature, for example 0 to -78C, to maximize the C02 adsorption.
The discs can then be packagecl under the same elevated pressure in containers similar to beverage cans provided with removable or pierceable covers. Where ~5 the CO2 adsorption was conducted under low temperature, the packaged discs can be stored in a household refrigerator freezer until needed. Preferably the container should be provided with a resealable cover to permit a number of discs to be packaged therein and removed as needed over a period of time. Upon resealing the remaining discs will provide pressure in the container.
When a carbonated beverage is to be prepared, the container is removed rom storage, the necessary number of charcoal discs are removed and the container is resealed and returned to storage. Although the discs should be used fairly promptly after removal from the pressuri~ed container, the release of the C2 from activated charcoal is sufficiently slow so 05 that the bulk of the CO2 is retained despite exposure to atmospheric pressure. For example, an activated charcoal held at about 100-110 psig and than vented to one atmosphere will, at two minutes after venting, retain cibout 50% more than its 1 atmosphere capaci-ty.
As discussed above, carbonation with a chemical "couple~' usually produces a salty taste which is unpleasant to a large percentage of the public.
This is one of the serious drawbacks of this type of point of consumption carbonation. However, the salt produced by the "couple" must reach a threshold concentration before the consumer becomes aware of the salty taste. Often 0.5 to 1.0 volumes of carbonation can be produced from a chemical couple before the consumer can perceive a salty off-flavor.
Therefore since there are economic advantage for using the "couple", carbonation can be achieved by combining a low level of chemical "couple" carbonation with -the carbonation from CO2 loaded charcoal to produce a high level of carbonation in soft drink ~5 beverages without a noticeable salty off-taste.
The following examples will serve to illustrate the subject inven-tion.
. . . _ Several adsorbents of varying types were examined for their adsorptive properties. These included activated carbons, natural polymeric materials and 05 various inorganic adsorbents. For use in carbonation, there are two important re~uiremen-ts for an adsorbent:
~irst, it must adsorb enough carbon dioxîde at ambient temperature so that an inordinate quantity will not be required for carbonation and secondly, the carbon dioxide adsorbed mus-t be released when the adsorbent is in contact with water for a short period of time.
The CO2 adsorption capacity of various adsorbents was measured on an all glass volumetric BET (Brunauer, Emmett, and Teller~ gas adsorption apparatus. Small amounts of weighed adsorbent were outgassed (<10 5 mm Hg) on the BET at ambien-t or elevated temperatures depending on the properties of -the sample. A measured aliquot of CO2 gas was then entered into the system and -the CO2 uptake by the adsorbent measured as a function of temperature and pressure. The CO2 adsorption capacities of the various adsorbents investigated were reported in cubic centimeters of C2 at STP (0C, 760 mm Hg~ per gram of adsorbent.
For screening purposes the volume of CO2 adsorbed per gram at 34C and one atmosphere of CO2 was taken as an indicator of the efficiency of an adsorbent in retaining CO2; the higher the volume of CO2 adsorbed, the more efficient is the adsorbent (i.e., less soiid is needed for delivering a certain volume of CO2). The temperature of 34C (93F) was chosen to represent approxima-tely the stora~e temperature duriny the summer mon-ths.
The results for those commercial charcoals ~hich showed superior adsorptive properties are presented in Table I below. Data for zeolite 13X, which has a larger adsorptive capacity than zeolite 05 lOX or the type A zeolites, is also listed for comparison purposes. The result for other commercial and experimental charcoals as well as for charcoals - prepared in the laboratory are presented in Table II
below. The adsorption data presented in both tables was obtained at 1 atmosphere pressure and, in most cases, at three temperatures, 34, minus 18 and minus 7~C.
~ 3g3 TABLE I
Pore Diameter (A) Volume of C0 Manufacturer's Adsorbed (cc(STP~/gm) Data Manufacturer 34C -18C -78C
05 Zeolite 13X 10 Union Carbide 82 111 ~153 Soconut Charcoal (PCB) 15-20 Calgon 52 121 ~ 250 Coconut Charcoal (208C) 7~ 8 Sutcliffe 44 100 ~ 204 Speakman Coconut Charcoal (AC~ 15-17 Barneby Cheney 48 108 7 304 10 Coconut Charcoal (BD~ 11 Barneby Cheney 50 -~
Saran*Charcoal 4-6 Dow Chemical 75 158 ---Carbosphere * 13 Alltec~ 72 -* Trade Mark ,~
.
PROCESS FOR PREPARING CARBONATED
LIQUIDS WITH ACTIVATED CHARCOAL
. _ Technical Field . _ _ .
05 This invention relates to carbonated beverages. More particularly, it relates to consumer or "at home" prepara-tion of carbonated beverages having substantially the same palatabili-ty and effervescence of bottled or canned carbonated beverages.
This invention especially relates -to the preparation of carbonated beverages from activated charcoal which contains adsorbed carbon dioxide.
Background of the Invention Attempts to commercialize point of consump-tion or at home preparation of carbonated beverages have not met with any lasting success over the years. The principal shortcoming of the several techniques has been that the consumer-prepared carbonated beverage has been significantly inferior in one or more aspects to the bottled or canned carbonated beverages available in s-tores and super-markets. The most common complaints leveled at the carbonated beverage prepared by the consumer is that , 3`
the quality and the guantity o~ the carbonation, the bubble size and the duration of the effervescence does not compare favorably with the commercially available bottled carbonated beverage.
05 On the other hand, there are si~nificant advantages to consumer preparation of carbonated beverages vis-a-vis packaged liquid carbonated beverages. Thus, the use of glass, metal or other bulky containers is avoided, the necessity of bottling, shipping and storing carbonated beverages consisting o~ a ma3or percentage of water is eliminated and the utility in terms of portability by the user is greatly enhanced. Thus, campers, packpackers, hun-ters, fishermen, outdoor spectators, housewives and travellers can enjoy a carbonated beverage without having to transport bulky and heavy quantities o~
the canned or bottled variety. Further, disposable and returnable cans and bottles would no longer be of major concern to environmentalists who have been ~0 seeking ways to conserve both the country's natuxal resources and natural beauty.
U.S. Patent No. 2,073,273 to We-ts-tein discloses a means to prepare a carbonated beverage wherein water plus sweetener and flavor is placed in a small pressure vessel and a metal cartridge contain-ing carbon dioxide is inserted into the sealed vessel where movement of the cartridge causes a piercing o~ the cartridge thereby injecting the carbon dioxide into the water to form the carbonated beverage. The carbon dioxide also pressurizes the vapor space above the liquid causing the carbonated beverage to pass out o~ -the vessel through a serving nozzle when an external valve is opened. This de~ice met wi-th some measure o~ success in preparing un~lavored and unsweetened carbonated water for home use, but the carbonation volume was lower than bottled club soda.
The prior art includes a significant number of dry compositions for use in preparing 05 carbonated beverages at home. In most of these a source of carbsnate and acid, kno~n in the art as a chemical "couple", are combined with sweeteners and a source of flavor so that upon addition of the composition to a glass of water, the "couple" reacts to yield carbon dioxide and at least some measure of carbonation to the beverage. U.S. Patent No. 2,603,569 to Alther discloses the carbonation of a citric acid-sucrose complex with a sodium bicarbonate-sucrose complex. U.S. Patent No. 2,742,363 to Hughes claims a combination of an alkali metal bicarbonate and a sulfonic acid ion exchange resin in i-ts hydrogen form. ~n U.S. Patent Nos. 2,851,359 and 2,953,459 to Diller a highly soluble phosphate and a slowly soluble phosphate are combinecl with an alkali metal or ammonium carbonate or bicarbonate to prolong the ebullition of the beverage. U.S. Patent No. 3,241,977 to Mitchell et al. discloses c:hemical carbonation with citric, adipic or tartaric acid in finely divided ~orm and which is saicl to approximate the carbonation sensation of cola-type beverages sold in air-tight bottles or cans which are produced by a satura-ted solution containing several volumes of carbon dioxide. U.S. Patent No. 3,~11,417 to Feldman et al. discloses a dry beverage composition adapted to be reconstituted with water to an effervescent beverage which includes as an essential carbona-ting ingredient, an organic compound having a carbonic acid anhydride group, capable of controlled hydrolysis in water to releas~ carbon dioxide at a substantially uniform rate. U.S. Patent No. 3,667,962 to Fritzberg et al. discloses a carbonation composition utilizing two distinct bodies formed from an a~ueous solution of a saccharide, one contains an edible food acid and -the other an edible bicarbonate. Upon addition 05 to water the two t.able-ts dissolve quickly and react to evolve carbon dioxide.
Many of the dry powder chemical couples have a common and acknowledged defect, an unpleasant taste in the beverage directly resulting from the components of the powder. U.S. Patent No. 2,742,363 to Hughes and U.S. Patent No. 3,476,520 to Hovey addressed this problem by placing the chemicals in a container which is pervious to gas and water but impervious to solid reactants and by-products. U.S.
Patent No. 2,975,603 to Barnes et al. takes another approach by utilizing carbonated ice containing at least 25 milliliters of carbon di.oxide per gram of ice as the source of carbonation.
U.S. Patent No. 2,882,244 to Milton discloses the preparation and composition of zeolite X.
Milton teaches that zeolite X adsorbs water more strongly than carbon dioxide and that a more strongly held adsorbate, such as water, will displace a less strongly held adsorbate, such as carbon dioxide.
Further, comparison data are presented which show that at low pressures, ziolite X has a higher adsorptive capacity for water and carbon dioxide than does charcoal. However, the data presented for charcoal are inconclusive on its relative adsorptive capacity for water and carbon dioxide since they were not measured at the same pressure. Further, the physical properties and nature of the charcoal are not presen-ted.
Milton also teaches that common adsorbents such as, charcoal and silica gel, behave differently from ziolite X and do not ~xhibit its molecular sieve action. Rather than showing preference for polar, polarizable lmsaturated molecules as does ziolite X, charcoal and silica gel are said to show a main preference based on volatility of the adsorbate.
05 U.S. Patent Nos. 3,888,998 to Sampson et al., 3,992,493 and 4,025,655 to Whyte et al. and 4,007,134, 4,110,255 and 4,147,808 to Liepa et al.
disclose carbonation methods, compositions and devices whereby carbon dioxide containing molecular sieves a~e used to carbonate aqueous solutions.
Sampson et al. and Whyte et al. teach the use of molecular sieves having at least 5 weight percent adsorbed carbon dioxide for effectin~ the carbonation of aqueous liquids. Molecular sieves having larger pore openings (greater than 6 Angstroms) were found to release carbon dioxide to aqueous liquids at a high rate but this rate is not sustained over a long period. Molecula:r sieves having small pore openings (3-5 Angstroms, particularly 3-4 Angstroms), on the other hand, released carbon dioxide to aqueous liquids at a slower rate but for a long period of time. In addition, the large pore sieves adsorbed suhstan-tially more C02 per unit weight than the 3-5A sieves. Liepa et al. disclose carbonation devices composed of molecular sieves formed into a rigid body having a specific surface area to mass ratio which may be achieved by providing vertical channels throu~h the rigid body. These patentees found that when carbon dioxide is adsorbed into these discs, it will be released when the disc is contacted with water. They also teach that common adsorbents, such as charcoal and silica gel, do not have the adsorptive capacity necessary to carbonate a beverage at the point of consumption.
The use of molecular sieves for carbonating li~uids may lead to the inefficient use of carbon dioxide. Rapid release rates of carbon dioxide into the liquid to be carbonated can result in the loss 05 of a major portion of the carbon dioxide from the liquid to the surrounding atmosphere. Carbonation processes which more efficiently utilize carbon dioxide are therefore highly desirable.
Thus, it is an object of this invention to provide a simple process for point of consumption preparation of carbonated beverages which increases the efficient use of carbon dioxide, i.e., substan-tially reduces the amount of carbon dioxide escaping from the beverage during the carbonation process, while producing a carbonated beverage having substan-tially the same taste and effervescence of the commercially available product.
Summary of the Invention In accordance with the present invention, it has been found that carbonated water and/or beverages can be prepared by c:ontacting water with activated charcoal having carbon dioxide adsorbed therein. More particularly, this invention is directed to a method of carbonating an aqueous liguid which comprises contacting an aqueous liquid with an effective amount of activated charcoal having adsorbed -therein at least 2C cm3 of carbon dioxide per gram of charcoal. In a preferred embodi~
ment, the carbonation is conducted in a closed vessel under superatmospheric pressure.
Brief Descriptlon of the Drawings The present invention will be more readily understood by reference to -the accompanying drawings.
Figure 1 is a graph of the volume of carbon dioxide adsorbed on two activated coconut charcoals versus adsorption pressure.
Figure 2 is a graph of the volume of 05 carbon dioxide adsorbed on two activated coconut charcoals versus the time after pressure on the charcoals was vented.
Figure 3 and 4 are graphs of the volumes of carbonation produced in water by various quantities of coconut charcoal and zeolite 13X versus the time of carbonation.
Description of the Preferred Embodiments Beverage carbonation with activated charcoal having carbon dioxide adsorbed thereon provides a system which makes more efficient use of the carbon dioxld~ than is obtained with a process which utilizes zeolites containing adsorbed carbon dioxide. Although zeolites adsorb more carbon dioxide per uni-t weight, under ambient conditions, than does activated charcoal, when the sieves are i.mmersed in water, the initial rate of CO2 releases from the! sieves is much higher than ~rom the activated charcoal. Conse~uently, the activated charcoal provides a higher Co2 retention efficiency in the beverage compared to molecular sieves. The fact that the charcoal surfaces are mostly hydrophobic in nature may explain why the activated charcoal exhibits a more controlled initial rate of CO2 release on immersion ln water, compared with the highly hydrophilic ~ionic) molecular sieves.
Activated charcoals are prepared by the destructiv~ pyrolysis of natural and syn-thetic organic materials. Among the widely used natural produc-ts are coal, petroleum, polysaccharides, such as sugars and starches and cellulosics. such as woody ~ 3 by-products, coconut shells, hard and soft woods, fruit pits and corncobs. Synthetic polymeric materials such as saran, polyfurfuryl alcohol and polystyrene-divinyl benzene copolymers, can be used 05 to prepare activated charcoals with very uniform mocroporous structures. These starting materials are converted to activated charcoals by first carbon-izing at 400-500C to eliminate the bulk of the volatile matter and then oxidizing (activating) with gas at ~00-1000C to develop the porosity and surface area. Not all activated charcoals may be employed in the sùbject invention. The activated charcoal must have an adsorptive capacity for carbon dioxide at ambient conditions and the adsorbed carbon dioxide must be released when the charcoal is contacted with wa-ter. Only activated charcoals having pores in -the r~nge of about 4 to about 20 Angstroms can adsorb C2 at ambient temperature and pressure. However, charcoals having pores as wide as about 50 Agstroms can be filled with adsorbed carbon dioxide at sub-ambient temperatures and/or pressures about 1 atmos-phere. Thus, activated charcoal having pore sizes of about 4 to about 50 Angstroms and having the ability to adsorb C02 and desorb it when contacted with water may usefully be employed in the subject invention, with activated charcoal prepared from natural products being preferred and activated charcoal prepared from coconut shells being parti-cularly preferred.
Carbon dioxide is adsorbed onto the activated charcoal by contacting the charcoal with gaseous or liquid carbon dioxide. Since water displaces the C2 from the charcoal, the adsorption ~or loading) should be conducted under anhydrous conditions. The charcoal should be dehydrated before being loaded with CO2 by such means as subjecting it to dry heat to reduce its adsorbed moisture conten-t. One conven-ient method of preparing the co2 loaded charcoal is 05 in a column packed with the activated charcoal. A
stream of heated dry gas, such as carbon dioxide, air or nitrogen, is passed through the column -to reduce the moisture content of the charcoal and then gaseous or liquid carbon dioxide is passed through the column to load the activated charcoal. The adsorption can be conducted at ambient or slightly above ambient temperature and substantially atmospheric pressure, i.e., just enough positive pressure to ensure a flow of carbon dioxide through the column.
Where hiyher loading of the activated charcoal is desired or where the subsequent carbonation is to be conducted in a closed vessel at superatmospheric pressure, -the CO2 adsorption onto the charcoal is conducted at sub-ambient tempexature or super-atmospheric pressure or, for maxirnum loading, acombination of both. Any sub-ambient temperature is useful with a practical limit being the sublimation temperature of dry ice at 1 atmosphere, minus 78.5C.
Elevated pressures of up to several hundred pounds, usually about 80 psig, preferclbly up to about 50 psig, can be usefully employed. To summariæe, -the C2 loading conditions include a temperature of about 35 to minus 78C and a pressure of 0 to about 80 psig.
To be usefully employed in the subject carbonation process, the activated charcoal should contain at least 20 cm3 to CO2 per gram of charcoal, preferably 40 cm3/gram. As used herein the volume of adsorbed CO2 is measured at standard conditions of temperature and pressure, OC and 1 atmosphere.
This minimum level is readily obtained at ambient conditions. Where lower temperatures and/or higher pressures are employed the adsorptive capacity of the useful activated charcoals is 400 cm3 of CO2/gram 05 or higher.
The loaded charcoal is a stable product and can be stored until it is desired to prepare carbonated beverages. However, since water will displace the adsorbed carbon dioxide from the activated charcoal, it is important that appropria-te storage conditions be used. Efficient storage may be provided by storing the charcoal under substan-tially anhydrous conditions. Where elevated pressures were used for the CO2 adsorption, the adsorption level may he maintained by storing the charcoal at substantially the same pressure employed for the adsorptio~ or at a storage pressure slightly above--the adsorption pressure. Similarly, where lower temperatures are employed to increase the CO2 adsorp-tion over that obtained at ambient or slightly aboveambient temperatures, the storage temperature should be no more than the adsorp-tion temperature to maintain the CO2 loading. The ac-tivated charcoal can be packaged under anhydrous conditions in sealed packages which can then be stored at a required temperature, for example, in a refrigerator or a freezer. Where elevated storage pressures are required, the storage vessel obviously must be capable of maintaining that pressure during the storage period. Since s-torage pressures of 80 psig are contemplated by this inven-tion, a soft drink can or similar metal container can safely serve as a storage vessel. By providing the proper storage containers or packages and the necessary storage temperature and/or pressure, activated charcoal containing adsorbed carbon dioxide can be stored essentially indefinitely. A shelf life of several months and usually substantially longer, can be readily achieved.
The water employed to prepare carbonated 05 beverages according to this invention may be any type of drinking water available to the user.
Household tap water, bottled water, fresh drinking water from a campsite stream, etc., are examples of water available at point of consumption preparation of these carbonated beverages.
In accordance with the practice of this invention water and activated charcoal containing at least 20 cm3 of adsorbed carbon dioxide per gram of charcoal are contacted in a vessel, Vi2 . drinking glass, pitcher, pressure vessel, etc. The water - displaces the carbon dioxide releasing it to the body of water where it is dissolved to produce carbonated water. In a preferred embodiment, color-ing, flavorin~ and sweetener are added to or dissolved in the water so as to produce a carbonated beverage.
The coloring, flavoring and swee-tener can conveniently be provided in a syrup form~ available commercially, or in a dry mix, also available commercially. In this Eashion, such familiar beverayes as carbonated cola, carbonated root beer, carbonated lemon-lime soda, carbonated cream soda, etc., can be prepared at home. Only the ingenuity of the user, the availa-bility of flavored syrup or dry mix and the individual tastes of the consumers limit the variety of carbonated beverages which may be prepared by the process of this invention.
The carbonation achieved by the prac-tice of this inven-tion under normal conditions of temper-ature and pressure generally exceeds 1 volume and generally is in the range of 1.3 - 1.5. C'arbonation in the soft drink beverage industry is expressed as "volumes of carbonation" or "volumes of C02" and is defined as -the volume of C02 (measured at standard conditions of 0C and 1 atmosphere) dissolved per 05 volume of carbonated liquid.
Where higher volumes of carbonation are desired, i.e., from 1.5 to about 4.0, the carbonation must be conducted, in accordance with the present invention, in a closed vessel at superatmospheric pressure of up to about 80 psig. In achieving these higher carbonation levels, it is preferred to use activated charcoal having higher loadings of C02, e.g., above about 80 cc/g, preferably about 100 cc/g. These levels may be achieved at loading conditions of reduced temperature and/or elevated - pressure. Since the upper limit of loading pressure is about 80 psig there is an inherent safety aspect in this superatmospheric carbonation, the maximum pressure that is developed in the closed vessel is that which was employed in preparing the loaded charcoal. Although it is preferred that a head space be provided above the li~uid in the closed carbonation vessel, this is not cri-tical when activa-ted charcoal is the source of the carbonation since this material releases the carbon dioxide at such a slow rate that it is rapidly taken up by the liquid being carbonated.
Thereore closed vessel carbonation with activated charcoal can be conducted without an appreciable head space. This is not the situation where molecular sieves are the carbonation medium. The rapid release of the carbon dioxide from molecular sieves requires that an appreciable head space (vapor space) be provided above the liquid where the carbonation is conducted in a closed vessel. Even where a head space is provided, the carbon dioxide released from molecular sieves may develop an undesirable high pressure.
The relative quantities of activated charcoal and water to be employed in practicing this 05 invention so as to prepare carbonated liquids depend, obviously, on a number of factors, such as, the volume of carbonation desired in the beverage, the quantity of carbonated beverage being prepared, the amount of carbon dioxide which escapes from the surface of the liquid and the quantity of carbon dioxide adsorbed on the charcoal. Generally, about 0.2 to about 12 grams of activated charcoal loaded with carbon dioxide will be reguixed to prepare one fluid ounce of carbonated beverage. This range provides for a carbonation volume of from 1.3 to - about 4~0, a C02 loading of 20 to 400 cm3/gram and a --C2 utilization of about 50%. Those skille~ in the art can appreciate that the necessary amoun~ is readily calculable or can be determined by a few sample preparations.
Carbonaton is usually achieved in accor-dance with the present invention by placing the C02 loaded activated charcoal in a vessel and adding the liquid to be carbonated so that it covers the charcoal, Since the charcoal remains in the vessel following carbonation, the carbonated liquid and the charcoal must be separa~ed by, for example, decanting, filtration or straining of the carbonated liquid.
Alternatively, the charcoal can be confined in a chamber in the vessel having a surface which is pervious to gas and liquid but impervious to solids.
In a similar fashion the loaded activated charcoal can be contained in an envelope or bag having a surface which permits the passage of CO2 and water but retains the solid charcoal within its interior.
When carbonation is conducted at super-atmospheric pressure, a closed vessel or assembly, capable of withstanding pressure of up to abou-t 80 psig can be employed. In one embodiment, a rigid 05 receptacle in the shape of a wide-mouth bottle serves as -the container for the liquid to be carbonated. A domed cover adap-ted to be affixed to the container serves as the receptacle for the charcoal. This domed cover is provided with a hinged screen which extends across the open end of the cover. When the cover is affixed to the container, the screen partitions off the inside of the cover from the lower containPr. The openings in the screen are sized to permit free passage of gas and liquid while preventing the passage of the activated charcoal in the form it is being employed. In use,-the domed cover is removed from the lower container, and tap water is placed in -the lower container.
Optionally, a flavored syrup or dry mix containing coloring, flavoring, and sweetener is admixed with the water in the lower container. The screened portion of the cover is swung back, the necessary quantity of CO2 loaded activated charcoal is placed inside the domed cover, the sc:reen is placed back into position and retained the:re by fastening means provided for -that purpose. The cover is then affixed to the lower container and the entire assembly is placed in an inverted position so as to bring the water and activated charcoal into contact. Following a sufficient period of time for the water to displace the carbon dioxide and effect carbonation of the liguid, the apparatus is returned to its upright position. A spring loaded, manually operated valve, provided in the domed cover for the purpose, is depressed -to relieve the pressure within the closed vessel. The cover is then removed to dispense the carbonated beverage into serving glasses.
In another embodiment, the charcoal and water are both placed in the same portion of the apparatus 05 and the cover is affixed. Following sufficient time for the carbonation, the cover is removed and the beverage is poured through a screen to separate the charcoal from the beverage.
The activated charcoal may usefully be employed in a variety of shapes and forms. Granules, powder or pellets are readily available forms of activated charcoal which may be employed. By combining these forms of charcoal with appropriate, inert binders, such as clay, etc. discs o activated charcoal may be prepared which can be employed in practicing this inventio~.
In a preferred embodiment, activated charcoal in the form of discs, is loaded with C02 at an elevatecl pressure of up to about 50 psig or up to about 80 psig and, optionally, a low temperature, for example 0 to -78C, to maximize the C02 adsorption.
The discs can then be packagecl under the same elevated pressure in containers similar to beverage cans provided with removable or pierceable covers. Where ~5 the CO2 adsorption was conducted under low temperature, the packaged discs can be stored in a household refrigerator freezer until needed. Preferably the container should be provided with a resealable cover to permit a number of discs to be packaged therein and removed as needed over a period of time. Upon resealing the remaining discs will provide pressure in the container.
When a carbonated beverage is to be prepared, the container is removed rom storage, the necessary number of charcoal discs are removed and the container is resealed and returned to storage. Although the discs should be used fairly promptly after removal from the pressuri~ed container, the release of the C2 from activated charcoal is sufficiently slow so 05 that the bulk of the CO2 is retained despite exposure to atmospheric pressure. For example, an activated charcoal held at about 100-110 psig and than vented to one atmosphere will, at two minutes after venting, retain cibout 50% more than its 1 atmosphere capaci-ty.
As discussed above, carbonation with a chemical "couple~' usually produces a salty taste which is unpleasant to a large percentage of the public.
This is one of the serious drawbacks of this type of point of consumption carbonation. However, the salt produced by the "couple" must reach a threshold concentration before the consumer becomes aware of the salty taste. Often 0.5 to 1.0 volumes of carbonation can be produced from a chemical couple before the consumer can perceive a salty off-flavor.
Therefore since there are economic advantage for using the "couple", carbonation can be achieved by combining a low level of chemical "couple" carbonation with -the carbonation from CO2 loaded charcoal to produce a high level of carbonation in soft drink ~5 beverages without a noticeable salty off-taste.
The following examples will serve to illustrate the subject inven-tion.
. . . _ Several adsorbents of varying types were examined for their adsorptive properties. These included activated carbons, natural polymeric materials and 05 various inorganic adsorbents. For use in carbonation, there are two important re~uiremen-ts for an adsorbent:
~irst, it must adsorb enough carbon dioxîde at ambient temperature so that an inordinate quantity will not be required for carbonation and secondly, the carbon dioxide adsorbed mus-t be released when the adsorbent is in contact with water for a short period of time.
The CO2 adsorption capacity of various adsorbents was measured on an all glass volumetric BET (Brunauer, Emmett, and Teller~ gas adsorption apparatus. Small amounts of weighed adsorbent were outgassed (<10 5 mm Hg) on the BET at ambien-t or elevated temperatures depending on the properties of -the sample. A measured aliquot of CO2 gas was then entered into the system and -the CO2 uptake by the adsorbent measured as a function of temperature and pressure. The CO2 adsorption capacities of the various adsorbents investigated were reported in cubic centimeters of C2 at STP (0C, 760 mm Hg~ per gram of adsorbent.
For screening purposes the volume of CO2 adsorbed per gram at 34C and one atmosphere of CO2 was taken as an indicator of the efficiency of an adsorbent in retaining CO2; the higher the volume of CO2 adsorbed, the more efficient is the adsorbent (i.e., less soiid is needed for delivering a certain volume of CO2). The temperature of 34C (93F) was chosen to represent approxima-tely the stora~e temperature duriny the summer mon-ths.
The results for those commercial charcoals ~hich showed superior adsorptive properties are presented in Table I below. Data for zeolite 13X, which has a larger adsorptive capacity than zeolite 05 lOX or the type A zeolites, is also listed for comparison purposes. The result for other commercial and experimental charcoals as well as for charcoals - prepared in the laboratory are presented in Table II
below. The adsorption data presented in both tables was obtained at 1 atmosphere pressure and, in most cases, at three temperatures, 34, minus 18 and minus 7~C.
~ 3g3 TABLE I
Pore Diameter (A) Volume of C0 Manufacturer's Adsorbed (cc(STP~/gm) Data Manufacturer 34C -18C -78C
05 Zeolite 13X 10 Union Carbide 82 111 ~153 Soconut Charcoal (PCB) 15-20 Calgon 52 121 ~ 250 Coconut Charcoal (208C) 7~ 8 Sutcliffe 44 100 ~ 204 Speakman Coconut Charcoal (AC~ 15-17 Barneby Cheney 48 108 7 304 10 Coconut Charcoal (BD~ 11 Barneby Cheney 50 -~
Saran*Charcoal 4-6 Dow Chemical 75 158 ---Carbosphere * 13 Alltec~ 72 -* Trade Mark ,~
-2~-TABLE II
Com~ercial and Experimental Charcoals Volume of C0 Pore Adsorbed tcc/2) 05 Charcoal Diameter (~) Manufacturer 34C-18C -78C
AB, Coconut charcoal 20-25 Barnebey Cheney43 85 ?244 SG~, Coal charcoal18 Calgon 37 g2 423 CAL, Coal 20 Calgon 36 99 402 BPL, Coco~ut 8-10 Calgon 38 --- ---10 PXC, Coconut ~10 Calgon 26 AFC, Coal N.A. Calgon Low activated coconut N.A. Walker, P.J.
(Univ. of Penn.) 54 Beechwood N.A.Yale University 52 PX-21* Petroleum <20Amoco 37 JXAC, Coal Union Carbide 28 Ambersorb*XE-347 Rohm & Haas 38 Laboratory~ E~ed Charcoals ActivationVolume of C0 A~sorbed Temp. (C)(cc/g) at 34C
Prepared From Cellulose (ashless800 43 filter paper) Cellulose 1000 48 Sugar (sucrose) 800 43 charcoal Birchwood 950 34 Polyfurfuryl Alcohol 700 27 (PFA) * Trade Mark l~'' '`i The data in Table I show that the commercial charcoals tested had somewhat lower capacities than æeolite 13X under essentially ambient conditions but that the charcoals exhibited superior adsorptive capacities 05 at low temperature (-78C is the approximate sublimation point of dry ice at one atmosphere). In addition, the COCOllUt charcoals adsorbed more than twice as much-C02 at minus 18C than at 34C while zeolite 13X shows an increase o~ only about 35%.
Althouyh the polymer based charcoals, saran and carbosphere, showed exceptional adsorptive capacities, they did not always release C02 upon contact with water. The coconut charcoals showed significant C02 adsorption and released it into water in a reasonably short time.
The effPct of pressure on the adsorptive capacity of two coconut charcoals of Example I, identified as PCB and 208C, was evaluated. The CO2 adsorption of 05 each was measured at pressures ranging from 0 to in excess of 100 psig. Following the Co2 adsorption measurements at the high pressure, the vessel was vented and the CO2 retained in each charcoal was measured. The results from the measurements made with increasing pressure are presented in Figure 1 where the CO2 adsorption on each charcoal is plotted against pressure. The CO~ retained on each charcoal during the venting of the closed vessel is presented in Figure 2 where the CO2 retained is plotted against time after venting. Figure 1 shows that a pressure ~
of 50 psig approximately doubles the CO~ adsorptive capacity of either coconut charcoal tested. Figure 2 shows that two minutes after the pressure vessel was opened and vented to one atmosphere the charcoals retained about 50% more C02 than their capacities at one atmosphere.
The CO~ adsorption of some of the adsorbents of Example 1 was loaded at 30C and approximately 80 psig and was measured at several different combinations 05 of temperature and pressure. The results are presented in Table III, together with the data from Example 1 which was obtained at 1 atmosphere and 34C.
TABLE III
Press. C0 A~sorbed Adsorbent ~ psig 2cm /g_ Coconut Charcoal 30 81 128 05 (208C3 -17.5 6 138 34 0 4~
_ Coconut Charcoal 30 78 130 (PCB) -17.~ ~2 ~139 -- ~-Coconut Charcoal 30 79 97 ~ (SGL) 0 25.5 103 -17.5 6.5 105 Petroleum Charcoal 30 80 215 (PX-21) Zeolite 13X 30 80 95 -17 ~ 0 101 These data show that within the range of temperatures and pressures evaluated, the C02 adsorbed i6 dependent upon temperature and pressure employed. Charcoal is a superior carbon dioxide adsorbent at low temperatures 05 and/or high pressures.
~26-. .
Carbonation of wat~r under ambient conditions of temperature and pressure was evaluated for the activated coconut charcoal and zeolite 13X of Example 05 1. The adsorption capacity of each was:
Volume adsorbed, cc.g Adsorbent 34C', l atm Coconut charcoal (PCB 4X10 mesh) 52 Zeolite 13X (1/16" pellets)82 Each test run was conducted as follows:
Eight ounces of distilled water in a drinking glass were cooled to 5C. Without stirring, two ice cubes were added, ~ollowed by either ten or fifteen grams of the CO2 loaded adsorbent. The carbonation in solution was measured as a function of time using an Orion specific ion CO2 electrode and was reported in volumes o carbonation (cubic centimeters, CO2 (STP) per milliliter of beverage).
The data for the ten gram tests are presented in Figure III and that for the fifteen gram tests in Figure IV. In each instance the volumes of carbonation are plotted against the time after in~roduction of the adsorbent into the water. These data show that the coconut charcoal carbonated the water -to a higher volume of carbonation than zeolite 13Xr even though the zeolite cntained significantly more CO2.
These data were evaluated by the performance factors used by Sampson and Whyte (U.S Patent Nos.
31888~998~ 3/~92~493 and 4,025, 655) to evaluate carbonation systems. This performance factor combines the fraction of saturation obtained (effectiveness) g3 with the efficiency of carbonation for a given time period (4 minutes in this instance~. These results are summarized in Table IV below:
TABLE IV
E'our-minute Weiqht of adsorbent Performance Factor ~
Coconut zeolite- zeolite 05gm/8 oz. water Charcoal 13X _ 13X(l) 6 ~ -- 0.32 0.44 ~.~6 --12 ~ - 0.31 0.38 0.19 ---24 ~ - 0.21 (1)Example IV, Table 5 of the Sampson and Whyte patents.
The data of the Sampson and Whyte patents are based on results obtained at 0C whereas the remaining results were obtained at 5~C.
Charcoal is less hydrophilic than zeolite and therefore releases its C02 more slowly allowing more to be dissolved into the water and less lost to the air. This difference in the release of C02 can be 05 seen not only in the levels of carbona-tion attained, but in the time taken to achieve these levels.
Zeolite has maximum carbonation at about one minute whereas charcoal has a maximum around 5 minutes.
This sustained release of the charcoal also means that CO~ was still being desorbed after ten minutes while zeolite 13X had been effectively desorbed by this time. The continued release of C02 bubbles from the charcoal simulated the look of a highly carbonated beverage.
~epetition of carbonation with 15g of coconut charcoal showed values ranging from 1.3-1.5 volumes.
Carbonation values of 1.3-1.5 volumes were also obtained when 20g charcoal were used.
Example 5 The ability of -the activated coconut charcoal and zeolite 13X of Example 4 to carbonate water was evaluated in the following manner. The adsorbed 05 carbon dioxide content of the charcoal and the zeolite was 52 and 82 cc/g, respectively.
A weighed amount of loaded adsorbent was placed in a porous bag and suspended in the headspace of a 180 ml container containing 126 ml water. The container was closed and inverted to wet the charcoal.
The system was either shaken or allowed to sit as specified and equilibrated in a cold water bath.
The equilibrium pressure and temperature were recorded.
Any pressure buildup generated during the carbonation was also noted. The results are presented in Table V.
TABIE V
Adsorbent Water Max. Press Volume of wt. (&) T~e: Handling (Rsi ~ Carbonation (F) (from equil-05 ibrium head-space pressure) Coconut Charcoal (PCB) 8.4 80 Shaken while 18 1.55 Carbonating Shaken 32 2.18 39 Shaken 34 3.15 Charcoal submerged 37 3.7 while carbonating Charcoal wet once 48 3.35 quickly, not in contact with water while carbonating Zeolite 13X
7.5 44 Zeolite submerged 50 2.55 47 Zeolite submerged ~80, ---vented quickly~L-80 psig Beverages having carbonation volumes greater than three volumes were obtained when 15g of coconut charcoal (PCB) were used to carbonate 126 ml water ~120g adsorbent/qt~ at 40F (4.5C). The C02 release 05 ~rom zeolite 13X, however, was so fast that -the initial pressure buildup was much greater than 80 psig and had to be vented which limited the carbonation volume to about 2.5. A typical beverage container can withstand only 80-100 psig. The coconut charcoal showed a more sus-tained release generating pressure of less than 50 psig even when the charcoal was wet once and the C02 was allowed to release into the vapor space rather than the beverage. A conventional glass or metal beverage container can sustain such a pressure and can be used to prepare carbonated - beverages from C02 loaded activated charcoal.
One of the coconut charcoals of Example 1 and a chemical "couple" were utilized together in a closed system to prcduce a carbonated beverage. The chemical 05 "couple" employed was sodium bicarbonate and citric acid.
Orange flavored carbonated beverages were prepared in the fashion of Example 5 by placing the necessary ~uantities of water, and orange flavored dry mix, the chemical "couple" and the CO2 loaded coconut charcoal ~208C) in the container. Various amounts of chemical "couple" and charcoal ~ere employed.
The ~olumes of carbonation obtained were measured with a CO2 electrode. The results are presented in 15 Table VI below.
TABLE VI
.
Vol. o~
Carbonation ~0 Coconut Charcoal Contributed by Total (208C~ grams~_. Chem ''Couple" Vol. Carbonation 1.2 2.3
Com~ercial and Experimental Charcoals Volume of C0 Pore Adsorbed tcc/2) 05 Charcoal Diameter (~) Manufacturer 34C-18C -78C
AB, Coconut charcoal 20-25 Barnebey Cheney43 85 ?244 SG~, Coal charcoal18 Calgon 37 g2 423 CAL, Coal 20 Calgon 36 99 402 BPL, Coco~ut 8-10 Calgon 38 --- ---10 PXC, Coconut ~10 Calgon 26 AFC, Coal N.A. Calgon Low activated coconut N.A. Walker, P.J.
(Univ. of Penn.) 54 Beechwood N.A.Yale University 52 PX-21* Petroleum <20Amoco 37 JXAC, Coal Union Carbide 28 Ambersorb*XE-347 Rohm & Haas 38 Laboratory~ E~ed Charcoals ActivationVolume of C0 A~sorbed Temp. (C)(cc/g) at 34C
Prepared From Cellulose (ashless800 43 filter paper) Cellulose 1000 48 Sugar (sucrose) 800 43 charcoal Birchwood 950 34 Polyfurfuryl Alcohol 700 27 (PFA) * Trade Mark l~'' '`i The data in Table I show that the commercial charcoals tested had somewhat lower capacities than æeolite 13X under essentially ambient conditions but that the charcoals exhibited superior adsorptive capacities 05 at low temperature (-78C is the approximate sublimation point of dry ice at one atmosphere). In addition, the COCOllUt charcoals adsorbed more than twice as much-C02 at minus 18C than at 34C while zeolite 13X shows an increase o~ only about 35%.
Althouyh the polymer based charcoals, saran and carbosphere, showed exceptional adsorptive capacities, they did not always release C02 upon contact with water. The coconut charcoals showed significant C02 adsorption and released it into water in a reasonably short time.
The effPct of pressure on the adsorptive capacity of two coconut charcoals of Example I, identified as PCB and 208C, was evaluated. The CO2 adsorption of 05 each was measured at pressures ranging from 0 to in excess of 100 psig. Following the Co2 adsorption measurements at the high pressure, the vessel was vented and the CO2 retained in each charcoal was measured. The results from the measurements made with increasing pressure are presented in Figure 1 where the CO2 adsorption on each charcoal is plotted against pressure. The CO~ retained on each charcoal during the venting of the closed vessel is presented in Figure 2 where the CO2 retained is plotted against time after venting. Figure 1 shows that a pressure ~
of 50 psig approximately doubles the CO~ adsorptive capacity of either coconut charcoal tested. Figure 2 shows that two minutes after the pressure vessel was opened and vented to one atmosphere the charcoals retained about 50% more C02 than their capacities at one atmosphere.
The CO~ adsorption of some of the adsorbents of Example 1 was loaded at 30C and approximately 80 psig and was measured at several different combinations 05 of temperature and pressure. The results are presented in Table III, together with the data from Example 1 which was obtained at 1 atmosphere and 34C.
TABLE III
Press. C0 A~sorbed Adsorbent ~ psig 2cm /g_ Coconut Charcoal 30 81 128 05 (208C3 -17.5 6 138 34 0 4~
_ Coconut Charcoal 30 78 130 (PCB) -17.~ ~2 ~139 -- ~-Coconut Charcoal 30 79 97 ~ (SGL) 0 25.5 103 -17.5 6.5 105 Petroleum Charcoal 30 80 215 (PX-21) Zeolite 13X 30 80 95 -17 ~ 0 101 These data show that within the range of temperatures and pressures evaluated, the C02 adsorbed i6 dependent upon temperature and pressure employed. Charcoal is a superior carbon dioxide adsorbent at low temperatures 05 and/or high pressures.
~26-. .
Carbonation of wat~r under ambient conditions of temperature and pressure was evaluated for the activated coconut charcoal and zeolite 13X of Example 05 1. The adsorption capacity of each was:
Volume adsorbed, cc.g Adsorbent 34C', l atm Coconut charcoal (PCB 4X10 mesh) 52 Zeolite 13X (1/16" pellets)82 Each test run was conducted as follows:
Eight ounces of distilled water in a drinking glass were cooled to 5C. Without stirring, two ice cubes were added, ~ollowed by either ten or fifteen grams of the CO2 loaded adsorbent. The carbonation in solution was measured as a function of time using an Orion specific ion CO2 electrode and was reported in volumes o carbonation (cubic centimeters, CO2 (STP) per milliliter of beverage).
The data for the ten gram tests are presented in Figure III and that for the fifteen gram tests in Figure IV. In each instance the volumes of carbonation are plotted against the time after in~roduction of the adsorbent into the water. These data show that the coconut charcoal carbonated the water -to a higher volume of carbonation than zeolite 13Xr even though the zeolite cntained significantly more CO2.
These data were evaluated by the performance factors used by Sampson and Whyte (U.S Patent Nos.
31888~998~ 3/~92~493 and 4,025, 655) to evaluate carbonation systems. This performance factor combines the fraction of saturation obtained (effectiveness) g3 with the efficiency of carbonation for a given time period (4 minutes in this instance~. These results are summarized in Table IV below:
TABLE IV
E'our-minute Weiqht of adsorbent Performance Factor ~
Coconut zeolite- zeolite 05gm/8 oz. water Charcoal 13X _ 13X(l) 6 ~ -- 0.32 0.44 ~.~6 --12 ~ - 0.31 0.38 0.19 ---24 ~ - 0.21 (1)Example IV, Table 5 of the Sampson and Whyte patents.
The data of the Sampson and Whyte patents are based on results obtained at 0C whereas the remaining results were obtained at 5~C.
Charcoal is less hydrophilic than zeolite and therefore releases its C02 more slowly allowing more to be dissolved into the water and less lost to the air. This difference in the release of C02 can be 05 seen not only in the levels of carbona-tion attained, but in the time taken to achieve these levels.
Zeolite has maximum carbonation at about one minute whereas charcoal has a maximum around 5 minutes.
This sustained release of the charcoal also means that CO~ was still being desorbed after ten minutes while zeolite 13X had been effectively desorbed by this time. The continued release of C02 bubbles from the charcoal simulated the look of a highly carbonated beverage.
~epetition of carbonation with 15g of coconut charcoal showed values ranging from 1.3-1.5 volumes.
Carbonation values of 1.3-1.5 volumes were also obtained when 20g charcoal were used.
Example 5 The ability of -the activated coconut charcoal and zeolite 13X of Example 4 to carbonate water was evaluated in the following manner. The adsorbed 05 carbon dioxide content of the charcoal and the zeolite was 52 and 82 cc/g, respectively.
A weighed amount of loaded adsorbent was placed in a porous bag and suspended in the headspace of a 180 ml container containing 126 ml water. The container was closed and inverted to wet the charcoal.
The system was either shaken or allowed to sit as specified and equilibrated in a cold water bath.
The equilibrium pressure and temperature were recorded.
Any pressure buildup generated during the carbonation was also noted. The results are presented in Table V.
TABIE V
Adsorbent Water Max. Press Volume of wt. (&) T~e: Handling (Rsi ~ Carbonation (F) (from equil-05 ibrium head-space pressure) Coconut Charcoal (PCB) 8.4 80 Shaken while 18 1.55 Carbonating Shaken 32 2.18 39 Shaken 34 3.15 Charcoal submerged 37 3.7 while carbonating Charcoal wet once 48 3.35 quickly, not in contact with water while carbonating Zeolite 13X
7.5 44 Zeolite submerged 50 2.55 47 Zeolite submerged ~80, ---vented quickly~L-80 psig Beverages having carbonation volumes greater than three volumes were obtained when 15g of coconut charcoal (PCB) were used to carbonate 126 ml water ~120g adsorbent/qt~ at 40F (4.5C). The C02 release 05 ~rom zeolite 13X, however, was so fast that -the initial pressure buildup was much greater than 80 psig and had to be vented which limited the carbonation volume to about 2.5. A typical beverage container can withstand only 80-100 psig. The coconut charcoal showed a more sus-tained release generating pressure of less than 50 psig even when the charcoal was wet once and the C02 was allowed to release into the vapor space rather than the beverage. A conventional glass or metal beverage container can sustain such a pressure and can be used to prepare carbonated - beverages from C02 loaded activated charcoal.
One of the coconut charcoals of Example 1 and a chemical "couple" were utilized together in a closed system to prcduce a carbonated beverage. The chemical 05 "couple" employed was sodium bicarbonate and citric acid.
Orange flavored carbonated beverages were prepared in the fashion of Example 5 by placing the necessary ~uantities of water, and orange flavored dry mix, the chemical "couple" and the CO2 loaded coconut charcoal ~208C) in the container. Various amounts of chemical "couple" and charcoal ~ere employed.
The ~olumes of carbonation obtained were measured with a CO2 electrode. The results are presented in 15 Table VI below.
TABLE VI
.
Vol. o~
Carbonation ~0 Coconut Charcoal Contributed by Total (208C~ grams~_. Chem ''Couple" Vol. Carbonation 1.2 2.3
3~ 2.0 3.0 1~0 0 3-5 The use of a ch~mical "couple" can significantly reduce the amount of charcoal required to carbonate a beverage in a closed container. The combination of chemical "couple" and charcoal can produce carbonation levels similar to that of commercial bottled or canned soft drinks.
In the foregoing examples, the volume of carbon 05 dioxide adsorbed by the activated charcoal or other adsorbent under test is reported in terms of standard temperature and pressure t0C. and 760mm) regardless of the conditions used for -the adsorption.
In the foregoing examples, the volume of carbon 05 dioxide adsorbed by the activated charcoal or other adsorbent under test is reported in terms of standard temperature and pressure t0C. and 760mm) regardless of the conditions used for -the adsorption.
Claims (24)
1. A process of carbonating an aqueous liquid which comprises contacting an aqueous liquid with an amount of an activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water and having adsorbed therein at least 20 cm3 of carbon dioxide per gram of charcoal, the amount of charcoal effective to produce carbonation of the liquid exceeding one volume of carbon dioxide at standard conditions per volume of aqueous liquid.
2. A process according to claim 1, wherein the activated charcoal has pore diameters in the range of 4 to 50 Angstroms.
3. A process according to claim 2, wherein the pore diameters are in the range of 4 to 20 Angstroms.
4. A process according to claim 1, wherein the charcoal is activated coconut charcoal.
5. A process according to claim 4, wherein the charcoal has adsorbed therein at least 40 cm3 of carbon dioxide per gram.
6. A process according to claim 1, wherein the carb-onation of the charcoal is supplemented by a chemical "couple".
said chemical "couple" being present in an amount which produces a salt concentration below the threshold level of taste.
said chemical "couple" being present in an amount which produces a salt concentration below the threshold level of taste.
7. A process according to claim 1 wherein the process is conducted in a closed vessel provided with minimum headspace.
8. A process of carbonating an aqueous liquid which comprises contacting an aqueous liquid with an amount of an act-ivated charcoal having a pore size in the range of about 4 to about 50 Angstroms diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water and having adsorbed therein at least 20 cm3 of carbon dioxide per gram of charcoal in a closed vessel without an appreciable head space, the amount of charcoal effective to produce carbonation of the liquid exceeding one volume of carbon dioxide at standard conditions per volume of liquid.
9. A process according to claim 8, wherein the charcoal is activated coconut charcoal.
10. A process according to claim 8 or 9, wherein the charcoal has adsorbed therein above about 80 cm3 of carbon dioxide per gram of charcoal.
11. A process for carbonating an aqueous liquid comprising (i) adsorbing on activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water, at a pressure of superatmospheric to about 80 psig., carbon dioxide in an amount of at least 20 cm3 of carbon dioxide per gram of charcoal; and (ii) contacting the aqueous liquid with an amount of the activated charcoal effective to produce carbonation of the liquid to exceed one volume of carbon dioxide at standard conditions per volume of aqueous liquid.
12. A process according to claim 11, wherein the pressure is superatmospheric to about 50 psig.
13. A process according to claim 11 or 12, wherein the carbon dioxide is adsorbed on the activated charcoal at a temperature of below about 35°C. to about minus 78.5 C.
14. A process for carbonating an aqueous liquid com-prising (i) adsorbing on activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water, at a temperature of below about 35°C. to about 78°C. and pressure of 0 to about 80 psig., carbon dioxide in an amount of at least 20 cm3 of carbon dioxide per gram of charcoal; and (ii) contacting the aqueous liquid in a closed vessel with minimum headspace with an amount of the activated charcoal effective to produce carbonation of the liquid to exceed one volume of carbon dioxide at standard conditions per volume of aqueous liquid.
15. A process according to claim 14, the charcoal having adsorbed thereon about 100 cm3 of carbon dioxide per gram of charcoal.
16. A carbonation composition for preparing carbon-ated aqueous beverages which comprises a dry beverage mix and an amount of an activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water and having adsorbed therein at least 20 cm3 of carbon dioxide per gram of charcoal, the amount of charcoal effective to produce carbonation exceeding one volume of carbon dioxide at standard conditions per volume of prepared beverage.
17. A carbonation composition according to claim 16, wherein the charcoal is activated coconut charcoal.
18. A carbonation composition according to claim 16, or 17 wherein the effective amount of charcoal is supplemented by a chemical "couple", the amount of said "couple" producing in the beverage a salt concentration below the threshold level of salt taste.
19. A carbonation composition according to claim 16, or 17 wherein the charcoal is in the form of a disc.
20. A carbonation package for preparing carbonated aqueous beverages which comprises a closed container under superatmospheric pressure containing activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to adsorb carbon dioxide and to desorb carbon dioxide upon contact with water and having adsorbed therein at least 20 cm of carbon dioxide per gram of charcoal, the amount of charcoal effective to produce carbonation exceeding one volume of carbon dioxide at standard conditions per volume of prepared beverage.
21. A carbonation composition for preparing carbonated beverages which comprises a dry flavored mix and an amount of an activated charcoal having a pore size in the range of about 4 to about 50 Angstroms in diameter and the ability to absorb carbon dioxide and to desorb carbon dioxide upon contact with water and having adsorbed therein at least 20 cm3 of carbon dioxide per gram of charcoal effective to produce carbonation exceeding one volume of carbon dioxide at standard conditions per volume of liquid.
22. A carbonation composition according to claim 21, wherein the charcoal is activated coconut charcoal.
23. A carbonation composition according to claim 21, wherein the effective amount of charcoal is supplemented by a chemical "couple", the amount of said "couple" producing in the beverage a salt concentration below the threshold level of salt taste.
24. A carbonation composition according to claim 21, 22 or 23, wherein the charcoal is in the form of a disc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8373679A | 1979-10-10 | 1979-10-10 | |
| US083,736 | 1979-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1160893A true CA1160893A (en) | 1984-01-24 |
Family
ID=22180353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000360978A Expired CA1160893A (en) | 1979-10-10 | 1980-09-24 | Process for preparing carbonated liquids with activated charcoal |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS5660630A (en) |
| AU (1) | AU540458B2 (en) |
| CA (1) | CA1160893A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114096163A (en) * | 2019-07-23 | 2022-02-25 | 迪睿合株式会社 | Health harmful substance remover and health food |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4675278B2 (en) * | 2006-05-30 | 2011-04-20 | 中国電力株式会社 | Recyclable carbonated beverage and method for regenerating carbonated beverage |
| JP4969683B2 (en) * | 2010-12-16 | 2012-07-04 | 中国電力株式会社 | Recyclable carbonated beverage and method for regenerating carbonated beverage |
-
1980
- 1980-09-19 AU AU62534/80A patent/AU540458B2/en not_active Ceased
- 1980-09-24 CA CA000360978A patent/CA1160893A/en not_active Expired
- 1980-10-09 JP JP14191680A patent/JPS5660630A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114096163A (en) * | 2019-07-23 | 2022-02-25 | 迪睿合株式会社 | Health harmful substance remover and health food |
Also Published As
| Publication number | Publication date |
|---|---|
| AU540458B2 (en) | 1984-11-22 |
| AU6253480A (en) | 1981-04-16 |
| JPS5660630A (en) | 1981-05-25 |
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