CA1225863A - Process for preparing a gasified ice product - Google Patents
Process for preparing a gasified ice productInfo
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- CA1225863A CA1225863A CA000468156A CA468156A CA1225863A CA 1225863 A CA1225863 A CA 1225863A CA 000468156 A CA000468156 A CA 000468156A CA 468156 A CA468156 A CA 468156A CA 1225863 A CA1225863 A CA 1225863A
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Abstract
PROCESS FOR PREPARING A GASIFIED ICE PRODUCT ABSTRACT The invention provides an improved process for preparing gasified ice products; particularly, a process is provided which more efficiently produces gasified ice products having good mechanical strength and provides uniform gas contents on a reproducible basis. According to the present invention, the reac-tion between a conditionally-stable-hydrate-forming gas and water is maintained within a dynamic reac-tion zone under carefully controlled conditions of gas to water feed ratio, system pressure and temper-ature to eliminate processing anamolies. 29008-E
Description
~2~8q~3 Case 2951 DESCRIPTION
05 PROCESS FOR PREPARING A GASIFIED ICE PRODUC~
Tçchnical Field The presen-t invention relates to gasified ice products; and, more particularly, to an improved process which çnables the production of gasified ice products which have uniform gas contents and struc-tural properties.
Gasified ice products are known whîch, due to the binding of the gas within a stabilized gas hydrate, ~ave enabled delivery of high volumes of gas from relatively small volumes of ice. These produc-ts have shown potential for storage and trans-port of gases of many types. Typically, the gas will be carbon dioxide and the product will be employed to carbonate an aqueous liquid in the simplified home preparation of carbonated beverages.
Unfortuna~ely, prQducts having commercially desir-able gas contents hex~tofo~e hav~ ~een dificult to produce çfficiently, have varied widely in gas contents between runs and within a single run, have released gas unevenly, and have required additiQnal processing to attain the desired mechanical strength.
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In its simplest form, the process for preparing gasified ice products has comprised contacting aqueous li~uid with gas under high pressure for a sufficient period of time to form a desired level of gas hydrate, and -then cooling to freeze the remain-~` ing unreacted li~uid and entrap gas hydrate.
It would appear -to be desirable to freeze the product in a chamber separate from the reactor to achieve the advantaye of controlling product shape and appearance for packaging; however, experience has shown that the products differ so widely in terms of gas content and are so subiect to fragment~
ing during shipment or st~rage, or popping when placed in an agueous liquid for use, that it has been necessary in the past to finelY divide the product and then reshape lt.
While the production of gasified ice products by continuous processing has been disclosed wherein a mixture of a suitable gas and water are pas~ed through a scraped-surface heat exchan~er under - conditions conducive to forming gas hydrate, the apparent straightforward simplicity of continuous processing has not been realized in commercial practice. The results achieved by current contin-uous processing technology have not enabled the manufacture of a uniform, reproducible and st~ble gasified ice product.
Back~round Art Barnes et al in u. s . Patents 2,975,603, 3,086,370 and 3,217,503 disclosed a process for producing gasified ice c~aractçrized by an extended ' storage life and its abilit~ to form effervescent j a~ueous solutions upon mixture with aqueous liquid.
According to one aspect of the disclosure, the gasified ice was prepared by subjecting a~ueous .
liquid to a suitable pressure of at least about 200 psig and preEerc~bly less than 600 psig; maintaining the aqueous liquid and the carbon dioxide in contact for a time sufficient to permit absoxption in the 05 li~uid of the gas in bound form and formation of gasified ice containing at least about 25-Z7.5 milliliters of gas per gram of ice; and withdrawing the gasified ice.
According to a specific example disclosed in U.S. 2,975,603, water was contacted with carbon dioxide at a pressure of 400 psig. The pressurized reaction vessel was placed within a constant temperature bath maintained at 0C during the period of contact. After 75 minutes, the vessel was removed from the bath, cooled to freeze the contents, depressurized and opened. The contents were removed, and the solid ice was stored for 24 hours at -10C to effect degasification. Testing of the degasified product revealed that it had a carbon dioxide content o 75 volumes carbon dioxide per gram of ice. While Barnes et al indicate only that a vigorous evolution of gas was observed, i* has been our e~perience with products prepared in accordance with this ge~eral proce~ure at high gas contents, that the product pops and cracks when placed in water and often splashes water from the container. Moreover, in order to remove the product from the pressure reactor, it is necessary to chip or chisel the ice out of the reaator vessel, resulting in a product with very uneven dimensions.
U.S. 3,086,37Q is similar, but additionally discloses that gasified ice products containing other gases such as nitrous oxide, certain sulfur-con~aining gases, certain chlorine-containing gases, various inert gases and carbon monoxide, could be formed.
. G' ' ' ~2S~63 A similar disclosure is found in U.S. 3,217,503 which again was a continuation-in-part of the applica-tion which resulted in the first-mentioned Barnes et al patent. This paten-t, however, describes in more detail the method for handling and transporting gasified ice to a desired point of liberation under atmospheric pressure while maintaining it at a temperature below its melting point.
Adler et al in U.S. 3,220,204 stated that while the prior art procedures of Barnes et al produce products which retain si~nificantly high levels of carbonation during refrigerated storage, the pro-ducts had a tendency to explode or pop (i.e., break apart and disintegrate with a loud noise) at an unpredictable point of time duriny dissolution.
They indicated that when the Barnes et al carbonated ice products were added to water or milk, they frequently exploded in the glass. A less spectac-ular product was required fox commercial success.
Their solution to the problem entailed provid-in~ a high liquid surface to gas contact during the preparation of the hydrate. To achieve this, they employed a thin film of water which was subjected to aarbon dioxide gas at a pressure and temperature above the eutectic point of the ~ater and at a temperature low enough to form a hydrate. A suspen-sion of hydrate in aqueous liquid was then trans~er-red to a freezing zone and was converted to a stable form by freezing at a temperature below -3C.
According to Example 1, a mi~ture of cooled water and carbon dioxide is fed into a scraped-wall ~ .,, heat exchanger at a high ratio of gas to water (calculated from the disclosed data to be a weigh-t ratio of about U.3~). After a residence time of about 2 minutes within the heat exchanger, the 05 reaction mixture exited as a hydrate slush having a temperature of about 1.5C. The process pressure was 250 psig. After freezing to -3C, the product exhibited a level of about 50 milliliters of carbon dioxide per gram of ice. Example 2 was similar except that the process pressure was reduced to 150 psig and the ratio of carbsn dioxide to water was increased (calculated to be a weight ratio of 0.66).
The product of Example 2 was said to contain about 32 milliliters of carbon dioxide per gram of ice.
15While it was disclosed by Adler et al that their process produced a carbonated ice product which was better able to withstand surrounding environments to which it would be exposed during packaging, handling and use without popping or exploding, these problems were not eliminated to the - extent necessary for a commercially acceptable product. Moreover, while the continuous process showed that it was capable of producing carbonated ice products with practically high levels of entrapped gas, reproducibilit~ both between process runs and within a single process run proved ; difficult. An added disadvantage was that the products would tend to break apar~ upon removal from the molds, leaving very little unbroken ice in rod form. In order to prepare products having he desired degree of uniformity and structural strength necessary to survive shipment ~nd reasonable length~
of commercial storage, it was found necessary to subdivide the ice and then reshape it into pieces of uniform size and proper~ies.
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~251~3 Extensive research with the Adler et al process has revealed that while the concept of pressure control is taught by Adler et al and apparently suitable means for obtaini~g the control are dis-05 closed, there are a number of fac-tors, which are not disclosed by Adler et al, which have heen found to be important to the production of a consistent, unifor~ly-carbonated, non-popping product at prac-tical carbonation levels by a continuous process which minimizes the amount of unusable product. The research has revealed that the processing condi-tions and apparatus employed by Adler et al make it dif-ficult to meet these criteria on a continous, re-producible basis. And, while Adler et al discloses cutting the product into individual segments, exper-ience has shown that there is such a wide variation in the properties of individual segments, that a commercially practical produ¢t can he made only if the product is first ground and then compressed into a briquette such as according to the disclosure of U.S. 3,333,969 to Mitchell et al.
Throughout this evolution of gasified ice products, Mitchell et al disclose in U.S. 3,333,969, that the probIem of uneven release of carbon dioxide had persisted. They indicated that an important problem prese~t in the handling and use o carbon-ated ice, particularly in the lower portion of the 10 to 118 volume range, was the uneven release o*
carbon dioxide from the carbonated iGe. They stated that this problem manifested itself in minor explo-sions or popping which, while not o~ dangerous nature where th~ gas was carbon dioxide, may disturb the user and splatter the li~uid in which it was placed. Mitchell et al proposed subdividing car-bonated ice into ~iscrete particles while main-"'' ' ~. , . .
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~58~3 taining the temperature of the ice below 0C, and then compacting the discrete particles to form them into an adhered mass or bri~uette. ~ri~uetting produced gasified i.ce products having commercially 05 satisfactory mechanical strength and also substan-tially eliminated the undesirable, spontaneous popping and exploding phenomena; however, i-t also resulted in the reduction of the level of carbona-tion in the final product and a faster ra*e of loss than from unground ice.
It is apparent from the foregoing discussion of the prior art that the problems of uneven release of gas from gasified ice products, and the ability to obtain uniform carbonation within a given run and on a reproducible basis, have long troubled those skilled in the art. Thus, there remains a need for an efficient, economical process that produces a gasified ice product having satisfactory mechanical strength and a uniform, non-popping gas con-tent, on a reproducible basis.
Disclosurç of Invention In accordance with the present in~ention, we provide an improved process for preparing gasified ice chaxacterized by a uniform gas content within the range of from about 35 to 60 milliliters of gas per gram of product and a high degree of mechanical strength in the frozen state. Also provided is the produ~t of this process~ In its broad aspec-ts, the process comprises: providing a Source of liquid water at a temperature bçlow about 5C~ providing a source of conditionally-stable-hydrate-forming gas at a temperature of about 5 to 10C; dispersing the gas within the water at a weight ratio of gas to water within the range of from about Q.10 to about . .
: . , ' 51~3 0.25 to provide a process feed s-tream; introducing the process feed stream into a dynamic reactlon zone at a tempera-ture within about l~C ~f the hydrate formation equilibrium temperature at a preselected 05 process pressure, within the range of from about 300 to about 450 psig, which is maintained within the dynamic reaction zone; maintaining contact between the gas and water under dynamic conditions for a period of time effective to form conditionally~
stable gas hydrate and to dissolve gas within the water to an extent effective to provide a uniform, flowable suspension of solid, gas-hydrate, crystal-like particles in a saturated aqueous solution of carbon dioxide; transporting the suspension to a pressurized freezing vessel which is in communica~
tion with the dynamic reaction zone and a pressure : control means comprising valve means and means for separating occluded gas from liquid and solid compo~
nents, said pressure control means bçing capable of controlling the system pressure to within 5 psig of the preselected pressure, closing the freezing chamber; and freezing the suspension under pressure.
In carrying out the process of this invention, the gasified ice products will preferably be prepar-ed from distilled ~r deionized water because they provide advantages in terms of reproducibility of Pxecise conditions and stability of the final pro-duct. While not preferred, the person of ordinary skill in the art may, however, employ various types of solutions, and in the case of food products such as beverages, various materials includiny suyar, color, flavor, acidulents and the like, knowing that the ease of process control or the stabil~ty of the final product may be decreased. Thus, the terms "water" and "aqueous liquid" will hereinafter be , , . .
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~'2~ i3 g employed to include not only chemically pure water per se, but wa-ter containing added materials such as those mentioned.
Also by way of definition, the term "dynamic 05 reaction zone" is meant to define a zo~e wherein vigorous agitation is maintained either by a mech-anical stirrer, a scraped-surface heat exchanger, an in-line mixer, or other means capable of maintaining constant relative motion between thç gas and liquid within the reaction zone. This term is specifically meant to distinguish from batch-type reactors where-in agitation is maintained for a brief period of time but then terminated while the material contin-ues to react and freeze in a statia condition.
Among the gases which are capable of forming conditionally-stable hydrates are those which form hydrates which appear to be characterized by a molecular complex between the gas and water under the controlled conditions o~ temperature and high pressure. All of the suitablç gases exist in the yaseous state at a~mospheric pressure at tempera-tures above 0C. Additionally, these gases combine with water to form gas hydrates containing six or more moles of water per mole of gas. The hydrates are further characterized by their ability to be stored in essentially stable condition at tempera-tures below about 0C and then be decomposed by melting in an aqueous liquid.
Specifically identiied as gases capable of forming conditionally~stable hydrates are various oxides of non metals, such as nitrous oxide; sulfur-containing gases including hydrogen sulfide; chlor-ine-containing gases, including chlorine and methyl-ene chloride; variQus inert gases such as helium, argon! krypton, and neon; carbon monoxide; and . . ... .
~2~ i3 carbon diogide. Preferably, the gas will be select-ed from the group consis-ting of these, and most preferably will comprise carbon dioxide, nitrous oxide, or chlorine, due to their adaptability to the 05 process and their wide-spread utilities. While not intending to be bound to the specific example of carbon dioxide, the present detailed description will fo~us on this as exemplary, due to its ready adaptability to use in prçparing carbonated bever-ages for whlch there appears to be a commerclalopportunity.
Brief Description of the Drawing The present invention will be better understood and its advantages will become more apparent when the following detailed description of the best mode for carrying out the invention is read in light of the accompanying drawing wherein:
the Figure is a schematic flow diagram of a partlcularly preferred processlng arrangement accord-ing to the invention.
Best Mode for Carrying Out the invention The lnventlon provldes a gaslfied ice product characterized by a uniform gas content within the range o from about 35 to about 60 milliliters of gas per gram of product, a high de~ree of mechanical strength in its frozen state, a vigorous, uniform evolution of gas when placed in an agueous li~uld, and a quiet, non-explosive character when open to air. In addltion to t~ese generalized desirable advantages of individual products according to the lnvention, the process 15 capable of providlng products of this type within reasonable commercial tolerances on a uniform basis with a minimum of `:,.;
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5~3~3 unusable product. The process, in fact, is capable of producing practical ~uantities of solid, pre-molded gasified ice products which can be prepared for commercial distribution by simply shaping into 05 suitably-sized individual rods or molding elongated rods and then cutting to a smaller desired length.
~ he following description will discuss a pre-ferred process where, in the prepara-tion of carbon-a~ed ice, a suspension of carbon dioxide hydrate in aqueous li~uid is prepared in a pressurized, dynamic reaction zone wherein the reaction is brought to a high degree of completion while maintained within the dynamic zone, is transported to a pressurized freezing vessel in co~nmunication with the dynamic 1~ reaction zone and also in communication with a pressure control means having the ability to tightly control the overall system pressure, and freezing within a closed chamber. The principles which apply to this particular reaction system can also be applied to the forma~ion of gasified ice products containing other suitable gases.
We have determined according to the invention that çlose control over all process feed streams and product lines is essential to the praduction o~
products having the properties necessary for com-mercial production on a commercially efficient basis. To achieve the necessary degree of process control, our pre~erred embodiment provides for the regulation and close monitoring of pressures and temperatures which in the past have been presumed to be self-regulating by virtue of the reaction. It has been determined, however, that the self-reyula-tion of the system operating conditions cannot be relied upon for obtaining good results on a repro-ducible basis. For example, the control of the : :; ...,.: , ' '' ' , .
~Z~8~3 inlet gas temperature and pressure have been found to be e~ually important with the control of the inle-t water temperature and pressure.
Referring to the drawing, there is seen inlet 05 water feed line 10 which conveys water to a deion-izer 12 of conventional construction and operatiQn.
It is preferred that the water either be distilled or deionized. From the deionizer 12, the feed water is fed through line 14 to water feed tank 16. The feed tank is preferably a jacketed holding tank having a heat tran~fer media such as a 40% solution of propylene glycol providing cooling to the jacket.
The heat transfer media is passed through the jacket by means of entrance line 18 and exit line 20, with the flow heing controlled by valve means ~2.
The water will preferably be added to the process as a liquid without any si~nificant amount of ice crystals formed therein and will have a temperature below about 5C. Where significant amounts of ice crystals are present, problems of metering and freeze-ups can occur. Most preferably, the water is maintained in a li~uid state at a temperature of from about 0 to about 2C.
From the tank i6, the water passes through line 24 and valve 26 to a strainer 28 which removes any particulate material which may be present. From ~trainer 28, the water flow is measured by a flow meter 30 prior to passage to pump 32. Thç pump 32 is capable of metering the f~ow of water to the system at constant rate and at a constant pressure.
Pressure from an external source (not shown) is maintained on the pump by mean~ of line 34 to assure constant pressure for the water exiting pump 3~. It is preferred that the pump be capable o~ continuous-ly feeding water, and thus process feed stream 68, ,~ ' ,~ " , : .
58~i3 at a flow rate which varies by no more than about 5%, preferably no more than 2%.
Similarly with the feed water supply means -described above, -the pressure and temperature of the ,`05 gas supply to the system is also closely controlled.
-To achieve this according to the preferred embodi-ment, liquified carbon dioxide is held within a suitable receiver 36 and passed by line 3~ to pump 40 capable of pumping the liquified gas via line 42 to a vaporizer 44 of conventional construction.
From the vaporizer 44, the now gaseous carbon diox-;ide is passed by via line 46 to a gas surge tank 48.
The pressure within line 46 is indicated by a suit-able pressure sensing device 50.
The p~rovision of a surge tank 48 for the gas-; eous feed is preferred because it was determined that in prior procedures, anomalies in gas feed flow ` would often cause a series of problems downstream `~ throughout the reaction and freezing stages. By providing the surge tank 48 which feeds the gas via line 52 past pressure gauge 54 and gas mass-flow control valve 56, it i$ now possible to better ' control the pressure of the gas supplied to the process. The pressure of the gas supply to cooler 58 at a pressure no higher than 200 psig greater than the predetermined process pressure which will be employed dow~stream in the reaction zone, freez-ing tube and process pressure control means.
In the gas cooler 58, the gas is preferably brought to a temperature of from about 5 to 10C, and most preferably a temperature of from about 7C
to about 8C. The gas cooler can comprise a heat exchanger of conventional construction for cooling gaseous materials.
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:: ' , " ~258~3 Gas from the gas cooler 58 is then passed via line 60 to dispersing means 62 which also receives water from pump 32. The dispersing device 62 can be a sparger, an in-line mixer, or any other device 05 suitable for finely dispersing the gas within the water. Prefexably, the dispersing device will be a sintered sparger, such as the type made from sinter-ed particulate polymers or metals having a pore size within the order of 0.5 microns.
It is preferred that the temperatures be con-trolled within the ranges described so that a maxi-mum amount of carbon dioxide can be immediately dissolved into the water such that reaction will proceed at the most rapid rate when the product reaches the reaction zone. And, because of the careful temperature control of both the gas and water feeds, the temperature of the process feed stream comprising water containing both dissolved and dispersed gas therein can be readily controlled to a temperature within about 2C of the hydrate formation equilibrium temperature at the preselected pressure for the reaction. This temperature can readily be determined by experimentation with the pressures and reactants desired. And, in the case of carbon dioxide, reference can be made to the C02-water-hydrate phase diagram described in commonly-assigned United States Patent No. 4,347,707, granted Sept. 7, 1982, an~ entitled "Gasified Ice Product and Process Having Improved Storage Stability". As shown in the drawing, the feed stream is passed from a first dispersing device 62 via line 64 to a secondary dispersing device 66 which can be employed if desired. In one preferred embodiment, device 66 can be a ~tatic mixer where the device 62 is a sintered metal sparger.
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~225B63 An important discovery according -to the inven-tion is that the weight ratio of the gas to the water in the process feed stream should be main-tained within the range of from about 0.1 to about 05 0.25. Preferably, the ratio will be maintained within the range of from about 0.14 to about 0.18.
And, it is also important to maintain this value constant with a fluctuation of no more than about 10%, preferably less than about 5%.
Where the ratio is below the minimum level within the range, the degree o~ hydrate ~ormation will be below those levels where practical commer-cial products can be achieved, it being virtually impossible to achieve a product containing more than 35 milliliters of carbon dioxide per gram of pro-duct. Whe~e the ratio is a~ove the ranges indicat-ed, the reaction will be so incomplete a~ter leaving the dynamic reaction zone (unless the time of expo-sure is significantly increased) that the rate of flow throughout the process becomes sporadic, caus-ing unexpected variations in process pressure and other anomalous results, not fully understood, which have the n~t effect of providing a final product which varies widely in its gas content and charac-teristics in terms of physical strength, uniform gasrelease and stability. A high gas water ra~io cauld also increase the solids level to the point of causing difficulties with tLansport of the slurry.
AccQrdingly, the ratio of gas to water must be carefully controlled prior to passing it via line 68 to the dynamia reaction zone which in the figure is shown to employ two scraped-surface hea~ exchangers 70 and 72 connected in series by means of line 74.
Naturally any number of heat e~changers may ~e utilized, the major consideratiQn being the amount of heat exchange sur~ace area which is present.
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The pressure within the dynamic reaction zone is maintained at a constant value within the range of from about 300 to about 450 psig, preferably within the range of from ahout 325 to about 400 05 psig. This is a factor in controlling the rate of reaction. When employing the feed ratio of gas to water within the ranges given above, pressures below the preferred ranges will yield products which do not have the minimum level of about 35 millillters lO of gas per gram of product within acceptable reac-tion times. And, pressures above the ma~imum will result in the sporadic formation of high levels of gas hydrate which tend to cause erratic flow pro-blems within the dynamic reaction zone and subse 15 quent processing lines. Accordingly, maintenance of the pxessure within the preferred range is important ` to th~ produc-tion of high quality product on a ,` reproducible basis.
The pressure maintained within the dynamic 20 reaction zone is controlled by pressure control means in CQmmUnication with the reaction zone as will be described later. During the stage of trans-porting the process reaction mixture from the reac-~` tion zone to the freezing chambers~ the pressure ~ 25 control means, to be described later, is also main-r tained in communication wi~h the freezing chamber.
Refering again to the scraped-surface heat exchangers 70 and 72, which comprise the dynamic ' reaction zone in the pro~ess ar~an~ement shown in i 30 the drawing, an in-line mi~r 76 is employe~ in txa~sfer li~e 74 tQ maintain th~ produc~ ~n a con~
sis~ently-uni~o.rm ~lowable cs~dition a~ it passes from one scraped-surface heat exchanger to the other, and to further aid in solubilizing the dis-persed gas into the li~uid.
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The scraped-surface heat exchangers can be of conventional construction such as a Votator scraped-wall heat exchanger (available from Chemetron Corp., Louisville, Kentucky) or a Contherm unit (available 05 from Alfa Laval, Inc., Fort Lee, New Jersey). Both scraped-surface heat exchangers 70 and 72 are jacket-ed with a heat exchange medium such as a propylene glycol solution which is circulated through the jacket to provide cooling and heat removal from the exothermic reaction as the process reaction mixture is continuously scraped from and replaced onto the internal surface of the heat exchangers 70 and 72.
Thus, as shown in the drawing, line 78 feeds heat exchange media to the jacket of heat exchanyer 70 and line 80 having flow control means 82 therein removes the heat exchange media therefrom. Similar-ly, heat exchanger 72 is supplied with heat exchange media by means of line 84, with the return line 86 having a flow control means 88 positioned therein.
In addition to the in-line mixer 76 in line 74, the pressure is constantly monitored by means of a suitable pressure sensing device 89. To further assure continuous, uniform flow of the process stream from scraped-surface heat exchanger 70 to scraped surface heat exchanger 72, care is taken to maintain uniform, smooth bends within line 74 which is also maintained free of internal obstructions.
Preferably, this process feed line and all those downstream lines for transporting the susp~nsion of gas hydrate particles will be free of obstructions and will be positioned to provide bends of no less than a 6 inches radius.
Contact is maintained within the dynamic reac-tion zone for a period of time effective to form conditionally-stable gas hydrate and to dissolve gas * Trade Mark ~.'.. ~ .
~2Si~q~3 within the water to an extent effective to provide a uniform, flowable suspension of solid gas hydrate crystal-like particles in a saturated aqueous solu tion of the gas, typically carbon di.oxide. Accord-05 ing to this invention, contact or residence within the dynamic reaction zone is kept between two and ei~ht minutes, preferably between 3 and 5 minutes and will typically be around four minutçs. The residence time will usually be divided equally among ~ lO two or more reaction vessels such as scraped surface ; heat exchangers 70 and 72. Preferably, the contact under dynamic conditions within the reaction zone is - maintained for a period o~ time effective to substan-tially eliminate bubbles of gas from the suspension.
While the absolute eliminatior, of gas bubbles is not essen~ial to the invention, primarily due to the control of the process feed stream and the pressure control means downstream of the reactor, it is important to prevent undue quantities of gas from being transported downstream of the reaction zone ~or the continuance of reaction in the absence of dynamic conditions, since this may cause sporadic fluctuations in the gua~tity of hydrate produc~d.
If desired, a sight glass 92 or other measurement device can be employed in line 90 to enable close monitoring of the rheological properties of the suspension.
The suspension is passed from the dynamic reaction zone through line 90 whiçh is continuously maintained in communication with a pressure control means which comprises a valve means 94 and a means 96 for separating occluded gas from liquid and solid components. The pressure control means is capable of controlling the system pressure to within 5 psig of the preselect.ed process pre~sure. The valve . ~
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-: . ~ . ,'~ , ' 25~3~;3 means is preferably a pneumatically opera-ted, self-adjusting back-pressure valve which is capable of closely controlling -the process pressure. The valve has a flexible internal diaphragm indicated in 05 phantom lines 98 and has a gaseous fluid con-trol means 100 which is operative to maintain the proper process pressure.
As shown in the drawing line 102 provides communication between the means 96 and valve means 94. Within line 102, ano-ther pressure measuring device 104 is preferably provided. Likewise, a pressure measuring device is preferably provided in line 90 as shown in the drawing as 106.
The means 96 which separates the occluded gas from liguid and solid components is preferably a jacketed tank having sufficient capacity to handle flow rates for this specific process. Heating fluid, such as 100F water will be passed through the outer jacket of the tank to melt incoming sus-pension and thereby release gas therefrom. Byseparating the gaseous components Erom -the solid and liguid components, we have fQund that it is possible to avoid intermittent pressure fluctuations due to areas of concentrated solid matçrial within the suspension which in the past have caused wide flua-tuation in process pressure. The medium for heating the jacket o~ the means 96 is supplied as shown in the drawing via line 108 and withdrawn via line 110.
Separating means 96 may con~ain a bottom drain valve (not shown) to remove liquid either during or after operation. Such liquid removal may be necessary during continuous operation to prevent liquid from passing to valve means 94.
The freezing chamber 120 can be positioned either vertically or horizontally. It has been ~ "
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found quite unexpectedly, however, that -the yield of unbroken solid ice, suitable for cutting into lengths of suitable ~ize for packaging, is improved where the tubes are positioned horizontally. Preferably, 05 the freezing chamber will comprise an elongated cylinder positioned at an angle of from 0 to about 30 from the horizontal. Where the amount of solid, severable carbonated ice is produced in this manner, a large amount of a highly attractive product ice can be prepared. Any ice which does not maintain its structural stability in solid form can be ground and then recompaçted as is known -to the art.
The final stage in processing relates to the freezing of the suspension to form a solid gas hydrate-containing product covered in a protec-tive layer of solid water ice. This coating may be saturated with gas and result from a slight surface melting of the product within the freezing chamber.
The water-ice coating may also include a layer which 2Q is applied to the product after or as it is removed from the freezing chamber. Conventional water spraying or dipping techniques may be used for this purpose.
According to the arrangement shown in the Figure, a bleed point 112 is positioned in line 90 for U$e when needed. From line 90, it is possible to direct flow into line 114 by closing valve 116, opening valve 118 and then providing direct communi-cation between the freezing chamber 120 and the reaction zone and the means for controlling pressure.
To direct flow through the freezing chamber 120, fill valve 122, vent valve 124 and valve 126 are all opened while bleed valve 128 and cross flow valve 130 are closed.
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Under steady state conditions, the pressure within the freezing chamber 120 will be stabilized by virtue of its communication with the reaction zone and the pressure control means to the pre-OS determined process pressure. Material will flow into the freezing chamber 120 until the chamber is filled and will then pass therefrom via line 132 to line 134 to the pressure control means downstream.
When liquid starts to overflow from the valve 94, it lO is preferred to maintain flow of suspension to the freezing chamber for another minute or so to assure uniformity of the product therein. At that time, flow to the freezing chamber 120 is terminated and flow to a similar freQzing chamber (not shown) is 15 started in the same manner, by closing and opening the appropriate process line valves.
The freezing chamber 120 itself can be suitably sized tc provide either individually molded product portions or a larger piece which is cut to size.
20 Typically, the chamber 120 will have an elongated shape, such as a long tube having a diameter of from about 1 to about 7 inches, preferably from about 2.5 ~; to about ~.5 inches, and a length of up to about 20 feet or more. Preferably, the internal surface of ~ 25 the freezing chamber will be smooth and corrosion i~ resistant, and will permit the simplified freezing ~ and demolding of product.
? ~ facilitate ~oth freezing and demolding, the freezing chamber is preferably jacketed and heat 30 exchange media is passed through the jacket, enter-3 ing by means of line 136 and being withdrawn by ' means of line 138. The product is preferably frozen by cooling in a stepwise manner, as per the afore-mentioned U.S. Patent 4,347,707 to a temperature of 10C. Upon stabilizing the frozen t ~5~3 ~ 22 --product the presswre is released to atmospheric conditions and a warm heat exchange medium applied to the tube jacket to cause a surface melt of the product thereby releasing it from the tube.
05 The carbonate~ ice prepared in the above manner can be packaged in a suitable container such as a can or styrofoam cup. When packaged in containers of this type, the carbonated ice will provid~ a high degree of storage stability at ambient pressure and at temperatures within the range of from about -5 to about -20F for a period of time in excess of 6 months. Alon~ with the carbonated ice, in the sam~
package or in a separate or adjoining package, there may be provided a composition for preparing a soft drink such as the kind which comprise a color, flavor, an edible acidulent, and sweetener, all of these ingredients being present in the amounts effective to provide the desired taste and eye appeal.
The following example is presented for the purpose of further illustrating and explaining the present invention and is not to be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are on a weight basis.
xample 1 This example illustrates the preparation of a carbonated ice product according to the present invention employing a process arrangemen-t as shown in the Figure. To achieve the results which have been established as optimum, the system is set to achieve the operating parameters se-t forth in -the following table:
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OPERATING P~RAMETERS VALU~
Wate~ flow rate 4.5 -~/min Sys-tem p~essure 350 psig CO2/H2O ratio (wt.) 0.16 05 Feed wate~ temperatu~e 32F
Temperature at the outlet of water pump 32 33~
Tempe~ature at the outlet of sparger 62 41E
C2 press~lre at the inlet o~ gas controller 500 psig C2 (g) temperature at the outlet of the gas cooler 58 hSF
Glycol heat ex~hange fluid inlet (supply) t~mperature at scraped-surface heat exchangers 70 ~ 72 18~
Glycol outlet temperature at scraped-surface heat exchangers 7Q & 72 25F
Glycol flow rate thru ; scraped-surface heat exch~ngers 70 & 72 2 gpm Product temperature at outlet of scraped-sur$ace heat exchangers 70 & 72 42F
' 20 i The process is initially started by preparing the carbon dioxide and water feed systems for flow and then starting the flow of water through the system. At this point, the scraped surface heat ~5 exchangers which in this case are Votator units, having an internal surface area of three square feet, are started at a speed of 750 rpm. The system pressure is allowe~ to build and the b~ck pressure valve 94 is set to the ~stabli$hed system pressure of 350 psig. Once the predetermin~d pressure i8 reached, the carbon dioxide flow is started and regulated by means of the controller 56 to maintain the proper flow rate to achieve the desired ratio of gas to water of Q.16. The gas temperature is main-tained at a temperature o~ about 45F by maintaining . .
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a cold water flow ~not shown) to heat exchanger 58.
Then, the hea-t exchange medium is begun to the jackets of both of the Votator heat exchangers operating at a shaft rpm of 750.
The system is allowed to stabilize for a period of time sufficient to achieve steady state opera-tion. For stabilizing, valves 118, 126 and 130 are opened and valves 116, 128, 122 and 124 are closed.
When the system has reached steady state operation, valve 130 is closed and valves 122 and 124 are opened on the freezing tube which has been pressur-ized to 350 psig to permi-t filling thereof to begin.
In this particular example, the freezing tube has a diameter of 2.5 inches and the length of 10 fee~.
While filling, the system pressure is main~ained at a CQnstant 350 psig. ~lso, ~hile filling the freez-ing tube, a 40~ solution o~ propylene glycol in water at a temperature of 18F is supplied to th~
~ jacket of the ~reezing tube.
'- 20 Filling is allowed to con~inue until liquid , starts to overflow at the outlet of the back pres-sure ~alve 94 indica-ting that the tube is filled.
The hydrate is permitted to continue to flow for an extra minute after which period of time valves 122 and 124 are closed and valve 130 is opened. The feed at this point in time can be switched to a~o-I ther freezing tube.
Supply of 18F propylene gly~ol solution to the jacket o~ the freezing tube is continued until the core temperature of the product reaches 32Fi and, at that point, the pressure is gradually reduced to 250 psig and colder propylene glycol, at a tempera-tuxe of 0E', is then supplied to the jacket of the freezing tube. Freezing is completed over a period of about 30 minutes while maintainin~ the product within the closed freezing tube.
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', ' ~.2;~ 3 When the core temperature of the carbonated ice reaches 15F or below, the produc-t is ready to be demolded. The pressure on the freezing tube is then gradually relieved. The tube is then opened at the 05 lower most end and the glycol supply to the tube is warmed to 85F to permit the product -to slide out.
~ le 2 The following example presents a comparison of results obtained by freezing a series of product suspensions prepared, according to Example 1, in tubes positioned either horizontally or vertically.
The horizontally positioned tube was at a 15 angle to the horizontal. The results are as follows:
AVERAGE GAS CONTENT
(cc/gram) Horizontal Tubes 45.4 45-~
47.5 44.4 Vçrtical Tubes 41.9 40.1 41.6 40.6 Yield of solid puck-shaped product ~ " thick) after demolding and cutting is about 2.5 times greater for the horizontal tube than i-t is for the ~ertical tube.
The above description is for the purpose of teaching the person of ordinary skill in the art how ' , :
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to practice the present invention. This description is not intended to detail all of -the obvious modifi-cations and variations of the invention which will become apparent to -the skilled worker upon reading.
05 However, applicants do intend to include all such ~ modifications and variations within the scope of ; their invention which is defined by the following claims.
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05 PROCESS FOR PREPARING A GASIFIED ICE PRODUC~
Tçchnical Field The presen-t invention relates to gasified ice products; and, more particularly, to an improved process which çnables the production of gasified ice products which have uniform gas contents and struc-tural properties.
Gasified ice products are known whîch, due to the binding of the gas within a stabilized gas hydrate, ~ave enabled delivery of high volumes of gas from relatively small volumes of ice. These produc-ts have shown potential for storage and trans-port of gases of many types. Typically, the gas will be carbon dioxide and the product will be employed to carbonate an aqueous liquid in the simplified home preparation of carbonated beverages.
Unfortuna~ely, prQducts having commercially desir-able gas contents hex~tofo~e hav~ ~een dificult to produce çfficiently, have varied widely in gas contents between runs and within a single run, have released gas unevenly, and have required additiQnal processing to attain the desired mechanical strength.
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In its simplest form, the process for preparing gasified ice products has comprised contacting aqueous li~uid with gas under high pressure for a sufficient period of time to form a desired level of gas hydrate, and -then cooling to freeze the remain-~` ing unreacted li~uid and entrap gas hydrate.
It would appear -to be desirable to freeze the product in a chamber separate from the reactor to achieve the advantaye of controlling product shape and appearance for packaging; however, experience has shown that the products differ so widely in terms of gas content and are so subiect to fragment~
ing during shipment or st~rage, or popping when placed in an agueous liquid for use, that it has been necessary in the past to finelY divide the product and then reshape lt.
While the production of gasified ice products by continuous processing has been disclosed wherein a mixture of a suitable gas and water are pas~ed through a scraped-surface heat exchan~er under - conditions conducive to forming gas hydrate, the apparent straightforward simplicity of continuous processing has not been realized in commercial practice. The results achieved by current contin-uous processing technology have not enabled the manufacture of a uniform, reproducible and st~ble gasified ice product.
Back~round Art Barnes et al in u. s . Patents 2,975,603, 3,086,370 and 3,217,503 disclosed a process for producing gasified ice c~aractçrized by an extended ' storage life and its abilit~ to form effervescent j a~ueous solutions upon mixture with aqueous liquid.
According to one aspect of the disclosure, the gasified ice was prepared by subjecting a~ueous .
liquid to a suitable pressure of at least about 200 psig and preEerc~bly less than 600 psig; maintaining the aqueous liquid and the carbon dioxide in contact for a time sufficient to permit absoxption in the 05 li~uid of the gas in bound form and formation of gasified ice containing at least about 25-Z7.5 milliliters of gas per gram of ice; and withdrawing the gasified ice.
According to a specific example disclosed in U.S. 2,975,603, water was contacted with carbon dioxide at a pressure of 400 psig. The pressurized reaction vessel was placed within a constant temperature bath maintained at 0C during the period of contact. After 75 minutes, the vessel was removed from the bath, cooled to freeze the contents, depressurized and opened. The contents were removed, and the solid ice was stored for 24 hours at -10C to effect degasification. Testing of the degasified product revealed that it had a carbon dioxide content o 75 volumes carbon dioxide per gram of ice. While Barnes et al indicate only that a vigorous evolution of gas was observed, i* has been our e~perience with products prepared in accordance with this ge~eral proce~ure at high gas contents, that the product pops and cracks when placed in water and often splashes water from the container. Moreover, in order to remove the product from the pressure reactor, it is necessary to chip or chisel the ice out of the reaator vessel, resulting in a product with very uneven dimensions.
U.S. 3,086,37Q is similar, but additionally discloses that gasified ice products containing other gases such as nitrous oxide, certain sulfur-con~aining gases, certain chlorine-containing gases, various inert gases and carbon monoxide, could be formed.
. G' ' ' ~2S~63 A similar disclosure is found in U.S. 3,217,503 which again was a continuation-in-part of the applica-tion which resulted in the first-mentioned Barnes et al patent. This paten-t, however, describes in more detail the method for handling and transporting gasified ice to a desired point of liberation under atmospheric pressure while maintaining it at a temperature below its melting point.
Adler et al in U.S. 3,220,204 stated that while the prior art procedures of Barnes et al produce products which retain si~nificantly high levels of carbonation during refrigerated storage, the pro-ducts had a tendency to explode or pop (i.e., break apart and disintegrate with a loud noise) at an unpredictable point of time duriny dissolution.
They indicated that when the Barnes et al carbonated ice products were added to water or milk, they frequently exploded in the glass. A less spectac-ular product was required fox commercial success.
Their solution to the problem entailed provid-in~ a high liquid surface to gas contact during the preparation of the hydrate. To achieve this, they employed a thin film of water which was subjected to aarbon dioxide gas at a pressure and temperature above the eutectic point of the ~ater and at a temperature low enough to form a hydrate. A suspen-sion of hydrate in aqueous liquid was then trans~er-red to a freezing zone and was converted to a stable form by freezing at a temperature below -3C.
According to Example 1, a mi~ture of cooled water and carbon dioxide is fed into a scraped-wall ~ .,, heat exchanger at a high ratio of gas to water (calculated from the disclosed data to be a weigh-t ratio of about U.3~). After a residence time of about 2 minutes within the heat exchanger, the 05 reaction mixture exited as a hydrate slush having a temperature of about 1.5C. The process pressure was 250 psig. After freezing to -3C, the product exhibited a level of about 50 milliliters of carbon dioxide per gram of ice. Example 2 was similar except that the process pressure was reduced to 150 psig and the ratio of carbsn dioxide to water was increased (calculated to be a weight ratio of 0.66).
The product of Example 2 was said to contain about 32 milliliters of carbon dioxide per gram of ice.
15While it was disclosed by Adler et al that their process produced a carbonated ice product which was better able to withstand surrounding environments to which it would be exposed during packaging, handling and use without popping or exploding, these problems were not eliminated to the - extent necessary for a commercially acceptable product. Moreover, while the continuous process showed that it was capable of producing carbonated ice products with practically high levels of entrapped gas, reproducibilit~ both between process runs and within a single process run proved ; difficult. An added disadvantage was that the products would tend to break apar~ upon removal from the molds, leaving very little unbroken ice in rod form. In order to prepare products having he desired degree of uniformity and structural strength necessary to survive shipment ~nd reasonable length~
of commercial storage, it was found necessary to subdivide the ice and then reshape it into pieces of uniform size and proper~ies.
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~251~3 Extensive research with the Adler et al process has revealed that while the concept of pressure control is taught by Adler et al and apparently suitable means for obtaini~g the control are dis-05 closed, there are a number of fac-tors, which are not disclosed by Adler et al, which have heen found to be important to the production of a consistent, unifor~ly-carbonated, non-popping product at prac-tical carbonation levels by a continuous process which minimizes the amount of unusable product. The research has revealed that the processing condi-tions and apparatus employed by Adler et al make it dif-ficult to meet these criteria on a continous, re-producible basis. And, while Adler et al discloses cutting the product into individual segments, exper-ience has shown that there is such a wide variation in the properties of individual segments, that a commercially practical produ¢t can he made only if the product is first ground and then compressed into a briquette such as according to the disclosure of U.S. 3,333,969 to Mitchell et al.
Throughout this evolution of gasified ice products, Mitchell et al disclose in U.S. 3,333,969, that the probIem of uneven release of carbon dioxide had persisted. They indicated that an important problem prese~t in the handling and use o carbon-ated ice, particularly in the lower portion of the 10 to 118 volume range, was the uneven release o*
carbon dioxide from the carbonated iGe. They stated that this problem manifested itself in minor explo-sions or popping which, while not o~ dangerous nature where th~ gas was carbon dioxide, may disturb the user and splatter the li~uid in which it was placed. Mitchell et al proposed subdividing car-bonated ice into ~iscrete particles while main-"'' ' ~. , . .
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~58~3 taining the temperature of the ice below 0C, and then compacting the discrete particles to form them into an adhered mass or bri~uette. ~ri~uetting produced gasified i.ce products having commercially 05 satisfactory mechanical strength and also substan-tially eliminated the undesirable, spontaneous popping and exploding phenomena; however, i-t also resulted in the reduction of the level of carbona-tion in the final product and a faster ra*e of loss than from unground ice.
It is apparent from the foregoing discussion of the prior art that the problems of uneven release of gas from gasified ice products, and the ability to obtain uniform carbonation within a given run and on a reproducible basis, have long troubled those skilled in the art. Thus, there remains a need for an efficient, economical process that produces a gasified ice product having satisfactory mechanical strength and a uniform, non-popping gas con-tent, on a reproducible basis.
Disclosurç of Invention In accordance with the present in~ention, we provide an improved process for preparing gasified ice chaxacterized by a uniform gas content within the range of from about 35 to 60 milliliters of gas per gram of product and a high degree of mechanical strength in the frozen state. Also provided is the produ~t of this process~ In its broad aspec-ts, the process comprises: providing a Source of liquid water at a temperature bçlow about 5C~ providing a source of conditionally-stable-hydrate-forming gas at a temperature of about 5 to 10C; dispersing the gas within the water at a weight ratio of gas to water within the range of from about Q.10 to about . .
: . , ' 51~3 0.25 to provide a process feed s-tream; introducing the process feed stream into a dynamic reactlon zone at a tempera-ture within about l~C ~f the hydrate formation equilibrium temperature at a preselected 05 process pressure, within the range of from about 300 to about 450 psig, which is maintained within the dynamic reaction zone; maintaining contact between the gas and water under dynamic conditions for a period of time effective to form conditionally~
stable gas hydrate and to dissolve gas within the water to an extent effective to provide a uniform, flowable suspension of solid, gas-hydrate, crystal-like particles in a saturated aqueous solution of carbon dioxide; transporting the suspension to a pressurized freezing vessel which is in communica~
tion with the dynamic reaction zone and a pressure : control means comprising valve means and means for separating occluded gas from liquid and solid compo~
nents, said pressure control means bçing capable of controlling the system pressure to within 5 psig of the preselected pressure, closing the freezing chamber; and freezing the suspension under pressure.
In carrying out the process of this invention, the gasified ice products will preferably be prepar-ed from distilled ~r deionized water because they provide advantages in terms of reproducibility of Pxecise conditions and stability of the final pro-duct. While not preferred, the person of ordinary skill in the art may, however, employ various types of solutions, and in the case of food products such as beverages, various materials includiny suyar, color, flavor, acidulents and the like, knowing that the ease of process control or the stabil~ty of the final product may be decreased. Thus, the terms "water" and "aqueous liquid" will hereinafter be , , . .
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~'2~ i3 g employed to include not only chemically pure water per se, but wa-ter containing added materials such as those mentioned.
Also by way of definition, the term "dynamic 05 reaction zone" is meant to define a zo~e wherein vigorous agitation is maintained either by a mech-anical stirrer, a scraped-surface heat exchanger, an in-line mixer, or other means capable of maintaining constant relative motion between thç gas and liquid within the reaction zone. This term is specifically meant to distinguish from batch-type reactors where-in agitation is maintained for a brief period of time but then terminated while the material contin-ues to react and freeze in a statia condition.
Among the gases which are capable of forming conditionally-stable hydrates are those which form hydrates which appear to be characterized by a molecular complex between the gas and water under the controlled conditions o~ temperature and high pressure. All of the suitablç gases exist in the yaseous state at a~mospheric pressure at tempera-tures above 0C. Additionally, these gases combine with water to form gas hydrates containing six or more moles of water per mole of gas. The hydrates are further characterized by their ability to be stored in essentially stable condition at tempera-tures below about 0C and then be decomposed by melting in an aqueous liquid.
Specifically identiied as gases capable of forming conditionally~stable hydrates are various oxides of non metals, such as nitrous oxide; sulfur-containing gases including hydrogen sulfide; chlor-ine-containing gases, including chlorine and methyl-ene chloride; variQus inert gases such as helium, argon! krypton, and neon; carbon monoxide; and . . ... .
~2~ i3 carbon diogide. Preferably, the gas will be select-ed from the group consis-ting of these, and most preferably will comprise carbon dioxide, nitrous oxide, or chlorine, due to their adaptability to the 05 process and their wide-spread utilities. While not intending to be bound to the specific example of carbon dioxide, the present detailed description will fo~us on this as exemplary, due to its ready adaptability to use in prçparing carbonated bever-ages for whlch there appears to be a commerclalopportunity.
Brief Description of the Drawing The present invention will be better understood and its advantages will become more apparent when the following detailed description of the best mode for carrying out the invention is read in light of the accompanying drawing wherein:
the Figure is a schematic flow diagram of a partlcularly preferred processlng arrangement accord-ing to the invention.
Best Mode for Carrying Out the invention The lnventlon provldes a gaslfied ice product characterized by a uniform gas content within the range o from about 35 to about 60 milliliters of gas per gram of product, a high de~ree of mechanical strength in its frozen state, a vigorous, uniform evolution of gas when placed in an agueous li~uld, and a quiet, non-explosive character when open to air. In addltion to t~ese generalized desirable advantages of individual products according to the lnvention, the process 15 capable of providlng products of this type within reasonable commercial tolerances on a uniform basis with a minimum of `:,.;
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5~3~3 unusable product. The process, in fact, is capable of producing practical ~uantities of solid, pre-molded gasified ice products which can be prepared for commercial distribution by simply shaping into 05 suitably-sized individual rods or molding elongated rods and then cutting to a smaller desired length.
~ he following description will discuss a pre-ferred process where, in the prepara-tion of carbon-a~ed ice, a suspension of carbon dioxide hydrate in aqueous li~uid is prepared in a pressurized, dynamic reaction zone wherein the reaction is brought to a high degree of completion while maintained within the dynamic zone, is transported to a pressurized freezing vessel in co~nmunication with the dynamic 1~ reaction zone and also in communication with a pressure control means having the ability to tightly control the overall system pressure, and freezing within a closed chamber. The principles which apply to this particular reaction system can also be applied to the forma~ion of gasified ice products containing other suitable gases.
We have determined according to the invention that çlose control over all process feed streams and product lines is essential to the praduction o~
products having the properties necessary for com-mercial production on a commercially efficient basis. To achieve the necessary degree of process control, our pre~erred embodiment provides for the regulation and close monitoring of pressures and temperatures which in the past have been presumed to be self-regulating by virtue of the reaction. It has been determined, however, that the self-reyula-tion of the system operating conditions cannot be relied upon for obtaining good results on a repro-ducible basis. For example, the control of the : :; ...,.: , ' '' ' , .
~Z~8~3 inlet gas temperature and pressure have been found to be e~ually important with the control of the inle-t water temperature and pressure.
Referring to the drawing, there is seen inlet 05 water feed line 10 which conveys water to a deion-izer 12 of conventional construction and operatiQn.
It is preferred that the water either be distilled or deionized. From the deionizer 12, the feed water is fed through line 14 to water feed tank 16. The feed tank is preferably a jacketed holding tank having a heat tran~fer media such as a 40% solution of propylene glycol providing cooling to the jacket.
The heat transfer media is passed through the jacket by means of entrance line 18 and exit line 20, with the flow heing controlled by valve means ~2.
The water will preferably be added to the process as a liquid without any si~nificant amount of ice crystals formed therein and will have a temperature below about 5C. Where significant amounts of ice crystals are present, problems of metering and freeze-ups can occur. Most preferably, the water is maintained in a li~uid state at a temperature of from about 0 to about 2C.
From the tank i6, the water passes through line 24 and valve 26 to a strainer 28 which removes any particulate material which may be present. From ~trainer 28, the water flow is measured by a flow meter 30 prior to passage to pump 32. Thç pump 32 is capable of metering the f~ow of water to the system at constant rate and at a constant pressure.
Pressure from an external source (not shown) is maintained on the pump by mean~ of line 34 to assure constant pressure for the water exiting pump 3~. It is preferred that the pump be capable o~ continuous-ly feeding water, and thus process feed stream 68, ,~ ' ,~ " , : .
58~i3 at a flow rate which varies by no more than about 5%, preferably no more than 2%.
Similarly with the feed water supply means -described above, -the pressure and temperature of the ,`05 gas supply to the system is also closely controlled.
-To achieve this according to the preferred embodi-ment, liquified carbon dioxide is held within a suitable receiver 36 and passed by line 3~ to pump 40 capable of pumping the liquified gas via line 42 to a vaporizer 44 of conventional construction.
From the vaporizer 44, the now gaseous carbon diox-;ide is passed by via line 46 to a gas surge tank 48.
The pressure within line 46 is indicated by a suit-able pressure sensing device 50.
The p~rovision of a surge tank 48 for the gas-; eous feed is preferred because it was determined that in prior procedures, anomalies in gas feed flow ` would often cause a series of problems downstream `~ throughout the reaction and freezing stages. By providing the surge tank 48 which feeds the gas via line 52 past pressure gauge 54 and gas mass-flow control valve 56, it i$ now possible to better ' control the pressure of the gas supplied to the process. The pressure of the gas supply to cooler 58 at a pressure no higher than 200 psig greater than the predetermined process pressure which will be employed dow~stream in the reaction zone, freez-ing tube and process pressure control means.
In the gas cooler 58, the gas is preferably brought to a temperature of from about 5 to 10C, and most preferably a temperature of from about 7C
to about 8C. The gas cooler can comprise a heat exchanger of conventional construction for cooling gaseous materials.
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:: ' , " ~258~3 Gas from the gas cooler 58 is then passed via line 60 to dispersing means 62 which also receives water from pump 32. The dispersing device 62 can be a sparger, an in-line mixer, or any other device 05 suitable for finely dispersing the gas within the water. Prefexably, the dispersing device will be a sintered sparger, such as the type made from sinter-ed particulate polymers or metals having a pore size within the order of 0.5 microns.
It is preferred that the temperatures be con-trolled within the ranges described so that a maxi-mum amount of carbon dioxide can be immediately dissolved into the water such that reaction will proceed at the most rapid rate when the product reaches the reaction zone. And, because of the careful temperature control of both the gas and water feeds, the temperature of the process feed stream comprising water containing both dissolved and dispersed gas therein can be readily controlled to a temperature within about 2C of the hydrate formation equilibrium temperature at the preselected pressure for the reaction. This temperature can readily be determined by experimentation with the pressures and reactants desired. And, in the case of carbon dioxide, reference can be made to the C02-water-hydrate phase diagram described in commonly-assigned United States Patent No. 4,347,707, granted Sept. 7, 1982, an~ entitled "Gasified Ice Product and Process Having Improved Storage Stability". As shown in the drawing, the feed stream is passed from a first dispersing device 62 via line 64 to a secondary dispersing device 66 which can be employed if desired. In one preferred embodiment, device 66 can be a ~tatic mixer where the device 62 is a sintered metal sparger.
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~225B63 An important discovery according -to the inven-tion is that the weight ratio of the gas to the water in the process feed stream should be main-tained within the range of from about 0.1 to about 05 0.25. Preferably, the ratio will be maintained within the range of from about 0.14 to about 0.18.
And, it is also important to maintain this value constant with a fluctuation of no more than about 10%, preferably less than about 5%.
Where the ratio is below the minimum level within the range, the degree o~ hydrate ~ormation will be below those levels where practical commer-cial products can be achieved, it being virtually impossible to achieve a product containing more than 35 milliliters of carbon dioxide per gram of pro-duct. Whe~e the ratio is a~ove the ranges indicat-ed, the reaction will be so incomplete a~ter leaving the dynamic reaction zone (unless the time of expo-sure is significantly increased) that the rate of flow throughout the process becomes sporadic, caus-ing unexpected variations in process pressure and other anomalous results, not fully understood, which have the n~t effect of providing a final product which varies widely in its gas content and charac-teristics in terms of physical strength, uniform gasrelease and stability. A high gas water ra~io cauld also increase the solids level to the point of causing difficulties with tLansport of the slurry.
AccQrdingly, the ratio of gas to water must be carefully controlled prior to passing it via line 68 to the dynamia reaction zone which in the figure is shown to employ two scraped-surface hea~ exchangers 70 and 72 connected in series by means of line 74.
Naturally any number of heat e~changers may ~e utilized, the major consideratiQn being the amount of heat exchange sur~ace area which is present.
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The pressure within the dynamic reaction zone is maintained at a constant value within the range of from about 300 to about 450 psig, preferably within the range of from ahout 325 to about 400 05 psig. This is a factor in controlling the rate of reaction. When employing the feed ratio of gas to water within the ranges given above, pressures below the preferred ranges will yield products which do not have the minimum level of about 35 millillters lO of gas per gram of product within acceptable reac-tion times. And, pressures above the ma~imum will result in the sporadic formation of high levels of gas hydrate which tend to cause erratic flow pro-blems within the dynamic reaction zone and subse 15 quent processing lines. Accordingly, maintenance of the pxessure within the preferred range is important ` to th~ produc-tion of high quality product on a ,` reproducible basis.
The pressure maintained within the dynamic 20 reaction zone is controlled by pressure control means in CQmmUnication with the reaction zone as will be described later. During the stage of trans-porting the process reaction mixture from the reac-~` tion zone to the freezing chambers~ the pressure ~ 25 control means, to be described later, is also main-r tained in communication wi~h the freezing chamber.
Refering again to the scraped-surface heat exchangers 70 and 72, which comprise the dynamic ' reaction zone in the pro~ess ar~an~ement shown in i 30 the drawing, an in-line mi~r 76 is employe~ in txa~sfer li~e 74 tQ maintain th~ produc~ ~n a con~
sis~ently-uni~o.rm ~lowable cs~dition a~ it passes from one scraped-surface heat exchanger to the other, and to further aid in solubilizing the dis-persed gas into the li~uid.
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The scraped-surface heat exchangers can be of conventional construction such as a Votator scraped-wall heat exchanger (available from Chemetron Corp., Louisville, Kentucky) or a Contherm unit (available 05 from Alfa Laval, Inc., Fort Lee, New Jersey). Both scraped-surface heat exchangers 70 and 72 are jacket-ed with a heat exchange medium such as a propylene glycol solution which is circulated through the jacket to provide cooling and heat removal from the exothermic reaction as the process reaction mixture is continuously scraped from and replaced onto the internal surface of the heat exchangers 70 and 72.
Thus, as shown in the drawing, line 78 feeds heat exchange media to the jacket of heat exchanyer 70 and line 80 having flow control means 82 therein removes the heat exchange media therefrom. Similar-ly, heat exchanger 72 is supplied with heat exchange media by means of line 84, with the return line 86 having a flow control means 88 positioned therein.
In addition to the in-line mixer 76 in line 74, the pressure is constantly monitored by means of a suitable pressure sensing device 89. To further assure continuous, uniform flow of the process stream from scraped-surface heat exchanger 70 to scraped surface heat exchanger 72, care is taken to maintain uniform, smooth bends within line 74 which is also maintained free of internal obstructions.
Preferably, this process feed line and all those downstream lines for transporting the susp~nsion of gas hydrate particles will be free of obstructions and will be positioned to provide bends of no less than a 6 inches radius.
Contact is maintained within the dynamic reac-tion zone for a period of time effective to form conditionally-stable gas hydrate and to dissolve gas * Trade Mark ~.'.. ~ .
~2Si~q~3 within the water to an extent effective to provide a uniform, flowable suspension of solid gas hydrate crystal-like particles in a saturated aqueous solu tion of the gas, typically carbon di.oxide. Accord-05 ing to this invention, contact or residence within the dynamic reaction zone is kept between two and ei~ht minutes, preferably between 3 and 5 minutes and will typically be around four minutçs. The residence time will usually be divided equally among ~ lO two or more reaction vessels such as scraped surface ; heat exchangers 70 and 72. Preferably, the contact under dynamic conditions within the reaction zone is - maintained for a period o~ time effective to substan-tially eliminate bubbles of gas from the suspension.
While the absolute eliminatior, of gas bubbles is not essen~ial to the invention, primarily due to the control of the process feed stream and the pressure control means downstream of the reactor, it is important to prevent undue quantities of gas from being transported downstream of the reaction zone ~or the continuance of reaction in the absence of dynamic conditions, since this may cause sporadic fluctuations in the gua~tity of hydrate produc~d.
If desired, a sight glass 92 or other measurement device can be employed in line 90 to enable close monitoring of the rheological properties of the suspension.
The suspension is passed from the dynamic reaction zone through line 90 whiçh is continuously maintained in communication with a pressure control means which comprises a valve means 94 and a means 96 for separating occluded gas from liquid and solid components. The pressure control means is capable of controlling the system pressure to within 5 psig of the preselect.ed process pre~sure. The valve . ~
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-: . ~ . ,'~ , ' 25~3~;3 means is preferably a pneumatically opera-ted, self-adjusting back-pressure valve which is capable of closely controlling -the process pressure. The valve has a flexible internal diaphragm indicated in 05 phantom lines 98 and has a gaseous fluid con-trol means 100 which is operative to maintain the proper process pressure.
As shown in the drawing line 102 provides communication between the means 96 and valve means 94. Within line 102, ano-ther pressure measuring device 104 is preferably provided. Likewise, a pressure measuring device is preferably provided in line 90 as shown in the drawing as 106.
The means 96 which separates the occluded gas from liguid and solid components is preferably a jacketed tank having sufficient capacity to handle flow rates for this specific process. Heating fluid, such as 100F water will be passed through the outer jacket of the tank to melt incoming sus-pension and thereby release gas therefrom. Byseparating the gaseous components Erom -the solid and liguid components, we have fQund that it is possible to avoid intermittent pressure fluctuations due to areas of concentrated solid matçrial within the suspension which in the past have caused wide flua-tuation in process pressure. The medium for heating the jacket o~ the means 96 is supplied as shown in the drawing via line 108 and withdrawn via line 110.
Separating means 96 may con~ain a bottom drain valve (not shown) to remove liquid either during or after operation. Such liquid removal may be necessary during continuous operation to prevent liquid from passing to valve means 94.
The freezing chamber 120 can be positioned either vertically or horizontally. It has been ~ "
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found quite unexpectedly, however, that -the yield of unbroken solid ice, suitable for cutting into lengths of suitable ~ize for packaging, is improved where the tubes are positioned horizontally. Preferably, 05 the freezing chamber will comprise an elongated cylinder positioned at an angle of from 0 to about 30 from the horizontal. Where the amount of solid, severable carbonated ice is produced in this manner, a large amount of a highly attractive product ice can be prepared. Any ice which does not maintain its structural stability in solid form can be ground and then recompaçted as is known -to the art.
The final stage in processing relates to the freezing of the suspension to form a solid gas hydrate-containing product covered in a protec-tive layer of solid water ice. This coating may be saturated with gas and result from a slight surface melting of the product within the freezing chamber.
The water-ice coating may also include a layer which 2Q is applied to the product after or as it is removed from the freezing chamber. Conventional water spraying or dipping techniques may be used for this purpose.
According to the arrangement shown in the Figure, a bleed point 112 is positioned in line 90 for U$e when needed. From line 90, it is possible to direct flow into line 114 by closing valve 116, opening valve 118 and then providing direct communi-cation between the freezing chamber 120 and the reaction zone and the means for controlling pressure.
To direct flow through the freezing chamber 120, fill valve 122, vent valve 124 and valve 126 are all opened while bleed valve 128 and cross flow valve 130 are closed.
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Under steady state conditions, the pressure within the freezing chamber 120 will be stabilized by virtue of its communication with the reaction zone and the pressure control means to the pre-OS determined process pressure. Material will flow into the freezing chamber 120 until the chamber is filled and will then pass therefrom via line 132 to line 134 to the pressure control means downstream.
When liquid starts to overflow from the valve 94, it lO is preferred to maintain flow of suspension to the freezing chamber for another minute or so to assure uniformity of the product therein. At that time, flow to the freezing chamber 120 is terminated and flow to a similar freQzing chamber (not shown) is 15 started in the same manner, by closing and opening the appropriate process line valves.
The freezing chamber 120 itself can be suitably sized tc provide either individually molded product portions or a larger piece which is cut to size.
20 Typically, the chamber 120 will have an elongated shape, such as a long tube having a diameter of from about 1 to about 7 inches, preferably from about 2.5 ~; to about ~.5 inches, and a length of up to about 20 feet or more. Preferably, the internal surface of ~ 25 the freezing chamber will be smooth and corrosion i~ resistant, and will permit the simplified freezing ~ and demolding of product.
? ~ facilitate ~oth freezing and demolding, the freezing chamber is preferably jacketed and heat 30 exchange media is passed through the jacket, enter-3 ing by means of line 136 and being withdrawn by ' means of line 138. The product is preferably frozen by cooling in a stepwise manner, as per the afore-mentioned U.S. Patent 4,347,707 to a temperature of 10C. Upon stabilizing the frozen t ~5~3 ~ 22 --product the presswre is released to atmospheric conditions and a warm heat exchange medium applied to the tube jacket to cause a surface melt of the product thereby releasing it from the tube.
05 The carbonate~ ice prepared in the above manner can be packaged in a suitable container such as a can or styrofoam cup. When packaged in containers of this type, the carbonated ice will provid~ a high degree of storage stability at ambient pressure and at temperatures within the range of from about -5 to about -20F for a period of time in excess of 6 months. Alon~ with the carbonated ice, in the sam~
package or in a separate or adjoining package, there may be provided a composition for preparing a soft drink such as the kind which comprise a color, flavor, an edible acidulent, and sweetener, all of these ingredients being present in the amounts effective to provide the desired taste and eye appeal.
The following example is presented for the purpose of further illustrating and explaining the present invention and is not to be taken as limiting in any regard. Unless otherwise indicated, all parts and percentages are on a weight basis.
xample 1 This example illustrates the preparation of a carbonated ice product according to the present invention employing a process arrangemen-t as shown in the Figure. To achieve the results which have been established as optimum, the system is set to achieve the operating parameters se-t forth in -the following table:
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OPERATING P~RAMETERS VALU~
Wate~ flow rate 4.5 -~/min Sys-tem p~essure 350 psig CO2/H2O ratio (wt.) 0.16 05 Feed wate~ temperatu~e 32F
Temperature at the outlet of water pump 32 33~
Tempe~ature at the outlet of sparger 62 41E
C2 press~lre at the inlet o~ gas controller 500 psig C2 (g) temperature at the outlet of the gas cooler 58 hSF
Glycol heat ex~hange fluid inlet (supply) t~mperature at scraped-surface heat exchangers 70 ~ 72 18~
Glycol outlet temperature at scraped-surface heat exchangers 7Q & 72 25F
Glycol flow rate thru ; scraped-surface heat exch~ngers 70 & 72 2 gpm Product temperature at outlet of scraped-sur$ace heat exchangers 70 & 72 42F
' 20 i The process is initially started by preparing the carbon dioxide and water feed systems for flow and then starting the flow of water through the system. At this point, the scraped surface heat ~5 exchangers which in this case are Votator units, having an internal surface area of three square feet, are started at a speed of 750 rpm. The system pressure is allowe~ to build and the b~ck pressure valve 94 is set to the ~stabli$hed system pressure of 350 psig. Once the predetermin~d pressure i8 reached, the carbon dioxide flow is started and regulated by means of the controller 56 to maintain the proper flow rate to achieve the desired ratio of gas to water of Q.16. The gas temperature is main-tained at a temperature o~ about 45F by maintaining . .
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a cold water flow ~not shown) to heat exchanger 58.
Then, the hea-t exchange medium is begun to the jackets of both of the Votator heat exchangers operating at a shaft rpm of 750.
The system is allowed to stabilize for a period of time sufficient to achieve steady state opera-tion. For stabilizing, valves 118, 126 and 130 are opened and valves 116, 128, 122 and 124 are closed.
When the system has reached steady state operation, valve 130 is closed and valves 122 and 124 are opened on the freezing tube which has been pressur-ized to 350 psig to permi-t filling thereof to begin.
In this particular example, the freezing tube has a diameter of 2.5 inches and the length of 10 fee~.
While filling, the system pressure is main~ained at a CQnstant 350 psig. ~lso, ~hile filling the freez-ing tube, a 40~ solution o~ propylene glycol in water at a temperature of 18F is supplied to th~
~ jacket of the ~reezing tube.
'- 20 Filling is allowed to con~inue until liquid , starts to overflow at the outlet of the back pres-sure ~alve 94 indica-ting that the tube is filled.
The hydrate is permitted to continue to flow for an extra minute after which period of time valves 122 and 124 are closed and valve 130 is opened. The feed at this point in time can be switched to a~o-I ther freezing tube.
Supply of 18F propylene gly~ol solution to the jacket o~ the freezing tube is continued until the core temperature of the product reaches 32Fi and, at that point, the pressure is gradually reduced to 250 psig and colder propylene glycol, at a tempera-tuxe of 0E', is then supplied to the jacket of the freezing tube. Freezing is completed over a period of about 30 minutes while maintainin~ the product within the closed freezing tube.
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', ' ~.2;~ 3 When the core temperature of the carbonated ice reaches 15F or below, the produc-t is ready to be demolded. The pressure on the freezing tube is then gradually relieved. The tube is then opened at the 05 lower most end and the glycol supply to the tube is warmed to 85F to permit the product -to slide out.
~ le 2 The following example presents a comparison of results obtained by freezing a series of product suspensions prepared, according to Example 1, in tubes positioned either horizontally or vertically.
The horizontally positioned tube was at a 15 angle to the horizontal. The results are as follows:
AVERAGE GAS CONTENT
(cc/gram) Horizontal Tubes 45.4 45-~
47.5 44.4 Vçrtical Tubes 41.9 40.1 41.6 40.6 Yield of solid puck-shaped product ~ " thick) after demolding and cutting is about 2.5 times greater for the horizontal tube than i-t is for the ~ertical tube.
The above description is for the purpose of teaching the person of ordinary skill in the art how ' , :
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to practice the present invention. This description is not intended to detail all of -the obvious modifi-cations and variations of the invention which will become apparent to -the skilled worker upon reading.
05 However, applicants do intend to include all such ~ modifications and variations within the scope of ; their invention which is defined by the following claims.
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Claims (18)
1. A process for preparing gasified ice characterized by a uniform gas content within the range of from about 35 to about 60 milliliters of gas per gram of product and a high degree of mechan-ical strength in the frozen state, which comprises:
providing a source of water at a temperature below about 5°C;
providing a source of conditionally-stable-hydrate-forming gas at a temperature of less than about 10°C;
dispersing the gas within the water at a weight ratio of gas to water within the range of from about 0.10 to about 0.25 to provide a process feed stream;
introducing the process feed stream into a dynamic reaction zone at a temperature within about 1°C of the hydrate formation equilibrium temperature at a preselected process pressure, within the range of from about 300 to about 450 psig, which is main-tained within the dynamic reaction zone;
maintaining contact between the gas and water in the feed stream under dynamic conditions for a period of time of from 2 to 8 minutes and effective to form conditionally-stable gas hydrate and to dissolve gas within the water to an extent effective to provide a uniform, flowable suspension of solid gas hydrate crystal-like particles in a saturated aqueous solution of carbon dioxide;
transporting the suspension to a pressurized freezing vessel which is in communication with the dynamic reaction zone and a pressure control means, comprising valve means and means for separating occluded gas from liquid and solid components, said pressure control means being capable of controlling the system pressure to within 5 psig of the pre-selected pressure;
closing the freezing chamber; and, freezing the suspension under pressure.
providing a source of water at a temperature below about 5°C;
providing a source of conditionally-stable-hydrate-forming gas at a temperature of less than about 10°C;
dispersing the gas within the water at a weight ratio of gas to water within the range of from about 0.10 to about 0.25 to provide a process feed stream;
introducing the process feed stream into a dynamic reaction zone at a temperature within about 1°C of the hydrate formation equilibrium temperature at a preselected process pressure, within the range of from about 300 to about 450 psig, which is main-tained within the dynamic reaction zone;
maintaining contact between the gas and water in the feed stream under dynamic conditions for a period of time of from 2 to 8 minutes and effective to form conditionally-stable gas hydrate and to dissolve gas within the water to an extent effective to provide a uniform, flowable suspension of solid gas hydrate crystal-like particles in a saturated aqueous solution of carbon dioxide;
transporting the suspension to a pressurized freezing vessel which is in communication with the dynamic reaction zone and a pressure control means, comprising valve means and means for separating occluded gas from liquid and solid components, said pressure control means being capable of controlling the system pressure to within 5 psig of the pre-selected pressure;
closing the freezing chamber; and, freezing the suspension under pressure.
2. A process according to Claim 1 wherein the contact under dynamic conditions is maintained for a period of time effective to substantially eliminate bubbles of gas from the suspension.
3. A process according to Claim 1 wherein the freezing chamber shapes the gasified ice into an elongated rod, and the rod is cut into a plurality of smaller lengths.
4. A process according to Claim 1 wherein the contact under dynamic conditions is maintained for from 3 to 5 minutes.
5. A process according to Claim 4 wherein the process pressure is maintained within the range of from about 325 to about 400 psig.
6. A process according to Claim 5 wherein the weight ratio of gas to water is within the range of from about 0.14 to about 0.18.
7. A process according to Claim 1 wherein the feed water has a temperature of from 0° to 2°C and the feed gas has a temperature of from 7° to 8°C.
8. A process according to Claim 1 wherein the freezing chamber comprises an elongated cylinder positioned at an angle of from 0° to 30° from the horizontal.
9. A process according to Claim 1 wherein the gas is fed from a surge tank maintained at a pres-sure no higher than 200 psig greater than the pro-cess pressure.
10. A process according to Claim 1 wherein the water feed stream is fed continuously with a varia-tion in flow rate of no more than 5%.
11. A process according to Claim 1 wherein the suspension of solid gas hydrate crystal-like parti-cles is fed alternately to one of a plurality of freezing chambers.
12. A process according to Claim 1 wherein the temperatures throughtout the system are controlled to prevent fluctuation by more than 5°C at any point in the process.
13. A process according to Claim 1 wherein the suspension of gas hydrate crystal-like particles is frozen to a temperature of less than about -10°C.
14. A process according to Claim 1 wherein all lines for transporting the suspension of gas hydrate crystal-like particles are maintained free of ob-structions and are positioned to provide bends of no less than a 6-inch radius.
15. A process according to Claim 1 wherein the gas is dispersed into the water by passing it through a sintered sparger.
16. A process according to Claim 1 wherein the water is distilled or deionized water.
17. A process according to Claim 1 wherein the gas is carbon dioxide.
18. A product prepared according to the pro-cess of Claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000468156A CA1225863A (en) | 1984-11-19 | 1984-11-19 | Process for preparing a gasified ice product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000468156A CA1225863A (en) | 1984-11-19 | 1984-11-19 | Process for preparing a gasified ice product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1225863A true CA1225863A (en) | 1987-08-25 |
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ID=4129183
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000468156A Expired CA1225863A (en) | 1984-11-19 | 1984-11-19 | Process for preparing a gasified ice product |
Country Status (1)
| Country | Link |
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| CA (1) | CA1225863A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017093084A1 (en) * | 2015-11-30 | 2017-06-08 | Unilever Plc | Process for the manufacture of a frozen product |
| CN108192684A (en) * | 2018-02-08 | 2018-06-22 | 青岛海洋地质研究所 | Continuous preparation device of blocky combustible ice and preparation method thereof |
| CN111320191A (en) * | 2019-12-30 | 2020-06-23 | 青海锂业有限公司 | Method for recycling lithium resources in lithium-containing salt mine |
-
1984
- 1984-11-19 CA CA000468156A patent/CA1225863A/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017093084A1 (en) * | 2015-11-30 | 2017-06-08 | Unilever Plc | Process for the manufacture of a frozen product |
| US10932479B2 (en) | 2015-11-30 | 2021-03-02 | Conopeo, Inc. | Process for the manufacture of a frozen product |
| CN108192684A (en) * | 2018-02-08 | 2018-06-22 | 青岛海洋地质研究所 | Continuous preparation device of blocky combustible ice and preparation method thereof |
| CN108192684B (en) * | 2018-02-08 | 2024-04-09 | 青岛海洋地质研究所 | Continuous preparation device and preparation method of blocky combustible ice |
| CN111320191A (en) * | 2019-12-30 | 2020-06-23 | 青海锂业有限公司 | Method for recycling lithium resources in lithium-containing salt mine |
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