in accordance with this invention there is provided an improved dry ice product manufactured in the form of blocks , pellets , flakes , powders , and other possible forms well known in the art containing carbon dioxide and ozone . the dry ice product is essentially free of water . what is meant by “ essentially free ” of water is that the dry ice product , if it contains water , will comprise less than 5 wt . % water . typically , the water content will be less than 1 wt . %. moisture levels of up to 5 , 000 ppm may be helpful in maintaining the desired shape of the product . the major constituent of the product is carbon dioxide . the ozone concentration in the product can vary widely and can depend upon the end use of the product and , in particular , the product being treated and the environment surrounding the treated product . only minute amounts of ozone are necessary for providing an antimicrobial effect . at the same time , osha limits the exposure levels of ozone to 0 . 1 ppm to 0 . 3 ppm in 8 hour and 15 minute shifts , respectively . accordingly , the amounts of ozone dispersed into an area must be kept at a minimum and to a level safe for persons handling the treated product . a non - limiting level of ozone in the dry ice product can range from 0 . 1 ppm and above . more typically , the ozone content of the dry ice product will range from about 1 to 100 ppm . ozone levels of 1 to 10 ppm by weight are believed to be effective for killing bacteria . ozone present in the product is made available for various applications during carbon dioxide sublimation with the additional benefits , i . e . chilling , of using dry ice . the product of this invention in which dry ice is combined with ozone provides an expendable form of refrigeration while simultaneously providing a method of biological treatment that does not expose humans coming in contact with the product to excessive levels of ozone . ozone gas is generally considered to be an unstable molecule that has a short shelf life . it is known that at lower temperatures ozone is more stable and has a reduced tendency to decompose to oxygen prior to providing any biological effect . dry ice at atmospheric pressure is at a temperature of − 109 . 9 ° f . the liquefication temperature of ozone is − 168 ° f . this means that the ozone contained in the dry ice product is close to the liquefaction point , but still well into the gas phase . accordingly , the ozone mixed with dry ice as in the product of this invention can be trapped in the structural lattices of the dry ice and / or by physical absorption onto the surface of the dry ice . the ozone in the dry ice is added for biological treatment . the most effective biocidal treatment occurs when the ozone is released in proportion with the dry ice sublimation . the exact form of the dry ice product can vary and , accordingly , a wide variety of forms can be manufactured and used depending upon the product to be treated and the purpose of such treatment such as , for example , storage , transport , commercial sale display , etc . thus , if the product to be treated is to be stored in large rooms , for example , blocks of dry ice ranging from 5 to 50 lbs . can be formed . likewise , if the product to be stored , transported , or displayed for sale requires direct contact of the dry ice product , smaller manufactured shapes can be provided . thus , for example , pellets in the range of 1 / 16 to 1 inch can be formed , or even powders such as snow , flakes , or chips can be formed by methods known in the art . while the manufacturing process of the dry ice product can vary widely and it is contemplated that any process which can incorporate ozone into dry ice can be found to yield a useful product , it has been found to be particularly useful to incorporate the ozone into the carbon dioxide during the dry ice manufacturing process . the traditional first step in making “ dry ice ” is to manufacture carbon dioxide liquid . this is done by compressing co 2 gas and removing any excess heat . the co 2 is typically liquefied at pressures ranging from 200 - 300 pounds per square inch and at a temperature of − 20 ° f . to 0 ° f . respectively . it is stored in a pressure vessel at lower than ambient temperature . the liquid pressure is then reduced below the triple point pressure of 69 . 9 psig by sending it through an expansion valve . this can be done in a single step or , in many cases , by reducing the liquid pressure to 100 psig at a temperature of − 50 ° f . as a first step to allow easy recovery of the flash gases . the liquid co 2 is expanded inside a dry ice manufacturing press to form a mixture of dry ice solid and cold gas . the cold gas is vented or recycled and the remaining dry ice snow is then compacted to form blocks . dry ice is typically compacted to a density of approximately 90 lb / ft3 . the present invention facilitates the above by directly contacting compressed ozone with carbon dioxide . in comparison , existing prior art as discussed previously dwells in using indirect methods to combine ozone with dry ice after the dry ice is manufactured . such products include substantial amounts of water ice and , accordingly , inherit the problems associated with melting . in general , to manufacture ozonated dry ice , compressed ozone at a pressure of at least 90 psig is combined with liquid carbon dioxide at a pressure above the triple point of co 2 ( 70 psig ), allowing the ozone to fully dissolve in the liquid co 2 . the feed gas for ozone injection can include o 2 , air , a mixture of o 2 and air or mixture of o 2 , air , and an inert gas , e . g . n 2 , c 2 , ar , kr , xe , ne . inert gas , if included with the ozone during contact with the co 2 , may comprise 10 - 99 % total concentration of injected gas in the process . the inert gases may be mixed with ozone or added separately during the process . the temperature of the ozone treatment is maintained at ambient or below . co 2 pressures ranging from 70 psig to 100 psig can be used during the mixing process . the ozone compression pressure will typically range from about 100 to 150 psig . higher ozone pressures can also be used when available . the liquid carbon dioxide / ozone mixture is then expanded to generate dry ice , “ snow ”, containing ozone , oxygen , and dry ice —“ ozonated dry ice .” this modified dry ice can then be collected or shaped such as by pressing or extrusion . this scheme can be successfully adapted to existing dry ice plants . methods of producing ozone are well known in the art . ozone is generated using oxygen or air . there are two primary methods of creating ozone from air : by an ultraviolet light generator light system or by an electrical discharge system . an ultraviolet light ozone generator typically consists of multiple ultraviolet light tubes within an aluminum housing . in a multiple tube apparatus , air enters the generator cavity and is subjected to the ultraviolet light and the ultraviolet light causes a disassociation of the oxygen molecules , which exists as o 2 , to 2 oxygen atoms . some of these oxygen atoms attach themselves to oxygen molecules to form ozone ( 03 ). the resulting ozone and sterile air mixture comprises approximately 0 . 2 percent of ozone by weight / weight of air . in the preferred mode , the ozone gas is generated from oxygen or oxygen - enriched air by a corona discharge device that produces concentrations ranging between about 1 % to about 15 % by weight of ozone . based on technologies available today , it is possible to generate ozone concentrations up to a maximum of 13 . 5 % with the remainder being oxygen and a small fraction of other gases . it is possible to use higher ozone concentrations for this application if the generator technology becomes available . higher concentrations of ozone are preferred . it is preferred to use oxygen compared to air due to the possibility of producing higher concentrations of ozone . it is industrially proven that ozone can be compressed to 150 psig using water ring compressors . it is feasible to safely compress an ozone / oxygen mixture containing 10 % by weight of ozone to 70 atm pressures . several others have tried ozone liquefication by using higher pressures without much success . fig1 and 2 depict alternative methods of forming the ozonated dry ice product of this invention . each figure represents a typical dry ice manufacturing process in which fig1 is a process used to form blocks of dry ice , while fig2 depicts a process used to form dry ice pellets . these processes can be modified to incorporate ozone into the dry ice product . first , with respect to fig1 , liquid carbon dioxide is stored in tank 2 , typically at pressures of 200 to 300 psig . the liquid carbon dioxide from storage tank 2 is then passed via line 4 to a low - pressure expansion tank 6 wherein the liquid co 2 is expanded to a pressure above the triple point of carbon dioxide ( 69 . 9 psig ). typically , the liquid co 2 is expanded to pressures of from about 70 to 100 psig in expansion tank 6 . what results is a mixture of gas and a dense , viscous carbon dioxide liquid . it is important that the liquid co 2 is not formed into solid dry ice at this point in as much as the solid in the piping would disadvantageously reduce transport of the liquid . ozone from an ozone generator 8 is then injected into the liquid carbon dioxide . injection of the ozone can be done in the low - pressure expansion tank although , as shown in fig1 , the ozone is mixed with the liquid co 2 after the liquid co 2 leaves expansion tank 6 via line 10 . ozone from the ozone generator 8 is compressed to pressures of from about 100 to 150 psig in compressor 12 and then fed via line 14 to mix with the liquid co 2 from line 10 . the mixture of ozone and liquid co 2 is passed via line 16 through an expansion orifice 18 into the dry ice press 20 . alternatively , although not shown , the mixture of ozone and liquid co 2 can be passed to a separate refrigeration unit , wherein the liquid co 2 is frozen into a solid containing the entrapped ozone . as further shown in fig1 , the mixture of liquid co 2 and ozone is allowed to expand inside the dry ice press 20 . during expansion , the liquid co 2 is converted to a solid form and the ozone is trapped in the structural lattices of dry ice and / or by physical absorption during dry ice formation . the major portion of the ozone will remain attached to the cold dry ice particles and only a small portion will exit dry ice press 20 with the flash gases via line 22 . once the dry ice solid is formed , the solid particles can be compressed via platen 24 in press 20 into ozonated dry ice blocks 26 . the ozone in dry ice necessary for biological treatment is slowly released as the carbon dioxide sublimes during use . higher concentrations and pressures of ozone are preferred to achieve higher concentrations of ozone in the dry ice product . the preferred concentration of ozone can vary depending upon the use of the dry ice and the product treated . by the above method it is possible to achieve higher concentrations of ozone compared to the prior art methods which have involved a mixture of ozonated water ice and dry ice . the present method is relatively easy to implement in existing dry ice plants with minimum capital requirement . referring now to fig2 which depicts a process used to form dry ice pellets , such process is similar to that shown in fig1 . with respect to fig2 , liquid carbon dioxide is stored in tank 30 , again , typically at pressures of 200 to 300 psig . the liquid carbon dioxide from storage tank 30 is then passed via line 32 directly to a dry ice pelletizer 34 . dry ice pelletizers are well known in the art . it is believed any dry ice pelletizer is capable of use with this invention . in the pelletizer , the liquid co 2 is expanded to a pressure below 70 psig . what results is a mixture of gas and carbon dioxide solid particles . ozone from the ozone generator 34 is compressed to pressures of at least about 100 psig in compressor 38 and then fed via line 40 to mix with the co 2 in the dry ice pelletizer 34 . ozone injection can be done prior to extrusion of the dry ice particles into pellets or the ozone can be mixed with the co 2 pellets after extrusion . the liquid co 2 is allowed to expand inside the dry ice pelletizer 34 and is converted to a solid form . while not wanting to be bound by any theory of operation , if the ozone is added during expansion , the ozone is believed to be trapped in the structural lattices of dry ice . if the co 2 is solid , either as particles or as extruded pellets during injection of the ozone , the ozone is believed to be contained in the dry ice by physical absorption . it is believed a major portion of the ozone will remain attached to the cold dry ice particles and only a small portion will exit with the flash gases from pelletizer 34 via line 42 . the solid co 2 particles are extruded into pellets , typically ranging from 1 / 16 to 1 in . as in the block dry ice , the ozone in dry ice pellets necessary for biological treatment is slowly released as the carbon dioxide sublimes during use . small amounts of adjuvants may be added into the dry ice manufacturing process to improve the ozone stability in dry ice . non - limiting useful adjuvants are as follows : a . water ( not to exceed 5 wt . % of dry ice ) b . gras ( generally recognized as safe ) grade acidulants such as citric acid , acetic acid , lactic acid c . gras grade surfactants such as polysorbate 60 / 65 / 80 d . gras grade food preservatives such as edta ( in any forms ), bha , bht , sodium nitrate ( in any forms ) e . gras gums such as carrageenan ( in any forms ), xanthan gum , furcelleran ( in any forms ), arabinogalactan f . any other gras grade food additives such as polyethylene glycol , sucrose fatty acid esters , fatty acids ( in any forms ) the ozonated dry ice product of this invention improves the biocidal efficacy of dry ice to better ensure safe food production and maintain wholesomeness of the finished products . ozone is effectively delivered into dry ice and at a desired concentration such that during dry ice sublimation , the ozone can exert the desired biocidal effect for disinfection and / or sanitation purposes . ozone gas is released as a process to disinfect food products through direct food contact and to ensure significant reductions of spoilage and pathogenic microorganisms . since ozone is more stable under cold environments , the present process provides the ultimate conditions for ozone to work at maximum reactivity . since the release of ozone from the dry ice is well regulated , food products receive ozone slowly and constantly during the entire storage thereof , and accordingly , shelf life and quality of the food product are enhanced . moreover , carbon dioxide chills the food products efficiently , further providing benefits to food products . the carbon dioxide slows down the growth of spoilage and pathogenic microorganisms in food , allowing the food products to last longer and safer . the carbon dioxide also slows down the enzymatic reactions in food , allowing the quality of food to be extended during storage . carbon dioxide from dry ice sublimation also penetrates into microbial cells , lowers the intracellular ph of microbial cells , and causes those microbial cells to be more sensitive to ozone . accordingly , a synergistic effect on biocidal efficacy can be achieved by combining dry ice and ozone . this example illustrates the injection of ozone into liquid co 2 . a vertical tubular reactor was provided made of ss 304 with a capacity of about 13 l . the top of this reactor included a lid containing inlet and exit ports for gaseous and liquid components . a liquid co 2 supply vessel provided a source of liquid co 2 . the following operating procedure was utilized to form ozonated dry ice snow . a valve on the co 2 supply vessel was opened and the reactor purged with gaseous co 2 from the supply vessel . the reactor was allowed to purge for about 1 - 2 minutes . this was done in order to allow the vessel to be purged and minimize the chances of forming a short circuit . after about 30 seconds , the reactor was again closed and the pressure adjusted to maintain 690 kpa ( 100 psig ) in the reactor . the valve for directing gaseous co 2 from the supply vessel was then closed . the co 2 liquid was then directed from the co 2 supply vessel . liquid co 2 was vented from the supply vessel until solid pieces of carbon dioxide began to appear in the vapor stream . liquid co 2 was then directed from the supply vessel to the reactor and the flow adjusted to increase or decrease the flow of the liquid co 2 into the reactor . the pressure in the reactor was kept at 690 - 827 kpa ( 100 - 120 psig ). it is important that the pressure does not go below the lower limit of this range . the pressure can be reduced in the reactor if pressure exceeds 827 kpa ( 120 psig ). it is also useful to determine the liquid level in the reactor via a dip tube . when the reactor was 66 % to 75 % full of liquid , liquid co 2 flow to the reactor was stopped and the liquid co 2 line from the supply vessel was vented to ensure that no liquid was left in the line . the line was brought back to atmospheric pressure . an insulated container was placed underneath the reactor to capture snow . a small amount of snow was allowed to flow from the reactor bottom in order to make sure the opening was clear . the snow produced was discarded . a backpressure regulator and reactor outlet was connected to an ozone destruction unit ( glass vessel containing mno 2 ). a gaseous ozone line was connected to the inlet of the reactor . the pressure of the ozone system was maintained higher than the pressure of the reactor . the ozone gas line was purged and then the inlet ozone line to the reactor was slowly opened to adjust the flow rate of ozone into the reactor such that the flow of gas at the ozone destruction unit outlet was slow and steady . a slight pressure increase in the reactor is normal , however , the pressure in the reactor was maintained such that reactor pressure did not increase by more than about 34 kpa ( 5 psig ). after the desired amount of ozone had been sent to the reactor or when the pressure of the ozone system approached the pressure of the reactor , the ozone inlet was closed . the ozone - containing dry ice “ snow ” was directed from the bottom of the reactor into an insulated container until enough snow had been produced . the ozone was produced from oxygen using an ozonia ® ozone generator cfs - 2 ( ozonia ® ltd ., switzerland ). the ozone was collected and then compressed to a maximum pressure of about 1034 kpa ( 150 psig ). approximately one liter of co 2 / o 3 snow was collected and placed into a beaker . ki solution was added . the snow was allowed to completely sublime while the ki solution was constantly washed over the snow . the solution was titrated with 0 . 1n na 2 s 2 o 3 . this procedure followed the iodometric method of determining the amount of ozone present in the sample . a first test run of the laboratory scale system described above produced about 4 to 5 kg of ozonated snow . the amount of liquid carbon dioxide in the reactor was about 9 l . approximately 2 liters of compressed gas was transferred into the liquid co 2 . the gas contained about 6 . 5 % ( wt / wt ) o 3 in o 2 with a gas pressure of about 814 kpa ( 118 psig ). the snow that was produced during this test had an ozone concentration of about 2 ppm .
a manufactured dry ice product containing ozone entrapped or absorbed on said dry ice . the dry ice product can be used to chill and preserve food products and provides the added benefit of ozonation of the food product to kill bacteria . novel processes for ozonating liquid and solid co 2 are provided .