Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
  • A61L2/20—Gaseous substances, e.g. vapours
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
  • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
  • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
  • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
  • A23L3/3409—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
  • A23L3/34095—Details of apparatus for generating or regenerating gases
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
  • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
  • A61L2/20—Gaseous substances, e.g. vapours
  • A61L2/202—Ozone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
  • B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/14—Production of inert gas mixtures; Use of inert gases in general
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
  • C01B13/10—Preparation of ozone
  • C01B13/11—Preparation of ozone by electric discharge
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J2219/0803—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
  • B01J2219/0805—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
  • B01J2219/0845—Details relating to the type of discharge
  • B01J2219/0849—Corona pulse discharge
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
  • B01J2219/0873—Materials to be treated
  • B01J2219/0881—Two or more materials
  • B01J2219/0883—Gas-gas

Definitions

• the present invention generally relates to a gaseous blend of C0 2 and O x and a method for applying the gaseous blend that can be utilized to significandy reduce the biological load on consumer products such as food products, botanicals and cosmetic ingredients, which have traditionally been treated with commercial sterilants or fumigants such as ethylene oxide, propylene oxide, methyl bromide, hydrogen phosphide, phosphine, steam (heat), irradiation, and the like.
• the gaseous blend of CO 2 and O x and method for applying the gaseous blend can also be used to reduce biological load in enclosed structures and on transportation containers (e.g., wooden pallets and crates), which are often used to store food products, as well as to reduce biological load on other commodities, and, in particular, on soil.
• transportation containers e.g., wooden pallets and crates
• U.S. Patents Nos. 5,624,635 and 5,566,627 disclose a method and apparatus for use of 0 3 to treat soil.
• U.S. Patent No. 4,200,656 discloses the use of CO 2 as a carrier for methyl bromide in fumigation.
• U.S. Patent No. 4,998,377 discloses the use of CO 2 as a carrier for methyl bromide and hydrogen phosphide in fumigation.
• U.S. Patent No. 5,678,352 discloses the use of CO 2 as a carrier for toxic agents such as methyl bromide during fumigation.
• U.S. Patent No. 5,464,457 discloses the use of an ammonium carbonate ingredient that decomposes to ammonia and C0 2 in order to fumigate a plot of soil.
• U.S. Patent No. 4,989,363 discloses application of CO 2 in pesticidal quantities for fumigation.
• the process disclosed in U.S. Patent No. 4,989,363 requires administration of C0 2 for a period of time of at least about 5 days.
• U.S. Patent No. 5,011,699 discloses the use of 0 3 and C0 2 in specified ratios, i.e., from 1:2 to 2:1, to sterilize foodstuffs at reduced temperatures.
• U.S. Patent No. 6,066,348 discloses the use of O 3 and CO 2 at reduced temperature to disinfect a foodstuff.
• Japanese Patent Publication No. 02076562A discloses the use of 0 3 , CO 2 and N gas to sterilize foodstuffs.
• U.S. Patent Nos. 6,283,193 and 6,334,979 disclose methods that use a gaseous mixture of oxygen-containing gases, i.e., O 3 , O z and O hereinafter referred to as O x , in a vacuum chamber to reduce biological loads on foodstuffs and other commodities.
• O x gaseous mixture of oxygen-containing gases
• O x has proven successful in controlling insects and microbiological concerns for selected fruits, vegetables and other botanicals, because of phyto-toxic issues and the fact that O 3 readily converts to oxygen when exposed to an oxygen-rich atmosphere, there remains a need to treat foodstuffs and other commodities that cannot withstand treatment under vacuum.
• a gaseous blend of C0 2 and O x having a specified ratio i.e., about 90-99% CO a and about 1-10% O x , preferably about 98-99% CO, and about 1-2% O x .
• This surprising discovery permits the application of gaseous O x to products in many environments.
• the gaseous blend of C0 2 and O x and the method for applying the gaseous blend of the present invention permit fumigation (hereinafter referred to as "biological burden reduction") of a commodity on-site where the commodity is normally stored, thereby eliminating the need to transfer the commodity to another location for treatment.
• the method of the present invention utilizes the gaseous blend of CO 2 and O x in a technologically advanced treatment system that overcomes limitations formerly encountered with C0 2 and/ or O 3 treatment on biological burden. Most importantly, the method of the present invention eliminates the need for complex systems often employed in prior art methods. The method may be employed on-site, thereby eliminating the need to transfer material to a special processing location.
• an object of the present invention to eliminate the health risks that are associated with the reduction of biological burden from food products and other commodities, building structures, transportation containers and soil.
• the inventive gaseous blend consists of about 90-99%, preferably about 98-99%, CO 2 and about 1-10%, preferably about 1-2%, O_.
• the inventive method for applying the gaseous blend comprises applying a continuous stream of CO 2 and O x gas to a material.
• the gaseous blend is applied at an elevated temperature, e.g., approximately 45°F to 140°F, and more preferably at about 85 °F to 115 °F.
• the continuous stream of C0 2 and O x gas can be prepared by any means.
• the continuous stream of O x gas may be prepared in an O x generation cell that contains a means for generating the O x gas at a pressure less than about 20 lbs/in 2 such as, for example, one or more of the following: corona discharge, electrical discharge, ultraviolet light, x-ray, radioactive isotope and electron beam.
• a means for generating the O x gas at a pressure less than about 20 lbs/in 2 such as, for example, one or more of the following: corona discharge, electrical discharge, ultraviolet light, x-ray, radioactive isotope and electron beam.
• CO 2 and smaller concentrations of CO can be added to the O x generation cell prior to production of O x , or CO 2 can be mixed into the O x gas flow immediately after its formation.
• the gaseous blend may then be passed through a commercially available catalytic destruct unit to eliminate any residual CO, O 3 and O ⁇ before the gas stream is discharged to the atmosphere.
• the present invention is also directed to treated food products and other commodities, building structures, transportation containers and/ or soil that result from use of the inventive gaseous blend of CO, and O x and method.
• FIGURE 1 is a schematic showing an embodiment of a method for using a continuous flow of CO, and O x to reduce biological burden in accordance with the method of the present invention.
• FIGURE 2 is a schematic showing another embodiment of a method for using a continuous flow of CO 2 and O x to reduce biological burden in accordance with the method of the present invention.
• like parts are designated by like reference numerals throughout the figures.
• O 3 The antibacterial potential of O 3 has been recognized for many years O 3 is widely used as a disinfectant for sewage treatment and for purification of drinking water. It has, however, failed to gain acceptance as a biological burden reduction treatment. The primary reason for this failure is that the O 3 molecule is highly unstable and quickly reverts to 0 2 if it does not encounter a susceptible substrate with which to react. O 3 also has the capacity to react with a broad array of substrates and would be expected to react with packaging materials surrounding the items being treated. This further reduces the number of O 3 molecules available to react with and inactivate microbial contaminants.
• U S. Patents Nos. 5,011,699 and 6,066,348 disclose previous attempts to use O 3 as a biological burden reduction treatment that include the reliance upon filling a chamber with O 3 and exposing the materials to be treated in static fashion for various periods of time without replenishment of 0 3 . Under these conditions, the concentration of O 3 within the chamber would be expected to rapidly decrease to a level below that required for effective biological burden reduction because of the short half life of O 3 , which is typically less than 20 minutes
• a further disadvantage of the static exposure technology is the reliance on simple diffusion to promote permeation of the O 3 molecules through packaging matenals and into the voids and interstices of the matenals being treated. Such methods, therefore, do not achieve adequate permeation of the 0 3 molecules into the material being treated.
• the method of the invention offers significant advances over the prior static biological burden reduction technology in that it provides a continuous flow of CO 2 and a continuous flow of O x throughout the treatment cycle and promotes rapid permeation of O x through packaging materials and into the voids and interstices of the materials undergoing treatment.
• the flow of CO is between about 90% and 99%, preferably between about 98% and 99%
• the flow of O x is between about 1% and 10%, preferably between about 1% and 2%
• Continuously supplying newly generated O x molecules to replace those molecules that have spontaneously degraded to inactive 0 2 and those that have reacted during the process ensures that the concentration of O x remains essentially the same throughout the process.
• the method of the invention also provides significant cost advantages over existing biological burden reduction technology.
• the most significant savings derive from the fact that the gaseous blend of C0 2 and O x may be generated and applied on site.
• O x is not flammable or explosive, facilities need not include damage-limiting construction or explosion-proof equipment.
• Another advantage of the method of the invention is that scrubbing will be easily accomplished using existing technology.
• O 3 is classified by the U.S. Food and Drug Ai ministration as a generally recognized as safe "GRAS" substance.
• the gaseous blend of CO 2 and O x and method of the invention has proven successful in the treatment of a wide variety of materials, including food products and other commodities, building structures, transportation containers and soil.
• the method of the present invention avoids many of the limitations of previous practices by avoiding the need for water sprays and/or water immersion of the substrate to be treated.
• Many products such as spices, flour-based products, sugar-based products, cosmetic bases, herbs, and botanicals, all of which are sensitive to high levels of moisture, can be treated using the method of the present invention.
• the method of the present invention also avoids the need to open conventional commercial packing before treatment, thereby avoiding unnecessary product degradation and loss.
• the product may be treated in situ utilizing conventional processing. Previous methods have required the product to be agitated, blended, bubbled or re-packaged during or immediately upon completion of the treatment.
• the extended half life of the O x radicals allows the active portions of the treatment gas to fully penetrate the substrate and act upon offending organisms.
• the stabilized O x gas mixture is further enhanced by the increased respiration rates of the offending organism(s) while in the presence of the permeated O x gases.
• a gaseous mixture comprised primarily of CO 2 , as well as smaller concentrations of O 3 , O, and carbon monoxide (CO), is used.
• the gaseous mixture is preferably fed through an ozone generator such as that described above where a gaseous blend is formed consisting of CO 2 , O 3 , O, and CO.
• This gaseous blend assists in the stabilization of the 0 3 molecules by dampening the molecular collision of the O 3 molecules, which would degrade this triatomic form of oxygen back to its diatomic form, atmospheric oxygen.
• the first benefit is to "tame" the O 3 so it has a chance to penetrate into the interstitial spaces of the material being treated.
• the CO 2 acts as a non- polar solvent to assist in the penetration of the gaseous blend into the material.
• the residual oxygen levels equal to or below normal atmospheric levels, oxidative damage to the material is highly reduced.
• the presence of high levels of C0 2 has been shown to enhance the effects of fumigants by promoting increased respiration in insects, thereby allowing the infusion of the fumigant into the insect spiracles and coming into direct contact with the insects' bodily fluids.
• the CO 2 can be mixed into an O 3 -rich gas flow immediately after the ozone generator to assist in the formation of the gaseous blend. According to this technique, no CO is formed because no CO 2 molecules are cleaved.
• a disadvantage of this system is the increased amount of oxygen required to produce the O 3 in the generator, which subsequently allows the O 3 to degrade at an accelerated rate.
• This gaseous blend is allowed to flow into, through and out of an impervious tarpaulin or sealed room as a continuous stream for a given period of time.
• Fans may be utilized to distribute the gaseous blend throughout the enclosed area to effect penetration into the commodity being treated.
• An outlet for excess gas allows for a constant release of gas through a catalytic bed consisting of, e.g., oxides of manganese, copper and aluminum to destruct any residual O 3 , O, and CO.
• This process has been demonstrated to operate at temperatures between 45° F and 140° F. Heating units can be incorporated into the fans to assist in bringing the temperature of the material to a desired temperature.
• the ideal temperature is 85° F to 115° F.
• Produce and the like generally require 1 to 24 hours treatment where other commodities such as grains may require treatment in excess of 48 hours.
• the concentration as measured directly from the O x generator can be adjusted to fall within the range of about 10 ppm to about 3,500 ppm, and more preferably about 10 ppm and 1,800 ppm, for food products, and up to about 20,000 ppm for building structures, transportation containers and soil, by using a starting gas mixture of about 90% to 100% CO,, preferably about 98% to 99%, and about 0% to 10%, preferably about 1% to 2% oxygen or air.
• the gas stream flowing through the ozone generator must be extremely dry, no additional moisture is required to humidify the material to be treated.
• Agricultural soil may be treated in accordance with the method of the invention, wherein the gaseous blend of CO, and O x is continuously fed under a gas impermeable membrane, e.g., a polyethylene film or a fumigation tarpaulin that has proven to be O 3 resistant.
• a gas impermeable membrane e.g., a polyethylene film or a fumigation tarpaulin that has proven to be O 3 resistant.
• This process would be typical of a methyl bromide soil fumigation that is routinely performed to control various insects, weed seeds, nematodes and fungal infections.
• the gaseous blend of C0 2 and O x would be destructed at an exit port.
• Infested structures may also be treated in accordance with the method of the invention, wherein the structure is first covered with a gas impermeable membrane and sealed for leaks, and wherein the gaseous blend of CO 2 and O x is then fed continuously and allowed to diffuse into the structure.
• the gaseous blend is evenly distributed using fans, which could also be used to supply any required additional heat.
• the gaseous blend of C0 2 and O x would exit a vent and be destructed using a destruct unit.
• the apparatus that may be used to practice the method if the invention includes, e.g., a shipping container 1 (FIGURE 1) or storage containers 1' (FIGURE 2) that is covered with an O 3 -resistant tarpaulin 2.
• the shipping container 1, or storage containers 1' contains material 3 to be treated.
• the shipping container 1, or storage containers 1' is connected via piping and appropriate control valves to a O x generator 4 at one end and to a destruct unit 5 at another.
• a first fan 6 is employed to draw gas from the O x generator 4 into the shipping container 1 or storage containers 1'.
• a second fan 6' is employed to draw gas from the shipping container 1 or storage containers 1' to the destruct unit 5.
• Either the first fan 6 or the second fan 6' may contain a heating means (not shown) to bring the shipping container 1 or the storage containers 1' to a desired temperature.
• a gas analyzer 7 is employed to determine the concentration of O 3 in the shipping container 1 or storage containers 1'.
• material 3 for which biological burden is to be reduced is placed within the shipping container 1 or storage containers 1'.
• a desired temperature is maintained via heating means (not shown).
• the process is then initiated by activating the O x generator 4.
• a stream of CO 2 gas, which may be added to the O x generator 4 or may be added after generation of O x , and C0 2 andO x gas is then drawn into, through and out of the shipping container 1 or storage containers 1' via the first fan 6 and the second fan 6'.
• the O x generator 4 operates continuously during the process. Exposure to the CO 2 and O x gas mixture may be varied in time from several minutes to several hours, depending on the material being treated.
• the O x generator 4 is inactivated and fresh air is allowed to enter the shipping container 1 or storage containers 1'. All gases may then be passed through destruct unit 5, which eliminates any residual CO, O 3 and O, before the gas stream is discharged to the atmosphere. The treated material 3 is then ready for use following appropriate tests to confirm biological burden reduction.
• the material can be treated by applying a continuous stream of O x and CO 2 under atmospheric conditions. This permits the treatment of the material under, e.g., a tarpaulin or in a sealed room, thereby removing the need for a vacuum chamber.
• the gaseous blend of CO 2 and O x and the method of the present invention were used to treat alfalfa pellets for animal feed.
• the alfalfa pellets were heavily infested with saw-toothed grain beede adults, grubs and eggs.
• the alfalfa pellets were placed in a breathable paper sack (sewn) and placed in a treatment room that was equipped with two circulation fans and a heater system.
• the gaseous blend described below was allowed to flow through the room. The following parameters were used:
• Example 1 The gaseous blend of C0 2 and O x and the method of the present invention were used to treat papaya fruits artificially laced with Drosophila fruit flies (adults only).
• the fruit was placed in normal shipping crates of cardboard construction.
• the fruit flies were placed in small glass tubes plugged with tissue and located in various locations within the shipping crates. The following parameters were used:
• the gaseous blend of CO, and O x and the method of the present invention were used to treat fresh strawberries.
• the strawberries were dipped into a buffered water solution containing a starting titre of 100,000 E. coll bacteria.
• the strawberries were allowed to air dry and placed into the treatment chamber along with several tubes containing Kve aphids.
• the glass tubes were plugged with tissue to retain the insects.
• a control set of plated strawberries was retained at room temperature for later enumeration. The following parameters were used:
• the gaseous blend of C0 2 and O x and the method for applying the gaseous blend of C0 2 and O x of the invention are an excellent substitute for commercial sterilants and fumigants in all of their current uses.
• the gaseous blend and method of the present invention and are also useful for the treatment of many food ingredients on which use of commercial sterilants and fumigants is not permitted, including cocoa beans, grains, and edible gums.
• Examples of commodities to be treated using the gaseous blend of CO 2 and O x and method of the invention include:

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• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
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• Polymers & Plastics (AREA)
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• Engineering & Computer Science (AREA)
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• 2002
  • 2002-03-15 BR BR0208152-0A patent/BR0208152A/pt not_active IP Right Cessation
  • 2002-03-15 EP EP02725205A patent/EP1385557A4/de not_active Withdrawn
  • 2002-03-15 WO PCT/US2002/008147 patent/WO2002074349A1/en not_active Application Discontinuation
  • 2002-03-15 JP JP2002573056A patent/JP2004532201A/ja active Pending

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