RU2804333C2 - Method and packaging for preserving food in hydrogen medium - Google Patents

Abstract

FIELD: food storage.

SUBSTANCE: invention is related to a method for preserving a food product in a hydrogen atmosphere in a package. A method (100) for storing a food product in an medium of hydrogen gas in a package (200) is proposed, including a) an inner space (220) surrounded by a hydrogen-permeable and air-tight sealable shell (210), and b) the inner space (220) containing space (221) for a food product, designed to receive a food product, and space (222) for hydrogen, designed to receive hydrogen gas, while c) space (221) for a food product and space (222) for hydrogen are connected to each other, in at least a gas-conducting manner, and d) at least a shell (210) or a sleeve (230) placed in the shell (210) and surrounding space (222) for hydrogen are dimensionally stable at negative pressure in space (222) for hydrogen relative to the environment surrounding the package (200), amounting to at least 200 mbar (0.02 MPa), said method characterized by the following stages: e) feeding (110) food product into at least space (221) for the food product, f) introducing (120) hydrogen gas into at least the hydrogen space (222), g) tightly sealing (130) the shell (210) after filling (110) with food and introducing (120) hydrogen gas, and h) creating (140) a negative pressure at least in space (222) for hydrogen relative to the environment surrounding the package (200), and i) creating (140) negative pressure includes diffusion of gaseous hydrogen through the shell (210) into the environment surrounding the package (200) after the shell (210) was sealed (130) in an airtight manner. A package (200) is proposed for storing a food product in an medium of hydrogen gas in this way, a) the package (200) includes an internal space (220) surrounded by a hydrogen-permeable and tightly sealable shell (210), b) the internal space (220) contains space (221) for the food product, designed to receive the food product, and space (222) for hydrogen, designed to receive gaseous hydrogen, and c) the space (221) for the food product and the space (222) for hydrogen are connected to each other in another at least gas-conducting manner, and which is characterized in that d) the shell (210) is dimensionally stable at a negative pressure in the space (222) for hydrogen relative to the environment surrounding the package (200) of at least 200 mbar (0.02 MPa), and contains a filling hole (250) configured to accommodate a media exchange device (240) for the simultaneous introduction of gaseous hydrogen through the inlet line (241) into the space (222) for hydrogen and the withdrawal of the food product through the outlet line (242) from internal space (220), or e) the shell (210) is at least partially flexible, and the sleeve (230) placed in the shell (210) and surrounding the space (222) for hydrogen is dimensionally stable at a negative pressure in the space (222) for hydrogen relative to the environment surrounding the package (200), which is at least 200 mbar (0.02 MPa). The use of said package (200) for preserving food product in a medium of hydrogen gas is also proposed in said method.

EFFECT: invention provides a cheap, simple and safe method for long-term, safe and environmentally friendly storage of a food product in a hydrogen medium and cost-effective packaging for this.

15 cl, 22 dwg

Description

Field of technology to which the invention relates

[1] The invention relates to a method for preserving a food product under a hydrogen atmosphere in a package having an interior space surrounded by a hydrogen permeable and airtight sealing shell, the interior space comprising a food product space for receiving the food product and a hydrogen space, designed to receive hydrogen gas, wherein the food space and the hydrogen space are connected to each other in at least a gas-conducting manner, and wherein the shell or sleeve surrounding the hydrogen space is dimensionally stable at a negative pressure in the hydrogen space relative to the surrounding packaging environment of at least 100 mbar (0.01 MPa).

[2] The invention also relates to packaging of the above type.

Prior Art

[3] Hydrogen has antioxidant effects and can keep food products shelf-stable and fresher for longer. Due to its antioxidant effect, hydrogen can influence the redox potential of a food product; this can be used, for example, in infant formula to better mimic the properties of natural breast milk, which has an oxidation reduction potential of up to -70 mV, in substitute products. The antioxidant effects of hydrogen can reduce or eliminate the need for other preservatives or antioxidants.

[4] There are already commercial suppliers selling hydrogen-enriched water in cans and bags. However, there are still no known solutions that would allow long-term storage of hydrogen in food packaging, since hydrogen can diffuse through conventional packaging materials and thus escape, which over time leads to complete leakage of hydrogen, which is dissolved in the food product and /or which is present in the packaging in addition to the food product.

[5] Hydrogen-enriched water is usually poured into flexible bags or metal cans made of a material that prevents hydrogen from diffusion at ambient pressure. In the case of flexible pouches, one or more thin metal foils are typically used to suppress hydrogen diffusion. To increase shelf life, filling is carried out either without gas, so that the package is completely filled with hydrogen-enriched water (mainly for beverage cans), or with a small amount of hydrogen gas in addition to hydrogen-enriched water (for film packaging).

[6] Patent application US20180213825A1 describes pouring hydrogen-enriched water into jars at or above atmospheric pressure, with the jars being completely filled with the enriched water.

[7] Hydrogen-enriched water can be further mixed with hydrogen gas bubbles for longer shelf life. Nano or microbubbles are usually used for this purpose because they remain stable in water longer than macroscopic bubbles.

[8] The above options for filling hydrogen enriched water only do not sufficiently delay the release of hydrogen gas from the package and, therefore, are not able to provide constant enrichment of water with hydrogen. According to US20180213825A1, the hydrogen content of water in existing packaging is reduced by approximately 14-75% within 6 months, depending on the type of packaging.

[9] For environmental and sustainability reasons, single-use packaging should be avoided. Since all hydrogen enriched water packaging on the market is still single-use packaging, there is a need for alternative packaging methods in the field.

[10] Hydrogen-enriched water is a therapeutic and health product, and therefore it is important to keep this water as pure as possible. Therefore, when designing packaging for hydrogen-enriched water, it is important to avoid as much as possible plastic and polymer materials, which, for example, can leach plasticizers into the water and are found in film packaging and in most cans inside, in contact with packaged foods. Glass bottles do not have an internal plastic coating and therefore seem to be preferred for keeping water clean.

[11] However, when glass bottles are completely or almost completely filled with water, for example, a problem arises that the bottles may burst when heated due to thermal expansion of the water, which poses a significant safety risk, especially in the case of glass bottles , due to the resulting fragments. In addition, water filled in this way and enriched with hydrogen does not last long. According to our own tests, after about a month there is almost no detectable hydrogen in the water (the remaining hydrogen content is approximately 0.3 ppm).

Technical problem

[12] The object of the invention is to provide an economical, simple and safe method for long-term, safe and environmentally friendly storage of a food product in a hydrogen atmosphere and cost-effective packaging for this.

Technical solution

[13] The present invention relates to the method according to claim 1, which solves a technical problem. The problem posed by the invention is also solved using packaging according to claim 9. Preferred embodiments follow from the dependent claims.

Description of Embodiments

[14] The method of the invention is used for preserving a food product, for example hydrogen enriched water, under a hydrogen atmosphere in a package.

[15] The package comprises an interior space surrounded by a hydrogen permeable and airtight sealing shell, the interior space comprising a food product space for receiving the food product and a hydrogen space for receiving hydrogen gas, the food product space and the hydrogen spaces are connected to each other in at least a gas-conducting manner. The food product space and the hydrogen space can be connected to each other in a fluid-conductive manner, in particular in a food-conductive manner. In particular, the hydrogen space and the food product space can be located directly next to each other, with at least one contact plane, i.e. without a physical barrier between the hydrogen space and the food product space.

[16] The shell and/or sleeve surrounding the hydrogen space is dimensionally stable at a negative pressure in the hydrogen space relative to the surrounding environment of the package of at least 100 mbar (0.01 MPa), preferably at least 200 mbar (0 .02 MPa), in particular at least 400 mbar (0.04 MPa), for example at least 600 mbar (0.06 MPa). Dimensional stability can be achieved, for example, due to a sufficiently rigid shell and/or sleeve material, a sufficiently thick material, a suitable shape of the shell and/or sleeve, for example, with projections, folds, corrugations and/or stiffeners, and/or supporting structure located in the shell and/or sleeve, for example, due to a mesh frame.

[17] If the food product is granular, for example in the form of a free-flowing powder, the food product may support the shell so that it is dimensionally stable in the food-filled state, and the voids between the grains of the food product may provide space for hydrogen.

[18] Since the food space and the hydrogen space are at least connected to each other in a gas-conducting manner, the same pressure prevails in both of them, and accordingly, for the purposes of the invention, the expression "negative pressure in the hydrogen space" is synonymous with the expression "negative pressure in the hydrogen space and the food space."

[19] The sleeve may include a hollow body containing, for example, plastic, metal and/or glass, for receiving hydrogen gas. The hollow body can accommodate a particularly large volume of hydrogen gas for a given mass and material cost.

[20] The sleeve may comprise, in particular, at least in its interior, a rigid open-cell foam material, including, for example, foam, rigid foam, airgel and/or metal foam for receiving hydrogen gas. The foam has the advantage of improved mechanical stability compared to a hollow body, in particular against pressure acting on the foam from the outside.

[21] The method includes filling at least the food product space with a food product, introducing hydrogen gas into at least the hydrogen space, sealing the casing in an airtight manner, preferably after filling and insertion, and creating a negative pressure in at least the hydrogen space. hydrogen relative to the environment surrounding the packaging.

[22] Hydrogen gas introduced into the hydrogen space is in gas conductive contact with the food product filling the food product space, whereby the food product is maintained by the hydrogen gas, and in particular, the hydrogen content of the hydrogen-enriched food product is maintained by contact with hydrogen gas.

[23] The solution according to the invention, consisting of filling under negative pressure in a package that is at least partially dimensionally stable, solves the problem associated with previous packages and opens up new possibilities of using the antioxidant properties of hydrogen for food preservation.

[24] Surprisingly, it has been found that hydrogen enriched water bottled by the method of the invention exhibits only a slight reduction in the hydrogen content of the water, despite the hydrogen permeable lining. This reduction can be observed already in the first month after filling, after which the hydrogen content remains constant for several months, unlike traditional filling methods. Compared to previous packages which constantly lose hydrogen, in the method according to the invention there is initially a rapid loss of hydrogen up to a certain negative pressure in the hydrogen space, but after this the loss of hydrogen slows down significantly and the hydrogen content of the food product can be maintained for a longer period than in known methods. Depending on the materials used, different time progressions of hydrogen loss and/or negative pressure may occur.

[25] Because hydrogen diffuses very easily through most materials, food products in conventional food packaging, such as beverage bottles, food cans, or food containers, are typically surrounded by a hydrogen-permeable shell. Surprisingly, it has been found that a hydrogen permeable shell is advantageous in the process of the invention. As a result of such coating, part of the filled hydrogen gas can escape from the airtightly sealed package, thereby creating a negative pressure or maintaining a predetermined negative pressure.

[26] To ensure that the hydrogen space does not collapse in the event of a negative pressure therein, which would reduce or completely balance the negative pressure, the package shell and/or sleeve is designed to be dimensionally stable. If, for example, hydrogen-enriched water is placed together with hydrogen gas in the same traditional packaging, such as a film bag or beverage can, the packaging cannot withstand the resulting negative pressure and becomes deformed. This leads to the complete release of hydrogen gas from the package.

[27] To prevent gases other than hydrogen from entering the package in the event of negative pressure, the envelope is designed to be sealed in an airtight manner. In particular, the shell material can be airtight, i.e., in particular, impermeable to nitrogen, oxygen, carbon dioxide and/or argon. "Airtight" in the context of the invention means that during a typical storage period of, for example, 0.5 to 2 years, the negative pressure of, for example, 100 mbar to 600 mbar (0.01 to 0.06 MPa) in the package is not significantly is reduced due to the penetration of components from the surrounding air.

[28] Many types of traditional food packaging, such as beverage bottles, cans, or containers, have an airtight seal. For example, food products in containers are often filled at a negative pressure of, for example, 600 mbar (0.06 MPa) relative to ambient air, and this negative pressure is maintained for the expected shelf life of the canned food, for example, two years.

[29] Even when using films as packaging material, an airtight seal that maintains its negative pressure over the intended storage period can be realized, as shown in commercially available food products packaged in negative pressure films, such as grains cereals or coffee beans.

[30] The generated negative pressure is preferably 50 mbar to 500 mbar (0.005-0.05 MPa), particularly preferably 100 mbar to 300 mbar (0.01-0.03 MPa). The created negative pressure is preferably from 100 mbar to 900 mbar (0.01-0.09 MPa), in particular from 200 mbar to 800 mbar (0.02-0.08 MPa), for example from 400 mbar to 600 mbar ( 0.04-0.06 MPa). The created negative pressure is preferably at least 100 mbar (0.01 MPa), in particular at least 200 mbar (0.02 MPa), for example at least 400 mbar (0.04 MPa).

[31] Said negative pressure values preferably refer to the equilibrium value to which the negative pressure approaches during storage of the food product in the package, or at which the negative pressure stabilizes. This equilibrium value can be reached, at least approximately, for example after a storage period of 30 days to 600 days, in particular 60 days to 500 days, for example 100 days to 400 days, after compaction.

[32] The package shell or hydrogen space sleeve is preferably dimensionally stable under appropriate negative pressure. Experiments have shown that the reduction of hydrogen content in a food product can be significantly slowed down or even prevented by negative pressure within the specified ranges. In addition, negative pressure within the specified value ranges can be maintained by packaging made from traditional materials for a typical storage period, for example, 0.5 to two years.

[33] Producing negative pressure preferably involves diffusion of hydrogen gas through the casing into the surrounding environment of the package after the casing has been sealed in an airtight manner. In particular, the creation of negative pressure can be achieved solely by diffusion of hydrogen gas through the shell into the environment surrounding the package. This makes the method particularly simple, in particular since pumping gas from the package is not necessary to create a negative pressure. This is particularly preferred for home applications of the method, since suitable devices for this pumping operation are not usually available here.

[34] Producing negative pressure preferably involves cooling the food product and/or hydrogen gas after sealing the casing in an airtight manner. By cooling the food product, the hydrogen gas and/or air contained in the packaging and the resulting reduction in volume, negative pressure can be created in a technically particularly simple manner, similar to hot filling of canned food.

[35] Creating a negative pressure preferably involves pumping gas, preferably air, from the interior before sealing the shell in an airtight manner and preferably before introducing hydrogen gas, the negative pressure during sealing is preferably between 50 mbar and 500 mbar (0.005-0.05 MPa) , especially preferably from 100 mbar to 300 mbar (0.01-0.03 MPa). By pumping out the gas, possible contamination of the food product by components contained in the gas can be prevented. Preferably, the gas is pumped out before filling the food product. The pumping operation is preferably performed before introducing hydrogen gas, so that no hydrogen gas is lost as a result.

[36] In the first embodiment of the method, the casing is dimensionally stable at a negative pressure in the internal space relative to the surrounding environment of the package of at least 100 mbar (0.01 MPa), and the food space and the hydrogen space are connected to each other conductive to the food product. In this embodiment, filling with food product includes completely filling the internal space with food product, and introduction of hydrogen gas occurs after filling and includes displacing food product from the hydrogen space.

[37] This first embodiment is particularly suitable for liquid food products, for example hydrogen enriched water. By initially completely filling the internal space with the food product, gases previously contained in the internal space, which could impair the shelf life of the food product, are removed. When hydrogen gas is introduced, part of the food product is displaced from the internal space, causing the hydrogen space to be filled with hydrogen gas.

[38] In this first embodiment, the food space and the hydrogen space are preferably adjacent to each other through a contact plane, without a physical barrier. The division of the internal space into food space and hydrogen space may change over time, for example depending on the level of filling of the internal space with food product. This allows the packaging to have a particularly simple design, for example comprising a standard drinks bottle.

[39] In a second embodiment of the method, the sleeve enclosing the hydrogen space is dimensionally stable at a negative pressure in the internal space relative to the environment surrounding the package of at least 100 mbar (0.01 MPa), and the sleeve hermetically seals the hydrogen space from the food product space. For example, the hydrogen space may be connected to the food space in a gas-conducting manner through a liquid-impermeable membrane or through a series of sufficiently small connection openings, without the food product being able to flow into the hydrogen space from the food space.

[40] In this second embodiment, the packaging shell may be flexible, at least in part, for example, may consist of a film. This makes this embodiment particularly suitable for dimensionally stable food products, the shape of which can be modified at least in part by a flexible casing, and whose entry into the hydrogen space can be relatively easily prevented, for example by a mesh.

[41] By having the shell at least partially flexible, more hydrogen gas can be introduced into the package and the shell expands such that a food product that, for example, has not previously been enriched with hydrogen can become enriched with hydrogen. When hydrogen gas escapes from the casing after it has been compacted, the casing is compressed again, for example until it comes into contact with a support structure and/or food product. Thanks to the dimensionally stable sleeve, hydrogen gas continues to remain in the hydrogen space, at least in gas-conducting contact with the food product, so that a given hydrogen concentration in the food product can be maintained during the intended storage period.

[42] In this second embodiment, the introduction of hydrogen gas includes completely filling the internal space with hydrogen gas, and the filling of the food product occurs after this introduction and includes displacing the hydrogen gas from the food space, wherein air is pumped out of the internal space preferably prior to the introduction , and the sleeve is dimensionally stable.

[43] By completely filling the internal space with hydrogen gas, in particular if the air has previously been evacuated from it, it is ensured that there are no foreign substances that could impair the shelf life of the food product in the internal space.

[44] In a third embodiment of the method, the sleeve enclosing the hydrogen space is dimensionally stable at a negative pressure in the internal space relative to the surrounding environment of the package of at least 100 mbar (0.01 MPa), and the sleeve hermetically seals the hydrogen space from the food product space.

[45] In this third embodiment, the packaging shell may be flexible, at least in part, for example, may consist of a film. This makes this embodiment particularly suitable for dimensionally stable food products, to the shape of which the flexible casing can at least partially adapt, and whose entry into the hydrogen space can be prevented relatively easily, for example by means of a mesh.

[46] In this third embodiment, the introduction of hydrogen gas into the hydrogen space occurs after the food space has been filled with food product, preferably with air being evacuated from the internal space before introduction, in particular before filling.

[47] Since the injection occurs after filling, only a small amount of hydrogen gas is required, making this method particularly economical. The pumping operation also ensures that there are no foreign substances left in the interior that could affect the shelf life of the food product. Pumping down after filling is disadvantageous for food products that have already been enriched with hydrogen before filling the package, since pumping down may result in the leakage of a significant portion of the enriched hydrogen.

[48] In any embodiment of the method, introducing hydrogen gas preferably involves filling the hydrogen-enriched food product. By enriching a food product, such as water, with hydrogen, the shelf life of the food product is increased and the consumer may experience the beneficial effects caused by the hydrogen when consuming the food product.

[49] After filling the fortified food product, at least part of the hydrogen therein can be transferred to the hydrogen space, whereby the above-mentioned advantages of the hydrogen space filled with hydrogen gas occur even if a smaller amount of hydrogen gas is introduced separately. In particular, with a smaller amount of separately introduced hydrogen gas, a predetermined hydrogen concentration in the food product can be achieved and can be maintained during the storage period.

[50] Hydrogen enrichment of the food product may be dissolved and/or contained therein, for example in the form of hydrogen bubbles. The bubbles may in particular be nano- or microbubbles, which can increase the total hydrogen content of the food product beyond the solubility limit of hydrogen in the food product. Bubbles below a certain size, for example 20 µm in water, preferably less than 20 µm, do not rise and can therefore remain stable in the food product throughout the storage period.

[51] When filling a hydrogen-enriched food product, the food product is preferably saturated with hydrogen and/or does not contain other gases. If the food product is saturated with hydrogen, the positive effect of hydrogen is especially pronounced.

[52] If the food product does not contain other gases, potentially adverse interactions of other gases with the food product are eliminated to preserve the food product, and a smaller amount of hydrogen gas must be introduced to achieve and maintain the desired hydrogen concentration in the food product during its shelf life.

[53] The food product is preferably hydrogen enriched and contains no gases other than hydrogen. Preferably, the food product should be degassed before hydrogen enrichment, for example by heating the food product.

[54] To introduce hydrogen gas, it is also possible for the source or reservoir of hydrogen gas to be located in an enclosure that is preferably sealed at a negative pressure in the hydrogen space, which then creates or releases hydrogen gas within the sealed enclosure.

[55] The creation can be accomplished, for example, by using a suitable metal in contact with water, preferably a catalyst. The chemical reaction can result in the formation of metal oxide and/or hydroxide and hydrogen gas.

[56] For example, the reservoir may contain compressed and/or liquefied hydrogen gas under pressure, which is released from the reservoir after the shell is sealed.

[57] The packaging of the invention is designed to preserve a food product under a hydrogen atmosphere using the method of the invention.

[58] The package comprises an interior space surrounded by a hydrogen permeable and airtight sealing shell, the interior space comprising a food product space for receiving the food product, and a hydrogen space for receiving hydrogen gas, and a food product space and spaces for hydrogen are connected in a gas-conducting manner to each other.

[59] In the filling position of the package, the hydrogen space is preferably located above the food space, so that hydrogen gas introduced into the inner space accumulates in the hydrogen space due to the density difference between the hydrogen gas and the food product moving under the influence of gravity .

[60] The packaging elements, in particular, can be designed as described in connection with the method according to the invention, which leads to the effects mentioned here.

[61] The shell can be dimensionally stable at a negative pressure in the hydrogen space relative to the environment surrounding the package of at least 100 mbar (0.01 MPa), preferably at least 200 mbar (0.02 MPa), in particular at least 400 mbar (0.04 MPa), for example at least 600 mbar (0.06 MPa), and may include a media exchange device for simultaneously introducing hydrogen gas through the inlet line into the hydrogen space and removing food products through the outlet line from the inner space.

[62] A casing that is stable under negative pressure with a media exchange device is particularly suitable for carrying out the method in the first embodiment described above. The fact that hydrogen gas can be introduced and preferably the liquid food product can be removed, for example displaced by hydrogen gas, at the same time makes the method particularly simple and prevents contamination of the internal space by foreign gases. This is especially important for home use of the method, where it is usually not possible to surround the package with a hydrogen atmosphere when introducing the food product.

[63] In particular, the media exchange device eliminates the need to immerse a bottle filled with water, with the filling hole facing down, into a larger vessel filled with water to introduce hydrogen into the bottle there and seal the bottle under the water to prevent foreign gases from entering the bottle .

[64] The shell may be at least partially flexible and the sleeve surrounding the hydrogen space may be dimensionally stable at a negative pressure in the hydrogen space relative to the surrounding environment of the package of at least 100 mbar (0.01 MPa), preferably at least 200 mbar (0.02 MPa), in particular at least 400 mbar (0.04 MPa), for example at least 600 mbar (0.06 MPa). The sleeve may include a hollow body and/or solid foam, and may in particular be constructed as described in connection with the method of the invention.

[65] A casing that is at least partially flexible and has a dimensionally stable sleeve is particularly suitable for the method in the second or third embodiment described above, in particular for a substantially dimensionally stable food product. In the case of a dimensionally stable food product, a casing that is at least partially flexible, for example a casing that consists at least in part of a film, is preferred since it can adapt to the shape of the food product.

[66] Additionally, the package can be made with less material if only the sleeve is dimensionally stable rather than the entire casing. Because the sleeve is dimensionally stable, when there is negative pressure in the hydrogen space, the space does not compress under ambient pressure. Thus, the negative pressure is maintained and the loss of hydrogen gas from the hydrogen space is slowed down by the negative pressure, whereby the food product is preserved for a storage period of, for example, 0.5 to two years by the hydrogen gas remaining in the hydrogen space. In particular, the hydrogen content of a hydrogen-enriched food product, such as water, is maintained throughout the entire storage period.

[67] The sheath and/or sleeve is dimensionally stable at a negative hydrogen space pressure of at least 0.1 bar (0.01 MPa), preferably at least 0.2 bar (0.02 MPa), particularly preferably at least 0.3 bar (0.03 MPa), most preferably 1 bar (0.1 MPa). The higher the negative pressure value at which the shell or sleeve is dimensionally stable, the higher the amount of negative pressure that can be permanently created in the hydrogen space. A high negative pressure value can particularly slow down the loss of hydrogen gas from the hydrogen space during storage of the food product in the package, thereby increasing the maximum storage time of the food product. Dimensional stability at a negative pressure of 1 bar (0.1 MPa) is particularly advantageous if the air is evacuated from the casing and/or sleeve by a vacuum pump before the package is filled with food product and/or hydrogen.

[68] The casing is preferably resistant to an excess pressure in the internal space relative to the environment surrounding the package of at least 0.5 bar (0.05 MPa), preferably at least 2 bar (0.2 MPa), especially preferably at least 8 bar (0.8 MPa). For example, for sterilization it may be necessary to heat the package after filling with food and seal the shell in an airtight manner, which temporarily creates excess pressure in the internal space. To prevent damage to the shell in the event of overpressure, it is preferable that it be made resistant to overpressure, i.e. so that the shell is airtight and dimensionally stable in the event of overpressure or deforms only elastically, so that it returns to its original shape when the overpressure is reduced.

[69] The sleeve preferably seals the hydrogen space, preferably in a liquid-tight manner, from the food space. This prevents the food product from entering the hydrogen space, making said space completely available for receiving hydrogen gas.

[70] The hose may, for example, be insulated with a gas-permeable and liquid-impermeable membrane. Alternatively or additionally, the hydrogen space and the food product space can be connected by a series of openings, in particular pores, which are so small that the food product cannot pass through them.

[71] The shell is preferably transparent, at least partially. Thanks to the transparent part, it is advantageously possible to check optically, in particular visually, the condition of the food product in the compacted casing. This represents a significant advantage over traditional packaging for hydrogen-containing food products, since traditional packaging is typically made of sheet metal or metal-coated plastic to reduce the diffusion of hydrogen from the packaging and is therefore completely opaque.

[72] The shell preferably consists mainly of glass and/or plastic, preferably plastic film. A glass shell has the advantage that glass does not release any foreign substances into the food product, such as plastic particles and/or plasticizers, which could impair its quality and/or shelf life. Additionally, the glass shell can be easily reused or recycled, for example through existing glass bottle storage systems, reducing any environmental pollution caused by packaging.

[73] Plastic casing, particularly plastic film, has the advantages of low production cost and light weight, which reduces the cost and energy consumption of packaging transportation.

[74] The casing preferably includes a filling opening that can be sealed in an airtight manner by means of a sealing means to fill the interior space with food product. For example, the casing may include a commercially available beverage bottle having a filling opening for filling with a beverage, the sealing means including a cap of the beverage bottle. If the casing includes a plastic film, the sealing means may include, for example, a seam for sealing a filling hole in the plastic film or between the plastic film and another component of the casing.

[75] For example, the filling hole may form an inlet line of the media exchange device. The outlet line may be located separately from the filling opening in a different area of the shell.

[76] The outlet line preferably opens into a hydrogen space adjacent to a contact plane between the hydrogen space and the food space. Here, the contact plane is preferably substantially horizontal in the filling position of the package, with the hydrogen space located above and the food space below the contact plane. This allows the food product present in the hydrogen space to exit through the outlet line when hydrogen gas is introduced, while the food product present in the food space remains there.

[77] The media exchange device is preferably configured to be placed in the filling opening in a state in which the filling opening is closed by the sealing means. This allows the casing to be sealed by the sealing means while the media exchange device is located in the filling opening, and allows the media exchange device to remain in the filling opening to store the food product in the package. Eliminating the need to remove the media exchange device reduces the risk of contamination of the interior with foreign gases that could affect the shelf life of the food product. This also simplifies the sequence of operations for filling the food product.

[78] For example, the media exchange device is designed in such a way that it can be partially inserted into the filling hole, while partially resting on the edge of the filling hole. The support portion of the media exchange device, which rests on the neck of the bottle, is preferably thin enough not to interfere with the application of the sealing means over it to seal the filling opening.

[79] By allowing the media exchange device to be located in the filling opening, a traditional package such as a beverage bottle can be modified with a media exchange device to form the packaging of the invention.

[80] The media exchange device preferably comprises a plug to be tightly inserted into the fill opening, the plug comprising an inlet for receiving an inlet line and an outlet for receiving a discharge line, the plug preferably comprising at least one seal for a preferably gas-tight seal between the plug and inlet line and/or outlet line.

[81] For insertion in a sealing manner, in particular an air sealing manner, the plug may comprise an elastic material, such as soft plastic or rubber, to seal contact with the edge of the filling opening. In particular, the plug may comprise elastic material. This prevents hydrogen gas or food product from escaping uncontrollably from the internal space between the edge of the filling hole and the plug during the introduction of hydrogen gas or preventing foreign gases from entering the internal space.

[82] The seal preferably includes an elastic material, such as soft plastic or rubber, to seal contact with the inlet line and/or outlet line. The seal may be integral with a plug, such as a plug made of an elastic material, or may comprise a separate component, such as an O-ring or a sealing insert.

[83] The inlet line and/or the outlet line may be located in a fixed or removable manner in the inlet opening or in the outlet opening, respectively. In particular, provision may be made to remove the inlet and/or outlet line from the plug before sealing the filling opening with a sealant. If the inlet line and/or outlet line is removable, the seal is preferably configured to seal between the particular line and the plug. This prevents hydrogen gas or food product from escaping uncontrollably from the internal space between the specific line and the plug, or preventing foreign gases from entering the internal space during the introduction of hydrogen gas.

[84] Preferably, the seal is configured to seal, preferably in an airtight manner, the inlet and/or outlet when the corresponding line is removed. This prevents hydrogen gas or food product from escaping uncontrollably from the interior through the filling hole, or preventing foreign gases from entering the interior after removing the inlet and/or outlet line and before sealing the fill hole with a seal.

[85] The removable inlet line and/or outlet line may include a stopper, particularly an adjustable stopper, that ensures that a particular line is inserted into the plug to an exact predetermined depth.

[86] The outlet line is preferably inserted or may be inserted into the plug so that it opens into the hydrogen space adjacent to the contact plane between the hydrogen space and the food space. In this case, the contact plane is practically horizontal in the filling position of the package, with the hydrogen space located above and the food space below the contact plane. This allows the food product present in the hydrogen space to exit through the outlet line when hydrogen gas is introduced, while the food product present in the food space remains there.

[87] Depending on the distance from the plug the outlet line enters the interior space, the volumetric ratio between the hydrogen space and the food space is determined for a given shell geometry by the position of the contact plane in the interior space defined by the inlet. This volume ratio may be selected depending on the type or pre-treatment of the food product such that sufficient hydrogen gas can be introduced into the hydrogen space for the intended storage period of the food product.

[88] By adjusting the distance of the outlet line inlet from the plug, for example by means of a restrictor, the media exchange device can be used with different shaped casings or for filling different food products with the volume ratio between hydrogen space and food space correspondingly set and , therefore, a set amount of hydrogen gas.

[89] Preferably, the media exchange device includes at least one valve for regulating the flow of media and/or for determining the direction of flow of media through the inlet line and/or outlet line. Preferably, the inlet line includes a check valve to prevent food or hydrogen gas from leaking from the interior through the inlet line.

[90] Preferably, the outlet line includes a closable outlet valve so that when the outlet valve is closed, the internal space can be overpressured by hydrogen gas introduced through the inlet line, whereby, for example, the food product can be enriched with a higher hydrogen concentration. In particular, the release valve may be designed as a pressure relief valve that automatically opens when a predetermined overpressure is reached in the internal space, for example to prevent damage to the shell due to excessive overpressure.

[91] The media exchange device preferably includes fastening means for detachably securing the media exchange device to the shell. The fastening means may, for example, comprise threads for screwing or screwing into a corresponding counter thread on the filling opening of the casing.

[92] For example, if the casing includes a conventional beverage bottle, the media exchange device may include threads configured to screw onto a mating thread typically provided for a beverage bottle cap. In particular, the media exchange device may include an additional mating thread onto which a cap can be screwed. Thus, the cap may be screwed onto a media exchange device screwed onto the beverage bottle to seal the filling opening of the beverage bottle while the media exchange device remains in the filling opening.

[93] The invention also relates to the use of a package according to the invention in a method according to the invention for storing a hydrogen-enriched food product in the package.

Brief description of drawings

[94] Further advantages, objects and features of the invention are made clear with reference to the following description and the accompanying drawings, in which the subject matter of the invention is shown by way of example. Elements that are at least substantially similar in function in the figures may be designated by the same reference numerals, however, these elements need not be referenced or explained in all of the figures.

[95] Figure 1 shows a schematic cross-sectional view of a food product stored in a package by the method of the invention.

[96] Figure 2 shows a schematic cross-sectional view of a food product stored in another package by the method of the invention.

[97] FIG. 3 is a schematic cross-sectional view of a food product stored in a conventional manner in a conventional package 200.

[98] FIG. 4 is a schematic cross-sectional view of a food product stored in a conventional manner in a conventional package 200.

[99] Figure 5 shows a schematic cross-sectional view of a food product stored in another package by the method of the invention.

[100] Fig. 6 shows a schematic representation of a food product stored in another package by the method of the invention.

[101] Figure 7 shows a schematic illustration of a package according to the invention.

[102] Figure 8 shows a schematic illustration of another package according to the invention.

[103] Figure 9 shows a schematic illustration of another package according to the invention.

[104] FIG. 10 shows schematic side views of embodiments of a package plug of the invention.

[105] Figure 11 shows schematic views of a package plug according to the invention.

[106] FIG. 12 shows schematic diagrams of another package plug according to the invention.

[107] FIG. 13 shows schematic diagrams of another package plug according to the invention.

[108] FIG. 14 is a schematic cross-sectional view of a package according to the invention.

[109] FIG. 15 is a schematic cross-sectional view of another package according to the invention.

[110] FIG. 16 is another schematic cross-sectional view of the package of FIG. 13.

[111] FIG. 17 shows a schematic representation of the method of the invention.

[112] FIG. 18 shows the hydrogen content of water stored by the method of the invention as a function of the storage period.

[113] FIG. 19 shows the pressure in a package of water stored by the method of the invention as a function of the storage period.

[114] FIG. 20 shows the hydrogen content of water stored by the method of the invention as a function of the hydrogen-filled volume.

[115] FIG. 21 shows the hydrogen content of water stored by the method of the invention as a function of the storage period.

[116] FIG. 22 shows the pressure in a package of water stored by the method of the invention as a function of the storage period.

Fig.1

[117] FIG. 1 is a schematic cross-sectional view of a food product, for example H ₂ O water enriched with H ₂ hydrogen, stored in a package 200 by the method 100 of the invention.

[118] The package 200 includes an airtight seal 210, such as a conventional negative pressure dimensional stable glass beverage bottle, having a food filling opening 250. The shell 210 surrounds an inner space including a hydrogen space 222 for housing hydrogen gas, and a food space 221 for housing a food product. In the example shown, hydrogen space 222 and food space 221 are directly adjacent to each other at contact plane 223, without a physical barrier.

[119] In the illustrated state, filling 110 with food product into the food product space 221 and introducing 120 hydrogen gas into the hydrogen space 222, as well as airtightly sealing 130 of the shell 210 with sealing means 251, such as a cap corresponding to a beverage bottle, is already completed.

[120] FIG. 1A shows the state before negative pressure is created 140 in the hydrogen space 222, and FIG. 1B shows the state after negative pressure is created 140.

[121] The illustrated shell 210 is dimensionally stable under negative pressure, for example, because it is made of glass. Therefore, the hydrogen space 222 is not compressed by negative pressure. Since the shell 210 is sealed in an airtight manner, air cannot enter the hydrogen space 222 from the outside, and therefore a negative pressure is maintained.

Fig.2

[122] Figure 2 shows a schematic cross-sectional view of a food product stored in another package 200 by the method 100 of the invention.

[123] FIG. 2 differs from FIG. 1 in that the casing 210 is not in the form of a beverage bottle, but in the form of a can. The shell 210 can be made dimensionally stable due to the corrugated shape of its outer wall, for example, as in known food cans, with a negative pressure in the hydrogen space 222. This allows the shell 210 to be made from a less rigid and therefore thinner, lighter and/or more economical material, such as sheet metal or plastic.

[124] Similar to FIG. 1A and FIG. 1B, FIG. 2A shows the state before negative pressure is created 140 in the hydrogen space 222, and FIG. 2B shows the state after negative pressure is created 140.

Fig.3

[125] FIG. 3 is a schematic cross-sectional view of a food product stored in a conventional manner in a conventional package 200.

[126] The package 200 differs from the package shown in FIG. 1 in that the shell 210 of the package 200 is not dimensionally stable under negative pressure in the hydrogen space 222 of the package 200, for example, because the package 200 is a conventional plastic bottle for drinks.

[127] If water H ₂ O enriched with hydrogen H ₂ fills the food space 221, and hydrogen gas H ₂ fills the hydrogen space 222 in such a package (Fig. 3A), hydrogen gas H ₂ can escape from the food space 222 hydrogen through the shell 210 of the package 200 and/or through the filling opening 250 sealed with sealing means 251.

[128] Since the shell 210 is not dimensionally stable, it is compressed by the negative pressure generated by the escaping hydrogen gas H ₂ in the hydrogen space 222, so that the hydrogen gas H ₂ and the hydrogen H ₂ contained in the water H ₂ O gradually escape completely until the shell 210 is compressed to the volume of water H ₂ O contained therein (FIG. 3B).

Fig.4

[129] FIG. 4 is a schematic cross-sectional view of a food product stored in a conventional manner in a conventional package 200.

[130] The package 200 differs from the package shown in FIG. 2 in that the shell 210 of the package 200 is not dimensionally stable under the negative pressure in the hydrogen space 222 of the package 200, for example, because the package 200 is a conventional beverage can. made of sheet metal.

[131] If such a package is filled with hydrogen-enriched water in the food space 221 and hydrogen gas H ₂ in the hydrogen space 222 (FIG. 4A), the hydrogen gas H ₂ can exit the hydrogen space 222 through the shell 210 of the package 200.

[132] Since the shell 210 is not dimensionally stable, it is compressed by the negative pressure generated by the escaping hydrogen gas H ₂ in the hydrogen space 222, so that the hydrogen gas H ₂ and the hydrogen contained in the water are gradually completely released until the shell 210 will not be compressed to the volume of water it contains (FIG. 4B).

Fig.5

[133] FIG. 5 is a schematic cross-sectional view of a food product LM stored in another package 200 by the method 100 of the invention.

[134] Unlike FIG. 1 and FIG. 2, the food product LM in FIG. 3 is a granular food product LM, such as cereal grains. Moreover, in the case of FIG. 5, the shell 210 of the package 200 is not dimensionally stable, but is composed of a flexible plastic film, for example.

[135] Thus, the shell 210 is compressed when a negative pressure 140 is created in the internal space 220. The compression stops as soon as the shell 210 comes into contact with the food product LM. Due to the granular structure of the LM food product, dimensionally stable spaces remain within the LM food product, which can serve as hydrogen space 222 in the context of the invention.

[136] Similar to FIG. 1A and FIG. 1B, FIG. 5A shows the state before negative pressure is created 140 in the hydrogen space 220, and FIG. 5B shows the state after negative pressure is created 140.

Fig.6

[137] FIG. 6 shows a schematic cross-sectional view of a food product LM stored in another package 200 by the method 100 of the invention. The LM food product may be a size-stable LM food product, such as a piece of meat.

[138] In the example illustrated in FIG. 6, the shell 210 of the package 200 comprises a flexible material, such as a plastic film, supported by a support structure 211, such as a frame disposed therein, such that the shell 210 is dimensionally stable under negative pressure conditions. internal space 220 packing 200.

Fig.7

[139] FIG. 7 shows a schematic illustration of a package 200 of the invention. The illustrated package 200 includes a flexible casing 210, such as one made of plastic film, and is particularly suitable for housing a dimensionally stable food product LM, such as a piece of meat. The package 200 includes several, for example, two sleeves 230. The sleeves 230 contain a hydrogen space 222 for containing hydrogen gas. The sleeves 230 may, for example, be designed as hollow cylinders.

[140] The sleeves 230 are configured to be dimensionally stable under negative pressure in the hydrogen space 222. The hydrogen space 222 is connected in a gas-conducting manner to the food space 221 for receiving the food product LM. To this end, the sleeves 230 may have a series of openings 231, which are preferably configured so that the food product LM cannot penetrate into the hydrogen space 222 through the openings 231, for example, because the openings 231 are too small for this purpose or are covered with a mesh or gas permeable membrane.

Fig.8

[141] FIG. 8 shows a schematic illustration of another package 200 of the invention. The illustrated package 200 differs from the package shown in FIG. 5 in that the sleeve 230 contained therein has a sponge-like structure or a honeycomb structure and, in particular, can be made in the form of a rigid foam material.

Fig.9

[142] FIG. 9 shows a schematic illustration of another package 200 of the invention. The illustrated package 200 includes a shell 210 surrounding an interior space 220. In this example, the shell 210 is dimensionally stable under negative pressure within the interior space 220. For example, the shell 210 may be cylindrical in shape, where a filling opening 250 for filling the interior space 220 with food product is located on at least one end surface, in particular on both end surfaces. The at least one filling opening 250 may be sealed in an airtight manner using a sealing means 251, such as a screw cap.

[143] The package 200 includes a media exchange device that may include, for example, an inlet line 241 for introducing hydrogen gas into the interior space 220 and an outlet line 242 for discharging a liquid food product from the interior space 220.

[144] In the example shown, the inlet line 241 is located in the first sealing means 251 and includes a valve 247. The valve 247 is configured, for example, as a check valve that prevents hydrogen gas or food product from flowing back from the interior space 220 into the inlet line 241.

[145] In the illustrated example, the outlet line 242 is located in the second sealing means 251 and also includes a valve 247. The valve 247 may be configured to control the flow of food product from the interior space 220 to the outlet line 242.

Fig.10

[146] FIG. 10 shows schematic side views of embodiments of a package plug 243 of the invention. The plug 243 may, for example, be substantially cylindrical in shape (FIG. 10A, FIGURE 10C) or conical in shape (FIG. 10B). To securely fit into the filling opening of the package 200, the plug 243 may include a support portion 249 for resting on the edge of the filling opening. The support portion 249 is preferably thin enough to seal the fill opening with suitable sealing means when the plug 243 is in the filling opening.

[147] To be able to be placed in a sealing manner in the fill opening, plug 243 may, for example, be made of an elastic material and/or may include an O-ring 248 to seal contact with the edge of the filling opening.

Fig.11

[148] FIG. 11 shows schematic views of a package plug 243 of the invention in longitudinal section (FIG. 11A) and in plan view (FIG. 11B). The plug 243 includes an inlet 244 and an outlet 245 for receiving an inlet line and an outlet line of the packaging media exchange device.

Fig.12

[149] FIG. 12 shows schematic views of a package plug 243 of the invention in longitudinal section (FIG. 12A) and in plan view (FIG. 12B). The plug 243 includes an inlet 244 and an outlet 245 for receiving an inlet line and an outlet line of the packaging media exchange device.

[150] The inlet 244 and/or the outlet 245 may include a seal 246 for sealing the inlet line and/or the outlet line. The seal 246 may comprise, for example, elastic foam located in a particular opening 244, 245.

Fig.13

[151] FIG. 13 shows schematic views of a package plug 243 of the invention in longitudinal section (FIG. 12A) and in plan view (FIG. 13B). The plug 243 includes an inlet 244 and an outlet 245 for receiving an inlet line and an outlet line of the packaging media exchange device.

[152] The openings 244, 245 may, for example, be formed as slits in the plug 243. The plug 243 is made, for example, of an elastic material so that the slots can be widened to accommodate an inlet line and an outlet line, and the plug 243 can fit snugly to the inlet line and outlet line as a seal 246.

Fig.14

[153] FIG. 14 is a schematic cross-sectional view of a package 200 of the invention. The illustrated package 200 includes an airtight seal 210, such as a beverage bottle, particularly one made of glass. In the filling hole 250 for filling the interior space of the housing 210 with food product, for example, water, a plug 243 is located as part of the media exchange device 240. Plug 243 includes, for example, an O-ring 248 that allows plug 243 to seal fill opening 250.

[154] The media exchange device 240 includes an inlet line 241 for introducing hydrogen gas into the hydrogen space 222 in the internal space and an outlet line 242 for withdrawing food product from the hydrogen space 222. Lines 241, 242 may, for example, be inserted into inlet 244 and outlet 245 of plug 243, in each case with a stop 260 defining the depth of insertion into plug 243.

[155] The outlet line 242 may include an outer portion 242A outside the shell 210 and an inner portion 242B in the interior. The inlet 239 of the exhaust line 242 in the inner space defines a contact plane 223, which is horizontal in the drawing, between the hydrogen space 222 and the food space 221 for receiving the food product into the inner space. In the illustrated example, hydrogen space 222 and food space 221 are directly adjacent to each other at contact plane 223, without a physical barrier.

[156] Preferably, at least the inlet line 241 and the outer portion 242A of the outlet line 242 are removably connected, for example, by a wedge to the plug 243. This allows the inlet line 241 and the outer portion 242A to be removed without removing the plug 243 from the fill opening 250. The fill opening 250 can then be sealed in an airtight manner using a sealing means, such as a screw cap typically used for beverage bottles.

[157] The inlet line 241 may include a valve 247, in particular a check valve, which prevents the backflow of hydrogen gas or food product from the interior into the inlet line 241.

Fig.15

[158] FIG. 15 is a schematic cross-sectional view of another package 200 of the invention. The package 200 shown in FIG. 15 differs from the package 200 shown in FIG. 12 in the following respects:

[159] In this example, inlet line 241 and outlet line 242 extend through inlet 244 and outlet 245 of plug 243, wherein plug 243 has a seal 246, such as sealing lips, to sealably connect lines 241, 242 to plug 243.

[160] In particular, outlet line 242 may include a restriction 260, such as a retaining ring, that allows outlet line 242 to pass through outlet 245 only to a predetermined depth. Preferably, the stop 260 is attached to the outlet line 242 so that various target depths can be set. To this end, the outlet line 242 may include, for example, a plurality of grooves 261 spaced apart along the outlet line 242 for mounting the restrictor 260.

Fig.16

[161] FIG. 16 shows another schematic cross-sectional view of package 200 of FIG. 13. Unlike the illustration in FIG. 13, here the inlet line 241 and outlet line 242 are removed from the plug 243. This allows a sealing means 251, such as a screw cap typically used for beverage bottles, to be used to seal the fill opening 250 in an airtight manner when plug 243 remains in fill hole 250.

[162] In FIG. 16, it is further seen that the seal 246 located in the inlet port 244 and the outlet port 245 can seal each opening 244, 245 after the inlet line and the outlet line are removed. This may prevent hydrogen gas from escaping from the interior space 220, at least temporarily, until the sealing means 251 is installed on the filling opening 250.

Fig.17

[163] FIG. 17 shows a schematic representation of a method 100 of the invention. The illustrated method 100 includes filling 110 with food product into a food product space in the interior of the package, which may be sealed in an airtight manner by a casing. Method 100 includes, for example, after filling 110, introducing hydrogen gas 120 into a hydrogen space in the interior space, the hydrogen space being connected to the food space in at least a gas-conducting manner. The method 100 includes an airtight seal 130 of the enclosure after filling 110 and insertion 120. The method 100 includes, for example, after sealing 130, creating a negative pressure 140 in at least the hydrogen space relative to the environment surrounding the package, wherein the enclosure or sleeve surrounding the hydrogen space are dimensionally stable under negative pressure.

Fig.18

[164] FIG. 18 shows the ppm content of hydrogen in water stored by the method of the invention as a function of the storage period t in days.

[165] The graph shows the measurement results for two independent experiments (circles with a dotted line, triangles with a dotted line). The lines in each case serve only to facilitate recognition. The hydrogen content was determined by titration with methylene blue in a solution with platinum nanoparticles (H2 Sciences Inc., USA). In this method, hydrogen can combine with methylene blue through platinum particles that serve as a catalyst, changing its color from blue to clear.

[166] For the experiments, a volume of approximately 50 ml of hydrogen gas was introduced into each glass bottle filled with water and having a total volume of 1 liter. Hydrogen gas was then added to the bottle. Before filling the bottle, the water had a hydrogen content of 1.6 ppm. The glass bottles are standard beverage bottles which, after introducing hydrogen gas, are sealed in an airtight manner with suitable plastic screw caps.

[167] Hydrogen-enriched water was pre-prepared in a water dispenser large enough so that the water had the same initial hydrogen content for all bottles in a series of tests. Distilled, non-degassed water was used. A separate bottle was used for each measurement point. The bottles were stored at a temperature of at least 16°C and in the dark.

[168] For comparison, the graph also shows data for storing hydrogen enriched water using a prior art method (US20180213825A1, FIG. 8) with the corresponding regression line (diamonds connected by a solid line).

[169] In the method according to the invention, initially, especially during the first 30 days, the same strong reduction in hydrogen content is observed as in the prior art method. However, after this, the reduction in the process of the invention slows down significantly and appears to stabilize at about 1.3-1.4 ppm, while the reduction continues without reduction in the prior art process. Thus, with a longer storage period, for example at least 180 days, a higher hydrogen content is achieved in the process of the invention than in the prior art process.

Fig.19

[170] Figure 19 shows the pressure p in mbar in a package of water stored by the method according to the invention, depending on the storage period t in days.

[171] The graph shows the measurement results for two independent experiments (circles, triangles). The pressure p inside the package relative to the ambient pressure of the package was measured using bottle pressure gauges, which are screwed onto the bottles or secured with hinged caps.

[172] Water is filled and stored as described for FIG. 18.

[173] Like the hydrogen content shown in FIG. 18, the package pressure also initially decreases relatively quickly, especially during the first 30 days. Thereafter, the pressure reduction slows significantly, as does the hydrogen reduction, and appears to stabilize at an equilibrium value of approximately -150 mbar to -250 mbar (- 0.015 to 0.025 MPa) relative to ambient pressure.

Fig.20

[174] FIG. 20 shows the ppm content of hydrogen in water stored by the method of the invention as a function of the filled volume V of hydrogen in ml after a storage period of 44 days.

[175] The hydrogen content is determined as described for FIG. 18. A predetermined volume V of hydrogen gas was introduced into water with an initial hydrogen content c of 1.6 ppm into a bottle with a total volume of 1 liter, and the bottle was completely filled with water before this introduction.

[176] Further filling and storage conditions are as described for FIG. 18.

[177] The graph shows that a certain minimum volume of hydrogen gas of 50 ml to 60 ml in the example given is required to obtain the maximum hydrogen content of the water during storage. Further increases in hydrogen volume do not increase the hydrogen content and should therefore be avoided for economic and safety reasons.

Fig.21

[178] FIG. 21 shows the ppm content of hydrogen in water stored by the method of the invention as a function of the storage period t in days, in experiments performed over a longer period of time from a series of tests already shown in Fig. 18.

[179] The hydrogen content is determined as described for FIG. 18.

[180] For the experiments, a volume of approximately 60 ml of hydrogen gas was introduced into each glass bottle filled with water and having a total volume of 1 liter. Before filling the bottle, the water had a hydrogen content of 1.6 ppm. The glass bottles are standard beverage bottles which, after introducing hydrogen gas, are sealed in an airtight manner with suitable plastic screw caps.

[181] Hydrogen enriched water was first prepared in a water dispenser large enough to ensure that the water had the same initial hydrogen content for all bottles in a series of tests. Distilled, non-degassed water was used. A separate bottle was used for each measurement point. The bottles were stored at 16°C to 26°C and at ambient pressures of 992 mbar to 1034 mbar (0.0992 to 0.1034 MPa) in the dark.

[182] As can be seen in FIG. 21, the hydrogen content, as already shown in FIG. 18, stabilizes after an initial decrease. The reduction occurs here during approximately the first 0.5 years of storage to a value of approximately 1.1 ppm, which is then maintained until at least a storage period of approximately 1.5 years. Thus, hydrogen enriched water can be stored significantly longer than using prior art storage methods.

Fig.22

[183] Fig. 22 shows the pressure p in mbar of a package of water stored by the method of the invention, as a function of the storage period t in days, in experiments carried out over a longer period of time from the series of tests already shown in Fig. 19.

[184] Filling and storage of water occurred as described for Fig. 21. The pressure p inside the package relative to the ambient pressure of the package was measured using bottle pressure gauges, which are screwed onto the bottles in place of a suitable cap or secured with hinged caps.

[185] The pressure in the package initially decreases relatively quickly, as shown in FIG. 19, especially during the first half of storage. The pressure decrease then slows significantly and appears to approach an equilibrium value of approximately -500 mbar (-0.05 MPa).

List of reference item numbers

100 - Method

110 - Filling

120 - Introduction

130 - Seal

140 - Creation

200 - Packaging

210 - Sleeve

211 - Support structure

220 - Interior space

221 - Space for food product

223 - Contact plane

230 - Sleeve

231 - Hole

239 - Inlet

240 - Media exchange device

214 - Inlet line

242 - Exhaust line

242A - External part

242B - Interior

243 - Plug

244 - Inlet

245 - Outlet

246 - Seal

247 - Valve

248 - O-ring

249 - Support part

250 - Filling hole

251 - Sealing means

252 - Thread

260 - Limiter

26 - Groove

c - Hydrogen content

H2 - Hydrogen

H2O - Water

LM - Food product

p - Pressure

t - Storage period

V - Volume of hydrogen

Claims (70)

1. A method (100) for storing a food product in an atmosphere of hydrogen gas in a package (200) comprising a) an internal space (220) surrounded by a shell (210) permeable to hydrogen and sealed in an airtight manner, wherein b) the inner space (220) contains a food space (221) for receiving food product, and a hydrogen space (222) for receiving hydrogen gas, wherein c) the food product space (221) and the hydrogen space (222) are connected to each other in at least a gas-conducting manner, and d) at least one of the shell (210) and the sleeve (230), located in the shell (210) and surrounding the space (222) for hydrogen, are dimensionally stable at negative pressure in the space (222) for hydrogen relative to the surrounding package (200 ) environment of at least 200 mbar (0.02 MPa), characterized by the following stages: e) filling (110) with food product at least space (221) for food product, f) introducing (120) hydrogen gas into at least the hydrogen space (222), g) an airtight seal (130) of the shell (210) after filling (110) with food product and introducing (120) hydrogen gas, and h) creating (140) a negative pressure in at least the space (222) for hydrogen relative to the environment surrounding the package (200), wherein i) creating (140) negative pressure involves diffusion of hydrogen gas through the shell (210) into the surrounding environment (200) after the shell (210) has been sealed (130) in an airtight manner. 2. Method (100) according to claim 1, characterized in that the negative pressure is from 200 mbar to 500 mbar (0.02-0.05 MPa), preferably from 200 mbar to 300 mbar (0.02-0.03 MPa). 3. Method (100) according to claim 1 or 2, characterized in that the negative pressure is at least 200 mbar (0.02 MPa), particularly preferably at least 400 mbar (0.04 MPa). 4. Method according to one of claims 1-3, characterized in that creating (140) a negative pressure involves pumping a gas, preferably air, from the interior space (220) before the airtight seal (130) of the shell (210) and preferably before introducing (120) hydrogen gas, the negative pressure during the seal (130) being preferably from 200 mbar to 500 mbar (0.02-0.05 MPa), especially preferably from 200 mbar to 300 mbar (0.02-0.03 MPa). 5. Method (100) according to one of claims 1-4, characterized in that a) the shell (210) surrounding the hydrogen space (222) is dimensionally stable at a negative pressure in the internal space relative to the environment surrounding the package (200) of at least 200 mbar (0.02 MPa), b) the food product space (221) and the hydrogen space (222) are connected to each other in a food conductive manner, c) filling (110) with food product includes completely filling the internal space (220) with food product, and d) introduction (120) of hydrogen gas occurs after filling (110) and involves displacing the food product from the hydrogen space (222). 6. Method (100) according to one of claims 1-4, characterized in that a) the sleeve (230) surrounding the hydrogen space (222) is dimensionally stable at a negative pressure in the internal space relative to the environment surrounding the package (200) of at least 200 mbar (0.02 MPa), b) the sleeve (230) hermetically isolates the space (222) for hydrogen from the space (221) for the food product, c) introducing (120) hydrogen gas involves completely filling the internal space (220) with hydrogen gas, and d) the introduction (110) of the food product occurs after the introduction (120) and includes the displacement of hydrogen gas from the food product space (221), f) in this case, air is preferably pumped out from the internal space (220) before insertion (120), and the sleeve is dimensionally stable. 7. Method (100) according to one of claims 1-4, characterized in that a) the sleeve (230) surrounding the hydrogen space (222) is dimensionally stable at a negative pressure in the internal space relative to the environment surrounding the package (200) of at least 200 mbar (0.02 MPa), b) the sleeve (230) hermetically isolates the space (222) for hydrogen from the space (221) for the food product, c) the introduction (120) of hydrogen gas into the hydrogen space (222) occurs after the food space (221) has been filled (110) with food, d) in this case, air is preferably pumped out from the internal space (220) before insertion (120), in particular before filling (110). 8. Method (100) according to one of claims 1 to 7, characterized in that a) introducing (120) hydrogen gas involves filling (110) a hydrogen-enriched food product, b) wherein the food product is preferably saturated with hydrogen and/or does not contain other gases. 9. Packaging (200) for storing a food product in an atmosphere of hydrogen gas according to one of claims 1 to 8, wherein a) the package (200) includes an internal space (220) surrounded by a hydrogen permeable and airtight sealing shell (210), b) the inner space (220) contains a food space (221) for receiving food product, and a hydrogen space (222) for receiving hydrogen gas, wherein c) the food product space (221) and the hydrogen space (222) are connected to each other in at least a gas-conducting manner, and characterized in that d) the shell (210) is dimensionally stable at a negative pressure in the hydrogen space (222) relative to the environment surrounding the package (200), amounting to at least 200 mbar (0.02 MPa), and contains a filling hole (250) made with the ability to accommodate a media exchange device (240) for simultaneously introducing hydrogen gas through the inlet line (241) into the hydrogen space (222) and removing the food product through the outlet line (242) from the internal space (220), or f) the shell (210) is flexible at least partially, and the sleeve (230) located in the shell (210) and surrounding the hydrogen space (222) is dimensionally stable at a negative pressure in the hydrogen space (222) relative to the surrounding package (200) environment of at least 200 mbar (0.02 MPa). 10. Packaging (200) according to claim 9, characterized in that a) the sheath (210) and/or sleeve (230) is dimensionally stable at a negative pressure in the hydrogen space (222) of at least 0.2 bar (0.02 MPa), preferably at least 0.3 bar (0.03 MPa), most preferably 1 bar (0.1 MPa); and/or b) the shell (210) is resistant to an excess pressure in the internal space (220) relative to the environment surrounding the package (200), amounting to at least 0.5 bar (0.05 MPa), preferably at least 2 bar (0.2 MPa ), particularly preferably at least 8 bar (0.8 MPa); and/or c) the sleeve (230) seals the hydrogen space (222) from the food space (221), preferably in a liquid-tight manner. 11. Packaging (200) according to one of paragraphs 9, 10, characterized in that shell (210) a) is at least partially transparent, and/or b) consists mainly of glass and/or plastic, preferably plastic film. 12. Packaging (200) according to one of paragraphs 9-11, characterized in that the shell (210) contains a filling hole (250), sealed in an airtight manner using a sealing means (251), for filling the internal space with food product, while the media exchange device (240) is configured to be placed in the filling hole (250), in a state , in which the filling hole (250) is closed by a sealing means (251). 13. Packaging (200) according to claim 12, characterized in that the media exchange device (240) includes a plug (243) configured to be inserted with a seal into the filling hole (250), wherein the plug (243) contains an inlet hole (244) for receiving an inlet line (241) and an outlet hole (245) for receiving the outlet line (242), the plug (243) preferably includes at least one seal (246) for sealing between the plug (243) and the inlet line (241) and/or the outlet line (242). 14. Packaging (200) according to one of paragraphs 9-13, characterized in that the media exchange device (240) contains at least one valve (247) for regulating the flow of media and/or for determining the direction of flow of media through the inlet line (241) and/or outlet line (242). 15. Use of a package (200) according to one of claims 9 to 14 for preserving a food product in an atmosphere of hydrogen gas in a method (100) according to one of claims 1 to 8.