JPH06319497A - Method to improve fragrance and flavor of stored beverage and edible oil - Google Patents

Abstract

PURPOSE: To improve the aromas and tastes of preserved beverages and cooking oil. CONSTITUTION: The beverage and/or cooling oil are in contact with noble gas, noble gas mixture or the mixture of at least one kind of noble gas and carrier gas during preserving or producing.

Description

Detailed Description of the Invention

Noble gases helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe)
And the ability of radon (Ra) to participate in chemical bonding with other atoms is extremely limited. In general, only krypton, xenon and radon induce reactions with very reactive atoms such as fluorine and oxygen and compounds so formed are explosively unstable. FACott
on and G. Wilkinson (Wiley, Third Edition) A
See dvanced Inorganic Chemistry. Xenon is known to exhibit certain pharmacological effects, such as anesthesia, but noble gases are generally considered to be inactive.

Usually, beverages and edible oils are
It is preserved by simply moving atmospheric oxygen from their immediate vicinity using an inert or non-reactive gas. It is known that oxygen can degrade many aroma and flavor components of a substance.

For example, JP 3058778 (89192663) describes the storage and aging of alcoholic beverages such as sake in an argon atmosphere. Argon is used here simply to replace oxygen.

JP 58101667 (88019147) describes a citrus beverage under the pressure of argon or nitrogen as an inactivating agent so that the foam attached to the pulp and released when decompressing is released. It is described to be sealed.

JP 60134823 describes the packaging of liquid food products. Here, argon or nitrogen as an inert gas is used to push the product into the packaging.

JP 7319947 (730618) describes the storage of fruit juice under an inert gas, where argon, helium and nitrogen are considered equally inert.

[0006] US 3128188 describes the storage of Ruh beer in an inert atmosphere.

US 309181 describes a gassing process for tomato juice or liquid foods or plant concentrates, wherein an inert gas or non-reactive gas containing argon, nitrogen, krypton or helium or mixtures thereof is described. The gas is completely equivalent.

US 3535124 describes a distribution system for fresh fruit juices in which an inert gas is used for deoxygenation during atomization.

[0009] US 4803090 states that while cooking food with oil,
It is stated that any inert gas can equally be used to replace oxygen. No significant change was seen in the oil.

Cooling of liquid food products can also be accomplished with any inert or non-reactive gas. See, for example, DE 2147880, ZA 7106193, FR 2107946 and GB 1371027.

US 4901887 describes a beverage dispenser pressurized with an inert or non-reactive gas.

WO 8600503, DE 3425088, AU 8546026, EP
189442 and DE 3448380 each maintain aroma,
It discloses the use of an inert or non-reactive gas in heating liquid foods while preventing boiling. Nitrogen and noble gases can equally be used as non-reactive gases.

DE 2736282, WO 7900092, HU H2477, GB 2
Each of 021070, DD 137571 and EP 6888 is a beer load tanker filling system using an inert or non-reactive gas that constitutes either carbon dioxide, nitrogen or a noble gas equivalent to the inert or non-reactive gas. Is described.

GB 1331533, FR 2089899, BE 765637, DE
2031068 and CH 522734 each describe a method of preserving alcoholic beverages in which oxygen is replaced by nitrogen, preferably at all stages of processing, including storage. Argon or other noble gases can also be used as they are all considered equally inert or non-reactive.

Thus, it is presently recognized that it is desirable to remove oxygen from the atmosphere in contact with beverages and edible oils. This can be done by physically replacing oxygen with an inert or non-reactive gas, as described above. In general, nitrogen is preferentially used except where carbon dioxide can be used because it is cheaper because of its low cost and ease of use. For example, carbon dioxide can be used in sparkling beverages. Argon and noble gases are also used,
They are explicitly described in this field as being inert or non-reactive gases such as nitrogen or as beings like carbon dioxide and are used as such.

Orange juice has been extracted from whole oranges, usually by exposure to oxygen, using various mechanical means. Bartholomai, A. 1987. Food F
actories-Processes, Equipment, Costs (VCH Publishe
rs, New York, NY). The loss of aroma due to oxidation is of major concern during processing and especially storage.

Orange juice is a complex mixture,
Over 150 orange juice volatile components have been reported and identified. Among them, 40 terpene hydrocarbons, 30 esters, 36 aldehydes and ketones,
36 alcohols and 10 volatile organic acids have been isolated. An example of a volatile chromatogram extracted from orange juice is Papanicolaou et al., J. Food Tec.
hnol. 13:51 IL 519 (1978).

During storage of orange juice, aroma and flavor compounds undergo a number of oxidative chemistries that lead to aroma degradation. These reactions can occur with atmospheric oxygen or oxygen from chemical sources.

Prior to pasteurization of orange juice, during storage, products of oxidative enzymatic reactions could accumulate to form off-flavored compounds. Bruemmer et al, J. Food Sc
i. 41: 186-189 (1976). In unpasteurized orange juice, acetaldehyde accumulation is probably the cause of diacetyl production in orange juice during storage. Diacetyl can result from the oxidation of acetoin.

Orange juice contains an important antioxidant, ascorbic acid (vitamin C). Often large amounts of this compound are added to commercial juices.
However, such large additions are preferably avoided or limited, and direct control of the chain of the oxidation reaction involving ascorbic acid is preferred. Of course, the oxygen decomposition of the aroma components in the upper space cannot be delayed at all with ascorbic acid in solution.

Citrus juices in particular are susceptible to degradative oxidation caused by the action of the enzyme oxidase or by the oxygen present in the atmosphere or in solution. This displacement of oxygen results in only a partial delay in oxidation.

The main problems of product quality in the citrus processing industry are transparency, color, taste, bitterness, loss of flavor, flavor oxidation.

Proper cloud retention, which the processor deals with by controlling clarity, is a decisive quality parameter for citrus juices. The enzymatic action of pectinsterase results in the disappearance of the appealing cloudiness of orange or other citrus juices during storage. The product of pectinsterase activity is pectic acid. It forms chelates with divalent cations to form insoluble pectate,
It causes the transparency of unwanted fruits.

Currently, the only means available to stabilize (deactivate) enzymes is heat. Unfortunately, heat also causes a loss of the citrus's inherent aroma, which makes the citrus juice highly appealing.

Naringin is the major causative agent of bitterness in some citrus juices. Naringinase is commonly used in the citrus industry to reduce bitterness. When present in high amounts, natural naringin 4 ′, 5,7-trihydroxyflavanone-7-rhamnoglucoside is a source of bitterness, a property that does not appeal to consumers of grapefruit and other juices. Naringinase is an enzyme complex with two types of activity (α-rhamnosidase and β-glucosidase activities) and catalyzes the breakdown of naringin into glucose and naringenin, which are not bitter.

Citrus juice can also be bitter-relieved by passing it through a hollow fiber system containing immobilized naringinase.

Several factors are important in storing orange juice or other citrus juices. That is, the sweetness consistency, sourness, color, and characteristic flavor to the consumer. Orange or other citrus juice is expected to be cloudy with suspended solids. The carbohydrate gum, pectin, aids suspension. The enzyme, pectinesterase, attacks pectin and makes the juice clear. Some other juices are preferably clear (eg apples, and cranberries). In these, enzymes can be added to promote transparency.

During storage of oranges or other citrus juices, aroma and flavor compounds undergo many oxidative chemical reactions resulting in aroma degradation. These reactions can be triggered by atmospheric oxygen or oxygen from a chemical source.

Prior to pasteurization of orange or other citrus juice, the products of oxidative enzymatic reactions deposit and form off-flavor compounds during storage (Bruemmer et al., 1976).
In orange or other citrus juices that are not pasteurized, acetaldehyde deposition appears to be due to diacetyl formation in the orange or other citrus juices during storage. Diacetyl can result from the oxidation of acetoin (Papanicoraou).

In addition, orange and other citrus juices contain an important antioxidant, ascorbic acid (vitamin C). Sometimes large amounts of this compound are added to commercial juices. In order to have better control over the oxidation reaction involving ascorbic acid, it is desirable to avoid the addition of ascorbic acid or reduce the amount of ascorbic acid added. Note that oxygen degradation of headspace aroma components is not prevented by ascorbic acid in solution.

At the same time, oil oxidation is a major spoilage phenomenon associated with the commercial manufacture or storage of oils. The presence of oxygen indicates that lipids and oils such as triglycerides, oxides, acids,
And cause oxidative conversion to other degraded forms. Enzymatic oxidation is particularly rapid, with lipoxygenase,
Damages contained enzymes such as peroxidase and other oxidases.

Generally, oxygen is used to remove headspace,
Excluded by vacuum storage, storage under nitrogen. Headspace removal requires careful monitoring of the procedure, resulting in overpressure problems or leaks during packaging. Vacuum storage is expensive and most oils are volatile or contain volatile aroma components. Storage under nitrogen is the best solution available today, but it is not fully satisfactory and is ineffective in improving the rate of enzyme degradation.

Currently, oils are extracted through pressure, centrifugation, filtration, solvent extraction or flocculation, or a combination thereof. The presence of oxygen causes the oxidative conversion of lipids and oils such as triglycerides into oxides, acids, and other degraded forms.

Oxidative deterioration is the most important deterioration phenomenon. This occurs even when atmospheric oxygen is removed, as the oxygen source is present in the oil. Enzymatic oxidation is especially fast,
Damages contained enzymes such as lipoxygenase, peroxidase, and other oxidases. Of course, this is a particularly troublesome problem with seed and vegetable oils for human consumption.

Generally, oxygen is used to remove headspace,
Break off contact with oil by vacuum storage or storage under nitrogen. Headspace removal requires careful monitoring of the procedure, resulting in overpressure problems or leaks during packaging. Vacuum storage is expensive and most oils are volatile or contain volatile aroma components. Storage under nitrogen is the best solution available today, but it is not fully satisfactory and is ineffective in improving the rate of enzyme degradation.

[0036] U.S. Patent 4,803,090, while cooking the food with oil, it is disclosed that may be used an inert gas as equivalents to replace the O _2. In particular, there was no noticeable change in the oil.

EP 189442 discloses the use of an inert gas for heating a liquid food product while maintaining its aroma and preventing boiling. In this case N ₂ or noble gases may be used as equivalents.

Several references are known that use argon to control the inert gas displacement in oxygen induced oxidation studies. However, in these studies, the effects of argon other than simple inert gas displacement have not been shown or claimed. For example, Peers and Sw
oboda (1982); Unbehend et al. (1973); Schsnept et al. (19
91)

Unfortunately, however, the headspace atmosphere of stored edible oils, especially seed oils, is replaced with oxygen by an inert gas, such as nitrogen or carbon dioxide, or a gas considered to be inert. Although it may be preferable to remove oxygen, simple replacement of atmospheric oxygen does not provide a suitable means of protection against seed oil oxidation.

In fact, seed oils and vegetable oils are rapidly oxidized under the conditions of normal manufacturing processes. This oxidation reduces the actual and commercial quality of the final product. Oxidation
It proceeds most rapidly in the presence of air or other oxygen source and is controlled in current processes to minimize this contact. Heretofore, an inert gas blanket was used in the final storage stage to minimize oxygen contact. However, their use of inert gases is neither particularly effective nor economical. Instead, simply removing the air by designing the device is the preferred method for minimizing oxygen-oil contact. This is sometimes combined with a blanket of nitrogen gas to prevent oxygen from accessing the oil. Other methods have been used, including steam stripping of air, but thermal degradation also increases oxidation. Therefore, this method also has no effect.

Oxidation of oils may occur because molecular oxygen may be found in water or in the oil product itself, or it may be donated from other molecules that are donors of oxygen under the conditions of manufacture. It is known to proceed even in the absence of air. Current methods do not adequately control these oxidation processes.

Beer, unlike wine, is also a highly volatile fermentation product from the perspective of aroma components and is produced according to a well-understood brewing process (Bartholomai, 1987). Continuous and batch fermentations with Saccharomyces yeast are regulated and optimized through all possible parameters, including possible storage of working solution or grain at any stage. Storage under nitrogen can prevent oxidation and is sometimes practiced,
Most manufacturers rely on heating or degassing to remove oxygen, accepting fairly high levels of oxidation as inevitable.

Accordingly, there is a need for a method of storing and / or maintaining a variety of beverage and edible oils that improves aroma and their fluidity. In particular, there is a need for a method that provides better control over the various oxidation reactions generally associated with citrus juice deterioration, and especially with respect to ascorbic acid. There was also a need for a method in which different juices were stored and / or maintained, thereby improving their aroma and aroma.

Furthermore, there is a particular need for a method in which edible oils, especially seed oils, can be preserved in order to improve their aroma and aroma.

[0045]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a method for storing beverage and edible oils.

It is also an object of the present invention to provide a method of improving the aroma and aroma of stored beverage and edible oils.

Further, the object of the present invention is to provide citrus fruits, beer,
And to provide a method for improving the aroma and aroma of edible oil.

A method for preserving beverage and edible oils, wherein the beverage and edible oil is a noble gas, a mixture of noble gases, or at least one noble gas for at least part of their manufacture or storage. The above and other objects are achieved by the method of contacting with a mixture containing.

[0049]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Drinking and edible oils undergo degradative oxidation, especially by enzymatic degradation by oxidases, or chemical oxidation by oxygen from headspace, solutions, or autologous sources. The physical displacement of oxygen partially delays the oxidation, but the effect provided is insufficient.

However, in accordance with the present invention, surprisingly, a method has been developed for storing beverages or edible oils. The method comprises the step of storing a noble gas, a mixture of noble gases, or at least one during storage of at least partial beverage or edible oil.
A method of contacting a mixture containing a rare gas of a seed with a beverage or edible oil.

As used herein, the phrase "contacting a beverage or edible oil" means contacting the headspace, or even the liquid surface, even below the surface of the beverage or edible oil. In particular, any one or any combination of these definitions is expressly meant to be within the scope of this definition and this phrase.

The term "rare gas" as used herein is also meant to include argon, xenon, krypton, and neon. Helium is not preferred as it leaks easily, but can be used. Radon is not used because it is radioactive and dangerous.

According to the invention, argon, xenon, krypton and neon can be used alone or in any combination. For example, a binary mixture of argon-xenon, krypton-xenon or xenon-neon, or, for example, a tertiary mixture of argon-xenon-.
Krypton may be used.

However, it is also possible to use mixtures which contain at least one noble gas together with one or more other carrier gases. Carrier gases include, for example, nitrogen, oxygen, carbon dioxide, nitrous oxide, and even helium.

In general, the advantages of the present invention are obtained under near vacuum, ie, in the pressure range of about 10 ^-8 torr to about 100 atmospheres. However, it is generally preferred to use a pressure of between about 0.001 and about 3 atmospheres. Furthermore, the temperature ranges are generally those usable for beverages and edible oils, as well as for different stages of the processing process, and the same temperatures as the preferred temperatures are used. For example, such temperatures can range from freezing temperatures to cooking temperatures. However, lower temperatures and ambient temperatures are commonly used for storage.

As mentioned above, a single noble gas, such as argon, or a mixture of noble gases may be used in the present invention. However, mixtures containing at least one noble gas and one or more carrier gases can also be used.

Any relative mixture of gases may be used, so long as the preservative effect of the noble gas component or two or more noble gas components outweighs any oxidative effect of a carrier gas such as oxygen. However, in general, each noble gas can be used in these mixtures in amounts of about 0 to 100% by volume, or any value in between. In addition, any relative mixture, ie, about 0 to 100% by volume, is used in the binary mixture. Of course, the total amount of gas is 100% by volume.

For example, in accordance with the present invention, an off-stream gas (of an inexpensive production plant having a composition of about 90% Kr and 10% Xe by volume% based on total gas volume (of
It is advantageous to use f-stream gases).

It is also effective to use a mixture containing an effective amount of one or more rare gases in the deoxygenated air.
In general, the term "deoxygenated air" as used herein means air having 15% by volume or less, or 10% by volume or less, preferably 5% by volume or less oxygen in the air.

Furthermore, the gas or gas mixture according to the invention, whether used as a gas or introduced into a beverage or an edible oil, or in the headspace of a storage means in order to create the desired atmosphere. May be introduced even at the top.

The color improvement of beer, olive oil and other oils, in particular orange juice, is dramatic, showing a very surprising and substantial improvement. Aroma is also a blind taste test for each product
According to.

As shown together in this application, noble gases, ie, argon, xenon, krypton, neon, singly or a mixture of helium, or nitrogen, or a small amount of oxygen, carbon dioxide, young. Storage of any liquid foodstuff or beverage under contamination with nitrous oxide
The retardation of oxidation is significantly improved compared to that obtained with nitrogen.

In particular, the benefits of the present invention are demonstrated over a wide range of temperatures, including cooking, or pasteurization, refrigeration, and freezing, including cryogenic freezing. The effect of the present invention is also observed at low pressure or very high pressure.

The present invention is used to enhance the aroma and aroma of any type of beverage and / or edible oil, especially during storage. However, in particular the invention is particularly advantageous for improving the aroma and aroma of edible oils such as citrus juices and seed oils. I. Use of the Invention for Maintaining the Aroma and Aroma of Citrus Juice According to one aspect of the invention, citrus juice by controlling the oxidative reactions that generally contribute to the degradation of citrus, especially those containing ascorbic acid. Alternatively, a method of storing the precursors thereof is provided. Very surprisingly, the process involves the addition of citrus juice or its precursor material to a noble gas, a mixture of noble gases in at least part of the manufacturing process of the citrus juice or the storage of this juice or its precursor. , Or by contacting with a gas containing at least one noble gas.

As used herein, the term "noble gas" refers to
It is meant to include argon, xenon, krypton, and neon. Helium is not used and radon is radioactive and not used.

It is fully expected herein that the term "citrus" will be broadly construed as scientifically acceptable. Thus, for example, lemon, orange, lime, grapefruit, Wenzhou mandarin orange, tangero may be used. The term "citrus" is also meant to include a portion of fruit such as skin and pulp, as well as extracts from them.

According to the invention, argon, xenon, krypton, and neon can be used alone or in any combination. For example, a binary mixture of argon-xenon, krypton-xenon or xenon-neon, or, for example, a tertiary mixture of argon-xenon-krypton may be used.

However, it is also possible to use mixtures which contain at least one noble gas together with one or more other carrier gases. Carrier gases can include, for example, nitrogen, carbon dioxide, nitrous oxide, helium, and oxygen at low concentrations.

In general, the advantages of the present invention are obtained under near vacuum, ie, in the pressure range of about 10 ^-8 torr to about 100 atmospheres. However, it is generally preferred to use a pressure between about 0.001 and about 10 atmospheres, more preferably between 0.001 and 3 atmospheres. Further, the temperature range can be from a freezing temperature to a cooking temperature, such as about −20 ° C. to about 300 ° C. However, lower temperatures and ambient temperatures are commonly used for storage.

As mentioned above, a single noble gas, such as argon, or a mixture of noble gases may be used in the present invention. However, mixtures containing at least one noble gas and one or more carrier gases can also be used.

According to the present invention, the top space (head space) of citrus juice or its precursor (precursor) stored in a storage means such as a tank or a bottle is simply sealed with an inert gas. Alternatively, a gas or gas mixture containing a noble (rare) gas selected from the group consisting of argon, krypton, xenon, and neon or mixtures thereof is sparged into citrus juice or its precursor, and / or Or by injecting on top of citrus and / or its precursor to saturate or substantially saturate the citrus juice and / or its precursor with said gas or gas mixture, unexpectedly, citrus juice and / or The color and / or flavor and / or aroma and / or shelf life of its precursors, in particular Substantially improving saturation or substantial saturation when the citrus juice and / or its precursor is maintained throughout the volume of the storage container for substantially the entire period of storage in the container. You can

The phrase "substantially saturating" completely and / or steadily saturates a citrus juice and / or its precursor with a gas or gas mixture (ie in a citrus juice and / or its precursor). It does not mean that it is necessary to have a maximum amount of solubilized gas). Usually, it will be necessary to saturate the citrus juice and / or its precursors to above 50%, preferably above 70% of its (complete) saturation level, with 80% or more being citrus juice or its It is considered to be the most appropriate level of precursor. Of course, supersaturation is also possible. This means that it is generally substantially, even if the citrus juice or its precursor was not saturated with the noble gas at least continuously or for a longer period during the storage of the citrus juice or its precursor in the container. If it remains saturated, it means that the results of the invention are usually obtained. It is believed that it is important that the total volume of the vessel is saturated or substantially saturated with one or a mixture of the above gases, but a portion of said volume is preferably saturated within a limited period of time. If not, or less saturated or substantially saturated than other parts of the volume of citrus juice or its precursor in the container, it is entirely possible to obtain the results of the invention.

At least one of the above gases must be present in order to obtain the benefits of the invention, but it may be diluted with some other gas, for example to make the invention economically valuable. can do. The diluent gas is
It is preferably selected from the group consisting of nitrogen, oxygen, nitrous oxide, air, helium and carbon dioxide. For oxygen-containing gases such as carbon dioxide and other reactive gases,
Its degradability is such that it certainly masks the effect of the noble gas in the mixture, which makes up more than 50% by volume, perhaps more than 30% by volume. If these mixtures contain 0 to 10% by volume of the other gas, the noble gas is still very effective, usually 10% to 2% depending on the type and conditions of the gas which can be easily determined by the person skilled in the art.
Even 0% by volume is still effective.

In the case of nitrogen and / or helium gas,
The effect in a mixture of Ar, Ne, Kr, Xe noble gases is linearly proportional to its concentration in the mixture, which means that nitrogen and / or helium cause the oxidation of citrus juice and / or its precursors. It proves to have virtually no effect on preventing. Thus, the mixture of noble gas and nitrogen and / or helium can include any amount (volume%) of nitrogen and / or helium. However, in reality, A
The lower the proportion of noble gas selected from the group consisting of r, Ne, Kr and Xe, the longer it takes to achieve saturation or substantial saturation of citrus juice and / or its precursors.

Active gas (Ar, Kr, Xe, and N
Among e), it is preferable to use argon because it is cheaper than other active gases. However, a mixture of argon and / or krypton and / or xenon is at least as effective as argon alone. Unexpectedly, a mixture containing 90 to 99% by volume of argon and 1 to 10% of Xe and / or Kr, as illustrated in the examples below (where they are nitrogen, helium or nitrous oxide). It is usually found to be the most effective (whether diluted with or without). The difference between the effects of active gas and nitrogen as defined above also indicates that a mixture of argon and oxygen or carbon dioxide has a similar (albeit diminished) effect to argon alone, but oxygen or carbon dioxide. It is also evidenced by the fact that nitrogen mixed with has no protective or conservative effect comparable to oxygen or carbon dioxide alone.

It is believed that saturation or substantial saturation of citrus juice and / or its precursors is an essential feature of the present invention and no one skilled in the art discloses or suggests such a feature.

In general, Xe is the most efficient gas according to the invention, followed by Kr, Ar and Ne. Alone or N ₂ , He, N ₂ O (or air,
A suitable mixture diluted with oxygen, or a small amount of hydrogen) of about 50% by volume each of the Ne / He mixture and a small amount of argon and / or oxygen (less than 2% by volume) or nitrogen (less than 1% by volume). And containing about 5-10% by volume of Xe and about 90-95% by volume of Kr.
Xe mixtures are preferred.

The temperature for carrying out the present invention is usually about 0.
To 60 ° C, preferably about 10 to 30 ° C.

The injection of the above-mentioned gas or gas mixture into the wine and / or the container, for example by sparging, is usually carried out at about 1 atm, but 2-3 atm is entirely possible and the degree of saturation depends on the pressure. The higher the level, the better. The pressure of the gas above the citrus juice and / or its precursors in the container is in each case preferably lower than 10 atm and it is usually acceptable to keep it below 3 atm.

Saturation or substantial saturation of wine can be carried out by various known methods, for example, thermogravimetric analysis or mass change weighing.

There are various methods for gas detection, quantification, and characterization, some of which are particularly suitable for measuring the saturation of a noble gas in a liquid sample.

The sample is usually completely evacuated due to zero% saturation as a control. The sample is then contacted with the noble gas and allowed to fully saturate so that noble gas from the reservoir is no longer lost by contact with the sample. The gas content of the saturated sample is then expelled by trapping or increasing the temperature, and the gas sample is quantitatively and spectroscopically identified. The analysis is performed on the headspace of trapped gases, stored gases, and other gases and does not analyze the sample directly.

Direct sample analysis methods are also possible, for example comprehensive GC / MS analysis, mass spectrometry, thermal conductivity analysis, GC.
Analysis and comparison with measured standards can be performed.

The simplest method is GC / MS analysis (gas chromatography / mass spectrum measurement), which allows direct determination of the gas composition. By preparing a standard absorption curve for any sample, saturation can be accurately determined at any time.

The GC / MS analysis is applied on the gas itself as in the headspace above the sample. This method also applies to the determination of the composition and quality of the gas or gas mixture released from the sample, or the composition and quality of the gas or gas mixture absorbed into the sample as the gas disappears.

An example of a suitable GC / MS method is the use of a 5 angstrom porous layer open tubular molecular sieve capillary glass column (0.32 mm diameter, 25 m length), eg isothermally at 75 ° C. or The separation can be carried out using several temperature gradient programs optimized for any gas or gas mixture, eg 35-250 ° C., where ultrapure helium, hydrogen carrier gas is eg 1. Used at a flow rate of 0 cc / min, the gas is detected based on its ionicity and quantified in the sample, measured for its unique mass spectrum.

Suitable experimental conditions were to completely evacuate the sample in a vacuum to remove any absorbed or dissolved gas, then add the gas or gas mixture to the sample (a) It involves measuring the uptake rate of each component that disappears from the gas, or (b) measuring the final composition of the gas headspace once equilibrium is reached. Both measurements are performed by the GC / MS method,
It can be performed in a batch system or a continuous system.

As a simplification of this analytical method, a heat conduction detector can be used and only GC can be used.
In this case, appropriate knowledge of the gas saturation process and calibrated curves are provided so that quantification and characterization of gases and gas mixtures can be done without the need for mass spectral analysis. Such a device is relatively inexpensive and portable.

A simpler method is the measurement of the mass change when a gas or gas mixture is incorporated in the sample, which is done by making use of standard curves or absorption data obtained from the literature.

Another method for such mass measurement is
Thermogravimetric analysis, which is fairly accurate, where the sample is saturated with gas and its mass change is related to thermal change.

For example, according to the invention, it is advantageous to use an inexpensive production plant exhaust gas stream having a composition of about 90% Kr and 10% Xe by volume based on total gas volume or Ne: He 1: 1. Is.

It is also advantageous to use a mixture containing an effective amount of one or more noble gases in deoxygenated air. In general, "deoxygenated air" as used herein means air having less than 15% by volume or 10% by volume, preferably less than 5% by volume of oxygen.

Furthermore, the gas or gas mixture according to the invention can be used as a gas or be introduced into the citrus juice or its precursors or in the headspace or at the top of the storage means to form the atmosphere. can do.

The color improvement of citrus juice is very dramatic and in itself a very surprising and significant improvement. In addition, the flavor is improved in blind tests on each product.

Noble gas argon, xenon, krypton,
Storage of any citrus fruit under either neon alone or a mixture thereof or nitrogen, a small amount of oxygen or carbon dioxide or a mixture with nitrous oxide,
Unexpectedly, it greatly improves the inhibition of oxidation compared to the case of using nitrogen.

As already mentioned, the effects of the present invention have been demonstrated over a wide range of temperatures, including those during cooking or pasteurization, refrigeration, and freezing, including low temperature freezing. This has also been observed at low pressures or very high pressures.

In general, the advantages of the present invention are preferred when whole citrus fruits, parts of citrus fruits, concentrates and / or juices are used with the gas of the present invention at any stage of the manufacturing process starting from peeling the fruits. Are obtained by contacting each step.

As used herein, the term "precursor" means any natural product that acts as a source of citrus juice or as a fragrance additive for citrus juice. Examples of precursors include whole fruits of citrus fruits, part of fruits such as pulp, seeds or skins, citrus oils, flowers, and extracts from them.

To further illustrate the present invention, an exemplary process for making frozen concentrated orange juice is described below by way of illustration only and not as a limitation of the present invention. This method is shown in FIG.

Step 1: Truck unloading system.

Step 2: Storage facility (eg, sump device), and orange cleaning, grading, and sizing.

Step 3: The orange rind is just rich in automatic oil, which when present in large amounts gives the juice a bitter taste. Nevertheless, a small amount of oil is needed to give orange juice its original taste. Furthermore, orange essential oil is a product with non-negligible added value because it is used as an aroma chemical in other products.
Therefore, the juice extractor is designed to ensure proper separation of the juice from the skin oil.

The first step in the extraction process is to remove the outer layer of the skin by passing the orange through a scarifier. Oil is an emulsion (formed by water spray)
As transferred to the essential oil recovery line,
It is centrifuged there.

The scarifier-treated orange is passed through a juice extractor.

Step 4: A finishing step separates seeds and bulk particles such as fruit films and cores from juice and small pulp particles.

Step 5: The juice is then transported to a holding tank where it is homogenized (standardized color and total solids;
Can be blended to obtain standardized sugar and acid content).

Step 6: A pasteurization step that is used as pasteurized juice when it is commercially available and consists of heating the juice to 145 to 160 ° F for 5 to 30 seconds. This results in inactivation of pectinesterase and reduction of microbial flora. The heat treatment process is tightly controlled to minimize the loss of fresh flavor.

In some processes, juice is depulped before evaporation. After preheating to 80 ° C in a flat plate preheater, the amount of pulp is changed from 10% to 1% by centrifugation.
Reduce to 2%. Then juice 5 in the heat exchanger
Cool to 0-60 ° C.

Step 7: Preheat the juice by flowing it into a heat exchanger before sending it to the evaporator.

Step 8: Concentrate the juice by evaporation. This is done under vacuum at the lowest temperature possible to avoid cooked odors. Evaporation causes an unavoidable loss of flavor. Juice (55 ° -Brix)
To a commercial concentration level (42 ° -Brix).

Several industrial alternatives have been considered to solve the problem of loss of flavor volatiles during evaporation.

Several methods of recovering flavor from the first stage of evaporation (eg distillation) are used commercially.
The flavor essence obtained can be returned to the final product.

Freeze-concentration, reverse osmosis, which is a low temperature process,
Alternatively, the concentration can be performed by a method other than evaporation, such as filtration through a selective membrane. In these cases, there is no heat-induced enzyme deactivation.

Freeze-concentration can be performed in various ways. The juice can be frozen through a scrape surface heat exchanger or by direct contact with a cryogenic liquid such as liquid nitrogen. Separation of ice from the orange slurry is performed by centrifugation or column washing to obtain a concentrate. Freeze concentration poses a problem of solids loss.

Step 9: Add the determined percentage of fresh untreated juice to the over-concentrated juice to make up for the loss of flavor. The final product has a solids concentration of 42% (42 ° -Brix) and has a flavor closer to that of fresh orange juice.

Step 10: Transfer the concentrate to the slush by passing it through a cold scraper surface heat exchanger. It is then packaged in containers (eg cans, or drums for further industrial use) and then frozen.

Step 11: The by-products of this step (50% of oranges) are dried rind (animal food), citrus molasses (concentrated wastewater), oil (flavoring chemicals), citrus flour (dry pulp, albedo). , Nucleus, membrane). Further Processing: Citrus Juice Reconstituted from Concentrate The water used for reconstitution from orange or other citrus concentrates is treated by passage to a pressure device, dechlorination filter and sterilization station.

The sugar is weighed, melted in the sugar melting tank and passed through a syrup filter.

The concentrate is transported, weighed and mixed with the syrup in the mixing tank in the appropriate proportions.

The reconstituted fruit juice is pasteurized through a heat exchanger, packaged and cooled in a cooling tunnel.

The resulting orange or other citrus juice is packaged after the enriched concentrate production rich Ono step 6 and cooled.

The present invention offers many advantages, some of which are noted.

First, any one of the noble gases argon, xenon, krypton, and neon, alone or a mixture thereof, nitrogen, or a small amount of oxygen or CO 2, N 2 or H 2.
By treating and storing oranges or other citrus fruits under any of the mixtures with e, unexpectedly, the inhibition of oxidation is greatly improved over that with nitrogen.

Secondly, peeling, extraction, pressing, separating, conveying, blending, storing and storing, depulping, pasteurization, heating,
Flavor and aroma, appearance, color of intermediate and final products by contacting the fruit or juice with noble gas either during the steps of evaporation, concentration, freeze concentration, reblending, aroma recovery, reconstitution or further processing. And quality is greatly improved.

This improvement can be achieved by heating or pasteurizing, refrigerating,
It has been proven over a wide range of temperatures, including temperatures such as during freezing, including low temperature refrigeration, and is also effective at low or very high pressures.

Furthermore, the noble gas, preferably argon, is more effective than nitrogen or carbon dioxide, and this effect is directly proportional to the degree of saturation of the product with the noble gas.

Although the present invention has been generally described above, the following examples are given for illustrative purposes only. The present invention is not limited to this.

Example 1 Several orange or other citrus juices, including freshly squeezed, reconstituted from concentrate, and pasteurized, Ar, Xe, Kr, Ne, He, N
After various storage under ₂ , CO ₂ , N ₂ O, O ₂ , air or decile binary or ternary mixtures of these gases, they were subjected to GC / MS analysis of the headspace.

FIG. 38 shows a GC / MS of orange juice aroma volatiles under argon. The various parameters applied are listed in FIG.

FIG. 39 shows the GC / MS of orange juice aroma volatiles under nitrogen. The various parameters applied are listed in FIG.

FIG. 40 shows the GC / MS of orange juice aroma volatiles under oxygen. The various parameters applied are listed in FIG.

From the comparison of FIGS. 38, 39 and 40,
One can see the damaging effect of oxygen, while the surprisingly good effect of argon compared to nitrogen.

Of note are the cyclohexanetetrol and tridecane peaks around 1853 seconds, which are well stored in argon, highly oxidized in nitrogen, and highly oxidized in oxygen (significant Siloxane column bleed is also present).

For example, glycosides present in the argon sample (having a peak at 1570 to 1596 seconds) are oxidized in the oxygen sample and are not present at all, and are present in trace amounts in the nitrogen sample. The same incremental oxidation difference is the nitrile at 870 seconds, the acid ester at 1040 seconds, the pyrans at 1149 seconds, the substituted cyclohexanone at 1217 seconds, 1378.
It is also observed for substituted propanol at seconds and substituted cyclohexane at 1490 seconds (identification from NBS data library).

To average the quantitative improvement over many compounds, it was observed that a 25-30% improvement in shelf life could be readily achieved by using the sum of differences method, and in general by using eg Argon according to the invention. Was done.

To further demonstrate the effects of the present invention, various gases or gas mixtures shown in Tables 1 and 2 below were used as storage gas for orange juice.

In the two tables below, orange juice color was measured by UV / Vis spectrophotometry, flavor and aroma were measured by the GC / MS method, and shelf life was measured by the GC / MJ method. The relative oxidation progress with time using the gases and gas mixtures of the invention was compared to storage by air, oxygen or nitrogen.

A panel of five panelists tested the color, flavor and aroma with blind samples in accordance with and including the above instrumental measurements.

[0139]

[Table 1]

[0140]

[Table 2] As used herein, "substantially" generally means at least 75%, preferably at least about 90%, more preferably at least about 95%. This extends not only to the storage period, but also to the volume of the storage means.

The present invention will be described below with reference to examples, but this is for illustration only, and the present invention is not limited thereto.

Example 2 Several orange or other citrus juices, including freshly squeezed, reconstituted from concentrate and pasteurized, were prepared using Ar, Xe, Kr, Ne, He, N.
After various storage under ₂ , CO ₂ , N ₂ O, O ₂ , air or decile binary or ternary mixtures of these gases, they were subjected to GC / MS analysis of the headspace.

Similar studies were conducted with various beers and aides. Beer was also studied by UV / visible spectrophotometry.

Edible oils including vegetable oil, corn oil, soybean oil, and olive oil were studied by high performance liquid chromatography.

FIG. 1 is a UV / VIS spectrum of beer oxidation after storage for 30 days under each gas, clearly showing the improved inhibition of beer oxidation under argon relative to nitrogen. . Suppression is 35% overall for up to 2 years.

2-4 show the GC / MS of beer under Ar, N ₂ and O ₂ , respectively. From these figures it is easily seen that beer volatiles deteriorate more rapidly under nitrogen than under argon than under argon.

For example, the peak at 1115 seconds is an oxidation product that increases during oxidation relative to the peak at 1234 seconds. The ratio shows that the oxidation is O ₂ > N ₂ > Ar, the improvement with argon being 30 to N 2.
About 25% after a day. Another example of this improvement is 750,
1190, 1225, 1520, 1840, 1890,
Seen at peaks at 1933 and 2360 seconds.

The International Bureau of Standards (NBS) library search shows that the peaks correspond to imidazole, substituted bicrooctane, substituted tridecane, alcohols, probably pentadecanol, cyclohexanetetrol, tetradecanediol, glycosides and substituted benzoic acid, respectively. It is identified as a thing.

FIGS. 5 to 7 are under Ar, and FIGS.
Under N _2, 11-13, shows the orange juice aroma volatiles GC / MS of O ₂ under, respectively. A comparison of the peaks shown in these figures shows that oxidation is better prevented by Ar than N ₂ .

Of note are the cyclohexanetetrol and tridecane peaks at around 1853 seconds, which are well stored in argon, highly oxidized in nitrogen, and highly oxidized in oxygen. Siloxane column bleed is also present).

For example, glycosides (peaking at 1570 to 1596 seconds) present in the argon sample are oxidized in the oxygen sample and are not present at all, and trace amounts are present in the nitrogen sample. The same incremental oxidation difference is the nitrile at 870 seconds, the acid ester at 1040 seconds, the pyrans at 1149 seconds, the substituted cyclohexanone at 1217 seconds, 1378.
It is also observed for substituted propanol at seconds and substituted cyclohexane at 1490 seconds (identification from NBS data library).

It has been observed that a 25-30% improvement in shelf life can easily be achieved by using the sum of differences method to average the quantitative improvement over many compounds, and in general by using eg Argon according to the invention. Was done.

Oxidation of olive oil and other edible oils, when stored with argon or other noble gases containing mixtures,
The weight% change of the initial oil component to the oxidant was measured by HPLC or T
There was consistently more than 30% inhibition as measured by LC.
Accurate compositional analysis of triglycerides and lipids was obtained using phenylmethyl silicone GC / MS.

FIG. 1 shows the UV / VIS spectrum of the oxidation of beer after storage for 30 days under the indicated different gases.

FIG. 2 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 3 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 4 is a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 5 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under argon.

FIG. 6 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under argon.

FIG. 7 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under argon.

FIG. 8 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under nitrogen.

FIG. 9 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under nitrogen.

FIG. 10 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under nitrogen.

FIG. 11 shows a GC / MS chromatogram plot of orange juice aroma volatiles after storage under oxygen for 30 days.

FIG. 12 shows a GC / MS chromatogram plot of orange juice aroma volatiles after storage under oxygen for 30 days.

FIG. 13 shows a GC / MS chromatogram plot of orange juice aroma volatiles after 30 days storage under argon.

FIG. 14 is a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 15 shows a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 16 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under oxygen.

FIG. 17 shows a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 18 shows a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 19 is a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 20 shows a GC / MS chromatogram plot of beer volatiles after storage under oxygen for 30 days.

FIG. 21 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 22 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 23 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 24 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 25 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 26 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 27 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under nitrogen.

FIG. 28 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 29 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 30 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 31 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 32 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 33 is a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 34 shows a GC / MS chromatogram plot of beer volatiles after 30 days storage under argon.

FIG. 35 schematically shows a method for producing soybean oil from soybean.

FIG. 36 shows crude soybean oil to refined salad oil,
1 schematically illustrates a method for producing refined margarine or shortening oil.

FIG. 37 schematically shows a method for producing orange juice from orange.

FIG. 38 shows a GC / MS of orange juice aroma volatiles under argon.

FIG. 39 shows a GC / MS of orange juice aroma volatiles under nitrogen.

FIG. 40 shows the GC / MS of orange juice aroma volatiles under oxygen.

In general, according to the invention, beverages can be stored, for example beer, ale, stout, soft drinks like all colas, citrus juices like all orange juice.

Examples of citrus and other juices include orange juice, lemon juice, lime juice, pineapple juice and apple juice,
It is not limited to this.

Furthermore, the effect of the present invention by using the gas, gas mixture, liquid or liquid mixture of the present invention during all processing steps or storage of beverages or edible oils, or one or any part thereof. It is understood that II. Use of the Invention in Preserving the Aroma and Freshness of Edible Oil According to the invention, the top space (headspace) of seed oil stored in a tank or bottle is simply gas-sealed with either an inert gas. Alternatively, a gas or gas mixture containing a noble gas selected from the group consisting of argon, krypton, xenon, and neon or mixtures thereof is sparged into the seed oil and / or its precursor components, and / or Unexpectedly, seed oil and / or precursor components thereof may be unexpectedly injected by saturating or substantially saturating the seed oil and / or precursor components thereof with the gas or gas mixture. And / or its precursor component color and / or flavor and / or aroma and / or shelf life, in particular said saturation or substantial saturation Can be preserved or substantially improved when the seed oil and / or its precursor components are maintained throughout the volume of the storage container for substantially the entire period of storage in the container. .

The phrase "substantially saturated" means that the seed oil and / or its precursor components are completely and / or permanently saturated with the gas or gas mixture (ie the seed oil and / or its precursor). It does not mean that it is necessary to have a maximum amount of solubilized gas therein). Usually, it will be necessary to saturate the seed oil and / or its precursors to above 50% of its (complete) saturation level, preferably above 70%, but 80% or more of the seed oil and / or Or considered to be the most appropriate level of its precursor. Of course, supersaturation is also possible. This means that seed oil and / or
Or even if the seed oil and / or its precursor was not saturated with the noble gas at least continuously or for a longer period of time during storage of the precursor in the container, it generally remains substantially saturated. If so, it means that the results of the present invention are usually obtained. It is believed that it is important that the total volume of the vessel is saturated or substantially saturated with one or a mixture of the above gases, but a portion of said volume is preferably saturated within a limited period of time. Not
Alternatively, it is entirely possible to obtain the results of the invention even if the seed oil and / or its precursor in the container is less saturated or substantially saturated than other parts of the volume.

As used herein, the term "noble gas" means Kr, Ar, Ne, or Xe. He is not used because it has no effect. Rn is radioactive,
Not useful.

The term "precursor" as used herein refers to the natural seed oil source, or any crude preliminary or intermediate refinement obtained prior to the final seed oil product. For example, the term "precursor" means raw soybean, cracked or dehulled soybean, crude soybean oil, degummed oil, neutralized oil or bleached oil. Any of these purified products can benefit from the present invention.

Furthermore, for odorless and / or tasteless seed oils, their quality can be more easily preserved. Seed oils, which have a characteristic odor and / or taste, can improve their quality in the sense that they can be more easily preserved and better maintained for longer than otherwise.

At least one of the above gases must be present in order to obtain the benefits of the invention, but it may be diluted with some other gas, for example to make the invention economically valuable. can do. The diluent gas is
It is preferably selected from the group consisting of nitrogen, oxygen, nitrous oxide, air, helium and carbon dioxide. For oxygen-containing gases such as carbon dioxide and other reactive gases,
Its degradability is such that it certainly masks the effect of the noble gas in the mixture, which makes up more than 50% by volume, perhaps more than 30% by volume. If these mixtures contain 0 to 10% by volume of the other gas, the noble gas is still very effective, usually 10% to 2% depending on the type and conditions of the gas which can be easily determined by the person skilled in the art.
Even 0% by volume is still effective.

In the case of nitrogen and / or helium gas,
The effect in a mixture of Ar, Ne, Kr, Xe noble gases is linearly proportional to its concentration in the mixture, which means that nitrogen and / or helium cause the oxidation of seed oil and / or its precursors. It proves to have virtually no effect on preventing. Thus, the mixture of noble gas and nitrogen and / or helium can include any amount (volume%) of nitrogen and / or helium. However, in reality, Ar, Ne,
The lower the proportion of noble gas selected from the group consisting of Kr and Xe, the longer it takes to achieve saturation or substantial saturation of the seed oil and / or its precursors.

Active gas (Ar, Kr, Xe, and N
Among e), it is preferable to use argon because it is cheaper than other active gases. However, a mixture of argon and / or krypton and / or xenon is at least as effective as argon alone. Unexpectedly, a mixture containing 90 to 99% by volume of argon and 1 to 10% of Xe and / or Kr, as illustrated in the examples below (where they are nitrogen, helium or nitrous oxide). It is usually found to be the most effective (whether diluted with or without). The difference between the effects of active gas and nitrogen as defined above also indicates that a mixture of argon and oxygen or carbon dioxide has a similar (albeit diminished) effect to argon alone, but oxygen or carbon dioxide. It is also evidenced by the fact that nitrogen mixed with has no protective or conservative effect comparable to oxygen or carbon dioxide alone.

It is believed that the saturation or substantial saturation of seed oil and / or its precursors is an essential feature of the invention and no one skilled in the art discloses or suggests such a feature.

In general, Xe is the most efficient gas according to the invention, followed by Kr, Ar and Ne. Alone or N2, He, N2 O (or air,
A suitable mixture diluted with oxygen, or a small amount of hydrogen) of about 50% by volume each of the Ne / He mixture and a small amount of argon and / or oxygen (less than 2% by volume) or nitrogen (less than 1% by volume). And containing about 5-10% by volume of Xe and about 90-95% by volume of Kr.
Xe mixtures are preferred.

The temperature for carrying out the present invention is usually about 0.
To 60 ° C, preferably about 10 to 30 ° C.

The injection of the gas or gas mixture into the seed oil or its precursor or container, for example by sparging, is usually carried out at 1 atm, but it is also possible to operate at 2 or 3 atm and, at higher pressures, saturation. Will also be higher. The gas pressure on the seed oil or its precursor in the container is preferably less than 10 atm in any case, and is usually kept at less than 3 atm.

The saturation or substantial saturation of the seed oil or its precursor can be measured by various known methods,
For example, thermogravimetric analysis or mass change weighing can be performed.

There are various methods of gas detection, quantification, and characterization, some of which are particularly suitable for measuring the saturation of a noble gas in a liquid sample.

The sample is usually completely evacuated due to zero% saturation as a control. The sample is then contacted with the noble gas and allowed to fully saturate so that noble gas from the reservoir is no longer lost by contact with the sample. The gas content of the saturated sample is then expelled by trapping or increasing the temperature, and the gas sample is quantitatively and spectroscopically identified. The analysis is performed on the headspace of trapped gases, stored gases, and other gases and does not analyze the sample directly.

Direct sample analysis methods are also possible, for example comprehensive GC / MS analysis, mass spectrometry, thermal conductivity analysis, GC.
Analysis and comparison with measured standards can be performed.

The simplest method is GC / MS analysis (gas chromatography / mass spectrum measurement), which allows direct determination of the gas composition. By preparing a standard absorption curve for any sample, saturation can be accurately determined at any time.

GC / MS analysis is applied on the gas itself as in the headspace above the sample. This method also applies to the determination of the composition and quality of the gas or gas mixture released from the sample, or the composition and quality of the gas or gas mixture absorbed into the sample as the gas disappears.

An example of a suitable GC / MS method is the use of a 5-Angstrol porous layer open tubular molecular sieve capillary glass column (diameter 0.32 mm, length 25 m), eg isothermally at 75 ° C. or The separation can be carried out using several temperature gradient programs optimized for any gas or gas mixture, eg 35-250 ° C., where ultrapure helium, hydrogen carrier gas is eg 1. Used at a flow rate of 0 cc / min, the gas is detected based on its ionicity and measured for its quantitation in the sample, its unique mass spectrum.

Suitable experimental conditions were to completely evacuate the sample in a vacuum to remove any absorbed or dissolved gas, then add the gas or gas mixture to the sample (a) It involves measuring the uptake rate of each component that disappears from the gas, or (b) measuring the final composition of the gas headspace once equilibrium is reached. Both measurements are performed by the GC / MS method,
It can be performed in a batch system or a continuous system.

As a simplification of this analytical method, a heat conduction detector can be used and only GC can be used.
In this case, appropriate knowledge of the gas saturation process and calibrated curves are provided so that quantification and characterization of gases and gas mixtures can be done without the need for mass spectral analysis. Such a device is relatively inexpensive and portable.

A simpler method is the measurement of the mass change when a gas or gas mixture is incorporated into the sample, which is done by making use of standard curves or absorption data obtained from the literature.

Another method for such mass measurement is
Thermogravimetric analysis, which is fairly accurate, where the sample is saturated with gas and its mass change is related to the thermal change.

In various steps for making oil from seeds or grains, contact with a noble gas can delay the oxidation of oil and improve the quality of oil. By making the contact between the oil and the rare gas more complete, and making the contact longer, it is possible to improve the oil better. This improvement is best achieved by maximizing the ratio of gas molecules per unit quantity of oil. A considerable improvement is seen by saturating the liquid oil with a noble gas under the best operating conditions. In particular, this improvement can be enhanced by increasing the pressure, lowering the temperature, mixing well and maximizing the other gas-oil contact.

In general, noble gases, especially argon, have the potential to suppress oxidation, and the oxidation in this case does not depend on the oxygen dissolved in the solution or on the outside. Furthermore, this oxidization suppressing action is extremely strong even if oxygen is present to some extent, depending on the conditions. In any case, since the rare gas is substantially saturated, a considerable effect can be obtained by adding it by spraying, gas sealing or pressurization.

By contacting a noble gas, preferably argon, with the seed oil in the seed oil production process, the rate of degradative oxidation reactions is significantly reduced and the final quality of the oil product is improved. Furthermore, the best results can be obtained by completely saturating the seed oil or its precursor with noble gases at all stages of the manufacturing process. In particular, the noble gas is saturated in the oil in the following steps.

For crushing / grinding, threshing, flaking, extraction, degumming, alkali refining, bleaching, hydrogenation, deodorization, dewaxing, etc., press, filtration, solvent removal, clarification, storage or container storage. And the steps of transferring, storing and the like.

The present invention can be advantageously applied to a single production step, a series of production steps, or all steps in refining seed oil or vegetable oil or in producing refined oil.

For example, a typical process for producing seed oil, that is, a process for producing soybean oil can be described as follows.

Step 1: Truck unloading system.

Step 2: Storage facilities and soybean drying, washing, conditioning and sorting.

Step 3: In preparation for soybean extraction, crushing and threshing are carried out to facilitate flaking. A corrugated roller is used for this crushing. Threshing is necessary to enhance extraction efficiency. Threshing is performed by methods such as air spraying, sieving, centrifugal separation, and specific gravity separation.

By flaking soybeans that have been crushed and threshed, the internal cell structure is divided, and the contact between the fruit portion and the extraction solvent is improved. This flaking is performed by heating crushed and threshed soybeans, steaming, and pressing through a differential roller mill.

Step 4: The flaked soybean is extracted with a continuous convection percolation extractor using hexane as a solvent. This solution is called a rich micelle and is sent to the solvent recovery system. Here the solvent is removed and a liquid solventless crude oil is produced. During this extraction, the solvent is kept at approximately 50 ° C. to facilitate solubilization of the oil from the flakes. The micelles are then separated from the flakes and distilled to recover crude soybean oil. The solvent is recovered for reuse. This crude soybean oil is then sent to a storage tank for further processing.

Step 5: For degumming, drying and cooling of crude soybean oil containing lecithin etc., crude soybean oil is mixed with hot water to coagulate phosphatide, which is later removed by centrifugation and then the oil is dried. , Cooled, and sent to a storage tank. The separated lysine sludge is dried by a gentle heat treatment under vacuum, then cooled and filled in a can, a drum can or the like.

Subsequent processing: Phospholipids or lecithin present in crude soybean oil precipitate during storage, leading to deterioration during oil use. Degumming involves the addition of small amounts of water or steam resulting in hydration of phospholipids and subsequent precipitation. To improve this hydration, acidic catalysts are optionally added with water. The deposited phospholipid is separated by centrifugation and dried under vacuum.

Step 6: Alkali refining is carried out to remove free fatty acids which impair the thermal stability of the oil. Alkali refining of degummed soybean oil removes free fatty acids, residual phospholipids, and pigments. Alkali refining neutralizes free fatty acids by the addition of caustic soda, soda ash, and combinations of these. Alkali needs to be done carefully to prevent further deterioration of the oil. The neutralized free fatty acid or soap is removed by centrifugation or precipitation. This alkali-refined oil is further washed with water to remove all residue, alkali,
The soap is removed and then dried.

Step 7: Bleaching is to adsorb and remove the dyes and pigments in the oil with activated carbon or the like. The bleach is simply dispersed in the oil and removed by filtration. The bleached oil is sent to a hydrogenation unit or a deodorizer depending on the application. Foods that require oxidative stability, margarine, bakery shortening, etc. require hydrogenation.

Step 8: Hydrogenation of vegetable oil substitutes for animal fat. Also, various vegetable oils are substituted with soybean oil. This hydrogenation is carried out by purging the oil with hydrogen gas at high temperature and high pressure in the presence of a catalyst. In this case nickel is used as a catalyst. The addition of hydrogen to fat saturates the molecular structure. The degree of saturation depends on the time, temperature and pressure during hydrogenation.

Step 9: Deodorization of oil is for removing undesired odor components, and thereby makes the food odorless and accompanied by a pleasant aroma. Deodorization is carried out with steam at high temperature and under vacuum to evaporate undesired odor components.

Step 10: Dewaxing is performed on the lightly hydrogenated oil used as salad oil.
This oil must remain transparent at refrigeration temperatures with oxidative stability. Dewaxing is cooling of oil,
It is carried out by filtration of cloudy components.

Step 11: Refined soybean oil is a highly unsaturated oil, which develops a unique aroma and odor after storage (called paint odor, fishy odor, etc.). The generation of such an odor is also called reversion.
This is due to the oxidation of linolenic acid and other acid components of oil. Exposure to air during processing, controlled hydrogenation to partially saturate the linolenic acid promotes the tendency of soybean oil to revert. A metal ion sequestering agent, such as citric acid, is occasionally added during the deodorizing step to deactivate oxidation-promoting metals such as iron and copper. Antioxidants may also be used.

Next, general steps for refining vegetable oil will be shown.

Step 1: Crude oil (eg peanut, soybean,
Pump sunflower, corn, cottonseed, etc.) to an external storage tank.

Step 2: The oil is transferred from the storage tank to a day tank having a neutralization site, where free fatty acid in the oil is neutralized by adding and mixing caustic soda under controlled conditions to carry out caustic refining. The neutralized free fatty acid (soapstock) is treated with phosphoric acid to first remove the gum in the oil. Then, the oil is washed to remove the residual soap, and further vacuum drying is performed.

Step 3: Bleaching is carried out under vacuum with the addition of a bleaching agent, the lightly colored bleaching oil is filtered, then transferred to a buffer tank and the next step is deodorization.

Step 4: Absolute pressure 2 to 6 mmH in the deodorizing step
g, temperature 220-275 [deg.] C. in a deodorizer, removing steam is passed through the oil. This method is semi-continuous. The deodorized oil is partially cooled, subjected to "polishing filtration" and then further cooled.

Step 5: The refined, bleached and deodorized cooking oil is filled in at the final stage of the step.

1 and 2 will be described below.

FIG. 1 illustrates the production of crude soybean oil from soybeans. Soybeans are first received, dried, washed and stored. The soybeans are then ground, for example by means of a corrugated roller. The ground soybeans are threshed, flaked, and solvent extracted using a continuous convection percolation extractor. Crude soybean oil is collected after the stripper has recovered the solvent.

In FIG. 1 a solvent condenser for hexane is shown in communication with the extractor. This condenser generally uses water.

FIG. 2 illustrates the production of refined salad oil, margarine and shortening oil. First, degumming of crude soybean oil is performed with water / steam to remove lecithin to obtain a degummed oil. The degummed oil is then alkali refined with caustic soda to form soap and a neutralized oil is obtained. This is then bleached with activated carbon, activated soil, etc. to form a cake and bleached oil. The bleached oil is hydrogenated and deodorized as shown in FIG. 2 to obtain refined salad oil, margarine, or shortening oil.

According to the invention, xenon, krypton,
Any noble gases such as argon, neon significantly inhibit oxidation during the production of seed oils and other vegetable oils. Helium is ineffective, however, mainly because of its low solubility and its tendency to be easily scattered from the device. However, helium can be used as a carrier gas. These gases can be applied at any stage of the manufacturing process in which oxidation usually occurs, and a remarkable effect can be obtained.

Although the application of this gas can obtain a remarkable effect by applying it to each of the above-mentioned steps, it is preferable to apply the method of the present invention to at least two steps, and more preferably to all the steps. Applying the method of the present invention in the process.

Although any rare gas can be applied, argon is more preferable because it has good solubility, exhibits excellent effects due to latent molecular properties, and is inexpensive. The application of this argon is sparging, pressure superimposition, pressure treatment, low temperature introduction,
Vacuum treatment followed by gas introduction, temperature swing of oil to cool degassed heated oil steam or pool by simultaneous introduction of gas, blanketing, introduction into covered equipment, or other means It could be done, and in reality could be done in the pilot.

The combination of argon and other rare gases (except helium) is used when there are special circumstances such as when it is difficult to completely saturate most of the process with argon, or when it is not preferable. Only more effective. For example, in high value oils, a gas mixture of 0.1-100% krypton or xenon in argon could be successfully finished and stored. In the low-value, high-volume production process of corn oil and soybean oil, the use of argon alone causes no problem.

This noble gas is effective in the presence of oxygen in a limited range. The effect of the noble gas is still effective even when the oxygen content as a% of saturation in the solution is in the range of 0.001 to 5%, or in the application atmosphere of 0.001 to 5%. Oxygen content of 5 in atmosphere
In the range of 10%, the effect is remarkably reduced, but some improvement can be seen depending on the conditions. 10-2
At 0%, the effect gradually disappears, and at 30%, no effect is seen. In a solution having an oxygen content of 5 to 100%, a considerable effect of a rare gas can be seen, but the effect becomes descent.

The present invention is effective for all seed oils and vegetable oils obtained by extraction or pressing.

In the present specification, the "rare gas" means a gas containing argon, xenon, krypton and neon, and since helium is also easily scattered, it can be used. Radon cannot be used due to its dangerous radioactivity.

According to the present invention, argon, xenon, krypton and neon can be used alone or in any combination. For example, a binary mixture of argon-xenon, krypton-xenon, xenon-neon and a ternary mixture of argon-xenon-krypton can be used.

As described above, the rare gas can be used alone or in combination, but it may contain one or more other carrier gases. As examples of the carrier gas, nitrogen, carbon dioxide, nitrous oxide, and helium can be used, and oxygen can also be used if the concentration is sufficiently low.

The effect of the present invention is that the pressure is close to vacuum, about 10 ^−8.
Can be obtained for pressures in the range of up to about 100 atmospheres, but it is generally preferred to use in the range of about 0.001 to 3 atmospheres. In addition, the temperature range is
The storage temperature of edible oil can be applied in the same range as various processing temperatures. For example, it is in the range of freezing temperature to cooking temperature. However, room temperature or lower temperatures are generally used for storage.

In the present invention, it is desirable to use an inexpensive production plant off thorium gas of about 90% by volume of krypton and 10% by volume of xenon, or Ne: He of 1: 1.

Furthermore, it is preferable to use a mixture containing an effective amount of a rare gas in deoxygenated air. By deoxygenated air is meant air containing less than 15% by volume oxygen, preferably less than 10% volume, more preferably less than 5% volume.

In the present invention, the gas or gas mixture is used as a gas, introduced into a drink, edible oil, housed in a headspace, or contained in a storage means to form the atmosphere. be able to.

In the case where a non-colored product is desired,
The color improvement in the oil is significant and O.
C. S. Can easily meet standard best color guidelines.

According to the blind taste test of oil in the case of soybean oil, which is desired to have no taste at all, the scent improvement is also remarkable.

Noble gases such as argon, xenon, krypton, and neon are used alone or in any combination, or they are mixed with nitrogen, a small amount of oxygen, carbon dioxide, and nitrous oxide, and liquid foods and drinks under the conditions are used. The improvement in the effect of inhibiting oxidation in storage is remarkable as compared with the one using nitrogen.

The effects of the present invention have been proved to be effective in a wide range of temperatures including cooking, sterilization, freezing, refrigeration and freezing. The same was true at low pressure or high pressure.

The present invention will be described below with reference to examples.

Example 3 Seed oil was made in the laboratory from soybean, corn, flaxseed, sunflower, safflower, rapeseed (or canda), cottonseed, peanut. Furthermore, cutting oil, chaoul gram oil, castor oil, olive oil were prepared as seeds and oils, and various commercially available seeds and vegetable oils were used to evaluate certain points in the production process. Targets for this evaluation included storage, heating, pressurization, addition, oxygen, and transport during the manufacturing process.

The two example processes were evaluated with the utmost care. That is, treatment of corn oil and treatment of soybean oil. Each of these steps was designed to be a small pilot scale pilot plant, and oil was obtained from corn grain and soybeans, much like a large scale manufacturing plant.

Oil quality is evaluated as “Official”.
Recommended Practices of
the American Oil Chemist
s'Society, 4th edition, 1991, Suppl
The tests included the following items.

Peroxide Color Refractive Index TOTOX Fat Stability (Active O ₂ ) Anididine Value Free Fatty Acids Accelerated Oxidation Other tests include:

Flavor test (standard sensory panel for aroma and scent) Gas chromatography / mass spectral analysis for aroma and scent components gc / ms, high performance liquid chromatography (HPLC)
And Thin Layer Chromatography (TLC) All tests were performed with oils processed and stored under the following atmospheres.

1. Air 2. Oxygen 3. Nitrogen 4. Carbon dioxide 5. Argon 6. Neon 7. Krypton 8. Xenon 9. Helium In addition, the tests were carried out with a mixture of noble gases. For example, a binary gas mixture and a binary gas mixture (for example, 90:
10Ar: Xe; 90:10 (90: 10Ar: X
e): (Ne)) was performed on at least one of each oil.

In addition, tests were conducted using the above 3-9 gases and combinations thereof, to which oxygen was added at 0.001%, 0.01%, 0.1%, 1.0% of the final composition. ,
2.0%, 3.0%, 5.0%, 10.0%, 15.0
%, 20.0%, 25.0%, 50.0%, 90.0%
To be added.

Further, the pressure was changed from vacuum to 100 atm.

In addition, the processing temperature is lower than that of the usual process (below the freezing temperature of the sample, at least -20).
It was carried out in a wide range from 0 ° C) to a higher temperature than the usual process (temperature higher than the complete thermal decomposition point of the sample, maximum + 1000 ° C).

In addition, a wide range of physical parameters were evaluated and handled in each experiment. For example, pH,
These include temperature, pressure, salt and ion concentrations, water content, sample aging, processing time, protein content, and physical shearing of the sample.

The best results obtained for the following tests and oil pairs are given as% of fully oxidised (oxygen saturated sample). These results were similar for samples taken at 30, 60, 90, 120 days after storage during processing, when corrected for the degree of oxidation of oxygen samples. Greater improvement was observed for longer storage times because oxidation is an ongoing process.

Tests: 1. Peroxide value <1.0 mEq / kg = no oxidation,
10 = oxidation 2. Fat stability (active O ₂ ) 3. Anisidine value <2.0 = no oxidation 4. Color 5. GC / MS fragrance 6. Free fatty acid 0.05 = no oxidation Gas used: 1. Oxygen 2. Air 3. Nitrogen 4. Carbon dioxide 5. Argon 6. Neon 7. Krypton 8. Xenon 9. helium

[0278]

[Table 3] In all cases, the combination of argon with xenon, krypton or neon showed some improvement over the argon alone. Further, in all examples, when oxygen was added to argon, xenon, krypton, or neon, the effect decreased linearly when the added amount was 5% or more, and the added amount was 0.001 to 0.001. 5
The effect decreased more exponentially at the concentration of%.

In each test of the other oils,
Similar results were obtained when expressed as a% of the maximum observed oxidation, but the actual values were different for each example.

As described above, the present invention provides a method for preserving seed oil or vegetable oil by contacting with the above-mentioned gas in storage.

The present invention further provides a method for inhibiting the oxidation of enzymes or other causes by contacting seed oil or vegetable oil with the above gas. This "oxidation by other causes" means all other forms of oxidation than by enzymes. This oxidation may be due to an internal oxygen donor in air or oil.

In the present specification, "substantially" means at least 75% or more, preferably 95% or more. This applies not only to the storage period, but also to the capacity of the storage means.

Although the present invention has been described above, naturally other modified examples are also included in the scope of the present invention.

[Brief description of drawings]

1 is a UV / VIS spectrogram of the oxidation of beer after 30 days storage under the indicated different gases.

FIG. 2 is a GC / MS chromatogram of beer volatiles after storage for 30 days under argon.

Figure 3: G of beer volatiles after 30 days storage under nitrogen
C / MS chromatogram diagram.

Figure 4: G of beer volatiles after storage under oxygen for 30 days
C / MS chromatogram diagram.

FIG. 5 is a GC / MS chromatogram of orange juice aroma volatiles after storage under argon for 30 days.

FIG. 6 is a GC / MS chromatogram diagram of orange juice aroma volatiles after storage for 30 days under argon.

FIG. 7: GC / MS chromatogram of orange juice aroma volatiles after 30 days storage under argon.

FIG. 8 is a GC / MS chromatogram diagram of orange juice aroma volatiles after storage under nitrogen for 30 days.

FIG. 9 is a GC / MS chromatogram of orange juice aroma volatiles after storage under nitrogen for 30 days.

FIG. 10: GC / MS chromatogram diagram of orange juice aroma volatiles after storage under nitrogen for 30 days.

FIG. 11: GC / MS chromatogram of orange juice aroma volatiles after storage under oxygen for 30 days.

FIG. 12 is a GC / MS chromatogram diagram of orange juice aroma volatiles after storage under oxygen for 30 days.

FIG. 13 is a GC / MS chromatogram diagram of orange juice aroma volatiles after storage for 30 days under argon.

FIG. 14: GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 15 is a GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 16 is a GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 17 is a GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 18 is a GC / MS chromatogram diagram of beer volatiles after storage under oxygen for 30 days.

FIG. 19 is a GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 20: GC / MS chromatogram of beer volatiles after storage under oxygen for 30 days.

FIG. 21 is a GC / MS chromatogram of beer volatiles after storage under nitrogen for 30 days.

FIG. 22 is a GC / MS chromatogram diagram of beer volatiles after storage for 30 days under nitrogen.

FIG. 23 is a GC / MS chromatogram of beer volatiles after 30 days storage under nitrogen.

FIG. 24 is a GC / MS chromatogram of beer volatiles after storage under nitrogen for 30 days.

FIG. 25 is a GC / MS chromatogram of beer volatiles after 30 days storage under nitrogen.

FIG. 26 is a GC / MS chromatogram of beer volatiles after storage under nitrogen for 30 days.

FIG. 27 is a GC / MS chromatogram of beer volatiles after storage under nitrogen for 30 days.

28 is a GC / MS chromatogram of beer volatiles after storage under argon for 30 days.

FIG. 29 is a GC / MS chromatogram of beer volatiles after storage under argon for 30 days.

FIG. 30: GC / MS chromatogram of beer volatiles after 30 days storage under argon.

FIG. 31 is a GC / MS chromatogram of beer volatiles after storage under argon for 30 days.

FIG. 32 is a GC / MS chromatogram of beer volatiles after 30 days storage under argon.

FIG. 33 is a GC / MS chromatogram of beer volatiles after 30 days storage under argon.

FIG. 34 is a GC / MS chromatogram of beer volatiles after storage under argon for 30 days.

FIG. 35 is a diagram schematically showing a method for producing soybean oil from soybean.

FIG. 36 schematically illustrates a method for producing refined salad oil, refined margarine or shortening oil from crude soybean oil.

FIG. 37 schematically illustrates a method for producing orange juice from oranges.

FIG. 38 shows a GC / MS of orange juice aroma volatiles under argon.

FIG. 39 shows a GC / MS of orange juice aroma volatiles under nitrogen.

FIG. 40 shows a GC / MS of orange juice aroma volatiles under oxygen.

Claims (23)

[Claims] 1. A method for improving the aroma and flavor of a beverage or an edible oil or both, wherein the food and / or edible oil is at least partly treated and / or preserved thereof with a noble gas or noble gas. A method characterized by contacting a gas mixture or a gas mixture containing at least one noble gas and a carrier gas. 2. The method of claim 1, wherein the beverage is selected from the group consisting of citrus fruit juice, beer and vegetable oil. 3. The method according to claim 1, wherein the noble gas is argon, neon, krypton, and / or xenon. 4. A process according to claim 1, wherein the mixture contains at least one noble gas and deoxygenated air. 5. A seed oil or vegetable oil or precursor thereof in the containment means, or in the containment means containing it, selected from the group consisting of argon, krypton, xenon, neon and mixtures thereof. Injecting a gas or gas mixture containing one and substantially saturating the seed oil or vegetable oil or precursor thereof with said gas or gas mixture, in said container of said seed oil or vegetable oil or precursor thereof 5. Saturation is maintained substantially throughout the volume of the seed oil or vegetable oil or precursors thereof or storage means thereof during substantially all periods of storage at. A method for improving the method for producing a seed oil or a vegetable oil or a precursor thereof according to any one of claims. 6. A seed or vegetable oil or precursor thereof in the containment means, or in the containment means containing it, selected from the group consisting of argon, krypton, xenon, neon and mixtures thereof. Injecting a gas or gas mixture containing one and substantially saturating the seed oil or vegetable oil or precursor thereof with said gas or gas mixture, in said container of said seed oil or vegetable oil or precursor thereof 6. Saturation is maintained substantially over the volume of the seed oil or vegetable oil or their precursors or their containment means during substantially all of the period of storage at. A method for controlling oxidative deterioration of seed oil or vegetable oil or their precursors according to any one of the items. 7. A citrus juice or precursor thereof in the containing means, or in a containing means containing it,
Injecting a gas or gas mixture containing one selected from the group consisting of argon, krypton, xenon, neon and mixtures thereof to substantially saturate the citrus juice or its precursor with the gas or gas mixture, 5. The saturation is maintained over the volume of the containment means during substantially all of the storage of the citrus juice or precursor thereof in the containment vessel.
A method for improving aroma and / or flavor of citrus juice or a precursor thereof according to any one of 1. 8. During the method of producing citrus juice,
A gas or gas containing one selected from the group consisting of argon, krypton, xenon, neon and a mixture thereof in the citrus juice or its precursor in the containing means or in the containing means containing the same. Injecting the mixture and substantially saturating the citrus juice or its precursor with the gas or gas mixture, and substantially during the period of the method by which the citrus juice or its precursor is produced, the volume of the containing means. A method for improving the process for producing citrus juice according to any one of claims 1 to 4 or claim 7, characterized in that said saturation is maintained substantially throughout 9. A method according to claim 1, wherein the gas is injected in gaseous form, in liquid form or in both forms. 10. The process according to claim 1, wherein seed oil, vegetable oil, citrus juice, beer or their precursors are saturated to more than 50% by volume of their full saturation. 11. A seed oil, a vegetable oil, a citrus juice, a beer or a precursor thereof is saturated to more than 70% by volume of its full saturation.
Method described in section. 12. The method according to claim 1, wherein seed oil, vegetable oil, citrus juice, beer or their precursors are saturated to more than 80% by volume of their full saturation.
Method described in section. 13. A method according to any one of claims 1 to 12, wherein the carrier gas is selected from the group consisting of nitrogen, oxygen, nitrous oxide, air, helium, carbon dioxide or mixtures thereof. 14. A gas mixture or component of a gas mixture comprising about 90 to 99% by volume argon and 1 to 10% by volume Xe and / or Kr. Method. 15. A method according to any one of the preceding claims, wherein the gas mixture or components of the gas mixture comprises about 50% by volume Ne and 50% by volume He. 16. The gas mixture or components of the gas mixture comprises about 5 to 10% by volume of Xe, and 90 to 9
16. A method according to any one of claims 1 to 15 comprising 5% by volume Kr. 17. The method according to claim 1, wherein the temperature is 0 ° C. to 40 ° C. 18. The method according to claim 1, wherein the temperature is 10 ° C. to 30 ° C. 19. The pressure is less than 10 atm.
20. The method according to any one of 1 to 19. 20. The method according to claim 1, wherein the pressure is less than 3 atm. 21. The method according to claim 1, wherein the pressure is 1 to 2 atmospheres. 22. The method according to claim 1, wherein the pressure is about 1 atmosphere. 23. The group of seed oils consisting of soybean oil, rapeseed oil, cottonseed oil, peanut oil, tung oil, tajushi oil, castor oil, olive oil, sunflower seed oil, safflower oil, corn oil and flaxseed oil. 23. selected from among
The method according to any one of 1.