JPH10185375A - Manufacture of ozone containing ice - Google Patents

Abstract

PROBLEM TO BE SOLVED: To perform a stable and low cost manufacture of ice containing ozone of high concentration which is suitable for a long period storing or a holding of freshness of perishable foods such as fresh fishes, vegetables, fruits and the like. SOLUTION: Pure water is processed with electrolysis to produce water containing ozone which is completely dissolved with a concentration of several ppm to several tens ppm or more. This water containing ozone is sent to an ice making system 5 while being preliminary cooled at a temperature of about 0 to 5 deg.C in a tank 2 having a cooling means 3. As the water is rapidly cooled under application of liquid refrigerant of -25 deg.C or less in such a way that the water is frozen within 3 minutes, ice having a high ozone concentration is manufactured. An ozone concentration of water containing ozone is preliminary adjusted in such a way that a concentration of ozone remaining in water produced by melting ozone containing ice may become more than 1ppm. In addition, ozone-containing water produced from pure water and sea water having a predetermined concentration of salt are mixed with each other to make sea water having a high concentration of ozone. When sea water containing ozone is rapidly cooled with liquid refrigerant of -25 deg.C or less to freeze within three minutes, sea water ice having a high concentration of ozone, not in a sherbet state is manufactured.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing ice containing a high concentration of ozone using fresh water or seawater, for example, sterilization in the preservation and transportation of fresh foods such as fresh fish, vegetables, fruits and the like and fresh flowers. The present invention relates to a method for producing ozone-containing ice used for maintaining freshness and deodorizing.

[0002]

2. Description of the Related Art In general, a method of cooling food using ice has been known for a long time as an effective means for preserving food. However, cooling with ice reduces the temperature of the food from 0 to
It is only lowered to about 5 ° C., which is unsuitable for long-term storage. In addition, since ozone exerts a strong sterilizing and deodorizing action due to its strong oxidizing power, and is self-decomposing into oxygen, it is safe, so it is effective for sterilization, freshness maintenance and deodorization in storage and transportation of fresh food. Is also well known in the art. However, using gaseous ozone as it is for preserving fresh food is inconvenient in handling.

Therefore, recently, a method of using ozone-containing water obtained by dissolving ozone in water or ozone-containing ice obtained by freezing the same has been proposed. In general, ozone-containing water is generated by a method in which ozone is generated using a conventional ozonizer by aerial discharge of air or oxygen, and the ozone is brought into gas-liquid contact by bubbling or the like to be dissolved in water.

However, since ozone is difficult to dissolve in water, the ozone-containing water generated by the above-mentioned conventional method has an ozone concentration of at most about 4 to 5 ppm, and it is difficult to produce a higher-concentration ozone-containing water. Met. In addition, since the ozone-containing water is in a state in which a large amount of ozone is dispersed in water in the form of fine bubbles, the ozone-containing water is diffused into the air in a short time, and the ozone concentration is reduced. In addition, a large amount of undissolved ozone is released into the atmosphere, which is not only inefficient, but also requires the provision of equipment such as an ozone decomposition catalyst to remove it. In addition, air generates NOx when generating ozone, and thus is not preferable as a raw material for ozone. On the other hand, in the case of oxygen, it is necessary to attach an oxygen cylinder or an oxygen producing device to the ozonizer.

[0005] Therefore, one joint applicant of the present application, as described in JP-A-3-267390, superimposes an anode electrode and a cathode electrode with a solid electrolyte membrane interposed therebetween and applies an anode to which a DC voltage is applied. A method was proposed in which water supplied to the electrode side was electrolyzed to directly generate ozone-containing water. Furthermore, a technique for improving this has been developed and disclosed in
As described in each of the publications Nos. 77 and 134678,
By forming the anode electrode and the cathode electrode to be overlapped with the solid electrolyte membrane sandwiched therebetween in a wire netting, and by lath netting on their outer surfaces and sandwiching them with a jacket from the outside,
The frequency of gas-liquid contact is increased so that a higher concentration of ozone-containing water can be obtained.

However, the half-life of ozone dissolved in ozone-containing water is very short, and in a test conducted by the present inventor, it was about 30 minutes for ozone-containing water at 10 ° C. at normal pressure. Therefore, even if such ozone-containing water is used as it is in fresh food, it is difficult to obtain a sufficient freshness maintaining / sterilizing effect.

On the other hand, ozone-containing ice gradually generates ozone while melting, so that the food can be cooled and the sterilizing effect of ozone can be maintained for a long period of time. Conventionally, ozone-containing ice is disclosed in, for example, Japanese Patent Application Laid-Open No. 60-295.
As described in JP-A-69, an ozone is generated by a normal ozonizer by means of aerobic discharge of air or oxygen, and dissolved in water by bubbling or the like to produce ozone-containing water, which is frozen by a normal ice making device. The method of manufacturing by making it is common.

[0008]

However, in the above-mentioned conventional method for producing ozone-containing ice, it was difficult to obtain high-concentration ozone-containing ice because the ozone concentration of the raw water was low. Further, in a conventional ice maker used conventionally, it takes a long time to freeze ozone-containing water, and during that time, the ozone concentration further decreases. Therefore, the ozone-containing ice obtained by the conventional method has an ozone concentration of at most 0.2 to 0.5 pp when it is melted.
m. For this reason, it was practically impossible to sterilize and maintain fresh food for a long period of time.

Further, Japanese Patent Application Laid-Open Nos. 8-134677 and
Even with high-concentration ozone-containing water generated by the method described in each of the publications 4678, the above-described conventional ice making method has a problem that the ozone concentration is significantly reduced in the freezing process. For this reason, it is practically difficult to produce ice with a high ozone concentration that enables sterilization and freshness maintenance of fresh food for a long period of time, and has not been put to practical use until now.

[0010] In particular, it is known that the storage of fresh fish and other marine products at an ice temperature, that is, around 0 ° C, is effective for maintaining freshness for a relatively long period of time. Is said not to change. With ice made of fresh water, the storage temperature of food is only about 0 to 2 ° C even when immersed in ice, but if you use ice made of seawater with a freezing point lower than fresh water,
This is advantageous because it can be stored at lower temperatures. Further, in the case of marine products, it is advantageous to use ice having substantially the same composition as seawater in terms of maintaining its quality. However, seawater has an ice temperature of about −3 to −4 ° C., and it is difficult to freeze the seawater with the above-described ordinary ice making device, and at most, it is only in a sherbet shape. As far as the inventor of the present application knows, it has not been practically used to produce ozone-containing ice by freezing ozone-containing seawater or to use it for preserving and transporting foods.

Therefore, the method for producing ozone-containing ice according to the present invention has been made in view of the above-mentioned conventional problems, and its object is to provide a comparative method which does not require large, complicated and expensive equipment. Simple equipment and equipment can produce high ozone-concentrated ozone-containing water and freeze it without substantially lowering its ozone concentration, thereby enabling fresh foods such as fresh fish and vegetables and fruits It is an object of the present invention to provide a practical method capable of stably and at low cost producing ozone-containing ice containing high-concentration ozone suitable for long-term storage and keeping freshness.

Further, the object of the present invention is to make practical use of seawater ice which can achieve a storage temperature below freezing point and contains a high concentration of ozone so as to be particularly suitable for preservation and freshness maintenance of fresh marine products such as fresh fish. It is an object of the present invention to provide a method that can be manufactured easily and stably at low cost by simple equipment and apparatus.

[0013]

The method for producing ozone-containing ice according to the present invention is intended to achieve the above-mentioned object, and is provided by directly dissolving ozone generated by electrolysis of water in the water. It is characterized by comprising a process of generating ozone-containing water and a process of freezing by rapidly cooling the ozone-containing water using a liquid refrigerant.

[0014] According to the present invention, compared with the conventional ozone gas bubbling, several ppm by electrolysis of water.
Ozone-containing water having a high ozone concentration of about 10 ppm to about 10 ppm and a maximum of about 30 ppm, and in which dissolved ozone is not easily reduced, can be obtained easily and inexpensively by a relatively simple apparatus, and furthermore, has a low freezing point By appropriately selecting the liquid refrigerant, the ozone-containing water can be frozen in a short time of only about several minutes while maintaining its ozone concentration at a high level. Ice is obtained.

In this case, it is advantageous to rapidly cool the ozone-containing water so that the ozone-containing water can be frozen within 3 minutes, because ozone-containing water can remain in an amount of 90% or more. The inventor of the present application has found that the above liquid refrigerant may be used. As such a liquid refrigerant, ethylene glycol, ethanol, methanol, acetone and the like are suitable.

Further, when the ozone-containing ice produced has an ozone concentration of 1 ppm or more dissolved in the water in which the ozone-containing ice is melted, the ozone-containing ice has an effective bactericidal action when used in fresh foods and the like. Can work to. this is,
When the ozone-containing water is generated, the ozone concentration can be easily adjusted by previously adjusting the ozone concentration to a high level as described above.

Further, according to the present invention, until the generated ozone-containing water is rapidly cooled, the ozone-containing water is preferably cooled to a temperature close to ice temperature.
Precooling at a temperature of ５5 ° C. is advantageous because it allows less ozone to be spontaneously vaporized and released from the ozone-containing water and keeps the ozone concentration higher.

When seawater is electrolyzed using the above-described method of the present invention, not only ozone but also NaCl contained therein is decomposed to produce chlorine gas and chlorine compounds such as hypochlorous acid. Therefore, it is necessary to provide a facility for removing the same, which is not particularly suitable for producing ozone-containing ice used for fresh foods and the like. Therefore, according to the present invention, a process of generating ozone-containing water by directly dissolving ozone generated by electrolysis of water into the water, and a process of mixing the generated ozone-containing water with seawater to mix ozone-containing seawater And a method of rapidly cooling ozone-containing seawater by using a liquid refrigerant to freeze the ozone-containing seawater, thereby providing a method for producing ozone-containing ice.

By mixing ozone-containing water and seawater in this way, seawater with a high ozone concentration can be obtained without producing by-products of chlorine compounds. It is possible to produce seawater ice with a high ozone concentration. At this time, the seawater is diluted by being mixed with the ozone-containing water. If the salt concentration is adjusted in advance, the ozone-containing seawater and / or ozone-containing ice can be formed to have a desired salt concentration. As the seawater mixed with the ozone-containing water, artificial seawater can be used for all or part thereof.

In the case of ozone-containing seawater, precooling is preferably performed at a temperature near the ice temperature, for example, at a temperature of 0 to 5 ° C. during the period from generation to rapid cooling in order to maintain a high ozone concentration. In particular, it is advantageous to freeze the ozone-containing seawater within 3 minutes when producing ozone-containing ice, since 90% or more of the ozone dissolved therein can remain, and for that purpose,- That the ozone-containing seawater may be frozen using a liquid refrigerant of 25 ° C. or less,
The present inventor has found out. As such a liquid refrigerant, similarly, ethylene glycol, ethanol, methanol, acetone and the like are suitable. Further, the concentration of ozone remaining in the seawater in which the produced ozone-containing ice is melted is 1 p.
When it is not less than pm, this ozone-containing ice is advantageous because its bactericidal action can be effectively exerted particularly when used for marine products.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents will be described below with reference to an embodiment shown in the drawings. FIG. 1 schematically shows a first embodiment of an ice making system for carrying out the method for producing ozone-containing ice according to the present invention. In the present embodiment, water is supplied to the ozone-containing water generator 1 to generate high-concentration ozone-containing water. The ozone-containing water generator 1 is disclosed in Japanese Patent Application Laid-Open No. 8-134.
As described in the specification of Japanese Patent No. 677, a wire mesh-like anode electrode made of a noble metal and a wire mesh-like cathode electrode are stacked on both sides of a thin sheet electrolyte membrane made of, for example, a fluorine-based cation exchange membrane. In addition, lath nets having relatively large mesh-like slits are superimposed on their outer surfaces, and these are sandwiched by jackets from both sides, so that water flows on both sides of the electrolytic membrane in the surface direction. A complicated labyrinth-like narrow flow path is formed.

When a predetermined voltage is applied between the two electrodes while supplying water to the channel, the water is electrolyzed on the anode electrode side to generate oxygen and ozone. The generated ozone violently causes gas-liquid contact in the water while passing through the maze-shaped flow path as it is, and directly dissolves in the water flowing in the flow path to generate high-concentration ozone-containing water. The ozone concentration of the ozone-containing water can be appropriately adjusted depending on the voltage applied to the electrode and the application time, and is usually several ppm.
A high ozone concentration of about 10 to 10 ppm and a maximum of about 30 ppm can be obtained. It is suitable to use pure water for this raw material water in consideration of by-products that may be generated by electrolysis. However, even if tap water, natural water from rivers and lakes or water containing various impurities and electrolytes such as calcium are treated in advance by a suitable treatment means such as a filter or an ion exchange resin, the generation of ozone-containing water can be achieved. Can be used for

In this ozone-containing water, since ozone is completely dissolved in water, the rate of vaporization and exit of ozone is lower than that of conventional ozone gas. According to the experiments of the present inventor, oxygen is produced from the atmosphere using the conventional technology, ozone gas is generated by a high-electrolysis-type ozone generator, and ozone-containing water generated by bubbling in water is 10 ° C. at normal pressure. , The ozone concentration was reduced by half in 12 minutes. In contrast, the ozone-containing water produced according to the present invention had a half-life of the ozone concentration of 30 minutes.

The produced ozone-containing water is supplied to a tank 2
To be temporarily stored. The tank 2 is a closed type and is always pre-cooled by a suitable cooling means 3 so as to maintain a low temperature of 0 to 5 ° C. at which the ozone-containing water inside does not freeze. This slows the rate at which ozone dissolved in the ozone-containing water evaporates and diffuses into the atmosphere,
The ozone concentration can be kept high. The ozone-containing water in the tank 2 is supplied to the ice making device 5 via the pipe 4. The conduit 4 is similarly cooled to a low temperature of 0-5 ° C. by suitable cooling means to prevent ozone in the ozone-containing water from escaping during transfer.

The ozone-containing water supplied to the ice making device 5 is
It is poured into a large number of ice cans of appropriate shape and volume as in conventional ice making equipment. The ice can of this embodiment has a thin rectangular box shape with a width of about 10 mm in order to produce plate-like ice. It is advantageous that the ice can be sealed after injection of the ozone-containing water, since the release of ozone during cooling can be suppressed. The ice can is placed in a refrigerant tank that circulates a liquid refrigerant cooled to a temperature of −25 ° C. or lower by a conventional refrigerator, for example, a Brinechler refrigerator. In this embodiment, the liquid refrigerant is -10
Ethylene glycol, ethanol, methanol, acetone and the like which have sufficient fluidity even at a temperature of not more than ° C are used.

By immersion in such a liquid refrigerant, the ozone-containing water in the ice can is rapidly cooled, and can be frozen in only about 3 minutes or at most several minutes. In fact, if the liquid refrigerant is properly selected, it can be cooled at an extremely low temperature of about -135 ° C. In the case of the prior art, since the cooling temperature is at most about −10 ° C., it takes two to four hours at the earliest to make ice, and ozone is present as bubbles in the produced ice. On the other hand, according to the present invention, the ice is frozen in a very short time as described above,
By limiting the escape of ozone from the ozone-containing water during cooling, high-quality ozone-containing ice having a higher ozone concentration and no bubble ozone is obtained.

After a lapse of a predetermined time, the ice can is lifted up from the refrigerant tank by a crane or the like, transported to an ice melting tank, and warmed with hot water, as in the prior art. Plate-shaped ozone-containing ice is separated and taken out of the ice can and transported and stored in an ice storage. In another embodiment, different shapes and volumes of ice cans can be used to freeze ozone-containing ice into ice cubes or various desired shapes rather than plates. The ozone-containing ice thus produced can be crushed and used in an appropriate size and shape according to its use.

Further, the inventors of the present application have tested that even in the case of the ozone-containing water produced according to the present invention, it is necessary to freeze it within 10 minutes in order to retain 70% or more of ozone, and It has been found that it is necessary to freeze ozone within 3 minutes in order to leave 90% or more of ozone. And it was confirmed that ozone-containing water can be frozen within 3 minutes by using a liquid refrigerant cooled to a temperature of -25 ° C or lower as described above.

According to the inventors of the present invention, in particular, when used in fresh foods and the like, in order for ozone-containing water to effectively exhibit the sterilizing and deodorizing effects of ozone, ozone-containing water of 1 ppm or more, preferably 2 ppm or more. It was confirmed that the concentration was necessary, and it was further effective when the concentration was 4 ppm or more. Such an ozone concentration needs to be maintained when the ozone-containing ice is melted, but according to the present invention, when the ozone-containing water is generated by the electrolysis of water as described above, the ozone concentration is sufficiently reduced. Can be easily realized by quick freezing with a liquid refrigerant.

FIG. 2 schematically illustrates a second embodiment of an ice making system for producing ozone-containing ice according to the present invention using seawater. In this embodiment, seawater is supplied from a tank 6 to a tank 2 for storing ozone-containing water. Thereby, the ozone-containing water generated by the ozone-containing water generation device 1 and the seawater are mixed, and high-concentration ozone-containing seawater is generated in the tank 2.

The tank 2 is pre-cooled by the cooling means 3 so that the temperature of the ozone-containing seawater becomes 0 to 5 ° C. as in the first embodiment. The tank 6 is previously cooled by a suitable cooling means 7 so that the temperature of the seawater becomes 0 to 5 ° C. in accordance with the temperature of the ozone-containing water in the tank 2. Furthermore, it is more expedient if the line 8 from the seawater tank 6 to the tank 2 is likewise precooled.

The seawater in the tank 6 has its salt concentration adjusted in advance so that the ozone-containing seawater and / or the finally generated ozone-containing ice have a desired salt concentration. For example, when using ozone-containing ice for fresh seafood, it is advantageous to make the salt concentration approximately equal to that of natural seawater and about 2 to 5%. The salt concentration of seawater can be easily adjusted by using artificial seawater for all or part thereof.

The ozone-containing seawater in the tank 2 is supplied to the ice making device 5 through the cooled pipe 4 in the same manner as in the first embodiment, and injected into a large number of ice cans having appropriate shapes and volumes. The ice can of this embodiment also has a thin rectangular box shape with a width of about 10 mm in order to produce plate-like ice similarly to the above-described embodiment, and contains ozone so that the emission of ozone during cooling can be suppressed. It can be sealed after water injection. The ice can is arranged in a refrigerant tank in which a liquid refrigerant is circulated. Also in this embodiment, as the liquid refrigerant,
As in the first embodiment, ethylene glycol, ethanol, methanol, acetone or the like is used.

According to the present inventor, natural seawater is -3 to-
It has been confirmed that the ozone-containing seawater of the present invention freezes completely at -25 ° C, while it freezes at about 4 ° C. Therefore, in the present embodiment, the liquid refrigerant is cooled to a temperature of -25C or lower, preferably -50C or lower by a conventional refrigerator such as a Brineller refrigerator. Thereby, the ozone-containing seawater in the ice can is rapidly cooled and can be frozen in only about 3 minutes. In fact, when a suitably selected liquid refrigerant was cooled to an ultra-low temperature of -64 to -75 ° C, it could be frozen in about 1.5 minutes.

After a predetermined time has passed, the ice can is lifted out of the refrigerant tank by a crane or the like, and is heated by hot water in an ice melting tank. Plate-shaped ozone-containing ice is separated and taken out of the ice can and transported and stored in an ice storage. In addition, the ozone-containing ice can be frozen not into a plate shape but into ice cubes or various desired shapes by using ice cans having different shapes and volumes. Can be used after crushed ice. Ozone-containing ice is separated and taken out of the ice can,
It is transported and stored in an ice storage.

The ozone-containing ice produced from seawater in this way has a very high ozone concentration by freezing in a very short time, and is of high quality without bubble ozone. And when it melts,
Since the water returns to seawater having a predetermined salt concentration, it is particularly advantageous for preserving marine products.

Furthermore, the surface temperature of the ice frozen from ordinary seawater and the ice frozen from the ozone-containing seawater according to the present invention, even when the salt concentration is the same, is large when left in an atmosphere of normal temperature and normal pressure. It turned out there was a difference. In the case of ordinary seawater, the temperature is about -3 to -4C, whereas in the case of the ozone-containing seawater of the present invention, the temperature is maintained at -8 to -10C. Therefore, when the ozone-containing ice of the present invention made from seawater is used for fresh foods and the like, in combination with the sterilizing and deodorizing action of ozone, it can be used at a lower temperature and for a longer period in a fresher state. It becomes possible to save.

[0038]

【Example】

(Example 1) Using the ice making system of FIG. 1, fresh water was electrolyzed to produce ozone-containing water having an ozone concentration of 15 ppm at a rate of 10 liters per minute. This is supplied to the ice making device without pre-cooling, and the width is 10 mm and the volume is 500 m
When the mixture was poured into a 1 l ice can and rapidly cooled with a liquid solvent at -64 ° C, it was completely frozen in 1.5 minutes, and plate-like ozone-containing ice was obtained. The ozone concentration of the ozone-containing water before freezing was 8.5 ppm, and the ozone concentration after the ozone-containing ice was melted was 3.5 ppm. From this, it is considered that the ozone concentration of the generated ozone-containing ice was about 6 ppm.

(Example 2) In the same manner as in Example 1,
Ozone-containing water with an ozone concentration of 15 ppm in fresh water at a rate of 10 per minute
Produced in liters, it was pre-cooled and fed to the ice maker. When poured into an ice can with a width of 10 mm and a capacity of 500 ml and rapidly cooled with a liquid refrigerant at -63 ° C,
It was completely frozen in 1.5 minutes and plate-like ozone-containing ice was obtained. The ozone concentration of the ozone-containing water before freezing is 10.
At 3 ppm, the ozone concentration after melting the ozone-containing ice was 4.6 ppm. From this, it is considered that the ozone concentration of the generated ozone-containing ice was about 7.5 ppm.

Comparative Example 1 Ozone gas was generated using a conventional ozone generator and dissolved in fresh water by bubbling to produce ozone-containing water having an ozone concentration of about 5 ppm.
This was poured into a 500-ml ice can with a width of 10 mm, cooled to -15 ° C in a normal freezer, and completely frozen in about 2 hours. The ozone concentration of the ozone-containing water before freezing was 1.3 ppm, and the ozone concentration after melting the ozone-containing ice was only 0.1 ppm. From this, the ozone concentration of the generated ozone-containing ice is at most about 0.4 pp
m.

Example 3 In the same manner as in Example 1 above,
Ozone-containing water with an ozone concentration of 15 ppm from fresh water at 1 minute
It was produced at a rate of 0 liter, which was pre-cooled and supplied to an ice making device. The mixture was poured into an ice can having a width of 10 mm and a volume of 500 ml, and rapidly cooled using ethylene glycol at −30 ° C. as a liquid refrigerant. The mixture was completely frozen in about 3 minutes, and plate-like ozone-containing ice was obtained.

This is crushed and filled in a storage container made of polystyrene foam, and a fresh horse mackerel (Aji) is stored therein, sealed, left at room temperature and normal pressure for 1 day, and then opened to store the horse mackerel. The situation was evaluated. Furthermore, fresh aji was similarly stored in a storage container made of styrene foam using ordinary ice, and the storage condition after leaving for one day was evaluated. The results of the comparison are shown in Table 1 below. In each case, about 30% of the ice in the container was melted at the time of opening. Aji using the ozone-containing ice of the present invention maintained the freshness in almost the same fresh state as before storage, but with normal ice, progress of decay was observed.

[0043]

[Table 1]

(Example 4) Artificial seawater was mixed with natural seawater, and its salt concentration was adjusted to three times. This was precooled and mixed with twice the amount of ozone-containing water having an ozone concentration of 15 ppm produced in the same manner as in Example 1 to produce ozone-containing seawater having the same salt concentration as natural seawater. The ozone concentration of this ozone-containing seawater was 8.5 ppm. This is width 10
When poured into an ice can having a volume of 500 ml and rapidly cooled with a liquid refrigerant at -72 ° C, it was completely frozen in 2.5 minutes, and plate-like ozone-containing ice was obtained. Since the ozone concentration after melting the ozone-containing ice was 3.6 ppm, it is considered that ozone-containing ice having an ozone concentration of about 6 ppm was generated. The surface temperature of the ozone-containing ice was -7 ° C.

(Example 5) Natural ionized water and artificial seawater were mixed to prepare seawater whose salt concentration was adjusted to three times. In the same manner as in Example 4, precooled seawater and twice the amount of ozone-containing water having an ozone concentration of 15 ppm were mixed to produce ozone-containing seawater having the same salt concentration as natural seawater. The ozone concentration of this ozone-containing seawater was 8.6 ppm. This is poured into an ice can with a width of 10 mm and a capacity of 500 ml,
When rapidly cooled with a liquid refrigerant at -72 ° C., it was completely frozen in 2.5 minutes, and plate-like ozone-containing ice was obtained.
The ozone concentration after melting the ozone-containing ice is 3.7.
ppm, it is considered that ozone-containing ice having an ozone concentration of about 6 ppm was generated. The surface temperature of the ozone-containing ice was -100 ° C.

(Embodiment 6) In the same manner as in Embodiment 1,
Ozone-containing water having an ozone concentration of 10 ppm was generated from fresh water, and artificial seawater having a salt concentration of 10% was mixed at a ratio of 6: 4 to generate ozone-containing seawater having an ozone concentration of 6 ppm and a salt concentration of 4%. This is supplied to an ice making device, and the width is 10 m.
When poured into an ice can having a volume of 500 ml and rapidly cooled using ethylene glycol at −30 ° C. as a liquid refrigerant, it was completely frozen in about 2 minutes, and plate-like ozone-containing ice was obtained.

This is crushed and filled in a storage container made of styrene foam, and a fresh horse mackerel (aji) is stored therein, sealed, left at room temperature and normal pressure for 3 days, and then opened to store the horse mackerel. The situation was evaluated. Further, the same storage container made of styrene foam was used to fill fresh ozone containing ozone-containing ice produced using fresh water in Example 3 above, and filled with normal ice to obtain fresh aji. Prepare the saved one,
The storage condition after leaving each for 3 days was evaluated. The results of these comparisons are shown in Table 2 below. In each case, about 70% of the ice in the container was melted at the time of opening.

[0048]

[Table 2]

The sea buckwheat of the present invention using the ozone-containing ice with seawater maintained the freshness in almost the same fresh state as before storage. In comparison, the ozone-containing ice of Example 3 did not cause spoilage, but slightly decreased freshness.
On the other hand, with normal ice, the decay progressed considerably.

[0050]

Since the present invention is configured as described above, it has the following effects. According to the method for producing ozone-containing ice of the present invention, high-concentration ozone-containing water is directly produced by electrolysis of water which does not require a conventional oxygen supply facility or a facility for removing released ozone, and a liquid refrigerant. It can be frozen in a very short time by using, and it is practical because ice with high ozone concentration can be easily manufactured at low cost. Without corrosion
It is possible to provide consumers always fresh at low cost.

Further, according to the present invention, by mixing ozone-containing water obtained by electrolysis of water with seawater, seawater having a high ozone concentration is produced without producing a chlorine compound as a by-product, and the water is not sherbet-shaped. Since seawater ice with ozone concentration can be easily manufactured at low cost, the storage temperature below the freezing point and the sterilizing and deodorizing effects of ozone can be achieved at the same time, and in particular, fresh seafood is stored and transported in a fresh state. Can be.

[Brief description of the drawings]

FIG. 1 is a view schematically showing a first embodiment of an ice making system for carrying out a method for producing ozone-containing ice according to the present invention.

FIG. 2 is a view schematically showing a second embodiment of the ice making system.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Ozone-containing water generator 2 Tank 3 Cooling means 4 Pipe line 5 Ice making device 6 Tank 7 Cooling means 8 Pipe line

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C02F 1/78 C02F 1/78 C25B 1/30 C25B 1/30

Claims (14)

[Claims] 1. A process of generating ozone-containing water by directly dissolving ozone generated by electrolysis of water into the water, and a process of freezing by rapidly cooling the ozone-containing water using a liquid refrigerant. A method for producing ozone-containing ice, comprising: 2. The method for producing ozone-containing ice according to claim 1, wherein preliminary cooling is performed until the generated ozone-containing water is rapidly cooled. 3. The method for producing ozone-containing ice according to claim 2, wherein said ozone-containing water is pre-cooled at a temperature of 0 to 5 ° C. 4. The method for producing ozone-containing ice according to claim 1, wherein said ozone-containing water is rapidly cooled using a liquid refrigerant of -25 ° C. or lower. 5. The method for producing ozone-containing ice according to claim 4, wherein ethylene glycol, ethanol, methanol or acetone is used as the liquid refrigerant. 6. An ozone concentration of water obtained by melting the ozone-containing ice is 1 ppm or more.
6. The method for producing ozone-containing ice according to any one of claims 1 to 5. 7. A process for producing ozone-containing water by directly dissolving ozone generated by electrolysis of water into the water, and producing the ozone-containing seawater by mixing the produced ozone-containing water with seawater. And rapidly cooling the ozone-containing seawater using a liquid refrigerant to freeze the ozone-containing seawater. 8. The production of ozone-containing ice according to claim 7, wherein the salt concentration of the seawater mixed with the ozone-containing water is adjusted in advance so that the ozone-containing seawater has a predetermined salt concentration. Method. 9. The method for producing ozone-containing ice according to claim 8, wherein artificial seawater is used for all or part of the seawater mixed with the ozone-containing water. 10. The method for producing ozone-containing ice according to claim 7, wherein preliminary cooling is performed until the generated ozone-containing seawater is rapidly cooled. 11. The method for producing ozone-containing ice according to claim 10, wherein said ozone-containing seawater is pre-cooled at a temperature of 0 to 5 ° C. 12. The ozone-containing seawater is frozen by using a liquid refrigerant of −25 ° C. or lower.
12. The method for producing ozone-containing ice according to any one of claims 11 to 11. 13. The liquid refrigerant, comprising ethylene glycol,
13. The method for producing ozone-containing ice according to claim 12, wherein ethanol, methanol or acetone is used. 14. The method for producing ozone-containing ice according to claim 7, wherein an ozone concentration of the water obtained by melting the ozone-containing ice is 1 ppm or more.