WO2010047385A1 - オゾン氷製造方法及びオゾン氷製造装置 - Google Patents
オゾン氷製造方法及びオゾン氷製造装置 Download PDFInfo
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- WO2010047385A1 WO2010047385A1 PCT/JP2009/068261 JP2009068261W WO2010047385A1 WO 2010047385 A1 WO2010047385 A1 WO 2010047385A1 JP 2009068261 W JP2009068261 W JP 2009068261W WO 2010047385 A1 WO2010047385 A1 WO 2010047385A1
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- Prior art keywords
- ice
- oxygen gas
- ozone
- bubbles
- produced
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/36—Freezing; Subsequent thawing; Cooling
- A23L3/37—Freezing; Subsequent thawing; Cooling with addition of or treatment with chemicals
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25C—PRODUCING, WORKING OR HANDLING ICE
- F25C1/00—Producing ice
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B4/00—General methods for preserving meat, sausages, fish or fish products
- A23B4/06—Freezing; Subsequent thawing; Cooling
- A23B4/08—Freezing; Subsequent thawing; Cooling with addition of chemicals or treatment with chemicals before or during cooling, e.g. in the form of an ice coating or frozen block
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2201/00—Preparation of ozone by electrical discharge
- C01B2201/60—Feed streams for electrical dischargers
- C01B2201/64—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2201/00—Preparation of ozone by electrical discharge
- C01B2201/80—Additional processes occurring alongside the electrical discharges, e.g. catalytic processes
- C01B2201/82—Treatment with ultraviolet light
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25C—PRODUCING, WORKING OR HANDLING ICE
- F25C2400/00—Auxiliary features or devices for producing, working or handling ice
- F25C2400/12—Means for sanitation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2303/00—Details of devices using other cold materials; Details of devices using cold-storage bodies
- F25D2303/08—Devices using cold storage material, i.e. ice or other freezable liquid
- F25D2303/085—Compositions of cold storage materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention relates to a method for producing ozone ice containing ozone gas as bubbles in ice and an apparatus for producing ozone ice.
- ozone ice containing bubbles of ozone gas in ice has been used to refrigerate raw foods such as fresh fish and vegetables, as well as to sterilize, disinfect and deodorize them.
- ozone gas has been attracting attention as an alternative to other sterilizing agents such as chlorinated sterilizing agents because it does not worry about secondary contamination due to self-decomposition into oxygen.
- the ozone ice production methods devised so far can be broadly classified into two.
- One is a method of cooling and freezing water containing ozone gas as bubbles (see, for example, Patent Document 1), and the other is a method of compressing while supplying ozone gas to ice powder (see, for example, Patent Document 2). ).
- Patent Document 1 describes a method for producing ozone ice by cooling and freezing ozone water in which ozone is dissolved in a pressurized state.
- Patent Document 2 describes a method of producing ozone ice by putting snowfall into a container and discharging the air inside and then compressing while feeding ozone gas.
- Patent Document 3 describes a method of producing ozone ice by cooling and freezing ozone water generated by an electrolysis method.
- Patent Document 4 and Non-Patent Document 1 describe a method of generating high-concentration ozone water at the anode by devising the electrode of the electrolytic cell and the component of the raw water used in the electrolysis method.
- the conventional method of cooling and freezing water containing ozone gas as bubbles and the method of compressing while supplying ozone gas to the ice powder decompose ozone ozone into more stable oxygen gas in a short time.
- an object of the present invention is to provide an ozone ice production method and an ozone ice production apparatus with improved storage stability of ozone ice.
- the present invention which was created to achieve the above object, produces ice containing oxygen gas as bubbles, irradiates the produced ice with ultraviolet light, ozonizes the oxygen gas in the ice, and produces ozone ice. It is a manufacturing method.
- the produced ice is irradiated with ultraviolet rays, so that the oxygen gas in the ice is ozone.
- ozone ice By cooling and freezing water containing oxygen gas generated in the anode as a bubble by electrolysis of water to produce ice containing oxygen gas as bubbles, the produced ice is irradiated with ultraviolet rays, so that the oxygen gas in the ice is ozone.
- Microbubble oxygen gas and water are mixed to form water containing oxygen gas as bubbles, water containing the oxygen gas is cooled and frozen to produce ice containing oxygen gas as bubbles, and ultraviolet light is applied to the produced ice.
- ozone gas may be produced by ozonizing oxygen gas in ice.
- Supply oxygen gas to ice powder, pressurize and sinter this to produce ice containing oxygen gas as bubbles, and irradiate the produced ice with ultraviolet rays to ozonize the oxygen gas in the ice and ozone Ice may be produced.
- the pressure sintering may be performed at a pressure of 20 MPa over 3 hours.
- Ozone ice may be produced by collecting natural ice such as sea ice and glaciers, producing ice containing oxygen gas as a gas component in the bubbles, and irradiating the produced ice with ultraviolet rays.
- the present invention also includes an electrolysis cell for electrolyzing water to produce water containing oxygen gas as bubbles, and water containing oxygen gas as bubbles, and cooling and freezing it to contain oxygen gas as bubbles.
- An ozone equipped with a cooling vessel for producing ice and an ultraviolet irradiator for irradiating the ice containing oxygen gas contained in the cooling vessel as bubbles and irradiating the oxygen gas in the ice into ozonized ozone It is an ice making device.
- the storage stability of ozone ice can be improved.
- FIG. 1 is a schematic diagram for explaining an ozone ice production method showing a preferred first embodiment of the present invention.
- the ozone ice manufacturing method produces ice (oxygen bubble-containing ice) 11 containing oxygen gas g2 as bubbles b, and irradiates the produced ice 11 with ultraviolet rays.
- ozone gas (ice containing ozone bubbles) 1 is produced by ozonizing oxygen gas g2 in ice 11.
- the density ⁇ of the ice 11 containing the oxygen gas g2 as the bubble b is 550 to 910 kg / m 3 so that the bubble b is contained in the ice 11 (so that the oxygen gas is confined as the bubble b in the ice 11).
- it is 830 to 870 kg / m 3 .
- Bubbles b exist because ice particles of 550 kg / m 3 or more are close to close-packing, but there are still many open pores that are connected to the outside of the gap. However, when it becomes 830 kg / m 3 or more, it becomes almost only bubbles. On the other hand, when it exceeds 870 kg / m 3 , there are too few bubbles and oxygen gas in the ice is reduced.
- the volume of the pure ice portion where water is frozen is 90% and the volume of the bubbles b is 10% with respect to the total volume of the ice 11.
- the density ⁇ of the ice 11 containing the oxygen gas g2 as the bubble b is, for example, the amount of microbubbles of oxygen gas mixed with water before cooling and freezing, the freezing speed, and when ice is produced by pressure sintering. Control is performed by adjusting the crystal grain size of the ice powder, the temperature during pressing, and the pressing pressure.
- FIG. 2 shows an example of bubbles of ice 11 produced by the pressure sintering method and containing oxygen gas g2 as bubbles b.
- the density ⁇ of the ice 11 in FIG. 2 is 870 kg / m 3
- the size of the bubble b is about 0.1 to 0.2 mm.
- the bubbles b occupy 5% of the total volume of the ice 11.
- the prepared ice 11 may be irradiated with ultraviolet rays having a wavelength of 130 to 242 nm, preferably 180 to 220 nm.
- the concentration of the ozone gas g3 in the ozone ice 1 is basically determined by the density ⁇ of the ice 11 containing the oxygen gas g2 as the bubble b, the wavelength of the irradiated ultraviolet ray, and the temperature, although it depends on the irradiation time of the ultraviolet ray. .
- the concentration of the ozone gas g3 in the ozone ice 1 is set to 1 to 30 ppm.
- the wavelength of the ultraviolet rays applied to the produced ice 11 is as follows: 1) oxygen molecules dissociate into oxygen atoms, 2) the generated ozone gas is difficult to decompose into oxygen gas, and 3) absorption by ice. The decision is made taking into account three main points that the effect is small.
- ozone gas As shown in Fig. 3 (Source: Hidetoshi Sugimitsu, “Basics and Applications of Ozone”, Kogyo Publishing Co., Ltd., 1996), ozone gas (O 3 ) is called the Hartley absorption band at a wavelength of 220 to 300 nm. Since it has a strong absorption band, when light in this wavelength range is irradiated onto ozone gas, the decomposition of ozone gas is prominent. That is, the generation of ozone gas by ultraviolet irradiation is a competitive reaction with the decomposition of ozone gas. Note that the absorption coefficient of oxygen molecules rapidly increases below a wavelength of 200 nm, and particularly in the wavelength region of 140 to 170 nm, ultraviolet absorption by oxygen molecules exceeds ultraviolet absorption by ozone gas.
- ice has an absorption edge near the wavelength of 200 nm, and the absorption coefficient is 180 nm. It is about 100m- 1 . Since the absorption coefficient is small at longer wavelengths, the influence of light absorption by ice is small.
- the ice 11 produced ultraviolet light of 180 to 220 nm, which is a wavelength region in which oxygen molecules are dissociated into oxygen atoms and the decomposition of the generated ozone gas is suppressed, and the absorption of ultraviolet light by ice is small. In practice, it is preferable to irradiate. In a proof-of-principle experiment described later, ultraviolet rays having a wavelength of 193 nm were used among ultraviolet rays emitted from a mercury lamp.
- the absorption coefficient of ultraviolet light having a wavelength of 193 nm is 1 to 2 m ⁇ 1 .
- the attenuation rate I (x) / I 0 of the incident light intensity due to the absorption of ice is the reflectivity when the incident light is vertically incident on the ice sample surface as R shown by the following equation (1). If the absorption coefficient of ice is ⁇ (m -1 ), the following equation (2)
- the ozone ice manufacturing method according to the first embodiment will be described in more detail with reference to FIG.
- FIG. 6 there are three methods for producing the ice 11 containing the oxygen gas g2 described in FIG. 1 as the bubbles b, namely, method 1) using a microbubble generator (microbubble generator).
- Method 2) Method of manufacturing using an electrolytic cell
- Method 3 There is a method of manufacturing using a pressure sintering container.
- the microbubble generator 62 is prepared.
- Oxygen gas g2 which is one of the raw materials, is supplied to the prepared microbubble generator 62 from an oxygen gas cylinder, and the oxygen gas g2 is converted into microbubbles having a bubble diameter of 100 ⁇ m or less.
- Microbubble oxygen gas g2 and another raw material water w are mixed to form water (oxygen bubble-containing water) bw1 containing oxygen gas as bubbles.
- the oxygen bubble-containing water bw1 is accommodated in the cooling vessel 63, and the oxygen bubble-containing water bw1 is cooled and frozen in the cooling vessel 63 to produce the ice 11 containing the oxygen gas g2 of FIG.
- an electrolysis cell 71 for electrolyzing water is prepared.
- the electrolysis cell 71 has a solid electrolyte membrane (cation exchange membrane) 72 sandwiched between an anode 73 and a cathode 74 from both sides, and a DC power source 75 is connected to the anode 73 and the cathode 74, and the anode side
- a water supply port 76 and a water discharge port 77 are provided.
- water w as a raw material is supplied to the prepared electrolytic cell 71, the water w is electrolyzed in the electrolytic cell 71, and water containing oxygen gas as bubbles (water + oxygen gas (the diameter of the bubbles is several). 10 ⁇ m microbubbles) (oxygen bubble-containing water)) bw2 and hydrogen gas gh.
- the hydrogen gas gh is discarded.
- the oxygen bubble-containing water bw2 is accommodated in the cooling vessel 63, and the oxygen bubble-containing water bw2 is cooled and frozen in the cooling vessel 63 to produce the ice 11 containing the oxygen gas g2 of FIG. Then, when the produced ice 11 is irradiated with ultraviolet rays from the ultraviolet irradiator 64 and the oxygen gas g2 in the ice 11 is ozonized, ozone ice 1 is obtained.
- a container (pressure-sintered container) 65 is prepared for pressurizing and sintering the ice powder contained in a sealed container at 0 ° C. or lower.
- An ice powder ip which is one of the raw materials, is accommodated in the prepared container 65 and sealed.
- the ice powder ip is produced by an ice powder manufacturing device (which may be a shaved ice manufacturing device or the like) that can crush block-shaped ice into ice powder.
- the sealed container 65 is decompressed to remove the air inside the container.
- oxygen gas g2 which is another raw material, is supplied from the oxygen gas cylinder, and in this state, pressure is sintered to the ice powder ip by applying a pressure of 20 MPa for 3 hours using, for example, a hydraulic jack.
- the ice 11 containing the oxygen gas g2 in the form of bubbles b is prepared.
- Ozone ice 1 is obtained by irradiating the produced ice 11 with ultraviolet rays from an ultraviolet irradiator 64.
- a refrigerant is used to cool the oxygen bubble-containing waters bw1 and bw2 or the ice powder ip.
- the cooling heat for cooling the refrigerant for example, low-temperature waste heat discharged from an LNG (liquefied natural gas) plant is used. Thereby, the added value of an LNG tank and its incidental equipment can also be improved.
- Method 2 it is not necessary to prepare an oxygen gas cylinder required for other methods, and that the bubble diameter of oxygen gas generated on the anode surface of the electrolysis cell 71 is as small as several tens ⁇ m (10 to 50 ⁇ m). It is in.
- the bubble diameter is small, when the oxygen bubble-containing water bw2 is cooled and frozen, the residence time of the bubbles in the oxygen bubble-containing water bw2 becomes longer, and therefore more bubbles b are included than when the bubble diameter is large. Ice 11 can be produced.
- the advantage of the method 3 is that the internal pressure (oxygen gas concentration) of bubbles contained in the ice can be increased as compared with other methods, that is, the ozone ice 1 having a higher concentration than the method 1 and the method 2 can be produced. It is in.
- the advantage of the method 1 and the method 2 is that the ozone ice 1 can be produced in a shorter time than the case of pressure sintering as in the method 3 because the oxygen bubble-containing waters bw1 and bw2 are cooled and frozen. Suitable for mass production.
- the ozone ice manufacturing method is a conventional method of cooling and freezing ozone water to manufacture ozone ice, and a method of manufacturing ozone ice by compressing while supplying ozone gas to ice powder. In contrast, it is not a method for producing ozone ice containing ozone gas in advance.
- ice 11 is produced in which oxygen gas g2 is confined as bubbles b.
- the produced ice 11 is irradiated with ultraviolet rays so that the oxygen gas g2 in the ice 11 is ozonized to easily obtain the ozone ice 1. It is done.
- the storage stability of ozone ice which was the problem of the conventional ozone ice manufacturing method can be improved, and the application range of ozone ice 1 is expanded.
- ozone ice has been produced from ozone water, and it has been necessary to store ozone ice at a temperature sufficiently lower than its melting point after producing ozone ice in order to suppress decomposition of ozone gas.
- the present invention irradiates the bubble-containing ice with ultraviolet rays to form ozone ice, the following three points can be given as specific effects.
- ice (oxygen bubble-containing ice) 11 which is the previous stage of ozone ice 1 can be used as a product, and it becomes possible to store ice 11 as a product near the melting point of ice. In order to suppress the decomposition of ozone gas, it is not necessary to store at a sufficiently low temperature.
- the ozone ice 1 is obtained by irradiating the ice 11 with ultraviolet rays during use, the ice 11 can be transported as a product over a long distance.
- the density ⁇ of the ice 11 containing the oxygen gas g2 as the bubble b is set to 830 to 870 kg / m 3 so that the bubble b is included in the ice 11,
- ozone ice 1 containing 3 ppm or more of ozone gas g3 required for storing fresh food can be produced.
- the method of artificially producing the ice 11 containing the oxygen gas g2 as the bubble b has been described.
- the ice 11 is natural ice in the natural world, such as the Antarctic and Greenland. It exists as (natural ice). Therefore, natural ice such as sea ice, drift ice, glaciers, and ice sheets is collected, and the structure of the collected natural ice (ice density, bubble components, etc.) is examined, and then the collected natural ice (oxygen gas is bubbled) What is produced by processing ice containing as a gas component therein into a desired size may be used as the ice 11.
- the present inventors also conducted a proof-of-principle experiment for the ozone ice production method according to this embodiment.
- the ice 11 containing the oxygen gas g2 described in FIG. 1 as the bubbles b was produced by rapidly cooling ion exchange water containing microbubbles in a liquid nitrogen atmosphere.
- the produced ice 11 is accommodated in a case 81 that transmits ultraviolet light and placed on a small tray 82, and the small tray 82 is immersed in a large tray 83 filled with liquid nitrogen n as a refrigerant.
- a mercury lamp 84 is provided as an ultraviolet irradiator on one side of the large tray 83, and a reflection mirror 85 that reflects ultraviolet rays having a wavelength of only 193 nm out of the ultraviolet rays of the mercury lamp 84 and irradiates the ice 11 is provided above the case 81.
- An aluminum foil 86 was set up on the inner surface of one side of the large tray 83 in order to prevent the light from the mercury lamp 84 from being directly irradiated onto the ice 11. After irradiating the ice 11 with ultraviolet rays of 193 nm for 15 minutes, the ice 11 was melted at room temperature, and potassium iodide was added. As a result, coloring by iodine was recognized, and it was confirmed that the ozone ice 1 described in FIG.
- an ozone ice manufacturing apparatus 90 is an ozone ice manufacturing apparatus used for the method 2 described above.
- the ozone ice production apparatus 90 contains an electrolytic cell 71 for generating water (oxygen bubble-containing water) bw2 containing oxygen gas as bubbles, and oxygen bubble-containing water bw2, which is cooled and frozen to produce oxygen gas g2.
- a cooling container 63 for producing ice containing oxygen bubbles (oxygen bubble-containing ice) 11 and oxygen bubble-containing ice 11 accommodated in the cooling container 63 are irradiated with ultraviolet rays, and the oxygen gas in the oxygen bubble-containing ice 11 is ozonized.
- an ultraviolet irradiator 64 for making ozone ice (ozone containing ice) 1.
- a water supply pipe 97 for supplying water w as a raw material to the electrolysis cell 71 is connected to the water supply port 76 of the electrolysis cell 71.
- an oxygen bubble-containing water supply pipe 98 Connected to the water discharge port 77 of the electrolysis cell 71 is an oxygen bubble-containing water supply pipe 98 that passes through an upper part of one side surface of a refrigerant chamber 92 described later and supplies oxygen bubble-containing water bw2 to a cooling chamber 91 described later. Is done.
- the cooling vessel 63 is formed with a rectangular or cylindrical cooling chamber 91 penetrating upward and downward at the center thereof, and is cooled by circulating a refrigerant c such as an antifreeze around the cooling chamber 91.
- a refrigerant chamber 92 is formed to keep the inside of the chamber 91 below 0 ° C.
- a concavo-convex portion 93 which has been subjected to concavo-convex processing for taking out the ozone ice 1 from the cooling chamber 91 using pressure melting of the ice, that is, pressing it from above and taking it out downward.
- a lower lid 94 made of a transmitting member such as quartz glass that transmits ultraviolet rays is provided at the lower portion of the cooling chamber 91.
- a refrigerant supply pipe 95 that supplies the refrigerant c into the refrigerant chamber 92 is connected to the lower part of one side of the refrigerant chamber 92, and the refrigerant c in the refrigerant chamber 92 is connected to the upper part of the other side of the refrigerant chamber 92.
- a refrigerant discharge pipe 96 that discharges to the outside of 92 is connected.
- the refrigerant supply pipe 95 and the refrigerant discharge pipe 96 are connected in the vicinity of the cold heat source to form a refrigerant circulation line, and circulate the refrigerant c while exchanging heat with the cold heat from the cold heat source.
- the cold heat source as described above, for example, low-temperature waste heat discharged from the LNG plant is used.
- a temperature sensor T such as a thermocouple is provided on the side surface of the refrigerant chamber 92 in order to measure the temperature of the refrigerant c. Based on a sensor signal from the temperature sensor T, control means such as a controller (not shown) The cooling freezing time of the oxygen bubble-containing water bw2 supplied into the cooling container 63 and the circulation amount of the refrigerant c are controlled.
- an ultraviolet irradiator 64 such as a mercury lamp that moves forward so as to face the lower lid 94 of the cooling chamber 91 during ice making and moves backward when the ice is taken out is provided so as to freely advance and retract.
- a pressurizing piston p1 for removing ice is provided so as to be movable up and down by a hydraulic drive mechanism d1.
- the pressurizing piston p1 serves as an upper lid of the cooling chamber 91 and serves to apply pressure to the oxygen bubble-containing ice 11 from above.
- a piston p2 for receiving ice is provided so as to be movable up and down by a hydraulic or pneumatic drive mechanism d2.
- the ice receiving piston p2 is provided with a heater for melting the bottom surface of the ozone ice 1 attached to the lower lid 94.
- an ice pushing piston p3 is provided by a hydraulic or pneumatic drive mechanism d3 so as to freely advance and retract.
- unloading means 99 such as a belt conveyor for unloading the ozone ice 1 to the outside.
- the lower lid 94 is attached to the lower part of the cooling chamber 91, the pressurized piston p1 is lowered to the vicinity of the upper part of the cooling chamber 91, the ultraviolet irradiator 64, the piston p2, p3 is set in the retracted state.
- the refrigerant c is circulated in the refrigerant chamber 92, water w as a raw material is supplied to the electrolysis cell 71 (F 1), and the water w is electrolyzed in the electrolysis cell 71.
- oxygen bubble-containing water bw2 is generated (F2, F3).
- the supplied oxygen bubble-containing water bw2 is supplied and stored in the cooling vessel 63, and the oxygen bubble-containing water bw2 is cooled and frozen in the cooling vessel 63 to produce the oxygen bubble-containing ice 11 (F4).
- the ultraviolet irradiator 64 is advanced so as to face the lower lid 94 of the cooling chamber 91, and the oxygen bubble-containing ice 11 is irradiated with ultraviolet rays from the lower side through the lower lid 94 (F5).
- the oxygen gas in 11 is ozonized, ozone ice 1 is obtained (F6).
- the ultraviolet irradiator 64 is moved backward to raise the piston p2.
- the lower lid 94 is heated using a heater provided on the piston p2, the bottom surface of the ozone ice 1 attached to the lower lid 94 is melted, the lower lid 94 is removed, and the pressurizing piston p1 is further lowered. Pressure is applied to the upper surface of the ozone ice 1 to push the ozone ice 1 downward and take it out of the cooling vessel 63 (F7).
- the piston p2 When the extracted ozone ice 1 is received by the piston p2, the piston p2 is lowered, the ozone ice 1 on the piston p2 is pushed from the side by the piston p3 and sent to the unloading means 99, and the ozone ice 1 is unloaded by the unloading means 99. To do.
- the ozone ice 1 is substantially continuously formed from the raw material water w except that the point where the oxygen bubble-containing water bw2 is cooled and frozen in the cooling vessel 63 is a batch type. Can be manufactured. Moreover, in the ozone ice manufacturing apparatus 1, it can implement
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Abstract
Description
方法1)マイクロバブル発生器(マイクロバブル発生装置)を利用して製造する方法
方法2)電解セルを利用して製造する方法
方法3)加圧焼結容器を利用して製造する方法
がある。
まず、マイクロバブル発生器62を用意する。用意したマイクロバブル発生器62に、酸素ガスボンベから原料の1つである酸素ガスg2を供給し、酸素ガスg2を気泡の径が100μm以下のマイクロバブルにする。マイクロバブルにした酸素ガスg2ともう1つの原料である水wとを混合し、酸素ガスを気泡として含む水(酸素気泡含有水)bw1にする。酸素気泡含有水bw1を冷却容器63に収容し、その冷却容器63で酸素気泡含有水bw1を冷却凍結し、図1の酸素ガスg2を気泡bとして含む氷11を作製する。そして、作製した氷11に、紫外線照射器(紫外線照射装置)64から紫外線を照射し、氷11中の酸素ガスg2をオゾン化すると、オゾン氷1が得られる。
まず、水を電気分解するための電解セル71を用意する。電解セル71は、図7に示すように、固体電解質膜(陽イオン交換膜)72を陽極73と陰極74とで両側から挟み、これら陽極73と陰極74に直流電源75を接続し、陽極側に水供給口76と水排出口77を設けて構成される。電解セル71では、水供給口76に水wを供給して両極73,74に直流電圧を印加した場合、陽極73において酸素ガスが発生し、発生した酸素ガスが水排出口77から電気分解されなかった水wと共に排出される。一方、陰極74においては、水素ガスが発生する。
まず、密閉容器内に収容した氷粉体を0℃以下で加圧して焼結するための容器(加圧焼結容器)65を用意する。用意した容器65に、原料の1つである氷粉体ipを収容して密閉する。氷粉体ipは、ブロック状の氷を破砕して氷粉体にできる氷粉体製造器(かき氷製造器などでもよい)で作製する。次に、密閉した容器65を減圧し、容器内部の空気を除去する。そして、酸素ガスボンベからもう1つの原料である酸素ガスg2を供給し、この状態で氷粉体ipに、例えば油圧ジャッキを用いて20MPaの圧力を3時間加えることにより加圧焼結し、図1の酸素ガスg2を気泡bとして含む氷11を作製する。作製した氷11に、紫外線照射器64から紫外線を照射することにより、オゾン氷1が得られる。
図1で説明した酸素ガスg2を気泡bとして含む氷11を、マイクロバブルを含むイオン交換水を液体窒素雰囲気において急速冷却することで作製した。
g2 酸素ガス
b 気泡
11 酸素ガスを気泡として含む氷
Claims (8)
- 酸素ガスを気泡として含む氷を作製し、作製した氷に紫外線を照射し、氷中の酸素ガスをオゾン化してオゾン氷を製造するオゾン氷製造方法。
- 作製した氷に、波長が130~242nmの紫外線を照射し、氷中の酸素ガスをオゾン化する請求項1記載のオゾン氷製造方法。
- 水の電気分解により陽極で発生した酸素ガスを気泡として含む水を冷却凍結して酸素ガスを気泡として含む氷を作製し、作製した氷に紫外線を照射し、氷中の酸素ガスをオゾン化してオゾン氷を製造する請求項1または2記載のオゾン氷製造方法。
- マイクロバブルにした酸素ガスと水を混合して酸素ガスを気泡として含む水にし、その酸素ガスを含有する水を冷却凍結して酸素ガスを気泡として含む氷を作製し、作製した氷に紫外線を照射し、氷中の酸素ガスをオゾン化してオゾン氷を製造する請求項1または2記載のオゾン氷製造方法。
- 氷粉体に酸素ガスを供給し、これを加圧焼結して酸素ガスを気泡として含む氷を作製し、作製した氷に紫外線を照射し、氷中の酸素ガスをオゾン化してオゾン氷を製造する請求項1または2記載のオゾン氷製造方法。
- 前記加圧焼結は、圧力20MPaで、3時間かけて行う請求項5記載のオゾン氷製造方法。
- 海氷、氷河などの天然氷を採取し、酸素ガスを気泡中のガス成分として含む氷を作製する請求項1または2記載のオゾン氷製造方法。
- 水を電気分解し、酸素ガスを気泡として含む水を生成するための電解セルと、酸素ガスを気泡として含む水を収容し、これを冷却凍結して酸素ガスを気泡として含む氷を作製する冷却容器と、その冷却容器に収容した酸素ガスを気泡として含む氷に紫外線を照射し、氷中の酸素ガスをオゾン化してオゾン氷にするための紫外線照射器とを備えたオゾン氷製造装置。
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AU2009307371A AU2009307371B2 (en) | 2008-10-23 | 2009-10-23 | Method for producing ozone ice and apparatus for producing ozone ice |
CN2009801417071A CN102197270A (zh) | 2008-10-23 | 2009-10-23 | 臭氧冰制造方法及臭氧冰制造装置 |
US13/125,233 US8535489B2 (en) | 2008-10-23 | 2009-10-23 | Method for manufacturing ozone ice and apparatus for manufacturing ozone ice |
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JP5280796B2 (ja) * | 2008-10-23 | 2013-09-04 | 株式会社Ihi | オゾン氷製造方法及びオゾン氷製造装置 |
JP5147674B2 (ja) * | 2008-12-19 | 2013-02-20 | 株式会社Ihi | オゾン氷製造方法及びオゾン氷製造装置 |
JP5664994B2 (ja) * | 2009-08-28 | 2015-02-04 | 学校法人 中央大学 | 氷の気泡含有率の高いオゾン氷、該オゾン氷の製造方法及び製造装置 |
JP2011080671A (ja) * | 2009-10-06 | 2011-04-21 | Ihi Plant Construction Co Ltd | オゾン含有氷の製造方法及びその装置 |
KR101218236B1 (ko) * | 2011-04-01 | 2013-01-03 | 김혜련 | 빙산수를 이용한 빙산 얼음 및 그의 제조장치, 그의 제조방법 |
CN102511538B (zh) * | 2012-01-13 | 2013-03-13 | 福建省宁德市华洋水产有限公司 | 一种大黄鱼冰温保鲜的方法 |
JP6385770B2 (ja) * | 2014-09-22 | 2018-09-05 | 株式会社Ihi | 高濃度オゾンハイドレートの製造方法及びその製造装置並びに高濃度オゾンハイドレート |
CN104784202A (zh) * | 2015-04-28 | 2015-07-22 | 郭淮铨 | 医用臭氧冰的制备方法 |
KR20200058011A (ko) | 2018-11-19 | 2020-05-27 | 엘지전자 주식회사 | 아이스 메이커 및 냉장고 |
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US8535489B2 (en) | 2013-09-17 |
KR20110079672A (ko) | 2011-07-07 |
CN105276884A (zh) | 2016-01-27 |
CN102197270A (zh) | 2011-09-21 |
JP4995173B2 (ja) | 2012-08-08 |
JP2010101560A (ja) | 2010-05-06 |
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