JP5614999B2 - Method and apparatus for producing ozone-containing hydrate - Google Patents

Description

  The present invention relates to a method and apparatus for producing a hydrate containing high-concentration ozone, and more particularly, to a method and apparatus for producing an ozone-containing hydrate capable of hydrating ozone at a low pressure of 0 ° C. or higher. .

  Ozone has a bactericidal action and self-decomposes over time to become oxygen, so that no harmful substances remain like chlorinated bactericides after sterilization. Widely used.

  The ozone is used in various forms such as ozone gas, ozone water, ozone ice, etc., but the concentration is as low as about 20-30 ppm, and long-term storage is difficult due to the self-decomposing action of ozone.

  As a method for storing ozone, as disclosed in Patent Document 1, it has been proposed to form a solid substance incorporating ozone by bringing ozone and water or ice into contact with each other to a predetermined temperature or lower.

  In this Patent Document 1, the temperature and pressure conditions when ozone is brought into contact with water or ice are 270 K (−3 ° C.) or less, 2 MPa or more, particularly 248 K (−25 ° C.) or less, 13 MPa or more. It is disclosed that a solid substance incorporating sucrose can be produced.

JP 2007-210881 A

  However, Patent Document 1 describes that a solid substance in which ozone is included in water can be produced, but water solidifies at 0 ° C. under atmospheric pressure, and the solidification temperature can be lowered by increasing the pressure. It is difficult to make ozone hydrate by contacting with ozone with supercooled water of 13 MPa or more and −25 ° C. or less, and in Patent Document 1, powder ice is filled in the reaction vessel. However, by supplying ozone gas into the reaction tank, it is considered that the ozone gas is included in the ice, and in reality, it is considered that not the ozone hydrate but ice containing ozone gas is produced.

  Therefore, this ozone-containing solid substance is a substance in which ozone gas is confined in ice, and unlike the hydrate enclosing ozone molecules, there is a problem that the self-decomposition of ozone gas cannot be avoided during storage.

  To produce ozone hydrate, ozone water can be made by enclosing ozone water in a reaction tank and cooling the reaction tank at a high pressure. There is a problem that hydrate cannot be produced, and it is also difficult to transfer ozone hydrate produced in the reaction vessel while maintaining the pressure and temperature when transferring it to another container.

  Accordingly, an object of the present invention is to solve the above-described problems and provide a method and apparatus for producing an ozone-containing hydrate that can be continuously produced at low pressure and near freezing and that can be stored easily. is there.

In order to achieve the above object, according to the first aspect of the present invention, cooling water is stored in a hydrate generator, a bubble generator is provided in the hydrate generator, and the pressure in the hydrate generator is set to 2. While maintaining at 5 to 3 MPa, ozone gas as guest gas, xenon or carbon dioxide gas is added to form a mixed gas, and the mixed gas is blown with microbubbles from the bubble generator, and the amount of guest gas blown into the cooling water is It blows so that it may become 100-400 mass parts with respect to 1000 mass parts of water, The ozone containing hydrate is produced | generated in the upper part of the said bubble generator, This produced | generated ozone containing hydrate is the bottom part of a hydrate generator by specific gravity difference The cooling water having a high unreacted temperature and high specific gravity, which has absorbed the heat of reaction, is sucked from the cooling water introduction portion located at the lower center of the bubble generator. This 0 ℃ as the following cooling water, a manufacturing method of the cooling water inlet of the upper and and said bubble generator from ozone-containing hydrate, characterized by injecting circulating in said hydrate generator below while It is.

According to a second aspect of the present invention , a hydrate storage container is connected to a lower portion of the hydrate generator, and the ozone-containing hydrate generated in the hydrate generator and accumulated at the bottom is caused to flow down to the hydrate storage container. The method for producing an ozone-containing hydrate according to claim 1, wherein the ozone-containing hydrate is stored .

Invention of Claim 3 is a manufacturing method of the ozone containing hydrate of Claim 1 or 2 which mixes carbon dioxide gas or xenon 10-30 times with respect to the mass of ozone gas, and makes it a mixed gas.

According to a fourth aspect of the present invention, there is provided a hydrate generator for storing cooling water, and a microbubble which is provided in cooling water in the hydrate generator and is a mixture gas obtained by adding xenon or carbon dioxide gas to ozone gas as a guest gas. And a bubble generator that is blown so that the amount of guest gas blown into the cooling water is 100 to 400 parts by mass with respect to 1000 parts by mass of water, and ozone gas and xenon or carbon dioxide gas in the bubble generator. 2.5 and guest gas supply line the mixed gas test sheet, and the guest gas discharge line connected to the top of the hydrate generator, connected to said guest gas discharge line, the pressure in the hydrate generator A gas phase pressure control valve maintained at 3 MPa and a cooling water inlet located at the lower center of the bubble generator and sucked from the cooling water at 0 ° C. or lower And a cooling water circulation line that circulates and circulates from an injection nozzle provided above the cooling water introduction part and below the bubble generator. .

The invention of claim 5 is the apparatus for producing ozone-containing hydrate according to claim 4, wherein a hydrate storage container for introducing and storing the generated ozone-containing hydrate is connected to the lower part of the hydrate generator. .

  According to the present invention, when ozone hydrate is generated, xenon or carbon dioxide gas is mixed as a guest gas in addition to ozone to make hydrate, so that the temperature of the cooling water is around 0 ° C. and the pressure is 3 MPa. In the following, an excellent effect of being able to form a hydrate and continuously generate an ozone-containing hydrate is exhibited.

It is a flowchart which shows one embodiment of this invention. It is the sectional view on the AA line of FIG. It is a figure which shows the state which preserve | saves a hydrate storage container in FIG. In this invention, it is a figure which shows the relationship between hydrate production | generation pressure and temperature.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  In FIG. 1, reference numeral 10 denotes a hydrate generator, which is formed by covering the outer periphery with a heat insulating cover 11.

  A ring-shaped bubble generator 12 is provided in the hydrate generator 10, and a shade-shaped anti-rotation plate 13 is provided below the bubble generator 12.

  Cooling water 14 is stored in the hydrate generator 10, and the cooling water 14 is circulated by a cooling water circulation line 15 as will be described later, and the temperature of the cooling water 14 is controlled to be close to 0 ° C.

  A guest gas supply line 16 for supplying ozone gas and xenon or carbon dioxide gas is connected to the bubble generator 12. The guest gas supply line 16 includes an oxygen gas supply line 18 to which an ozone generator 17 is connected, and a mixed gas supply line 20 made of xenon or carbon dioxide connected to an ozone-containing oxygen line 19 downstream of the ozone generator 17. Consists of.

  The oxygen gas supply line 18 is connected to an oxygen storage container 21 for storing oxygen at high pressure, such as an oxygen cylinder, and oxygen is supplied to the oxygen gas supply line 18 on the outlet side of the oxygen storage container 21 at a predetermined pressure (2.72 MPa). A release valve (PCV-1) 22 for discharging is connected, and an oxygen flow rate controller (FIC-1) 23 and an oxygen flow rate adjusting valve 24 are connected to the downstream side thereof.

  The mixed gas supply line 20 is connected to a mixed gas storage container 25 for storing mixed gas, such as carbon dioxide gas or xenon gas cylinder, at a high pressure. The mixed gas supply line 20 on the outlet side of the mixed gas storage container 25 is supplied with a predetermined pressure. (For example, in the case of a raw material component to be described later, a release valve (PCV-2) 26 that discharges at 2.7 MPa) is connected, and a mixed gas flow rate controller (FIC-2) 27 and a mixed gas flow rate control valve are arranged downstream thereof. 28 is connected.

  The cooling water circulation line 15 is provided opposite to the cooling water introduction part 30 for sucking the cooling water directly under the anti-swirl plate 13 and the upper part of the anti-swirl plate 13, and as shown in FIG. Cooling water injection nozzles 31 a and 31 b for injecting cooling water in the tangential direction on the inner surface, a circulation pump 33 is connected to the cooling water circulation line 15, and the temperature is adjusted between the inlet 30 and the suction side of the circulation pump 33. A valve 32 is connected, and a cooler 34, a cooling water flow meter 35, and a cooling water amount adjusting valve 36 are connected from the discharge side of the circulation pump 33 to the cooling water injection nozzles 31a and 31b.

  A cooling water supply line 38 is connected to the cooling water circulation line 15 between the circulation pump 33 and the cooler 34. A water supply pump 40 is connected to the cooling water supply line 38, and the water supply pump 40 sucks supply water in the supply water tank 41, and passes through a supply water flow meter 42 and a supply water flow rate adjustment valve (FCV-4) 43. Supply water is supplied to the cooling water circulation line 15. The replenishing water tank 41 is replenished with clean water (replenishing water) through the check valve 44 and the ball tap 45 so as to always have a predetermined liquid level.

  A discharge line 48 for discharging the generated ozone-containing hydrate 47 is connected to the lower portion of the hydrate generator 10, and hydrate storage containers 50a and 50b are connected to the discharge line 48 via hydrate introduction opening / closing valves 49a and 49b, respectively. Is connected. As with the hydrate generator 10, the outer periphery of the hydrate storage containers 50 a and 50 b is thermally insulated by the heat insulating cover 11.

  A guest gas discharge line 51 is connected to the top of the hydrate generator 10, a gas phase pressure control valve (PCV-4) 52 is connected to the discharge line 51, and an ozonolysis device 53 is connected to the downstream side thereof. Is done.

  A guest gas circulation line 54 is connected to the upper portion of the hydrate generator 10, and the guest gas in the gas phase portion of the hydrate generator 10 passes through the guest gas circulation line 54 in the ozone generator 17 of the guest gas supply line 16. Returned to the downstream side. A circulation gas blower 55, a circulation gas pressure control valve 56, and an ozone regenerator 57 are connected to the guest gas circulation line 54.

  Hydrate storage containers 50a and 50b are provided on the mass meters 51a and 51b, and the hydrate mass to be stored is measured. A gas discharge line 59 is connected to the hydrate storage containers 50a and 50b for discharging the gas in the storage containers 50a and 50b to the downstream side of the gas phase pressure control valve 52 via the on-off valves 58a and 58b when the hydrate is stored. Is done.

  A cooler 34 for cooling the cooling water in the cooling water circulation line 15 is incorporated in the refrigeration cycle 60. The refrigeration cycle 60 includes a refrigerant compressor 61 that compresses refrigerant, a condenser 62 that cools the compressed refrigerant with cooling water, a condensed refrigerant receiver 63 that stores condensed refrigerant from the condenser 62, and refrigerant from the receiver 63. An expansion valve (TCV-2) 64 for depressurizing the refrigerant, a cooler 34 as an evaporator for introducing the depressurized refrigerant to cool the cooling water in the cooling water circulation line 15, and a refrigerant evaporated in the cooler 34 are stored. The suction drum 65 circulates the evaporated gas to the refrigerant compressor 61.

  A circulating water temperature controller 66 is connected to the cooling water circulation line 15 on the downstream side of the cooler 34, and the valve opening degree of the expansion valve 64 is controlled so that the temperature becomes a predetermined temperature.

  Next, the control system of FIG. 1 will be described.

  The oxygen flow rate controller 23 detects the oxygen flow rate in the oxygen gas supply line 18 and controls the oxygen flow rate control valve 24 so that the flow rate becomes a predetermined flow rate. The mixed gas flow rate control meter 27 is mixed in the mixed gas supply line 20. The gas (carbon dioxide) flow rate is detected, and the mixed gas flow rate adjustment valve 28 is controlled so as to be a predetermined flow rate.

  The detected values of the oxygen flow controller 23 and the mixed gas flow controller 27 are input to the guest gas controller 70, and the guest gas controller 70 outputs the guest gas amount to the cooling water flow meter 35 of the cooling water circulation line 15. Then, the cooling water flow meter 35 controls the cooling water amount adjusting valve 36 so that the cooling water amount matches the guest gas amount. In addition, the hydrate generator 10 is provided with a cooling water temperature controller 71 that detects the temperature of the cooling water 14, and the guest gas controller 70 detects that the cooling water temperature detected by the cooling water temperature controller 71 is a predetermined value. The temperature control valve 32 is controlled so that

  A hydrate surface measuring device 72 for detecting the liquid level of the generated ozone-containing hydrate 47 is provided at the lower portion of the hydrate generator 10, and the hydrate surface measuring device 72 uses the hydrate introduction opening / closing valves 49a and 49b. Control is performed to open any one, and when the amount of the ozone-containing hydrate 47 in the hydrate generator 10 is reduced, control is performed to close the opened hydrate introduction opening / closing valve 49a (or 49b). .

  The mass meters 51a and 51b detect the mass of the hydrate storage containers 50a and 50b, and first open and close the hydrate introduction opening / closing valve 49a (or 49b) of one of the hydrate storage containers 50a (or 50b). 58a (or 58b) is opened, and the ozone-containing hydrate 47 is controlled to be introduced into the hydrate storage container 50a. When the amount of the ozone-containing hydrate 47 introduced reaches a predetermined mass, the hydrate introduction opening / closing valve 49a The on-off valve 58a is closed and the other hydrate introduction on-off valve 49b and on-off valve 58b are opened to switch from the hydrate storage container 50a to the hydrate storage container 50b.

  A cooling water level gauge 73 is provided in the upper part of the hydrate generator 10, and the detected value is input to the makeup water controller 74. The make-up water controller 74 receives the flow value of the make-up water flow meter 42 in the cooling water supply line 38, whereby the make-up water controller 74 controls the feed water flow rate adjusting valve 43 and supplies it to the coolant circulation line 15. The amount of cooling water to be replenished is adjusted, and the liquid level detected by the cooling water level gauge 73 is controlled to be constant.

  A gas phase pressure detector 75 for detecting the pressure of the gas phase in the hydrate generator 10 is connected to the top of the hydrate generator 10, and the detected value is input to the gas phase pressure controller 76. The gas phase pressure controller 76 controls the gas phase pressure control valve 52 of the exhaust line 51 and the circulation gas pressure control valve 56 of the guest gas circulation line 54 so that the pressure in the gas phase portion becomes a set value.

  Further, an ozone analyzer 77 for detecting the ozone concentration in the gas phase portion is connected to the upper portion of the hydrate generator 10, and the ozone regenerator 57 is controlled according to the detected ozone concentration of the ozone analyzer 77. Adjust the amount of ozone regeneration.

  Next, a method for producing an ozone-containing hydrate using the apparatus shown in FIG. 1 will be described.

First, in order to increase the amount of ozone stored per unit volume in the present invention, ozone gas as a guest gas is used to produce only hydrate at a hydrate generation temperature of 0 ° C. or higher in the hydrate generator 10. In addition, xenon (Xe) or carbon dioxide (CO ₂ ) is added as a mixed guest gas to hydrate ozone (O ₃ ).

  Here, a case where carbon dioxide gas is used as the mixed guest gas will be described.

  First, the cooling water 14 required for hydrate generation is stored in the hydrate generator 10, and the hydrate generator 10 has hydrates from the cooling water injection nozzles 31 a and 31 b of the cooling water circulation line 15 as shown in FIG. 2. Cooling water is jetted along the circumferential wall of the rate generator 10 to rotate the cooling water 14 in the hydrate generator 10.

  A gas mixture is blown out from the bubble generator 12 into the cooling water 14 swirling in the hydrate generator 10 through the guest gas supply line 16 as microbubbles. That is, oxygen is supplied from the oxygen gas supply line 18 through the ozone generator 17 to be ozonized, oxygen and ozone are supplied from the ozone-containing oxygen line 19, and carbon dioxide is supplied from the mixed gas supply line 20 to the ozone-containing oxygen line 19. The gas is blown into the cooling water 14 from the bubble generator 12 through the guest gas supply line 16 in the form of microbubbles.

  The bubble diameter is reduced to about 230 μm or less in order to increase the reaction speed, and is sprayed so as to be dispersed toward the center of the rotating cooling water 14 and descends along the inner peripheral wall of the hydrate generator 10. Collisions with the ozone-containing hydrate 47 are avoided.

  Circulating cooling water supply conditions from the cooling water injection nozzles 31a and 31b of the cooling water circulation line 15 are a supply amount and a temperature that absorb the ozone-containing hydrate generation heat and promote the generation.

  For example, when the ozone-containing hydrate production conditions are a pressure of 2.5 MPa or more and a temperature of 0 to 2 ° C., the supply temperature of the circulating cooling water is 0 ° C. or less (no freezing even at 0 ° C. or less due to freezing point depression). The amount of water that can be maintained is supplied.

  If the hydration proceeds at a temperature of about 274 K (about 1 ° C.), the temperature of the unreacted water that has absorbed the reaction heat rises from 0 ° C., and is supplied with circulating cooling water (about 272.2 K, 0.2 ° C).

  Since the specific gravity of the cooling water whose temperature is increased by the hydrate reaction is heavier than that of the cooling water whose temperature is low, which is injected from the cooling water injection nozzles 31a and 31b, the bubble generator which is the injection point of the mixed gas is used. If the circulating cooling water is supplied at a position lower than 12, the circulating cooling water rises as indicated by the arrows due to the difference in specific gravity and continuously contacts the ejected bubbles.

  Since the ozone-containing hydrate 47 generated in the hydrate generation region (the upper portion of the bubble generator 12) in the hydrate generator 10 has a higher specific gravity than the cooling water 14, the centrifugal force due to the swirling flow of the circulating cooling water. While being pushed toward the inner peripheral wall side of the hydrate generator 10, the hydrate 47 descends as shown by the arrows while swirling on the inner peripheral wall side due to the specific gravity difference with the cooling water 14 (swirling downward flow). Accordingly, the circulating cooling water jetted from the jet nozzles 31a and 31b rises (turning upward flow) while turning near the center.

  The reason for swirling the cooling water 14 in the hydrate generator 10 is that, besides the centrifugal separation of heavy components (hydrate) by the centrifugal force described above, heat transfer (reaction heat) that becomes a dominant factor in the hydrate reaction rate. Removal). In other words, both the microbubbles and the cooling water become an upflow and normally co-flow, so the water around the bubble is accompanied and hinders heat transfer, but by rotating the cooling water, a horizontal flow of the cooling water can be made. For this reason, since the microbubbles tend to rise strongly due to the difference in buoyancy, a deviation occurs in the flow direction between the microbubbles. For this reason, the quantity of the cooling water accompanying a bubble periphery reduces, and since it contacts with the cooling water with a low temperature instead, heat transfer is accelerated | stimulated.

  A swirl prevention plate 13 for preventing swirling flow is provided below the injection nozzles 31a and 31b, and swiveling is stopped below the swirl. Hydrate 47 descending along the inner peripheral wall sinks to the bottom of the hydrate generator 10 below the anti-rotation plate 13 and stacks the cooling water whose specific gravity increases due to the increase in temperature due to hydration. The air is sucked from the cooling water introduction part 30 provided at the lower center of the anti-swirl plate 13 and introduced into the cooling water circulation line 15, cooled by the cooler 34, and again injected from the injection nozzles 31 a and 31 b and circulated.

  The ozone-containing hydrate 47 accumulated at the bottom of the hydrate generator 10 is sent to one of the hydrate storage containers 50a, 50b via the discharge line 48.

  The unreacted mixed gas rising in the water in the reaction region of the hydrate generator 10 is discharged to the gas phase portion at the top of the generator 10. Since the released gas is composed of a large amount of carbon dioxide gas, oxygen, and ozone, it is sucked by the circulating gas blower 55 and sent again to the guest gas supply line 16 for circulation.

  In the equilibrium reaction, the ozone concentration in the circulating gas is hydrated in a large amount in the hydrate generator 10, so that the carbon dioxide concentration decreases and the ozone concentration increases, but the circulating gas blower 55 If the circulation use is repeated, the ozone concentration decreases, so the ozone analyzer 77 detects the ozone concentration in the gas phase, and if the ozone concentration is low, the ozone regenerator 57 is activated to increase the ozone concentration. The gas is fed into the guest gas supply line 16.

  The gas phase pressure of the hydrate generator 10 is detected by a gas phase pressure detector 75, and when the detected pressure rises above a set value, the internal gas is passed through the ozone decomposer 53 by the gas phase pressure control valve 52. To the atmosphere.

  High temperature water (0 ° C. or higher) separated from the ozone-containing hydrate 47 by standing under the anti-swirl plate 13 of the hydrate generator 10 is sucked by the circulation pump 33 and required via the cooler 34. Cooled at a temperature (about 0 ° C. in the present embodiment) and circulated and supplied again to the hydrate generator 10, the cooling water shortage due to the hydrate detection is detected by the cooling water level gauge 73. The supply water controller 74 controls the supply water flow rate adjustment valve 43 of the cooling water supply line 38 to supply the insufficient cooling water to the cooling water circulation line 15 as appropriate. .

  In addition, carbon dioxide gas, oxygen, and ozone, which are guest gases, are supplied from the oxygen storage container 21 and the mixed gas storage container 25 for the production amount of the ozone-containing hydrate. At this time, the supply amount of the guest gas is controlled. The guest gas controller 70 controls the supply amount of the guest gas according to the detection value of the cooling water flow meter 35 that detects the circulating cooling water amount circulating in the cooling water circulation line 15.

  In this case, the ozone concentration in the hydrate produced by the hydrate generator 10 is, for example, 1608 kg of carbon dioxide gas, 880 kg of oxygen with respect to 1000 kg of water under the temperature conditions of a pressure of 2.5 MPa and a temperature of 0 ° C. When the guest gas controller 70 advances the hydration reaction by controlling the supply amount of each guest gas so that ozone becomes a mixed gas of 115 kg, the ozone concentration of the ozone-containing hydrate 47 reaches about 5400 ppm. Even when mixed with water, the concentration of ozone is about 4,000 ppm, and a high-concentration ozone-containing hydrate 47 is obtained, which can be stored at an order of magnitude higher than conventional production methods.

  The ozone-containing hydrate 47 maintains fluidity while partially containing water, and is filled from the bottom of the hydrate generator 10 into one of the hydrate storage containers 50a and 50b with its own weight difference.

  Here, when the filling of the hydrate storage container 50a is completed, the mass meter 51a closes the hydrate introduction opening / closing valve 49a, opens the other hydrate introduction opening / closing valve 49b, and switches to the other hydrate storage container 50b. .

  After filling the hydrate storage container 50 with the ozone-containing hydrate 47 in this manner, the hydrate introduction opening / closing valve 49 is closed and the hydrate storage container 50 is removed from the hydrate introduction opening / closing valve 49.

  At this time, although not shown in FIG. 1, the on-off valve 81 provided in the hydrate storage container 50 is closed as shown in FIG. 3, and the hydrate storage container 50 is stored in the storage container 80. Cooling the temperature in the storage container 80 with the cooler 84 connected to the refrigerator 83 and maintaining the storage container 80 at a temperature of 0 ° C. or less with the flow rate adjusting valve 85 to preserve the ozone-containing hydrate for a long period of time. Can do. Hydrate has a structure in which one molecule of ozone gas is included in the host water, so if it is kept at a temperature and pressure that can maintain the hydrate during storage, ozone will not be decomposed and stored for a long time. Is possible.

  When ozone is used, the hydrate storage container 50 is taken out from the storage container 80, the on-off valve 81 is opened, and the pressure in the hydrate storage container 50 is sequentially released to decompose the ozone-containing hydrate. Thus, the guest gas containing ozone can be released, and ozone gas can be injected in the same manner as a normal gas cylinder.

  Next, the pressure and temperature for producing the ozone-containing hydrate will be described with reference to FIG.

FIG. 4 shows components as raw materials and their hydrate components.
Component H ₂ O CO ₂ O ₂ O ₃
Raw material (kg / h) 1,000 1,608 880 115
Hydrate (kg / h) 1,000 307.5 25.5 7.3
O ₃ concentration (ppm) 5,474
This shows the relationship between the pressure and temperature when producing the ozone-containing hydrate. The ozone-containing hydrate can be produced at 2.50 MPa at a temperature of 0 ° C. and 3.10 MPa at a temperature of 2 ° C. Is shown.

  As described in the conventional example, if ozone hydrate is produced with ozone gas alone, it can be produced only under low temperature and high pressure conditions, and the ozone concentration can only be as low as about 13 ppm. By generating a hydrate with a guest gas mixed with carbon dioxide or the like, it becomes possible to obtain a high-concentration ozone-containing hydrate at around 0 ° C. and 3 MPa or less and an ozone concentration of about 5000 ppm.

  The above composition (ozone concentration about 5000 ppm) is a prediction by a statistical thermodynamic model that predicts the hydrate phase equilibrium. In this model, the Langmuir constant of ozone (a model parameter serving as an index indicating the ease of incorporation of a guest substance into the hydrate) is 2.5 times that of oxygen. This is a value estimated based on the following experimental facts.

  As a result of an experiment in which the present inventors made a hydrate by contacting a mixed gas of ozone and oxygen, water, and carbon tetrachloride, and measured the composition in the hydrate, ozone was 2.5. It was confirmed that it was concentrated about twice and incorporated into the hydrate. By this experiment, it is possible to hydrate with an ozone concentration of about 5000 ppm.

  In the hydration, the amount of other gas containing oxygen (carbon dioxide gas, xenon) with respect to ozone gas should be 5 times or more, preferably 20 times or more by mass, but when the amount of other gas increases, hydrate gas Since the ozone concentration in the inside decreases, the amount of other gases is preferably about 10 to 30 times that of ozone gas.

  The amount of guest gas blown into the cooling water is 100 to 400 parts by mass, preferably 200 to 100 parts by mass with respect to 1,000 parts by mass of water so that the amount of guest gas exceeds the amount of guest with respect to the host forming the hydrate. 300 parts by mass is good.

Next, an example of a more specific device configuration and raw material pressure, temperature, and flow rate according to the present invention will be described.
1) Specifications for producing ozone hydrate from 1m ³ of water Raw material and amount of components produced;
H ₂ O 1,000kg / h
CO ₂ amount 307.5kg / h
O ₂ amount 25.5 kg / h
O ₃ amount 7.3 kg / h
Hydrate production conditions:
Pressure 2.5 MPa
Temperature 273K
Specific gravity of generated hydrate 1,150kg / m ³
Circulating cooling water volume 196,000kg / h
Pressure 2.8 MPa
Temperature -1 ° C
Circulating gas volume 2,064kg / h
Pressure 2.7 MPa
Temperature 25 ° C
Supply water volume 1,000kg / h
Pressure 2.8 MPa
Temperature 25 ° C
2) Equipment specifications (a) Hydrate generator Radix 1 Model Cylindrical saddle Design pressure 3.0 MPa
Design temperature 0 ℃
Diameter 0.8m
Generator height 8.4m
(B) Bubble generator Flow rate 48m ³ / h
Bubble diameter 0.00023m
Density 54kg / m ³
(C) Circulating gas blower Number of units 1 Inhalation amount 2,490kg / h
Suction pressure 2.50 MPa
First stage discharge pressure 2.70 MPa
Compressor motor horsepower 7.5kW
(D) Oxygen storage container Base number 38 Model Cylindrical saddle type Design pressure resistance 20MPa
Maximum temperature 55 ° C
Diameter 0.25m
0.8m in height
Capacity 0.039M ^3/1 group weight 10 kg / m ³ 1 group density 263 kg / m ³
Storage time 12h
(E) Carbon dioxide storage container Number of bases 477 Type Cylindrical bowl Design pressure 15 MPa
Maximum temperature 55 ° C
Diameter 0.25m
0.8m in height
Capacity 0.039M ^3/1 group weight 8 kg / m ³ 1 group density 197 kg / m ³
Storage time 12h
(F) Ozone generator Radix 1 Design pressure 3 MPa
Design temperature 55 ℃
O ₂ flow rate inlet 33kg / h
Exit 30kg / h
O ₃ flow rate 3kg / h
Pressure 0.106 MPa
Temperature 25 ° C
(G) Ozone regenerator Base number 1 unit Design pressure 3 MPa
Design temperature 0 ℃
Flow rate Inlet CO ₂ 1,301 kg / h
O ₂ 862 kg / h
O ₃ 100 kg / h
Total 2,263kg / h
Outlet CO ₂ 1,301 kg / h
O ₂ 855 kg / h
O ₃ 108 kg / h
(H) Circulation pump Base number 1 unit Flow rate 195,670kg / h
Differential pressure 0.39 MPa
Required motor horsepower 33kW
(I) Water cooler Base number 1 Unit Exchange heat quantity 195,670 kcal / h
Circulating cooling water volume 195,670kg / h
Inlet temperature 0.0 ℃
Outlet temperature -10 ° C
Cooling transmission area 87m ²
Refrigerant evaporation temperature -5 ℃
(J) Water supply pump Flow rate 1,000kg / h
Differential pressure ΔP 2.7 MPa
Required motor horsepower 1.9kW
(K) Replenishment water tank Number of bases 1 Model Cylindrical saddle type Design pressure 0.105 MPa
Temperature 35 ° C
Volume 36m ³
Diameter 3m
5m height
(L) Hydrate storage container Base 52 / h
Type Cylindrical bowl Production quantity Hydrate 1,340kg / h
Water volume 50% 670kg / h
Total 2,010 kg / h
1.8m ³ / h
Design pressure 3MPa
-25 ° C
Diameter 0.25m
Container height 0.8m
Capacity 0.039M ^3/1 group (m) refrigerator (refrigerating cycle)
Base 1 Refrigerant R404A
Refrigerant amount 7,801 kg / h
Compressor motor horsepower 170kW
(N) Ozone decomposer Number of units 1 unit Flow rate Inlet O ₂ 25.5 kg / h
O ₃ 7.3 kg / h
Outlet O ₂ 32.8 kg / h
Pressure 0.106 MPa
Temperature 0 ℃

  As mentioned above, although the specific example of the apparatus structure of ozone containing hydrate manufacture and the flow volume, pressure, and temperature of a raw material was demonstrated, this invention is not limited to this, It is made to contain in the ozone containing hydrate to manufacture. Of course, the mixing ratio of each guest gas may be changed according to the ozone concentration.

DESCRIPTION OF SYMBOLS 10 Hydrate generator 12 Bubble generator 14 Cooling water 15 Cooling water circulation line 16 Guest gas supply line 18 Oxygen supply line 20 Contaminated gas supply line 47 Ozone containing hydrate 50a, 50b Hydrate storage container

Claims (5)

While storing cooling water in the hydrate generator and providing a bubble generator in the hydrate generator, maintaining the pressure in the hydrate generator at 2.5 to 3 MPa, on the other hand, ozone gas as a guest gas, Xenon or carbon dioxide gas is added to form a mixed gas, and the mixed gas is blown from the bubble generator with microbubbles, and the amount of guest gas blown into the cooling water is 100 to 400 parts by weight with respect to 1000 parts by weight of water. The ozone-containing hydrate is generated at the top of the bubble generator, and the generated ozone-containing hydrate is lowered to the bottom of the hydrate generator due to the difference in specific gravity. The cooling water with high specific gravity is sucked from the cooling water introduction part located at the lower center of the bubble generator and this is used as cooling water of 0 ° C. or lower. Method for producing an ozone-containing hydrate, characterized in that serial jetting circulation from above a and said bubble generator of the cooling water inlet portion into said hydrate generator below. The hydrate storage container is connected to the lower part of the hydrate generator, and the ozone-containing hydrate generated in the hydrate generator and accumulated at the bottom is stored by flowing down into the hydrate storage container. the method for producing ozone-containing hydrate. The manufacturing method of the ozone containing hydrate of Claim 1 or 2 which mixes carbon dioxide gas or xenon 10-30 times with respect to the mass of ozone gas to make a mixed gas. A hydrate generator for storing cooling water, and provided in the cooling water in the hydrate generator, and a mixed gas obtained by adding xenon or carbon dioxide gas to ozone gas as a guest gas is blown into the cooling water with microbubbles, guest amount of gas blown into the cooling water, to subject the sheet to a mixed gas of ozone and xenon or carbon dioxide gas to the bubble generator and the bubble generator to be blown so that 100 to 400 parts by mass relative to water 1000 parts by guests A gas supply line; a guest gas discharge line connected to the top of the hydrate generator; and a gas phase pressure control connected to the guest gas discharge line to maintain the pressure in the hydrate generator at 2.5 to 3 MPa. The cooling water is sucked from the valve and the cooling water introduction part located at the lower center of the bubble generator, and the cooling water Above a and said bubble generator ozone-containing hydrate production apparatus characterized by comprising a cooling water circulation line for injecting the circulation from the injection nozzle provided in a position lower than the inlet section. The apparatus for producing an ozone-containing hydrate according to claim 4, wherein a hydrate storage container for introducing and storing the generated ozone-containing hydrate is connected to a lower portion of the hydrate generator.

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