JP2020083701A - Ozone hydrate production device and method of producing ozone hydrate - Google Patents

Abstract

To produce ozone hydrate having a target ozone density.SOLUTION: An ozone hydrate production device 100 comprises: a composition measuring unit 190 for measuring a composition of a raw material gas to be supplied to a gas liquid mixing unit 140; a gas flow rate measuring unit 192 for measuring a flow rate of the raw material gas being supplied to the gas liquid mixing unit 140; a temperature measuring unit 194 for measuring a cooling temperature of a cooling unit (first cooling unit 150); a pressure measuring unit 196 for measuring a pressure in at least one of a circulation path 110, the gas liquid mixing unit 140, the cooling part, and a storage unit 120; and a control unit 200 for, on the basis of the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature and the pressure, controlling at least one of the raw material gas supply unit 180, the cooling unit, and a pressure adjustment unit 122.SELECTED DRAWING: Figure 1

Description

The present invention relates to an ozone hydrate production apparatus for producing ozone hydrate and a method for producing ozone hydrate.

In recent years, the use of ozone hydrate for sterilization of foods, containers, rooms, etc. has been studied. Ozone hydrate is produced by mixing a raw material gas containing ozone and raw material water and cooling the mixture to a predetermined temperature.

Further, as a technique for efficiently producing ozone hydrate, an ozone hydrate production apparatus for mixing a raw material gas containing ozone and carbon dioxide with raw material water has been developed (for example, Patent Document 1).

JP, 2016-204216, A

In the above-mentioned ozone hydrate manufacturing apparatus, ozone hydrate accumulates in the apparatus as the manufacturing time elapses. Then, the flow paths such as the pipes constituting the device are narrowed, and the flow rate of the raw material water is reduced. Therefore, even if the supply amount of the raw material gas, the temperature of the mixture of the raw material gas and the raw material water, and the pressure inside the apparatus are the same, the ozone concentration in the produced ozone hydrate is stable. There is a problem not to do.

In view of such a problem, the present invention has an object to provide an ozone hydrate manufacturing apparatus capable of manufacturing an ozone hydrate having a target ozone concentration, and an ozone hydrate manufacturing method.

In order to solve the above problems, an ozone hydrate manufacturing apparatus of the present invention is a gas-liquid that mixes a raw material gas containing ozone and an auxiliary gas and a raw material water, which is provided in the circulation path for circulating the raw material water. A mixing section, a raw material gas supply section for supplying a raw material gas to the gas-liquid mixing section, a cooling section provided in the circulation path for cooling the raw material water, and a circulation path provided with ozone hydrate and unreacted gas. A storage unit for storing the raw material water, a pressure adjusting unit for adjusting the pressure of at least one of the circulation path, the gas-liquid mixing unit, the cooling unit, and the storage unit, and the gas-liquid mixing unit. A composition measuring section for measuring the composition of the raw material gas, a gas flow rate measuring section for measuring the flow rate of the raw material gas supplied to the gas-liquid mixing section, a temperature measuring section for measuring the cooling temperature by the cooling section, a circulation path, Based on the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure, a pressure measuring portion that measures the pressure of at least one of the gas-liquid mixing portion, the cooling portion, and the storage portion, And a control unit that controls at least one of the supply unit, the cooling unit, and the pressure adjusting unit.

Further, the ozone hydrate manufacturing apparatus is provided with a water flow rate measuring unit that measures the flow rate of the raw material water flowing through the circulation path, and the control unit adds the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure to At least one of the raw material gas supply unit, the cooling unit, and the pressure adjusting unit may be controlled based on the flow rate of the raw material water.

In order to solve the above problems, the method for producing ozone hydrate according to the present invention is a composition of a raw material gas containing ozone and an auxiliary gas, which is supplied to a gas-liquid mixing section provided in a circulation path in which raw material water circulates. And a step of measuring the flow rate of the raw material gas supplied to the gas-liquid mixing section, a step of measuring the cooling temperature by the cooling section provided in the circulation path for cooling the raw material water, the circulation path, the gas A step of measuring the pressure of at least one of the liquid mixing section, the cooling section, and the storage section that is provided in the circulation path and stores ozone hydrate, unreacted gas, and raw material water; Based on the composition, the flow rate of the raw material gas, the cooling temperature, and the pressure, the pressure of at least one of the circulation path, the gas-liquid mixing section, the cooling section, and the storage section, and the raw material supplied to the gas-liquid mixing section. Controlling the composition of the gas and at least one of the cooling parts.

According to the present invention, it becomes possible to manufacture an ozone hydrate having a target ozone concentration.

It is a figure explaining the schematic structure of the ozone hydrate manufacturing apparatus concerning this embodiment. It is a figure explaining the schematic structure of a source gas supply part. It is a flow chart explaining the flow of concentration adjustment processing by the ozone hydrate manufacturing device concerning this embodiment. It is a figure explaining the schematic structure of the ozone hydrate manufacturing apparatus of a modification.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The dimensions, materials, and other specific numerical values shown in the embodiments are merely examples for facilitating the understanding of the invention, and do not limit the invention unless otherwise specified. In this specification and the drawings, elements having substantially the same function and configuration are denoted by the same reference numerals to omit redundant description, and elements not directly related to the present invention are omitted. To do.

FIG. 1 is a diagram illustrating a schematic configuration of an ozone hydrate manufacturing apparatus 100 according to this embodiment. As shown in FIG. 1, the ozone hydrate manufacturing apparatus 100 includes a circulation path 110, a storage section 120, a pressure adjusting section 122, a circulating water pump 130, a gas-liquid mixing section 140, and a first cooling section 150. A hydrate pump 160, a second cooling unit 162, a makeup water supply unit 170, a source gas supply unit 180, a composition measurement unit 190, a gas flow rate measurement unit 192, a temperature measurement unit 194, and a pressure measurement unit. 196, the water flow rate measurement part 198, and the control part 200 are included. It should be noted that in FIG. 1, solid arrows indicate flows of gas, liquid, and solid, and broken arrows indicate flows of signals. Further, in the present embodiment, a case where carbon dioxide is used as an auxiliary gas will be described as an example.

The circulation path 110 is a flow path through which at least raw material water circulates. The circulation path 110 is configured by a ring-shaped pipe arranged outside the storage section 120. The circulation path 110 is connected to a vertically lower part of the storage section 120 (where the raw water is stored).

The storage section 120 is provided in the circulation path 110. The storage unit 120 is configured by, for example, a cylindrical container covered with a heat insulating material. The storage unit 120 includes a hydrate (ozone hydrate, oxygen hydrate, carbon dioxide hydrate, and ozone-carbon dioxide hydrate) generated in a first cooling unit 150 described later, raw water, and unreacted gas. To store. The ozone hydrate is a hydrate in which ozone is included as guest molecules. The oxygen hydrate is a hydrate in which oxygen is included as a guest molecule. Carbon dioxide hydrate is a hydrate in which carbon dioxide is included as a guest molecule. Ozone-carbon dioxide hydrate is a hydrate in which ozone and carbon dioxide are included as guest molecules.

The circulating water pump 130 is provided in the circulation path 110. The circulating water pump 130 has a suction port connected to the storage section 120 side and a discharge port connected to the gas-liquid mixing section 140 side described later. The circulating water pump 130 is driven according to the control processing by the control unit 200. When the circulating water pump 130 is driven, the raw material water stored in the storage section 120 circulates in the circulation path 110 and the storage section 120.

The gas-liquid mixing section 140 is provided on the discharge side of the circulating water pump 130 in the circulation path 110. The gas-liquid mixing unit 140 mixes the raw material gas (ozone, oxygen, and carbon dioxide) supplied from the raw material gas supply unit 180 described below with the raw material water supplied from the circulating water pump 130. The gas-liquid mixing section 140 is configured by, for example, a mixer in which the bubbles (micro bubbles) of the source gas are substantially evenly distributed in the liquid phase (source water).

The first cooling unit 150 (cooling unit) is provided between the gas-liquid mixing unit 140 and the storage unit 120 in the circulation path 110. The first cooling unit 150 is supplied with raw material water (hereinafter sometimes referred to as “mixed water”) in which the raw material gas is mixed (dissolved) by the gas-liquid mixing unit 140. The first cooling unit 150 is, for example, a shell-and-tube or double-tube heat exchanger, and cools the mixed water with a cooling medium such as R-404A. The first cooling unit 150 cools the mixed water to the ozone hydrate generation temperature condition (for example, about 272K (-1°C) to 275K (2°C)) under the ozone hydrate generation pressure condition. As a result, the hydrate is generated in the first cooling unit 150. The ozone hydrate generation pressure condition (saturation pressure condition) is, for example, 1.2 MPa to 3.5 MPa.

Further, in the present embodiment, carbon dioxide is contained in the raw material gas as an auxiliary gas. Carbon dioxide functions as a promoter that promotes the reaction of ozone hydrate formation. By generating carbon dioxide by including carbon dioxide in the raw material gas, it is possible to reduce the generation pressure of ozone hydrate and increase the generation temperature. As a result, the design pressure of the gas-liquid mixing section 140, the subsequent equipment, the piping and the like can be reduced. Therefore, the ozone hydrate manufacturing apparatus 100 can reduce the cost required for pressurizing the raw material gas, the gas-liquid mixing section 140, the subsequent equipment and piping, and the like.

Further, the gas-liquid mixing section 140 brings ozone and water into contact with each other in a bubble diameter suitable for the reaction. This makes it possible to avoid abnormal pressure rise in the bubbles due to the extremely small bubbles. Therefore, it is possible to prevent the ozone from being attenuated due to the temperature rise due to the abnormal pressure increase. Furthermore, since it is possible to prevent the hydrate from becoming finer, it becomes possible to generate a hydrate that is easy to separate in the storage section 120.

In this way, the hydrate generated in the first cooling unit 150 is sent to the storage unit 120. The hydrate formation reaction is carried out by mixing and contacting the raw material water and the bubbles (micro bubbles). Therefore, the hydrate formation reaction time varies depending on the surface area of the bubbles and the state of mixing with water. For example, when the bubble diameter is 100 μm to 200 μm, the yield is about 80% and is about 5 to 15 seconds. Therefore, the hydrate is generated not only in the first cooling unit 150 but also while the mixed water is sent from the first cooling unit 150 to the storage unit 120.

Further, when the ozone concentration in the gas in the first cooling unit 150 becomes less than the ozone hydrate production concentration condition, the ozone hydrate production reaction does not proceed. Therefore, the unreacted gas that has become less than the ozone hydrate production concentration condition is sent to the storage unit 120 as a mixture together with the hydrate and the raw material water.

Then, the storage section 120 further generates hydrate and separates the mixture into hydrate, unreacted gas, and raw material water. The specific gravity of hydrate is about 1.15, which is larger than the specific gravity of raw water of about 1.0. Therefore, due to the difference in specific gravity, the hydrate settles at the bottom of the storage section 120, and the unreacted gas, which is a gas, stays in the gas phase section above the storage section 120. That is, the mixture can be separated into the hydrate, the unreacted gas, and the raw material water simply by introducing the mixture into the storage section 120 and allowing it to stand still.

In addition, in the ozone hydrate manufacturing apparatus 100 of the present embodiment, the mixture is injected and introduced in the tangential direction of the storage section 120. As a result, the ozone hydrate production apparatus 100 can swirl the mixture in the storage section 120 to agglomerate the hydrate crystals to facilitate separation, thereby improving the separation efficiency. Further, the ozone hydrate manufacturing apparatus 100 can improve the contact efficiency between the bubbles of the unreacted gas and water, and can improve the hydrate generation efficiency in the storage section 120.

In this way, the hydrate separated by the storage section 120 is sent to the second cooling section 162 by the hydrate pump 160. Then, in the second cooling unit 162, the hydrate is cooled to about -25°C in order to reduce the attenuation rate when stored for a long period of time. The hydrate cooled by the second cooling unit 162 is stored in the storage unit.

Further, the raw material water accompanying the hydrate introduced into the hydrate pump 160 is about 60 mass% to about 90 mass %, and the raw material water accompanying the hydrate is, for example, 30% by the hydrate pump 160. The water is reduced to about mass%. In this way, the separated water separated by the hydrate pump 160 is introduced into the circulation path 110 via the valve 164.

On the other hand, the raw material water separated by the storage section 120 is circulated in the circulation path 110 by the circulating water pump 130 together with the separated water. Further, the unreacted gas separated by the storage section 120 is exhausted to the outside (for example, dezonizer) through the pipe 122a and the pressure adjusting section 122.

The pressure adjusting unit 122 is composed of a valve whose opening can be changed. The pressure adjusting unit 122 is provided in the pipe 122 a connected to the upper portion of the storage unit 120. The opening of the pressure adjusting unit 122 is adjusted by the control unit 200 so that the pressure of the gas phase (unreacted gas) in the storage unit 120 is maintained at a predetermined target pressure.

The makeup water supply unit 170 supplies the circulation path 110 with the amount of water (crystal water) reduced by the generation of hydrate (crystal water). As a result, the raw material gas in the unreacted gas can be absorbed and recovered in the storage section 120.

The raw material gas supply unit 180 supplies the raw material gas to the gas-liquid mixing unit 140. FIG. 2 is a diagram illustrating a schematic configuration of the raw material gas supply unit 180. As shown in FIG. 2, the raw material gas supply unit 180 includes an ozone generator 250, an ozone supply pipe 252, a flow rate adjustment valve 254, an auxiliary gas supply source 260, an auxiliary gas supply pipe 262, and a flow rate adjustment valve 264. And a source gas supply pipe 270. Note that, in FIG. 2, solid arrows indicate the flow of gas, and broken arrows indicate the flow of signals.

The ozone generator 250 is, for example, an ozonizer. Ozone is supplied to the ozone generator 250 from an oxygen supply source (not shown) (for example, an oxygen cylinder, a PSA (Pressure Swing Adsorption) device, or the like). Then, in the ozone generator 250, a gas containing ozone (for example, 10 mass% or more and about 0.4 MPa) is generated by exposing oxygen to the discharge environment. The gas containing ozone and oxygen generated in the ozone generator 250 (hereinafter, simply referred to as “ozone”) is supplied to the gas-liquid mixing section 140 through the ozone supply pipe 252 and the raw material gas supply pipe 270.

The ozone supply pipe 252 connects the ozone generator 250 and the raw material gas supply pipe 270. The flow rate adjustment valve 254 is provided in the ozone supply pipe 252. The flow rate adjusting valve 254 is a valve whose opening can be changed.

The auxiliary gas supply source 260 is a supply source of carbon dioxide (auxiliary gas). The auxiliary gas supply source 260 is, for example, a container that stores carbon dioxide, such as a liquefied carbon dioxide cylinder. The carbon dioxide stored in the auxiliary gas supply source 260 is supplied to the gas-liquid mixing section 140 through the auxiliary gas supply pipe 262 and the raw material gas supply pipe 270.

The auxiliary gas supply pipe 262 connects the auxiliary gas supply source 260 and the raw material gas supply pipe 270. The flow rate adjustment valve 264 is provided in the auxiliary gas supply pipe 262. The flow rate adjusting valve 264 is a valve whose opening can be changed.

Returning to FIG. 1, the composition measuring unit 190 is provided in the source gas supply pipe 270. The composition measuring unit 190 measures the composition of the raw material gas passing through the raw material gas supply pipe 270. That is, the composition measuring unit 190 measures the composition of the raw material gas supplied to the gas-liquid mixing unit 140. The composition measuring unit 190 is, for example, a gas chromatograph analyzer.

The gas flow rate measuring unit 192 is provided in the source gas supply pipe 270. The gas flow rate measuring unit 192 measures the flow rate of the raw material gas passing through the raw material gas supply pipe 270. That is, the gas flow rate measuring unit 192 measures the flow rate of the raw material gas supplied to the gas-liquid mixing unit 140. The gas flow rate measuring unit 192 is a flow meter.

The temperature measuring unit 194 measures the cooling temperature of the mixed water by the first cooling unit 150. More specifically, the temperature measurement unit 194 includes a thermometer provided between the gas-liquid mixing unit 140 and the first cooling unit 150 in the circulation path 110, and the first cooling unit 150 and the storage section in the circulation path 110. 120 and a thermometer provided between them. The temperature measuring unit 194 derives the cooling temperature of the mixed water by the first cooling unit 150 based on the measurement values of both thermometers. That is, the temperature measuring unit 194 has a temperature of the mixed water flowing between the first cooling unit 150 and the storage unit 120 and a temperature of the mixed water flowing between the gas-liquid mixing unit 140 and the first cooling unit 150. The difference is derived as the cooling temperature.

The pressure measurement unit 196 measures the pressure inside the storage unit 120. Specifically, the pressure measuring unit 196 measures the pressure of the gas phase in the storage unit 120.

The water flow rate measurement unit 198 measures the flow rate of the raw material water flowing through the circulation path 110. In the present embodiment, the water flow rate measuring unit 198 measures the flow rate of the raw material water flowing from the storage unit 120 to the circulating water pump 130 in the circulation path 110. The water flow rate measuring unit 198 is a flow meter.

The control unit 200 is composed of a semiconductor integrated circuit including a CPU (central processing unit). The control unit 200 reads out a program and parameters for operating the CPU itself from a ROM (Read Only Memory). The control unit 200 manages and controls the entire ozone hydrate manufacturing apparatus 100 in cooperation with a RAM (Random Access Memory: readable/writable memory) as a work area and other electronic circuits.

In the present embodiment, the control unit 200 refers to the estimation function stored in a memory (not shown), and based on the composition of the source gas, the flow rate of the source gas, the cooling temperature, the pressure, and the flow rate of the source water, the source gas. At least one of the flow rate adjusting valves 254, 264, the first cooling unit 150, and the pressure adjusting unit 122 that configure the supply unit 180 is controlled.

The estimation function associates the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, the pressure, and the flow rate of the raw material water with the ozone concentration in the produced hydrate. The estimation function is the measured value of the composition of the raw material gas (experimental value), the measured value of the raw material gas flow rate, the measured value of the cooling temperature, the measured value of the pressure, the measured value of the raw material water flow rate, and the manufactured hide. It is created by statistically analyzing the measured value of ozone concentration in the rate. The statistical analysis is, for example, multiple regression analysis. The estimation function may be created using a physical model (for example, thermodynamics) in addition to the statistical analysis.

For example, when the estimated value of the ozone concentration in the hydrate derived by referring to the estimation function is less than the lower limit value of the target range, the control unit 200 controls the first cooling unit 150 to set the cooling temperature. Lower. On the other hand, the control unit 200 controls the first cooling unit 150 to control the cooling temperature when the estimated value of the ozone concentration in the hydrate derived by referring to the estimation function exceeds the upper limit value of the target range. To raise.

Further, when the estimated value of the ozone concentration in the hydrate, which is derived by referring to the estimation function, is less than the lower limit value of the target range, the control unit 200 controls the raw material gas supply unit 180 to control the raw material gas. Increase the ozone concentration inside. More specifically, the control unit 200 increases the opening degree of the flow rate adjusting valve 254 and decreases the opening degree of the flow rate adjusting valve 264. On the other hand, when the estimated value of the ozone concentration in the hydrate, which is derived by referring to the estimation function, exceeds the upper limit value of the target range, the control unit 200 controls the raw material gas supply unit 180 to control the raw material gas. Decrease the ozone concentration. More specifically, the control unit 200 decreases the opening degree of the flow rate adjusting valve 254 or increases the opening degree of the flow rate adjusting valve 264.

In addition, when the estimated value of the ozone concentration in the hydrate derived by referring to the estimation function is less than the lower limit value of the target range, the control unit 200 reduces the opening degree of the pressure adjusting unit 122, The pressures of the circulation path 110, the storage section 120, the gas-liquid mixing section 140, and the first cooling section 150 are increased. On the other hand, when the estimated value of the ozone concentration in the hydrate, which is derived by referring to the estimation function, exceeds the upper limit value of the target range, the control unit 200 increases the opening degree of the pressure adjustment unit 122 to circulate. The pressures of the passage 110, the storage section 120, the gas-liquid mixing section 140, and the first cooling section 150 are reduced.

[Method for producing ozone hydrate]
Next, a method for manufacturing ozone hydrate using the ozone hydrate manufacturing apparatus 100 will be described. In the initial state, the control unit 200 opens the flow rate adjusting valves 254 and 264 so that the flow rate of the raw material gas supplied to the gas-liquid mixing section 140 becomes a predetermined supply flow rate and the raw material gas has a predetermined composition. Adjust. Further, the control unit 200 controls the circulating water pump 130 so that the flow rate of the raw material water circulating in the circulation path 110 becomes a predetermined circulating flow rate. Further, the control unit 200 operates the first cooling unit 150 so that the cooling temperature by the first cooling unit 150 becomes a predetermined temperature. Further, the control unit 200 adjusts the opening degree of the pressure adjusting unit 122 so that the pressure of the storage unit 120 becomes a predetermined pressure.

In this way, at least the raw material water circulates in the circulation path 110, the raw material water and the raw material gas are mixed by the gas-liquid mixing section 140, and the mixed water (the raw material water and the raw material gas) is cooled by the first cooling section 150. Thereby, in the ozone hydrate manufacturing apparatus 100, ozone hydrate, oxygen hydrate, carbon dioxide hydrate, and ozone-carbon dioxide hydrate are generated. The generated hydrate (ozone hydrate, oxygen hydrate, carbon dioxide hydrate, and ozone-carbon dioxide hydrate), the unreacted gas, and the raw material water are stored in the storage unit 120. The mixture is gas-solid separated into hydrate, unreacted gas, and raw material water in the storage section 120.

Then, in the present embodiment, the density adjustment processing is repeatedly performed by an interrupt that occurs at predetermined time intervals.

FIG. 3 is a flowchart illustrating the flow of concentration adjustment processing by the ozone hydrate manufacturing apparatus 100 according to this embodiment. As shown in FIG. 3, the concentration adjusting process according to the present embodiment includes a composition measuring step S110, a gas flow rate measuring step S120, a cooling temperature measuring step S130, a pressure measuring step S140, and a water flow rate measuring step S150. It includes an estimated value derivation step S160, a determination step S170, and an adjustment step S180. Hereinafter, each step will be described in detail.

[Composition measuring step S110]
The composition measuring unit 190 measures the composition of the raw material gas supplied to the gas-liquid mixing unit 140.

[Gas flow rate measuring step S120]
The gas flow rate measuring unit 192 measures the flow rate of the raw material gas supplied to the gas-liquid mixing unit 140.

[Cooling temperature measuring step S130]
The temperature measuring unit 194 measures the cooling temperature of the mixed water by the first cooling unit 150.

[Pressure measurement step S140]
The pressure measurement unit 196 measures the pressure inside the storage unit 120.

[Water flow rate measuring step S150]
The water flow rate measurement unit 198 measures the flow rate of the raw material water flowing through the circulation path 110.

[Estimated value derivation step S160]
The control unit 200 refers to the estimation function stored in the memory, and measures the composition of the raw material gas measured in the composition measuring step S110, the flow rate of the raw material gas measured in the gas flow rate measuring step S120, and the cooling temperature measuring step S130. The ozone concentration in the hydrate is estimated based on the cooling temperature, the pressure measured in the pressure measuring step S140, and the flow rate of the raw material water measured in the water flow rate measuring step S150.

[Determination Step S170]
The control unit 200 determines whether the estimated value of the ozone concentration derived in the estimated value deriving step S160 is within the target range. As a result, when it is determined that the estimated value is within the target range (YES in S170), the control unit 200 ends the density adjustment process. On the other hand, when it is determined that the estimated value is outside the target range (NO in S170), the control unit 200 shifts the processing to the adjusting step S180.

[Adjustment step S180]
When the estimated value of the ozone concentration is less than the lower limit value of the target range, the control unit 200 controls the first cooling unit 150 to reduce the cooling temperature or controls the raw material gas supply unit 180. The ozone concentration in the raw material gas is increased, or the opening of the pressure adjusting unit 122 is reduced to increase the pressures of the circulation path 110, the storage unit 120, the gas-liquid mixing unit 140, and the first cooling unit 150.

On the other hand, when the estimated value of the ozone concentration exceeds the upper limit value of the target range, the control unit 200 controls the first cooling unit 150 to raise the cooling temperature or control the raw material gas supply unit 180. , Lowering the ozone concentration in the raw material gas or increasing the opening of the pressure adjusting unit 122 to lower the pressures of the circulation path 110, the storage unit 120, the gas-liquid mixing unit 140, and the first cooling unit 150. ..

As described above, the ozone hydrate production apparatus 100 and the ozone hydrate production method of the present embodiment can estimate the ozone concentration in the hydrate by referring to the estimation function. This makes it possible to estimate the ozone concentration in the hydrate more quickly (real time) than in the conventional technique in which the hydrate is dissolved and the ozone concentration is directly measured by titration.

Further, the control unit 200 controls at least one of the raw material gas supply unit 180, the first cooling unit 150, and the pressure adjusting unit 122 based on the estimated ozone concentration. The ozone hydrate of

The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but it goes without saying that the present invention is not limited to such embodiments. It is obvious to those skilled in the art that various changes or modifications can be conceived within the scope of the claims, and it should be understood that these also belong to the technical scope of the present invention. To be done.

For example, in the above-described embodiment, the configuration in which the pressure adjusting unit 122 adjusts the pressure of the storage unit 120 is taken as an example. However, the pressure adjustment unit 122 may adjust the pressure of at least one of the circulation path 110, the gas-liquid mixing unit 140, and the storage unit 120. For example, the pressure adjusting unit 122 may adjust the pressure of the circulation path 110 or the gas-liquid mixing unit 140.

Further, in the above-described embodiment, the configuration in which the ozone hydrate manufacturing apparatus 100 includes the water flow rate measurement unit 198 is taken as an example. However, the water flow rate measuring unit 198 is not an essential component. When the water flow rate measuring unit 198 is not provided, the control unit 200 uses the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure as input values.

Further, in the above embodiment, the case where the control unit 200 takes the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, the pressure, and the flow rate of the raw material water as input values is taken as an example. However, in addition to the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, the pressure, and the flow rate of the raw material water, the control unit 200 determines the composition of the unreacted gas (the unreacted gas exhausted from the pipe 122a), The structure of the gas-liquid mixing section 140 (the sparger pore size or the structure of the gas-liquid mixer) may be used as the input value.

Further, in the above-described embodiment, the case where the control unit 200 sets at least one of the raw material gas supply unit 180, the first cooling unit 150, and the pressure adjustment unit 122 as a control target has been described as an example. However, the control unit 200 may control the circulating water pump 130 so that the estimated value falls within the target range based on the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure.

Further, in the above embodiment, the case where carbon dioxide is included in the raw material gas as the auxiliary gas has been described as an example. However, the type of the auxiliary gas is not limited as long as it is a gas that promotes the production of ozone hydrate. For example, xenon may be included in the raw material gas as an auxiliary gas.

Further, in the above embodiment, the ozone hydrate manufacturing apparatus 100 in which the first cooling unit 150 is provided on the downstream side of the gas-liquid mixing unit 140 has been described. However, the positional relationship between the gas-liquid mixing section 140 and the first cooling section 150 is not limited. FIG. 4 is a diagram illustrating a schematic configuration of an ozone hydrate manufacturing apparatus 300 of a modified example. As shown in FIG. 4, the ozone hydrate manufacturing apparatus 300 may include a gas-liquid mixing section 140 on the downstream side of the first cooling section 150.

It should be noted that each step of the density adjustment processing in the present specification does not necessarily have to be processed in time series in the order described as a flowchart, and may include processing in parallel or by a subroutine.

INDUSTRIAL APPLICATION This invention can be utilized for the ozone hydrate manufacturing apparatus and the manufacturing method of an ozone hydrate.

100, 300 Ozone hydrate production apparatus 110 Circulation path 120 Storage section 122 Pressure adjusting section 140 Gas-liquid mixing section
150 First cooling unit (cooling unit)
180 Raw Material Gas Supply Section 190 Composition Measuring Section 192 Gas Flow Measuring Section 194 Temperature Measuring Section 196 Pressure Measuring Section 198 Water Flow Measuring Section 200 Control Section

Claims (3)

A circulation path through which raw material water circulates,
A gas-liquid mixing section which is provided in the circulation path and which mixes a raw material gas containing ozone and an auxiliary gas and the raw material water,
A source gas supply unit for supplying the source gas to the gas-liquid mixing unit,
A cooling unit which is provided in the circulation path and cools the raw water;
A storage unit that is provided in the circulation path and stores ozone hydrate, unreacted gas, and the raw material water,
A pressure adjusting unit that adjusts the pressure of at least one of the circulation path, the gas-liquid mixing unit, the cooling unit, and the storage unit;
A composition measuring unit for measuring the composition of the raw material gas supplied to the gas-liquid mixing unit,
A gas flow rate measuring section for measuring a flow rate of the raw material gas supplied to the gas-liquid mixing section;
A temperature measuring unit for measuring a cooling temperature by the cooling unit,
A pressure measuring unit that measures the pressure of at least one of the circulation path, the gas-liquid mixing unit, the cooling unit, and the storage unit;
Control for controlling at least one of the raw material gas supply unit, the cooling unit, and the pressure adjusting unit based on the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure. Department,
Ozone hydrate manufacturing apparatus equipped with. A water flow rate measuring unit for measuring the flow rate of the raw material water flowing through the circulation path,
The control unit, in addition to the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure, based on the flow rate of the raw material water, the raw material gas supply unit, the cooling unit, and, The ozone hydrate manufacturing apparatus according to claim 1, wherein at least one of the pressure adjusting units is controlled. A step of measuring the composition of a raw material gas containing ozone and an auxiliary gas, which is supplied to a gas-liquid mixing section provided in a circulation path in which the raw material water circulates,
Measuring the flow rate of the raw material gas supplied to the gas-liquid mixing section,
A step of measuring a cooling temperature by a cooling unit which is provided in the circulation path and cools the raw material water;
The pressure of at least one of the circulation path, the gas-liquid mixing section, the cooling section, and a storage section which is provided in the circulation path and stores ozone hydrate, unreacted gas, and the raw material water. And the step of measuring
Based on the composition of the raw material gas, the flow rate of the raw material gas, the cooling temperature, and the pressure, at least one of the circulation path, the gas-liquid mixing section, the cooling section, and the storage section Controlling the pressure, the composition of the source gas supplied to the gas-liquid mixing section, and at least one of the cooling sections;
A method for producing an ozone hydrate containing:

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