JP6427455B2 - Ozone hydrate manufacturing apparatus and ozone hydrate manufacturing method - Google Patents

Description

  The present invention relates to an ozone hydrate production apparatus that produces ozone hydrate in which ozone is included as a guest substance, and an ozone hydrate production method.

  Clathrate hydrate is a crystal in which molecules other than water molecules are included in a clathrate structure (a cage-like structure) formed by hydrogen bonds between water molecules. Water molecules that form a cage-like structure in clathrate hydrate are referred to as host molecules, and molecules to be included (wrapped) are referred to as guest substances (guest molecules). Among such clathrate hydrates, those containing ozone as a guest substance are called ozone hydrates and are used for sterilization of food, containers, indoors and the like.

  As a manufacturing technology of ozone hydrate, while pressure-rising and mixing the source gas containing ozone and water to predetermined pressure, the technology which cools to predetermined temperature and generates ozone hydrate is developed (for example, , Patent Document 1). Further, Patent Document 1 describes that ozone hydrate can be generated at a low pressure by mixing carbon dioxide with water as an adjuvant, in addition to ozone, as compared with the case where no adjuvant is added. .

  When carbon dioxide is added as an adjuvant in the formation of ozone hydrate, it is preferable to use high purity carbon dioxide. Therefore, as a technology for producing high purity carbon dioxide, carbon dioxide hydrate including carbon dioxide as a guest substance is produced, and the produced carbon dioxide hydrate is pyrolyzed to produce high purity carbon dioxide. Technologies have been developed (e.g., Patent Document 2).

JP 2012-240901 JP 2001-96133 A

  When carbon dioxide of high purity is produced using the technology of Patent Document 2 and ozone dioxide is produced using this carbon dioxide as an adjuvant, carbon dioxide hydrate is thermally decomposed. If it does so, the thermal energy required for the production | generation of a carbon dioxide hydrate, the thermal energy required for the thermal decomposition of a carbon dioxide hydrate, and the thermal energy required for the production | generation of an ozone hydrate will be required, and the subject that a manufacturing cost will be increased.

  Then, an object of this invention is to provide the ozone hydrate manufacturing apparatus and ozone hydrate manufacturing method which can manufacture an ozone hydrate at low cost in view of such a subject.

  In order to solve the above-mentioned subject, the ozone hydrate production device of the present invention has at least the first mixing part which mixes the carbon dioxide hydrate which included carbon dioxide as a guest substance, and ozone, and it is ozone It is characterized by having an ozone hydrate generation part which generates ozone hydrate included as a substance.

  Further, a first separation unit for separating a first unreacted gas from a first mixture containing at least ozone hydrate and a first unreacted gas, which is generated as a result of generating ozone hydrate in the ozone hydrate generating unit; And an ozone absorbing portion for absorbing at least ozone into water to generate ozone absorbed water among the first unreacted gas separated by the first separating portion, the first mixing portion comprising carbon dioxide hydrate and ozone In addition, mix ozone absorption water.

  In addition, the carbon dioxide hydrate production unit includes a carbon dioxide hydrate production unit that produces carbon dioxide hydrate, and the carbon dioxide hydrate production unit mixes a cooling unit that cools the feed water, carbon dioxide, and the cooled feed water. A carbon dioxide hydrate producing unit having at least a mixing unit and producing carbon dioxide hydrate, and carbon dioxide hydrate produced as a result of producing carbon dioxide hydrate in the carbon dioxide hydrate producing unit, and a second unreacted gas And at least carbon dioxide among the second unreacted gas separated by the second separation unit, and a second separation unit separating the second unreacted gas from the second mixture containing the raw material water and water. And a carbon dioxide absorption unit that generates carbon dioxide absorption water, and the cooling unit cools the carbon dioxide absorption water as raw material water.

  The second separation unit separates the carbon dioxide hydrate from the second mixture, and the first mixing unit mixes the carbon dioxide hydrate separated by the second separation unit with ozone.

  The second separation unit separates the raw material water from the second mixture, and the carbon dioxide absorbing unit causes the raw material water separated by the second separation unit to absorb the second unreacted gas to generate carbon dioxide absorbed water. Do.

  Further, the system includes a boiler for burning liquefied natural gas, and a generator for generating electricity by the heat of the combustion exhaust gas generated in the boiler, and the second mixing unit mixes the combustion exhaust gas containing carbon dioxide into the raw material water.

  Further, the cooling unit cools the raw water by the liquefied natural gas.

  In order to solve the above-mentioned subject, the ozone hydrate manufacturing method of the present invention mixes ozone with carbon dioxide hydrate which included carbon dioxide as a guest substance, and ozone, and ozone hydride which included ozone as a guest substance. And generating a rate.

  According to the present invention, it is possible to produce ozone hydrate at low cost.

It is a figure for demonstrating the schematic structure of an ozone hydrate manufacturing apparatus. It is a figure for demonstrating the schematic structure of a carbon-dioxide hydrate production unit. It is a figure for demonstrating the specific example of a gas supply source. It is a figure for demonstrating the schematic structure of an ozone hydrate manufacturing unit. It is a flowchart explaining the flow of a process of the ozone hydrate manufacturing method. It is a flow chart explaining a flow of processing of a carbon dioxide hydrate formation process.

  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 and the like shown in this embodiment are merely examples for facilitating the understanding of the invention, and do not limit the present invention unless otherwise specified. In the specification and the drawings, elements having substantially the same functions and configurations will be denoted by the same reference numerals to omit repeated description, and elements not directly related to the present invention will not be illustrated. Do.

(Ozone Hydrate Production Equipment 100)
FIG. 1 is a view for explaining a schematic configuration of the ozone hydrate production apparatus 100. As shown in FIG. As shown in FIG. 1, the ozone hydrate production apparatus 100 includes a carbon dioxide hydrate production unit 110, an ozone hydrate production unit 120, and a central control unit 130. In FIG. 1, the flow of carbon dioxide hydrate is indicated by a solid arrow, and the flow of control is indicated by a broken arrow.

  In the ozone hydrate production apparatus 100 of the present embodiment, the carbon dioxide hydrate production unit 110 produces carbon dioxide hydrate, and the ozone hydrate production unit 120 is produced by the carbon dioxide hydrate production unit 110. Produces ozone hydrate without pyrolyzing rates.

  The central control unit 130 is constituted by a semiconductor integrated circuit including a CPU (central processing unit), reads a program, parameters and the like for operating the CPU itself from a ROM (Read Only Memory: read only memory), and serves as a work area. The entire ozone hydrate manufacturing apparatus 100 is managed and controlled in cooperation with a random access memory (RAM) or other electronic circuits. In the present embodiment, the central control unit 130 controls opening and closing of valves constituting the carbon dioxide hydrate production unit 110 and the ozone hydrate production unit 120, and drives a pump.

  Hereinafter, specific configurations of the carbon dioxide hydrate production unit 110 and the ozone hydrate production unit 120 will be described.

(CO 2 hydrate production unit 110)
FIG. 2 is a view for explaining a schematic configuration of the carbon dioxide hydrate production unit 110. As shown in FIG. As shown in FIG. 2, the carbon dioxide hydrate production unit 110 includes a gas supply source 210, a raw material cooling unit 220 (cooling unit), a carbon dioxide hydrate generation unit 240, and a raw material separation unit 250 (second separation unit). ), A separated water heating unit 260, and a carbon dioxide absorbing unit 270.

  The gas supply source 210 supplies a raw material gas containing carbon dioxide to the carbon dioxide hydrate generation unit 240. FIG. 3 is a view for explaining a specific example of the gas supply source 210. As shown in FIG. As shown in FIG. 3, the gas supply source 210 according to the present embodiment includes a boiler 310, a generator 312, a first exhaust cooling unit 314, a water separation unit 316, a breathing tank 318, and a compressor 320. , And a second exhaust gas cooling unit 322.

  The boiler 310 is supplied with oxygen-enriched gas produced by a PSA (pressure swing adsorption) device or the like, and fuel such as LNG (liquefied natural gas), city gas (for example, city gas 13A), etc. The combustion gas is burned to generate a flue gas. In the present embodiment, the boiler 310 is supplied with, for example, an oxygen-enriched gas containing 93% by volume of oxygen. Therefore, water (steam) is contained in the combustion exhaust gas generated in the boiler 310 at about 60% by volume.

  The generator 312 generates electricity with the heat of the combustion exhaust gas generated by the boiler 310. The first exhaust gas cooling unit 314 further cools the combustion exhaust gas heat-recovered by the generator 312 to about normal temperature (for example, 25 ° C.), condenses water vapor, and generates condensed water.

  The water separation unit 316 is introduced with the combustion exhaust gas cooled by the first exhaust gas cooling unit 314, and separates the condensed water from the combustion exhaust gas. The combustion exhaust gas from which the condensed water has been removed by the water separation unit 316 contains 80% by volume or more of carbon dioxide.

  The compressor 320 pressurizes the combustion exhaust gas from which the condensed water has been removed by the water separation unit 316 to a carbon dioxide hydrate generation pressure condition (for example, about 2.5 MPa to about 3.5 MPa). The second exhaust gas cooling unit 322 cools the boosted combustion exhaust gas. Thus, the combustion exhaust gas (raw material gas) which has been pressurized to the pressure generating condition of carbon dioxide hydrate by the compressor 320 and cooled by the second exhaust gas cooling unit 322 is a gas-liquid mixing unit of the carbon dioxide hydrate generation unit 240 described later It will be introduced at 242.

  A flow rate adjustment valve 324 is provided between the water separation unit 316 and the compressor 320, and the central control unit 130 adjusts the opening degree according to the target amount of carbon dioxide hydrate to be generated.

  Further, a drain trap 316 a is connected to the water separation unit 316, and the drain trap 316 a discharges the condensed water separated in the water separation unit 316 to the outside of the water separation unit 316. Further, the water separation unit 316 is provided with a pressure control valve 316 b, and excess combustion exhaust gas is exhausted from the water separation unit 316 via the pressure control valve 316 b. Thereby, the pressure in the water separation unit 316 can be maintained in a predetermined range. The water separation unit 316 is connected to a breathing tank 318 made of stainless steel bellows or a flexible synthetic resin to absorb load fluctuation of the boiler 310 and load fluctuation or pulsation of the compressor 320. Thus, the pressure of the flue gas introduced into the compressor 320 is maintained within a predetermined range.

  Referring back to FIG. 2, the raw material cooling unit 220 is connected to a carbon dioxide absorbing unit 270 described later via a valve 274 and a pump 272. The carbon dioxide absorption water is introduced from the carbon dioxide absorption unit 270 into the raw material cooling unit 220, and the carbon dioxide absorbed water is used as the raw material water, and the generation temperature conditions of carbon dioxide hydrate (for example, 272K (-1 ° C) to 277K ( Cool to about 4 ° C)). When starting the carbon dioxide hydrate production unit 110, raw material water is introduced from the raw material water tank 202 to the carbon dioxide absorbing unit 270 through the pump 204, and from the carbon dioxide absorbing unit 270 through the pump 272 and the valve 274, the raw material cooling unit Raw water is introduced at 220. The raw material cooling unit 220 is, for example, a shell-and-tube type heat exchanger, and cools the raw material water by LNG.

  The carbon dioxide hydrate generation unit 240 includes a gas-liquid mixing unit 242 (second mixing unit), and generates carbon dioxide hydrate. The gas-liquid mixing unit 242 mixes the combustion exhaust gas (raw material gas) supplied from the gas supply source 210 with the raw material water cooled by the raw material cooling unit 220. The gas-liquid mixing unit 242 is configured by, for example, a mixer that performs stirring so that bubbles (microbubbles) of the source gas are substantially evenly distributed in the liquid phase (raw material water).

  As described above, the pressure of the combustion exhaust gas introduced into the gas-liquid mixing unit 242 satisfies the generation pressure condition of carbon dioxide hydrate by the compressor 320, and the temperature of the raw material water introduced into the gas-liquid mixing unit 242 These conditions satisfy the above-mentioned temperature at which the raw material cooling unit 220 generates carbon dioxide hydrate. For this reason, carbon dioxide hydrate can be generated only by mixing (contacting) the combustion exhaust gas and the raw material water in the gas-liquid mixing unit 242.

  In addition, when the raw material cooling unit 220 cools the carbon dioxide absorbed water, carbon dioxide hydrate is generated in the raw material cooling unit 220 using carbon dioxide contained in the carbon dioxide absorbed water as a guest substance. Therefore, carbon dioxide absorbed water containing a small amount of carbon dioxide hydrate is introduced into the gas-liquid mixing unit 242. Thereby, in the gas-liquid mixing unit 242, carbon dioxide hydrate can be generated with the carbon dioxide hydrate generated by the raw material cooling unit 220 as a core. Therefore, it is possible to accelerate the reaction of generating carbon dioxide hydrate in the gas-liquid mixing unit 242.

  In addition, when producing gas hydrates, such as a carbon dioxide hydrate, reaction heat arises. In the present embodiment, since the cooled raw water (carbon dioxide absorbed water) is brought into direct contact with the raw material gas, the reaction heat can be directly absorbed (heat exchange) by the sensible heat of the raw water, and cooling from the outside The heat of reaction can be efficiently removed as compared with the case of indirectly performing heat exchange such as the configuration. As a result, the reaction for producing gas hydrate can be promoted, and the gas-liquid mixing unit 242 can efficiently produce carbon dioxide hydrate.

  Thus, the carbon dioxide hydrate generated in the carbon dioxide hydrate generation unit 240 is delivered to the raw material separation unit 250. In addition, since the formation reaction of the gas hydrate is determined by the mixed contact of the raw material water and the bubbles (micro bubbles), not only the gas-liquid mixing unit 242 but also the carbon dioxide hydrate generation unit 240 is delivered to the raw material separation unit 250 Carbon dioxide hydrate is also produced during the Further, 100% of carbon dioxide hydrate is not generated in the carbon dioxide hydrate generation unit 240, and the raw material separation unit 250 includes carbon dioxide hydrate and raw material unreacted gas (carbon dioxide, nitrogen, etc.) The raw material mixture (2nd mixture) comprised including raw material water is introduce | transduced.

  The raw material separation unit 250 separates the raw material mixture into carbon dioxide hydrate, raw material unreacted gas (second unreacted gas), and raw material water. Specifically, the specific gravity of carbon dioxide hydrate is about 1.12, which is larger than the specific gravity of raw material water of about 1.0. Therefore, due to the specific gravity difference, the carbon dioxide hydrate settles to the bottom of the raw material separation unit 250, and the raw material unreacted gas is retained at the top of the raw material separation unit 250. That is, it is possible to separate into carbon dioxide hydrate, raw material unreacted gas, and raw material water only by introducing the raw material mixture into the raw material separation unit 250 and leaving it to stand.

  Thus, the carbon dioxide hydrate separated by the raw material separation unit 250 is introduced by the hydrate pump 252 to the ozone hydrate production unit 120 described later via the valve 254. In addition, although mentioned later in detail, the production pressure conditions of a carbon dioxide hydrate are higher than the production pressure conditions of an ozone hydrate. Therefore, carbon dioxide hydrate is introduced from the raw material separation unit 250 to the ozone hydrate production unit 120 by the pressure difference between the raw material separation unit 250 and the ozone hydrate generation unit 430 without providing any transfer means. Become.

  On the other hand, the raw material water separated by the raw material separation unit 250 is delivered to the separated water heating unit 260 via the valve 258.

  In addition, the raw material unreacted gas is introduced into the carbon dioxide absorbing unit 270 via the valve 256. In addition, since the raw material mixture is sequentially introduced into the raw material separation unit 250, the pressure is higher than that of the carbon dioxide absorbing unit 270. Therefore, the raw material non-reacted gas is introduced from the raw material separation unit 250 to the carbon dioxide absorption unit 270 by the pressure difference between the raw material separation unit 250 and the carbon dioxide absorption unit 270 without providing any transfer means. Further, the central control unit 130 controls the opening degree of the valve 256 so that the pressure in the raw material separation unit 250 is in a predetermined range.

  The separated water heating unit 260 includes a heating unit 262, and heats the raw material water separated by the raw material separating unit 250 to, for example, about 25 ° C. to 50 ° C. to degas carbon dioxide from the raw material water. Thus, the deaerated carbon dioxide is introduced into the gas cooling unit 264b through the valve 264a, cooled to normal temperature (for example, about 25 ° C.) by the gas cooling unit 264b, and condensed water is removed, and then ozone hydrate is obtained. It will be sent to the manufacturing unit 120.

  On the other hand, the raw material water from which carbon dioxide generated in the separated water heating unit 260 has been degassed is cooled by the second water cooling unit 276 by the pump 266 to about a temperature at which carbon dioxide hydrate is not generated. It is introduced at 270.

  The carbon dioxide absorption unit 270 is configured of a packed tower filled with Raschig rings or a tray-type gas-liquid contact tower. In the carbon dioxide absorption unit 270, any one of the raw material water cooled by the second water cooling unit 276 (the raw material water delivered from the raw material water tank 202 and the raw material water degassed by the separated water heating unit 260) Or both) and the raw material unreacted gas separated in the raw material separator 250 are introduced. Then, by bringing the raw material water and the raw material unreacted gas into gas-liquid contact in the carbon dioxide absorbing unit 270, carbon dioxide in the raw material unreacted gas is absorbed by water, and carbon dioxide absorbed water is generated. Become.

  Moreover, since carbon dioxide is low concentration in the feed water deaerated in the separated water heating unit 260, the carbon dioxide absorption unit 270 introduces carbon dioxide in the carbon dioxide absorption unit 270 by introducing the raw material water into the carbon dioxide absorption unit 270. It can be efficiently absorbed in water.

  Then, the carbon dioxide absorbed water generated in the carbon dioxide absorbing unit 270 is delivered to the raw material cooling unit 220 by the pump 272, cooled in the raw material cooling unit 220, and introduced into the gas-liquid mixing unit 242. That is, in the gas-liquid mixing unit 242, carbon dioxide-absorbing water in which carbon dioxide that has not reacted in the previous reaction for producing carbon dioxide hydrate is absorbed is mixed with combustion exhaust gas to generate carbon dioxide hydrate. It will be done. Therefore, unreacted carbon dioxide generated in the process of carbon dioxide hydrate formation can be reused, and carbon dioxide hydrate can be produced at low cost.

  On the other hand, in the carbon dioxide absorbing portion 270, the gas (nitrogen or the like) which is not absorbed by water is discharged to the outside through the valve 270a.

(Ozone Hydrate Production Unit 120)
FIG. 4 is a view for explaining a schematic configuration of the ozone hydrate production unit 120. As shown in FIG. As shown in FIG. 4, the ozone hydrate production unit 120 includes an ozone supply source 410, a precooling unit 420, an ozone hydrate generation unit 430, a product separation unit 440 (first separation unit), and an ozone absorbing unit. And 450. FIG.

  The ozone supply source 410 includes, for example, an oxygen storage tank (or PSA apparatus) and an ozone generator. The oxygen stored in the oxygen storage tank is introduced into an ozone generator, and the oxygen is exposed to the discharge environment in the ozone generator to generate a gas (for example, 10% by volume or more) containing ozone. It becomes.

  A gas containing ozone generated in the ozone supply source 410 (hereinafter simply referred to as “ozone”) is introduced into the ozone hydrate generation unit 430 via the valve 412. Further, carbon dioxide delivered from the separated water heating unit 260 of the carbon dioxide hydrate production unit 110 is introduced into the ozone hydrate generation unit 430 together with ozone via the valve 414.

  The central control unit 130 determines the amount of ozone and the amount of carbon dioxide according to the concentration of carbon dioxide at the inlet of the ozone hydrate generation unit 430, and the determined amount of ozone and carbon dioxide The opening degree of the valve 412 and the valve 414 is controlled so as to be introduced into the ozone hydrate generation unit 430.

  The carbon dioxide hydrate separated by the raw material separation unit 250 of the carbon dioxide hydrate production unit 110 is introduced into the precooling unit 420, and the temperature of the inlet of the ozone hydrate generation unit 430 is the temperature condition for ozone hydrate generation ( For example, the carbon dioxide hydrate is cooled to about 272 K (-1 ° C.) to 275 K (2 ° C.).

  The ozone hydrate generation unit 430 includes a solid-gas liquid mixing unit 432 (first mixing unit), and generates ozone hydrate. The solid-gas liquid mixing unit 432 includes carbon dioxide hydrate cooled by the precooling unit 420, raw water separated from the product separation unit 440 described later, ozone absorbed water sent from the ozone absorbing unit 450, carbon dioxide, Mix the ozone. The solid-gas-liquid mixing unit 432 is configured by, for example, a mixer that stirs so that bubbles of ozone and carbon dioxide are substantially evenly distributed in the liquid phase (raw material water and ozone absorbed water).

  As described above, the pressure of the carbon dioxide hydrate introduced into the solid-gas liquid mixing unit 432 satisfies the generation pressure condition of carbon dioxide hydrate (for example, about 2.5 MPa to about 3.5 MPa). Moreover, the formation pressure conditions of ozone hydrate are 2.2 Mpa-3.0 Mpa, for example, and are about 0.3-0.5 Mpa low pressure from the generation pressure conditions of a carbon dioxide hydrate. Further, as described above, the precooling unit 420 cools the temperature of the inlet of the ozone hydrate generation unit 430 so as to satisfy the generation temperature of the ozone hydrate.

  Therefore, the pressure is maintained in the solid-gas-liquid mixing unit 432 so as to satisfy the pressure generation condition of the ozone hydrate, and the ozone hydride is simply mixed with the carbon dioxide hydrate, the raw material water, the ozone absorbing water, the carbon dioxide and the ozone. Rates can be generated.

  As described above, reaction heat is generated when gas hydrate such as ozone hydrate is produced. In this embodiment, since the cooled raw water (ozone absorbed water) and the carbon dioxide hydrate are brought into direct contact with ozone, the reaction heat is directly absorbed by the sensible heat of the raw water and the latent heat of the carbon dioxide hydrate (heat The heat of reaction can be efficiently removed as compared with the case of indirect heat exchange such as a configuration of cooling from the outside. As a result, the gas hydrate formation reaction can be promoted, and ozone gas hydrate can be efficiently generated in the solid-gas liquid mixing unit 432.

  Thus, the ozone hydrate generated in the ozone hydrate generation unit 430 is delivered to the product separation unit 440. In addition, since the formation reaction of the gas hydrate is determined by the mixed contact of the raw material water and the bubbles (micro bubbles), not only the solid-gas liquid mixing unit 432 but also the ozone hydrate generation unit 430 sends it to the product separation unit 440 In the meantime, ozone hydrate will be produced. In addition, 100% of ozone hydrate is not generated in the ozone hydrate generation unit 430, and the product separation unit 440 includes ozone hydrate, carbon dioxide hydrate, and generation unreacted gas (ozone, dioxide A product mixture (first mixture) comprising carbon, nitrogen, etc.) and feed water is introduced.

  As described above, the ozone hydrate generating unit 430 can generate ozone hydrate by a simple means such as only mixing ozone with carbon dioxide hydrate. Therefore, it is not necessary to thermally decompose carbon dioxide hydrate, and energy required for the thermal decomposition can be reduced. In addition, conventionally, energy for cooling raw material water for producing carbon dioxide hydrate and energy for cooling raw material water for producing ozone hydrate have been required. However, in the present embodiment, since the ozone hydrate is generated using heat (cold heat) of carbon dioxide hydrate, it is possible to omit the cooling of the raw material water required for the generation of the ozone hydrate. . Therefore, the energy required for cooling can be reduced.

  The product separation unit 440 separates the product mixture into ozone hydrate and carbon dioxide hydrate, generated unreacted gas (first unreacted gas), and raw material water. Specifically, the specific gravity of the mixture of ozone hydrate and carbon dioxide hydrate is about 1.15, which is larger than the specific gravity of raw material water of about 1.05. Therefore, due to the difference in specific gravity, the ozone hydrate and the carbon dioxide hydrate settle on the bottom of the product separation unit 440, and the generated unreacted gas is retained on the top of the product separation unit 440. That is, the product mixture can be separated into ozone hydrate and carbon dioxide hydrate, generated unreacted gas, and raw material water only by introducing the product mixture into the product separation unit 440 and leaving it to stand.

  Thus, the ozone hydrate separated by the product separation unit 440 is supplied by the hydrate pump 442 to the supply destination via the valve 444. The ozone hydrate is maintained at about -25.degree. C. or less to be supplied to the supply destination or stored at the supply destination in order to reduce the attenuation rate when stored for a long period of time.

  On the other hand, the raw material water separated by the product separation unit 440 is sent to the hydrate pump 252 of the carbon dioxide hydrate production unit 110 by the pump 448. The raw material water thus sent by the pump 448 is used as a transport water for carbon dioxide hydrate and is also delivered to the solid-gas liquid mixing unit 432 by the hydrate pump 252 for use as cooling water.

  In addition, the generated unreacted gas is introduced into the ozone absorbing unit 450 via the pressure control valve 446. In addition, since the product mixture is sequentially introduced into the product separation unit 440, the pressure is higher than that of the ozone absorbing unit 450. Therefore, even if the transfer means is not provided, the generated unreacted gas is introduced from the product separation unit 440 to the ozone absorption unit 450 due to the pressure difference between the product separation unit 440 and the ozone absorption unit 450. Further, the opening degree of the pressure control valve 446 is controlled by the central control unit 130 so that the pressure in the product separation unit 440 falls within a predetermined range.

  The ozone absorbing unit 450 is configured of a packed tower filled with Raschig rings, or a tray-type gas-liquid contact tower. In the ozone absorbing unit 450, raw water cooled to a temperature (for example, about 4 ° C.) at which ozone hydrate is not generated by the first water cooling unit 456 (raw water delivered from the raw water tank 402 by the pump 404) And the generated unreacted gas separated in the product separation unit 440 are introduced. Then, by bringing the raw material water and the generated unreacted gas into gas-liquid contact in the ozone absorbing unit 450, ozone in the generated unreacted gas is absorbed by the water, and ozone absorbed water is generated.

  Then, the ozone absorbing water generated in the ozone absorbing unit 450 is delivered to the solid-gas liquid mixing unit 432 by the pump 452. That is, in the solid-gas-liquid mixing unit 432, ozone is mixed with ozone-absorbing water in which ozone that did not contribute to the reaction in the previous reaction for generating ozone hydrate is absorbed to generate ozone hydrate. Become. Therefore, unreacted ozone generated in the process of ozone hydrate generation can be reused, and ozone hydrate can be produced at low cost.

  On the other hand, in the ozone absorbing unit 450, the gas (ozone, carbon dioxide, nitrogen) which is not absorbed by water is delivered to the deozoner (not shown) through the valve 450a. Then, the ozone is reduced to less than 0.5 ppm in the deionizer and discharged to the outside.

(Ozone hydrate manufacturing method)
Subsequently, an ozone hydrate production method using the ozone hydrate production apparatus 100 will be described. FIG. 5 is a flowchart for explaining the process flow of the ozone hydrate production method.

  First, the central control unit 130 controls the carbon dioxide hydrate production unit 110 to produce carbon dioxide hydrate (carbon dioxide hydrate production step S510). The specific treatment of the carbon dioxide hydrate production step S510 will be described in detail later. The central control unit 130 introduces the manufactured carbon dioxide hydrate into the precooling unit 420. Then, the pre-cooling unit 420 cools the carbon dioxide hydrate so that the temperature at the inlet of the ozone hydrate generation unit 430 becomes the temperature condition for ozone hydrate generation (cooling step S520).

  The central control unit 130 includes the carbon dioxide hydrate cooled by the precooling unit 420, the ozone generated by the ozone supply source 410, the carbon dioxide generated by the carbon dioxide hydrate production unit 110, and the ozone absorbing unit 450. The carbon dioxide hydrate production unit 110 and the ozone hydrate production unit 120 (valve 412, valve 414, pump 452, valve 454) are controlled such that the generated ozone absorbed water is introduced into the solid-gas liquid mixing unit 432. (Ozone introduction step S530).

  Then, the solid-gas liquid mixing unit 432 mixes the carbon dioxide hydrate, the ozone, the carbon dioxide, the ozone absorbing water, and the raw material water to generate an ozone hydrate (ozone hydrate generating step S540).

  The product separation unit 440 separates the product mixture generated in the ozone hydrate generation step S540 into ozone hydrate and carbon dioxide hydrate, generated unreacted gas, and raw material water (separation step S550). Then, the central control unit 130 drives and controls the hydrate pump 442, opens the valve 444, and supplies the separated ozone hydrate to the supply destination.

  On the other hand, central control unit 130 opens pressure control valve 446 and delivers the generated unreacted gas separated in product separation unit 440 to ozone absorbing unit 450. Further, the central control unit 130 controls the pump 448 to separate the separated raw water into the outlet (inlet of the hydrate pump 252) of carbon dioxide hydrate in the raw material separation unit 250 of the carbon dioxide hydrate production unit 110. Introduce.

  The ozone absorbing unit 450 absorbs ozone in the generated unreacted gas into the raw material water to generate ozone absorbed water (ozone absorbed water generation step S560).

  Then, the generated ozone absorbed water is sent to the solid-gas liquid mixing unit 432 by the pump 452, and the process from the carbon dioxide hydrate manufacturing process S510 is repeatedly performed.

(Carbon dioxide hydrate production process S510)
FIG. 6 is a flowchart for explaining the process flow of the carbon dioxide hydrate production step S510.

  First, the central control unit 130 drives the pump 272 to introduce carbon dioxide absorbed water from the carbon dioxide absorbing unit 270 into the raw material cooling unit 220 (carbon dioxide absorbed water introduction step S510-1). Then, the raw material cooling unit 220 cools the carbon dioxide absorbed water to the generation temperature condition of the carbon dioxide hydrate using the raw material water (cooling step S510-3).

  The carbon dioxide-absorbing water cooled by the raw material cooling unit 220 and the combustion exhaust gas generated by the gas supply source 210 are introduced into the gas-liquid mixing unit 242, and the gas-liquid mixing unit 242 To form carbon dioxide hydrate (carbon dioxide hydrate formation step S510-5).

  The raw material separation unit 250 separates the raw material mixture generated in the carbon dioxide hydrate formation step S510-5 into carbon dioxide hydrate, raw material unreacted gas, and raw material water (separation step S510-7). Then, the central control unit 130 drives and controls the hydrate pump 252, opens the valve 254, and sends out the separated carbon dioxide hydrate to the precooling unit 420 of the ozone hydrate production unit 120. The raw material water separated in the separation step S550 is introduced into the inlet of the hydrate pump 252. Further, the central control unit 130 opens the valve 258 and sends the separated raw water to the separated water heating unit 260.

  The separated water heating unit 260 heats the introduced raw material water to degas the carbon dioxide (heating step S510-9).

  Meanwhile, the central control unit 130 opens the valve 256 and drives the pump 204 to deliver the raw material unreacted gas separated in the raw material separation unit 250 and the raw material water to the carbon dioxide absorbing unit 270. Further, central control unit 130 drives pump 266 to deliver the raw material water degassed in separated water heating unit 260 to carbon dioxide absorbing unit 270.

  The carbon dioxide absorbing unit 270 absorbs carbon dioxide in the raw material unreacted gas into the raw material water to generate carbon dioxide absorbed water (carbon dioxide absorbed water generation step S510-11).

  And the produced | generated carbon dioxide absorption water is sent to the raw material cooling part 220 by the pump 272, and the process from a carbon dioxide absorption water introduction process S510-1 will be repeatedly performed.

  As explained above, according to the ozone hydrate manufacturing apparatus 100 concerning this embodiment and the ozone hydrate manufacturing method using the same, ozone hydrate is generated using heat (cold heat) which carbon dioxide hydrate has It is possible to omit the cooling of the raw material water required for the generation of ozone hydrate. Further, compared with the prior art, it is not necessary to thermally decompose carbon dioxide hydrate, and energy required for the thermal decomposition can be reduced. Therefore, it is possible to produce ozone hydrate at low cost.

  Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, it goes without saying that the present invention is not limited to such embodiments. It is obvious that those skilled in the art can conceive of various changes or modifications within the scope of the claims, and it is naturally understood that they are also within the technical scope of the present invention. Be done.

  For example, in the above-described embodiment, the gas supply source 210 includes the boiler 310, and the combustion exhaust gas generated by the boiler 310 is used as the source gas and supplied to the carbon dioxide hydrate generation unit 240 as an example. However, the configuration of the gas supply source 210 is not limited as long as it can supply carbon dioxide to the carbon dioxide hydrate generating unit 240. For example, the gas supply source 210 may be a gas engine, a gas turbine, a combustion furnace, a blast furnace, a gas cylinder or the like. When the concentration of impurities in the source gas is high, the amount of gas discharged from the carbon dioxide absorbing unit 270 is increased. Therefore, in this case, a turbine (expander) coaxial with the compressor 320 of the gas supply source 210 is provided, and the compressor 320 is driven by rotating the turbine by the gas discharged from the carbon dioxide absorbing unit 270. It can also be done. This makes it possible to reduce the power of the compressor 320.

  Moreover, in the said embodiment, the structure by which raw material water is introduce | transduced from the raw material water tank 402 was mentioned as the example, and the ozone absorption part 450 was demonstrated. However, the raw material water deaerated by the separated water heating unit 260 of the carbon dioxide hydrate production unit 110 may be introduced into the ozone absorbing unit 450. The raw material water deaerated by the separated water heating unit 260 contains almost no dissolved substance, so ozone can be efficiently absorbed in the ozone absorbing unit 450.

  Moreover, in the said embodiment, the structure which discards the condensed water isolate | separated by the water separation part 316 was mentioned as the example, and was demonstrated. However, condensed water may be used as raw material water.

  Further, the product separation unit 440 and the raw material separation unit 250 may have a cylindrical main body, and the mixture may be injected by being injected in the tangential direction of the main body. According to this configuration, the mixture can be swirled in the main body to aggregate hydrate crystals and facilitate separation, and the separation efficiency can be improved.

  In addition, each process of the ozone hydrate manufacturing method of this specification does not necessarily need to process in time series along the order described as the flowchart, and may include parallel processing. For example, the above steps in the ozone hydrate production method may be performed as a continuous process or may be performed as a batch process.

  INDUSTRIAL APPLICABILITY The present invention can be used in an ozone hydrate production apparatus that produces ozone hydrate in which ozone is included as a guest substance, and an ozone hydrate production method.

100 Ozone Hydrate Production Equipment 110 Carbon Dioxide Hydrate Production Unit 220 Raw Material Cooling Unit (Cooling Unit)
240 Carbon Dioxide Hydrate Generator 242 Gas-Liquid Mixing Unit (Second Mixing Unit)
250 Raw Material Separation Unit (Second Separation Unit)
270 Carbon Dioxide Absorber 310 Boiler 312 Generator 430 Ozone Hydrate Generator 432 Solid-Gas-Liquid Mixer (First Mixer)
440 Product separation unit (first separation unit)
450 ozone absorption unit

Claims (8)

  An ozone hydrate generating unit having at least a first mixing unit for mixing ozone with carbon dioxide hydrate in which carbon dioxide is included as a guest substance and ozone, and generating ozone hydrate including the ozone as a guest substance; An ozone hydrate producing apparatus characterized by comprising. A first separation unit for separating the first unreacted gas from a first mixture containing at least the ozone hydrate and the first unreacted gas produced as a result of generating the ozone hydrate in the ozone hydrate generating unit When,
An ozone absorbing portion for absorbing at least ozone into water of the first unreacted gas separated by the first separating portion to generate ozone absorbed water;
Equipped with
The ozone hydrate production apparatus according to claim 1, wherein the first mixing unit mixes the ozone absorbed water with the carbon dioxide hydrate and the ozone. Including a carbon dioxide hydrate production unit for producing the carbon dioxide hydrate,
The carbon dioxide hydrate production unit is
A cooling unit for cooling the raw water,
A carbon dioxide hydrate generation unit having at least a second mixing unit for mixing carbon dioxide and the cooled raw water, wherein the carbon dioxide hydrate is generated;
From the second mixture containing the carbon dioxide hydrate, the second unreacted gas, and the raw material water produced as a result of generating the carbon dioxide hydrate in the carbon dioxide hydrate generation unit, the second unreacted gas A second separation unit for separating
Among the second unreacted gas separated by the second separation unit, at least carbon dioxide is absorbed by water to generate a carbon dioxide absorbed water, and a carbon dioxide absorption unit,
Equipped with
The ozone hydrate manufacturing apparatus according to claim 1 or 2, wherein the cooling unit cools the carbon dioxide absorbed water as the raw material water. The second separation unit separates the carbon dioxide hydrate from the second mixture,
The ozone hydrate manufacturing apparatus according to claim 3, wherein the first mixing unit mixes the carbon dioxide hydrate separated by the second separation unit with the ozone. The second separation unit separates the raw material water from the second mixture,
The said carbon dioxide absorption part makes the said raw material water isolate | separated by the said 2nd isolation | separation part absorb the said 2nd unreacted gas, and produces | generates the said carbon-dioxide absorption water, It is characterized by the above-mentioned. Ozone hydrate production equipment. A boiler for burning liquefied natural gas,
A generator that generates electricity with the heat of the combustion exhaust gas produced in the boiler;
Equipped with
The ozone hydrate production apparatus according to any one of claims 3 to 5, wherein the second mixing unit mixes the combustion exhaust gas containing the carbon dioxide into the raw material water.   The ozone hydrate production apparatus according to claim 6, wherein the cooling unit cools the raw water by the liquefied natural gas.   A method for producing ozone hydrate, comprising the step of mixing ozone with carbon dioxide hydrate containing carbon dioxide as a guest substance and ozone to form ozone hydrate containing the ozone as a guest substance. .

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