Clathrate hydrate generator and heat pump system

Abstract

To provide a technology for improving energy consumption efficiency in a heat pump system.SOLUTION: A clathrate hydrate generator for generating a clathrate hydrate using water and gas comprises: a reaction vessel having an internal reaction surface on which a clathrate hydrate is generated; a water film forming part that forms a water film, which is a film of water, on the reaction surface; a sliding part disposed in the reaction vessel and moving while rubbing against the reaction surface; a gas supply path for supplying gas into the reaction vessel; a temperature adjustment part for adjusting a temperature of the reaction surface; and a through-hole having an opening on a portion of the reaction surface and penetrating the reaction vessel. The clathrate hydrate formed on the reaction surface is scraped off by the sliding part and discharged to the outside of the reaction vessel through the through-hole.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] The present invention relates to a clathrate hydrate generator and a heat pump system using clathrate hydrates. [Background technology]

[0002] Conventionally, heat pumps that combine gas compression / expansion and heat exchange have been used. For example, Patent Document 1 discloses a vehicle air conditioning system that includes an expansion valve that expands condensed refrigerant and is interconnected via a refrigerant line, an evaporator that evaporates the expanded refrigerant through heat exchange with air, and a compressor that compresses the evaporated gaseous refrigerant.

[0003] Although heat pumps are characterized by their ability to efficiently obtain thermal energy using little electrical energy, with the recent rise in awareness of environmental issues, there is a demand for even greater improvements in energy consumption efficiency. To address this, heat pump systems utilizing the decomposition / formation of clathrate hydrates have been proposed (see, for example, Patent Documents 2 and 3 and Non-Patent Document 1). The heat of decomposition / formation of clathrate hydrates is more than 10 times the latent heat of evaporation / condensation of ordinary refrigerants, such as those used in the heat pump described in Patent Document 1, and therefore, improvements in energy consumption efficiency are expected. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-076792 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-101140 [Patent Document 3] Japanese Patent Publication No. 2022-087404 [Non-patent literature]

[0005] [Non-Patent Document 1] T. Ogawa et al., Applied Energy, 26, 2157 (2006). Summary of the Invention [Problem to be solved by the invention]

[0006] In the heat pump systems that utilize the decomposition / generation of clathrate hydrates disclosed in Patent Documents 2 and 3 and Non-Patent Document 1, further improvements in energy consumption efficiency are desired.

[0007] The present disclosure has been made to solve the above-mentioned problems, and aims to provide a technique for improving energy consumption efficiency in a heat pump system. [Means for solving the problem]

[0008] The present invention has been made to solve at least part of the above-mentioned problems, and can be realized in the following aspects.

[0009] (1) According to one embodiment of the present disclosure, there is provided a clathrate hydrate generator for generating clathrate hydrates from water and a gas. This clathrate hydrate generator comprises a reaction vessel having an internal reaction surface on which the clathrate hydrates are generated, a water film forming unit that forms a water film on the reaction surface, a sliding unit that is disposed within the reaction vessel and rubs against the reaction surface, a gas supply channel for supplying the gas into the reaction vessel, a temperature adjusting unit that adjusts the temperature of the reaction surface, and a through-hole that has an opening in a portion of the reaction surface and penetrates the reaction vessel, and the clathrate hydrates formed on the reaction surface can be scraped out by the sliding unit and discharged outside the reaction vessel through the through-hole.

[0010] According to this configuration, since the water film forming section is provided, a thin water film is formed on the reaction surface, and clathrate hydrates are generated on the reaction surface when gas is supplied from the gas supply channel. The clathrate hydrates formed on the reaction surface are then scraped out by the sliding section and discharged outside the reaction vessel, thereby reducing the amount of water discharged from the clathrate hydrate generator together with the clathrate hydrates. Therefore, when a clathrate hydrate generator having this configuration is used in a heat pump system, the amount of water supplied to the decomposition section can be reduced, and excess liquid (water) is supplied to the decomposition section. This suppresses a decrease in cooling output due to the use of part of the latent heat of decomposition to cool the liquid (water) (sensible heat loss). As a result, the energy consumption efficiency (COP) can be improved.

[0011] (2) In the clathrate hydrate generator of the above form, the water film forming unit may include a liquid reservoir that stores water to be supplied to the reaction surface and sponge blades that absorb water from the liquid reservoir and wet the reaction surface, and the sliding unit may include scraping blades, and the sponge blades and scraping blades may be attached alternately to a rotating shaft to form an impeller.

[0012] According to this configuration, the water film forming section is composed of a liquid reservoir and sponge blades, so the clathrate hydrate producing section can be simply configured. Furthermore, since the sponge blades and scraping blades are alternately attached to the rotating shaft to form an impeller, when a water film is formed on the reaction surface and clathrate hydrate is produced, the clathrate hydrate is scraped out by the scraping blades. Thus, according to this configuration, clathrate hydrate can be continuously discharged, so the clathrate hydrate production capacity (production amount per unit time) can be improved.

[0013] (3) In the clathrate hydrate generator of the above embodiment, the water film forming unit may include shower impellers that diffuse and discharge water onto the reaction surface, the sliding unit may include scraping blades, and the shower impellers and scraping blades may be attached alternately to a rotating shaft to form an impeller. In this manner, a water film can be formed by the shower impellers. Since the shower impellers and scraping blades are attached alternately to the rotating shaft to form an impeller, when a water film is formed on the reaction surface and clathrate hydrates are produced, the clathrate hydrates are scraped out by the scraping blades. In this manner, with this configuration, clathrate hydrates can be continuously discharged, thereby improving the clathrate hydrate production capacity (amount produced per unit time).

[0014] (4) In the clathrate hydrate generator of the above embodiment, the temperature control unit may include a heat medium flow path through which a heat medium flows. This is preferable when used in a heat pump system, because it allows the temperature of the reaction surface to be controlled by heat exchange with the outside of the heat pump system.

[0015] (5) The clathrate hydrate generator of the above embodiment may further include a pressure gauge that detects the pressure inside the reaction vessel, and a pressure control unit that controls the pressure inside the reaction vessel based on the value detected by the pressure gauge. In this way, the reaction rate of clathrate hydrates can be controlled.

[0016] (6) In the clathrate hydrate generator of the above embodiment, the thickness of the water film may be 590 μm or less, thereby further reducing the amount of water discharged from the clathrate hydrate generator together with the clathrate hydrate.

[0017] (7) According to another aspect of the present disclosure, there is provided a heat pump system including any of the clathrate hydrate generators of the above aspects, and transporting heat by repeating a process of decomposing and generating clathrate hydrates.

[0018] This type of heat pump system transports heat using the latent heat (heat of decomposition and formation) of clathrate hydrates. Because the heat of decomposition and formation of clathrate hydrates is greater than the heat associated with the condensation and evaporation of the refrigerant, it can improve energy consumption efficiency compared to conventional heat pumps that use the heat exchange associated with the condensation and evaporation processes of the refrigerant. Furthermore, since it is equipped with one of the above-mentioned clathrate hydrate generators, it is possible to reduce the amount of water supplied to the decomposition section, and excess liquid (water) is supplied to the decomposition section, suppressing a decrease in cooling output due to the use of part of the latent heat of decomposition to cool the liquid (water) (sensible heat loss). As a result, the energy consumption efficiency (COP) can be improved.

[0019] The present disclosure can be realized in various forms, for example, in the form of an apparatus equipped with a clathrate hydrate generator, a heat utilization device having a heat pump system, a control method for a heat pump system, a method for generating cold heat, a method for generating hot heat, etc. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is an explanatory diagram schematically illustrating a basic configuration of a heat pump system according to a first embodiment. [Figure 2] FIG. 2 is an explanatory diagram illustrating the generation of cold heat in an air conditioning apparatus. [Figure 3] FIG. 1 is an explanatory diagram illustrating heat generation in an air conditioning apparatus. [Figure 4] 10 is a flowchart showing the flow of temperature control in the control unit. [Figure 5] FIG. 1 is a diagram showing the relationship between the power COP and the gas-solid-liquid ratio. [Figure 6] FIG. 1 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator. [Figure 7] FIG. 2 is an explanatory diagram conceptually showing the internal configuration of a clathrate hydrate generator. [Figure 8] FIG. 1 is an explanatory diagram conceptually showing the production and discharge of clathrate hydrate solids. [Figure 9]FIG. 1 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator according to a second embodiment. [Figure 10] FIG. 10 is an explanatory diagram showing the internal configuration of a clathrate hydrate generator according to a second embodiment. [Figure 11] FIG. 10 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator according to a third embodiment. [Figure 12] FIG. 10 is an explanatory diagram showing the production and discharge of clathrate hydrate solids in the third embodiment. [Figure 13] FIG. 10 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator according to a fourth embodiment. [Figure 14] FIG. 10 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator according to a fifth embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0021] First Embodiment FIG. 1 is an explanatory diagram schematically illustrating the basic configuration of a heat pump system 100 according to a first embodiment. The heat pump system 100 transports heat by using a heat medium to repeatedly undergo decomposition and formation processes of clathrate hydrates. Clathrate hydrates are ice-like compounds (clathrate compounds) in which gas molecules are enclosed in cages formed by hydrogen bonds between water molecules. Heat is generated during the formation process in which clathrate hydrates are formed from water and gas, and heat is absorbed during the decomposition process in which the clathrate hydrates are separated into water and gas. The heat pump system 100 according to this embodiment transports heat by utilizing the latent heat (heat of decomposition and formation) of the clathrate hydrate. In the following description, clathrate hydrates are also referred to as "clathrate hydrate solids."

[0022] The heat pump system 100 includes a generator 10 into which gas and water are introduced and clathrate hydrates are produced; a decomposition section 20 into which the clathrate hydrates are decomposed and a decomposition product (a mixed phase of gas and water) is discharged; a first main flow path 30 through which a heat transfer medium flows from the generator 10 to the decomposition section 20; and a second main flow path 40 through which the heat transfer medium flows from the decomposition section 20 to the generator 10. FIG. 1 shows the phase changes of the heat transfer medium flowing through the first main flow path 30 and the second main flow path 40, with the clathrate hydrates indicated by dashed lines, the decomposition product (a mixed phase of gas and water) indicated by dashed lines, the gas phase indicated by dashed lines, and the water phase indicated by solid lines. The generator 10 of the heat pump system 100 of this embodiment includes a clathrate hydrate generator 70 (described below), which discharges a mixture of clathrate hydrate solids and gas (containing no liquid phase or a small amount of liquid phase). Therefore, the clathrate hydrate comes out of the production section 10 in the form of a gas-solid mixture containing the clathrate hydrate solid and unreacted gas. Note that the gas-solid mixture of the clathrate hydrate may contain a small amount of water.

[0023] Gases that can be used to produce clathrate hydrates include hydrocarbon gases such as methane, ethane, propane, ethylene, and acetylene; fluorocarbon gases such as HFCs (hydrofluorocarbons) and HCFCs (hydrochlorofluorocarbons); rare gases such as argon and krypton; carbon dioxide (CO2); nitrogen; air; ammonia; and xenon (Xe). Gases with properties such as a high maximum equilibrium temperature, a low equilibrium pressure, and a small change in pressure relative to temperature are preferred because they can achieve a high COP. These gases may be used alone or in combination to achieve desired properties. Combining different gases allows for adjustment of the phase change conditions of clathrate hydrates. Additives (auxiliaries) may also be added to water to adjust the phase change conditions of clathrate hydrates.

[0024] As shown in the figure, the heat pump system 100 includes a heat dissipation section 12 that causes the heat medium to dissipate heat by heat exchange between the heat medium in the generation section 10 and a heat source outside the heat pump system 100, and a heat absorption section 22 that causes the heat medium to absorb heat by heat exchange between the heat medium in the decomposition section 20 and a heat source outside the heat pump system. Heat exchangers are used as the heat dissipation section 12 and the heat absorption section 22.

[0025] The heat pump system 100 includes, in the first main flow path 30, a gas-solid separation section 52 that separates gas from a gas-solid mixture of clathrate hydrates, and a pressure reduction section 24 that reduces the pressure of the heat transfer medium in the decomposition section 20, in that order from upstream. The second main flow path 40 also includes, in that order from upstream, a first gas-liquid separation section 14 that separates the decomposition product, which is a mixed phase of gas and water delivered from the decomposition section 20, into gas and liquid, a compression section 16 that compresses the gas separated by the first gas-liquid separation section 14, and a second gas-liquid separation section 56 that separates compressor oil from the gas that has passed through the compression section 16. As shown in the figure, the gas-solid separation section 52 is located upstream of the pressure reduction section 24, and therefore the gas pressure of the gas separated by the gas-solid separation section 52 is high and equivalent to the gas pressure of the gas compressed by the compression section 16. The first gas-liquid separation section 14 in this embodiment is also simply referred to as the "gas-liquid separation section."

[0026] The first main flow path 30 includes an eleventh flow path 32 connecting the production section 10 and the gas-solid separation section 52, a twelfth flow path 34 connecting the gas-solid separation section 52 and the pressure reduction section 24, and a thirteenth flow path 36 connecting the pressure reduction section 24 and the decomposition section 20. The second main flow path 40 includes a first flow path 41 connecting the decomposition section 20 and the first gas-liquid separation section 14, a second flow path 42 connecting the first gas-liquid separation section 14 and the compression section 16, a third flow path 48 connecting the first gas-liquid separation sections 14 and 56, a fourth flow path 44 connecting the second gas-liquid separation section 56 and the production section 10, and a fifth flow path 43 connecting the first gas-liquid separation section 14 and the production section 10. The fifth flow path 43 is provided with a liquid transfer pump 15 that sends the water separated in the first gas-liquid separation section 14 to the production section 10. Furthermore, the heat pump system 100 includes a first sub-flow path 60 for supplying the water separated by the gas-solid separation unit 52 to the compression unit 16. In the example shown in FIG. 1 , the first sub-flow path 60 merges with the second flow path 42.

[0027] The gas-solid separation section 52 separates gas from a gas-solid mixture containing clathrate hydrate solids and unreacted gas. The separated gas flows into the compression section 16 via the first sub-channel 60 and the second channel 42. The gas-solid separation section can be of a surface tension type, centrifugal force type, multi-stage filter type, cyclone type, or other type. In the case of a cyclone-type gas-solid separation section, it is expected that the solid phase and the gas phase after separation will be 100% and 100%, respectively (volume ratio). The pressure reduction section 24 can be an expansion valve, a capillary tube, or the like.

[0028] The heat transfer medium delivered from the decomposition section 20 is a mixed phase containing water and gas resulting from the decomposition of clathrate hydrates. The mixture of gas and water produced by the decomposition of clathrate hydrates in the decomposition section 20 is called a "decomposition product."

[0029] The first gas-liquid separation unit 14 can be a gas-liquid separator of various types, such as a surface tension type, a cyclone type, a filter type, a centrifugal type, or a cooling type. In the case of a surface tension type gas-liquid separator, it is expected that the gas phase after separation will be 100% refrigerant gas, and the liquid phase will be 30 / 70% refrigerant gas / water (volume ratio). The water separated in the first gas-liquid separation unit 14 is supplied to the generation unit 10 via a fifth flow path 43. In this embodiment, an electric compressor is used as the compression unit 16.

[0030] The second gas-liquid separation unit 56 may be of a surface tension type, centrifugal force type, multi-stage filter type, cyclone type, or the like. When a centrifugal force type gas-liquid separation unit is used, it is expected that the gas phase after separation will be 100% refrigerant gas, and the liquid phase will be refrigerant gas / compressor lubricating oil at a volume ratio of 10 / 90%. The compressor oil separated by the second gas-liquid separation unit 56 is returned to the compression unit 16 via the third sub-flow path 80. This prevents damage to the compression unit 16 and a deterioration in sealing performance. By using a substance used as an auxiliary agent as compressor oil, damage to the compression unit 16 can be prevented even in a configuration without the second gas-liquid separation unit 56.

[0031] Heat transport in the heat pump system 100 of this embodiment will be described below. The heat medium at the outlet side of the decomposition section 20 in FIG. 1 is in a decomposed state (a mixed phase of gas and water) and is at low temperature and low pressure. The decomposition product as the heat medium flows through the first flow path 41 into the first gas-liquid separation section 14. The decomposition product is decomposed into gas and water in the first gas-liquid separation section 14. The gas flows through the second flow path 42 into the compression section 16, is pressurized by the compression section 16, and flows into the generation section 10 through the second gas-liquid separation section 56 and the fourth flow path 44. The gas is pressurized and heated by compression by the compression section 16. Meanwhile, the water is forced through the fifth flow path 43 by the liquid feed pump 15 and flows into the generation section 10. The gas at the inlet side of the generation section 10 is at high temperature and pressure.

[0032] The high-pressure gas and water (heat medium) that flow into the generation section 10 are cooled by heat dissipation in the heat dissipation section 12. Specifically, the heat exchanger that serves as the heat dissipation section 12 exchanges heat between the heat medium in the generation section 10 and a heat source outside the heat pump system, cooling the heat medium. When heat equivalent to the heat of generation is released from the heat medium, the state of the heat medium crosses the phase equilibrium line of the heat medium and becomes a clathrate hydrate state (high pressure) on the outlet side of the generation section 10. The clathrate hydrate discharged from the generation section 10 is a gas-solid mixture containing unreacted gas. The heat medium flows from the generation section 10 to the decomposition section 20 due to the pressure difference between the generation section 10 and the decomposition section 20.

[0033] The clathrate hydrate as the heat transfer medium flows through the first main flow path 30, is depressurized by the depressurization section 24, and flows into the decomposition section 20. The clathrate hydrate is depressurized and cooled by the decomposition section 24. That is, the heat transfer medium is a low-pressure clathrate hydrate on the inlet side of the decomposition section 20. The low-pressure clathrate hydrate (heat transfer medium) that flows into the decomposition section 20 is heated by the heat absorption section 22. Specifically, the heat exchanger serving as the heat absorption section 22 exchanges heat between the heat transfer medium in the decomposition section 20 and a heat source outside the heat pump system, and the heat transfer medium absorbs the external heat and is heated. When the heat transfer medium absorbs heat equivalent to the heat of decomposition, the state of the heat transfer medium crosses the phase equilibrium line of the heat transfer medium and reaches a low-temperature, low-pressure decomposition state (a mixture of gas and water) on the outlet side of the decomposition section 20.

[0034] In this way, in the heat pump system 100 of this embodiment, heat equivalent to the heat of decomposition and formation of clathrate hydrates can be pumped from an object outside the heat pump system 100 and provided to another object outside the heat pump system 100. The heat exchanger serving as the heat release section 12 and the heat exchanger serving as the heat absorption section 22 may perform heat exchange inside or outside the generation section 10 and the decomposition section 20, respectively.

[0035] As described above, in the first main flow path 30 of the heat pump system 100 of this embodiment, the gas-solid separation section 52 is provided between the production section 10 and the pressure reduction section 24. The gas-solid mixture mainly containing clathrate hydrate solids and discharged from the production section 10 flows into the gas-solid separation section 52, where the gas is separated, and the mixture flows into the decomposition section 20 in a state mainly containing clathrate hydrate solids.

[0036] Because the gas-solid separation section 52 is located upstream of the pressure reduction section 24, the gas separated in the gas-solid separation section 52 is in a high-pressure state. If the gas-solid separation section 52 is not provided, the excess gas in the gas-solid mixture mainly containing clathrate hydrate solids is reduced in pressure in the pressure reduction section 24 and flows into the compression section 16 in a low-pressure state, where it is compressed. In contrast, in the heat pump system 100 of this embodiment, before the clathrate hydrate slurry flowing through the first main flow path 30 is reduced in pressure, the excess gas in the clathrate hydrate slurry is separated by the gas-solid separation section 52 and supplied to the compression section 16 in a high-pressure state. This makes it possible to suppress a decrease in compressor efficiency and improve the energy consumption efficiency (COP).

[0037] The heat pump system 100 of this embodiment can be applied to, for example, an air conditioner having at least one of the functions of cooling, heating, dehumidification, and humidification. In addition, the heat pump system 100 can be applied to various heat utilization devices (including plants and systems) that transfer heat to and from a heat source, such as cooling devices (heat sinks, etc.), heating devices (floor heating devices, etc.), hot water supply devices, refrigeration devices, dehydration devices, heat storage devices, snow melting devices, and drying devices. High energy efficiency can be achieved in these heat utilization devices by using the heat pump of this embodiment. An example in which the heat pump system 100 of this embodiment is applied to an air conditioner will be described below.

[0038] Fig. 2 is an explanatory diagram that schematically shows the generation of cold heat in the air conditioning device 110 of this embodiment. Fig. 3 is an explanatory diagram that schematically shows the generation of hot heat in the air conditioning device 110. In Figs. 2 and 3, the same components as in Fig. 1 are assigned the same reference numerals, and reference is made to the preceding explanation.

[0039] This air conditioner 110 has the function of cooling and heating indoor air and is equipped with the above-mentioned heat pump system 100. As shown in the figure, the air conditioner 110 is equipped with a first generation / decomposition section 11a, a first heat exchanger 11b, a first main flow path 30, a gas-solid separation section 52, a pressure reduction section 24, a second generation / decomposition section 13a, a second heat exchanger 13b, a second main flow path 40, a first gas-liquid separation section 14, a compression section 16, a second gas-liquid separation section 56, and a control section 90. The first generation / decomposition section 11a and the first heat exchanger 11b are disposed in the indoor unit, and the second generation / decomposition section 13a and the second heat exchanger 13b are disposed in the outdoor unit.

[0040] The control unit 90 is a computer including a ROM, a RAM, and a CPU. The control unit 90 controls the entire air conditioner 110, including the cold heat generation process and the hot heat generation process (described later).

[0041] In the air conditioning apparatus 110, the first main flow path 30 includes an eleventh flow path 32 connecting the second generation / decomposition section 13a and the gas-solid separation section 52, a twelfth flow path 34 connecting the gas-solid separation section 52 and the pressure reduction section 24, a thirteenth flow path 36 connecting the pressure reduction section 24 and the first generation / decomposition section 11a, a thirty-first flow path 31 connecting the eleventh flow path 32 and the thirteenth flow path 36, and a thirty-third flow path 33. An on-off valve V1 is provided in the eleventh flow path 32, an on-off valve V2 in the thirteenth flow path 36, an on-off valve V3 in the 31st flow path 31, and an on-off valve V4 in the thirty-third flow path 33.

[0042] In the air conditioner 110, the second main flow path 40 includes a first flow path 41 connecting the first production / decomposition section 11a and the first gas-liquid separation section 14, a second flow path 42 connecting the first gas-liquid separation section 14 and the compression section 16, a third flow path 48 connecting the compression section 16 and the second gas-liquid separation section 56, a fourth flow path 44 connecting the second gas-liquid separation section 56 and the second production / decomposition section 13a, and a fifth flow path 43 connecting the first gas-liquid separation section 14 and the production section 10. The second main flow path 40 further includes a sixth flow path 46 connecting the first flow path 41 and the fourth flow path 44, a seventh flow path 47, and an eighth flow path 45 connecting the fifth flow path 43 and the first production / decomposition section 11a. An on-off valve V5 is provided in the first flow path 41, an on-off valve V6 in the fourth flow path 44, an on-off valve V7 in the sixth flow path 46, an on-off valve V8 in the seventh flow path 47, an on-off valve V9 in the fifth flow path 43, and an on-off valve V10 in the eighth flow path 45.

[0043] As shown in Fig. 2, when the air conditioner 110 is used for cooling, the first generation / decomposition section 11a arranged in the indoor unit functions as the decomposition section 20, and the first heat exchanger 11b functions as the heat absorption section 22. The first heat exchanger 11b takes in indoor air and exchanges heat between the heat medium in the first generation / decomposition section 11a and the indoor air, causing the heat medium to absorb heat equivalent to the heat of decomposition. This reduces the temperature of the indoor air taken in by the first heat exchanger 11b (generating cold), and the cooled air is released into the room.

[0044] When the air conditioner 110 is used for cooling, the second generation / decomposition unit 13a arranged in the outdoor unit functions as the generation unit 10, and the second heat exchanger 13b functions as the heat radiator 12. The second heat exchanger 13b takes in outdoor air (e.g., atmospheric air) and exchanges heat between the heat medium in the second generation / decomposition unit 13a and the outdoor air, radiating heat equivalent to the generated heat to the heat medium. This increases the temperature of the outdoor air taken in by the second heat exchanger 13b, and the heated air is released outdoors.

[0045] As shown in FIG. 2, when the control unit 90 of the air conditioner 110 is executing cold heat generation control, on-off valves V1, V2, V5, V6, and V9 are open, and on-off valves V3, V4, V7, V8, and V10 are closed. Therefore, the heat transfer medium discharged from the second generation / decomposition unit 13a flows into the first generation / decomposition unit 11a through the 11th flow path 32, the 12th flow path 34, and the 13th flow path 36, and then returns to the second generation / decomposition unit 13a through the 1st flow path 41, the 2nd flow path 42, the 3rd flow path 48, the 4th flow path 44, and the 5th flow path 43. During cooling, the heat transfer medium circulates through these flow paths. The high-pressure gas separated in the gas / solid separation unit 52 flows into the compression unit 16 through the 1st sub-flow path 60 and the 2nd flow path 42. In FIG. 2, flow paths through which the heat transfer medium does not flow are indicated by dotted lines.

[0046] On the other hand, as shown in Fig. 3, when the air conditioner 110 is used for heating, the first generation / decomposition unit 11a arranged in the indoor unit functions as the generation unit 10, and the first heat exchanger 11b functions as the heat dissipation unit 12. The first heat exchanger 11b takes in indoor air, exchanges heat between the heat medium in the first generation / decomposition unit 11a and the indoor air, and releases heat equivalent to the generated heat to the heat medium. This increases the temperature of the indoor air taken in by the first heat exchanger 11b (heat generation), and the heated air is released into the room.

[0047] When the air conditioner 110 is used for heating, the second generation / decomposition section 13a arranged in the outdoor unit functions as the decomposition section 20, and the second heat exchanger 13b functions as the heat absorption section 22. The second heat exchanger 13b takes in outdoor air (e.g., atmospheric air) and exchanges heat between the heat medium in the second generation / decomposition section 13a and the outdoor air, causing the heat medium to absorb heat equivalent to the heat of decomposition. This reduces the temperature of the outdoor air taken in by the second heat exchanger 13b, and the cooled air is released outdoors.

[0048] 3, when heat generation control is being executed by the control unit 90 of the air conditioner 110, on-off valves V1, V2, V5, V6, and V9 are closed, and on-off valves V3, V4, V7, V8, and V10 are open. Therefore, the heat medium discharged from the second generation / decomposition unit 13a flows into the first gas-liquid separation unit 14 through the fourth flow path 44, the seventh flow path 47, and the first flow path 41. The gas separated by the first gas-liquid separation unit 14 flows into the first generation / decomposition unit 11a through the second flow path 42, the third flow path 48, the fourth flow path 44, and the sixth flow path 46. Meanwhile, the water separated by the first gas-liquid separation unit 14 flows into the first generation / decomposition unit 11a through the fifth flow path 43 and the eighth flow path 45. The heat transfer medium sent out from the first generation / decomposition section 11a returns to the second generation / decomposition section 13a through the 13th flow path 36, the 33rd flow path 33, the 11th flow path 32, the 12th flow path 34, the 13th flow path 36, the 31st flow path 31, and the 11th flow path 32. During heating, the heat transfer medium circulates through these flow paths. The high-pressure gas separated in the gas / solid separation section 52 flows into the compression section 16 through the first sub-flow path 60 and the second flow path 42. In FIG. 3, flow paths through which the heat transfer medium does not flow are indicated by dotted lines.

[0049] 4 is a flowchart showing the temperature control procedure in the control unit 90. When the control unit 90 starts temperature control, it operates in cold energy generation mode in step S102. In the cold energy generation mode, the control unit 90 opens on-off valves V1, V2, V5, V6, and V9 and closes on-off valves V3, V4, V7, V8, and V10 (FIG. 2). As a result, in the cold energy generation mode, the heat transfer medium (decomposition product) sent from the first generation / decomposition unit 11a flows through the above-mentioned flow path into the second generation / decomposition unit 13a, where clathrate hydrates are generated, and the heat transfer medium mainly containing clathrate hydrate solids flows through the above-mentioned flow path into the first generation / decomposition unit 11a.

[0050] In step S104, the control unit 90 compares the temperature with a threshold value, and operates in the cold energy generation mode until the temperature falls below the threshold value (NO in step S104). When the temperature falls below the threshold value (YES in step S104), the process proceeds to step S106. Here, the temperature is the room temperature (the value detected by the room temperature sensor). The threshold value can be set arbitrarily, and in this embodiment, it is set to 15°C.

[0051] In step S106, the control unit 90 operates in the heat generation mode. In the heat generation mode, the control unit 90 closes the on-off valves V1, V2, V5, V6, and V9 and closes the on-off valves V3, V4, V7, V8, and V10 (FIG. 3). As a result, in the heat generation mode, the heat transfer medium (mainly containing clathrate hydrate solids) delivered from the first generation / decomposition unit 11a flows into the second generation / decomposition unit 13a through the above-mentioned flow path, and the heat transfer medium (decomposition product) decomposed in the second generation / decomposition unit 13a flows into the first generation / decomposition unit 11a through the above-mentioned flow path.

[0052] In step S108, the control unit 90 compares the temperature with the threshold value, and operates in the heat generation mode until the temperature exceeds the threshold value (NO in step S108). When the temperature exceeds the threshold value (YES in step S108), the process returns to step S102. Here, the temperature is the room temperature (the value detected by the room temperature sensor), and the threshold value is the same as the threshold value used in step S104.

[0053] Until an instruction to power off the air conditioner 110 is input, the control unit 90 performs control in the cold heat generation mode or the hot heat generation mode, and when the control unit 90 detects that the power has been turned off, it ends the temperature control.

[0054] Figure 5 shows the relationship between the power COP and the gas-solid-liquid ratio. In the example shown in Figure 5, the COP is calculated by changing the solid fraction in the gas-solid-liquid mixed phase. The calculation results for the solid-liquid mixed phase are shown by filled triangles, and the calculation results for the gas-solid-liquid mixed phase are shown by open triangles.

[0055] In the example shown in Figure 5, a clathrate hydrate generator 70 shown in Figure 6 (described later) was created on a laboratory scale, and a production experiment was actually conducted at the laboratory level, and the COP was calculated based on the measured production reaction rate. The production experiment was conducted under the following conditions, and the COP was calculated. The temperature of the heat medium on the inlet side of the production section 10 was 20°C, and the temperature of the heat medium on the outlet side of the decomposition section 20 was 10°C. The rotation speed of the compression section 16 was 800 rpm. The volume of the refrigerant gas in the production section 10 was 91%. The refrigerant gas was refrigerant R32.

[0056] As shown in the figure, when a solid-liquid mixed phase is compared with a gas-solid-liquid mixed phase, the solid-liquid mixed phase has a better COP overall. In other words, the COP is improved by separating gas (refrigerant gas) from a mixture containing clathrate hydrate solids. Focusing on the solid-liquid mixed phase, the COP improves as the solid fraction in the mixed phase increases (the liquid fraction decreases). As described above, the clathrate hydrate generator 70 used in the heat pump system 100 of this embodiment discharges a mixture of clathrate hydrate solids and gas (which contains no liquid phase or a small amount of liquid phase), thereby improving the COP.

[0057] Fig. 6 is an explanatory diagram conceptually showing the configuration of the clathrate hydrate generator 70 of this embodiment. In the drawings following Fig. 6, mutually perpendicular X, Y, and Z axes are shown to identify directions. For convenience, in this specification, the positive direction of the Z axis is referred to as the upward direction, and the negative direction of the Z axis is referred to as the downward direction.

[0058] The clathrate hydrate generator 70 comprises a reaction vessel 71 having therein a reaction surface 711 on which clathrate hydrates are produced, a water film forming unit 73 which forms a water film WF on the reaction surface 711, a sliding unit 72 which is disposed within the reaction vessel 71 and rubs against the reaction surface 711, a gas supply path 74 for supplying gas into the reaction vessel 71, a temperature adjusting unit 75 which adjusts the temperature of the reaction surface 711, and a through-hole 76 which has an opening 761 in part of the reaction surface 711 and passes through the reaction vessel 71, and the clathrate hydrates formed on the reaction surface 711 can be scraped out by the sliding unit 72 and discharged to the outside of the reaction vessel 71 through the through-hole 76.

[0059] Reaction vessel 71 has a vessel body 712 and a lid 713. An O-ring is sandwiched between vessel body 712 and lid 713, and they are fastened together with screws to seal reaction vessel 71. Reaction vessel 71 is preferably made of a material with good heat exchange properties (for example, copper, aluminum, stainless steel, etc.).

[0060] The water film forming unit 73 includes a liquid reservoir 731 that stores water to be supplied to the reaction surface 711, and two sponge blades 732 that absorb water from the liquid reservoir 731 and wet the reaction surface 711. The reaction vessel 71 has a water supply channel 733 that penetrates the lid 713, and water W is supplied to the liquid reservoir 731 through the water supply channel 733. In this embodiment, the fifth flow path 43 shown in FIG. 1 is connected to the water supply channel 733, and water separated in the first gas-liquid separation unit 14 is supplied to the liquid reservoir 731. In this embodiment, the two sponge blades 732 are attached to the rotating shaft 721 and rotate while in contact with the reaction surface 711. The water contained in the sponge blades 732 is applied to the reaction surface 711, thereby forming a water film. The thickness of the water film is not particularly limited, but a thinner water film is preferable. For example, a thickness of 590 μm or less is preferable because it allows the clathrate hydrate solid fraction in the heat medium discharged from the clathrate hydrate generator 70 to be 30% or more, as described below. The water film thickness can be determined based on the target temperature difference and solid fraction within the water film. For example, if the temperature difference is ≦5 K (described below) and the solid fraction is 30%, the water film thickness will be 590 μm.

[0061] Target output Q=5kW / m 2The required gas flow rate can be calculated using the following formula: The gas is assumed to be HFC-32. Required gas flow rate = Q [kJ / s m2] / heat of formation [kJ / mol-gas] x molecular weight [kg / mol] / density [kg / m3] =5 / 72×0.052 / 22=approx. 0.00017[m / s] = approx. 0.17 mm / s

[0062] Required water film thickness = Q[kJ / s m2] / (heat of formation [kJ / mol-H2O] / molecular weight [kg / mol] x density [kg / m3]) =5 / (12.5 / 0.018×998) =5 [kJ / s m 2 ] / (6.93×105[kJ / m 3 ]) =about 7[μm / s] Here, the heat of formation [kJ / mol-gas] is the heat of formation per mole of HFC-32, and the heat of formation [kJ / mol-H2O] is the heat of formation per mole of H2O.

[0063] When the clathrate hydrate solids rate of the heat transfer medium discharged from the clathrate hydrate generator 70 is 30% or more and a water film of 20 μm is formed by the sponge blade, the temperature difference ΔT in the water film is as follows. ΔT=Q[W / m 2 ] / thermal conductivity [W / m / K] × water film thickness [m] × heat transfer area [m 2 ] =5000 / 0.6×(20×10 -6 ) x 1 =0.17[K] When the allowable temperature range inside the water film is ≦5[K], the water film thickness will be approximately 590μm or less due to the relationship between film thickness and temperature difference described above. If the temperature difference inside the water film becomes large, heat conduction within the water film becomes a barrier and the reaction rate decreases, so if the allowable temperature range inside the water film is ≦5[K], an appropriate reaction rate can be obtained.

[0064] FIG. 7 is an explanatory diagram conceptually showing the internal configuration of the clathrate hydrate generator 70. FIG. 7 shows the sliding unit 72 and the water film forming unit 73 as viewed from above (from the positive direction of the Z axis). The sliding unit 72 is equipped with two scraping blades 722. The scraping blades 722 have sufficient hardness and strength to be able to scrape the clathrate hydrate solid from the reaction surface 711, and can be made of, for example, silicone. The two scraping blades 722 are attached to a rotating shaft 721. As shown in the figure, the sponge blades 732 and the scraping blades 722 are attached alternately to the rotating shaft 721 to form an impeller.

[0065] 6, the gas supply path 74 is formed in the lid 713 of the reaction vessel 71. In this embodiment, the fourth flow path 44 (FIG. 1) is connected to the gas supply path 74, and high-temperature, high-pressure gas separated in the first gas-liquid separation unit 14 and compressed in the compression unit 16 is supplied into the reaction vessel 71 via the gas supply path 74.

[0066] Temperature control unit 75 includes a heat medium flow path 751, and controls the temperature of reaction surface 711 by heat exchange between the heat medium flowing through heat medium flow path 751 and container body 712. In this embodiment, cooling water is used as the heat medium, but in other embodiments, oil, gas, or the like may be used as the heat medium. In this embodiment, the cooling water flowing through heat dissipation unit 12 (FIG. 1) flows through heat medium flow path 751.

[0067] The clathrate hydrate generator 70 further includes a pressure gauge 77 that detects the pressure inside the reaction vessel 71. By controlling the pressure inside the reaction vessel 71 based on the detection result of the pressure gauge 77, the output of the reaction for producing clathrate hydrate solids can be controlled, and the amount of water discharged from the clathrate hydrate generator 70 can be reduced. The pressure inside the reaction vessel 71 may be controlled, for example, by a control unit that controls the entire heat pump system 100, or by a control unit included in the pressure gauge 77. The pressure inside the reaction vessel 71 can be controlled by the compression pressure of the compression unit 16. In other embodiments, the pressure gauge 77 may be provided in a flow path between the compressor and the generator.

[0068] In the clathrate hydrate generator 70, a water film WF is formed on the reaction surface 711 by the water film forming section 73, gas is supplied via the gas supply path 74, and the temperature of the reaction surface 711 and the gas pressure inside the reaction vessel 71 are appropriately controlled, whereby a clathrate hydrate solid is produced on the reaction surface 711, and the amount of water discharged from the clathrate hydrate generator 70 can be reduced.

[0069] As shown in Figures 6 and 7, the outer end of sponge blade 732 is placed in liquid reservoir 731 and is immersed in water while rotating around rotation shaft 721. Therefore, sponge blade 732 continues to form a water film WF on reaction surface 711 while rotating. Note that, as shown in Figure 7, opening 761 of through-hole 76 is formed in a portion of reaction surface 711, so that water film WF is not formed in that portion. Scraping blade 722 scrapes against reaction surface 711 while rotating around rotation shaft 721.

[0070] In FIG. 7, the reaction surface 711 is shown divided into four regions R1 to R4. In regions R1 and R3, a water film WF is formed by the sponge blade 732, and clathrate hydrate solids are produced. In regions R2 and R4, clathrate hydrate solids are scraped out by the scraping blade 722, and the reaction surface 711 is renewed. When the rotating shaft 721 rotates as indicated by the arrows in the figure, the two scraping blades 722 rub against regions R1 and R3, respectively. This causes clathrate hydrate solids to be scraped off from the reaction surface 711. Meanwhile, the two sponge blades 732 wet regions R2 and R4, respectively, and form a water film WF. This causes clathrate hydrate solids to be formed in regions R2 and R4.

[0071] 8 is an explanatory diagram conceptually illustrating the generation and discharge of clathrate hydrate solids. As shown on the left side of FIG. 8, the water film WF formed on the reaction surface 711 by the sponge blade 732 becomes clathrate hydrate solids CH, which are then scraped out by the scraping blade 722 as it rotates. The scraping blade 722 removes the clathrate hydrate solids CH from the reaction surface 711, thereby refreshing the reaction surface 711. In this embodiment, the eleventh flow path 32 shown in FIG. 1 is connected to the through-hole 76, and the clathrate hydrate solids discharged from the clathrate hydrate generator 70 are supplied to the decomposition section 20 via the first main flow path 30.

[0072] As shown on the right side of Figure 8, the sponge blades 732 containing water wet the reaction surface 711 renewed as described above, forming a water film WF, and clathrate hydrate solids are produced. As described above, the scraping blades 722 and sponge blades 732 are alternately attached to the rotating shaft 721 to form an impeller (Figure 7), and as the blades rotate around the rotating shaft 721, the state shown on the left side of Figure 8 and the state shown on the right side are alternately repeated, and clathrate hydrate solids are discharged.

[0073] As described above, the heat pump system 100 of this embodiment transports heat by utilizing the latent heat (heat of decomposition and formation) of clathrate hydrates. The heat of decomposition and formation of clathrate hydrates is greater than the heat associated with the condensation and evaporation of the refrigerant. Therefore, energy consumption efficiency can be improved compared to conventional heat pumps that utilize the exchange of heat associated with the condensation and evaporation processes of the refrigerant.

[0074] The clathrate hydrate generator 70 included in the heat pump system 100 of this embodiment is equipped with a water film forming section 73, which forms a thin water film WF on the reaction surface 711. When gas is supplied from the gas supply channel 74, clathrate hydrate solid CH is generated on the reaction surface 711. Because clathrate hydrate solid CH is formed from the water film WF formed on the reaction surface 711, there is little excess water. Furthermore, the clathrate hydrate solid CH formed on the reaction surface 711 is scraped out by the sliding section 72 and discharged outside the reaction vessel 71, reducing the amount of water discharged together with the clathrate hydrate from the clathrate hydrate generator. Therefore, in the heat pump system 100 using the clathrate hydrate generator 70, the amount of water supplied to the decomposition section 20 can be reduced, and excess liquid (water) is supplied to the decomposition section 20. This suppresses a decrease in cooling output due to the use of a portion of the latent heat of decomposition to cool the liquid (water) (sensible heat loss). As a result, the energy consumption efficiency (COP) can be improved.

[0075] In addition, the heat pump system 100 is equipped with a gas-solid separation section 52, and can supply the gas in the heat medium, which mainly contains clathrate hydrate solids discharged from the generation section 10, to the compression section 16 under high pressure, thereby suppressing a decrease in the compressor efficiency of the compression section 16 and improving the energy consumption efficiency (COP).

[0076] Furthermore, according to the heat pump system 100 of this embodiment, water can be separated from the decomposition product, which is a mixed phase of gas and water, by the first gas-liquid separation unit 14, and the gas from which the water has been separated can be compressed by the compression unit 16. Therefore, compared to the case where the decomposition product, which is a mixed phase of gas and water, is compressed as is, the work of the compression unit 16 is reduced by the amount of work required to compress the water, and the energy consumption efficiency of the heat pump system can be improved.

[0077] Second Embodiment Fig. 9 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator 70A of the second embodiment. Fig. 10 is an explanatory diagram conceptually showing the internal configuration of the clathrate hydrate generator 70A of the second embodiment. The clathrate hydrate generator 70A has shower impellers 734 instead of the sponge impellers 732 of the clathrate hydrate generator 70 of the first embodiment. In the following embodiments, the same components as those of the first embodiment are designated by the same reference numerals, and the preceding explanations are to be referred to.

[0078] The shower impeller 734 diffuses and discharges water onto the reaction surface 711. In the clathrate hydrate generator 70A of this embodiment, the water film forming section 73 has two shower impellers 734 instead of the two sponge impellers 732, and does not have a liquid reservoir section 731. Therefore, the internal shape of the vessel body 712A is different from that of the vessel body 712 of the first embodiment. In addition, a water supply channel 733 is formed in the rotation shaft 721, and water is supplied to the shower impeller 734 via the water supply channel 733.

[0079] In Figure 10, similar to Figure 7, the reaction surface 711 is divided into four regions R1 to R4. In regions R1 and R3, a water film WF is formed by the shower impeller 734, and clathrate hydrate solids are produced. In regions R2 and R4, clathrate hydrate solids are scraped out by the scraper blades 722, and the reaction surface 711 is renewed. When the rotating shaft 721 rotates as indicated by the arrows in the figure, the two scraper blades 722 rub against regions R1 and R3, respectively. This causes the clathrate hydrate solids to be scraped off from the reaction surface 711. Meanwhile, the two shower impellers 734 wet regions R2 and R4, respectively, and form a water film WF. This causes clathrate hydrate solids to be formed in regions R2 and R4.

[0080] The clathrate hydrate generator 70A of the present embodiment is provided with the shower impeller 734, which allows a thin water film WF to be formed on the reaction surface 711. Therefore, similar to the clathrate hydrate generator 70 of the first embodiment, it is possible to reduce the amount of water discharged together with the clathrate hydrate solid from the clathrate hydrate generator 70A.

[0081] Third Embodiment 11 is an explanatory diagram conceptually showing the configuration of a clathrate hydrate generator 70B of the third embodiment. In the clathrate hydrate generator 70B of this embodiment, the reaction surface 711 is disposed vertically (in the Z-axis direction). The liquid reservoir 731 is formed at the bottom of the reaction vessel 71B. Gas is supplied into the reaction vessel 71B via a gas supply channel (not shown).

[0082] Sponge blade 732 and scraping blade 722 are arranged at a predetermined distance, and as shown in Figure 11, sponge blade 732 moves from bottom to top while in contact with reaction surface 711, then leaves reaction surface 711 (moves in the positive direction of the Y axis), moves downward, passes through liquid reservoir 731, and again comes into contact with reaction surface 711. As sponge blade 732 passes through liquid reservoir 731, water is absorbed into sponge blade 732. As shown in Figure 11, after sponge blade 732 moves over reaction surface 711, a water film WF is formed.

[0083] 12 is an explanatory diagram conceptually illustrating the production and discharge of clathrate hydrate solids in the clathrate hydrate generator 70B of the third embodiment. As shown on the left side of FIG. 12, clathrate hydrate solids are produced in the region of the reaction surface 711 through which the sponge blade 732 has passed. As indicated by the black arrows in the figure, when the sponge blade 732 and the scraping blade 722 move upward (positive direction of the Z axis), a water film WF is formed in the region through which the sponge blade 732 has passed, and then clathrate hydrate solids CH are produced. In the region through which the scraping blade 722 has passed, the clathrate hydrate solids CH are scraped off, and the reaction surface 711 is renewed (the diagram on the right side of FIG. 12). The scraped clathrate hydrate solids CH are discharged to the outside of the clathrate hydrate generator 70B through the through-holes 76. In this manner, also in the clathrate hydrate generator 70B of this embodiment, the clathrate hydrate solid CH is discharged by repeating the formation of the water film WF and the scraping out of the clathrate hydrate solid CH.

[0084] As in the first embodiment, the clathrate hydrate generator 70B of this embodiment can also form a thin water film WF on the reaction surface 711 using the sponge blades 732, thereby reducing the amount of water discharged together with the clathrate hydrate solids from the clathrate hydrate generator 70B.

[0085] <Fourth embodiment> FIG. 13 is an explanatory diagram conceptually illustrating the configuration of a clathrate hydrate generator 70C of the fourth embodiment. FIG. 13(A) shows the external appearance of the clathrate hydrate generator 70C, and FIG. 13(B) shows the internal configuration of the clathrate hydrate generator 70C. The clathrate hydrate generator 70C of this embodiment is cylindrical, with a heat transfer medium flow path (not shown) formed on the side to control the temperature of the reaction surface 711. The inner surface of the reaction vessel 71C is the reaction surface 711. The clathrate hydrate generator 70C is disposed such that its longitudinal direction is along the Y-axis. A liquid reservoir 731 is formed below the internal space of the reaction vessel 71C. Two sponge blades 732 and two scraping blades 722 are alternately attached to the rotation shaft 721 to form an impeller.

[0086] The sponge blades 732 suck up water from the liquid reservoir 731 at the bottom, wetting the reaction surface 711 and forming a water film WF. The gas and water react to produce clathrate hydrate solids. The produced clathrate hydrate solids are removed by the scraping blades 722, refreshing the reaction surface 711. The removed clathrate hydrate solids are transported to through-holes 76 formed in part of the reaction surface 711 and discharged from the clathrate hydrate generator 70C. This also allows a thin water film WF to be formed on the reaction surface 711, thereby reducing the amount of water discharged together with the clathrate hydrate solids from the clathrate hydrate generator 70C.

[0087] Fifth Embodiment FIG. 14 is an explanatory diagram conceptually illustrating the configuration of a clathrate hydrate generator 70D of the fifth embodiment. The clathrate hydrate generator 70D of the fifth embodiment does not include a sponge impeller 732 or a shower impeller 734, and forms a water film WF without using the sponge impeller 732 or the shower impeller 734. The reaction vessel 71D has a thin recess 78, the bottom of which is the reaction surface 711. The reaction vessel 71D is equipped with a water supply channel 733 and a water discharge channel 735 connected to the reaction surface 711. In the clathrate hydrate generator 70D, a water supply unit such as a microsyringe pump (not shown) connected to the water supply channel 733 intermittently supplies water to the reaction surface 711, thereby supplying a required amount of water to the reaction surface 711. The water supply channel 733 and the water supply unit in this embodiment are also referred to as a "water film forming unit."

[0088] A water film WF is formed on the reaction surface 711, and when the gas and water react, clathrate hydrate solids are produced. The produced clathrate hydrate solids are removed by the scraping blades 722, refreshing the reaction surface 711. The removed clathrate hydrate solids are transported to through-holes 76 formed in part of the reaction surface 711 and discharged from the clathrate hydrate generator 70D. This also allows a thin water film WF to be formed on the reaction surface 711, thereby reducing the amount of water discharged together with the clathrate hydrate solids from the clathrate hydrate generator 70D.

[0089] <Modification of this embodiment> The present invention is not limited to the above-described embodiment, and can be embodied in various forms without departing from the spirit of the invention. For example, the following modifications are also possible.

[0090] In the above embodiment, the temperature control unit includes a heat transfer medium flow path formed in the reaction vessel 71 , but the heat transfer medium flow path may be formed outside the reaction vessel 71 .

[0091] The temperature control unit does not need to include a heat transfer medium flow path. For example, when the clathrate hydrate generator is used alone and not in a heat pump system, the temperature control unit may be configured with, for example, a Peltier element. Alternatively, a heater, a fan, or the like may be provided. This also allows the temperature of the reaction surface to be appropriately controlled.

[0092] The clathrate hydrate generator does not need to be equipped with a pressure gauge 77. By supplying gas compressed to a predetermined constant pressure by the compression unit 16 to the clathrate hydrate generator 70, clathrate hydrates can be generated.

[0093] The heat pump system 100 may be provided with a mixing section between the second gas-liquid separation section 56 and the generation section 10, which mixes the water separated by the first gas-liquid separation section 14 with the gas compressed by the compression section 16.

[0094] In the above embodiment, the clathrate hydrate generator is applied to a heat pump system, but it can also be applied to various other systems, such as a gas separation system that separates and removes specific gases.

[0095] In the above embodiment, an example has been shown in which clathrate hydrates are produced while water is being supplied to the liquid reservoir 731 and the shower impeller 734. However, a configuration may also be adopted in which a predetermined amount of water is stored in advance in the liquid reservoir 731 and the shower impeller 734.

[0096] The present disclosure has been described above based on embodiments and modifications, but the above-described embodiments are intended to facilitate understanding of the present disclosure and are not intended to limit the present disclosure. The present disclosure may be modified or improved without departing from the spirit and scope of the claims, and equivalents thereof are included in the present disclosure. Furthermore, if a technical feature is not described as essential in this specification, it may be deleted as appropriate.

[0097] The present invention can also be realized as the following application examples. [Application example 1] A clathrate hydrate generator for generating clathrate hydrates from water and gas, comprising: a reaction vessel having a reaction surface therein on which the clathrate hydrate is produced; a water film forming unit that forms a water film on the reaction surface; a sliding part disposed in the reaction vessel and sliding on the reaction surface; a gas supply path for supplying the gas into the reaction vessel; a temperature control unit that controls the temperature of the reaction surface; a through-hole having an opening in a part of the reaction surface and penetrating the reaction vessel; Equipped with the clathrate hydrate formed on the reaction surface can be scraped out by the sliding part and discharged to the outside of the reaction vessel through the through-hole. Clathrate hydrate generator. [Application example 2] The clathrate hydrate generator according to Application Example 1, The water film forming unit is a liquid reservoir for storing water to be supplied to the reaction surface; a sponge blade that absorbs water from the liquid reservoir and wets the reaction surface; Equipped with The sliding portion includes a scraping blade, The sponge blades and the scraping blades are alternately attached to a rotating shaft to form an impeller. Clathrate hydrate generator. [Application example 3] The clathrate hydrate generator according to Application Example 1 or Application Example 2, the water film forming unit includes shower blades that diffuse and discharge water onto the reaction surface; The sliding portion includes a scraping blade, The shower vanes and the scraping vanes are alternately attached to a rotating shaft to form an impeller. Clathrate hydrate generator. [Application example 4] The clathrate hydrate generator according to any one of Application Examples 1 to 3, The temperature adjustment unit is A heat medium flow path through which the heat medium flows is provided. Clathrate hydrate generator. [Application example 5] The clathrate hydrate generator according to any one of claims 1 to 4, moreover, a pressure gauge for detecting the pressure inside the reaction vessel; a pressure control unit that controls the pressure inside the reaction vessel based on the detection value of the pressure gauge; A clathrate hydrate generator comprising: [Application Example 6] The clathrate hydrate generator according to any one of claims 1 to 5, The thickness of the water film is 590 μm or less. Clathrate hydrate generator. [Application Example 7] 1. A heat pump system, comprising: The clathrate hydrate generator according to any one of Application Examples 1 to 6 is provided, Heat is transported by repeating the decomposition and formation processes of clathrate hydrates. Heat pump system. [Explanation of symbols]

[0098] 10...Generation section 11a...First generation / decomposition part 11b…First heat exchanger 12...Heat radiation part 13a…Second generation / decomposition part 13b…Second heat exchanger 14...First gas-liquid separation section 15...Liquid transfer pump 16...Compression section 20…Disassembly part 22...heat absorption part 24...Decompression section 30...First main channel 31~34, 36, 41~48...flow path 40…Second main flow path 52... Gas-solid separation section 56...Second gas-liquid separation section 60...First sub-channel 70, 70A, 70B, 70C, 70D...clathrate hydrate generator 71, 71A, 71B, 71C, 71D...Reaction vessel 72...Sliding part 73…Water film forming part 74...Gas supply line 75...Temperature control section 76...Through hole 77...Pressure gauge 78...recess 80...Third sub-channel 90...Control unit 100...Heat pump system 110...Air conditioning equipment 711...Reaction surface 712, 712A...Container body 713…Lid part 721...Rotation axis 722...Scraping wing 731...liquid reservoir 732...Sponge wings 733…Water supply channel 734...Shower wing 735…Water discharge channel 751...heat transfer medium flow path 761...Opening R1~R4…area V1 to V10: On-off valves W…Water WF…Water film

Claims

1. A clathrate hydrate generator for generating clathrate hydrates from water and gas, comprising: a reaction vessel having a reaction surface therein on which the clathrate hydrate is produced; a water film forming unit that forms a water film on the reaction surface; a sliding part disposed in the reaction vessel and sliding on the reaction surface; a gas supply path for supplying the gas into the reaction vessel; a temperature control unit that controls the temperature of the reaction surface; a through-hole having an opening in a part of the reaction surface and penetrating the reaction vessel; Equipped with the clathrate hydrate formed on the reaction surface can be scraped out by the sliding part and discharged to the outside of the reaction vessel through the through-hole. Clathrate hydrate generator.

2. The clathrate hydrate generator according to claim 1, The water film forming unit is a liquid reservoir for storing water to be supplied to the reaction surface; a sponge blade that absorbs water from the liquid reservoir and wets the reaction surface; Equipped with The sliding portion includes a scraping blade, The sponge blades and the scraping blades are alternately attached to a rotating shaft to form an impeller. Clathrate hydrate generator.

3. The clathrate hydrate generator according to claim 1, the water film forming unit includes shower blades that diffuse and discharge water onto the reaction surface; The sliding portion includes a scraping blade, The shower vanes and the scraping vanes are alternately attached to a rotating shaft to form an impeller. Clathrate hydrate generator.

4. The clathrate hydrate generator according to claim 1, The temperature adjustment unit is A heat medium flow path through which the heat medium flows is provided. Clathrate hydrate generator.

5. The clathrate hydrate generator according to claim 1, moreover, a pressure gauge for detecting the pressure inside the reaction vessel; a pressure control unit that controls the pressure inside the reaction vessel based on the detection value of the pressure gauge; A clathrate hydrate generator comprising:

6. The clathrate hydrate generator according to claim 1, The thickness of the water film is 590 μm or less. Clathrate hydrate generator.

7. 1. A heat pump system, comprising: The clathrate hydrate generator according to any one of claims 1 to 6 is provided, Heat is transported by repeating the decomposition and formation processes of clathrate hydrates. Heat pump system.

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