Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
  • F24H15/00—Control of fluid heaters
  • F24H15/20—Control of fluid heaters characterised by control inputs
  • F24H15/212—Temperature of the water
  • F24H15/215—Temperature of the water before heating
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
  • F24H15/00—Control of fluid heaters
  • F24H15/30—Control of fluid heaters characterised by control outputs; characterised by the components to be controlled
  • F24H15/305—Control of valves
  • F24H15/32—Control of valves of switching valves
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24H—FLUID HEATERS, e.g. WATER OR AIR HEATERS, HAVING HEAT-GENERATING MEANS, e.g. HEAT PUMPS, IN GENERAL
  • F24H4/00—Fluid heaters characterised by the use of heat pumps
  • F24H4/02—Water heaters
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B1/00—Compression machines, plants or systems with non-reversible cycle
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B27/00—Machines, plants or systems, using particular sources of energy
  • F25B27/02—Machines, plants or systems, using particular sources of energy using waste heat, e.g. from internal-combustion engines
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
  • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
  • F25B30/00—Heat pumps
  • F25B30/02—Heat pumps of the compression type

Definitions

• the present invention relates to a heat recovery device and a heat recovery method for cleaning materials, as well as a method for manufacturing materials using the heat recovery method.
• the supply of cleaning fluid to material cleaning equipment and heating media such as hot water to be replenished in the cleaning fluid tank is generally achieved using well-known electric heaters or heaters heated by steam.
• heaters are used to raise the temperature to the desired temperature using resistance or induction heating, the heaters consume a lot of power.
• steam when using steam to raise the temperature to the desired temperature, the amount of steam used is also large.
• Patent Document 1 proposes a device that uses a heat pump to improve the thermal utilization efficiency of a heat source.
• the present invention was made in consideration of the above circumstances, and aims to provide a heat recovery device and heat recovery method that maximizes energy-saving effects in material cleaning processes. It also aims to propose a material manufacturing method using this heat recovery method.
• the inventors conducted extensive experiments and research to solve the above problems. As a result, they discovered that by combining a heat pump and a heat exchanger, it is possible to maximize energy conservation effects by supplying heat at the appropriate temperature and flow rate to the heat pump. In addition, they discovered that by directly or indirectly using water used at the business premises, it is possible to purify the liquid fed into the heat pump's heat exchanger.
• a heat recovery device comprising: a drainage path through which wastewater used in the cleaning process of materials whose temperature has increased flows; a makeup water path through which makeup water for the cleaning process flows; a first circulation path through which a first heat medium circulates; a first heat exchanger provided in the drainage path and the makeup water path and performing heat exchange between the drainage and the makeup water; a second heat exchanger provided in the drainage path downstream of the first heat exchanger and performing heat exchange between the drainage and the first heat medium; a heat pump whose low-temperature side is connected to the first circulation path and whose high-temperature side is connected downstream of the first heat exchanger in the makeup water path; and a control unit that controls the first heat exchanger so that the coefficient of performance of the first heat exchanger and the heat pump is improved when the makeup water, whose temperature has been raised through the first heat exchanger, is further raised in temperature by the heat of the drainage recovered in the first heat medium and by electricity to
• control unit controls the first heat exchanger so as to reduce the temperature of the wastewater to a temperature range in which the wastewater does not freeze due to heat exchange in the second heat exchanger due to the performance of the heat pump.
• control unit controls the first heat exchanger so that the temperature of the wastewater used in the cleaning process of materials whose temperature has increased is 10°C or higher after heat exchange.
• a heat recovery device comprising: a second circulation path through which a second heat medium circulates; and a third heat exchanger provided downstream of the first heat exchanger in the makeup water path, which performs heat exchange between the makeup water and the second heat medium; wherein the makeup water path is connected to the high-temperature side of the heat pump, but instead of the makeup water path being connected to the high-temperature side of the heat pump.
• the heat recovery method further includes a make-up water heating step in which a third heat exchanger further heats the make-up water by heat exchange between the make-up water heated through the first heat exchanger and a second heat medium circulated and connected to the high-temperature side of the heat pump, instead of the make-up water heating step.
• a method for manufacturing materials comprising a washing step of heating makeup water used in the washing treatment of materials using the heat recovery method described in [5] or [6] above.
• the present invention provides a heat recovery device and method that uses a heat pump and heat exchanger to supply a heat medium energy-efficiently and at low cost. Furthermore, by using this heat recovery method to heat makeup water in the material washing process, it is possible to produce energy-efficient, environmentally friendly materials.
• FIG. 1 is a system diagram showing a heat recovery device according to an embodiment of the present invention.
• FIG. 10 is a system diagram showing a heat recovery system according to another embodiment of the present invention.
• FIG. 1 is a system diagram showing a conventional method for heating makeup water for cleaning liquid.
• FIG. 2 is a system diagram showing an example in which a flow path changing unit is provided in the heat recovery device according to the embodiment.
• FIG. 10 is an enlarged system diagram showing an example of the configuration of the flow path changing unit according to the another embodiment.
• FIG. 10 is a system diagram showing another example in which a flow path changing unit is provided in the heat recovery device according to the other embodiment.
• 10A and 10B are enlarged system diagrams showing an example of the configuration of the flow path changing section of the other example, in which FIG.
• FIG. 10A shows the second flow path changing section
• FIG. 10B shows the first flow path changing section.
• This is a graph showing the heat distribution when the heat recovery device of the above embodiment is used to recover the maximum amount of heat from the wastewater in the first heat exchanger, and when the heat is recovered so as to maximize the coefficient of performance of the heat pump.
• a heat recovery apparatus used in a cleaning process 100 for a steel sheet S is shown in Figure 1.
• the heat recovery apparatus according to this embodiment includes a drainage path through which drainage water 10, 10A, and 10B flows, a make-up water path through which make-up water 20 and 20A flows, and a first circulation path through which a first heat medium 4A circulates.
• the heat recovery apparatus according to this embodiment includes a first heat exchanger 1 connected to the drainage path and the make-up water path.
• heat exchange occurs between the high-temperature drainage water 10 used in the cleaning process of the steel sheet S and the make-up water 20 for the cleaning process, thereby raising the temperature of the make-up water 20 and lowering the temperature of the high-temperature drainage water 10 after cleaning.
• the temperature of the makeup water 20A heated by the heat pump 4 is preferably less than 100°C, and the temperature of the post-wash wastewater 10A sent to the heat pump for heat recovery is preferably less than 90°C.
• Figure 2 also shows a system diagram of a heat recovery device according to another embodiment.
• the system is equipped with a second circulation path through which the second heat medium 4B circulates, and a third heat exchanger 3.
• the second circulation path is connected to the condenser 41 on the high-temperature side of the heat pump 4, and the second heat medium 4B is heated.
• the third heat exchanger is connected to the second circulation path and downstream of the first heat exchanger 1 in the makeup water path, and performs heat exchange between the makeup water heated by the first heat exchanger 1 and the second heat medium 4B.
• the makeup water 20 becomes makeup water 20A with a further increased temperature, and the second heat medium 4B is cooled and circulated.
• the makeup water 20 has better properties than the wastewater 10 after cleaning, but by locating the third heat exchanger 3 and the second circulation path through which the second heat medium 4B circulates on the high-temperature side of the condenser 41 of the heat pump 4, it is possible to use liquid with even better properties in the heat pump 4.
• a heating means such as steam 51 or a heater 52, may be used in the cleaning liquid temperature adjustment process 200.
• the heating means further heats makeup water 20A, which is made by directly or indirectly heating makeup water 20 at a temperature lower than the set temperature required for the cleaning process using a heat pump 4.
• the control unit controls the first heat exchanger 1 so as to improve the coefficient of performance of the first heat exchanger 1 and the heat pump 4.
• the coefficient of performance of the first heat exchanger 1 and the heat pump 4 refers to the sum of the power consumption of the heat pump 4, the heat recovery amount of the first heat exchanger 1, and the heat recovery amount of the heat pump 4, divided by the power consumption of the heat pump 4.
• the first heat exchanger 1 is controlled to perform heat exchange at the maximum output of its performance.
• second heat exchanger 2 there is a risk that the temperature of the wastewater 10A will become lower than necessary, causing problems with the subsequent heat recovery by the heat pump 4 (second heat exchanger 2).
• the wastewater 10B may freeze during the subsequent heat recovery by the heat pump 4 (second heat exchanger 2), potentially clogging the piping.
• the heating means can be steam 51 or an electric heater 52.
• steam 51 is the heating means
• the temperature and flow rate of the preheated makeup water 20 and the amount of steam used to heat the preheated makeup water 20A to the required supply temperature are controlled so that net energy consumption is minimized, taking into account steam losses from the steam source to the supply destination at the business facility.
• the condenser (radiator) 41 on the high-temperature side of the heat pump 4 is connected to the piping downstream of the first heat exchanger 1 of the makeup water path ( Figure 1), or to the second circulation path ( Figure 2) through which the second heat medium 4B circulates.
• the makeup water 20 heated in the first heat exchanger 1 is heated by heat exchange in the third heat exchanger 3 with the second heat medium 4B, which has been heated using the thermal energy obtained through heat exchange in the condenser (radiator) 41 of the heat pump 4.
• the piping of the makeup water path, and in the example of Figure 2, the piping of the second circulation path are preferably equipped with temperature sensors to measure fluid temperature on the inlet and outlet sides of the condenser (radiator) 41. Air or an inert gas can be used as the second heat medium, or a liquid such as water.
• the data obtained by the temperature sensor can be used to control the operation of the heat pump 4.
• Feedback control and feedforward control can be used alone or in combination.
• feedback control can be performed by calculating a temperature gap from the temperature of the preheated makeup water 20A and the set temperature of that preheated water, and using this result to calculate and output the amount of power consumed by the heat pump 4, or feedforward control can be performed by calculating the amount of power consumed by the heat pump 4 from the inlet temperature, flow rate, and temperature of the first heat medium (chilled water) 4A connected to the low-temperature side of the heat pump 4.
• these controls can be performed by either the compressor 43, the expansion valve 44, or both.
• the temperature of the preheated make-up water 20A produced by the heat pump 4 is preferably set based on the flow rate and the output of a heating means such as steam 51, taking into consideration high overall energy efficiency.
• heating means such as steam 51 is provided to heat the preheated make-up water 20A to the set temperature, and make-up water for washing materials is preferably supplied via the heating means.
• the makeup water that enters the rinse circulation tank 5 is obtained by heating preheated makeup water 20A with steam or the like. Therefore, compared to when room temperature makeup water is heated to the set temperature with steam 51, this embodiment reduces the amount of steam used to heat the makeup water, thereby saving energy. Furthermore, even if the set temperature of makeup water 20A is high enough that a heat pump cannot achieve it, the necessary makeup water can be obtained at low cost. Specifically, preheated makeup water 20A and steam 51 are used in combination to generate makeup water at the set temperature. Initial controllability is also improved. Furthermore, the number of heat pumps 4 that generate makeup water to be preheated can be determined based on the capacity of the heat pumps 4 and the specifications (flow rate, temperature) of the heat recovery device.
• a flow path change unit may be provided in the first circulation path between the second heat exchanger 2 and the heat pump 4, and in the second circulation path between the third heat exchanger 3 and the heat pump 4, to control the temperatures of the first heat medium 4A and the second heat medium 4B.
• the flow path change unit may include a three-way valve or a bypass valve.
• Figure 4 is a system diagram showing the state in which a flow path change unit 6 is provided in the first circulation path between the second heat exchanger 2 and the heat pump 4.
• Figure 5 is a system diagram showing an enlarged configuration of the flow path change unit 6.
• the flow path change unit 6 is provided with a three-way valve 6B or a bypass valve.
• the temperature of the first heat transfer medium 4A at the inlet that passes through the first circulation path and enters the evaporator 42 of the heat pump 4 is defined as TCi, and the upper limit of the target temperature of the first heat transfer medium 4A at the inlet is defined as TC.
• the second control unit 8 Based on TCi measured by a measuring unit 7 such as a thermocouple, the second control unit 8 performs feedback or feedforward control on the flow path changing unit 6 so that TCi ⁇ TC.
• the flow path changing unit 6 changes the flow path of the heat transfer medium in the first circulation path between the second heat exchanger 2 and the evaporator 42 of the heat pump 4.
• the flow path changing unit 6 adjusts the flow path and flow rate based on actual measurements, enabling accurate temperature control of the fluid.
• a flow rate adjustment valve 6A may be provided to ensure a constant flow rate in both paths.
• the valve opening of the flow rate adjustment valve 6A may be set in advance, or may be feedback-controlled or feedforward-controlled by the second control unit 8. This reduces flow rate fluctuations even when the flow path and flow rate are adjusted by the flow path changing unit 6, allowing for more accurate temperature control of the first heat medium 4A.
• Figure 6 is a system diagram in which flow path change units 61, 62 are provided in the first circulation path and the second circulation path, respectively, in the heat recovery device of another embodiment shown in Figure 2.
• Figure 7(a) is a system diagram showing an enlarged view of the flow path change unit 62 provided in the second circulation path.
• Figure 7(b) is a system diagram showing an enlarged view of the flow path change unit 61 provided in the first circulation path.
• a three-way valve 6B or a bypass valve is provided in the flow path change units 61, 62.
• the temperature of the second heat medium 4B at the outlet of the condenser 41 of the heat pump 4 after passing through the second circulation path is defined as THo, and the upper limit of the target temperature of the second heat medium 4B at the outlet is defined as TH.
• the third control unit 82 Based on THo measured by a measuring unit 7 such as a thermocouple, the third control unit 82 performs feedback or feedforward control on the flow path changing unit 62 so that THo ⁇ TH. Under the control of the third control unit 82, the flow path changing unit 62 changes the flow path of the second heat medium 4B in the second circulation path between the third heat exchanger 3 and the condenser 41 of the heat pump 4.
• the flow path changing unit 62 adjusts the flow path and flow rate based on actual measurements, enabling accurate temperature control of the second heat medium 4B.
• a flow rate adjustment valve 6A may also be provided on the flow path change unit 62 side of the second circulation path, taking into account the difference in pressure loss between the bypass path and the heat exchanger path. This reduces flow rate fluctuations regardless of whether the flow path and flow rate are adjusted by the flow path change unit 62, allowing for even more accurate temperature control of the second heat medium 4B.
• control unit 61 The function of the flow path change unit 61 provided in the first circulation path and the operation of the second control unit 81 are the same as the function of the flow path change unit 6 and the operation of the second control unit 8.
• control unit, second control unit, and third control unit may each be configured as physically different units, or may be configured as the same physical unit.
• the heat recovery method of this embodiment effectively utilizes the heat of the wastewater from the rinse circulation tank, which has not been utilized in the past. It increases the temperature of the hot water supplied to the rinse circulation tank, and reduces the amount of steam used to heat the cleaning solution in the rinse circulation tank, thereby achieving energy savings.
• the first heat exchange process heat is exchanged between the post-wash wastewater 10 used in the washing process of materials, the temperature of which has risen in the first heat exchanger 1, and the make-up water 20 for the washing process. This is to raise the temperature of the make-up water for the washing process using the heat from the post-wash wastewater, the temperature of which has risen.
• the second heat exchanger 2 exchanges heat between the post-cleaning wastewater 10A, whose temperature has been lowered in the first heat exchange process, and the first heat medium 4A, which is circulated and connected to the low-temperature side of the heat pump. This is to further transfer the heat of the post-cleaning wastewater 10A, whose temperature has been lowered in the first heat exchange process, to the first heat medium 4A, which is circulated and connected to the low-temperature side of the heat pump.
• the heat pump 4 is used to further heat the makeup water 20, which has been heated through the first heat exchanger 1, using the heat recovered in the first heat medium 4A and the electricity supplied to the compressor 43 and evaporator 42.
• the high-temperature makeup water 20A is then supplied to the rinse circulation tank.
• the heat recovered from the wastewater and the electricity used to operate the heat pump contribute to raising the temperature of the makeup water.
• the temperature of the first heat medium 4A supplied to the low-temperature side of the heat pump 4 decreases, and the first heat exchanger 1 is controlled so that the coefficient of performance of the entire heat recovery device system is improved even if the coefficient of performance of the heat pump 4 itself decreases.
• the coefficient of performance of the heat pump 4 refers to the sum of the power consumption of the heat pump 4 and the heat recovery amount of the heat pump 4 divided by the power consumption of the heat pump 4.
• the coefficient of performance of the entire heat recovery device system refers to the sum of the power consumption of the heat pump 4, the heat recovery amount of the first heat exchanger 1, and the heat recovery amount of the heat pump 4 divided by the power consumption of the heat pump 4.
• the first heat exchanger 1 may be controlled so that the temperature of the wastewater 10A is reduced to a temperature range in which the wastewater 10B does not freeze due to heat recovery by the second heat exchanger 2, due to the performance of the heat pump 4.
• the first heat exchanger may be controlled so that the temperature of the post-wash wastewater 10, which has been used in the material washing process and has been increased, is raised to 10°C or higher through heat exchange with the makeup water 20.
• the temperature of the makeup water sent to the rinse circulation tank is higher than in heat recovery methods using conventional heat recovery devices, so the amount of heating by steam 51 or heater 52 in the rinse circulation tank can be reduced compared to conventional methods. In other words, less electricity is required for heating, achieving energy savings.
• the temperature of makeup water 20A heated by the heat pump is set to less than 100°C so as not to exceed the set temperature of the cleaning liquid in the rinse circulation tank. Furthermore, the temperature of wastewater 10A sent to the heat pump for heat recovery is set to less than 90°C, taking into account the specified temperature of the heat pump's heat source.
• the heating step involves heating makeup water 20A preheated by a heat pump in a rinse circulation tank.
• the water is heated to a temperature lower than the set temperature required for the cleaning process.
• the heat recovery method according to this embodiment can be applied to a material manufacturing method that includes a cleaning process in which make-up water used in the cleaning process of materials is heated.
• the material is a metal material, more specifically, a steel material.
• Steel materials include steel plates, thick plates, steel sections, steel bars, wire rods, etc.
• the coefficient of performance can be improved by using the specific control method of the control unit that controls the first heat exchanger described above.
• the specific control method described above reduces the temperature of the wastewater to a temperature range where the wastewater will not freeze, ensuring the safety of the system and reducing maintenance costs.
• system efficiency can be optimized and energy consumption can be reduced.
• heat recovery efficiency can be improved.
• Example 1 Steel plates were washed at a steel mill using the heat recovery system, cleaning process, and cleaning liquid temperature adjustment process shown in FIG. 1 .
• the heat recovery system included a first heat exchanger, a second heat exchanger, and a heat pump.
• the output of the first heat exchanger was controlled to maximize the amount of heat recovered by the first heat exchanger, while preventing the wastewater from freezing during heat exchange by the second heat exchanger.
• the temperature of the makeup water supplied to the first heat exchanger was 10°C
• the temperature of the post-cleaning wastewater was 70°C.
• the post-cleaning wastewater whose temperature had been lowered through the first heat exchanger, was utilized as a low-temperature heat source for the heat pump to recover heat.
• the makeup water which had been heated through the first heat exchanger, was then further heated using the heat and electricity recovered by the heat pump. Subsequently, makeup water heated to a high temperature by a heat pump was supplied to a rinse circulation tank, where it was heated by steam to produce a cleaning liquid in the rinse circulation tank.
• the inlet and outlet temperatures of the first heat medium to the low-temperature side evaporator of the heat pump were 20°C and 10°C, and the inlet and outlet temperatures to the high-temperature side condenser were 65°C and 75°C.
• the temperature of the makeup water heated by the heat pump was 67°C.
• the temperature of the wastewater sent to the second heat exchanger for heat recovery i.e., the post-wash wastewater cooled through the first heat exchanger, was 30°C, and the temperature after the second heat exchange was 26°C.
• FIG. 8 (a) An example of the invention with excellent total performance.
• steam usage ST was reduced by approximately 83% compared to conventional steam heating SH, to 16.7% of the total heating amount.
• the power input EP to the heat pump 4 was 3.9% of the total heating amount, and together with the heat recovery HR of 9.3%, 13.2% of the total heating amount was obtained.
• the first heat exchanger 1 obtained heat recovery HR of 70.2% of the total heating amount.
• the coefficient of performance for the heat pump 4 was 3.4, but the total coefficient of performance including heat recovery was 17.7, including auxiliary equipment such as the cooling water circulation pump, and a good result was obtained.
• the heat recovery system included a first heat exchanger, a second heat exchanger, and a heat pump.
• the temperature of the makeup water supplied to the first heat exchanger was 10°C
• the temperature of the post-cleaning wastewater was 70°C.
• Heat was recovered by using the post-cleaning wastewater, whose temperature had been lowered through the first heat exchanger, as a low-temperature heat source for the heat pump.
• the makeup water, which had been heated through the first heat exchanger was then further heated using the heat and electricity recovered in the heat pump.
• the makeup water, heated to a high temperature by the heat pump was then supplied to a rinse circulation tank, where it was heated with steam, and a cleaning liquid was produced in the rinse circulation tank.
• the inlet and outlet temperatures of the first heat transfer medium to the low-temperature evaporator of the heat pump were 40°C and 30°C, and those to the high-temperature condenser were 65°C and 75°C.
• the temperature of the makeup water heated by the heat pump was 47°C.
• the temperature of the wastewater sent to the heat pump for heat recovery i.e., the post-wash wastewater cooled through the first heat exchanger
• the results are shown in Figure 8 (b) as an example of high heat pump performance.
• the steam consumption ST was reduced by approximately 54% compared to the conventional steam heating SH.
• the input power EP to the heat pump 4 was 4.2% of the total heating amount, and together with the heat recovery HR of 14.3%, 18.5% of the total heating amount was obtained.
• the first heat exchanger 1 obtained heat recovery HR of 35.1% of the total heating amount.
• the coefficient of performance of the heat pump 4 was 4.4, which was better than that of Example 1.
• the total coefficient of performance, including heat recovery and auxiliary equipment such as the cooling water circulation pump, was a good 10.6, but was lower than Example 1. This is because the temperature after the second heat exchange was 43°C, which was good for the heat pump's heat source water conditions, and although the heat pump's coefficient of performance was high, 43°C waste heat remained.
• the heat recovery device and heat recovery method used in the material cleaning process of the present invention can be applied to any process that utilizes heat, not just specific processes.

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• 2025
  • 2025-01-20 JP JP2025516011A patent/JPWO2025238924A1/ja active Pending
  • 2025-01-20 WO PCT/JP2025/001585 patent/WO2025238924A1/ja active Pending

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