JP4811984B2 - Thermally driven supercritical fluid supply system - Google Patents

Description

  The present invention relates to a heat-driven high-pressure fluid supply apparatus that does not require a movable machine such as a high-pressure pump or a compressor in an apparatus for supplying a high-pressure process fluid such as subcritical or supercritical high-temperature high-pressure water. More specifically, heat-driven high-pressure fluid supply that enables constant-volume heating, constant-pressure heating, and filling processes to be sequentially repeated with a plurality of dischargers, and allows high-pressure process fluid to be discharged continuously by thermal expansion. The apparatus is capable of supplying a high-pressure process fluid quickly and efficiently by setting a heat medium system flow path and switching a valve. The present invention relates to a high-pressure process fluid processing system that uses a high-pressure fluid such as a subcritical or supercritical fluid and does not use a movable machine such as a pump or a compressor in the technical field of high-pressure processes such as extraction separation and organic synthesis reaction. Is possible.

  Conventionally, a reaction process using a high-temperature and high-pressure fluid, for example, a subcritical or supercritical fluid, has a wide range of extraction of fragrance, treatment of waste, synthesis reaction of organic compounds, etc. (see Patent Documents 1, 2, and 3). Although it is used in the technical field, it is attracting attention as a unique reaction that has not occurred in the fluid. In order to make the fluid high temperature and high pressure such as subcritical or supercritical, various kinds of pumps, compressors, etc. A high pressure generator was used. High-pressure carbon dioxide and water are extremely stable, safe substances that do not harm the human body, are environmentally friendly substances, and have excellent solubility as extraction, washing, waste treatment, organic A wide range of applications such as synthesis are expected and studied. However, in order to supply a high-temperature and high-pressure fluid, it is necessary to use specially-designed high-pressure generating machinery. Also, when using high-pressure machines, problems such as leakage of high-pressure fluid, generation of dust from moving parts, noise, etc. occur. In particular, maintenance of high-pressure machines requires advanced expertise. It is an obstacle to the widespread use and widespread use of processes for various operations.

  In selecting compressors, pumps, reactors, etc. for high-pressure operation, the equipment to be used is generally determined by the operating pressure, fluid flow rate, operating temperature, etc., but high-pressure processes such as subcritical or supercritical In many cases, the type of fluid, flow rate, pressure, and the like are greatly different from those of ordinary chemical processes. For this reason, the compressor itself often becomes special, and its selection is not easy. In addition, the pressure conditions of actual operations and experiments may be limited by the specifications of existing high-pressure generators, and it may be difficult to operate under optimum conditions such as experiments or reaction processes. In addition, the use of special equipment also contributes to an increase in the cost of the high-pressure fluid supply device.

  Therefore, a high-pressure fluid supply system that does not use a pump in a process that uses a subcritical or supercritical fluid has been proposed (see Patent Document 4). However, this system requires a density difference to drive fluid transportation, and there is a limit to the application of differential pressure during fluid transportation. For example, when a condenser and an evaporator are installed and a differential pressure is generated using the density difference between the gas and liquid, the head is attached by the difference in level between the condenser and the evaporator. Installation location is limited. In addition, the diameter of piping for transportation and fittings such as valves must be determined in consideration of pressure loss, and there is a problem that considerable measures are required for mass processing.

  In addition, although a heat-driven supercritical water supply device (see Patent Document 5) that does not have a movable part has been reported, although the outline of the drive principle of the heat drive system is shown, it can also be said to be the heart of it, There is no specific description of the heating / cooling method or the apparatus therefor, and only insufficient technical information has been obtained to put such a system into practical use and to construct a thermal drive system.

  Recently, synthetic reactions of various organic compounds have been reported due to instantaneous reactions in supercritical water, and in these reactions, the residence time in the reactor is often less than a few seconds. Therefore, an operation of supplying excessively high pressure water previously heated to the reaction temperature to the reactor has been performed, and a new ultrahigh pressure fluid supply system that can be adapted to such an operation has been desired. .

International Publication No. WO99 / 53002 Japanese Patent Laid-Open No. 10-118609 JP 2002-285258 A Japanese Patent No. 3079157 JP 2003-126673 A

  Under such circumstances, the present inventors have developed a new heat-driven high-pressure fluid supply device that makes it possible to drastically solve the problems in the prior art in view of the prior art. As a result of intensive research with the goal of, we have found a method that enables efficient heating of the process fluid (hereinafter also referred to as fluid) in the dispenser and quick refilling of the process fluid. The invention has been completed. The present invention makes it possible to obtain a high-pressure fluid such as subcritical or supercritical without using a special mechanical operation by substantially giving a pressure difference only by changing the state of the fluid due to the transfer of thermal energy. An object of the present invention is to enable efficient heating and quick refilling of a process fluid in a discharger in a possible heat-driven high-pressure fluid supply apparatus. Another object of the present invention is to set an efficient heat medium flow path system for heating and cooling the process fluid in the discharger. It is another object of the present invention to supply a high-pressure fluid such as a supercritical fluid that is clean stably and efficiently. It is another object of the present invention to provide a high-pressure fluid supply apparatus that does not generate high-pressure medium leakage, dust from moving parts, noise, and the like. Another object of the present invention is to provide a heat-driven high-pressure fluid supply apparatus capable of providing a high-temperature and high-pressure reaction field in chemical synthesis technology, extraction technology, industrial waste treatment technology, and the like. is there.

The present invention for solving the above-mentioned problems has one or more discharge devices formed in the heat medium flow path, a heater, and a cooler, and the process fluid in the discharge device has a constant volume. heating, by repeating the processes of constant pressure heating and filling, a heat-driven pressure medium supply device which high pressure process fluid is discharged, 1) the dispenser and heater, cooler, heat medium flow path Either all connected in series, and the heat medium flow path is configured in a single circulation without branching or isolation, or 2) the heat medium flow path is only for the circulation of the heating system and the circulation of the cooling system The heating system is a series circulation of a heater and a heated discharger, and the cooling system is a series circulation of a cooler and a cooled discharger so that there is no branching or isolation. A high-pressure fluid supply device;

  In the apparatus of the present invention, (1) each discharge device, a heater, and a cooler are connected in series to form a heating channel and a cooling channel. The discharge device connected to the most downstream side and completed the filling process is configured to be connected to the most downstream side of the heating flow path, and (2) a thermally driven high-pressure fluid supply device having n discharge devices In the above, the heat medium inlet of the i-th (i is an integer from 1 to n) discharger is the heater outlet, the cooler outlet, and the i + 1th heat medium outlet (the first when i + 1 is n + 1). Connected, the heat medium outlet of the i-th discharger is connected to the heater inlet, the cooler inlet, and the heat medium inlet of the i-1th discharger (nth when i-1 is 0). (3) The process fluid is filled in the discharger by cooling the discharger, (4) Process (5) The process fluid is filled into the dispenser due to the level difference between the body storage tank and the dispenser, and (5) the process fluid is filled into the dispenser by pumping the process fluid. 6) It further has a heat medium flow path that can be circulated from the heater directly to the heater, and a heat medium flow path that can be circulated directly from the cooler to the cooler, and the heating flow path and the cooling flow path are formed independently. (7) a heat exchanger capable of exchanging heat between the heat medium flowing into the cooler and the heat medium flowing into the heater is provided, and (8) the process fluid is A subcritical or supercritical fluid, (9) the process fluid is water or carbon dioxide, and (10) the constant volume heating is performed at a temperature of 250 ° C. or lower and a pressure of 400 MPa or lower. (11) The above constant pressure heating is performed at 800 ° C. or lower. Rukoto, it is an a preferred embodiment. Moreover, this invention is a high pressure fluid utilization apparatus characterized by using the high pressure fluid supplied from said heat drive type high pressure fluid supply apparatus as a reaction field.

Next, the present invention will be described in more detail.
The present invention includes one or more dischargers, heaters, and coolers formed in a heat medium flow path, and constant volume heating, constant pressure heating, and filling of the process fluid in the dischargers. A heat-driven high-pressure medium supply device that discharges a high-pressure process fluid by repeating each process, and the heat medium flow path is configured so that each discharger, heater, and cooler have a cascade structure. It has a feature in being.

  Examples of the process fluid of the present invention include water and carbon dioxide, but are not limited thereto. The high-pressure process fluid supplied by the heat-driven high-pressure fluid supply apparatus of the present invention is, for example, a subcritical or supercritical fluid. For example, an organic synthesis reactor, extractor, or dye using a high-pressure process fluid as a reaction field. Supplied and used in a vessel, crystallizer, etc. In addition, examples of the heat medium used in the present invention include water and heat medium oil, but the heat medium is appropriately selected according to the heating temperature condition and the like, and is not limited thereto.

  Next, a discharger for supplying a high-pressure process fluid used in the present invention will be described with reference to the schematic diagram shown in FIG. The discharger is a heat-insulated high-pressure vessel and includes a fluid filling valve V1 and a high-pressure fluid discharge valve V2. Furthermore, a heat transfer tube is provided through which a heat medium for heating and cooling the filled fluid is circulated. A high-pressure process fluid is discharged and supplied by repeating the following constant volume heating, constant pressure heating, and filling process with respect to the process fluid accommodated in the discharger.

Constant-volume heating process: Both valves are closed with the dispenser filled with fluid, and heated to a predetermined pressure in a sealed state.
Constant pressure heating process: The pressure control valve V2 on the discharge side is opened, heating is continued with the internal pressure kept constant, and fluid discharge due to thermal expansion is promoted. The discharged fluid is sent to a high-pressure fluid utilization process. When the temperature reaches a predetermined temperature, the heating is terminated.
Filling process: V1 is opened after draining or cooling the residual fluid, and the fluid in the storage tank is refilled.
The constant volume heating process is preferably performed under conditions of a temperature of 250 ° C. or lower and a pressure of 400 MPa or lower, and the constant pressure heating process is preferably performed at a temperature of 800 ° C. or lower.

Specific examples of the process of filling the discharger with fluid in the present invention are as follows: (1) using cooling, (2) using difference in level of fluid, and (3) using pumping. explain.
(1) Filling by constant pressure cooling When the discharge by constant pressure heating is finished, the fluid in the discharger is in a supercritical state of, for example, high temperature and high pressure. From this state, filling can be performed by performing two processes of constant volume cooling and constant pressure cooling. First, when the discharge is completed, the discharge valve V2 is closed and sealed. In this state, a low-temperature heat medium is passed through the heat transfer tube to cool the tube at a constant volume. Since the temperature decreases with the density kept constant, the internal pressure decreases. When the pressure finally becomes equal to the initial pressure, that is, the pressure of the filling fluid, the constant volume cooling is finished, and the next constant pressure cooling is started. In the constant pressure cooling, only the filling valve V1 is opened. When V1 is opened and cooling is performed, the internal fluid pressure tends to decrease, but since a pressure difference is generated with the fluid outside V1, the fluid is automatically filled. When the supercritical fluid is cooled to a constant volume, it is often separated into a gas and a liquid. In this case as well, the gas phase portion is condensed by constant pressure cooling, and the pressure tends to decrease. A pressure difference is generated and filling is performed.

(2) Filling with high and low level differences Fig. 2 shows a schematic diagram of filling with high and low level differences. In this case, in addition to V1 and V2, a valve V3 for collecting the residual fluid is added, and a path to a condenser installed at a position physically higher than the discharger is added. In addition, a storage tank is installed at a height intermediate between the condenser and the discharger. Similar to the filling by cooling, when the discharge is finished, V1, V2 and V3 are closed, and constant volume cooling is started. When V3 is opened when the pressure has dropped to some extent, the internal high-pressure steam escapes to the condenser. Subsequently, when V1 is opened, the fluid in the storage tank flows into the discharger due to the level difference. The fluid that remains inside either evaporates and moves to the condenser, or is pushed out as it is, again evaporates into the condenser, condenses and returns to the storage tank.

(3) Filling by pumping The outline of filling by pumping is as follows: V1 and V2, in addition to valve V3 for recovering residual fluid, a condenser installed, and a path from the discharger to the condenser and storage tank In addition, a pump is installed between the storage tank and the discharger. When the discharge of the high-pressure process fluid from the discharger is finished, V1, V2 and V3 are closed and constant volume cooling is started. When V3 is opened at a stage where the pressure has dropped to some extent, the internal high-pressure steam escapes to the condenser. When V1 is subsequently opened and the pump is operated, the fluid in the storage tank is filled into the discharger. The fluid that remains inside either evaporates and moves to the condenser, or is pushed out as it is, evaporates and enters the condenser, condenses and returns to the storage tank.

The merits and demerits will be briefly described by comparing these exemplified filling methods based on different mechanisms. Filling by cooling does not require a new valve or condenser and can be realized with a very simple configuration. However, depending on the fluid used, a high cooling capacity is required in order to perform sufficient cooling. On the other hand, depending on the level difference, there are disadvantages such as adding a valve and a condenser and installing the tank at a high position, the device becomes complicated and large, and the resistance due to the complicated flow path increases. Since it is sufficient to perform cooling, it is not necessary to lower the temperature of the heat medium so much. In addition, if a sufficient level difference is taken, filling can be performed quickly. According to pumping, the powerful filling action of the pump increases the scope of the system and enables flexible operation, but a new movable pump needs to be added.

Next, the heat medium piping network and valve switching according to the present invention will be described.
In the present invention, a high-pressure supercritical fluid is discharged while the discharger is performing constant pressure heating. The heating before that and the subsequent cooling and filling are preparation stages for discharge. Therefore, in order to realize continuous discharge, it is necessary to use a plurality of dischargers and shift the discharge timing. At this time, it is important how the heat medium network is assembled and the heat efficiency is good, and at what timing the heating and cooling should be switched. In contrast, two types of heat medium piping networks and respective valve switching rules will be described with specific examples.

(1) About a single heating medium system This uses one kind of heating medium, and performs heating and cooling of a discharger. For example, FIG. 3 shows a piping flow diagram of the heat medium system when there are four dischargers. Each of the dischargers 1 to 4 is provided with valves V1, V2 or V3 for filling and discharging the process fluid. Here, only the flow of the heat medium is considered. Is omitted. The discharger shown in the figure includes five valves each for controlling the flow of the heat medium. In FIG. 3, the number of ejectors is four, but this is only an example, and in practice it can be any natural number. The heating medium system piping rule when the number of dischargers is generally n is shown. The heat medium system includes n discharge devices, one heater, one cooler, a valve and a pump for adjusting the flow rate and pressure of the heat medium, and a heat exchanger. The heat medium inlet of the i-th (i is 1 to n) discharger has three locations: the heater outlet, the cooler outlet, and the heat medium outlet of the i + 1-th discharger (first when i + 1 is n + 1). Connect to and install a valve on each. The heating medium outlet is connected to the heating medium inlet of the heater inlet, the cooler inlet, and the heating medium inlet of the (i-1) th (or nth when i-1 is 0) discharge valve. The cooler outlet is connected to the heater inlet in addition to each discharger, and the heater outlet is also connected to the cooler inlet. If necessary, install heat exchangers just before the heater entrance and just before the cooler entrance.

The rules for switching valves are as follows.
(A) The heat medium flow path should be a single circulation so that there is no branching or isolation. That is, each discharger, heater, and cooler are all connected in series.
(B) The discharger that has finished heating and discharging is connected to the most downstream side of the cooling path.
(C) The discharger that has finished cooling and filling is connected to the most downstream side of the heating path.
Next, valve switching in accordance with this rule will be described in the case of using four dischargers. First, it starts from a state where all the dispensers are filled with fluid. It is arbitrary how many dispensers start to be heated at the start, but all are heated here.

  The high-temperature heat medium exiting the heater heats the discharger 4 through V42. Although the temperature drops slightly, it still has sufficient heat, so this is introduced into the discharger 3 via V33. Similarly, it flows from V23 to the discharger 2 and from V13 to the discharger 1. Then enter the cooler through V15. At this stage, since it is not necessary to cool any of the dischargers, it returns to the heater via V52. All valves other than those listed here are closed. If this operation is continued, the discharger 4 heated at the highest temperature reaches a predetermined pressure and starts discharging. When the heating is further continued, the discharger 3 having the next highest temperature starts discharging. Similarly, the discharge device 2 and the discharge device 1 start discharging, but the discharge device 4 that has reached a predetermined temperature shifts to a cooling process.

  When only the discharger 4 is cooled, the high-temperature heat medium from the heater flows from V23 to the discharger 3, from V23 to the discharger 2, and from V13 to the discharger 1. Enter the cooler via. Subsequently, the heat medium exiting the cooler cools the discharger 4 via V41 and returns to the heater via V44. All valves other than those listed here are closed. When the discharger 3 finishes discharging and enters the cooling process, the heat medium enters the cooler through the discharger 2 and the discharger 1 from the heater, and the heat medium exiting the cooler is the discharger 4 and the discharger 3. Cool down and return to the heater. When the discharger 4 that has entered the cooling process has finished filling and is ready for heating again, it receives heat downstream of the discharger 1. That is, the flow of hot water becomes a loop of a heater, a discharger 2, a discharger 1, a discharger 4, a cooler, a discharger 3, and a heater.

  As described above, if the operation is continued with the rule that the discharger that has finished heating is connected to the most downstream side of cooling and the discharger that has finished cooling and filling is connected to the most downstream side of heating, All the dischargers can be heated and cooled with a single heating medium. If the temperature of the heat medium entering the heater is lower than the temperature of the heat medium entering the cooler, the heat efficiency can be improved by performing heat exchange using the regenerative heat exchanger shown in FIG.

(2) About individual heating medium system In this system, two types of heating medium are used, and heating and cooling of the discharger are performed by separate heating media. A specific example of an individual heat medium system that is an extension of a single heat medium system is to add several paths, valves, and pumps to the single heat medium system. FIG. 4 shows a piping diagram when the piping system has four discharge devices. Again, the number of ejectors is arbitrary as in the single heat medium system. The difference from the single heat medium system is that a path from the heater to the heater, a path from the cooler to the cooler, and a pump and a valve for adjusting the flow rate and pressure of the heat medium are added.

As for valve switching, the individual heat transfer system piping is the same operation as before by applying single heat transfer system valve switching, which is just adding two new paths to the single heat transfer system. Is possible. Furthermore, the valve switching rule for performing heating and cooling by individual heat medium circulation is as follows.
(A) The heat medium flow path is only for circulation of the heating system and circulation of the cooling system, so that there is no branching or isolation. That is, the heating system is a series circulation of a heater and a heated discharger, and the cooling system is a series circulation of a cooler and a cooled discharger.
(B) The discharger that has finished heating and discharging is connected to the most downstream side of the cooling path.
(C) The discharger that has finished cooling and filling is connected to the most downstream side of the heating path.

  Therefore, an operation example in the case of four dischargers will be shown. As with a single heat transfer system, start by heating all four heaters. The heat medium exiting from the heater flows from V42 to the discharger 4, from V33 to the discharger 3, from V23 to the discharger 2, from V13 to the discharger 1, and returns to the heater through V14. At this time, since there is no discharger to be cooled, the heat medium exiting the cooler immediately returns to the cooler via V54. All valves other than those shown here are closed. First, the discharger 4 finishes discharging and moves to a cooling process. In this case, the heat medium discharged from the heater is heated in the order of the discharger 3, the discharger 2, and the discharger 1, and returns to the heater. The heat medium exiting the cooler cools the discharger 4 through V41 and returns from V45 to the cooler. Next, when the discharger 3 shifts to the cooling process, cooling is performed downstream of the discharger 4. The flow of the heat medium at that time includes a heater, a discharger 2, a discharger 1, a heating system for the heater, a cooler, a discharger 4, a discharger 3, and a cooling system for the cooler. When the discharger 4 finishes cooling / filling and shifts to the heating process again, it is connected downstream of the discharger 1. The flow of the heat medium at that time is composed of a heater, a discharger 2, a discharger 1, a discharger 4, a heating system of the heater, a cooler, a discharger 3, and a cooling system of the cooler.

  As described above, the discharger that has finished heating is connected to the most downstream side of cooling, and the discharger that has finished cooling and filling is connected to the most downstream side of heating. The heat medium from the most downstream side of heating is returned to the heater, and the heat medium from the most downstream side of cooling is returned to the cooler. If the temperature of the heat medium returning to the heater is lower than the temperature of the heat medium returning to the cooler, the heat efficiency can be improved by using a heat exchanger as shown in FIG.

  Next, in the thermally driven high-pressure fluid supply apparatus of the present invention, an operation example in the case where the working fluid is carbon dioxide and the cooling method is adopted as the filling method will be described using specific numerical values based on simulations. To do. The purpose of operation is to discharge carbon dioxide at an initial state of 5 ° C. and 4 MPa to 20 MPa. The condition for termination of discharge was when the temperature reached 150 ° C. The result of the simulation is shown in FIG. In FIG. 5, the temperature change of each discharger, the temperature change of the combined discharger fluid, the pressure change of each discharger, the density change of each discharger, the discharge flow rate from each discharger, and these were combined. The flow rate of the discharge fluid is shown. Initially, the number of ejectors during heating starts from four. Immediately after the start, the uppermost discharger 4 of the heating path reaches a predetermined pressure of 20 MPa, and discharge starts. Subsequently, the discharge is started with the discharge device 3, the discharge device 2, and the discharge device 1, but after 41 seconds from the start, the discharge device 4 reaches 150 ° C. and ends the discharge. At this stage, the discharger 4 enters the cooling path and the temperature starts to drop. After 113 seconds, filling of the discharger 1 is completed, and the first cycle is completed. In the first cycle, all the dischargers are heated at the same time, so the discharge flow rate is large. In the second cycle, the temperature peaks of each discharger appear periodically, so at an appropriate timing. It can be seen that the heating medium is switched. In addition, the flow rate graph shows that the discharge flow rate of each discharger is intermittent, but when all of them are merged, although some pulsation is seen, continuous discharge is performed.

  As described above, the single heat medium system and the individual heat medium system are shown, but the feature common to these is that the heating and cooling have a series cascade structure. As a result, the high temperature discharger is heated by the high temperature heating medium, and the low temperature discharger is heated by the downstream low temperature heating medium. Discharging is performed. In addition, a series of cooled discharge devices and cooling heat medium, and a series of heated discharge devices and heating heat medium are arranged in an array equivalent to a counter-current heat exchanger. good.

  The feature of the single heat medium system is that the heat medium flows only by a single circulation, so that heating and cooling can be performed simultaneously with one pump, and the structure of the apparatus can be simplified. Moreover, the heating heat medium which came out of the heater becomes low temperature, enters into a cooler, continues cooling, becomes high temperature, and returns to a heater. That is, since heat is regenerated between heating and cooling, thermal efficiency is good. However, if the temperature of the heat medium returning to the heater is lower than the temperature of the heat medium returning to the cooler, the heat efficiency is conversely reduced, so it is preferable to use a regenerative heat exchanger.

  On the other hand, since individual heating medium systems are independent of heating and cooling, different substances can be used for the heating and cooling heating medium. Thereby, heating / cooling can be performed with a larger temperature difference. In this case as well, it is necessary to use a heat exchanger depending on the temperature of the heating medium returning to the heater / cooler. In addition, when the same material is used for heating and cooling in an individual heating medium system, the heat exchanger can be operated by using a single heating medium system valve switching rule and an individual heating medium system valve switching rule depending on the situation. A decrease in thermal efficiency can be avoided without using.

  The present invention uses (1) a process fluid that is a high-pressure fluid such as a supercritical or subcritical fluid without using movable machinery such as a special compression device by applying a pressure difference only by thermal energy. A high-pressure field suitable for a processing system can be efficiently provided. (2) A high-pressure fluid supply apparatus that does not require a high-pressure pump device for delivery and that has a simplified structure can be constructed. 3) It becomes possible to stably maintain the high pressure fluid at a desired pressure and flow rate. (4) Since no special mechanical operation is used, leakage of high pressure medium, dust from moving parts, noise, etc. (5) It is possible to easily provide a high-temperature and high-pressure reaction field, and a technical field of high-pressure reaction using a high-pressure fluid such as a supercritical fluid. In Te, it is possible to form efficiently a high-pressure field, special effect can be attained.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

  In the present embodiment, a single heat medium type heat-driven high-pressure fluid supply apparatus including four dischargers was constructed. FIG. 3 shows a piping flow diagram of the heat medium system. Each discharger includes a process fluid filling valve V1 and a discharge V2 or a condenser communication V3. For example, each discharger is configured as shown in FIG. 1 or FIG. In order to clearly show the flow of the heat medium, the flow path of the process fluid is omitted. The heat medium system of this example was composed of four dischargers, one heater, one cooler, a valve and pump for adjusting the flow rate and pressure of the heat medium, and a regenerative heat exchanger. The discharger shown in the figure includes five valves each for controlling the flow of the heat medium. For example, when the number of the discharge devices is 4 and the piping of the heat medium system is shown for the third discharge device, the heat medium inlet is the heater outlet, the cooler outlet, and the fourth discharge device. It connected to three places of the heat-medium exit, and installed the valve in each. The heat medium outlet was connected to the heater inlet, the cooler inlet, and the heat medium inlet of the second discharger, and a valve was installed. The cooler outlet was connected to the heater inlet in addition to each discharger, and the heater outlet was also connected to the cooler inlet. The piping of other discharge devices was performed in the same manner as the third discharge device illustrated. If necessary, heat exchangers can be installed just before the heater entrance and just before the cooler entrance.

  By switching each valve described above, each discharger, heater, and cooler are all connected in series, the discharger that has finished heating and discharging is the most downstream of the cooling path, and the discharger that has finished cooling and filling is the heating path. It was controlled to connect to the most downstream side. By operating the high-pressure fluid supply apparatus shown in FIG. 3, it was possible to heat and cool all the dischargers with a single heat medium, and to supply a continuous high-pressure process fluid.

In this example, to construct the heat-driven high-pressure fluid supply device of the individual heating medium system having four dispenser. This device has a structure in which a pump and a valve for adjusting the flow rate and pressure of the heat medium are added to the above single heat medium supply system device by adding a path from the heater to the heater and from the cooler to the cooler. It was. The piping diagram is shown in FIG. Each valve switching was possible by operating in the same manner as the valve switching described for the single heat medium system, but in this embodiment, in order to perform heating and cooling by individual heat medium circulation, For switching, the heating system is a series circulation of the heater and the heated discharger, the cooling system is a series circulation of the cooler and the cooled discharger, and the discharger that has finished heating and discharge is connected to the most downstream of the cooling path. The discharger after cooling and filling was connected to the most downstream side of the heating path. If the temperature of the heat medium returning to the heater is lower than the temperature of the heat medium returning to the cooler, the heat efficiency was improved by using a heat exchanger as shown in FIG.

In this example, carbon dioxide was used as the process fluid, and a 20 MPa supercritical carbon dioxide fluid was formed by a single heat medium system. As the high-pressure fluid supply apparatus, the apparatus having the configuration shown in FIG. 3 is used. The operating condition is that carbon dioxide having an initial state of 5 ° C. and 4 MPa is supplied to the discharger, and the pressure is increased to 20 MPa and discharged. did. The time when the discharge was finished was when the temperature of carbon dioxide in the discharger reached 150 ° C. Water was used as a heating medium. The initial state was started by a constant volume heating process in which 5 ° C. and 4 MPa carbon dioxide were sealed in a discharger and heated. In response to heating, the pressure in the discharger increases along the constant volume heating curve of carbon dioxide (density: 896 kg / m ³ ) shown in FIG. Was achieved by raising the temperature to 28 ° C. Here, the constant volume heating process was completed, and the next constant pressure heating process was started. From the discharger, 20 MPa carbon dioxide was discharged and started to be supplied to the critical fluid utilization process. In maintaining the pressure of carbon dioxide at 20 MPa, the temperature was raised to compensate for the reduced pressure due to the decreased amount of discharged carbon dioxide. The density-temperature relationship (constant pressure heating curve of carbon dioxide (pressure: 20 MPa)) at this time is shown in FIG. 28 ° C., 20 MPa high pressure carbon dioxide, according to FIG. 7, with a density of 896Kg / ^{m 3,} which upon pressure heating at 0.99 ° C., a density of 327 kg / ^{m 3.} Therefore, 569 kg / m ³ of carbon dioxide corresponding to the difference between the two values was discharged as a high-pressure fluid of 20 MPa.

  Next, the process proceeds to a constant pressure cooling process, the discharger is hermetically sealed, and the inside of the discharger is brought to a low pressure state by cooling to about 5 ° C. with the heat medium cooled by the cooler. When the process was switched to the constant pressure cooling process, carbon dioxide was naturally supplied from the process fluid storage tank into the low pressure discharge device and returned to the initial state. By repeating such a process with four ejectors, it was possible to continuously supply high-pressure carbon dioxide to the supercritical fluid utilization process.

  As described in detail above, the present invention substantially gives a pressure difference only by a change in the state of the fluid due to the transfer of thermal energy, thereby subcritical to supercritical, etc. without using any special mechanical operation. In a heat-driven high-pressure fluid supply apparatus capable of obtaining a high-pressure fluid, it is possible to efficiently heat and quickly refill the process fluid in the discharger. Further, the present invention makes it possible to set an efficient heat medium flow path system for heating and cooling the process fluid in the discharger. The present invention makes it possible to provide a heat-driven high-pressure fluid supply device capable of continuously discharging a high-pressure process fluid, and a high-temperature high-pressure processing system using the device. It is possible to obtain a high-pressure medium such as subcritical or supercritical without using a mechanical operation. Furthermore, the present invention provides a high-temperature and high-pressure reaction field free from leakage of high-pressure medium, dust from moving parts, noise, etc., for example, chemical synthesis technology, extraction technology, industrial waste processing technology. In addition, the high-pressure field necessary for the high-temperature and high-pressure processing technology field using a supercritical fluid or the like can be efficiently supplied.

The conceptual diagram of the structure of a discharger is shown. The conceptual diagram of the structure which fills a fluid with a fluid by the level difference of a dispenser and a storage tank is shown. The example of piping of the single heat medium system of this invention is shown. The example of piping of a separate heat carrier system of the present invention is shown. The result of the numerical simulation of this invention is shown. Each drawing shows, in order from the top, the temperature change of the discharge fluid, the pressure change of each discharger, the density change of each discharger, the discharge flow rate from each discharger, and the flow rate of the discharge fluid that merges them. A constant volume heating curve of carbon dioxide (density: 896 kg / m ³ ) is shown. A constant pressure heating curve (pressure: 20 MPa) of carbon dioxide is shown.

Claims (13)

It has one or more dischargers formed in the heat medium flow path, a heater, and a cooler, and each process of constant volume heating, constant pressure heating and filling is repeated for the process fluid in the discharger. by, a heat-driven pressure medium supply device which high pressure process fluid is discharged, 1) the dispenser and heater, cooler, in the heat medium flow path, is connected with all the series, Netsunakadachiryu The path is configured as a single circulation, so that there is no branching or isolation, or 2) The heating medium flow path is only the circulation of the heating system and the circulation of the cooling system, and the heating system is the heater and the heated discharge The heat-driven high-pressure fluid supply device is characterized in that the serial circulation and cooling system of the cooler are configured by serial circulation of the cooler and the cooled discharger so that there is no branching or isolation .   Each discharger, heater, and cooler are connected in series to form a heating channel and cooling channel, and the discharger that has completed heating and discharging is connected to the most downstream side of the cooling channel, and the filling process is performed. The thermally driven high-pressure fluid supply apparatus according to claim 1, wherein the completed discharger is configured to be connected to the most downstream of the heating flow path.   In the heat-driven high-pressure fluid supply apparatus having n dischargers, the heat medium inlet of the i-th (i is an integer from 1 to n) discharger is the heater outlet, the cooler outlet, and the i + 1th ( When i + 1 is n + 1, it is connected to the first heat medium outlet, and the heat medium outlet of the i th discharger is the heater inlet, the cooler inlet, and the i−1 th (i−1 is 0). The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein the heat-driven high-pressure fluid supply apparatus is connected to a heat medium inlet of an n th discharger.   The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein a process fluid is filled in the discharger by cooling the discharger.   The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein the process fluid is filled in the discharger due to a difference in level between the process fluid storage tank and the discharger.   The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein the process fluid is filled in the discharger by pumping the process fluid.   A heating medium flow path that can be circulated from the heater directly to the heater, and a heat medium flow path that can be circulated from the cooler directly to the cooler are further provided, and the heating flow path and the cooling flow path are formed independently. Item 2. The heat-driven high-pressure fluid supply device according to item 1.   The heat-driven high-pressure fluid supply apparatus according to claim 1, further comprising a heat exchanger capable of exchanging heat between the heat medium flowing into the cooler and the heat medium flowing into the heater.   The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein the process fluid is a subcritical or supercritical fluid.   The heat-driven high-pressure fluid supply apparatus according to claim 1, wherein the process fluid is water or carbon dioxide.   The heat-driven high-pressure fluid supply apparatus according to claim 10, wherein the constant volume heating is performed at a temperature of 250 ° C. or less and a pressure of 400 MPa or less.   The thermally driven high-pressure fluid supply apparatus according to claim 10, wherein the constant pressure heating is performed at 800 ° C or lower.   13. A high-pressure fluid utilization apparatus characterized in that a high-pressure fluid supplied from the heat-driven high-pressure fluid supply apparatus according to any one of claims 1 to 12 is used as a reaction field.

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