JP2006159165A - Reacting device for high-temperature and high-pressure fluid and manufacturing device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reaction device for a high-temperature and high-pressure fluid of microscale and a manufacturing device for the high-temperature and high-pressure fluid capable of increasing temperature in a short time. <P>SOLUTION: In a reacting device for a high-temperature and high-pressure fluid which makes a working fluid react in a high-temperature and high-pressure field, the reaction device for the high-temperature and high-pressure fluid is sequentially arranged a preheater, a reactor and a cooler, in which heat of a metal thin tube in the preheater is generated by a direct energizing or an electromagnetic induction system and a temperature of the working fluid in the metal thin tube is increased by an indirect heat exchange and the manufacturing device for the high-temperature and high-pressure fluid is comprised of the preheater. This invention make it possible to rapidly produce a high-temperature and to effectively control temperature and perform chemical reaction. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a high-temperature and high-pressure fluid reaction device and a high-temperature and high-pressure fluid production device for performing, for example, a chemical reaction in a high-temperature and high-pressure field composed of a working fluid in a fine high-pressure channel. In a high-temperature and high-pressure fluid reaction apparatus having a preheater, a reactor, and a cooler capable of rapidly heating and cooling a fluid, by heating a metal thin tube in the preheater by direct energization or electromagnetic induction, The present invention relates to a high-temperature and high-pressure fluid reaction apparatus for indirectly heating a working fluid in a metal thin tube. The present invention provides a new high-temperature and high-pressure fluid reactor in the technical field related to a high-temperature and high-pressure process widely used in the fields of chemical process technology, energy conversion technology, waste decomposition technology, and the like. The present invention is useful for providing a reaction apparatus (microreactor) and a high-temperature / high-pressure fluid production apparatus (micro heat exchanger) that can achieve cooling and perform microscale high-temperature and high-pressure reactions.

  Conventionally, in technical fields such as chemical synthesis and biochemical analysis, development of a reaction device called a microreactor that performs chemical reaction by forming and laminating minute channels and reaction chambers on a thin metal plate or glass or resin substrate And use is progressing. This microreactor can reduce the overall dimensions of the device, and the surface area per specific volume (specific surface area) of the internal fluid is extremely large. Therefore, reaction and mixing at the reactant interface can be performed efficiently, and heat transfer. However, these existing devices and systems are not designed to withstand high temperatures and pressures, and are mainly used near normal temperatures and pressures. (See Patent Documents 1 and 2).

  On the other hand, in the reaction technology using supercritical fluid, pure water and carbon dioxide are brought into a supercritical state exceeding the thermodynamic critical point, which is the eigenvalue of each physical property, and they are used as a chemical reaction field. Development is active. The range of applications extends to a wide range of industrial fields, from fine chemicals to nanomaterial synthesis, production of new fuels for automobiles, semiconductor manufacturing, waste treatment, cosmetics production, detoxification treatment of toxic substances such as PCB, and oxidative decomposition treatment. Therefore, the range of use as a low environmental load type fluid reaction technology is expected to expand more and more. In particular, in the reaction technology using supercritical water in the case of using water, the thermodynamic critical point (22.1 MPa, 374 ° C.) is high temperature and high pressure. The reaction apparatus must be devised to increase the pressure resistance under high temperature conditions.

  The aforementioned microreactor uses a small flow path space, so the pressure receiving area is small, so there is a possibility that the pressure resistance performance can be increased. Further, on the chemical reaction surface, the reaction at the reactant interface is possible. -It has favorable characteristics such as efficient mixing. For example, a new low environmental load type chemical raw material production method using supercritical water and a microreactor has been reported (see Patent Document 3). In this method, the internal space of a thin metal tube having a small inner diameter and pressure resistance is used as a microreactor as it is, and the temperature of the solution is adjusted by directly mixing high-temperature and high-pressure water in a supercritical state with a normal temperature reaction solution. A chemical reaction apparatus is used in which the reaction is started by raising the temperature and the temperature is maintained by an external incubator. In addition, by combining such supercritical fluid reaction technology and microreactor technology, an efficient and low environmental impact chemical reaction method using only water without using a catalyst has been demonstrated. In putting micro-scale supercritical reactors into practical use, rapid heat exchange, rapid temperature rise, short-time reaction, and rapid cooling enable equipment cost reduction, energy saving, side reaction suppression, high yield. Rate and high selectivity can be realized. However, when the reaction solution is rapidly heated or cooled by direct heat exchange, for example, direct injection of supercritical water or cooling water, the reaction solution and the reaction product to be recovered become a large amount of supercritical water for heating, etc. Therefore, there is a problem that the amount of fluid to be treated is inevitably increased, which is economically disadvantageous.

JP 2004-195433 A JP 2003-119497 A JP 2003-201277 A

  Under such circumstances, in view of the above prior art, the present inventors, for example, in a chemical reaction apparatus in which a supercritical fluid reaction technology using pure water and a microreactor technology are fused, Based on the knowledge that it is necessary to provide a supercritical water reactor that realizes rapid temperature rise and cooling, regardless of dilution of the object to be processed, in operation under pressure and temperature conditions above the critical point. As a result of diligent research, the inventors have found that the intended purpose can be achieved by direct energization or indirect heating by an electromagnetic induction method, leading to the present invention. The present invention provides a microscale high-temperature and high-pressure fluid reactor and high-temperature and high-pressure fluid manufacturing that achieves efficient temperature control and energy efficiency by downsizing the entire device and reducing the heat dissipation area that increases heat loss. The object is to provide an apparatus. Another object of the present invention is to provide a high-temperature and high-pressure fluid reactor capable of avoiding an increase in fluid throughput by realizing a rapid temperature change of a fluid to be circulated by an indirect heat exchange method using a metal as a medium. It is what. In addition, the present invention provides a high-temperature and high-pressure fluid reaction apparatus in which the working fluid in the metal thin tube is heated by Joule heating that directly energizes the metal thin tube, or by eddy current generated by an electromagnetic induction coil disposed outside. It is intended to do.

  In order to solve the above problems, the present invention relates to a high-temperature and high-pressure fluid reaction apparatus provided with a preheater, a reactor, and a cooler, and a preheater composed of a metal thin tube and a working fluid in the metal thin tube. , A high-temperature and high-pressure fluid reaction apparatus characterized by having a means for indirect heating by direct energization or electromagnetic induction. This high-temperature and high-pressure fluid reactor has (1) a preheater and a reactor that are separately or integrally configured, (2) the inner diameter of the metal thin tube is 1 mm or less, and (3) the preheater (4) The cooler is composed of a single metal thin tube or a metal thin tube having a structure in which a plurality of metal thin tubes are assembled by a multi-way joint structure. 5) The cooler is an indirect heat exchanger that indirectly cools the working fluid in the metal thin tube with a refrigerant. (6) The working fluid is water, carbon dioxide, alcohols, hydrocarbons, or these. A mixed fluid consisting of two or more, or a mixed fluid obtained by adding a reaction substrate to these fluids; (7) the working fluid is a subcritical or supercritical fluid; (8) the preheater It has a function of raising the temperature in 1 second or less. It is set to. The present invention also provides a high-temperature and high-pressure fluid reactor characterized by combining a plurality of the high-temperature and high-pressure fluid reactors described above as one module.

  The present invention also relates to a high-temperature and high-pressure fluid manufacturing apparatus that heats a working fluid to produce a high-temperature and high-pressure fluid, and a thin metal tube for heating the working fluid, and a direct current or electromagnetic induction system for the working fluid in the thin metal tube A high-temperature and high-pressure fluid production apparatus, characterized in that it has means for indirectly heating by means of. This high-temperature and high-pressure fluid production apparatus has (1) the inner diameter of the metal capillary is 1 mm or less, (2) the metal capillary is single, and (3) the working fluid is water, carbon dioxide, alcohols , Hydrocarbons, or a mixed fluid composed of two or more of these, or a mixed fluid obtained by adding a reaction substrate to these, (4) the working fluid is a subcritical or supercritical fluid, (5) ) Having a function of raising the temperature of the working fluid in 1 second or less is a preferred embodiment.

Next, the present invention will be described in more detail.
The present inventors examined the possibility of a short-time temperature increase by the indirect heat exchange method when developing a supercritical fluid reaction device by an indirect heat exchange method using a micro heat exchanger. The axial temperature rising process of high-pressure water flowing through a monotube having an inner diameter of 0.25 mm and od / id = 3 was determined. FIG. 1 shows the result of estimating the temperature rise of high-pressure water of 27 ° C. flowing inside the tube with respect to the axial direction with the surface temperature of the tube being 400 ° C. From this result, it was found that heating the high-pressure water from 27 ° C. to 400 ° C. can be sufficiently performed with a temperature rising time of about 0.01 to 0.05 seconds. It has been found useful for manufacturing.

  Based on these results, the present invention constructs a high-temperature and high-pressure fluid reaction apparatus and its manufacturing apparatus by an indirect heat exchange method using a micro heat exchanger, and heats a metal thin tube by direct energization or electromagnetic induction, The internal working fluid is heated by indirect heat exchange, rapidly becoming a high temperature and high pressure state, allowing the reaction to proceed, and then cooling at high speed to stop the reaction, allowing the reaction to be performed on a microscale. Reactor. In addition, the present invention is a new reaction apparatus in which high-temperature and high-pressure technology and microreactor technology are combined. By reducing the inner diameter of the metal thin tube to 1 mm or less, the diffusion of heat and substance inside the tube is completed in a short distance, and the working fluid is The temperature raising time for raising the temperature to the predetermined temperature can be set to 1 second or less. Further, the temperature can be made uniform and a plurality of kinds of substances can be mixed efficiently.

  In the present invention, the “working fluid” is a fluid that can form a high-temperature and high-pressure reaction field, for example, water, carbon dioxide, alcohols, hydrocarbons, or a mixed fluid composed of two or more of these, or It is a mixed fluid obtained by adding a reaction substrate to these. Further, in the present invention, “high temperature and high pressure” means a state of higher temperature and higher pressure than normal temperature and normal pressure, and the specific range thereof is suitable for the characteristics of the working fluid and the reaction substrate. It is appropriately selected depending on the reaction temperature and pressure.

  As technical means and element devices necessary for constructing the reaction apparatus of the present invention, for example, (1) a single metal thin tube having an inner diameter of 1.0 mm or less and having high pressure resistance is directly energized or A preheater that generates heat by electromagnetic induction and rapidly heats the working fluid (pure water, aqueous solution, carbon dioxide, etc.) that circulates inside thereof, and (2) a preheater brings the reaction temperature to a predetermined reaction temperature. Reaction with a single flow path that keeps the temperature of the fluid reached constant and allows the reaction inside the fluid to proceed, and a heat insulation mechanism or auxiliary heat-retaining heating mechanism to prevent heat dissipation from the surface (3) Fluid filter, (4) In order to rapidly cool the fluid and stop the reaction, the fluid is evenly dispersed in a plurality of metal capillaries by a single metal capillary or multi-way joint structure and assembled again The flow path structure In addition, a heat exchanger having a jacket structure that allows a refrigerant to flow outside thereof, (5) a pressure reducing valve that lowers the pressure of the fluid to return to normal pressure, and (6) a temperature at which each part measures temperature and pressure. Sensor / pressure sensor, (7) for supplying power to the preheater that heats the fluid passing through the inside of the metal thin tube by direct energization or electromagnetic induction, for example, a power supply device such as a transformer and its control device, And (8) metal joining techniques such as metal brazing and arc welding that can withstand high temperatures and pressures, which are used to connect these components to each other.

  In order to perform the reaction by heating, reacting, and cooling the working fluid with the high-temperature and high-pressure fluid reaction apparatus of the present invention, first, the working fluid in a normal temperature and normal pressure state is pressurized to a predetermined pressure by a high-pressure pump, By passing through the preheater, which is pumped to the preheater at a flow rate, the working fluid is rapidly heated to the target temperature to initiate a chemical reaction, then the fluid enters the reactor and during its transit time Then, the reaction proceeds while the reaction temperature is maintained, and the fluid that has passed through the reactor enters a heat exchanger for cooling, is rapidly cooled to stop the reaction, passes through a pressure reducing valve, and then is kept at normal temperature. It is carried out by returning to the pressure state and collecting the reaction solution.

Next, each element which comprises the high temperature / high pressure fluid reaction apparatus of this invention is demonstrated.
The preheater is composed of a single metal thin tube having an inner diameter / outer diameter ratio and a certain length selected so as to satisfy a predetermined pressure resistance performance. Although it is determined by examining the electric resistance value, the electric power and heat transfer capacity necessary for heating the fluid passing through the inside, and the pressure loss due to the fluid passing through the inside, for example, the outer diameter is 1.5 to 6. It consists of a thin metal tube having a diameter of 4 mm, an inner diameter of 0.2 to 1.0 mm, and a length of 200 to 600 mm. An electrode terminal portion is joined to both ends of the thin tube. The pair of electrode terminals are connected to the power supply device by a metal bus bar having good conductivity, and the metal thin tube is energized directly to heat the metal thin tube, thereby raising the working fluid therein to a predetermined temperature. Warm up. At this time, since a large current flows in the contact surface between the metals at the connection portion of the electrode terminal, the electrode terminal is made to have a large contact area by using a metal terminal having good conductivity, for example, a pure copper block. It is connected to the bus bar so as to sandwich the whole. The energized metal thin tube generates heat according to the amount of current by Joule heating, and the fluid is heated by exchanging heat with the working fluid flowing through the inner wall. In this case, as the metal thin tube material, for example, stainless steel and nickel alloy are preferable, and nickel alloy, particularly Inconel 625 is more preferable. The energized portion is electrically insulated from the other components of the apparatus, and the current flows only in the preheater portion.

  In addition, as the heating means of the present invention, an induction heating method in which an induction eddy current is generated by placing a metal thin tube inside an electromagnetic induction coil is possible. In that case, it is necessary to select a ferromagnetic material as the material of the metal thin tube, but, for example, iron, stainless steel, nickel alloy or the like is preferable, and nickel alloy, particularly Inconel 625 is more preferable.

  The metal thin tube of the present invention has pressure resistance that can withstand high pressure inside, heat resistance that can withstand high temperature inside, and corrosion resistance to substances used inside or generated after the reaction. Although it must be, the material is selected according to the heating means of the metal thin tube. In order to make the metal thin tube pressure resistant, for example, the material of the metal thin tube is made excellent in strength, or the metal thin tube is surrounded by a pressure resistant material. In order to make the metal thin tube heat resistant and corrosion resistant, for example, it is preferable that the material of the metal thin tube is heat resistant and corrosion resistant, but corrosion resistance may be imparted by lamination or surface treatment.

  Further, the present invention includes a mechanism for measuring the surface temperature and controlling the input power in order to prevent an excessive temperature rise of the metal thin tube. In order to prevent heat dissipation from the heat generating portion, the outside of the metal thin tube is covered with a suitable heat insulating material or heat insulating mechanism. The heat insulating structure is for preventing energy loss when the inside of the metal thin tube is heated or cooled, and various forms can be adopted. The heat insulating structure may function as a jacket pipe or the like for flowing or heating the inside of the metal thin tube by flowing a heat medium (heat medium) outside the metal thin tube. The material of the heat insulating structure must be stable to the heat medium when functioning as a jacket pipe or the like, but may be a material having a low thermal conductivity. From the viewpoint of durability, ceramics such as zirconia ceramics may be used. Are preferred. Further, the heat insulating structure may be covered with a high-strength material or the like.

  The reactor of the present invention comprises a single flow path having an inner diameter / outer diameter ratio and a certain length selected so as to satisfy a desired pressure resistance performance, and the length is determined based on the fluid flow rate and the target reaction. Although it is selected according to time, for example, it is composed of a metal thin tube having an outer diameter of 1.5 to 6.4 mm, an inner diameter of 0.2 to 1.0 mm, and a length of 200 to 600 mm. In addition, for the purpose of maintaining the fluid at a predetermined reaction temperature, various forms of heat insulation structures or auxiliary heat-retaining heating mechanisms are provided, but simple heat insulation can be achieved by winding a heat insulating material such as silica wool around the entire reaction tube. It can be a structure.

  The cooler of the present invention is a single metal thin tube or an assembly of a plurality of metal thin tubes having an inner diameter / outer diameter ratio and a certain length selected so as to satisfy a predetermined pressure resistance performance, Usually, it consists of a thin metal tube having an inner diameter of 0.2 to 1.0 mm and a length of 200 to 2000 mm. The metal thin tube is composed of a single thin tube and has a sufficient cooling capacity. On the other hand, a structure may be provided in which the fluid is equally divided into a plurality of flow paths by the multi-way joint structure, rapid cooling is performed, and the multi-way joint structure is assembled again. Such a flow path is installed, for example, in a cooling jacket through which a refrigerant flows, and is a countercurrent heat exchanger as a whole. If a multi-way joint structure is adopted, for example, a multi-way joint that uses five metal capillaries and is assembled by fitting both ends into the multi-way joint structure has one fine hole in the inner central axis. The internal flow paths of the five metal thin tubes are converged at one end of the fine holes and the internal flow paths are in circulation. The high-temperature and high-pressure fluid equally divided into five metal flow paths at the inlet of the cooler exchanges heat with the refrigerant (for example, water) flowing around the metal thin tubes while flowing in the individual metal thin tubes. And rapidly cooled to a temperature of about room temperature. Thereafter, they merge again at the outlet side and are led to the pressure reducing valve.

  In the present invention, as a pressurizing pump, a pressure temperature monitoring device, a heating power source, and their control devices that pressurize a working fluid to a predetermined pressure and send it to a preheater, devices used in a normal supercritical reaction technical field, etc. Is appropriately selected and used.

  The present invention relates to a high-temperature and high-pressure fluid reaction apparatus that realizes rapid heating and rapid cooling of a working fluid by an indirect heat exchanger, and directly applies a high-temperature and high-pressure fluid or a cooling fluid by a conventional direct heat exchange method. Compared with the injection method, the amount of processing fluid is minimized, and it becomes possible to construct a micro-scale reaction apparatus with a simple process. Moreover, the high temperature / high pressure fluid reaction apparatus of this invention can construct | assemble the high temperature / high pressure fluid reaction apparatus which carried out the numbering-up structure by combining several in parallel and / or in series as a module.

  As described above, the high-temperature and high-pressure fluid reactor according to the present invention has a structure in which (1) metal capillaries having high pressure resistance are connected in series, and high-speed fluid exchange is achieved by rapid heat exchange by indirect heating. As a micro-scale chemical reaction device that can realize heating and cooling, it has a simple and versatile structure. (2) By using a metal thin tube with a small inner diameter, the surface area per unit volume of the internal fluid is increased. (3) The chemical reaction can be performed in a short time. (4) The high temperature and high pressure conditions exceeding the thermodynamic critical point of water can be quickly created and the temperature can be efficiently achieved by the fine channel structure. Control and chemical reaction can be performed. (5) The circular metal capillaries have the minimum structural volume necessary to achieve pressure resistance and a structure with a heat dissipation area. Standing (6) The energy utilization efficiency defined by the ratio of the increase in energy of the fluid to be heated and the input power can be made extremely high. (7) The entire apparatus can be made compact. 8) Since the internal volume of the apparatus is small, a special effect that it is excellent in safety is achieved.

  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 following examples, an example was shown in which the whole was made of a nickel alloy having excellent high-temperature strength and chemical stability to achieve a high-temperature and high-pressure supercritical state using water or carbon dioxide as a working fluid. However, the working fluid and the material are not necessarily limited, and it is needless to say that these are appropriately selected depending on the use condition and purpose of use of the apparatus.

  In this embodiment, a single metal thin tube and a preheater having current-carrying electrodes at both ends thereof, a reactor having a heat insulating function by a heat insulating material, and a cooler in which the outside of the single metal thin tube is covered with a cooling jacket are provided. A supercritical water reactor was constructed. The entire configuration of the apparatus is shown in FIG. An aqueous solution (water and reaction substrate) pressurized to a pressure of 22.1 MPa or more by a high-pressure pump is transported from the water tank to the preheater, and in the preheater, the critical temperature of water by Joule heating that is directly energized Heated to 374 ° C or higher. The aqueous solution thus brought into the supercritical state was introduced into the reactor, the supercritical state was maintained, and the reaction was allowed to proceed. After the reaction, the aqueous solution was indirectly heat-exchanged by a cooler, cooled to near room temperature, and then recovered by reducing the pressure to normal pressure using a pressure reducing valve. In addition to this, in this example, sensors for measuring the pressure and temperature of each part were appropriately disposed, the operation state of the reaction apparatus was appropriately monitored, and appropriate reaction conditions were maintained by controlling various devices. . The preheater, the reactor, and the cooler will be described in detail below.

(Preheater)
In this example, a preheater having a metal tube having a length of 210 mm and a nickel tube (Inconel 625) having an outer diameter of 1.6 mm and an inner diameter of 0.25 mm was used. It has a structure in which a nickel alloy (MA718) electrode terminal portion having a diameter of 10 mm and a length of 30 mm is joined to both ends of the metal thin tube, and a fine hole having a diameter of 0.5 mm passes through the center. Therefore, a structure communicating with the flow path in the above-described metal thin tube was adopted. The other end of this fine hole was connected to the upstream and downstream piping of the preheater. The pair of electrode terminals were connected to the power supply device by a metal bus bar having good conductivity extended from the power supply device, and were energized. The energized metal thin tube generated heat according to the amount of current by Joule heating, and heated the fluid by exchanging heat with the working fluid flowing through the inner wall.

(Reactor)
The reactor was composed of a metal thin tube made of nickel alloy (Inconel 625) having an outer diameter of 3.18 mm and an inner diameter of 0.5 mm, and its length was 350 mm. Further, the temperature of the internal working fluid was maintained as a simple heat insulating structure by winding a silica wool heat insulating material around the reactor.

(Cooler)
The cooler is composed of a single metal thin tube made of a nickel alloy (Inconel 625) having an outer diameter of 1.6 mm, an inner diameter of 0.25 mm, and a length of 1000 mm, and exchanges heat with a refrigerant (for example, water) flowing around the cooler. And rapidly cooled to a temperature of about room temperature.

  In this example, a reaction apparatus was constructed in the same manner as in Example 1 except that an induction heating method in which an induction eddy current was generated by placing a metal thin tube inside the electromagnetic induction coil was employed as the heating means. As a material for the metal thin tube, it is necessary to select a ferromagnetic material, and a nickel alloy was adopted. In addition, in order to prevent an excessive temperature rise of the metal thin tube, a mechanism for measuring the surface temperature and controlling the input power was installed. In order to prevent heat dissipation from the heat generating portion, the outside of the metal thin tube was covered with a suitable heat insulating material or heat insulating mechanism.

  In this example, the reaction was carried out in the same manner as in Example 1 except that a cooling device having a structure in which the working fluid was evenly divided into a plurality of flow paths to perform rapid cooling and to collect again by a multi-way joint structure was used. A device was constructed. This metal thin tube assembly is installed in a cooling jacket through which a refrigerant flows, and becomes a countercurrent heat exchanger as a whole. A nickel alloy (Inconel 625) having an outer diameter of 1.6 mm, an inner diameter of 0.25 mm, and a length of 210 mm. ) Using 5 thin tubes, both ends were fitted into a multi-way joint structure and assembled. The multi-way joint was made of nickel alloy (MA718). The inner central axis of the multi-way joint structure is formed with one fine hole machining (inner diameter 0.5 mm), and the internal flow paths of the five metal capillaries are focused on one end of the fine hole and the internal flow The road is in circulation. The high-temperature and high-pressure fluid equally divided into five metal capillaries at the inlet of the cooler was cooled to near room temperature while flowing through the individual metal capillaries.

  In this example, a supercritical water reactor in which a preheater and a reactor were integrated was constructed. The overall configuration of the apparatus is shown in FIG. This reactor heats water transported at a high pressure in the upstream preheater part to a temperature above the critical point by Joule heat that is directly applied to the metal thin tube, and then reacts in the reactor part in the downstream part. Heating by direct energization was performed to maintain the temperature. Thus, it became easy to maintain the reaction temperature and pressure in the reactor in a supercritical state by heating both the preheater and the reactor.

  In this example, a supercritical fluid production apparatus was constructed. A thin tube made of nickel alloy (Inconel 625) having an outer diameter of 1.6 mm and an inner diameter of 0.25 mm, and a length of 210 mm was used. This metal thin tube has a structure in which an electrode terminal portion made of a nickel alloy (MA718) having a diameter of 10 mm and a length of 30 mm is joined to both ends of the metal thin tube. Therefore, a structure communicating with the flow path in the above-described metal thin tube was adopted. The pair of electrode terminals were connected to the power supply device by a metal bus bar having good conductivity extended from the power supply device and energized. The energized metal thin tube generates heat according to the amount of current by Joule heating, and the fluid is heated by exchanging heat through the inner wall with the working fluid flowing inside the tube. Water that has been pressurized to a pressure of 22.1 MPa or higher by a high-pressure pump is introduced into the thin tube of the apparatus, and the water in the metal thin tube is heated to a temperature of 375 ° C. or higher by Joule heat that is applied to the metal thin tube. In the apparatus, it was converted to supercritical water and supplied to an external reactor. Further, the liquefied carbon dioxide pressurized to 7.4 MPa or more by the high pressure pump is introduced into the thin tube of the apparatus, and the liquefied carbon dioxide in the metal thin tube is heated to 31 ° C. by Joule heat applied to the metal thin tube. It was heated as described above, converted into supercritical carbon dioxide in this apparatus, and supplied to the reaction apparatus outside the apparatus.

  In this example, the high-temperature and high-pressure fluid reaction apparatus according to the present invention was used as a module, and a high-temperature and high-pressure micro-reaction apparatus was stacked and numbered up in order to be combined in parallel. Specifically, five reactors of Example 1 were stacked horizontally and vertically, and metal thin tubes were assembled at both ends, and the upstream side was a high pressure pump and the downstream side was a single pressure reducing valve. Connected. As a result, when the processing amount was 3 kg / h in the single module system, the processing amount was 15 kg / h by the parallel processing of five modules. Moreover, the same numbering-up configuration was possible by combining the high-temperature and high-pressure fluid reactor of the present invention sideways.

  In the apparatus configuration in Example 3, the result of the apparatus test actually performed by setting the pressure temperature condition exceeding the thermodynamic critical point of water will be described. The working fluid is pure water, pure water near room temperature is heated to 400 ° C. by a preheater, and further cooled to room temperature by a cooler. The heating / cooling capability of the apparatus was evaluated by changing the flow rate of pure water pumped by the high-pressure pump and recording the pressure, temperature, and power consumption of each part of the apparatus. Table 1 shows an example of the test results. The test results show that approximately 75% to 94% of the power input to the preheater is efficiently converted to fluid energy passing through the interior. The energy utilization efficiency required by dividing the fluid energy increase by the input power is extremely high, indicating that the energy saving performance of this device is very high. Table 2 is a result of estimating the overall heat transfer coefficient, the passage time of the preheater, and the heating rate of the fluid, which are indices indicating the level of the heat transfer capacity, and is 0.1 seconds or less due to the extremely high heat transfer capacity. It became clear that extremely fast fluid heating could be realized. Similarly, Table 3 shows the result of estimating the performance of the cooler. As with the preheater, high heat transfer capacity and a large cooling rate were obtained, and it was revealed that the passing high-temperature and high-pressure water was cooled to room temperature within 0.5 seconds. As can be seen from these results, it is clear that the high-temperature and high-pressure fluid reaction apparatus according to the present invention realizes a short heating / cooling process of 1 second or less, which is desirable for the apparatus, and high-speed control. Furthermore, since the energy utilization efficiency is high, it has been shown that it has the capability as a high-temperature and high-pressure fluid production apparatus with high energy saving performance.

  As described above, the present invention relates to a high-temperature and high-pressure fluid reactor capable of performing a chemical reaction under a high-temperature and high-pressure condition exceeding a thermodynamic critical point such as water, carbon dioxide, and alcohol. Yes, for example, a highly versatile high-temperature high-pressure fluid reaction apparatus having a simple configuration by joining metal capillaries having an inner diameter of 1.0 mm or less in diameter and having pressure resistance in a straight line or in part in parallel. It is related to. The supercritical fluid reactor of the present invention is not limited to water or an aqueous solution as a working fluid flowing through the inside, and can be widely used as a high-temperature and high-pressure reactor using other fluids. Further, it can be used in fields such as chemical process technology under high temperature and high pressure conditions by supercritical fluid reaction, energy conversion technology and waste decomposition technology, and can be applied to chemical plants. Moreover, the preheater of the high-temperature / high-pressure fluid reaction apparatus of the present invention can be used for various test studies as a high-temperature / high-pressure fluid production apparatus. In addition, since the high-pressure fluid reactor of the present invention can be combined as a module in parallel and / or in series, a high-temperature and high-pressure microreactor device with an increased throughput and / or function can be configured. In addition to the reaction apparatus, it can be used as a general-purpose high-temperature high-pressure microreactor apparatus.

The estimation result of the high-speed temperature rising process of the high-pressure water which passes the inside of the energization heating partial flow path of a preheater is shown. 1 shows a high-temperature and high-pressure fluid reactor comprising a preheater, a reactor, and a heat exchanger (cooler) according to the present invention. 1 shows a high-temperature and high-pressure fluid reactor constituted by integrating a preheater and a reactor according to the present invention.

Claims (16)

  In a high-temperature and high-pressure fluid reaction apparatus provided with a preheater, a reactor, and a cooler, a preheater composed of a metal thin tube and means for indirectly heating the working fluid in the metal thin tube by direct energization or electromagnetic induction. And a high-temperature and high-pressure fluid reactor.   The high-temperature and high-pressure fluid reactor according to claim 1, wherein the preheater and the reactor are configured separately or integrally.   The high-temperature and high-pressure fluid reactor according to claim 1 or 2, wherein the inner diameter of the metal thin tube is 1 mm or less.   The high-temperature high-pressure fluid reactor according to any one of claims 1 to 3, wherein the preheater is composed of a single metal thin tube.   The high-temperature and high-pressure fluid reactor according to any one of claims 1 to 4, wherein the cooler is composed of a single metal thin tube or a metal thin tube having a structure in which a plurality of metal thin tubes are assembled by a multi-way joint structure.   The high-temperature and high-pressure fluid reaction apparatus according to claim 5, wherein the cooler is an indirect heat exchanger that indirectly cools the working fluid in the metal thin tube with a refrigerant.   The high temperature according to any one of claims 1 to 6, wherein the working fluid is water, carbon dioxide, alcohols, hydrocarbons, a mixed fluid composed of two or more thereof, or a mixed fluid obtained by adding a reaction substrate to these fluids. High pressure fluid reactor.   8. The high-temperature and high-pressure fluid reactor according to claim 7, wherein the working fluid is a fluid in a subcritical or supercritical state.   The high-temperature and high-pressure fluid reactor according to any one of claims 1 to 8, wherein the preheater has a function of raising the temperature of the working fluid in 1 second or less.   A high-temperature and high-pressure fluid reactor according to any one of claims 1 to 9, wherein a plurality of the high-temperature and high-pressure fluid reactors are combined as one module.   In a high-temperature and high-pressure fluid manufacturing apparatus that heats a working fluid to produce a high-temperature and high-pressure fluid, a metal thin tube for heating the working fluid, and means for indirectly heating the working fluid in the metal thin tube by direct energization or electromagnetic induction, A high-temperature and high-pressure fluid manufacturing apparatus characterized by comprising:   The high-temperature and high-pressure fluid manufacturing apparatus according to claim 11, wherein the inner diameter of the metal thin tube is 1 mm or less.   The high-temperature and high-pressure fluid manufacturing apparatus according to claim 11, wherein the metal thin tube is a single one.   The high temperature according to any one of claims 11 to 13, wherein the working fluid is water, carbon dioxide, alcohols, hydrocarbons, a mixed fluid composed of two or more thereof, or a mixed fluid obtained by adding a reaction substrate to these fluids. High pressure fluid production equipment.   The high-temperature and high-pressure fluid manufacturing apparatus according to claim 14, wherein the working fluid is a fluid in a subcritical or supercritical state.   The high-temperature and high-pressure fluid production apparatus according to claim 11, wherein the high-temperature and high-pressure fluid production apparatus has a function of raising the temperature of the working fluid in 1 second or less.

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