JP2014221446A - Reaction apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reaction apparatus which uses a microwave as a heat source and with which temperature of a liquid to be heated can be controlled to be constant while accurately measuring absorbed electric power of the microwave used for heating the liquid to be heated.SOLUTION: A liquid to be heated in a thermostat bath is irradiated with a microwave from an inlet side coaxial waveguide converter via a microwave inlet. Electric power of the microwave absorbed by the liquid to be heated is calculated by using: electric power of the microwave introduced from the inlet side coaxial waveguide converter; electric power of the microwave guided from a microwave outlet of the thermostat bath to an outlet side coaxial waveguide converter; and reflective electric power of the microwave returned to a microwave oscillator. When temperature of the liquid to be heated is elevated due to an exothermic reaction, the temperature of the liquid to be heated is kept to be equal to temperature before the reaction by reducing electric power of the microwave to be absorbed.

Description

  The present invention relates to a reaction apparatus, and more particularly to a reaction apparatus capable of controlling the temperature of the liquid to be heated to be constant while irradiating microwaves to the liquid to be heated in a reaction vessel.

  As a microwave heating device that controls the temperature of the object to be heated while irradiating microwaves, an outer tube that circulates a heat medium for heat exchange with a low dielectric constant is provided around the circulation tube through which the object to be heated flows. The thing is known (for example, refer patent document 1). Moreover, in the reaction apparatus for measuring the amount of reaction heat, it includes a reaction tank, a temperature sensor, a heater device, a jacket, a chiller unit, an air blow device, and a control device. By controlling the heater device and the like by the control device, the liquid agent in the reaction vessel There is known a heating / cooling mechanism for enhancing the heating / cooling effect (see, for example, Patent Document 2).

JP 2010-192147 A JP 2012-166181 A

  In the heating apparatus described in Patent Document 1, since microwaves are absorbed by the heat medium flowing between the outer tube and the flow tube, the amount of microwaves consumed to heat the object to be heated (electric power) Could not be measured accurately. In addition, when performing calorimetric measurement with the heat flow method, it is necessary to submerge a calibration heater for calibrating the reaction calorie in the object to be heated, but because of the effects of microwave heating and radio wave leakage, Calibration could not be performed. For this reason, since the amount of reaction heat cannot be measured, the progress of the microwave reaction could not be confirmed. Furthermore, the structure around the circulation pipe is also fragile, it is difficult to raise the temperature of the non-heating liquid having a low dielectric constant, there is a problem that the energy efficiency is low, and the temperature range is narrow. Further, the heating / cooling mechanism described in Patent Document 2 does not use microwaves as a heating source for the object to be heated (liquid agent), and thus cannot be said to have sufficiently high heating efficiency.

  Therefore, the present invention uses a microwave as a heating source and uses a metal thermostat to accurately measure the absorbed power of the microwave used to heat the liquid to be heated, which is the object to be heated. An object of the present invention is to provide a reaction apparatus capable of controlling the temperature of the liquid to be heated to be constant.

  In order to achieve the above object, the reaction apparatus of the present invention includes a reaction vessel capable of containing a liquid to be heated, a metal thermostat having a reaction vessel insertion hole through which the reaction vessel can be inserted, and an opposite of the thermostat. A microwave inlet and a microwave outlet provided to face the pair of side surfaces, an inlet-side coaxial waveguide converter connected to the microwave inlet, and an outlet-side coaxial waveguide connected to the microwave outlet. A wave tube converter, an inlet-side power detection means for measuring the microwave power output from the microwave oscillator and introduced into the reaction vessel via the inlet-side coaxial waveguide converter, and the inlet-side coaxial waveguide An outlet-side power detection means for measuring the microwave power introduced from the wave tube converter and led to the outlet-side coaxial waveguide converter through the reaction vessel, and the reflected wave of the microwave returned to the microwave oscillator Based on the reflected power detecting means for measuring the power, the microwave power measured by the inlet side power detecting means, the microwave power measured by the outlet side power detecting means, and the microwave power measured by the reflected power detecting means The absorption power calculation means for calculating the microwave power absorbed by the liquid to be heated, the reactive chemical liquid injection part for injecting the reactive chemical liquid into the reaction container, and the temperature of the heated liquid in the reaction container are measured. The temperature measurement means for heating, the heating means for heating the thermostat, the cooling means for cooling the thermostat, the thermostat temperature measurement means for measuring the temperature of the thermostat, and the liquid temperature measurement means for measurement Measured by the temperature of the liquid to be heated or the temperature of the thermostat measured by the temperature measuring means of the thermostat, the temperature control means for controlling the heating means and the cooling means, and the temperature measurement means for the temperature of the liquid to be heated. Microwave output control means for controlling the power of the microwave output from the microwave oscillator based on the temperature of the liquid to be heated or the set output, and using the microwave single mode (TE10 mode) as a heat source, The traveling wave is not absorbed by the thermostat and can be directly irradiated with microwaves by hitting the liquid to be heated only once, and the liquid to be heated disposed in the thermostat is It is characterized by being arranged at an optimum position for absorption of the microwave single mode.

  Furthermore, the reaction apparatus of the present invention has an observation window and a light extraction window for observing the state in the reaction vessel on a side surface of the thermostatic chamber different from the microwave inlet and the microwave outlet. It is characterized by being provided facing each other. The microwave is 2.45 GHz, and the reaction vessel is formed of a material that hardly absorbs the microwave.

  In addition, the inlet-side coaxial waveguide converter has a shape in which the height dimension is constant toward the microwave inlet and the width dimension is gradually narrowed. It is characterized in that the height dimension is constant toward the wave outlet and the width dimension is gradually narrowed.

  Further, the reaction vessel is inserted into the reaction vessel insertion hole in a state of being held by a holding cylinder holding the reaction vessel, and the holding cylinder has openings corresponding to the microwave introduction port and the microwave outlet port, respectively. The holding cylinder has an outer shape corresponding to the reaction vessel insertion hole, and the outer shape of the reaction vessel to be used is selected from a plurality of types of holding tubes having different inner shapes in contact with the reaction vessel. A holding cylinder having an inner shape corresponding to the shape is selected and used.

  According to the reactor of the present invention, a metal thermostat is used, and a microwave inlet and a microwave outlet are provided on the side of the thermostat, so that microwaves are not absorbed by the thermostat, Microwaves are irradiated from the inlet-side coaxial waveguide converter to the liquid to be heated in the thermostatic chamber through the microwave inlet, and the microwave power introduced from the inlet-side coaxial waveguide converter and the microwave in the thermostatic chamber It is possible to calculate the microwave power absorbed in the liquid to be heated from the microwave power derived from the wave outlet to the outlet coaxial waveguide converter and the reflected microwave power returned to the microwave oscillator. it can. When the temperature of the liquid to be heated rises due to an exothermic reaction, the temperature of the liquid to be heated can be kept at the same temperature as before the reaction by reducing the absorbed power of the microwave. Moreover, since the absorbed power of the microwave can be measured accurately, the enthalpy, reaction speed, safety confirmation and reaction progress of the microwave reaction can be confirmed. Furthermore, since the thermostat is made of metal, the structure is robust, and safety and usability can be improved. Further, even a non-heated liquid having a low dielectric constant can be efficiently heated and a wide temperature range can be obtained.

  Furthermore, by adjusting the power of the microwave output from the microwave oscillator while keeping the temperature of the thermostat constant, the temperature of the liquid to be heated whose temperature changes due to reaction heat can be kept constant, The heat of reaction [W] and the amount of heat of reaction [J] can be calculated by calculating using the microwave power absorbed at this time. Furthermore, while maintaining the microwave power constant, measure the temperature change of the liquid to be heated while keeping the temperature of the constant temperature bath constant, or adjust the temperature of the constant temperature bath to keep the temperature of the liquid to be heated constant. The reaction heat [W] and the reaction heat quantity [J] can also be calculated by changing the values. Therefore, the calorific value can be measured by a heat flow method without using a calibration heater.

It is a block diagram which shows one example of a reactor of this invention. It is sectional drawing which shows an example which made the reaction part of the reaction apparatus batch type. FIG. 3 is a sectional view taken along line III-III in FIG. 2. It is a disassembled perspective view of a batch type reaction part similarly. It is a perspective view of a batch type reaction part similarly. It is sectional drawing which shows an example which made the reaction part of the reaction apparatus the flow type. It is a perspective view of a flow type reaction part similarly. It is explanatory drawing which shows the state at the time of reaction in a batch type and a flow type. An example of a state in which the temperature of the liquid to be heated that has been changed by the reaction using the batch-type reaction unit is kept constant by adjusting the microwave power based on the measured temperature of the liquid to be heated. It is explanatory drawing which shows. It is explanatory drawing which shows an example of the state when it is made to hold | maintain constant the temperature of the to-be-heated liquid similarly temperature-changed by reaction by adjusting the temperature of a thermostat based on the temperature of the to-be-heated liquid measured. . It is explanatory drawing which shows an example of a state when it is made to hold | maintain constant the temperature of the thermostat which changes the temperature with the to-be-heated liquid similarly temperature-changed by reaction based on the temperature of the measured thermostat. When the experiment was performed in the state shown in FIG. 9, the temperature of the liquid to be heated when the liquid to be heated and the reaction chemical liquid were reacted, the power of the microwave measured by the inlet side power detection means, and the liquid to be heated It is a figure which shows an example of the change with the electric power of the microwave which absorbed. FIG. 10 is also a diagram illustrating an example of changes in values when an experiment is performed in the state illustrated in FIG. 9. It is a figure which shows an example of a change of each value when experimenting in the state shown in FIG. It is a figure which shows the other example of a change of each value when experimenting in the state shown in FIG.

  1 to 5 show an example in which a batch-type reaction vessel is used as a reaction vessel of the reaction apparatus of the present invention. A reaction vessel 11 composed of a test tube or the like that can contain a liquid to be heated L, and a microwave The reaction portion 13 is formed of a metal material that does not absorb water, for example, a rectangular parallelepiped shaped constant temperature bath 12 made of aluminum having good thermal conductivity. An optical fiber temperature sensor 14 that does not absorb or reflect microwaves is inserted inside the reaction vessel 11, and an insertion portion 15 a of the optical fiber temperature sensor 14 is inserted into the upper opening of the reaction vessel 11. A cap member 15 including a reactive chemical liquid injection portion 15 b used when injecting a reactive chemical liquid into the reaction vessel 11 and a gas purge pipe 15 c that discharges gas from the reaction vessel 11 is attached.

  The thermostatic chamber 12 is provided with a reaction vessel insertion hole 17 through which the reaction vessel 11 can be inserted directly or via a holding cylinder 16 in a state of penetrating through the central portion of the thermostatic bath 12 in the vertical direction, and a pair of opposed chambers. On the two surfaces, a microwave inlet 18 and a microwave outlet 19 having the same rectangular shape are provided facing each other in a penetrating state. An observation window 20 for observing the state in the reaction vessel 11 and a light-extracting window 21 are respectively provided facing each other on the other two surfaces of the pair of thermostatic chambers 12 in a penetrating state.

  Further, inside the thermostatic chamber 12 at a position removed from the microwave inlet port 18, the microwave outlet port 19, the observation window 20, and the light extraction window 21, as a cooling means for adjusting the thermostatic chamber 12 to a preset temperature. The cooling water flow path 22, the heater 23 as a heating means, and a temperature sensor 24 as a constant temperature bath temperature measurement means for measuring the temperature of the constant temperature bath 12 are provided, and the cooling connected to the cooling water flow path 22 is provided. The water pipe 22a is provided with an electromagnetic valve 22b that controls the flow of cooling water. Further, a thermostatic chamber temperature control unit 25 for controlling the heater 23 and the electromagnetic valve 22b based on the temperature measured by the temperature sensor 24 is provided. The thermostatic chamber temperature control unit 25 is basically the thermostatic chamber 12. Is maintained at a constant temperature.

  The holding cylinder 16 is for holding the reaction vessel 11 and inserting it into the reaction vessel insertion hole 17 when using the reaction vessel 11 having an outer diameter smaller than the inner diameter of the reaction vessel insertion hole 17. Similar to the thermostatic bath 12, it is formed in a bottomed cylindrical shape in which a pair of halves 16a, 16a made of aluminum having good thermal conductivity are combined. Inside the halves 16a and 16a, holding grooves 16b and 16b having shapes corresponding to the outer shape of the reaction vessel 11 are provided from the upper end to the vicinity of the lower end, respectively, and ring-shaped coil springs are provided on the upper and lower outer peripheries. Circumferential grooves 16c and 16c for mounting 26 are provided. Further, openings 16d and 16e corresponding to the microwave introduction port 18, the microwave lead-out port 19, the observation window 20, and the light extraction window 21 are provided in the intermediate portion in the vertical direction, respectively.

  When the reaction vessel 11 is held by the holding cylinder 16, the reaction vessel 11 is sandwiched between the holding grooves 16b and 16b of the halves 16a and 16a, and coil springs 26 are attached to the upper and lower circumferential grooves 16c and 16c to halve the reaction vessel 11. By tightening the bodies 16a, 16a, the reaction vessel 11 is sandwiched in the holding grooves 16b of the halves 16a, 16a. At this time, a ring-shaped synthetic resin spacer 27 having an appropriate height is disposed on the bottom of the holding cylinder 16 also as a cushioning material, and the position of the liquid L to be heated in the reaction vessel 11 is changed to the microwave inlet 18 or A state corresponding to the position of the microwave outlet 19 is set. In addition, a cylindrical shielding member 28 that covers the holding cylinder 16 is provided on the top of the thermostatic chamber 12 to prevent leakage of microwaves to the outside. A support plate 29 that prevents microwave leakage and supports the holding cylinder 16 from below is attached to the bottom surface of the thermostatic bath 12. The magnetic plate charged into the reaction vessel 11 is placed below the support plate 29. A magnetic stirrer 30 for rotating the stirrer 30a is disposed (see FIG. 8A).

  The microwave inlet 18 is connected to an inlet-side coaxial waveguide converter 31 for introducing a microwave into the reaction vessel 11 through the microwave inlet 18, and is connected to the inlet-side coaxial waveguide converter 31. Is provided with a microwave oscillator 33 via a tuner 32 for impedance adjustment. The microwave oscillator 33 also has functions as an entrance-side power detection unit and a reflected power detection unit that measure the output microwave power and the reflected wave power from the entrance-side coaxial waveguide converter 31. Thus, the microwave power introduced into the reaction vessel 11 can be accurately measured. The microwave outlet 19 is provided with an outlet-side coaxial waveguide converter 35 provided with outlet-side power detection means 34 as a function of measuring the power of the microwave that has passed through the reaction vessel 11.

  The inlet-side coaxial waveguide converter 31 and the outlet-side coaxial waveguide converter 35 are formed in a rectangular tube shape as a whole, and the connection portion with the thermostatic chamber 12 is connected to the microwave inlet 18 and the microwave outlet 19. A coaxial connector for providing antennas (conductor rods) 31a and 35a in each converter via a coaxial cable is provided at the end opposite to the thermostatic bath 12 at the end opposite to the constant temperature bath 12. Provided antenna mounting portions 31b and 35b are provided. Further, the top and bottom top plates 36a and bottom plates 36b of the converters 31 and 35 are formed in parallel over the entire length, and the inner surfaces of the front and rear side plates 36c and 36d are the microwave inlet port 18 or the microwave outlet port 19 of the thermostatic bath 12. It is formed in a slope shape that gradually expands from the side toward the antenna mounting portions 31b and 35b. For example, the distance from the thermostatic bath 12 to the antenna mounting portions 31b and 35b is normally set to about 70 to 122 mm, and the width dimension on the antenna mounting portions 31b and 35b side is 2 to 2 with respect to the width dimension on the thermostatic bath 12 side. It is set to be about 3 times.

  The microwave oscillator 33 is provided with microwave output control means 37 for adjusting the power of the 2.45 GHz microwave output from the microwave oscillator 33. The microwave output control means 37 is basically configured as follows. In addition, the microwave power output from the microwave oscillator 33 is set to be adjusted so that the temperature of the liquid L to be heated measured by the optical fiber temperature sensor 14 is maintained at a predetermined temperature. Yes.

  The microwave power measured by the inlet-side power detector of the inlet-side coaxial waveguide converter 31 and the microwave power measured by the outlet-side power detector of the outlet-side coaxial waveguide converter 35 are: In order to heat the liquid L to be heated, that is, the electric power absorbed in the liquid to be heated L in the reaction vessel 11 by calculating the difference between the two by inputting to the calculation recording means 38 having the absorbed electric power calculation means. The power used can be determined.

  As shown in FIG.6 and FIG.7, the said thermostat 12 can respond also to a flow-type reaction tube. In the following description, the same components as those of the reaction apparatus shown in the batch system are denoted by the same reference numerals, and detailed description thereof is omitted.

  The flow-type reaction tube 41 is provided with a large-diameter reaction portion 41b at a portion corresponding to the position of the microwave inlet 18 and the microwave outlet 19 in the middle of the small-diameter flow tube 41a extending in the vertical direction. Similarly to the tube 16, the tube is inserted into the reaction vessel insertion hole 17 of the thermostatic bath 12 while being held by the flow tube holding tube 42 formed by combining the halves 42 a and 42 a. The flow pipe holding grooves 42b and 42b formed in the respective halves 42a and 42a of the flow pipe holding cylinder 42 are provided with a large diameter groove portion 42c capable of accommodating the large diameter reaction portion 41b at the intermediate portion, and the large diameter. Small-diameter groove portions 42d that can accommodate the small-diameter flow pipes 41a are respectively provided above and below the groove portions 42c. Further, when the reaction tube 41 is held in the flow tube holding cylinder 42, a ring-shaped synthetic resin spacer 43 serving as a position adjustment and cushion for the large diameter reaction portion 41b is provided below the large diameter reaction portion 41b. Be placed. Furthermore, the outer periphery of the flow tube holding cylinder 42 protruding up and down in the constant temperature bath 12 while being inserted into the reaction vessel insertion hole 17 is covered with the same shielding member 44 as described above, and leakage of the microwave MW to the outside is prevented. Is prevented.

  As shown in FIG. 8A, when the batch-type reaction vessel 11 is used, the cooling water is circulated from the cooling water circulation device 51 to the cooling water flow path 22 of the thermostatic bath 12, and the heater 23 is controlled to control the temperature. While maintaining the tank 12 at a constant temperature lower than the preset temperature of the heated liquid L, the heated liquid L is heated by irradiating the heated liquid L stirred by the magnetic stirrer 30a with the microwave MW. As a result, the liquid L to be heated is held at the set temperature of the liquid L to be heated.

  In addition, as shown in FIG. 8B, when a flow type reaction tube 41 is used, pumps 52a and 53a are used to pump the first reaction liquid container 52 and the second reaction liquid container 53, respectively, to be heated liquid L. The supplied first reaction liquid and second reaction liquid are mixed in the mixing unit 54, the mixed liquid is circulated from the lower part of the reaction tube 41 to the reaction tube 41, and the product liquid after the reaction from the upper part of the reaction tube 41. May be taken out into the product liquid container 55. Moreover, it is preferable to provide the mixing part 54 with stirring means 56 such as a magnetic stirrer in order to sufficiently mix the first reaction liquid and the second reaction liquid. In the case of the flow type as well, the liquid mixture is heated by irradiating the liquid mixture with microwave MW while maintaining the constant temperature bath 12 at a constant temperature lower than the preset liquid mixture temperature. Hold at the set temperature. Thereby, a 1st reaction liquid and a 2nd reaction liquid can be made to react continuously at fixed temperature, and the product liquid of the stable state can be obtained.

  FIG. 9 to FIG. 11 show examples of control methods when the reaction heat quantity is measured using the batch-type reaction vessel 11. The method for measuring the amount of reaction shown in FIG. 9 adjusts the power of the microwave MW based on the temperature of the liquid to be heated L, and the method shown in FIG. The temperature shown in FIG. 11 is for adjusting the amount of heating or cooling of the thermostatic bath based on the temperature of the thermostatic bath 12.

  9, the thermostatic chamber temperature control unit 25 controls the electromagnetic valve 22b and the heater 23 in the cooling water flow path 22 based on the temperature of the thermostatic chamber 12 measured by the temperature sensor 24, and the thermostatic chamber. 12 is maintained at a constant temperature, and the microwave output control means 37 adjusts the output of the microwave oscillator 33 based on the temperature of the liquid to be heated L measured by the optical fiber type temperature sensor 14. It is set to keep the temperature constant.

  In the reaction heat quantity measurement method shown in FIG. 10, the microwave output control means 37 outputs a microwave MW with a constant power from the microwave oscillator 33, and the thermostat temperature control unit 25 measures with the optical fiber temperature sensor 14. The temperature of the liquid to be heated L is set to be constant by controlling the electromagnetic valve 22b and the heater 23 of the cooling water passage 22 based on the temperature of the liquid to be heated L. At this time, the temperature sensor 24 only measures the temperature of the thermostatic bath 12.

  In the reaction heat quantity measurement method shown in FIG. 11, the microwave output control means 37 outputs a microwave MW having a constant power from the microwave oscillator 33, and the thermostatic chamber temperature control unit 25 is controlled by the temperature sensor 24. The temperature of the liquid L to be heated is set to be constant by controlling the solenoid valve 22b and the heater 23 of the cooling water passage 22 based on the temperature of 12 and adjusting the temperature of the thermostatic bath 12. At this time, the optical fiber temperature sensor 14 only measures the temperature of the liquid L to be heated.

  In any case, the microwave single mode (TE10 mode) is used as a heat source, and the microwave traveling wave passes through the liquid L to be heated only once without being absorbed by the thermostat 12. Therefore, the liquid L to be heated can be directly irradiated with the microwave, and the liquid L to be heated disposed in the thermostat 12 is disposed at an optimum position for absorption of the microwave single mode. In addition, measurement information and control information of the optical fiber temperature sensor 14, temperature sensor 24, thermostatic chamber temperature control unit 25, and microwave output control means 37 are taken into a calculation recording means (not shown) to perform processing such as storage and recording. Is called.

  In the control method shown in FIG. 9, in a state where the temperature of the liquid L to be heated is kept constant, a predetermined amount of the reactive chemical liquid is injected (dropped) into the reaction vessel 11 from the reactive chemical liquid injection section 15b, The liquid L to be heated is reacted with the reactive chemical solution. At this time, when the temperature of the liquid to be heated L mixed with the reaction chemical liquid increases due to the reaction heat, the microwave output control means 37 causes the microwave oscillator 33 to respond to the temperature increase of the liquid to be heated L measured by the optical fiber type temperature sensor 14. By reducing the output (electric power), the temperature of the liquid L to be heated is made the same as the temperature before the reaction.

  From the temperature Tr of the liquid L to be heated at this time, from the waveguide inlet power MWin in the microwave MW output from the microwave oscillator 33 to the inlet-side coaxial waveguide converter 31, from the waveguide inlet power MWin The time-dependent change of the power P of the microwave absorbed by the liquid to be heated L calculated by subtracting the power derived from the microwave outlet 19 (exit-side power MWout) and the reflected power MWref returned to the microwave oscillator 33 is illustrated. 12 shows. In the experiment shown in FIG. 12, the set temperature of the liquid L to be heated is 50 ° C.

  Until the temperature Tr of the liquid L to be heated is first heated to 50 ° C., the microwave waveguide power MWin output from the microwave oscillator 33 and the microwave power P absorbed by the liquid L to be heated are used. Both show high values, but when the temperature Tr of the liquid L to be heated reaches a constant state of 50 ° C. after about 300 seconds, both the electric powers MWin and P become substantially constant values. When 600 seconds have passed and the reaction liquid is injected to react the heated liquid L and the reaction liquid, the temperature Tr of the liquid L to be heated once decreases due to mixing of the normal temperature reaction liquid. , P temporarily rise, but when the temperature Tr of the liquid L to be heated rises due to reaction heat, the microwave output control means 37 according to the temperature rise of the liquid L to be heated measured by the optical fiber type temperature sensor 14. Decreases the microwave waveguide inlet power MWin output from the microwave oscillator 33, and the microwave power P absorbed by the liquid L to be heated is reduced accordingly, whereby the temperature Tr of the liquid L to be heated is reduced. Approaches 50 ° C. After the completion of the reaction, the temperature rise due to the reaction heat disappears, so both electric powers MWin and P rise little by little to keep the temperature Tr of the liquid L to be heated at 50 ° C.

  FIG. 13 shows changes with time of the temperature Tr, the heat of reaction (calorie) dQ, and the reaction rate Xconv of the liquid L to be heated obtained from FIG. The amount of heat dQ is a corrected amount of heat obtained by calculating from the absorbed power P. The sum of the heat quantity dQ is the reaction heat quantity Q, and the thermal conversion rate of the reaction heat quantity Q is the reaction rate Xconv.

  When the temperature Tr of the liquid L to be heated rises due to reaction heat, the amount of heat dQ increases from around 700 seconds, and the reaction rate Xconv increases rapidly at first, and then gradually increases. When the reaction is completed in the vicinity of 900 seconds, the amount of heat dQ becomes zero, and the reaction rate Xconv is stabilized at 1. Therefore, the amount of heat dQ while the reaction proceeds and the reaction rate Xconv becomes 0 to 1 (reaction completion) set to the baseline is the reaction heat amount when the liquid L to be heated reacts with the reaction chemical solution, and the reaction rate Xconv Becomes the reaction rate, that is, the reaction progress. Therefore, it is possible to obtain the amount of reaction heat and the progress of the reaction in a short time with a simple operation of measuring the change in the absorbed power P and performing arithmetic processing.

  That is, in this reaction calorimetry, while maintaining the temperature of the thermostat 12 at a constant temperature that is 10 to 20 ° C. lower than the set temperature of the heated liquid L, the heated liquid L in the reaction vessel 11 is maintained at a constant temperature. In this way, the microwave power (power P absorbed by the liquid L to be heated) is continuously adjusted. When the reaction starts in this state and the temperature Tr of the liquid L to be heated rises due to reaction heat, the microwave power P absorbed by the liquid L to be heated decreases by an amount equal to the amount of heat dQ generated by the reaction. .

  Here, the absorbed power P [W] includes the microwave power (inlet side power MWin) [W] introduced from the microwave inlet 18 and the power (outlet side power MWout) derived from the microwave outlet 19 [ W] and the power returned to the microwave oscillator 33 (reflected power MWref [W]) can be obtained by Equation 1.

  P [W] = MWin−MWout−MWref Equation 1

  Further, the heat quantity change PC [W] of the liquid L to be heated is obtained by the difference between the set power MWinSET [W] of the microwave introduced from the microwave introduction port 18 and the absorbed power P [W], that is, Equation 2. Can do.

  PC [W] = MWinSET-P Equation 2

  Then, as shown in Expression 3, the base line BL is determined from the heat amount change PC [W], and the value obtained by subtracting this is the actual heat generation amount dQ (dot Q) [W], and this heat generation amount dQ [W ] Is integrated every second to obtain the reaction heat quantity Q [J].

  Q [J] = Σ (PC−BL) Equation 3

On the other hand, the method of adjusting the temperature of the constant temperature bath 12 based on the temperature of the liquid L to be heated (internal temperature mode) shown in FIG. It is also possible to measure the calorific value of the reaction. In this internal temperature mode, the internal and external temperatures of the temperature Tr of the liquid L to be heated and the temperature Tj of the thermostat 12 are balanced before and after the reaction, and a steady state in which the internal and external temperature difference is constant. At this time, the microwave absorption amount (absorbed power) P [W] of the liquid L to be heated, which is a non-heated material, becomes constant by irradiating the microwave with a constant output, and this is used as a reference to determine the temperature equilibrium state Even if it changes, it becomes a new temperature equilibrium in the steady state, and the temperature difference inside and outside also changes and becomes a constant temperature difference. When the change amount (Tr−Tj) of the internal / external temperature difference obtained by subtracting the internal / external temperature difference in the two steady states is ΔT ₀ [K], the variable UA [W required for the calculation of the heat flow HF [W] / K] or overall heat transfer coefficient U [W / m ² . K] can be obtained by the following formula 4 or formula 5, and thus, the reaction heat quantity can be measured by the heat flow HF [W] even in the microwave heating.

UA [W / K] = P [W] ÷ ΔT ₀ [K] Equation 4
U [W / m ² . K] = P [W] ÷ ΔT ₀ [K] ÷ A [m ² ]...

  The microwave absorption amount (absorbed power) P [W] is calculated from the waveguide inlet power MWin [W], the waveguide outlet power MWout [W], and the reflected power MWref [W] according to Equation 6. Can be sought.

  P [W] = MWin−MWout−MWref Equation 6

In addition, the heat flow HF [W] is the overall heat transfer coefficient U [W / m ² . K], heat transfer area A [m ² ], temperature Tr [° C.] of the liquid L to be heated, temperature Tj [° C.] of the constant temperature bath 12, reaction mass (reaction mass) mr [g], specific heat c [J / g. K], the temperature change rate dTr / dt [K / s] of the liquid L to be heated, and the energy loss dQdos [W] due to the temperature difference between the reactant chemical liquids.

HF = UA * ΔT ₀ + mr * c * (dTr / dt) + dQdos Equation 7

  The actual heat value dQ [W] is obtained by determining and subtracting the baseline baseline from the obtained heat flow HF. As shown in Equation 8, the value obtained by integrating this heat value dQ every second is the integrated heat value Q [ J].

  Q [J] = Σ (HF-baseline) Equation 8

  Here, according to the formula 7, the heat flow HF depends on the difference between the temperature Tr of the liquid L to be heated and the temperature Tj of the thermostat 12 and is not affected by the ambient temperature. If the temperature Tr of L fluctuates, it can be corrected by the product of the reaction mass mr, the specific heat c, and the temperature change rate dTr / dt, so that it can be handled regardless of whether the reaction rate is fast or slow. Recognize. And in Formula 7, when there is no loss of dripping and the temperature Tr of the liquid L to be heated is constant, the heat flow HF can be expressed by the following Formula 9.

HF = UA * ΔT ₀ Formula 9

  In Equation 7 and Equation 9, when heat flow HF is replaced with microwave absorption (absorbed power) P [W] and developed, a calibration equation for obtaining specific heat c shown in Equation 10 and a general heat transfer shown in Equation 11 A calibration equation for obtaining the coefficient UA [W / K] is obtained.

c = {P-UA * (Tr-Tj)} / (mr * dTr / dt) Equation 10
UA = P ÷ ΔT ₀ Equation 11

  The specific heat c is measured while the temperature of the reaction solution rises, and the variable UA is measured when the reaction solution temperature is stable. Therefore, the heat of reaction can be obtained with high accuracy by performing calibration twice before and after the reaction. Can do. An example of a change in each value when the experiment is performed in the internal temperature mode is shown in FIGS. In FIG. 15, the dropping rate (0 to 1): Xdos, the reaction rate (0 to 1): Xconv, the unreacted chemical solution accumulation rate (0 to 1): Xacum, and the actual calorific value [W]: dQ are shown. Yes.

  DESCRIPTION OF SYMBOLS 11 ... Reaction container, 12 ... Constant temperature bath, 13 ... Reaction part, 14 ... Optical fiber type temperature sensor, 15 ... Cap member, 15a ... Insertion part of optical fiber type temperature sensor, 15b ... Reactant liquid injection part, 15c ... Gas purge pipe, 16 DESCRIPTION OF SYMBOLS ... Holding cylinder, 16a ... Half-divided body, 16b ... Holding groove, 16c ... Circumferential groove, 16d, 16e ... Opening, 17 ... Reaction container insertion hole, 18 ... Microwave inlet, 19 ... Microwave outlet, 20 ... Observation window, DESCRIPTION OF SYMBOLS 21 ... Light extraction window, 22 ... Cooling water flow path, 22a ... Cooling water piping, 22b ... Solenoid valve, 23 ... Heater, 24 ... Temperature sensor, 25 ... Constant temperature chamber temperature control part, 26 ... Coil spring, 27 ... Product made from synthetic resin Spacer, 28 ... shielding member, 29 ... support plate, 30 ... magnetic stirrer, 30a ... magnetic stirrer, 31 ... inlet side coaxial waveguide converter, 31a ... antenna, 31b ... a Tena mounting part, 32 ... tuner, 33 ... microwave oscillator, 34 ... exit side power detection means, 35 ... exit side coaxial waveguide converter, 35a ... antenna, 35b ... antenna mounting part, 36a ... top plate, 36b ... Bottom plate, 36c, 36d ... side plate, 37 ... microwave output control means, 38 ... calculation recording means, 41 ... reaction tube, 41a ... small diameter flow pipe, 41b ... large diameter reaction section, 42 ... flow tube holding cylinder, 42a ... Half-divided body, 42b ... retaining groove for flow pipe, 42c ... large diameter groove, 42d ... small diameter groove, 43 ... synthetic resin spacer, 44 ... shielding member, 51 ... cooling water circulation device, 52 ... first reaction liquid container, 53 ... Second reaction liquid container, 52a, 53a ... pump, 54 ... mixing section, 55 ... product liquid container, 56 ... stirring means, L ... liquid to be heated, MW ... microwave

Claims (6)

  A reaction vessel capable of containing a liquid to be heated, a metal thermostat having a reaction vessel insertion hole through which the reaction vessel can be inserted, and a microwave guide provided to face a pair of opposite side surfaces of the thermostat An inlet and a microwave outlet, an inlet-side coaxial waveguide converter connected to the microwave inlet, an outlet-side coaxial waveguide converter connected to the microwave outlet, and output from a microwave oscillator Inlet side power detection means for measuring the power of the microwave introduced into the reaction vessel via the inlet side coaxial waveguide converter, and the outlet side through the reaction vessel introduced from the inlet side coaxial waveguide converter An exit side power detection means for measuring the power of the microwave led to the coaxial waveguide converter, a reflected power detection means for measuring the reflected power of the microwave returned to the microwave oscillator, and the entrance side power Based on the microwave power measured by the detection means, the microwave power measured by the outlet side power detection means, and the microwave power measured by the reflected power detection means, the microwave absorbed by the liquid to be heated is measured. Absorbed power calculation means for calculating electric power, reactive chemical liquid injection part for injecting a reactive chemical liquid into the reaction container, heated liquid temperature measuring means for measuring the temperature of the heated liquid in the reaction container, and the thermostatic chamber A heating means for heating the heating chamber, a cooling means for cooling the constant temperature bath, a constant temperature bath temperature measurement means for measuring the temperature of the constant temperature bath, and a temperature of the heated liquid measured by the heated liquid temperature measurement means or the constant temperature bath temperature measuring means Based on the temperature or setting output of the liquid to be heated measured by the liquid temperature measuring means to be heated and the temperature control means for controlling the heating means and the cooling means based on the temperature of the constant temperature bath measured in step And a microwave output control means for controlling the power of the microwave output from the microwave oscillator. The microwave single mode is used as a heat source, and the microwave traveling wave is not absorbed by the thermostat and is once applied to the liquid to be heated. It is possible to directly irradiate the liquid to be heated with the microwave by passing through it, and the liquid to be heated arranged in the thermostat is arranged at an optimum position for absorption of the microwave single mode. A reactor characterized by.   The temperature chamber is provided with an observation window and a light extraction window facing each other on the side surface of the temperature chamber different from the microwave inlet and the microwave outlet. The reaction apparatus according to claim 1, wherein   3. The reaction apparatus according to claim 1, wherein the microwave is 2.45 GHz, and the reaction vessel is formed of a material that hardly absorbs the microwave.   The inlet-side coaxial waveguide converter has a shape in which the height dimension is constant toward the microwave inlet and the width dimension is gradually narrowed, and the outlet-side coaxial waveguide converter is The reactor according to any one of claims 1 to 3, wherein the reactor has a shape in which the height dimension is constant toward the outlet and the width dimension is gradually narrowed.   The reaction container is inserted into the reaction container insertion hole while being held by a holding cylinder that holds the reaction container, and the holding cylinder is provided with openings corresponding to the microwave introduction port and the microwave outlet port, respectively. The reaction apparatus according to any one of claims 1 to 4, wherein the reaction apparatus is provided.   The holding cylinder has an inner shape corresponding to the outer shape of the reaction container to be used from among a plurality of types of holding cylinders having outer shapes corresponding to the reaction container insertion holes and different inner shapes contacting the reaction container. 6. The reaction apparatus according to claim 5, wherein a holding cylinder is selected and used.

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