WO2024255052A1 - 一种微尺度下动态追踪参比连续量热的装置及方法 - Google Patents

一种微尺度下动态追踪参比连续量热的装置及方法 Download PDF

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WO2024255052A1
WO2024255052A1 PCT/CN2023/126374 CN2023126374W WO2024255052A1 WO 2024255052 A1 WO2024255052 A1 WO 2024255052A1 CN 2023126374 W CN2023126374 W CN 2023126374W WO 2024255052 A1 WO2024255052 A1 WO 2024255052A1
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reaction
microchannel
chip
injection pump
microscale
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French (fr)
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陶胜洋
徐一鸣
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Dalian University of Technology
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Dalian University of Technology
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N25/00—Investigating or analyzing materials by the use of thermal means
    • G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
    • G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
    • G01N25/4806—Details not adapted to a particular type of sample
    • G01N25/4826—Details not adapted to a particular type of sample concerning the heating or cooling arrangements

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  • the present invention relates to the technical field of reaction heat measurement, and in particular to a device and method for dynamic tracking reference continuous calorimetry at a microscale.
  • the calorimetric data of the reaction can be obtained by a calorimeter.
  • the most widely used calorimetric method is intermittent calorimetry.
  • continuously operated microreactors have been increasingly used in the production and process development of chemical products.
  • harsh process conditions can be accurately controlled.
  • the small reaction system reduces the amount of waste generated, the operation process is safer, and the energy consumption is lower.
  • Measuring the reaction calorimetry under continuous flow conditions can obtain higher yields, conversion rates and selectivity, and is also conducive to process automation.
  • patent CN114199937A discloses a calorimetric test method and device for ultra-low temperature reactions, which can realize ultra-low temperature constant temperature calorimetric testing of semi-batch reactions.
  • this invention cannot realize the calorimetry of continuous flow reactions.
  • Patent CN109459161A discloses a calorimetric test method and device for tubular reactions, which realizes the calorimetric testing of exothermic and endothermic tubular reactions, but its calibration process is complicated and the calculation is cumbersome.
  • Patent CN110988035A discloses a method and device for testing continuous flow reaction heat using reference calorimetry, which realizes the test of reaction heat during continuous flow reactions, but its device structure is complicated, and the calorimetric process takes too long, and there is still a large error between the calorimetric result and the theoretical value.
  • a micro-reaction chip was used to measure the reaction heat of acetic anhydride hydrolysis. The test process was complicated, and the process needed to be corrected before each calorimetry measurement. In addition, the environmental impact could not be completely eliminated, resulting in large errors.
  • a device and method for dynamic tracking of reference continuous calorimetry at a microscale are provided.
  • the present invention mainly utilizes the reference calorimetry method to effectively eliminate the influence of the environment on the calorimetric process.
  • the dynamic tracking method is used to simulate the reaction endothermic and exothermic processes with high precision, and the heat of reaction is measured quickly and accurately.
  • the technical problem of the difficulty in measuring the heat of reaction under continuous flow conditions is solved.
  • a device for dynamic tracking reference continuous calorimetry at a microscale comprising:
  • Material inlet and outlet system is connected to the microscale continuous reaction system; the material inlet and outlet system is controlled by the central control and data acquisition system to inject materials into the microscale continuous reaction system;
  • a microscale continuous reaction system a microchannel reaction chip B in the microscale continuous reaction system is used for material reaction; a microchannel reference chip A in the microscale continuous reaction system is used for simulating the endothermic and exothermic process of the reaction in the microchannel reaction chip B, and indirectly obtaining the endothermic and exothermic heat in the microchannel reaction chip B;
  • Central control and data acquisition system controls the operation of the entire device and collects heat absorption and release data, and calculates the reaction heat based on the heat absorption and release.
  • the material inlet and outlet system includes an injection pump controller, a recovery tank A, a recovery tank B and an injection pump, and the injection pump controller is connected to the injection pump to control the operating state and operating parameters of the injection pump;
  • the injection pumps include a first injection pump A, a second injection pump A, a quencher injection pump A, a first injection pump B, a second injection pump B and a quencher injection pump B.
  • first injection pump A is connected to the first feed port A on the microchannel reference chip A through the material preheating aluminum block and the material inlet and outlet interface A
  • second injection pump A is connected to the second feed port A on the microchannel reference chip A through the material preheating aluminum block and the material inlet and outlet interface A
  • quenching agent injection pump A is connected to the quenching agent feed port A on the microchannel reference chip A through the material preheating aluminum block and the material inlet and outlet interface A
  • the recovery tank A is connected to the discharge port A on the microchannel reference chip A through the material preheating aluminum block and the material inlet and outlet interface A;
  • the first injection pump B is connected to the first feed port B on the microchannel reference chip B through the material preheating aluminum block and the material inlet and outlet interface B
  • the second injection pump B is connected to the second feed port B on the microchannel reference chip B through the material preheating aluminum block and the material inlet and outlet interface B
  • the quenching agent injection pump B The recovery tank B is connected to the quenching agent feed port B on the microchannel reference chip B through the material preheating aluminum block and the material inlet and outlet interface B
  • the recovery tank B is connected to the outlet B on the microchannel reference chip B through the material preheating aluminum block and the material inlet and outlet interface B.
  • the microscale continuous reaction system comprises a visual window, a microchannel chip, a heating film, a thermoelectric power generation sheet and a constant temperature device which are arranged in sequence from top to bottom;
  • the microchannel chip comprises a microchannel reference chip A and a microchannel reaction chip B arranged front and back, the inlet and outlet of the microchannel reference chip A and the microchannel reaction chip B are on the same side, and the channels of the microchannel reference chip A and the microchannel reaction chip B are on the same side;
  • the visual window includes a material inlet and outlet visual window and a channel visual window.
  • the material inlet and outlet visual window is arranged above the inlet and outlet sides of the microchannel reference chip, and the channel visual window is arranged above the channel side of the microchannel reference chip;
  • the heating film includes an exothermic reaction tracking heating film A and an endothermic reaction tracking heating film B, wherein the exothermic reaction tracking heating film A is arranged below the microchannel reference chip A, and the endothermic reaction tracking heating film B is arranged below the microchannel reaction chip B;
  • thermoelectric power generation sheet comprises a thermoelectric power generation sheet A and a thermoelectric power generation sheet B.
  • the thermoelectric power generation sheet A is arranged below the heat-tracing exothermic reaction heating film A
  • the thermoelectric power generation sheet B is arranged below the heat-tracing endothermic reaction heating film B.
  • the constant temperature device includes a material preheating aluminum block and a reaction constant temperature aluminum block.
  • the material preheating aluminum block is arranged below the feed port side of the microchannel chip, and the reaction constant temperature aluminum block is arranged below the channel port side of the microchannel chip.
  • the material preheating aluminum block is provided with two grooves at positions corresponding to the feed port sides of the microchannel reference chip A and the microchannel reaction chip B.
  • the grooves are respectively provided with material inlet and outlet interface blocks A and material inlet and outlet interface blocks B.
  • the material inlet and outlet interface blocks A and material inlet and outlet interface blocks B are provided with through holes for allowing the pipeline of the injection pump to pass through.
  • the central control and data acquisition system includes a data acquisition card and a central control and data acquisition device
  • the positive and negative electrodes of the programmable DC power supply A are respectively connected to the tracking exothermic reaction heating film A
  • the positive and negative electrodes of the programmable DC power supply B are respectively connected to the tracking endothermic reaction heating film B
  • the data acquisition card is respectively connected to the thermoelectric power generation sheet A and the thermoelectric power generation sheet B
  • the central control and data acquisition device are respectively connected to the programmable DC power supply A, the programmable DC power supply B, the data acquisition card and the injection pump controller.
  • the present invention also provides a method for dynamically tracking reference continuous calorimetry at a microscale.
  • the realization of any device for dynamically tracking reference continuous calorimetry at a microscale comprises the following steps:
  • a quenching agent is added to the microchannel reference chip A and the microchannel reaction chip B at the same flow rate through the quenching agent injection pump A and the quenching agent injection pump B to perform a quenching reaction;
  • the voltage signal TEC of the thermoelectric generator A and the voltage signal TER of the thermoelectric generator B are collected by the data acquisition card;
  • the output power of the programmable DC power supply A is used to calculate and track the heat generation power of the exothermic reaction heating film A, and the heat Q of the reaction process is calculated by the residence time of the material in the reaction chip, and then the reaction heat ⁇ H is calculated;
  • the output power of the programmable DC power supply B is used to calculate and track the heat generation power of the endothermic reaction heating film B, and the heat release Q of the reaction process is calculated by the residence time of the material in the reaction chip, and then the reaction heat ⁇ H is calculated.
  • the temperature of the material preheating aluminum block and the reaction constant temperature aluminum block is set according to the reaction conditions, and the temperature is increased or decreased to the target temperature at a constant rate.
  • calculation and tracking of the heating power of the exothermic reaction heating film A includes the following steps:
  • the microchannel reaction chip B When TEC>TER at the beginning, the microchannel reaction chip B is undergoing an exothermic reaction.
  • the output voltage of the programmable DC power supply A is changed to control the heat generation power of the heating film A for tracking the exothermic reaction, and the heat generation process of the exothermic reaction in the microchannel reaction chip B is simulated.
  • the difference ⁇ V i between TEC and TER approaches , the real-time output voltage U PC of the programmable DC power supply A is obtained, thereby calculating the heat generation power P A of the heating film A for tracking the exothermic reaction;
  • the microchannel reaction chip B When TEC ⁇ TER at the beginning, the microchannel reaction chip B is undergoing an endothermic reaction.
  • the output voltage of the programmable DC power supply B is changed to control the heating power of the heating film B that tracks the endothermic reaction, and compensate the endothermic heat of the endothermic reaction in the microchannel reaction chip B.
  • the absolute value ⁇ V i of the difference between TEC and TER approaches , the real-time output voltage U PR of the programmable DC power supply B is obtained, and the heating power PB of the heating film B that tracks the endothermic reaction is calculated.
  • RA is the resistance of the heating film A for tracking the exothermic reaction
  • RB is the resistance of the heating film B for tracking the exothermic reaction.
  • the residence time t of the material in the reaction chip is calculated according to the volume flow rate set by the injection pump:
  • V is the volume of the reaction channel of the microchannel reference chip A and the microchannel reaction chip B
  • q V1 is the volume flow rate of the material set by the first injection pump A and the first injection pump B
  • q V2 is the volume flow rate of the material set by the second injection pump A and the second injection pump B
  • q V is the volume flow rate of a reactant, and c is the molar concentration of a reactant
  • the present invention has the following advantages:
  • the device of the present invention uses a microscale reaction chip with high mass and heat transfer efficiency, can realize single reaction with high reactant concentration, and greatly reduces the amount of material consumed in the calorimetric process. Compared with intermittent calorimetry, continuous calorimetry can make reaction conditions easier to control and improve the safety of the process, and can realize calorimetry of dangerous chemical reactions.
  • the device of the present invention is provided with a microchannel reference chip A and a microchannel reaction chip B at the same time.
  • the structures of the two chips are exactly the same. Samples are injected simultaneously during the reaction process, and the flow rate is strictly controlled, thereby eliminating the influence of the environment on the calorimetric process. At the same time, the heat carried away by the material flow is deducted to obtain the real heat change of the reaction.
  • the present invention uses a central control and data acquisition device to realize the control of the injection pump, system temperature and DC power supply, including realizing online real-time control of the injection pump start and stop, setting flow rate and setting working time by establishing a communication link between the central control and data acquisition device and the injection pump controller; realizing online real-time control of the injection pump start and stop, setting flow rate and setting working time by establishing a communication link between the central control and data acquisition device and the programmable DC power supply A and the programmable DC power supply B.
  • the DC power supply is now controlled online in real time to switch on and off, and the power supply output voltage is dynamically controlled during the experiment; the temperature of the material preheating aluminum block and the reaction constant temperature aluminum block is controlled by establishing communication between the central control and data acquisition device and the constant temperature pump; at the same time, data collection and processing are performed online, and the voltage signal of the data acquisition card is collected in real time by linking the central control and data acquisition device and the data acquisition card.
  • the whole calorimetric process of the present invention is fast, and accurate calorimetric data can be obtained without correction before each calorimetric measurement.
  • test method of dynamically tracking reference calorimetry of the present invention can provide more practical and effective guidance for engineering design, process safety and process optimization to achieve energy conversion and transfer design.
  • FIG1 is a schematic diagram of the structure of the present invention.
  • FIG. 2 is an exploded view of the microscale continuous reaction system of the present invention.
  • FIG. 3 is a schematic diagram of the structure of the micro-reaction chip of the present invention.
  • FIG. 4 is a schematic diagram of the structure of the thermostat of the present invention.
  • FIG. 5 is a dynamic tracking reference logic diagram of the present invention.
  • FIG. 6 is a diagram showing experimental results of Example 1 of the present invention.
  • FIG. 8 is a diagram showing the experimental results of the third embodiment of the present invention.
  • spatially relative terms such as “above”, “above”, “on the upper surface of”, “above”, etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as “above other devices or structures” or “above other devices or structures” will be positioned as “below other devices or structures” or “below their position devices or structures”. Thus, the exemplary term “above” can include both “above” and “below”. The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.
  • the present invention provides a micro-scale dynamic tracking reference continuous calorimetric device, including a material inlet and outlet system, a micro-scale continuous reaction system, and a central control and data acquisition system.
  • the first injection pump B75, the second injection pump B76, the quenching agent injection pump B77 and the recovery tank B78 are respectively connected to the first feed port B221, the second feed port B222, the quenching agent feed port B223 and the discharge port B224 on the microchannel reaction chip B22 through the material preheating block 61 and the material inlet and outlet interface block B52.
  • the microscale continuous reaction system includes a material inlet and outlet visual window 11, a channel visual window 12, a microchannel reference chip A21, a microchannel reaction chip B22, a tracking exothermic reaction heating film A31, a tracking endothermic reaction heating film B32, a thermoelectric power generation sheet A41, a thermoelectric power generation sheet B42, a material inlet and outlet interface block A51, a material inlet and outlet interface block B52, a material preheating aluminum block 61, and a reaction constant temperature aluminum block 62. Arrange them in sequence according to FIG. 2 and fix them with screws around.
  • the microchannel reference chip A21 and the microchannel reaction chip B22 have the same structure, the tracking exothermic reaction heating film A31 and the tracking endothermic reaction heating film B32 have the same model, and the thermoelectric power generation sheet A41 and the thermoelectric power generation sheet B42 are of the same model.
  • the present invention also provides a method for testing the heat of a continuous flow reaction using a dynamic tracking reference continuous calorimeter at a microscale, comprising the following steps:
  • the microchannel reference chip A21 and the microchannel reaction chip B22 have the same structure. Materials are continuously added to the microchannel reference chip A21 and the microchannel reaction chip B22 at the same flow rate. The materials introduced into the microchannel reference chip A21 by the first injection pump A71 and the second injection pump A72 are single solvents, and the materials introduced into the microchannel reaction chip B22 by the first injection pump B75 and the second injection pump B76 are raw materials for the test reaction. Quenching agents are added to the microchannel reference chip A21 and the microchannel reaction chip B22 at the same flow rate by the quenching agent injection pump A73 and the quenching agent injection pump B77, and the reaction is quenched in time to ensure the safety of the experiment. The residence time of the reaction is controlled by controlling the speed of adding materials.
  • the real-time output voltage U PC (in V) of the programmable DC power supply A33 is obtained, and the heat generation power PA (in mW) of the exothermic reaction heating film A31 is calculated and tracked.
  • the endothermic reaction For example, by changing the output voltage of the programmable DC power supply B34 to control the heating power of the endothermic reaction heating film B32, the heat absorption of the endothermic reaction in the microchannel reaction chip B22 is compensated.
  • the methods specifically include:
  • the residence time of the reaction is controlled by the feeding speed.
  • the injection pumps are simultaneously started and the feeding is continuous through the central control system.
  • the voltage signals TEC and TER of the thermoelectric generator A and the thermoelectric generator B are obtained in real time online through the data acquisition system during the reaction process.
  • the output voltage U PC of the programmable DC power supply A and the output voltage U PR of the programmable DC power supply B are set to 0 V. Wait for 10 minutes until the voltage signals TEC and TER of the thermoelectric generator A and the thermoelectric generator B tend to be stable.
  • Table 1 shows the values of ⁇ i and ⁇ Vi corresponding to the values of i in FIG5 when they are 1, 2, 3, and 4, respectively. If TEC>TER at the initial stage, it is determined that an exothermic reaction is taking place in the microchannel reaction chip B. The heat generation power of the exothermic reaction heating film A is tracked by changing the output voltage of the programmable DC power supply A. The heat generation process in the microchannel reaction chip B is simulated in the microchannel reference chip A until the absolute value ⁇ Vi of the difference between TEC and TER is less than 1mV.
  • the heat generation of the exothermic reaction heating film A is the heat generation of the reaction in the microchannel reaction chip B.
  • the output voltage U PC of the programmable DC power supply A is recorded at this time.
  • the heat generation power PA of the exothermic reaction heating film A is:
  • RA is the resistance of the heating film A for tracking the exothermic reaction (unit: ⁇ );
  • TEC ⁇ TER it is determined that an endothermic reaction is taking place in the microchannel reaction chip B.
  • the output voltage of the programmable DC power supply B is changed to control the heating power of the tracking endothermic reaction heating film B, and the endothermic heat of the endothermic reaction in the microchannel reaction chip B is compensated until the absolute value ⁇ V i of the difference between TEC and TER is less than 1mV.
  • ⁇ V i the difference between TEC and TER
  • RB is the resistance of the heating film B for tracking the exothermic reaction (unit: ⁇ );
  • V is the volume of the reaction channel of microchannel reference chip A and microchannel reaction chip B (unit ⁇ l)
  • q V1 is the volume flow rate of the material set by the first injection pump A and the first injection pump B (unit ⁇ l/min)
  • q V2 is the volume flow rate of the material set by the second injection pump A and the second injection pump B (unit ⁇ l/min).
  • q V is the volume flow rate of a reactant (in ⁇ l/min)
  • c is the molar concentration of a reactant (in mol/l).
  • the accuracy of the device is verified by heating the tracking endothermic reaction heating film B to simulate the exothermic reaction in the microchannel reaction chip B.
  • the experimental results are shown in FIG6 .
  • Water was added to the microchannel reference chip A and the microchannel reaction chip B at a rate of 1 ml/min through the first feed port A and the first feed port B, respectively, and the system temperature was 30°C.
  • This embodiment takes the dilution of 96% concentrated sulfuric acid to 80% by mass with water as an example to illustrate the calorimetric method of the present invention, and further verifies the accuracy of the method through calculation.
  • the experimental results are shown in FIG7 .
  • (1) Loading Load water into 5 syringes and install them in the first injection pump A, the second injection pump A, the quencher injection pump A, the second injection pump B and the quencher injection pump B respectively; load concentrated sulfuric acid with a mass fraction of 96% into a syringe and install it in the first injection pump B; set the temperature of the material preheating aluminum block and the reaction constant temperature aluminum block to 25°C.
  • q V is the volume flow rate of a reactant (in ⁇ l/min)
  • c is the molar concentration of a reactant (in mol/l).
  • This example takes the diazotization reaction of aniline hydrochloride and sodium nitrite as an example to illustrate the application of the present invention in the calorimetry of dangerous reactions with rapid and strong heat release.
  • the experimental results are shown in FIG8 .
  • (1) Loading water is loaded into four syringes and respectively loaded into the first injection pump A, the second injection pump A, the quencher injection pump A, and the quencher injection pump B; 2.3 ml of aniline and 6.5 ml of concentrated hydrochloric acid are mixed and diluted with water to 250 ml to prepare an aniline hydrochloride solution, which is loaded into a syringe and transferred to the first injection pump B; 1.8113 g of sodium nitrite is diluted with water to 250 ml to prepare a sodium nitrite aqueous solution, the molar ratio of aniline hydrochloride to sodium nitrite is 1:1.05, and the temperature of the material preheating aluminum block and the reaction constant temperature aluminum block is set to 0°C.
  • the output voltage U PC of the programmable DC power supply A and the output voltage U PR of the programmable DC power supply B are set to 0V, and wait for 10 minutes until the voltage signals TEC and TER of the thermoelectric generator A and the thermoelectric generator B tend to be stable.
  • the total material consumption in the calorimetric process is less than 20 ml, and the device operates safely and stably with high signal sensitivity.

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Abstract

一种微尺度下动态追踪参比连续量热的装置及方法，该装置包括：物料进出系统；该物料进出系统与微尺度连续反应系统相连；该物料进出系统受中央控制和数据采集系统控制，向微尺度连续反应系统注入物料；微尺度连续反应系统；该微尺度连续反应系统中的微通道反应芯片B（22）用以发生物料反应；该微尺度连续反应系统中的微通道参比芯片A（21）用以模拟微通道反应芯片B（22）中反应的吸放热过程，并间接获得微通道反应芯片B（22）中的吸放热量；中央控制和数据采集系统；该中央控制和数据采集系统采集吸放热量并根据吸放热量计算出反应热。该方法整个量热过程操作简单、快速，无需反复矫正就可以保证量热的准确性。

Description

一种微尺度下动态追踪参比连续量热的装置及方法 技术领域
本发明涉及反应热测量技术领域，具体而言，尤其涉及一种微尺度下动态追踪参比连续量热的装置及方法。
背景技术
测量化学反应的量热数据对于反应过程安全和反应器设计、操作以及放大来说都是至关重要的。通过量热仪可以获得反应的量热数据。目前广泛使用的量热方式为间歇量热。近年来连续操作的微反应器已经越来越多地用于化学产品的生产和工艺开发中。利用微反应技术，可以精确控制苛刻的工艺条件。在微反应器中，由于反应体系小使得产生的废料减少，操作过程更安全，能源消耗更低。在连续流动条件下测量进行反应量热，可以获得更高的产量、转化率和选择性，同时有利于工艺自动化。由于微通道反应器的体积小，比表面积大，使得在稳定状态下，具有高传热效率，尤其是对于快速强放热反应来说，其优势更明显，传统的间歇量热仪中产生的量热数据无法完全推广到连续流的微反应器中。因此，连续流动条件下的反应量热具有更大的优势。
现有的测量反应热技术中，专利CN114199937A公开了一种超低温反应的量热测试方法及装置，可实现半间歇反应的超低温恒温量热测试。然而，该发明无法实现连续流动反应的量热。专利CN109459161A公开了一种管式反应的量热测试方法及装置，实现了放热、吸热管式反应量热测试，但是其校正过程复杂，计算繁琐。专利CN110988035A公开了一种利用参比量热测试连续流反应热方法及装置，实现了连续流反应过程中反应热的测试，但是其装置结构复杂，且量热过程耗时过长，量热结果与理论值仍存在较大误差。对于微尺度连续量热的典型文献“Characterization of reaction enthalpy and kinetics in a microscale flow platform”，使用微反应芯片测量醋酸酐水解的反应热，测试过程复杂，每次量热前均需要对过程进行矫正，且无法完全消除环境影响，导致误差较大。
发明内容
根据上述提出连续流动条件下的反应热测量困难的技术问题，而提供一种微尺度下动态追踪参比连续量热的装置及方法。本发明主要利用参比量热的方法，有效的消除环境对量热过程的影响。利用动态追踪的方法，高精度地模拟反应吸、放热过程，快速准确地测量出反应热。解决了连续流动条件下的反应热测量困难的技术问题。
本发明采用的技术手段如下：
一种微尺度下动态追踪参比连续量热的装置，包括：
物料进出系统；所述物料进出系统与微尺度连续反应系统相连；所述物料进出系统受中央控制和数据采集系统控制，向微尺度连续反应系统注入物料；
微尺度连续反应系统；所述微尺度连续反应系统中的微通道反应芯片B用以发生物料反应；所述微尺度连续反应系统中的微通道参比芯片A用以模拟微通道反应芯片B中反应的吸放热过程，并间接获得微通道反应芯片B中的吸放热量；
中央控制和数据采集系统；所述中央控制和数据采集系统控制整套装置的运行以及采集吸放热量数据，并根据吸放热量计算出反应热。
进一步地，所述物料进出系统包括注射泵控制器、回收罐A、回收罐B和注射泵，所述注射泵控制器与注射泵相连控制注射泵运行状态和运行参数；
所述注射泵包括第一注射泵A、第二注射泵A、淬灭剂注射泵A、第一注射泵B、第二注射泵B和淬灭剂注射泵B。
进一步地，所述第一注射泵A通过物料预热铝块和物料进出接口A与微通道参比芯片A上的第一进料口A相连，所述第二注射泵A通过物料预热铝块和物料进出接口A与微通道参比芯片A上的第二进料口A相连，所述淬灭剂注射泵A通过物料预热铝块和物料进出接口A与微通道参比芯片A上的淬灭剂进料口A相连，所述回收罐A通过物料预热铝块和物料进出接口A与微通道参比芯片A上的出料口A相连；
所述第一注射泵B通过物料预热铝块和物料进出接口B与微通道参比芯片B上的第一进料口B相连，所述第二注射泵B通过物料预热铝块和物料进出接口B与微通道参比芯片B上的第二进料口B相连，所述淬灭剂注射泵B 通过物料预热铝块和物料进出接口B与微通道参比芯片B上的淬灭剂进料口B相连，所述回收罐B通过物料预热铝块和物料进出接口B与微通道参比芯片B上的出料口B相连。
进一步地，所述微尺度连续反应系统包括由上至下依次设置的可视窗、微通道芯片、加热薄膜、温差发电片和恒温装置；
所述微通道芯片包括前后设置的微通道参比芯片A和微通道反应芯片B，所述微通道参比芯片A和微通道反应芯片B的进、出料口处于同一侧，所述微通道参比芯片A和微通道反应芯片B的通道处于同一侧；
所述可视窗包括物料进出可视窗和通道可视窗，所述物料进出可视窗设置于微通道参比芯片的进、出料口侧上方，所述通道可视窗设置于微通道参比芯片通道侧上方；
所述加热薄膜包括追踪放热反应加热薄膜A和追踪吸热反应加热薄膜B，所述追踪放热反应加热薄膜A设置于微通道参比芯片A下方，所述追踪吸热反应加热薄膜B设置于微通道反应芯片B下方；
所述温差发电片包括温差发电片A和温差发电片B，所述温差发电片A设置于追踪放热反应加热薄膜A下方，所述温差发电片B设置于追踪吸热反应加热薄膜B下方；
所述恒温装置包括物料预热铝块和反应恒温铝块，所述物料预热铝块设置于微通道芯片的进料口侧下方，所述反应恒温铝块设置于微通道芯片的通道口侧下方，所述物料预热铝块相对应微通道参比芯片A和微通道反应芯片B的进料口侧的位置上开设有两个凹槽，所述凹槽内分别设置有物料进出接口块A和物料进出接口块B，所述物料进出接口块A和物料进出接口块B上开设有用以使注射泵的管道通过的通孔。
进一步地，所述中央控制和数据采集系统包括数据采集卡和中央控制及数据采集器，所述可编程直流电源A的正负极分别与追踪放热反应加热薄膜A相连，所述可编程直流电源B的正负极分别与追踪吸热反应加热薄膜B相连，所述数据采集卡分别与温差发电片A和温差发电片B相连，所述中央控制及数据采集器分别与可编程直流电源A、可编程直流电源B、数据采集卡和注射泵控制器相连。
本发明还提供了一种微尺度下动态追踪参比连续量热的方法，基于上述 任一项微尺度下动态追踪参比连续量热的装置实现，包括如下步骤：
向微通道参比芯片A和微通道反应芯片B中以相同的流速同时连续加入物料，通过第一注射泵A和第二注射泵A向微通道参比芯片A中通入单一溶剂，通过第一注射泵B和第二注射泵B向微通道反应芯片B中通入测试反应的原料；
通过淬灭剂注射泵A和淬灭剂注射泵B以相同的流速同时向微通道参比芯片A和微通道反应芯片B中加入淬灭剂，进行淬灭反应；
通过数据采集卡采集温差发电片A的电压信号TEC和温差发电片B的电压信号TER；
对于放热反应，通过可编程直流电源A的输出功率计算追踪放热反应加热薄膜A的发热功率，通过物料在反应芯片中的停留时间计算反应过程的放热量Q，进而计算反应热△H；
对于吸热反应，通过可编程直流电源B的输出功率计算追踪吸热反应加热薄膜B的发热功率，通过物料在反应芯片中的停留时间计算反应过程的放热量Q，进而计算反应热△H。
进一步地，根据反应条件设定物料预热铝块和反应恒温铝块的温度，以恒定的速率升温或降温至目标温度。
进一步地，计算追踪放热反应加热薄膜A的发热功率包括如下步骤：
当初始时TEC>TER，则微通道反应芯片B中进行的是放热反应，改变可编程直流电源A的输出电压控制追踪放热反应加热薄膜A的发热功率，模拟在微通道反应芯片B中放热反应的放热过程，当TEC和TER的差值△Vi趋于时，得到实时的可编程直流电源A的输出电压UPC，从而计算追踪放热反应加热薄膜A的发热功率PA；
当初始时TEC＜TER，则微通道反应芯片B中进行的是吸热反应，通过改变可编程直流电源B的输出电压控制追踪吸热反应加热薄膜B的发热功率，补偿在微通道反应芯片B中吸热反应的吸热量，当TEC和TER差值的绝对值△Vi趋于时，得到实时的可编程直流电源B的输出电压UPR，计算追踪吸热反应加热薄膜B的发热功率PB。
进一步地，发热功率的计算公式如下：

其中，RA为追踪放热反应加热薄膜A的电阻，RB为追踪放热反应加热薄膜B的电阻。
进一步地，反应热△H的计算步骤如下：
据注射泵设定的体积流量计算物料在反应芯片中的停留时间t：
其中，V为微通道参比芯片A和微通道反应芯片B反应通道的体积，qV1为第一注射泵A和第一注射泵B设定的物料的体积流量，qV2为第二注射泵A和第二注射泵B设定的物料的体积流量；
根据加热薄膜的发热功率计算反应过程的吸、放热量Q：
Q＝P×t
其中，当对于放热反应来说P＝PA，对于吸热反应来说P＝PB；
计算反应物的物质的量n：
其中，qV为某一反应物的体积流量，c为某一反应物的物质的量浓度；
反应热△H为：
较现有技术相比，本发明具有以下优点：
本发明装置使用微尺度反应芯片，具有高传质传热效率，可以实现高反应物浓度单反应，同时大大减小了量热过程消耗的物料的量，连续量热相较于间歇量热，反应条件更容易控制，同时提高了过程的安全性，可以实现危险化学反应的量热。
本发明装置同时设置微通道参比芯片A和微通道反应芯片B，两个芯片结构完全相同，反应过程中同时进样，并严格控制流速，消除了环境对量热过程的影响，同时扣除了物料流动带走的热量，获得反应真实的热量变化。
本发明使用中央控制及数据采集器，可以实现对注射泵、体系温度和直流电源的控制，包括通过建立中央控制及数据采集器和注射泵控制器的通讯链接实现在线实时控制注射泵启停、设置流量和设置工作时间；通过建立中央控制及数据采集器和可编程直流电源A、可编程直流电源B的通讯链接实 现直流电源的在线实时控制直流电源的开关、实验过程中动态控制电源输出电压；通过建立中央控制及数据采集器和恒温泵的通讯控制物料预热铝块和反应恒温铝块的温度；同时在线进行数据采集和处理，通过链接中央控制及数据采集器和数据采集卡，实时采集数据采集卡的电压信号。
本发明整个量热过程快速，无需每次量热前矫正，就可以获得准确的量热数据。
通过本发明动态追踪参比量热的测试方法获得的表观结果，可为实现能量转化与传递设计的工程设计，过程安全和工艺优化骑到更加切实有效的指导作用。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图做以简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明结构示意图。
图2为本发明微尺度连续反应系统爆炸图。
图3为本发明微反应芯片结构示意图。
图4为本发明恒温装置结构示意图。
图5为本发明动态追踪参比逻辑图。
图6为本发明实施例一实验结果图。
图7为本发明实施例二实验结果图。
图8为本发明实施例三实验结果图。
图中：11、物料进出可视窗；12、通道可视窗；21、微通道参比芯片A；211、第一进料口A；212、第二进料口A；213、淬灭剂进料口A；214、出料口A；22、微通道反应芯片B；221、第一进料口B；222、第二进料口B；223、淬灭剂进料口B；224、出料口B；31、追踪放热反应加热薄膜A；32、追踪吸热反应加热薄膜B；33、可编程直流电源A；34、可编程直流电源B；4、数据采集卡；41、温差发电片A；42、温差发电片B；51、物料进出接口块A；52、物料进出接口块B；61、物料预热铝块；611、恒温油通道A；62、 反应恒温铝块；621、恒温油通道B；7、注射泵控制器；71、第一注射泵A；72、第二注射泵A；73、淬灭剂注射泵A；74、回收罐A；75、第一注射泵B；76、第二注射泵B；77、淬灭剂注射泵B；78、回收罐B；8、中央控制及数据采集器。
具体实施方式
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
除非另外具体说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本发明的范围。同时，应当清楚，为了便于描述，附图中所示出的各个部分的尺寸并不是按照实际的比例关系绘制的。对于相关领域普通技术人员己知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为授权说明书的一部分。在这里示出和讨论的所有示例中，任向具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它示例可以具有不同的值。应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。
在本发明的描述中，需要理解的是，方位词如“前、后、上、下、左、 右”、“横向、竖向、垂直、水平”和“顶、底”等所指示的方位或位置关系通常是基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，在未作相反说明的情况下，这些方位词并不指示和暗示所指的装置或元件必须具有特定的方位或者以特定的方位构造和操作，因此不能理解为对本发明保护范围的限制：方位词“内、外”是指相对于各部件本身的轮廓的内外。
为了便于描述，在这里可以使用空间相对术语，如“在……之上”、“在……上方”、“在……上表面”、“上面的”等，用来描述如在图中所示的一个器件或特征与其他器件或特征的空间位置关系。应当理解的是，空间相对术语旨在包含除了器件在图中所描述的方位之外的在使用或操作中的不同方位。例如，如果附图中的器件被倒置，则描述为“在其他器件或构造上方”或“在其他器件或构造之上”的器件之后将被定位为“在其他器件或构造下方”或“在其位器件或构造之下”。因而，示例性术语“在……上方”可以包括“在……上方”和“在……下方”两种方位。该器件也可以其他不同方式定位(旋转90度或处于其他方位)，并且对这里所使用的空间相对描述作出相应解释。
此外，需要说明的是，使用“第一”、“第二”等词语来限定零部件，仅仅是为了便于对相应零部件进行区别，如没有另行声明，上述词语并没有特殊含义，因此不能理解为对本发明保护范围的限制。
如图1-4所示，本发明提供了一种微尺度下动态追踪参比连续量热装置，包括物料进出系统、微尺度连续反应系统以及中央控制和数据采集系统。
物料进出系统包括注射泵控制器7，第一注射泵A71，第二注射泵A72，淬灭剂注射泵A73，回收罐A74，第一注射泵B75，第二注射泵B76，淬灭剂注射泵B77，回收罐B78。其中，注射泵控制器7控制系统内所有注射泵的运行状态和运行参数。第一注射泵A71、第二注射泵A72、淬灭剂注射泵A73和回收罐A74通过物料预热铝块61和物料进出接口块A51分别连接在微通道参比芯片A21上的第一进料口A211、第二进料口A212、淬灭剂进料口A213和出料口A214。第一注射泵B75、第二注射泵B76、淬灭剂注射泵B77和回收罐B78通过物料预热快61和物料进出接口块B52分别连接在微通道反应芯片B22上的第一进料口B221、第二进料口B222、淬灭剂进料口B223和出料口B224。
微尺度连续反应系统包括物料进出可视窗11，通道可视窗12，微通道参比芯片A21，微通道反应芯片B22，追踪放热反应加热薄膜A31，追踪吸热反应加热薄膜B32，温差发电片A41，温差发电片B42，物料进出接口块A51，物料进出接口块B52，物料预热铝块61，反应恒温铝块62。按图2依次布置，四周用螺丝固定。其中微通道参比芯片A21和微通道反应芯片B22结构完全相同，追踪放热反应加热薄膜A31和追踪吸热反应加热薄膜B32型号完全相同，温差发电片A41和温差发电片B42为同一型号。
中央控制和数据采集系统包括可编程直流电源A33，可编程直流电源B34，数据采集卡4，中央控制及数据采集器8。其中可编程直流电源A33的正负电极通过电线与追踪放热反应加热薄膜A31相连，可编程直流电源B34的正负电极通过电线与追踪吸热反应加热薄膜B32相连，数据采集卡4与温差发电片A41和温差发电片B42相连。中央控制及数据采集器8通过通讯线与可编程直流电源A33、可编程直流电源B34、数据采集卡4和注射泵控制器7相连。
本发明还提供了一种利用微尺度下动态追踪参比连续量热装置测试连续流反应热方法，包括如下步骤：
微通道参比芯片A21和微通道反应芯片B22结构完全相同，向微通道参比芯片A21和微通道反应芯片B22中以相同的流速同时连续加入物料，其中通过第一注射泵A71和第二注射泵A72向微通道参比芯片A21中通入的物料为单一溶剂，通过第一注射泵B75和第二注射泵B76向微通道反应芯片B22中通入的物料为测试反应的原料，通过淬灭剂注射泵A73和淬灭剂注射泵B77以相同的流速同时向微通道参比芯片A21和微通道反应芯片B22中加入淬灭剂，及时淬灭反应，以保障实验安全。通过控制加料的速度来控制反应的停留时间。通过数据采集卡4收集温差发电片A41和温差发电片B42的电压信号TEC和TER(单位为mV)。温差发电片A41和温差发电片B42为两个相同的型号的温差发电片。对于放热反应来说，通过改变可编程直流电源A33的输出电压控制追踪放热反应加热薄膜A31的发热功率，模拟在微通道反应芯片B22中放热反应的放热过程，当TEC和TER的差值△Vi(单位为mV)趋于0时，得到实时的可编程直流电源A33的输出电压UPC(单位V)，计算追踪放热反应加热薄膜A31的发热功率PA(单位mW)。对于吸热反应 来说，通过改变可编程直流电源B34的输出电压控制追踪吸热反应加热薄膜B32的发热功率，补偿在微通道反应芯片B22中吸热反应的吸热量，当TEC和TER差值的绝对值△Vi(单位为mV)趋于0时，得到实时的可编程直流电源B34的输出电压UPR(单位V)，计算追踪吸热反应加热薄膜B32的发热功率PB(单位mW)。通过物料在反应芯片中的停留时间计算反应过程的吸、放热量Q(单位mJ)，进而计算反应热△H(单位kJ/mol)。
方法具体包括：
(1)装料，选择与第一注射泵B和第二注射泵B中的反应原料比热容相等的溶剂装入三个注射器，分别装在第一注射泵A、第二注射泵A和淬灭剂注射泵A中，将反应原料装入两个注射器，分别装在第一注射泵B和第二注射泵B中，将淬灭剂装入注射器并装在淬灭剂注射泵B中，根据反应条件设定物料预热铝块和反应恒温铝块的温度，以恒定的速率升温或降温至目标温度。
(2)进料，根据反应条件设定注射器进料速度，并控制第一注射泵A和第一注射泵B流速一致，第二注射泵A和第二注射泵B流速一致，淬灭剂注射泵A和淬灭剂注射泵B流速一致，通过加料的速度控制反应的停留时间，通过中央控制系统同时开启注射泵并连续进料，通过数据采集系统实时在线在即反应过程中温差发电片A和温差发电片B的电压信号TEC和TER，设定可编程直流电源A的输出电压UPC和可编程直流电源B的输出电压UPR为0V，等待10分钟至温差发电片A和温差发电片B的电压信号TEC和TER趋于稳定。
(3)动态追踪参比量热，如图5所示，表1为图5中i的值分别为1、2、3、4时所对应的Δi和ΔVi的值。若初始时TEC>TER，则判断微通道反应芯片B中进行的是放热反应，通过改变可编程直流电源A的输出电压控制追踪放热反应加热薄膜A的发热功率，在微通道参比芯片A中模拟微通道反应芯片B中的放热过程，直至TEC和TER差值的绝对值△Vi小于1mV，此时认为追踪放热反应加热薄膜A的发热量即为微通道反应芯片B中反应的放热量，记录此时可编程直流电源A的输出电压UPC，则追踪放热反应加热薄膜A的发热功率PA为：
表1
式中RA为追踪放热反应加热薄膜A的电阻(单位Ω)；
若初始时TEC<TER，则判断微通道反应芯片B中进行的是吸热反应，通过改变可编程直流电源B的输出电压控制追踪吸热反应加热薄膜B的发热功率，补偿在微通道反应芯片B中吸热反应的吸热量，直至TEC和TER差值的绝对值△Vi小于1mV，此时认为追踪吸热反应加热薄膜B的发热量即为微通道反应芯片B中反应的吸热量，记录此时可编程直流电源B的输出电压UPR，则追踪吸热反应加热薄膜B的发热功率PB为：
式中RB为追踪放热反应加热薄膜B的电阻(单位Ω)；
(4)计算反应热，根据注射泵设定的体积流量计算物料在反应芯片中的停留时间t(单位s)：
式中V为微通道参比芯片A和微通道反应芯片B反应通道的体积(单位μl)，qV1为第一注射泵A和第一注射泵B设定的物料的体积流量(单位μl/min)，qV2为第二注射泵A和第二注射泵B设定的物料的体积流量(单位μl/min)。
根据加热薄膜的发热功率(公式(1)、(2))计算反应过程的吸、放热量Q(单位mJ)：
Q＝P×t       (4)
式中，对于放热反应来说P＝PA，对于吸热反应来说P＝PB。
计算反应物的物质的量n(单位mol)：
式中qV为某一反应物的体积流量(单位μl/min)，c为某一反应物的物质的量浓度(单位mol/l)。
则反应过程的摩尔反应热△H(kJ/mol)为：
实施例一
本实施例通过给追踪吸热反应加热薄膜B加热模拟在微通道反应芯片B中的放热反应，以此来验证该装置的准确性，实验结果如图6所示。
在第一进料口A和第一进料口B中以1ml/min速度分别向微通道参比芯片A和微通道反应芯片B中加入水，体系温度为30℃。
首先通过可编辑直流电源B对追踪吸热反应加热薄膜B通入电压UPR＝3.18V，待信号稳定后，逐次增加可编辑直流电源A的输出电压，直至TEC和TER差值的绝对值△Vi小于1mV，记录此时UPC＝3.1773V。误差为0.85％。
实施例二
本实施例以用水将质量分数为96％的浓硫酸稀释至80％为例，对本发明的量热此时方法进行说明，同时进一步通过计算验证方法的准确性。实验结果如图7所示。
第一注射泵A、第二注射泵A、淬灭剂注射泵A、第二注射泵B和淬灭剂注射泵B中均为水，第一注射泵B中为质量分数为96％的浓硫酸，设定qV1＝60μl/min，qV2＝22.15μl/min，体系温度为25℃。
实验步骤
(1)装料，将水装入5个注射器，分别装在第一注射泵A、第二注射泵A、淬灭剂注射泵A、第二注射泵B和淬灭剂注射泵B中，将质量分数为96％的浓硫酸装入注射器别装在第一注射泵B中，设定物料预热铝块和反应恒温铝块的温度为25℃。
(2)进料，根据反应条件设定注射器进料速度，并控制第一注射泵A和第一注射泵B流速一致，qV1＝60μl/min，第二注射泵A和第二注射泵B流速一致，qV2＝22.15μl/min，淬灭剂注射泵A和淬灭剂注射泵B流速一致为100μl/min，通过中央控制系统同时开启注射泵并连续进料，通过数据采集系统实时在线在即反应过程中温差发电片A和温差发电片B的电压信号TEC和TER，设定可编程直流电源A的输出电压UPC和可编程直流电源B的输出电压UPR为0V，等待10分钟至温差发电片A和温差发电片B的电压信号TEC和TER趋于稳定。
(3)动态追踪参比量热，如图5，初始时TEC>TER，判断微通道反应 芯片B中进行的是放热反应，改变可编程直流电源A的输出电压控制追踪放热反应加热薄膜A的发热功率，在微通道参比芯片A中模拟微通道反应芯片B中的放热过程，直至TEC和TER差值的绝对值△Vi小于1mV，记录此时可编程直流电源A的输出电压UPC＝3.6970V，则追踪放热反应加热薄膜A的发热功率PA＝436.246mW。
(4)计算反应热，根据注射泵设定的体积流量计算物料在反应芯片中的停留时间t(单位s)：
计算反应过程的放热量Q(单位mJ)：
Q＝436.246×131.47＝57351.88
计算反应物的物质的量n(单位mol)：
式中qV为某一反应物的体积流量(单位μl/min)，c为某一反应物的物质的量浓度(单位mol/l)。
则反应过程的摩尔反应热△H(kJ/mol)为：
(5)结果验证。查阅文献，浓硫酸质量分数从96％稀释至80％的稀释热为23.69591kJ/mol，本方法获得的稀释热与文献中报道值误差为1.9％。
实施例三
本实施例以苯胺盐酸盐与亚硝酸钠发生的重氮化反应为例，对本发明在快速强放热的危险反应量热中的应用进行说明。实验结果如图8所示。
实验步骤
(1)装料，将水装入4个注射器，分别装在第一注射泵A、第二注射泵A、淬灭剂注射泵A、和淬灭剂注射泵B中，将2.3ml的苯胺和6.5ml的浓盐酸混合后用水定容至250ml，配置成苯胺盐酸盐溶液，装入注射器转载第一注射泵B中，将1.8113g亚硝酸钠用水定容至250ml，配置成亚硝酸钠水溶液，苯胺盐酸盐和亚硝酸钠的摩尔比为1:1.05，定物料预热铝块和反应恒温铝块的温度为0℃。
(2)进料，根据反应条件设定注射器进料速度，并控制第一注射泵A和第一注射泵B流速一致，qV1＝1350μl/min，第二注射泵A和第二注射泵B 流速一致，qV2＝1350μl/min，淬灭剂注射泵A和淬灭剂注射泵B流速一致为1000μl/min，通过中央控制系统同时开启注射泵并连续进料，通过数据采集系统实时在线在即反应过程中温差发电片A和温差发电片B的电压信号TEC和TER，设定可编程直流电源A的输出电压UPC和可编程直流电源B的输出电压UPR为0V，等待10分钟至温差发电片A和温差发电片B的电压信号TEC和TER趋于稳定。
(3)动态追踪参比量热，如图5，初始时TEC>TER，判断微通道反应芯片B中进行的是放热反应，改变可编程直流电源A的输出电压控制追踪放热反应加热薄膜A的发热功率，在微通道参比芯片A中模拟微通道反应芯片B中的放热过程，直至TEC和TER差值的绝对值△Vi小于1mV，记录此时可编程直流电源A的输出电压UPC＝3.6210V，则追踪放热反应加热薄膜A的发热功率PA＝416.415mW.
(4)计算反应热，根据注射泵设定的体积流量计算物料在反应芯片中的停留时间t(单位s)：
计算反应过程的放热量Q(单位mJ)：
Q＝416.415×4＝1665.66
在本实施案例中，量热过程总消耗物料不到20ml，且装置运行安全稳定，信号灵敏性高。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种微尺度下动态追踪参比连续量热的装置，其特征在于，包括：
    物料进出系统；所述物料进出系统与微尺度连续反应系统相连；所述物料进出系统受中央控制和数据采集系统控制，向微尺度连续反应系统注入物料；
    微尺度连续反应系统；所述微尺度连续反应系统中的微通道反应芯片B(22)用以发生物料反应；所述微尺度连续反应系统中的微通道参比芯片A(21)用以模拟微通道反应芯片B中反应的吸放热过程，并间接获得微通道反应芯片B(22)中的吸放热量；
    中央控制和数据采集系统；所述中央控制和数据采集系统控制整套装置的运行以及采集吸放热量数据，并根据吸放热量计算出反应热。
  2. 根据权利要求1所述的微尺度下动态追踪参比连续量热的装置，其特征在于，所述物料进出系统包括注射泵控制器(7)、回收罐A(74)、回收罐B(78)和注射泵，所述注射泵控制器(7)与注射泵相连控制注射泵运行状态和运行参数；
    所述注射泵包括第一注射泵A(71)、第二注射泵A(72)、淬灭剂注射泵A(73)、第一注射泵B(75)、第二注射泵B(76)和淬灭剂注射泵B(77)。
  3. 根据权利要求2所述的微尺度下动态追踪参比连续量热的装置，其特征在于，
    所述第一注射泵A(71)通过物料预热铝块(61)和物料进出接口A(51)与微通道参比芯片A(21)上的第一进料口A(211)相连，所述第二注射泵A(72)通过物料预热铝块(61)和物料进出接口A(51)与微通道参比芯片A(21)上的第二进料口A(212)相连，所述淬灭剂注射泵A(73)通过物料预热铝块(61)和物料进出接口A(51)与微通道参比芯片A(21)上的淬灭剂进料口A(213)相连，所述回收罐A(74)通过物料预热铝块(61)和物料进出接口A(51)与微通道参比芯片A(21)上的出料口A(214)相连；
    所述第一注射泵B(75)通过物料预热铝块(61)和物料进出接口B(52)与微通道参比芯片B(22)上的第一进料口B(221)相连，所述第二注射泵B(76)通过物料预热铝块(61)和物料进出接口B(52)与微通道参比芯片B(22)上的第二进料口B(222)相连，所述淬灭剂注射泵B(77)通过物料预热铝块(61)和物料进出接口B(52)与微通道参比芯片B(22)上的淬灭剂进料口B(223)相连，所述回收罐B(78)通过物料预热铝块(61)和物料进出接口B(52)与微通道参比芯片B(22)上的出料口B(224)相连。
  4. 根据权利要求1所述的微尺度下动态追踪参比连续量热的装置，其特征在于，所 述微尺度连续反应系统包括由上至下依次设置的可视窗、微通道芯片、加热薄膜、温差发电片和恒温装置；
    所述微通道芯片包括前后设置的微通道参比芯片A(21)和微通道反应芯片B(22)，所述微通道参比芯片A(21)和微通道反应芯片B(22)的进、出料口处于同一侧，所述微通道参比芯片A(21)和微通道反应芯片B(22)的通道处于同一侧；
    所述可视窗包括物料进出可视窗(11)和通道可视窗(12)，所述物料进出可视窗(11)设置于微通道参比芯片的进、出料口侧上方，所述通道可视窗(12)设置于微通道参比芯片通道侧上方；
    所述加热薄膜包括追踪放热反应加热薄膜A(31)和追踪吸热反应加热薄膜B(32)，所述追踪放热反应加热薄膜A(31)设置于微通道参比芯片A(21)下方，所述追踪吸热反应加热薄膜B(32)设置于微通道反应芯片B(22)下方；
    所述温差发电片包括温差发电片A(41)和温差发电片B(42)，所述温差发电片A(41)设置于追踪放热反应加热薄膜A(31)下方，所述温差发电片B(42)设置于追踪吸热反应加热薄膜B(32)下方；
    所述恒温装置包括物料预热铝块(61)和反应恒温铝块(62)，所述物料预热铝块(61)设置于微通道芯片的进料口侧下方，所述反应恒温铝块(62)设置于微通道芯片的通道口侧下方，所述物料预热铝块(61)相对应微通道参比芯片A(21)和微通道反应芯片B(22)的进料口侧的位置上开设有两个凹槽，所述凹槽内分别设置有物料进出接口块A(51)和物料进出接口块B(52)，所述物料进出接口块A(51)和物料进出接口块B(52)上开设有用以使注射泵的管道通过的通孔。
  5. 根据权利要求1所述的微尺度下动态追踪参比连续量热的装置，其特征在于，所述中央控制和数据采集系统包括数据采集卡(4)和中央控制及数据采集器(8)，所述可编程直流电源A(33)的正负极分别与追踪放热反应加热薄膜A(31)相连，所述可编程直流电源B(34)的正负极分别与追踪吸热反应加热薄膜B(32)相连，所述数据采集卡(4)分别与温差发电片A(41)和温差发电片B(42)相连，所述中央控制及数据采集器(8)分别与可编程直流电源A(33)、可编程直流电源B(34)、数据采集卡(4)和注射泵控制器(7)相连。
  6. 一种微尺度下动态追踪参比连续量热的方法，基于权利要求1-5中任一项权利要求所述的微尺度下动态追踪参比连续量热的装置实现，其特征在于，包括如下步骤：
    向微通道参比芯片A(21)和微通道反应芯片B(22)中以相同的流速同时连续加入 物料，通过第一注射泵A(71)和第二注射泵A(72)向微通道参比芯片A(21)中通入单一溶剂，通过第一注射泵B(75)和第二注射泵B(76)向微通道反应芯片B(22)中通入测试反应的原料；
    通过淬灭剂注射泵A(73)和淬灭剂注射泵B(77)以相同的流速同时向微通道参比芯片A(21)和微通道反应芯片B(22)中加入淬灭剂，进行淬灭反应；
    通过数据采集卡(4)采集温差发电片A(41)的电压信号TEC和温差发电片B(42)的电压信号TER；
    对于放热反应，通过可编程直流电源A的输出功率计算追踪放热反应加热薄膜A(31)的发热功率，通过物料在反应芯片中的停留时间计算反应过程的放热量Q，进而计算反应热△H；
    对于吸热反应，通过可编程直流电源B的输出功率计算追踪吸热反应加热薄膜B(32)的发热功率，通过物料在反应芯片中的停留时间计算反应过程的放热量Q，进而计算反应热△H。
  7. 根据权利要求6所述的微尺度下动态追踪参比连续量热的方法，其特征在于，根据反应条件设定物料预热铝块(61)和反应恒温铝块(62)的温度，以恒定的速率升温或降温至目标温度。
  8. 根据权利要求7所述的微尺度下动态追踪参比连续量热的方法，其特征在于，计算追踪放热反应加热薄膜A(31)的发热功率包括如下步骤：
    当初始时TEC>TER，则微通道反应芯片B(22)中进行的是放热反应，改变可编程直流电源A(33)的输出电压控制追踪放热反应加热薄膜A(31)的发热功率，模拟在微通道反应芯片B(22)中放热反应的放热过程，当TEC和TER的差值△Vi趋于0时，得到实时的可编程直流电源A(33)的输出电压UPC，从而计算追踪放热反应加热薄膜A(31)的发热功率PA；
    当初始时TEC＜TER，则微通道反应芯片B(22)中进行的是吸热反应，通过改变可编程直流电源B(34)的输出电压控制追踪吸热反应加热薄膜B(32)的发热功率，补偿在微通道反应芯片B(22)中吸热反应的吸热量，当TEC和TER差值的绝对值△Vi趋于0时，得到实时的可编程直流电源B(34)的输出电压UPR，计算追踪吸热反应加热薄膜B(32)的发热功率PB。
  9. 根据权利要求8所述的微尺度下动态追踪参比连续量热的方法，其特征在于，发热功率的计算公式如下：

    其中，RA为追踪放热反应加热薄膜A的电阻，RB为追踪放热反应加热薄膜B的电阻。
  10. 根据权利要求9所述的微尺度下动态追踪参比连续量热的方法，其特征在于，反应热△H的计算步骤如下：
    据注射泵设定的体积流量计算物料在反应芯片中的停留时间t：
    其中，V为微通道参比芯片A和微通道反应芯片B反应通道的体积，qV1为第一注射泵A和第一注射泵B设定的物料的体积流量，qV2为第二注射泵A和第二注射泵B设定的物料的体积流量；
    根据加热薄膜的发热功率计算反应过程的吸、放热量Q：
    Q＝P×t
    其中，当对于放热反应来说P＝PA，对于吸热反应来说P＝PB；
    计算反应物的物质的量n：
    其中，qV为某一反应物的体积流量，c为某一反应物的物质的量浓度；
    反应热△H为：
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