Multi-band mixed light heating program-controlled temperature thermogravimetric reaction system and testing method

Abstract

The present invention discloses a multi-band mixed-light heating programmed temperature thermogravimetric reaction system and a testing method, including: a solar light simulation component for simulating and generating high-intensity light radiation; a frequency modulation component for adjusting the frequency of the light radiation; a light shielding component for regulating the radiation intensity; a thermochemical reaction chamber for providing a reaction site for the sample; a high-precision thermogravimetric component for real-time measurement of the mass change of the sample; a high-precision temperature measurement and control component for real-time measurement of the sample temperature; a crucible pushing component for pushing the crucible; and a gas analysis component for filtering and real-time analysis of the composition and yield of the outlet gas. Based on frequency division technology, high-precision temperature measurement technology, and high-precision thermogravimetric technology, the system can control the light heating temperature under different frequency light heating energy supply conditions, and accurately measure the temperature distribution, mass change, product distribution, and yield in the thermochemical conversion process of the sample in real time, facilitating in-depth study of various thermochemical conversion processes.

Description

Technical Field

[0001] The present invention belongs to the technical field of new energy preparation, and particularly relates to a multi-band mixed light heating program-controlled thermogravimetric reaction system and a testing method thereof. Background Art

[0002] In the past few decades, with the rapid growth of the global population and the improvement of the industrialization level, the energy demand has increased rapidly. The use of a large amount of fossil fuels has caused severe environmental problems. In recent years, China has attached great importance to the global environmental pollution problem and put forward policies such as the "dual carbon strategy". Solar energy is the most important renewable energy, with huge total amount, wide distribution, clean and pollution-free, and can be directly developed and utilized. Coal is still the main energy consumed in China, and its efficient and clean use and low-carbon utilization of resources are important research directions at present. Biomass is considered to be the most promising energy to solve the greenhouse effect. Efficient utilization of this ubiquitous energy can effectively alleviate the increasingly severe environmental problems. Solar gasification technology refers to the process of converting raw materials into high-quality product gas by chemical means under the drive of solar energy, which is one of the important technologies for biomass utilization.

[0003] At present, the biomass and pulverized coal gasification test platforms mainly rely on tube furnaces for heating, which are difficult to simulate the process of solar-driven gasification and have a low heating rate. The temperature measurement mostly uses the furnace body temperature, which has a large deviation from the actual temperature of the sample. The tube furnace cannot accurately measure the mass change of the sample in real time. A few photothermal gravimetric experimental platforms can achieve full-spectrum solar heating, but it is difficult to control the heating rate and ignores the influence of radiation frequency, and cannot realize the coupled heating of single-band or multi-band light radiation. Summary of the Invention

[0004] Aiming at the problems existing in the above-mentioned prior art, the purpose of the present invention is to provide a multi-band mixed light heating program-controlled thermogravimetric reaction system and a testing method thereof.

[0005] To achieve the above purpose, the present invention first provides a multi-band mixed light heating program-controlled thermogravimetric reaction system, including:

[0006] A sunlight simulation component, including a plurality of simulation light sources, which are used to simulate the sun to generate light radiation and gather the light radiation;

[0007] A frequency modulation component, including multi-stage different types of filter films arranged on the optical path. The filter films can transmit light radiation of a specific frequency and reflect light radiation of other frequency bands. By adjusting the light radiation of each simulation light source through the filter films and irradiating the sample with light radiation of different frequency bands at the same time, multi-band light heating is realized;

[0008] A light-shielding component is arranged on the optical path of the light radiation after frequency modulation by a frequency modulation component, and is used to block and reflect part of the light radiation, thereby adjusting the intensity of the light radiation for the reaction.

[0009] A photo-thermal chemical conversion reaction chamber includes a heating furnace body, a reaction chamber, a reaction gas pipeline, and a crucible. The heating furnace body is used for heat preservation and heating of the entire reaction chamber. A light-transmitting window is arranged above the heating furnace body to ensure that light radiation passes through and reaches the sample. The reaction chamber is arranged inside the heating furnace body. The reaction chamber is a sealed quartz tube. After the light radiation enters the reaction chamber, it is focused inside the reaction chamber. The crucible is located at the light radiation focus inside the reaction chamber. The reaction gas pipeline is located above the crucible and is used to provide the reaction gas required for the reaction.

[0010] A high-precision thermogravimetric component includes a support rod, a sealed chamber, and a precision balance. The sealed chamber is connected to the photo-thermal chemical conversion reaction chamber through a flange. A flow meter is arranged on one side of the sealed chamber, and the flow meter is used to control the flow rate of the protective gas entering the sealed chamber. The electronic balance is arranged inside the sealed chamber and is used to measure the mass change of the sample in real time. One end of the support rod is fixed on the electronic balance, and the other end is used to hold the crucible.

[0011] The high-precision temperature measurement and control component includes a temperature measurement thermocouple module and a controller. The temperature measurement thermocouple module is used to detect the reaction temperature of the sample. A light heating control program is input into the controller. The light heating control program includes the heating rate and heating time of different heating segments. The controller is used to adjust the heating temperature in real time according to the set light heating control program and the detected temperature of the sample.

[0012] A gas analysis component includes a gas filtration and cleaning device and a flue gas analysis device. The gas filtration and cleaning device is used to clean and dry impurity gases and corrosive gases to prevent them from entering the flue gas analysis device and causing damage to the device. The flue gas analysis device is an on-line gas component measurement device and is used to measure the component information of the gas in real time and record it.

[0013] As a preferred solution of the present invention, the filter film is a thin film or sheet made of a multi-layer polymer or semiconductor material. The semiconductor material is silicon dioxide, silicon, or titanium dioxide.

[0014] As a preferred solution of the present invention, the light-shielding component is composed of a plurality of light-shielding sheets. The light-shielding component switches light-shielding sheets with different numbers and different light-shielding degrees according to the signal given by the controller to control the light-shielding degree of the light-shielding component, and further finely adjusts the light-shielding degree of a single light-shielding sheet by adjusting the current magnitude of the controller to realize the adjustment of the intensity of the light radiation.

[0015] As a preferred embodiment of the present invention, the reaction chamber includes a high-transmission window quartz tube portion and a laterally placed T-shaped quartz tube portion. The T-shaped quartz tube portion includes a vertical tube section and a horizontal tube section provided on the outer side surface of the vertical tube section. The vertical tube section is disposed inside the heating furnace body, and the horizontal tube section is provided on a channel opened on the side wall of the heating furnace body and is connected to a reaction gas pipeline, a non-contact thermocouple, and an outlet gas pipeline; the high-transmission window quartz tube portion is connected to the upper end of the vertical tube section through a sealing flange.

[0016] As a preferred embodiment of the present invention, the thermogravimetric reaction system of the present invention further includes a crucible pushing assembly, and the crucible pushing assembly includes an electric control pushing clamp and a guide rail. The guide rail is provided on the horizontal tube section of the reaction chamber, and the electric control pushing clamp is provided on the guide rail. The electric control pushing clamp is used to pick up the crucible and perform pushing and retrieval.

[0017] The present invention also provides a thermogravimetric reaction test method based on the above thermogravimetric reaction system, including the following steps:

[0018] 1) Connect each component of the thermogravimetric reaction system. After loading the sample into the crucible, place the crucible on the support rod and set the required optical heating temperature control program in the controller;

[0019] 2) Turn on the high-precision thermogravimetric component, the high-precision temperature measurement and control component, and the gas analysis component to perform real-time data acquisition; turn on the flow meter, and introduce the protective gas from the flow meter; introduce the reaction gas from the reaction gas pipeline; detect other components in the reaction chamber through the flue gas analysis device;

[0020] 3) After waiting for the component information of the gas measured by the flue gas analysis device to remain stable; turn on the optical heating temperature increase program through the controller, and then the sunlight simulation component, the frequency modulation component, and the light shielding component are automatically turned on; the simulation light source of the sunlight simulation component emits converged light radiation, the frequency modulation component filters and frequency-modulates the light radiation through the filter, and the light radiation after filtering and frequency modulation is then adjusted by the light shielding component to adjust the light radiation intensity, and finally focuses on the sample to heat the sample;

[0021] 4) The temperature of the sample rises according to the set program and reacts with the reaction gas; the high-precision thermogravimetric component, the high-precision temperature measurement and control component, and the gas analysis component record the temperature change and mass change data of the sample and the component and flow data of the outlet gas in real time, and transmit them to the controller, and summarize and display them on the liquid crystal display screen.

[0022] Compared with the prior art, the beneficial effects of the present invention are:

[0023] 1) By adjusting the light radiation of different solar light simulation components through multiple frequency modulation components, multi-band light radiation is formed and enters the thermal chemical reaction chamber together to heat the sample, realizing the hybrid heating of multi-band light radiation, which helps to study the influence of the superposition of light radiation in different bands on the endothermic and catalytic effects of thermal chemical reactions.

[0024] 2) By arranging a high-precision thermogravimetric component, the problem of being unable to obtain the sample mass change data in real time during the thermal chemical reaction process is solved.

[0025] 3) By arranging a contact temperature measurement component in the support rod and a non-contact temperature measurement component above the sample, the real-time temperature and temperature distribution of the sample under light heating are measured at multiple points, solving the problem of difficult temperature measurement under light heating and the problem that contact temperature measurement affects high-precision weighing.

[0026] 4) By setting the heating-up program of light heating in the controller, the base values of various control parameters corresponding to different heating times are automatically generated, and based on the measured sample temperature, the control parameters of the solar light simulation component, the light-shielding component, and the frequency modulation component are adjusted in real time, finally realizing the program-controlled temperature of light heating, fundamentally solving the problem that the light heating rate is too fast and difficult to control the temperature, and helping to study the influence of different light heating rate on thermal chemical reactions.

[0027] 5) By arranging a crucible pushing component, the automatic pushing of the crucible at high temperature is realized, solving the problem that traditional thermogravimetry can only place the sample first and then start the slow heating test from room temperature, which helps to study the thermal chemical reactions at different temperatures. Description of the Drawings

[0028] Figure 1 Schematic diagram of the adjustable frequency / multi-band light heating program-controlled thermogravimetric reaction system according to the first embodiment of the present invention;

[0029] In the figure, 1a - the first solar light simulation component, 1b - the second solar light simulation component, 2a - the first frequency modulation component, 2b - the second frequency modulation component, 3a - the first light-shielding component, 3b - the second light-shielding component, 4a - the heating furnace body, 4b - the reaction chamber, 4c - the reaction gas pipeline, 4d - the crucible, 5a - the support rod, 5b - the reflector, 5c - the sealing chamber, 5d - the electronic balance, 6 - the flowmeter, 7a - the first contact thermocouple a, 7b - the second contact thermocouple b, 7c - the third contact thermocouple c, 7d - the non-contact thermocouple, 7e - the controller, 8a - the electric control pushing clamp, 8b - the guide rail, 9 - the sample, 10 - the gas pipeline, 11a - the gas filtration and cleaning device, 11b - the flue gas analysis device. Detailed Embodiments

[0030] The present invention will be further described and explained below in conjunction with specific embodiments. The described embodiments are only examples of the present disclosure and do not delimit the scope of limitation. The technical features of each embodiment of the present invention can be combined accordingly without conflict.

[0031] The present invention realizes multi-band radiation hybrid heating by adjusting the radiation frequency of the frequency modulation component, realizes real-time and accurate measurement of the sample mass by using a high-precision thermogravimetric component, realizes real-time measurement and control of the sample temperature by using a high-precision temperature measurement and control component, and uses a crucible pushing component to send the crucible into the reaction chamber at high temperature, solving the problems of inaccurate temperature measurement and program temperature control, inability to adjust light radiation, and inability to perform multi-band light radiation heating in solar thermochemical conversion tests.

[0032] The present invention provides an adjustable frequency / multi-band light heating program temperature-controlled thermogravimetric reaction system, including: a solar light simulation component, a frequency modulation component, a light shielding component, a thermochemical conversion reaction chamber, a high-precision thermogravimetric component, a high-precision temperature measurement and control component, a crucible pushing component, and a gas analysis component;

[0033] The solar light simulation component is used to generate high-intensity light radiation to simulate highly concentrated solar energy.

[0034] The frequency modulation component is used to adjust the frequency of the light radiation. The light radiation of a specific frequency can pass through the filter and enter the reactor, reflecting the light radiation of other frequency bands. By relying on multiple different filters, the adjustment of the target radiation frequency can be achieved. Multiple frequency modulation components constitute a frequency modulation system. The light radiation of each simulated light source is adjusted through the filter, and the light radiation of different frequency bands is simultaneously irradiated onto the sample to achieve multi-band light heating. The frequency modulation component is composed of multiple filters, and the filter can be a film or sheet made of a multi-layer polymer, semiconductor (silica / silicon / titanium dioxide) material. The frequency modulation component can switch the number and type of filters according to the signal given by the controller, and then adjust the solar-like radiation of a specific frequency band to enter the thermochemical conversion reaction chamber. The way to switch the filter is an electronically controlled turntable type.

[0035] The light shielding component is used to block and reflect part of the light radiation, and then adjust the intensity of the light beam entering the thermochemical reaction chamber according to the requirement.

[0036] The thermochemical reaction chamber includes a heating furnace body, a reaction chamber, a reaction gas pipeline, and a crucible; the heating furnace body is used for heat preservation and heating of the entire reaction chamber; the reaction chamber is a sealed quartz tube for realizing the sealing of the entire device; the reaction gas pipeline is located above the crucible and is used to provide the reaction gas required by the reaction chamber; the crucible is used to store the sample and is located near the focus of the light radiation.

[0037] The high-precision thermogravimetric component includes a support rod, a reflector, a sealed cavity and an electronic balance. The support rod is used to support the crucible and is connected to the electronic balance; the reflector is used to reflect light radiation; the electronic balance is used to measure the mass change of the sample in real time; the electronic balance is placed in the sealed cavity, and the sealed cavity is connected to the thermochemical conversion reaction chamber through a flange.

[0038] The high-precision temperature measurement and control component includes a first contact thermocouple, a second contact thermocouple, a third contact thermocouple, a non-contact thermocouple and a controller. The three contact thermocouples are located in the center of the support rod, and the upper ends are inserted into the sample through the holes under the crucible; the non-contact thermocouple is located above the surface of the sample; the light heating program temperature control is adjusted by the controller according to the set heating program and the sample temperature obtained by feedback, and adjusts 7 control parameters to control the real-time light heating power, the focus of the light spot and the uniformity of the light spot.

[0039] The crucible pushing component includes an electric control pushing clamp and a guide rail for fixing the position. The electric control pushing clamp is used to pick up the crucible and push it into the reaction chamber, and returns after being placed at the designated position on the weighing platform of the balance. The guide rail is used to fix the route for the pushing clamp to enter.

[0040] The gas analysis component includes a gas filtration and cleaning device and a flue gas analysis device. The gas filtration and cleaning device is used to clean and dry the impurity gas and corrosive gas to prevent it from entering the flue gas analysis device and causing damage to the device. The flue gas analysis device is a professional on-line gas component measurement device, which can measure the component information of the gas in real time and record it.

[0041] The light-shielding component is composed of multiple light-shielding sheets; the light-shielding component controls the light-shielding degree of the light-shielding component by electrically controlling different numbers and different light-shielding degrees of the light-shielding sheets according to the signal given by the controller, and can further finely adjust the light-shielding degree of a single electrically controlled light-shielding sheet by adjusting the current magnitude, so as to achieve high-precision adjustment of the intensity of the solar-like radiation entering the photo-thermal chemical reaction chamber.

[0042] There is a high-transmission window above the thermochemical conversion reaction chamber to ensure that the high-intensity radiation passes through and reaches the sample; above the thermochemical conversion reaction chamber, two sections of quartz tubes are connected, including the high-transmission window quartz tube part and the lower T-shaped quartz tube. The two are connected by a sealed flange, and the high-transmission quartz tube part is easy to disassemble and replace.

[0043] The thermochemical reaction chamber is designed as a T-shaped quartz tube and is placed vertically. There are openings on the upper, lower and right sides and are sealed by flanges. The right side is connected to the reaction gas pipeline, the non-contact thermocouple and the outlet gas pipeline.

[0044] The core reaction zone of the thermochemical reaction chamber should preferably be arranged in the middle position, more than 5 cm away from the detachable high-transparency quartz tube above, and more than 10 cm away from the sealed chamber for placing the electronic balance below; the crucible containing the sample is placed circularly in the core reaction zone.

[0045] The crucible includes, but is not limited to, ceramics, alumina, and aluminum crucibles, and the shape is not limited to circular or square.

[0046] The quartz tube of the thermochemical reaction chamber is wrapped by an electric heating furnace body for the purpose of heat preservation and heating, and the heating devices include, but are not limited to, resistance wires, silicon carbide rods, silicon molybdenum rods, etc.

[0047] The samples include, but are not limited to, carbon-containing samples such as pulverized coal, biomass powder, and garbage powder, and the biomass powder includes, but is not limited to, bamboo, rice husk, wheat straw, bagasse, pine powder, chestnut shell, corn cob, etc.

[0048] The reaction gases used in the thermochemical conversion reaction chamber include, but are not limited to, carbon dioxide, oxygen, nitrogen, argon, water vapor, etc.

[0049] The main chemical reaction equations occurring in the thermochemical conversion reaction chamber are 2C(s)+H2O(g)→2CO(g)+H2(s) and 2C(s)+CO2(g)→2CO(g).

[0050] The photocatalysts include, but are not limited to, SrTiO3, TiO2, ZnS, CdS, Ru, Pt, Ni, Co, and their composites.

[0051] The gasification catalysts include, but are not limited to, K2CO3, Na2CO3, KCl, NaCl, and their composites.

[0052] The support rod includes upper and lower parts. The upper part supports the crucible and wraps the thermocouple; the lower part has a reflective platform and a base connected to the balance. The upper surface of the reflective platform is made of a high-reflectivity mirror material, which plays a role in reflecting light radiation, can protect the balance below and recycle energy, and the lower surface is a circuit board connected to the thermocouple data; the upper and lower surfaces of the support rod are connected by electrical sockets. The sealed chamber can be a front-opening sealed chamber made of stainless steel, with a circular hole above connected to the thermochemical conversion reaction chamber, circuit boards connected to the control are arranged on both sides, and data lines and power lines are connected to the outside of the sealed chamber through interfaces, and an air inlet is arranged.

[0053] The high-precision balance includes, but is not limited to, electronic balances or mechanical balances from manufacturers such as Mettler Toledo, Sartorius, Beijing Hengjiu, and Changshu Shuangjie, and the accuracy range is from one-thousandth of a gram to one-ten-millionth of a gram.

[0054] The first contact temperature-measuring thermocouple, the second contact temperature-measuring thermocouple, and the third contact temperature-measuring thermocouple are located inside the support rod, protruding from the support platform above and inserted into the crucible from the bottom. The number of thermocouples is 3; the three contact thermocouples (a, b, c) are respectively inserted from the left edge, the center, and the right edge at the bottom of the circular crucible (4d). The insertion points on the left and right sides are equidistant from the center and the connecting line passes through the center of the circle to achieve multi-point temperature measurement; the contact thermocouples a and c symmetrically arranged on both sides of the sample are used to determine whether the solar-like radiation focus is aligned with the center of the sample, and the contact thermocouple b arranged at the center of the sample is used together with the contact thermocouples a and c on both sides of the sample to measure the uniformity of the solar-like radiation spot. The lower parts of the three contact temperature-measuring thermocouples (a, b, c) are connected to the reflector through sockets. The circuit board is arranged on the lower surface of the reflector and connected to the circuit board on the side of the sealed cavity through thin copper wires to reduce the influence on weighing while achieving high-precision temperature measurement. The thermocouple of the non-contact temperature-measuring component is located above the crucible. The temperature-measuring head is obliquely inserted above the raw material at a certain angle, and the tail passes through the flange and is connected to the controller for correcting the measured value of the sample temperature.

[0055] Thermocouples include but are not limited to K-type, J-type, T-type, E-type, N-type, S-type, B-type and other thermocouples. The materials used for thermocouples include but are not limited to platinum, rhodium, copper, nickel, chromium, iron, silicon, magnesium, etc.

[0056] There are a total of 7 regulation parameters for the light heating program temperature control, including 4 regulation parameters for the solar light simulation components: output power, focal length, height, and irradiation angle; 2 regulation parameters for the light shielding components: the number of light shielding sheets and the light shielding degree; and 2 regulation parameters for the filtering components: the number and type of filter sheets.

[0057] The shape of the electric control push clamp can be a square or circular clamp, or a square or circular pusher. The materials can be high-temperature resistant materials such as alumina ceramics, ordinary ceramics, steel, molybdenum, tungsten, etc.

[0058] The guide rail can be a sliding guide rail, a rolling guide rail, a gas guide rail, a magnetic levitation guide rail, etc. The materials can be high-temperature resistant materials such as alumina ceramics, ordinary ceramics, steel, molybdenum, tungsten materials, etc.

[0059] The gas filtration and cleaning device consists of seven-stage gas washing and filtration, which are water washing, acid washing, alkali washing, organic solvent cleaning, water washing, adsorption, and drying in sequence; the flue gas analysis device is an infrared flue gas analyzer and an on-line gas chromatograph.

[0060] Example 1

[0061] As Figure 1As shown, in the first exemplary embodiment of the present invention, an adjustable frequency / multi-band optical heating program-controlled thermogravimetric reaction system is provided, including a first sunlight simulation component 1a, a second sunlight simulation component 1b, a first frequency modulation component 2a, a second frequency modulation component 2b, a first light shielding component 3a, a second light shielding component 3b, a heating furnace body 4a, a reaction chamber 4b, a reaction gas pipeline 4c, a crucible 4d, a support rod 5a, a reflector 5b, a sealing chamber 5c, an electronic balance 5d, a flow meter 6, a first contact thermocouple 7a, a second contact thermocouple 7b, a third contact thermocouple 7c, a non-contact thermocouple 7d, a controller 7e, an electrically controlled push clamp 8a, a guide rail 8b, a sample 9, a gas pipeline 10, a gas filtration and cleaning device 11a, and a flue gas analysis device 1b.

[0062] The sunlight simulation component preferably uses 2 xenon lamp simulation light sources, which are technically mature and have stable light source intensity, and are used to generate high-intensity light radiation to the frequency modulation component. The simulation light source is fixed and supported by a steel frame, and the height, angle, power, and focal length of the simulation light source can be electrically controlled.

[0063] The frequency modulation component preferably selects a nano-film stacked with multi-layer polymer or semiconductor such as Si / TiO2 / SiO2. It is technically mature, and the frequency modulation range is multiple ranges such as 800 - 1100nm, 400 - 800nm, 200 - 400nm, above 1100nm, and full spectrum, and the required filter can be switched through an electrically controlled turntable.

[0064] In this embodiment, the heating furnace body preferably uses a customized tube furnace heated by a resistance wire, which has stable performance, mature program-controlled temperature technology, and excellent heat preservation performance.

[0065] The reaction chamber is composed of a high-transmittance quartz window and a T-shaped reaction tube, and preferably uses a customized quartz material, which has the advantages of mature technology, good performance, high temperature resistance, and low price.

[0066] The core reaction area of the photo-thermal chemical reaction chamber should preferably be arranged in the middle position, maintaining a distance of more than 5CM from the detachable high-transmittance quartz tube above and a distance of more than 10CM from the sealing chamber below; the crucible containing the sample is circular and placed in the core reaction area.

[0067] The crucible uses a customized circular alumina crucible, which matches the size of the high-intensity radiation spot, can withstand a high temperature of 1600°C, and is inexpensive. Three holes are opened at the bottom of the crucible, one hole is located at the center of the crucible bottom, and the other two are located at the edge of the crucible bottom, and the three holes are on the same straight line;

[0068] In this embodiment, the sample uses wheat straw powder screened through a 100-mesh sieve.

[0069] The support rod adopts a customized ceramic structure, which is rigid and can wrap the thermocouple, has high temperature resistance and low cost, and a small platform is designed at the top to facilitate the support of the crucible.

[0070] The lower part base of the support rod adopts a customized plastic base, one end is fixedly matched with the weighing pan of the electronic balance, and the other end is fixedly connected with the reflector structure through a plug-in type.

[0071] The reflector is made of plastic material, can be connected with the base through a plug-in type below, the upper surface is wrapped with aluminum foil for reflection, and the thermocouple power supply and data connection are arranged on the lower surface.

[0072] The electronic balance adopts a Mettler Toledo one in a hundred thousandth electronic balance, which has good stability and high precision, and can provide high-precision thermogravimetric measurement.

[0073] The sealed chamber adopts a customized stainless steel sealed chamber, there is a movable interface on the upper surface which is connected to the quartz tube through a flange, and a window is arranged in the front to monitor the situation of the balance and the reflector.

[0074] The high-precision temperature measurement and control component consists of a first contact thermocouple, a second contact thermocouple, a third contact thermocouple, a non-contact thermocouple and a controller. The contact thermocouples and the non-contact thermocouple select armored K-type thermocouples, which can measure the temperature from -200 to 1300 °C and have low cost.

[0075] The controller selects a customized commercial controller and system supporting the tube furnace, which can control the solar light simulation component, the frequency modulation component and the light shielding component at the same time, can program control the heating rate of the light heating, can record the temperature data of the thermocouple and the mass data of the electronic balance in real time. The controller can determine the base value of the required regulation parameters according to the set heating program, and can correct the regulation parameters in real time based on the measured sample temperature to realize program temperature control under light heating.

[0076] The crucible pushing mechanism adopts a temperature-resistant pushing clamp, and the pushing clamp sends the crucible to the designated position of the weighing platform in the furnace according to the set guide rail and returns.

[0077] The flowmeter is an Alicat mass flowmeter from the United States, which has high precision and good stability.

[0078] The reaction gas pipeline is a customized stainless steel pipeline for the transmission of water vapor and has a low price.

[0079] The gas washing and filtering device selects a commercial gas washing device, which is successively water washing, secondary water washing, acid washing, alkali washing, organic solvent cleaning, water washing, activated carbon adsorption and discolored silica gel drying to prevent tar, acid / alkaline gases from entering the flue gas analyzer.

[0080] A test method for a multi-band mixed-light heating programmed temperature-controlled thermogravimetric reaction system, comprising the following steps:

[0081] 1) Turn on and connect each component of the multi-band mixed-light heating programmed temperature-controlled thermogravimetric reaction system. Load the sample 9 into the crucible 4d. Turn on the flowmeter 6, introduce the reaction gas and the protective gas, and wait until the atmosphere data measured by the flue gas analysis device remains stable. Set the required light heating temperature control program in the controller 7e.

[0082] 2) Turn on the real-time data acquisition of the high-precision thermogravimetric component 5, the high-precision temperature measurement and temperature control component 7, and the gas analysis component 11 on the controller 7e.

[0083] 3) Turn on the light heating temperature increase program through the controller 7e (heat to 900 °C at a heating rate of 30 K / min and hold for 30 minutes). Subsequently, the solar light simulation component 1, the frequency modulation component 2, and the light shielding component 3 are automatically turned on, and the multi-band mixed solar-like radiation intensity entering the thermochemical reaction chamber 4 is actually regulated according to the light heating temperature increase program and the measured sample temperature.

[0084] 4) The temperature of the sample 9 rises according to the set program and reacts with the reaction gas. The high-precision thermogravimetric component, the high-precision temperature measurement and temperature control component, and the gas analysis component record the temperature change and mass change data of the sample, as well as the component and flow data of the outlet gas in real time, and transmit them to the controller 7e for summary display on the liquid crystal display screen.

[0085] The above embodiments only represent several implementation manners of the present invention. The description is relatively specific and detailed, but it should not be construed as a limitation to the scope of the patent of the present invention. For those of ordinary skill in the art, without departing from the concept of the present invention, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention.

Claims

1. A multi-band mixed-light heating programmed temperature-controlled thermogravimetric reaction system, characterized in that, Comprising: A sunlight simulation component, including a plurality of simulation light sources, which are used to simulate the sun to generate light radiation and converge the light radiation; A frequency modulation component, including multiple levels of different types of filter plates arranged on the light path. The filter plates can transmit light radiation of a specific frequency and reflect light radiation in other frequency bands. By adjusting the light radiation of each simulation light source through the filter plates and irradiating the sample with light radiation in different frequency bands simultaneously, multi-band light heating is achieved; A light shielding component, arranged on the light path of the light radiation after frequency modulation by the frequency modulation component, used to block and reflect part of the light radiation, thereby adjusting the light radiation intensity for the reaction; A photo-thermal chemical conversion reaction chamber, including a heating furnace body (4a), a reaction chamber (4b), a reaction gas pipeline (4c), and a crucible (4d). The heating furnace body (4a) is used for heat preservation and heating of the entire reaction chamber. A light-transmitting window is arranged above the heating furnace body (4a) to ensure that the light radiation passes through and reaches the sample; The reaction chamber (4b) is arranged inside the heating furnace body (4a). The reaction chamber (4b) is a sealed quartz tube. After the light radiation enters the reaction chamber (4b), it is focused inside the reaction chamber (4b). The crucible (4d) is located at the light radiation focus inside the reaction chamber (4b), and the reaction gas pipeline (4c) is located above the crucible, used to provide the reaction gas required for the reaction; A high-precision thermogravimetric component, including a support rod (5a), a sealed chamber (5c), and an electronic balance (5d); The sealed chamber (5c) is connected to the photo-thermal chemical conversion reaction chamber (4) through a flange. A flow meter (6) is arranged on one side of the sealed chamber (5c), and the flow meter (6) is used to control the flow rate of the protective gas entering the sealed chamber (5c); The electronic balance (5d) is arranged inside the sealed chamber (5c) to measure the mass change of the sample in real time; One end of the support rod (5a) is fixed on the electronic balance (5d), and the other end is used to hold the crucible; A high-precision temperature measurement and control component, including a temperature measurement thermocouple module and a controller (7e). The temperature measurement thermocouple module is used to detect the reaction temperature of the sample. The light heating temperature control program is input into the controller (7e), and the light heating temperature control program includes the heating rate and heating time of different heating sections; The controller (7e) is used to adjust the heating temperature in real time according to the set light heating temperature control program and the detected temperature of the sample; A gas analysis component, including a gas filtration and cleaning device (11a) and a flue gas analysis device (11b); The gas filtration and cleaning device (11a) is used to clean and dry impurity gases and corrosive gases to prevent them from entering the flue gas analysis device (11b) and causing damage to the device; The flue gas analysis device (11b) is an on-line gas component measurement device, used to measure the component information of the gas in real time and record it.

2. The thermogravimetric reaction system according to claim 1, characterized in that The filter plate is a thin film or sheet made of a multi-layer polymer or semiconductor material; The semiconductor material is silicon dioxide, silicon, or titanium dioxide.

3. The thermogravimetric reaction system according to claim 1, wherein, The light-shielding component is composed of multiple light-shielding sheets; the light-shielding component switches different numbers and different light-shielding degrees of light-shielding sheets according to the signal given by the controller (7e) to control the light-shielding degree of the light-shielding component (3), and further finely adjusts the light-shielding degree of a single light-shielding sheet by adjusting the current magnitude by the controller (7e), so as to realize the adjustment of the intensity of light radiation.

4. The thermogravimetric reaction system according to claim 1, characterized in that, The reaction chamber (4b) includes a high-transmission window quartz tube part and a laterally placed T-shaped quartz tube part. The T-shaped quartz tube part includes a vertical tube section and a horizontal tube section arranged on the outer side surface of the vertical tube section. The vertical tube section is arranged inside the heating furnace body (4a), and the horizontal tube section is arranged on a channel opened on the side wall of the heating furnace body (4a) and is connected to the reaction gas pipeline (4c), the non-contact thermocouple (7d) and the gas outlet pipeline; the high-transmission window quartz tube part is connected to the upper end of the vertical tube section through a sealing flange.

5. The thermogravimetric reaction system according to claim 4, characterized in that, It further includes a crucible pushing component. The crucible pushing component includes an electric control pushing clamp (8a) and a guide rail (8b). The guide rail (8b) is arranged on the horizontal tube section of the reaction chamber (4b), and the electric control pushing clamp (8a) is arranged on the guide rail. The electric control pushing clamp (8a) is used to pick up the crucible (4d) and perform pushing and retrieving.

6. The thermogravimetric reaction system according to claim 1, characterized in that, The temperature-measuring thermocouple module includes a non-contact thermocouple (7d) and a first contact-type temperature-measuring thermocouple (7a), a second contact-type temperature-measuring thermocouple (7b) and a third contact-type temperature-measuring thermocouple (7c) arranged inside the support rod (5a); three holes are opened at the bottom of the crucible (4d). One hole is located at the center of the bottom of the crucible (4d), and the other two are located at the bottom edge of the crucible (4d), and the three holes are on the same straight line; the first contact-type temperature-measuring thermocouple (7a), the second contact-type temperature-measuring thermocouple (7b) and the third contact-type temperature-measuring thermocouple (7c) are inserted into the sample from the holes at the bottom of the crucible (4d); the non-contact thermocouple (7d) is located above the sample; the controller (7e) controls the real-time heating temperature by adjusting the control parameters; the control parameters include the output power, focal length, height and irradiation angle of the simulated light source, the number and light-shielding degree of the light-shielding sheets, and the number and types of the filter sheets.

7. The thermogravimetric reaction system according to claim 6, wherein The thermogravimetric reaction system controls the temperature through the following steps: 1) Set the base values of the control parameters corresponding to different heating times in the controller (7e) according to the reaction process. 2) Turn on the controller (7e), and then turn on the sunlight simulation component, the frequency modulation component and the light-shielding component (3); the controller (7e) controls each control parameter changing with time according to the set program. 3) Four temperature data of the sample are measured in real time by the high-precision temperature measurement and control component and fed back to the controller (7e); the controller (7e) regulates the adjustment parameters according to the real-time progress of the reaction. Among them, by adjusting three regulation parameters of the focal length, height and irradiation angle of the sunlight simulation component, it is ensured that the light radiation spot is aligned with the center of the sample and has a high uniformity. By adjusting five regulation parameters of the power of the sunlight simulation component, the number and shading degree of the shading sheets of the shading component, and the number and type of the filter sheets of the filtering component, the temperature control error caused by different samples, different use environments and equipment loss factors is corrected.

8. The thermogravimetric reaction system according to claim 1, characterized in that, The support rod (5a) includes two parts, the upper part supports the crucible (4d) and wraps the thermocouple; the lower part has a reflector (5b) and a base connected to the balance. The upper surface of the reflector (5b) is made of a high-reflectivity mirror material, which plays a role in reflecting light-like radiation, protects the balance below and recycles energy, and the lower surface is provided with a circuit board for thermocouple data connection; The upper and lower parts of the support rod (5a) are connected by an electrical socket to ensure data connection and detachable replacement; there is a circular hole above the sealed cavity (5c) for sealing connection with the thermochemical conversion reaction chamber. Circuit boards connected to the controller (7e) are arranged on both sides of the sealed cavity (5c), and a protective gas inlet connected to the flowmeter (6) is provided on the sealed cavity (5c).

9. The thermogravimetric reaction system according to claim 1, characterized in that, The gas filtration and cleaning device (11a) consists of seven-stage washing and filtration, which are water washing, acid washing, alkali washing, organic solvent cleaning, water washing, adsorption and drying in sequence; the flue gas analysis device (11b) includes an infrared flue gas analyzer and an on-line gas chromatograph.

10. A thermogravimetric reaction test method based on the thermogravimetric reaction system described in claim 1, characterized in that, It includes the following steps: 1) Install each component of the thermogravimetric reaction system. After loading the sample (9) into the crucible (4d), place the crucible (4d) on the support rod (5a) and set the required light heating and temperature control program in the controller (7e); 2) Turn on the high-precision thermogravimetric component, the high-precision temperature measurement and control component and the gas analysis component to collect real-time data; turn on the flowmeter (6), and introduce the protective gas from the flowmeter (6); introduce the reaction gas from the reaction gas pipeline (4c); detect other components in the reaction chamber (4b) through the flue gas analysis device (11b); 3) After waiting for the component information of the gas measured by the flue gas analysis device (11b) to remain stable; turn on the light heating and temperature rising program through the controller, and then the sunlight simulation component, the frequency modulation component and the shading component are automatically turned on; the simulation light source of the sunlight simulation component emits converged light radiation, the frequency modulation component filters and frequency-modulates the light radiation through the filter sheet, and the light radiation after filtering and frequency modulation is then adjusted in light radiation intensity through the shading component. After the light radiation adjusts the radiation intensity, it passes through the light-transmitting window arranged above the heating furnace body (4a) and finally focuses on the sample to heat the sample; 4) The temperature of the sample rises according to the set program and reacts with the reaction gas; the high-precision thermogravimetric component, the high-precision temperature measurement and control component, and the gas analysis component record the temperature change and mass change data of the sample and the component and flow data of the outlet gas in real time, and transmit them to the controller, which are summarized and displayed on the display screen of the controller.

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