CN112697832B - In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and use method - Google Patents
In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and use method Download PDFInfo
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Abstract
The invention discloses an in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and a use method thereof, wherein the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform consists of two parts, namely a gas distribution system device and an in-situ reaction tank device; the air distribution system device consists of an external steel cylinder, a pressure reducer, a filter, a needle valve, an electronic pressure gauge, a mass flowmeter, a one-way valve, an unloading valve, a temperature measuring point, a ball valve and a back pressure valve, and is assisted with a display panel for accurate control and real-time switching; the in-situ reaction tank device consists of a double-layer glass sleeve, a light source and a resonant cavity of the electron paramagnetic resonance spectrometer. The platform is simple to operate and convenient to detach, can operate based on the original electron paramagnetic resonance instrument, realizes the experimental conditions of in-situ (reaction temperature is less than or equal to 250 ℃) and quasi-in-situ (reaction temperature is more than 250 ℃) illumination or heating, and can realize the reaction system pressure of <10Mpa.
Description
Technical Field
The invention relates to the technical field of paramagnetic resonance, in particular to an in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and a use method thereof.
Background
The electron paramagnetic resonance spectrometer can provide atomic and electronic scale information, so that the electron paramagnetic resonance spectrometer has great help in understanding the reaction process, and can provide more reaction information under in-situ conditions if the existing electron paramagnetic resonance spectrometer is transformed into an in-situ device. Under the state of the art of the prior art, electron paramagnetic resonance spectroscopy can only meet the test conditions in an air atmosphere and at lower temperature, and has a defect for in-situ reaction tests at high temperature, high pressure and gas mobile phase.
For electron paramagnetic resonance testing, there is still some technical blank such as: 1. the daily test is usually a test under an air atmosphere condition, and the test requiring a specific atmosphere condition cannot meet the requirement; 2. when testing under specific atmosphere conditions, only normal-pressure operation can be realized, and impurities such as air, water and the like are easy to mix in a testing system, so that an accurate testing result cannot be obtained; 3. if the system needs to be heated in the in-situ reaction process, the existing instrument conditions only meet the lower reaction temperature, and the system exceeding the upper limit of the reaction temperature of the instrument cannot be tested; 4. when testing under specific atmosphere conditions, the conditions of gas flow testing cannot be met, so that the gas and a sample to be tested are not in uniform contact, and the gas components cannot be accurately controlled, so that the expected test effect cannot be achieved.
Disclosure of Invention
The technical problems to be solved are as follows:
the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform constructed by the invention is used for supplementing and perfecting the existing instrument platform, so that the existing electron paramagnetic resonance spectrometer has in-situ (the temperature is less than or equal to 250 ℃) and quasi-in-situ (the temperature is more than 250 ℃) heterogeneous catalysis (one or more reaction gases, and the reaction pressure is less than 10 MPa) testing functions. The in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform is built to provide powerful support for exploring the research of the active site of the catalyst under in-situ experiment or working condition (such as the valence state change of paramagnetic active metal, the generation and quenching of oxygen vacancies, etc.).
The technical scheme is as follows:
an in-situ and quasi-in-situ heterogeneous catalytic electron paramagnetic resonance platform has two modes, namely in-situ test and quasi-in-situ test. The heterogeneous catalysis electron paramagnetic resonance platform in the in-situ test mode consists of a gas distribution system device and an in-situ reaction tank device, wherein the gas distribution system device consists of a plurality of groups of gas inlet pipelines, a group of total path unloading valves, an electron pressure gauge, a temperature measuring point and a group of exhaust pipelines, each group of gas inlet pipelines consists of a gas metering device and a one-way valve, wherein the gas metering device is externally connected with a steel bottle, a pressure reducer, a filter, a needle valve, a ball valve, the electron pressure gauge, a mass flowmeter or a rotameter and the like, and the exhaust pipe consists of the temperature measuring point, a back pressure valve and an exhaust pipeline; the in-situ reaction tank device consists of two ball valves or needle valves, a filter, a double-layer glass sleeve, an external light source and an electron paramagnetic resonance spectrometer resonant cavity. The heterogeneous catalysis electron paramagnetic resonance platform in the quasi-in-situ test mode is composed of a gas distribution system device and a quasi-in-situ reaction tank device, wherein the gas distribution system device is the same as the gas distribution system device in the in-situ test mode, and the reaction tank device is composed of two ball valves or needle valves, a filter, a double-layer glass sleeve, a temperature measuring point and a reaction furnace capable of carrying out illumination/heating.
As a preferred technical scheme of the invention: each of the multiple groups of air inlet pipelines is respectively filled with reaction gas (pure gas or mixed gas) required by multiphase catalytic reaction, the reaction gas is provided by an external steel bottle, the partial pressure of the steel bottle is regulated by a pressure reducer, the system pressure is regulated by a back pressure valve, tiny particles in the gas are removed by a filter to protect a gas metering device such as a mass flowmeter or a rotameter, and a needle valve is connected to slowly regulate the flow rate of the gas entering the gas metering device such as the mass flowmeter or the rotameter so as to avoid the damage of the gas metering device such as the mass flowmeter or the rotameter caused by the impact of atmospheric gas; the needle valve is connected with an electronic pressure gauge to accurately measure the pressure entering a gas metering device such as a mass flowmeter or a rotameter, the gas flow passing through a gas path is regulated and controlled through the gas metering device such as the mass flowmeter or the rotameter, and a one-way valve is additionally arranged to control the direction of the gas flow so as to prevent the pollution or inaccurate gas distribution of the gas path caused by back mixing of reaction gas.
As a preferred technical scheme of the invention: each path of the multi-group air inlet pipeline can regulate and control a mass flowmeter or a rotameter and other gas metering devices through a display panel, a computer terminal or an operation panel of an instrument of the air distribution system, so that the accurate control of the flow of gas components is realized. The air intake lines may be one or more groups.
As a preferred technical scheme of the invention: the multiple groups of air inlet pipelines are summarized in a group of total pipelines, wherein the unloading valve is used for preventing risks caused by overhigh system pressure, the back pressure valve is used for adjusting the system pressure, and the electronic pressure gauge is used for measuring the system pressure.
As a preferred technical scheme of the invention: the reaction tank device is connected with a group of exhaust pipelines, and has the functions of exhausting the reacted gas and regulating the system pressure. If the operation is normal pressure operation, the back pressure valve is regulated to be in a normal pressure state; if the pressurizing operation is needed, the back pressure valve is regulated until the system reaches the required reaction pressure.
As a preferred technical scheme of the invention: the in-situ reaction tank device is connected to the air inlet pipe main passage and then is arranged in the resonant cavity of the electron paramagnetic resonance spectrometer, and an external light source is arranged to meet the requirements of in-situ multiphase photocatalytic reaction; two ball valves or needle valves are used to ensure an internal sealed environment when the reaction cells are independent. The reaction tank is a double-layer glass sleeve, quartz is selected as a material, and the outer diameter is designed according to the inner diameter of the cavity. If higher reaction pressure is needed, the wall thickness of the quartz reaction tank needs to be increased. The reaction gas can flow in from the sleeve outer tube, and after fully contacting with the catalyst, flows out of the system through the small-diameter quartz tube at the inner side of the double-layer sleeve, or flows into the reaction tank through the small-diameter quartz tube at the inner side of the double-layer sleeve, and after fully contacting with the catalyst, flows out of the system from the sleeve outer tube. Heating gas can be introduced into the lower part of the reaction tank to heat the reaction, and the temperature can reach 250 ℃ at most.
As a preferred technical scheme of the invention: and the quasi-in-situ reaction tank device is connected with the air inlet pipe main passage and then performs quasi-in-situ reaction outside the electron paramagnetic resonance spectrometer. The quasi-in-situ reaction tank is a double-layer glass sleeve, quartz is selected as a material, the outer diameter of the quartz is designed according to the inner diameter of a cavity, the quartz is used for a reaction system with the reaction temperature higher than 250 ℃, after quasi-in-situ reaction is carried out outside the electron paramagnetic resonance spectrometer, ball valves or needle valves (4-2 and 4-3) at two ends are closed, the inlet and outlet ends of the reaction tube are sealed to avoid contact with air, and then the quartz is put into the cavity of the electron paramagnetic resonance spectrometer for testing.
As a preferred technical scheme of the invention: the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform can control the operation of reaction gas, heating or illumination and the like on a system, and in-situ characterize the electron paramagnetic resonance signal change of the reaction system under normal pressure to a pressurized state, so as to define the reaction mechanism of the system; for a reaction system (the reaction temperature is more than 250 ℃) which cannot meet the instrument condition of the electron paramagnetic resonance spectrometer, the device can be used for carrying out quasi-in-situ operation on the reaction system, so that the electron paramagnetic signal characterization under different system requirements is realized, and the reaction mechanism of the system is clarified.
The application method of the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform comprises the following steps:
the first step: adding a sample to be detected into the double-layer glass sleeve to enable the filling height of the sample to be detected to be 2.5cm, placing the double-layer glass sleeve into a reaction furnace, connecting the front end of a ball valve or a needle valve (4-2) with an air inlet pipe main way, and connecting the tail end of the ball valve or the needle valve (4-3) with an exhaust pipeline.
And a second step of: opening an external steel cylinder main valve, initially adjusting the pressure of the steel cylinder by using a pressure reducer, accurately reading the pressure of the depressurized gas by using an electronic pressure gauge, slowly opening a needle valve (4-1), accurately regulating and controlling the air inlet flow by adjusting the numerical value of a gas metering device such as a mass flowmeter or a rotameter at a display panel, an instrument panel or a control terminal of a gas distribution system, and adjusting a back pressure valve to control the gas pressure of the system so as to meet the experimental requirements.
And a third step of: the back pressure valve can be regulated to select the exhaust pipeline to be in a pressurizing mode or a normal pressure mode according to the requirements of a reaction system.
Fourth step: and (3) carrying out heating activation pretreatment on the catalyst.
Fifth step: closing the gas path, disconnecting the ball valve or needle valve (4-2) from the gas inlet pipe main path and connecting the ball valve or needle valve (4-3) with the gas exhaust pipe, and vertically inserting the double-layer glass sleeve into the resonant cavity of the electron paramagnetic resonance spectrometer.
Sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the activated catalyst.
Seventh step: and reconnecting ball valves or needle valves (4-2, 4-3) to the gas distribution pipeline and the gas exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases to the double-layer glass sleeve, and heating the double-layer glass sleeve by a paramagnetic resonance instrument or measuring an electron paramagnetic resonance spectrogram of the heterogeneous catalysis under the in-situ condition by illumination of an external light source.
Eighth step: if the temperature required by the reaction is more than 250 ℃, the reaction tank is put back into the reaction furnace after the sixth step to be reconnected with the ball valve or the needle valve (4-2, 4-3) to the air distribution pipeline and the air exhaust pipeline, the heating/illumination reaction is carried out, the ball valve or the needle valve (4-2, 4-3) is closed after the reaction is finished, the connection between the ball valve or the needle valve (4-2, 4-3) and the air distribution pipeline and the air exhaust pipeline is disconnected, and the double-layer glass sleeve is vertically inserted into the resonant cavity of the electron paramagnetic resonance spectrometer to carry out electron paramagnetic resonance detection.
As a preferred technical scheme of the invention: if the catalytic reaction does not need to be carried out by introducing gas, a ball valve or a needle valve (4-2, 4-3) can be disconnected after activation, and electron paramagnetic resonance detection can be directly carried out by using the double-layer glass sleeve, so as to obtain an electron paramagnetic resonance spectrogram.
The beneficial effects are that:
1. the in-situ and quasi-in-situ multiphase catalysis electron paramagnetic resonance platform can realize accurate control and real-time switching of the flow of gas components by opening valves of an air inlet pipeline and an air outlet pipeline and utilizing a display panel, an instrument panel or a control terminal of a gas distribution system to adjust gas metering devices such as a mass flowmeter or a rotameter, and the like, realizes continuous reaction under the condition of steady flow reaction gas, and has the advantages of simplicity in operation, strong gas circulation, controllable gas components and stable system pressure.
2. Through changing the external steel bottle, the gas type can be flexibly selected according to the reaction system to be tested, and the in-situ or quasi-in-situ reaction under various atmosphere conditions can be satisfied.
3. The air distribution system device provided by the invention has the advantages of small occupied space, portability, great improvement of the use advantages of the air distribution system and capability of meeting the requirements of conventional tests and in-situ tests at any time.
4. The in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform can realize the experimental conditions of in-situ (reaction temperature is less than or equal to 250 ℃) and quasi-in-situ (reaction temperature is more than 250 ℃) illumination or heating, and the pressure of a reaction system is less than 10MPa.
Drawings
Fig. 1: the structure of the in-situ heterogeneous catalysis electron paramagnetic resonance platform is schematically shown.
Fig. 2: the invention provides a schematic diagram of an in-situ and quasi-in-situ heterogeneous catalytic electron paramagnetic resonance platform air inlet pipeline structure.
Fig. 3: the in-situ heterogeneous catalysis electron paramagnetic resonance platform in-situ reaction device is structurally schematic.
Fig. 4: the invention provides a schematic diagram of an exhaust pipeline structure of an in-situ and quasi-in-situ heterogeneous catalytic electron paramagnetic resonance platform.
Fig. 5: the quasi-in-situ heterogeneous catalytic electron paramagnetic resonance platform quasi-in-situ reaction device is structurally schematic.
Reference numerals illustrate: 1. the device is externally connected with a steel bottle, a pressure reducer, a filter, a ball valve or needle valve, an electronic pressure gauge, a gas metering device, a mass flowmeter or a rotameter and the like, wherein the gas metering device comprises a steel bottle, a pressure reducer, a filter, a ball valve or needle valve, an electronic pressure gauge, a mass flowmeter or a rotameter and the like, a one-way valve, an unloading valve, a pressure measuring valve, a temperature measuring point, a backpressure valve, a pressure valve, an evacuation pipe, an electron paramagnetic resonance spectrometer resonant cavity and a double-layer glass sleeve.
Detailed Description
The following examples further illustrate the invention but are not to be construed as limiting the invention and are intended to provide alternatives and modifications to the method, steps or conditions of the invention without departing from the spirit and nature of the invention.
Example 1
As shown in fig. 1, fig. 2, fig. 3 and fig. 4, the in-situ heterogeneous catalysis electron paramagnetic resonance platform is composed of a gas distribution system device and an in-situ reaction tank device, wherein the gas distribution system device is composed of a plurality of groups of gas inlet pipelines, a group of total path unloading valves 8, an electron pressure gauge 5-2, a temperature measuring point 9-1 and a group of gas exhaust pipelines, each group of gas inlet pipelines is respectively composed of a gas metering device 6 and a one-way valve 7, such as an external steel bottle 1, a pressure reducer 2, a filter 3-1, a needle valve 4-1, an electron pressure gauge 5-1, a mass flowmeter or a rotameter, and the like, and the gas exhaust pipeline is composed of a temperature measuring point 9-2, a back pressure valve 10 and an emptying pipe 11; the in-situ reaction tank device consists of two ball valves or needle valves 4-2 and 4-3, a filter 3-2, a double-layer glass sleeve 13, an external light source and an electron paramagnetic resonance spectrometer resonant cavity 12; the reaction tank device is connected with a group of exhaust pipelines, and has the functions of exhausting the reacted gas and regulating the system pressure. If the operation is normal pressure operation, the back pressure valve is regulated to be in a normal pressure state; if the pressurizing operation is needed, the back pressure valve is regulated until the system reaches the required reaction pressure.
The in-situ reaction tank device is connected to the air inlet pipe main passage and then is arranged in the resonant cavity 12 of the electron paramagnetic resonance spectrometer, and an external light source is arranged to meet the requirement of in-situ multiphase photocatalytic reaction; two ball or needle valves 4-2, 4-3 are used to ensure an internal sealed environment when the reaction cells are independently present. The reaction tank is a double-layer glass sleeve 13, quartz is selected as a material, and the outer diameter is designed according to the inner diameter of the cavity 12. If higher reaction pressure is needed, the wall thickness of the quartz reaction tank needs to be increased. The reaction gas can flow in from the sleeve outer tube, after fully contacting with the catalyst, flows out of the system through the small-diameter quartz tube inside the double-layer sleeve 13, or flows into the reaction tank through the small-diameter quartz tube inside the double-layer sleeve 13, and flows out of the system from the sleeve outer tube after fully contacting with the catalyst. Heating gas can be introduced into the lower part of the reaction tank to heat the reaction, and the temperature can reach 250 ℃ at most.
The in-situ reaction tank device is connected with the gas distribution system device, the gas inlet type, the gas component and the gas flow are accurately regulated by regulating each valve of the gas distribution system device and a display panel, an instrument panel or a control terminal, and the system is heated or irradiated to in-situ characterize the electron paramagnetic resonance signal change of the reaction system under the state from near normal pressure to pressurized, so that the reaction mechanism of the system is clarified.
An in-situ heterogeneous catalysis electron paramagnetic resonance platform using method comprises the following steps:
the first step: and adding a sample to be detected into the double-layer glass sleeve 13 to enable the filling height of the sample to be detected to be 2.5cm, placing the double-layer glass sleeve 13 into a reaction furnace, connecting the front end of the ball valve or needle valve 4-2 with an air inlet pipe main line, and connecting the tail end of the ball valve or needle valve 4-3 with an exhaust pipeline.
And a second step of: the method comprises the steps of opening a main valve of an external steel cylinder 1, initially adjusting the pressure of the steel cylinder by using a pressure reducer 2, accurately reading the pressure of the depressurized gas by an electronic pressure gauge 5, slowly opening a needle valve 4-1, accurately adjusting and controlling the air inlet flow by adjusting the numerical value of a gas metering device 6 such as a mass flowmeter or a rotameter at a display panel, an instrument panel or a control terminal of a gas distribution system, and adjusting a back pressure valve 10 to control the pressure of the gas of the system so as to meet experimental requirements.
And a third step of: the back pressure valve 10 can be adjusted to select the exhaust line to be in a pressurized mode or an atmospheric mode according to the requirements of the reaction system.
Fourth step: and (3) carrying out heating activation pretreatment on the catalyst.
Fifth step: closing the gas path, disconnecting the ball valve or needle valve 4-2 from the gas inlet pipe and connecting the ball valve or needle valve 4-3 with the gas exhaust pipe, and vertically inserting the double-layer glass sleeve 13 into the electron paramagnetic resonance spectrometer resonant cavity 12.
Sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the activated catalyst.
Seventh step: and reconnecting ball valves or needle valves 4-2 and 4-3 to the gas distribution pipeline and the gas exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases to the double-layer glass sleeve 13, and heating the double-layer glass sleeve 13 by a paramagnetic resonance instrument or measuring an electron paramagnetic resonance spectrogram of the heterogeneous catalysis under the in-situ condition by illumination of an external light source.
Example 2
As shown in fig. 1, fig. 2, fig. 4 and fig. 5, a quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform is composed of a gas distribution system device and a quasi-in-situ reaction tank device, wherein the gas distribution system device is composed of a plurality of groups of gas inlet pipelines, a group of total path unloading valves 8, an electron pressure gauge 5-2, a temperature measuring point 9-1 and a group of gas exhaust pipelines, each group of gas inlet pipelines is respectively composed of a gas metering device 6 and a check valve 7, such as an external steel bottle 1, a pressure reducer 2, a filter 3-1, a needle valve 4-1, an electron pressure gauge 5-1, a mass flowmeter or a rotameter, and the like, and the gas exhaust pipeline is composed of a temperature measuring point 9-2, a back pressure valve 10 and an emptying pipe 11; the quasi-in-situ reaction tank device consists of two ball valves or needle valves 4-2 and 4-3, a filter 3-2, a double-layer glass sleeve 13, a temperature measuring point 9-3 and a reaction furnace capable of carrying out illumination/heating; the reaction tank device is connected with a group of exhaust pipelines, and has the functions of exhausting the reacted gas and regulating the system pressure. If the operation is normal pressure operation, the back pressure valve is regulated to be in a normal pressure state; if the pressurizing operation is needed, the back pressure valve is regulated until the system reaches the required reaction pressure.
And the quasi-in-situ reaction tank device is connected with the air inlet pipe main passage and then performs quasi-in-situ reaction outside the electron paramagnetic resonance spectrometer. The quasi-in-situ reaction tank is a double-layer glass sleeve 13, quartz is selected as a material, the outer diameter is designed according to the inner diameter of the cavity 12, the quasi-in-situ reaction tank is used for a reaction system with the reaction temperature higher than 250 ℃, after quasi-in-situ reaction is carried out outside the electron paramagnetic resonance spectrometer, ball valves or needle valves 4-2 and 4-3 at two ends are closed, the inlet and outlet ends of the reaction pipe are sealed to avoid contact with air, and then the reaction system is placed into the cavity of the electron paramagnetic resonance spectrometer for testing.
The quasi-in-situ reaction tank device is connected with the gas distribution system device, the gas inlet type, the gas component and the gas flow are accurately regulated by regulating each valve of the gas distribution system device and a display panel, an instrument panel or a control terminal, and the system is heated or illuminated in an external reaction furnace of the electron paramagnetic resonance spectrometer, so that the electron paramagnetic resonance signal change of the reaction system under the experimental condition that the quasi-in-situ characterization reaction temperature is more than 250 ℃ from near normal pressure to a pressurized state is utilized, and the reaction mechanism of the system is clarified.
A quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform using method comprises the following steps:
the first step: and adding a sample to be detected into the double-layer glass sleeve 13 to enable the filling height of the sample to be detected to be 2.5cm, placing the double-layer glass sleeve 13 into a reaction furnace, connecting the front end of the ball valve or needle valve 4-2 with an air inlet pipe main line, and connecting the tail end of the ball valve or needle valve 4-3 with an exhaust pipeline.
And a second step of: the method comprises the steps of opening a main valve of an external steel cylinder 1, initially adjusting the pressure of the steel cylinder by using a pressure reducer 2, accurately reading the pressure of the depressurized gas by an electronic pressure gauge 5, slowly opening a needle valve 4-1, accurately adjusting and controlling the air inlet flow by adjusting the numerical value of a gas metering device 6 such as a mass flowmeter or a rotameter at a display panel, an instrument panel or a control terminal of a gas distribution system, and adjusting a back pressure valve 10 to control the pressure of the gas of the system so as to meet experimental requirements.
And a third step of: the back pressure valve 10 can be adjusted to select the exhaust line to be in a pressurized mode or an atmospheric mode according to the requirements of the reaction system.
Fourth step: and (3) carrying out heating activation pretreatment on the catalyst.
Fifth step: closing the gas path, disconnecting the ball valve or needle valve 4-2 from the gas inlet pipe and connecting the ball valve or needle valve 4-3 with the gas exhaust pipe, and vertically inserting the double-layer glass sleeve 13 into the electron paramagnetic resonance spectrometer resonant cavity 12.
Sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the activated catalyst.
Seventh step: the reaction tank is put back into the reaction furnace to be connected with the ball valve or the needle valve 4-2 and 4-3 to the air distribution pipeline and the air exhaust pipeline again, and then the heating/illumination reaction is carried out, after the reaction is finished, the ball valve or the needle valve 4-2 and 4-3 is closed, the links between the ball valve or the needle valve 4-2 and 4-3 and the air distribution pipeline and the air exhaust pipeline are disconnected, and the double-layer glass sleeve 13 is vertically inserted into the resonant cavity 12 of the electron paramagnetic resonance spectrometer to carry out electron paramagnetic resonance detection.
Claims (9)
1. An in-situ and quasi-in-situ heterogeneous catalytic electron paramagnetic resonance platform, which is characterized in that: the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform has two modes of in-situ test and quasi-in-situ test;
the heterogeneous catalysis electron paramagnetic resonance platform in the in-situ test mode is composed of a gas distribution system device and an in-situ reaction tank device, wherein the gas distribution system device is composed of a plurality of groups of gas inlet pipelines, a group of total path unloading valves (8), a second electron manometer (5-2), a temperature measuring point (9-1) and a group of exhaust pipelines, each group of gas inlet pipelines is composed of an external steel bottle (1), a pressure reducer (2), a filter (3-1), a first needle valve (4-1), a first electron manometer (5-1), a gas metering device (6) and a one-way valve (7), and each exhaust pipeline is composed of a temperature measuring point (9-2), a back pressure valve (10) and an exhaust pipeline (11);
the in-situ reaction tank device consists of a second ball valve or needle valve (4-2) and a third ball valve or needle valve (4-3), a filter (3-2), a double-layer glass sleeve (13), an external light source and an electron paramagnetic resonance spectrometer resonant cavity (12);
the heterogeneous catalysis electron paramagnetic resonance platform in the quasi-in-situ test mode is composed of a gas distribution system device and a quasi-in-situ reaction tank device, wherein the gas distribution system device is the same as the gas distribution system device in the in-situ test mode, and the reaction tank device is composed of a second ball valve or needle valve (4-2), a third ball valve or needle valve (4-3), a filter (3-2), a double-layer glass sleeve (13), a temperature measuring point (9-3) and a reaction furnace capable of carrying out illumination/heating;
each of the multiple groups of air inlet pipelines is respectively filled with reaction gas required by multiphase catalytic reaction, the reaction gas is provided by an external steel bottle (1), the system pressure is initially regulated by a pressure reducer (2), a filter (3-1) is connected to remove tiny particles in the gas to protect a gas metering device (6), and a first needle valve (4-1) is connected to slowly regulate the flow rate of the air entering the gas metering device (6) to avoid the damage to the gas metering device (6) caused by the impact of atmospheric air flow; the first needle valve (4-1) is connected with the first electronic pressure gauge (5-1) to accurately measure the pressure entering the gas metering device (6), the gas flow passing through the gas path is regulated and controlled by the gas metering device (6), and the one-way valve (7) is additionally arranged to control the direction of the gas flow so as to prevent the gas path pollution or inaccurate gas distribution caused by back mixing of the reaction gas;
the in-situ reaction tank device is connected to the air inlet pipe main passage and is arranged in the resonant cavity (12) of the electron paramagnetic resonance spectrometer, and an external light source is arranged to meet the requirements of in-situ multiphase photocatalytic reaction; the second ball valve or needle valve and the third ball valve or needle valve are used for ensuring the internal sealing environment when the reaction tanks independently exist; the reaction tank is a double-layer glass sleeve (13), quartz is selected as a material, and the outer diameter is designed according to the inner diameter of a resonant cavity (12) of the electron paramagnetic resonance spectrometer; if higher reaction pressure is needed, increasing the wall thickness of the quartz reaction tank; the reaction gas flows in from the outer tube of the sleeve, flows out of the system through the small-diameter quartz tube at the inner side of the double-layer glass sleeve (13) after fully contacting with the catalyst, or flows into the reaction tank through the small-diameter quartz tube at the inner side of the double-layer glass sleeve (13), and flows out of the system from the outer side of the sleeve after fully contacting with the catalyst;
and heating gas is introduced into the lower part of the reaction tank to heat the reaction, and the temperature can reach 250 ℃ at most.
2. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: the gas metering device (6) is a mass flowmeter or a rotameter; the reaction gas is pure gas or mixed gas.
3. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: each of the multiple groups of air inlet pipelines regulates and controls the gas metering device (6) through a display panel of a gas distribution system, a computer terminal or an operation panel of an instrument, so that the accurate control of the flow of gas components is realized; the air inlet pipeline is one or more groups.
4. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: the multiple groups of air inlet pipelines are summarized in a group of total pipelines, wherein a back pressure valve (10) is used for adjusting the system pressure, and a second electronic pressure gauge (5-2) is used for measuring the system pressure.
5. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: the reaction tank device is connected with a group of exhaust pipelines, and has the functions of exhausting the reacted gas and regulating the system pressure; if the operation is normal pressure operation, the back pressure valve is regulated to be in a normal pressure state; if the pressurizing operation is needed, the back pressure valve is regulated until the system reaches the required reaction pressure.
6. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: the quasi-in-situ reaction tank device is connected to the air inlet pipe main passage and then performs quasi-in-situ reaction outside the electron paramagnetic resonance spectrometer; the quasi-in-situ reaction tank is a double-layer glass sleeve (13), quartz is selected as a material, the outer diameter is designed according to the inner diameter of a resonant cavity (12) of the electron paramagnetic resonance spectrometer, the quasi-in-situ reaction tank is used for a reaction system with the reaction temperature higher than 250 ℃, after quasi-in-situ reaction is carried out outside the electron paramagnetic resonance spectrometer, a second ball valve or needle valve and a third ball valve or needle valve which are positioned at two ends are closed, the inlet and outlet ends of the reaction pipe are sealed to avoid contact with air, and then the reaction system is placed into the cavity of the electron paramagnetic resonance spectrometer for testing.
7. The in-situ and quasi-in-situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 1, wherein: the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform controls the reaction gas and heats and irradiates the system, so that electron paramagnetic resonance signal change of the reaction system under normal pressure to pressurized state is represented in situ, and the reaction mechanism of the system is defined; for a reaction system which cannot meet the instrument condition of the electron paramagnetic resonance spectrometer and has the reaction temperature higher than 250 ℃, the device is utilized to perform quasi-in-situ operation on the reaction system, so that the electron paramagnetic signal characterization under different system requirements is realized, and the system reaction mechanism is clarified.
8. A method of using the in situ and quasi-in situ heterogeneously catalyzed electron paramagnetic resonance platform according to any one of claims 1 to 7, comprising the steps of:
the first step: adding a sample to be detected into the double-layer glass sleeve (13) to enable the filling height of the sample to be detected to be 2.5cm, placing the double-layer glass sleeve (13) into a reaction furnace, connecting the front end of a second ball valve or needle valve (4-2) with an air inlet pipe main way, and connecting the tail end of a third ball valve or needle valve (4-3) with an exhaust pipeline;
and a second step of: opening a main valve of an external steel cylinder (1), initially adjusting the pressure of the steel cylinder by using a pressure reducer (2), accurately reading the pressure of the depressurized gas by using a first electronic pressure gauge (5-1), slowly opening a first needle valve (4-1), accurately regulating and controlling the inflow rate by adjusting the value of a gas metering device (6) on a display panel, an instrument panel or a control terminal of a gas distribution system, and adjusting a back pressure valve (10) to control the gas pressure of the system so as to meet experimental requirements;
and a third step of: according to the requirements of a reaction system, the back pressure valve (10) is regulated to select an exhaust pipeline to be in a pressurizing mode or a normal pressure mode;
fourth step: carrying out heating activation pretreatment on the catalyst;
fifth step: closing the gas path, disconnecting the connection between the second ball valve or needle valve (4-2) and the gas inlet pipe main path and between the third ball valve or needle valve (4-3) and the gas exhaust pipe, and vertically inserting a double-layer glass sleeve (13) into the electron paramagnetic resonance spectrometer resonant cavity (12);
sixth step: performing electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram of the activated catalyst;
seventh step: reconnecting the second ball valve or needle valve and the third ball valve or needle valve to an air distribution pipeline and an air exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases to the double-layer glass sleeve (13), and heating the double-layer glass sleeve (13) through a paramagnetic resonance instrument or carrying out illumination measurement on an electron paramagnetic resonance spectrogram of heterogeneous catalysis under an in-situ condition by an external light source;
eighth step: if the temperature required by the reaction is higher than 250 ℃, the reaction tank is placed back into the reaction furnace after the sixth step to be reconnected with the second ball valve or needle valve and the third ball valve or needle valve to the air distribution pipeline and the air exhaust pipeline, heating/illumination reaction is carried out, after the reaction is finished, the second ball valve or needle valve and the third ball valve or needle valve are closed, the connection between the second ball valve or needle valve and the third ball valve or needle valve and the air distribution pipeline is disconnected, and the double-layer glass sleeve (13) is vertically inserted into the electron paramagnetic resonance spectrometer resonant cavity (12) to carry out electron paramagnetic resonance detection.
9. The method of using an in situ and quasi-in situ heterogeneously catalyzed electron paramagnetic resonance platform according to claim 8, wherein: if the catalytic reaction does not need to be carried out by introducing gas, the second ball valve or needle valve and the third ball valve or needle valve are disconnected after the catalytic reaction is activated, and electron paramagnetic resonance detection is directly carried out by using the double-layer glass sleeve (13), so as to obtain an electron paramagnetic resonance spectrogram.
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