CN112697832A - In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and using method - Google Patents
In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and using 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 using method thereof, which consists of a gas distribution system device and an in-situ reaction tank device; the gas distribution system device consists of an external steel cylinder, a pressure reducer, a filter, a needle valve, an electronic pressure gauge, a mass flow meter, a one-way valve, an unloading valve, a temperature measuring point, a ball valve and a back pressure valve, and is assisted by a display panel for precise 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 an electron paramagnetic resonance spectrometer. The platform is simple to operate and convenient to disassemble, can be operated based on the original electron paramagnetic resonance instrument, realizes the experimental conditions of in-situ (the reaction temperature is less than or equal to 250 ℃)/quasi-in-situ (the reaction temperature is more than 250 ℃) illumination or heating, and can realize the pressure of a reaction system of less than 10 Mpa.
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 using method thereof.
Background
The electron paramagnetic resonance spectrometer can provide atom and electron scale information, and is greatly helpful for understanding the reaction process, for example, the existing electron paramagnetic resonance spectrometer can be modified into an in-situ device, and more reaction information under in-situ conditions can be provided. Under the technical level of the existing instruments, an electron paramagnetic resonance spectrometer can only meet the test conditions in an air atmosphere and at a lower temperature, and is still deficient in-situ reaction tests at a high temperature, a high pressure and a gas mobile phase.
For electron paramagnetic resonance testing, there are still some technological gaps, 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 the test under the specific atmosphere condition is carried out, the normal pressure operation can only be realized, and impurities such as air, moisture and the like are easily mixed in a test system, so that an accurate test result cannot be obtained; 3. if the system needs to be heated in the in-situ reaction process, the existing instrument only meets the lower reaction temperature, and the system exceeding the upper limit of the reaction temperature of the instrument cannot be tested; 4. when a test under a specific atmosphere condition is performed, the condition of a gas flow test cannot be met, so that the gas is not uniformly contacted with a sample to be tested, and the gas components cannot be accurately controlled, so that an expected test effect cannot be achieved.
Disclosure of Invention
The technical problem to be solved is as follows:
the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform built by the invention is used for supplementing and perfecting the existing instrument platform, so that the existing electron paramagnetic resonance spectrometer has the 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 10MPa) test functions. The establishment of the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform provides strong support for exploring the research of the catalyst active site under the in-situ experiment or working condition (such as valence state change of paramagnetic active metal, generation and quenching of oxygen vacancy and the like).
The technical scheme is as follows:
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 under the in-situ test mode consists of two parts, namely a gas distribution system device and an in-situ reaction pool device, wherein the gas distribution system device consists of a plurality of groups of gas inlet pipelines, a group of main unloading valves, an electronic pressure gauge, a temperature measuring point and a group of gas exhaust pipelines, each group of gas inlet pipelines respectively consists of a gas metering device such as an external steel cylinder, a pressure reducer, a filter, a needle valve, a ball valve, an electronic pressure gauge, a mass flow meter or a rotor flow meter and a one-way valve, and the gas exhaust pipelines consist of a temperature measuring point, a back pressure valve; 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 under 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 under the quasi-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 performing illumination/heating.
As a preferred technical scheme of the invention: each path of the multiple groups of air inlet pipelines is respectively introduced with a reaction gas (pure gas or mixed gas) required by multiphase catalytic reaction, the reaction gas is provided by an external steel cylinder, the pressure of the steel cylinder is regulated by a pressure reducer, the system pressure is regulated by a back pressure valve, a filter is connected to remove tiny particles in the gas so as to protect gas metering devices such as a mass flowmeter or a rotor flowmeter, and a needle valve is connected afterwards to slowly regulate the gas flow entering the gas metering devices such as the mass flowmeter or the rotor flowmeter so as to avoid the gas metering devices such as the mass flowmeter or the rotor flowmeter from being damaged by the impact of atmospheric flow; the back of the needle valve is connected with an electronic pressure gauge to accurately measure the pressure entering a gas metering device such as a mass flow meter or a rotor flow meter, the gas flow passing through a gas circuit is regulated and controlled by the gas metering device such as the mass flow meter or the rotor flow meter, and a check valve is additionally arranged to control the gas flow direction so as to prevent the gas circuit from being polluted or inaccurate in gas distribution caused by back mixing of reaction gas.
As a preferred technical scheme of the invention: each path of the multiple groups of gas inlet pipelines can regulate and control gas metering devices such as a mass flow meter or a rotor flow meter and the like through a display panel of the gas distribution system, a computer terminal or an operation panel of the instrument, so that the accurate control of the gas component flow is realized. The air inlet pipeline can be one group or a plurality of groups.
As a preferred technical scheme of the invention: the multiple groups of air inlet pipelines are gathered in a group of main 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 back of the reaction pool device is connected with a group of exhaust pipelines which have the functions of exhausting gas after reaction and regulating the pressure of the system. If the operation is normal pressure, adjusting a back pressure valve to a normal pressure state; if the pressurization operation is needed, the backpressure valve is adjusted 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 circuit and then is arranged in a resonant cavity of the electron paramagnetic resonance spectrometer, and a light source is arranged outside to meet the requirements of in-situ multiphase photocatalytic reaction; two ball valves or needle valves are used to ensure the internal sealed environment when the reaction cells are independent. The reaction tank is a double-layer glass sleeve, the material is quartz, 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 outer pipe of the double-layer sleeve, and flows out of the system through the small-diameter quartz pipe on the inner side of the double-layer sleeve after being fully contacted with the catalyst, or flows into the reaction tank through the small-diameter quartz pipe on the inner side of the double-layer sleeve, and flows out of the system from the outer pipe of the double-layer sleeve after being fully contacted 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.
As a preferred technical scheme of the invention: and the quasi-in-situ reaction tank device is connected behind the air inlet pipe main circuit and 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 is designed according to the inner diameter of the cavity and 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 reaction tube is placed 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 be used for in-situ characterizing the electron paramagnetic resonance signal change of a reaction system under the state from normal pressure to pressurization by controlling reaction gas and heating or illuminating the system and the like, so as to clarify the reaction mechanism of the system; for a reaction system (reaction temperature is more than 250 ℃) which can not meet the instrument conditions of an electron paramagnetic resonance spectrometer, the device can be used for carrying out quasi-in-situ operation on the reaction system, the electron paramagnetic signal characterization under different system requirements is realized, and the reaction mechanism of the system is determined.
The use method of the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform comprises the following steps:
the first step is as follows: adding a sample to be detected into the double-layer glass sleeve to ensure that the filling height of the sample to be detected is 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 a main pipeline of an air inlet pipe, and connecting the tail end of the ball valve or the needle valve (4-3) with an exhaust pipeline.
The second step is that: the external steel cylinder main valve is opened, the pressure reducer is used for preliminarily adjusting the pressure of the steel cylinder, the electronic pressure gauge is used for accurately reading the gas pressure after pressure reduction, the needle valve (4-1) is slowly opened, the numerical value of a gas metering device such as a mass flow meter or a rotor flow meter is accurately regulated and controlled to control the gas inlet flow at a display panel, an instrument panel or a control terminal of a gas distribution system, and the back pressure valve is adjusted to control the gas pressure of the system so as to meet the experimental requirement.
The third step: the back pressure valve can be adjusted to select the exhaust pipeline to be in a pressurization mode or a normal pressure mode according to the requirements of the reaction system.
The fourth step: the catalyst is pretreated by heating and activating.
The fifth step: and closing the gas path, disconnecting the ball valve or the needle valve (4-2) from the gas inlet pipe main path and the ball valve or the needle valve (4-3) from the gas exhaust pipeline, and vertically inserting the double-layer glass sleeve into the resonant cavity of the electron paramagnetic resonance spectrometer.
And a sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram after the catalyst is activated.
The seventh step: reconnecting the ball valve or the needle valve (4-2, 4-3) to the gas distribution pipeline and the exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases into the double-layer glass sleeve, and heating the double-layer glass sleeve by a paramagnetic resonance instrument or performing illumination measurement on the double-layer glass sleeve by an external light source to obtain an electron paramagnetic resonance spectrogram of the heterogeneous catalysis under the in-situ condition.
Eighth step: if the temperature required by the reaction is more than 250 ℃, the reaction tank is placed back into the reaction furnace after the sixth step to be reconnected with the ball valves or the needle valves (4-2 and 4-3) to the gas distribution pipeline and the gas exhaust pipeline, heating/illumination reaction is carried out, the ball valves or the needle valves (4-2 and 4-3) are closed after the reaction is finished, the link between the ball valves or the needle valves (4-2 and 4-3) and the gas distribution pipeline and the gas exhaust pipeline is disconnected, and the double-layer glass sleeve is vertically inserted into a resonant cavity of an electron paramagnetic resonance spectrometer to carry out electron paramagnetic resonance detection.
As a preferred technical scheme of the invention: if gas does not need to be introduced in the catalytic reaction, the ball valve or the needle valve (4-2, 4-3) can be disconnected after activation, and the double-layer glass sleeve is directly utilized for electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram.
Has the advantages that:
1. the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform can realize accurate control and real-time switching of gas component flow by opening a gas inlet pipeline and a gas exhaust pipeline valve and adjusting gas metering devices such as a mass flow meter or a rotor flow meter by using a display panel, an instrument panel or a control terminal of a gas distribution system, realizes continuous reaction under the condition of steady flow reaction gas, and has the advantages of simple operation, strong gas circulation, controllable gas components and stable system pressure.
2. By changing the external steel cylinder, 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 met.
3. The gas distribution system device provided by the invention has the advantages of small occupied space and portability, greatly improves the use advantages of the gas distribution system, and can meet 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 (the reaction temperature is less than or equal to 250 ℃) and quasi-in-situ (the reaction temperature is more than 250 ℃) illumination or heating, and the pressure of a reaction system is less than 10 MPa.
Drawings
FIG. 1: is a schematic structural diagram of the in-situ heterogeneous catalysis electron paramagnetic resonance platform.
FIG. 2: the invention is a schematic diagram of the structure of an air inlet pipeline of an in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform.
FIG. 3: is a structural schematic diagram of the in-situ reaction device of the in-situ heterogeneous catalytic electron paramagnetic resonance platform.
FIG. 4: the invention is a schematic structural diagram of an exhaust pipeline of an in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform.
FIG. 5: is a structure schematic diagram of the quasi-in-situ reaction device of the quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform.
Description of reference numerals: 1. the device comprises an external steel cylinder, 2, a pressure reducer, 3, a filter, 4, a ball valve or a needle valve, 5, an electronic pressure gauge, 6, a gas metering device such as a mass flow meter or a rotor flow meter, 7, a one-way valve, 8, an unloading valve, 9, a temperature measuring point, 10, a back pressure valve, 11, an emptying pipe, 12, a resonant cavity of an electron paramagnetic resonance spectrometer, 13 and a double-layer glass sleeve.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention and all such alterations and modifications in the process, steps or conditions are within the scope of the invention as defined by the appended claims.
Example 1
As shown in fig. 1, 2, 3 and 4, the in-situ multi-phase catalytic electron paramagnetic resonance platform consists of two parts, namely 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 main unloading valves 8, an electronic pressure gauge 5-2, a temperature measuring point 9-1 and a group of gas outlet pipelines, each group of gas inlet pipelines respectively consists of an external steel cylinder 1, a pressure reducer 2, a filter 3-1, a needle valve 4-1, the electronic pressure gauge 5-1, a gas metering device 6 such as a mass flow meter or a rotor flow meter and a one-way valve 7, and the gas outlet pipelines consist of the temperature measuring point 9-2, a backpressure 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 a resonant cavity 12 of an electron paramagnetic resonance spectrometer; the back of the reaction pool device is connected with a group of exhaust pipelines which have the functions of exhausting gas after reaction and regulating the pressure of the system. If the operation is normal pressure, adjusting a back pressure valve to a normal pressure state; if the pressurization operation is needed, the backpressure valve is adjusted until the system reaches the required reaction pressure.
The in-situ reaction tank device is connected to the air inlet pipe main and then arranged in the resonant cavity 12 of the electron paramagnetic resonance spectrometer, and a light source is arranged outside to meet the requirements of in-situ heterogeneous photocatalytic reaction; two ball valves 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, the material is quartz, 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 outer pipe of the double-layer sleeve, and flows out of the system through the small-diameter quartz pipe on the inner side of the double-layer sleeve 13 after being fully contacted with the catalyst, or flows into the reaction tank through the small-diameter quartz pipe on the inner side of the double-layer sleeve 13, and flows out of the system from the outer pipe of the double-layer sleeve after being fully contacted 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 types, the gas components and the gas flow are accurately adjusted by adjusting valves, display panels, instrument panels or control terminals of the gas distribution system device, and the electron paramagnetic resonance signal change of the reaction system from near normal pressure to a pressurized state is represented in situ by performing operations such as heating or illumination on the system, so that the reaction mechanism of the system is determined.
An in-situ heterogeneous catalysis electron paramagnetic resonance platform using method comprises the following steps:
the first step is as follows: adding a sample to be detected into the double-layer glass sleeve 13 to ensure that the filling height of the sample to be detected is 2.5cm, placing the double-layer glass sleeve 13 into a reaction furnace, connecting the front end of a ball valve or a needle valve 4-2 with an air inlet pipe main line, and connecting the tail end of the ball valve or the needle valve 4-3 with an exhaust pipe.
The second step is that: the method comprises the steps of opening a main valve of an external steel cylinder 1, primarily adjusting the pressure of the steel cylinder by using a pressure reducer 2, accurately reading the gas pressure after pressure reduction through an electronic pressure meter 5, slowly opening a needle valve 4-1, accurately regulating and controlling the gas inlet flow through adjusting 6 numerical values of gas metering devices such as a mass flow meter or a rotor flow meter 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 the experimental requirements.
The third step: the back pressure valve 10 can be adjusted to select the exhaust pipeline to be in a pressurization mode or a normal pressure mode according to the requirements of the reaction system.
The fourth step: the catalyst is pretreated by heating and activating.
The fifth step: and closing the gas path, disconnecting the ball valve or needle valve 4-2 from the gas inlet pipe main path and the ball valve or needle valve 4-3 from the gas exhaust pipeline, and vertically inserting the double-layer glass sleeve 13 into the resonant cavity 12 of the electron paramagnetic resonance spectrometer.
And a sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram after the catalyst is activated.
The seventh step: reconnecting the ball valve or the needle valve 4-2 and 4-3 to the gas distribution pipeline and the exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases into 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, 2, 4 and 5, the quasi-in-situ multi-phase catalytic electron paramagnetic resonance platform consists of two parts, namely a gas distribution system device and a quasi-in-situ reaction tank device, wherein the gas distribution system device consists of a plurality of groups of gas inlet pipelines, a group of main unloading valves 8, an electronic pressure gauge 5-2, a temperature measuring point 9-1 and a group of gas exhaust pipelines, each group of gas inlet pipelines respectively consists of an external steel cylinder 1, a pressure reducer 2, a filter 3-1, a needle valve 4-1, the electronic pressure gauge 5-1, a gas metering device 6 such as a mass flow meter or a rotor flow meter and a one-way valve 7, and the gas exhaust pipelines consist of the 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 performing illumination/heating; the back of the reaction pool device is connected with a group of exhaust pipelines which have the functions of exhausting gas after reaction and regulating the pressure of the system. If the operation is normal pressure, adjusting a back pressure valve to a normal pressure state; if the pressurization operation is needed, the backpressure valve is adjusted until the system reaches the required reaction pressure.
And the quasi-in-situ reaction tank device is connected behind the air inlet pipe main circuit and 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 and 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 reaction tube 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 types, gas components and gas flow rate are accurately adjusted by adjusting valves, display panels, instrument panels or control terminals of the gas distribution system device, the system is heated or illuminated in an external reaction furnace of the electron paramagnetic resonance spectrometer, quasi-in-situ characterization is carried out on the change of electron paramagnetic resonance signals of the reaction system from near normal pressure to a pressurized state under the experimental condition that the reaction temperature is higher than 250 ℃, and the reaction mechanism of the system is determined.
A quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform using method comprises the following steps:
the first step is as follows: adding a sample to be detected into the double-layer glass sleeve 13 to ensure that the filling height of the sample to be detected is 2.5cm, placing the double-layer glass sleeve 13 into a reaction furnace, connecting the front end of a ball valve or a needle valve 4-2 with an air inlet pipe main line, and connecting the tail end of the ball valve or the needle valve 4-3 with an exhaust pipe.
The second step is that: the method comprises the steps of opening a main valve of an external steel cylinder 1, primarily adjusting the pressure of the steel cylinder by using a pressure reducer 2, accurately reading the gas pressure after pressure reduction through an electronic pressure meter 5, slowly opening a needle valve 4-1, accurately regulating and controlling the gas inlet flow through adjusting 6 numerical values of gas metering devices such as a mass flow meter or a rotor flow meter 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 the experimental requirements.
The third step: the back pressure valve 10 can be adjusted to select the exhaust pipeline to be in a pressurization mode or a normal pressure mode according to the requirements of the reaction system.
The fourth step: the catalyst is pretreated by heating and activating.
The fifth step: and closing the gas path, disconnecting the ball valve or needle valve 4-2 from the gas inlet pipe main path and the ball valve or needle valve 4-3 from the gas exhaust pipeline, and vertically inserting the double-layer glass sleeve 13 into the resonant cavity 12 of the electron paramagnetic resonance spectrometer.
And a sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram after the catalyst is activated.
The seventh step: and the reaction tank is placed back into the reaction furnace to be reconnected with the ball valves or the needle valves 4-2 and 4-3 to the gas distribution pipeline and the gas exhaust pipeline, heating/illumination reaction is carried out, the ball valves or the needle valves 4-2 and 4-3 are closed after the reaction is finished, the links between the ball valves or the needle valves 4-2 and 4-3 and the gas distribution pipeline and the gas 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 for electron paramagnetic resonance detection.
Claims (10)
1. An in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform 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 under the in-situ test mode is composed of a gas distribution system device and an in-situ reaction pool device, wherein the gas distribution system device is composed of a plurality of groups of gas inlet pipelines, a group of main line unloading valves (8), an electronic pressure gauge (5-2), a temperature measuring point (9-1) and a group of gas outlet pipelines, each group of gas inlet pipelines is respectively composed of an external steel cylinder (1), a pressure reducer (2), a filter (3-1), a needle valve (4-1), the electronic pressure gauge (5-1), a mass flow meter or a rotor flow meter and other gas metering devices (6) and a one-way valve (7), and the gas outlet pipeline is composed of a temperature measuring point (9-2), a back pressure valve (10) and an emptying pipeline (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 heterogeneous catalysis electron paramagnetic resonance platform under 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 under the quasi-in-situ test mode, and the reaction tank device is composed 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 performing illumination/heating.
2. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: each path of the multiple groups of air inlet pipelines is respectively introduced with a reaction gas (pure gas or mixed gas) required by multiphase catalytic reaction, the reaction gas is provided by an external steel cylinder (1), the pressure reducer (2) is used for preliminarily adjusting the system pressure, a filter (3-1) is connected to remove tiny particles in the gas so as to protect a gas metering device (6) such as a mass flow meter or a rotor flow meter, and a needle valve (4-1) is connected to slowly adjust the gas flow entering the gas metering device (6) such as the mass flow meter or the rotor flow meter so as to avoid the gas metering device (6) such as the mass flow meter or the rotor flow meter from being damaged by the impact of atmospheric flow; an electronic pressure gauge (5-1) is connected behind the needle valve (4-1) to accurately measure the pressure entering a gas metering device (6) such as a mass flow meter or a rotor flow meter, the gas flow passing through a gas circuit is regulated and controlled by the gas metering device (6) such as the mass flow meter or the rotor flow meter, and a check valve (7) is additionally arranged to control the direction of the gas flow so as to prevent the gas circuit from being polluted or the gas distribution from being inaccurate due to back mixing of reaction gas.
3. The plurality of sets of air intake circuits of claim 2, wherein: each path of the multiple groups of gas inlet pipelines can regulate and control a gas metering device (6) such as a mass flow meter or a rotor flow meter through a display panel of the gas distribution system, a computer terminal or an operation panel of an instrument, so that the accurate control of the gas component flow is realized. The air inlet pipeline can be one group or a plurality of groups.
4. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: the multiple groups of air inlet pipelines are gathered in a group of main pipelines, wherein a back pressure valve (10) is used for adjusting the system pressure, and an electronic pressure gauge (5-2) is used for measuring the system pressure.
5. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: the back of the reaction pool device is connected with a group of exhaust pipelines which have the functions of exhausting gas after reaction and regulating the pressure of the system. If the operation is normal pressure, adjusting a back pressure valve to a normal pressure state; if the pressurization operation is needed, the backpressure valve is adjusted until the system reaches the required reaction pressure.
6. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: the in-situ reaction tank device is connected to the air inlet pipe main path and then arranged in a resonant cavity (12) of an electron paramagnetic resonance spectrometer, and a light source is arranged outside to meet the requirements of in-situ heterogeneous photocatalytic reaction; two ball valves or needle valves (4-2, 4-3) are used to ensure the internal sealed environment when the reaction cells are independent. The reaction tank is a double-layer glass sleeve (13), the material is quartz, 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 outer pipe of the double-layer sleeve, and flows out of the system through the small-diameter quartz pipe on the inner side of the double-layer sleeve (13) after fully contacting with the catalyst, or flows into the reaction tank through the small-diameter quartz pipe on the inner side of the double-layer sleeve (13) and flows out of the system from the outer side of the sleeve 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 upper limit of the temperature of an electron paramagnetic instrument).
7. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: and the quasi-in-situ reaction tank device is connected behind the air inlet pipe main circuit and 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) and is used for a reaction system with the reaction temperature higher than 250 ℃, ball valves or needle valves (4-2 and 4-3) at two ends are closed after quasi-in-situ reaction is carried out outside the electron paramagnetic resonance spectrometer, the inlet and outlet ends of the reaction tube are sealed to avoid contact with air, and then the reaction tube is placed into the cavity of the electron paramagnetic resonance spectrometer for testing.
8. The in-situ and quasi-in-situ multi-phasic catalytic electron paramagnetic resonance platform of claim 1, wherein: the in-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform can perform operations such as reaction gas control, heating and illumination on a system, in-situ characterization of electron paramagnetic resonance signal changes of the reaction system under the state from normal pressure to pressurization, and definition of a system reaction mechanism; for a reaction system (reaction temperature is more than 250 ℃) which can not meet the instrument conditions of an electron paramagnetic resonance spectrometer, the device can be used for carrying out quasi-in-situ operation on the reaction system, the electron paramagnetic signal characterization under different system requirements is realized, and the reaction mechanism of the system is determined.
9. A method of using the in-situ and quasi-in-situ multi-phase catalytic electron paramagnetic resonance platform of any one of claims 1 to 8, characterized by the steps of:
the first step is as follows: adding a sample to be detected into the double-layer glass sleeve (13) to ensure that the filling height of the sample to be detected is 2.5cm, placing the double-layer glass sleeve (13) into a reaction furnace, connecting the front end of a ball valve or a needle valve (4-2) with an air inlet pipe main line, and connecting the tail end of the ball valve or the needle valve (4-3) with an exhaust pipeline.
The second step is that: open external steel bottle (1) main valve, utilize pressure reducer (2) to carry out primary control to steel bottle pressure, accurately read the gas pressure after the decompression through electron pressure meter (5), slowly open needle valve (4-1), at gas distribution system's display panel, instrument panel or control terminal through adjusting gas metering device (6) numerical value such as mass flow meter or rotameter accurate regulation and control air intake flow, adjust back pressure valve (10) and come control system gas pressure to make it satisfy the experiment needs.
The third step: the back pressure valve (10) can be adjusted to select the exhaust pipeline to be in a pressurization mode or a normal pressure mode according to the requirements of the reaction system.
The fourth step: the catalyst is pretreated by heating and activating.
The fifth step: and (3) closing the gas path, disconnecting the ball valve or the needle valve (4-2) from the gas inlet main path and the ball valve or the needle valve (4-3) from the gas exhaust path, and vertically inserting the double-layer glass sleeve (13) into the resonant cavity (12) of the electron paramagnetic resonance spectrometer.
And a sixth step: and carrying out electron paramagnetic resonance detection to obtain an electron paramagnetic resonance spectrogram after the catalyst is activated.
The seventh step: reconnecting the ball valve or the needle valve (4-2, 4-3) to the gas distribution pipeline and the exhaust pipeline, repeating the second step and the third step, introducing one or more specified reaction gases into the double-layer glass sleeve (13), and heating the double-layer glass sleeve (13) by a paramagnetic resonance instrument or performing illumination measurement on the double-layer glass sleeve by an external light source to obtain an electron resonance paramagnetic wave spectrogram of the heterogeneous catalysis under the in-situ condition.
Eighth step: if the temperature required by the reaction is more than 250 ℃, the reaction tank is placed back into the reaction furnace after the sixth step to be reconnected with the ball valves or the needle valves (4-2 and 4-3) to the gas distribution pipeline and the gas exhaust pipeline, heating/illumination reaction is carried out, the ball valves or the needle valves (4-2 and 4-3) are closed after the reaction is finished, the link between the ball valves or the needle valves (4-2 and 4-3) and the gas distribution pipeline and the gas exhaust pipeline is disconnected, and the double-layer glass sleeve (13) is vertically inserted into a resonant cavity (12) of an electron paramagnetic resonance spectrometer to carry out electron paramagnetic resonance detection.
10. A method of using the in-situ and quasi-in-situ multi-phase catalytic electron paramagnetic resonance platform of claim 9, wherein: if gas does not need to be introduced in the catalytic reaction, the ball valve or the needle valve (4-2, 4-3) can be disconnected after activation, and the double-layer glass sleeve (13) is directly utilized to carry out electron paramagnetic resonance detection, so that an electron paramagnetic resonance spectrogram is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113670967A (en) * | 2021-08-10 | 2021-11-19 | 电子科技大学长三角研究院(湖州) | In-situ vacuum reaction system for dynamically detecting defects |
| CN113702413A (en) * | 2021-08-30 | 2021-11-26 | 兰州大学 | Heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and using method |
| CN117169795A (en) * | 2023-11-02 | 2023-12-05 | 中国科学院精密测量科学与技术创新研究院 | Multichannel distributed in-situ solid nuclear magnetic resonance heating device and method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030040116A1 (en) * | 2000-02-08 | 2003-02-27 | Canos Avelino Corma | Catalytic testing device and method for its use in material testing |
| CN105628810A (en) * | 2015-12-26 | 2016-06-01 | 中国科学院福建物质结构研究所 | In-situ capture heterogeneous catalytic reaction intermediate product device and use method thereof |
| CN106442377A (en) * | 2016-09-24 | 2017-02-22 | 大连理工大学 | Real-time double-beam in-situ infrared spectrum system and method thereof |
| WO2019174108A1 (en) * | 2018-03-13 | 2019-09-19 | 上海科技大学 | Combination structure of uhv device interconnected in-situ reaction cell and built-in mass spectrum electric quadrupole rod |
| JP2020093248A (en) * | 2018-11-29 | 2020-06-18 | 国立研究開発法人物質・材料研究機構 | Catalytic reaction device using field effect, method for controlling catalytic function by using field effect, method for using catalytic reaction device, and method for producing product molecule |
-
2020
- 2020-12-18 CN CN202011499968.5A patent/CN112697832B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030040116A1 (en) * | 2000-02-08 | 2003-02-27 | Canos Avelino Corma | Catalytic testing device and method for its use in material testing |
| CN105628810A (en) * | 2015-12-26 | 2016-06-01 | 中国科学院福建物质结构研究所 | In-situ capture heterogeneous catalytic reaction intermediate product device and use method thereof |
| CN106442377A (en) * | 2016-09-24 | 2017-02-22 | 大连理工大学 | Real-time double-beam in-situ infrared spectrum system and method thereof |
| WO2018053978A1 (en) * | 2016-09-24 | 2018-03-29 | 大连理工大学 | Real-time double light beam in-situ infrared spectroscopy system and method thereof |
| WO2019174108A1 (en) * | 2018-03-13 | 2019-09-19 | 上海科技大学 | Combination structure of uhv device interconnected in-situ reaction cell and built-in mass spectrum electric quadrupole rod |
| JP2020093248A (en) * | 2018-11-29 | 2020-06-18 | 国立研究開発法人物質・材料研究機構 | Catalytic reaction device using field effect, method for controlling catalytic function by using field effect, method for using catalytic reaction device, and method for producing product molecule |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113670967A (en) * | 2021-08-10 | 2021-11-19 | 电子科技大学长三角研究院(湖州) | In-situ vacuum reaction system for dynamically detecting defects |
| CN113702413A (en) * | 2021-08-30 | 2021-11-26 | 兰州大学 | Heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and using method |
| CN113702413B (en) * | 2021-08-30 | 2023-09-29 | 兰州大学 | Heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and use method |
| CN117169795A (en) * | 2023-11-02 | 2023-12-05 | 中国科学院精密测量科学与技术创新研究院 | Multichannel distributed in-situ solid nuclear magnetic resonance heating device and method |
| CN117169795B (en) * | 2023-11-02 | 2024-02-27 | 中国科学院精密测量科学与技术创新研究院 | Multichannel distributed in-situ solid nuclear magnetic resonance heating device and method |
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