An in-situ testing device and method for catalyst reaction

Abstract

The present invention discloses an in-situ test device and a test method for catalyst reactions, which can be used for in-situ synchrotron radiation testing during the process of heterogeneous catalyst reactions and obtain high-quality X-ray absorption and X-ray diffraction spectra during the catalytic reaction process, providing basic data for further developing efficient heterogeneous catalysts. The structure of the present invention is simple, and the flow state of the reaction gas can be controlled by controlling the size of the catalyst powder sample particles, the inner diameter of the sample tube, and the flow rate of the high-pressure gas. It can be used to monitor the in-situ catalyst structure evolution law during the fixed-bed catalytic reaction process, solving the problems that the previous equipment could not reflect the true in-situ spectroscopic information of heterogeneous catalytic reactions, had poor signals, and could not simultaneously achieve multiple spectroscopic monitoring, and has important value and significance for promoting the development of heterogeneous catalysts.

Description

Technical Field

[0001] The present invention relates to the technical field of in-situ testing of catalysts, and particularly to an in-situ testing device and method for catalyst reactions. Background Art

[0002] Research and development of high-performance catalysts is of great significance for promoting the green, low-carbon and sustainable development of the chemical industry. To control and improve the performance of catalysts, it is first necessary to explore the key surface and interface structures (such as coordination, electronic and crystal structures, etc.) that play a catalytic role, and reveal their mechanisms of action in real catalytic processes, so as to conduct rational design of catalysts under the guidance of reasonable mechanisms. For heterogeneous catalysts, especially metals and oxides, they are usually composed of complex crystalline and amorphous substances. Under real reaction conditions, the interaction between such crystals and amorphous substances and reaction molecules further undergoes dynamic structural evolution. Since conventional laboratory structure analysis methods cannot quickly and finely detect such dynamics, it is difficult to truly and clearly characterize the structure of catalysts during the reaction process, and thus it is impossible to understand the mechanism of catalyst action from the essence.

[0003] Using X-rays generated by synchrotron radiation to study the catalytic behavior of catalysts in-situ is an important research field in the field of heterogeneous catalysis in recent years. Through X-ray Absorption Fine Structure (abbreviated as: XAFS), especially the Quick XAFS (abbreviated as: QXAFS), it is possible to in-situ monitor the electrons, valence states, and coordination structures of catalytic materials during the reaction process at the second level and characterize their dynamics. In addition, the time resolution of synchrotron radiation X-ray powder diffraction technology (abbreviated as: XRD) is higher (at the millisecond level), and it can obtain microscopic information such as the phase, grain size, lattice strain, and defects of catalysts. Currently, synchrotron radiation testing devices for in-situ testing of catalysts often have problems such as large device structure, poor compatibility, complex operation, and limited application range, making it difficult to simultaneously perform XAFS and XRD tests on catalysts. Moreover, since the samples of currently designed synchrotron radiation devices usually adopt the tablet pressing mode, there is a large difference from the actual granular catalysts in the reaction process, and it is difficult to truly reveal the structural changes of catalysts in the in-situ flow field. In addition, the conventional use of window plates such as quartz brings strong absorption and non-sample diffraction signals, resulting in poor signal quality of in-situ test results, difficulty in separating the window plate diffraction data from the samples, and affecting the analysis and application of data. Therefore, it is necessary to develop a portable in-situ synchrotron radiation device with a flow field structure close to real catalytic reaction processes such as fixed beds, which can simultaneously perform spectroscopy tests such as XAFS (X-ray Absorption Fine Structure) and XRD (X-ray diffraction) to overcome the problems existing in the above-mentioned existing synchrotron radiation testing devices. Summary of the Invention

[0004] The object of the present invention is to provide an in-situ test device and test method for catalyst reactions, which can be used for in-situ synchrotron radiation testing during the process of heterogeneous catalyst reactions, and obtain high-quality X-ray absorption (i.e., XAFS data) and X-ray diffraction spectra (i.e., XRD spectral data) during the catalytic reaction process, providing basic data for further developing efficient heterogeneous catalyst design to solve the problems existing in the above-mentioned prior art.

[0005] To achieve the above object, the present invention provides the following solutions:

[0006] The present invention provides an in-situ test device for catalyst reactions, comprising:

[0007] A sample tube, which is used to contain a catalyst powder sample;

[0008] A sample stage, on which the sample tube is installed, and a temperature detection device and a sample heating device capable of heating the sample tube are arranged on the sample stage;

[0009] An X-ray emission device, which is arranged above the sample stage and is used to vertically emit X-rays to the sample tube;

[0010] A gas supply device, which includes a gas storage bottle. The gas storage bottle is connected to the inlet end of the sample tube through a pipeline and is used to provide high-pressure gas into the sample tube; a pressure reducing valve and a flow meter are sequentially arranged between the gas storage bottle and the sample tube along the gas flow direction;

[0011] A liquid supply device, which includes a liquid raw material tank, a liquid chromatography feed pump, and a vaporization device connected in sequence. The liquid chromatography feed pump is used to pump the reaction liquid in the liquid raw material tank into the vaporization device, and the vaporization device is connected to the inlet end of the sample tube and is used to vaporize the reaction liquid and introduce it into the sample tube;

[0012] A control system, which is communicatively connected to the temperature detection device, the sample heating device, and the flow meter.

[0013] Optionally, it further includes a sample stage support frame, which includes:

[0014] A base;

[0015] An upright support, which is perpendicular to the base and the bottom end of the upright support is connected to one side of the base;

[0016] A horizontal bracket, one end of the horizontal bracket is connected to the top end of the vertical bracket, and the installation height of the horizontal bracket on the vertical bracket is adjustable. The sample stage is arranged on the upper surface of the horizontal bracket.

[0017] Optionally, two sample tube mounting blocks arranged symmetrically at intervals are provided on the upper surface of the sample stage. Sample tube insertion holes are formed in both of the two sample tube mounting blocks. The sample tube sequentially passes through the sample tube insertion holes on the two sample tube mounting blocks. An exposure area is formed between the two sample tube mounting blocks to expose the part of the sample tube filled with the catalyst powder sample.

[0018] Two fan-shaped notches symmetrically distributed on both sides of the sample tube are also formed between the two sample tube mounting blocks, and the vertices of the two fan-shaped notches are respectively communicated with both ends of the exposure area.

[0019] Optionally, the sample stage is a stainless steel sample stage or a pure copper sample stage; the temperature detection device and the sample heating device are a thermocouple and a heating rod respectively, and both the thermocouple and the heating rod are inserted into the sample stage.

[0020] Optionally, the sample tube is a polyimide tube or a beryllium tube; the outer diameter of the sample tube is 0.4 mm to 3 mm, and the wall thickness is 0.08 mm to 0.6 mm.

[0021] Optionally, a reaction product cooling device is further included. The reaction product cooling device includes a cold trap and a back pressure valve connected in sequence through a pipeline, and the cold trap is connected to the outlet end of the sample tube.

[0022] Optionally, the gasification device is a gasification tank, and the flowmeter is connected to the gasification tank to realize the confluence of the high-pressure gas and the gasified reaction liquid; heating tapes are wound around the outside of the gasification tank and on the pipeline between the gasification tank and the sample tube to heat the high-pressure gas and the gasified reaction liquid.

[0023] Optionally, two pipeline plugging members are arranged at intervals in the sample tube. A sample reaction area is formed between the two pipeline plugging members. The catalyst powder sample is placed in the sample reaction area, and the sample reaction area is used to be exposed to the exposure area; wherein, the pipeline plugging member includes a liner tube and quartz wool.

[0024] Optionally, the X-ray emission device is detected by an amorphous silicon flat panel detector.

[0025] Optionally, the air pressure range in the sample tube is 0 MPa to 10 MPa, and the temperature range is 0 °C to 600 °C.

[0026] The present invention also provides a method for in-situ testing of a catalyst reaction implemented by using the in-situ testing device for a catalyst reaction described in any one of the above, including:

[0027] Loading a catalyst powder sample to be tested into the sample tube, and installing the sample tube on the sample stage;

[0028] Starting the X-ray emission device, the temperature detection device and the sample heating device;

[0029] Pumping a reaction liquid into the gasification device through the liquid chromatography feed pump, and the gasification device gasifies the reaction liquid and introduces it into the sample tube; meanwhile, hydrogen is introduced into the sample tube from the gas storage bottle;

[0030] Changing the heating temperature of the sample heating device to test XAFS data and XRD spectrum data under different temperature conditions.

[0031] Optionally, setting the heating rate of the sample heating device to 5 °C / min, and setting the target temperatures to 60 °C, 90 °C, 120 °C, 150 °C and 180 °C, and testing the XAFS data and XRD spectrum data during the heating process and under different temperature conditions.

[0032] Optionally, the XAFS data is processed by Athena software, and the XRD spectrum data is processed by FIT2D software.

[0033] Optionally, the liquid products in the sample tube are recovered in a cold trap after cooling, and the gas products become atmospheric pressure through a back pressure valve and are discharged outdoors.

[0034] The present invention has achieved the following technical effects compared with the prior art:

[0035] The in-situ testing device for a catalyst reaction proposed by the present invention can be used for in-situ synchrotron radiation testing during the process of a heterogeneous catalyst reaction, and can obtain high-quality X-ray absorption and X-ray diffraction spectra during the catalytic reaction process, providing basic data for further developing efficient heterogeneous catalysts. The structure of the present invention is simple, and the flow state of the reaction gas can be controlled by controlling the size of the catalyst powder sample particles, the inner diameter of the sample tube, and the flow rate of the high-pressure gas. It can be used to monitor the in-situ catalyst structure evolution law during the fixed-bed catalytic reaction process, solving the problems that the previous equipment cannot reflect the true in-situ spectroscopy information of heterogeneous catalytic reactions, has poor signals, and cannot simultaneously achieve multiple spectroscopy monitoring, and has important value and significance for promoting the development of heterogeneous catalysts.

[0036] The present invention also provides a method for in-situ testing of catalyst reactions implemented based on the above-mentioned in-situ testing device for catalyst reactions. This method can achieve in-situ synchrotron radiation testing during the reaction process of heterogeneous catalysts and obtain high-quality X-ray absorption and X-ray diffraction spectra during the catalytic reaction process, providing basic data for further developing efficient heterogeneous catalyst design. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0038] Figure 1 Structural schematic diagram of the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0039] Figure 2 Schematic three-dimensional structure diagram of the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0040] Figure 3 Front view of the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0041] Figure 4 Top view of the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0042] Figure 5 Left view of the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0043] Figure 6 Structural schematic diagram of the sample tube in the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0044] Figure 7 Installation schematic diagram of the heating rod in the in-situ testing device for catalyst reactions disclosed in the embodiments of the present invention;

[0045] Figure 8 Dynamic synchrotron radiation XAFS spectrogram during the in-situ hydrogenation of levulinic acid in aqueous phase by the Pt-TiO2 / α-Al2O3 catalyst obtained in the embodiments of the present invention;

[0046] Figure 9 Dynamic synchrotron radiation XRD spectrogram during the in-situ hydrogenation of levulinic acid in aqueous phase by the Pt-TiO2 / α-Al2O3 catalyst obtained in the embodiments of the present invention.

[0047] Among them, the reference numerals are:

[0048] 1 - Connection kit a; 2 - Upright bracket; 3 - Connection kit b; 4 - Base fixing hole; 5 - Base; 6 - Horizontal bracket; 7 - Connection kit c; 8 - Sample stage; 9 - Catalyst powder sample; 10 - Sample tube; 11 - Thermocouple jack; 12 - Heating rod; 13 - Thermocouple; 14 - Reaction gas cylinder; 15 - Pressure reducing valve; 16 - Electronic flowmeter; 17 - 1 - Liquid raw material tank; 17 - 2 - High performance liquid chromatography feed pump; 18 - Vaporization tank; 19 - Cold trap; 20 - Back pressure valve; 21 - Amorphous silicon area detector; 22 - Control system. Detailed implementation mode

[0049] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0050] One of the purposes of the present invention is to provide a catalyst reaction in-situ testing device, which can be used for in-situ synchrotron radiation testing during the multi-phase catalyst reaction process, and obtain high-quality X-ray absorption and X-ray diffraction spectra during the catalytic reaction process, providing basic data for further developing efficient multi-phase catalyst design.

[0051] Another purpose of the present invention is to provide a catalyst reaction in-situ testing method implemented based on the above catalyst reaction in-situ testing device.

[0052] To make the above purposes, features and advantages of the present invention more obvious and understandable, the present invention will be further described in detail below in conjunction with the accompanying drawings and specific implementation modes.

[0053] Embodiment 1

[0054] As Figure 1 shown, this embodiment provides a catalyst reaction in-situ testing device, which is specifically a testing device for in-situ synchrotron radiation X-ray absorption and diffraction of multi-phase catalytic fixed bed reactions, mainly composed of connection kit a 1, upright bracket 2, connection kit b 3, base 5, horizontal bracket 6, connection kit c 7, sample stage 8, sample tube 10, thermocouple jack 11, heating rod 12, thermocouple 13, reaction gas cylinder 14, pressure reducing valve 15, electronic flowmeter 16, liquid raw material tank 17 - 1, high performance liquid chromatography feed pump 17 - 2, vaporization tank 18, cold trap 19, back pressure valve 20, amorphous silicon area detector 21, and a control system 22 with data acquisition and processing functions. The above connection kit a 1, connection kit b 3, and connection kit c 7 all include through holes, threaded holes, and screws. Among them:

[0055] The reaction gas cylinder 14, pressure reducing valve 15, and electronic flowmeter 16 are connected in sequence through 1 / 8-inch steel pipes; the electronic flowmeter 16 is connected to the high-performance liquid chromatography feed pump 17-2 and vaporization tank 18 through a 1 / 8 steel pipe and a tee; if there are multiple gases, the parallel quantity of the reaction gas cylinder 14, pressure reducing valve 15, and electronic flowmeter 16 can be increased through a tee or a four-way; the outlet of the vaporization tank 18 is connected to the inlet end of the sample tube 10 through a 1 / 8 steel pipe and a 1 / 16 to 1 / 8 reducing structure; the reaction gas cylinder 14 mainly provides the high-pressure gas required for the in-situ catalytic reaction, and the outlet pressure is controlled by the pressure reducing valve 15 and connected to the electronic flowmeter 16; the outlet of the sample tube 10 is connected to the cold trap 19 through a 1 / 16 to 1 / 8 reducing structure and a 1 / 8 steel pipe, and the cold trap 19 is connected to the electronic pressure gauge through a 1 / 8 steel pipe; the electronic pressure gauge is connected to the cold trap 19 and the back pressure valve 20 through a 1 / 8 steel pipe and a tee; the sample tube 10 passes through the sample tube socket of the sample tube mounting block on the sample stage 8 and is fixed on both sides through a connection kit and a liner, and the middle part of the sample tube 10 is exposed so that X-rays can pass through; the thermocouple 13 is inserted into the thermocouple socket 11 on the sample stage 8 below the middle part of the sample tube 10; the direction of the high-energy synchrotron X-ray is perpendicular to the sample tube 10 and passes through the middle of the sample. The synchrotron X-ray absorption second ionization chamber is placed along the X-ray direction to detect the X-rays emitted from the sample to test and obtain the transmission absorption spectrum signal; when the sample content is low, a fluorescence or solid detector can be used to obtain the absorption spectrum along the direction perpendicular to the sample tube; the synchrotron X-ray diffraction signal is detected by an amorphous silicon planar detector. The reaction gas flow rate, sample temperature, pressure data, and control are completed through the control system 22, and the control system 22 can process XAFS data (i.e., X-ray absorption spectrum) and XRD spectrum data (i.e., X-ray diffraction spectrum).

[0056] In this embodiment, the energy of the synchrotron X-ray is the high-energy X-ray of the element to be tested at 8-50 keV. The energy fixed at the element edge before is used for XRD testing while XAFS testing is being carried out.

[0057] In this embodiment, the material of the sample tube 10 can be polyimide or beryllium, with a wall thickness of 0.08 mm to 0.6 mm and an outer diameter of 0.4 mm to 3 mm. When the reaction pressure is 0 to 3 MPa and the temperature is < 300 °C, XAFS data with a higher signal-to-noise ratio can be obtained using a polyimide tube. Under the condition of ensuring that the in-situ catalytic reaction conditions are met, the sample tube is mainly made of polyimide. The catalyst powder sample 9 to be measured is first formed and sieved before use, and the particle size is between 400 mesh and 100 mesh. The catalyst powder sample 9 to be measured is fed into the sample tube 10 through a steel tube with a diameter of 0.4 mm to 0.8 mm. The length of the sample in the sample tube 10 is 5 mm to 10 mm, and both ends are blocked and fixed with quartz wool and a liner tube to ensure that the airflow passing through the sample does not cause the sample to move. During the experiment, by adjusting the height of the sample stage 8, it is ensured that the centers of the sample tube 10, the thermocouple 13, the sample, and the synchrotron X-ray irradiation center are basically coincident. For the XAFS signal of the sample, by finely adjusting the position of the sample stage and comparing the rapid scan signal of the XAFS device, the spectral quality is optimized.

[0058] In this embodiment, the above-mentioned thermocouple 13 for temperature measurement is preferably a K-type thermocouple. The parallel distance between the sample tube 10 and the thermocouple 13 is 0 to 0.2 mm. The sample stage 8 is in contact with both ends of the sample tube 10, and the middle part of the sample tube 10 is heated by conduction and radiation through the sample stage 8. Before use, it is necessary to correct the actual temperature inside the sample tube 10 and the temperature of the sample stage 8, and the temperature difference is 10 °C to 30 °C.

[0059] In this embodiment, the sample stage 8 is preferably made of 304 stainless steel or pure copper, and a sufficient arc-shaped space is left in the middle of the upper part, so that XRD signals can be collected in the range of 180 degrees. The volume of the cold trap 19 is 1 mL to 10 mL, the material is 304 stainless steel, and the pressure limit of use is 10 MPa.

[0060] In this embodiment, the liquid flow rate is controlled by the high-performance liquid chromatography feed pump 17-2, and the flow rate range is 0 mL / min to 1.000 mL / min.

[0061] In this embodiment, the vaporization tank 18 and the pipeline from the vaporization tank 18 to the sample tube 10 are heated by a heating tape, and the temperature range is 25 °C to 200 °C. The ultimate working pressure of the back pressure valve 20 is 10 MPa to 15 MPa.

[0062] In this embodiment, the heating rod 12 has an internal electric heating wire, and the material is a 5 mm rod-shaped structure of iron-chromium-aluminum alloy wire, nickel-chromium alloy wire or tungsten wire. It can be simply inserted and removed from the sample stage 8, which is convenient for the installation of the sample tube 10. The heating temperature can reach 800 °C. Due to the characteristics of the polyimide and beryllium tube materials, the operating temperature is optimized to 0 to 600 °C.

[0063] In this embodiment, the amorphous silicon planar detector 21 is a PerkinElmer XRD1622 detector or an energy-resolving detector. Among them, the diffraction data obtained by the PerkinElmer XRD1622 detector is a binary diffraction ring picture file, and the FIT2D software (an existing data processing software) is used to convert the diffraction ring into a spectrum of intensity and diffraction angle. The energy-resolving detector can achieve picosecond-level synchrotron radiation infrared spectroscopy detection and obtain surface dynamic reaction information.

[0064] In this embodiment, the electronic flowmeter 16 is a high-precision electronic mass flowmeter with a flow range of 0 - 50 ccm.

[0065] During the in-situ hydrogenation of levulinic acid in aqueous phase over the Pt-TiO2 / α-Al2O3 catalyst, the dynamic synchrotron radiation XAFS and XRD spectra were obtained by testing. The Pt-TiO2 / α-Al2O3 catalyst was prepared by atomic layer deposition technology. First, a 40-cycle titanium oxide film (3 nm) was deposited on the surface of α-Al2O3 nanospheres, and then 30 cycles of platinum were deposited. Platinum nanoparticles with a size of 2 nm were loaded on the surface of the titanium oxide film. Then, the Pt-TiO2 / α-Al2O3 catalyst was loaded into the sample tube 10. After that, liners were placed at both ends of the sample tube 10, and the prepared sample tube 10 was placed on the sample stage 8. The middle 3 mm of the sample tube 10 was in the middle of the upper sector-shaped groove (i.e., the above-mentioned sector-shaped notch) of the sample stage 8 to ensure that the synchrotron radiation X-ray vertically passed through the sample tube 10 and to ensure that the X-ray diffraction spectrum passed through the rotation center of the amorphous silicon planar detector. The XAFS and XRD spectra of the initial state of the test sample were measured, and the best spectroscopic information was obtained by finely adjusting the height of the sample stage 10.

[0066] When conducting the in-situ test experiment: adjust the reaction gas cylinder 14, pressure reducing valve 15, and electronic flowmeter 16, and introduce hydrogen into the sample tube 10. After detecting no air leakage, increase the system pressure to 2 MPa and set the hydrogen flow rate to 10 mL / min. Set the temperature of the heating tape to 60 °C, and then turn on the high-performance liquid chromatography feed pump 17-2 to continuously introduce a 10 wt% aqueous solution of levulinic acid into the system at a flow rate of 0.001 mL / min. The liquid is vaporized in the vaporization tank 18 and then passes through the sample tube 10 together with hydrogen. The liquid product is recovered in the cold trap 19 after cooling, and the gas product is discharged to the outside of the room at atmospheric pressure through the back pressure valve 20. Set the heating rate of the heating rod 12 to 5 °C / min, and the target temperatures are set to 60, 90, 120, 150, and 180 °C. The XAFS and XRD spectra during the heating process and under different temperature conditions were measured. The XAFS data was processed by the Athena software (an existing data processing software), and the XRD spectra were processed by FIT2D. Figure 8Research and analysis show that Pt particles are in the metallic state during the in-situ process. With the change of temperature, the Pt-Pt coordination number dynamically changes between 9.3 and 10. At the same time, the XRD pattern shows that in addition to the significant diffraction peak of α-Al2O3, there is also a typical diffraction peak of Pt metal particles, and the intensity of this peak dynamically changes with the change of temperature. These results indicate that the Pt-TiO2 / α-Al2O3 catalyst interacts with reactants and solvent water during the in-situ reaction process, and the Pt particles dynamically change within a certain range.

[0067] It can be seen that the in-situ test device for catalyst reaction proposed by this technical solution has a simple structure. The flow state of the reaction gas can be controlled by controlling the size of the catalyst powder sample particles, the inner diameter of the sample tube, and the flow rate of the high-pressure gas. It can be used to monitor the in-situ catalyst structure evolution law during the fixed-bed catalytic reaction process. Through the open arc groove design of the sample stage, it can ensure that high-energy X-rays pass through, and at the same time collect the transmission XAFS absorption spectrum in the ray direction, the vertical ray square XAFS fluorescence spectrum, and the XRD signal at 180-degree azimuth, and obtain the changes in the valence state, coordination structure, and crystal structure information of the sample during the catalytic in-situ reaction process on the same time scale. In addition, using a polyimide tube as the sample tube with a thinner tube wall (0.001 - 0.1 mm) not only has the advantages of good flexibility and strength, can improve the signal-to-noise ratio of the XAFS signal, can control the optimal thickness of the sample penetrated by X-rays by fine-tuning the height of the tube, and obtain the highest signal-to-noise ratio. Using beryllium as the sample tube can increase the temperature and pressure range of the in-situ test and has a good transmission signal. The related system solves the problems that the previous equipment cannot reflect the true in-situ spectroscopic information of the heterogeneous catalytic reaction, has poor signals, and cannot simultaneously achieve multiple spectroscopic monitoring, and has important value and significance for promoting the development of heterogeneous catalysts.

[0068] It should be noted that for those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention, and any reference signs in the claims should not be regarded as limiting the claims involved.

[0069] In the present invention, specific examples are used to illustrate the principle and implementation manner of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those of ordinary skill in the art, according to the idea of the present invention, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation on the present invention.

Claims

1. An in-situ test device for catalyst reaction, characterized in that, Comprising: A sample tube for containing a catalyst powder sample therein. A sample stage support frame, which includes a base, a vertical support, and a horizontal support. The vertical support is perpendicular to the base, the bottom end of the vertical support is connected to one side of the base, one end of the horizontal support is connected to the top end of the vertical support, and the installation height of the horizontal support on the vertical support is adjustable. A sample stage, which is arranged on the upper surface of the horizontal support. The sample tube is installed on the sample stage, and a temperature detection device and a sample heating device capable of heating the sample tube are arranged on the sample stage. Two symmetrically arranged sample tube mounting blocks with a gap are provided on the upper surface of the sample stage. Sample tube insertion holes are formed in both of the two sample tube mounting blocks. The sample tube sequentially passes through the sample tube insertion holes on the two sample tube mounting blocks. An exposure area is formed between the two sample tube mounting blocks to expose the part of the sample tube filled with the catalyst powder sample. Two fan-shaped notches symmetrically distributed on both sides of the sample tube are also formed between the two sample tube mounting blocks, and the vertices of the two fan-shaped notches are respectively communicated with both ends of the exposure area. An X-ray emission device, which is arranged above the sample stage and is used to vertically emit X-rays to the sample tube. A gas supply device, which includes a gas storage bottle. The gas storage bottle is connected to the inlet end of the sample tube through a pipeline and is used to provide high-pressure gas into the sample tube. A pressure reducing valve and a flow meter are sequentially arranged between the gas storage bottle and the sample tube along the gas flow direction. A liquid supply device, which includes a liquid raw material tank, a liquid chromatography feed pump, and a vaporization device connected in sequence. The liquid chromatography feed pump is used to pump the reaction liquid in the liquid raw material tank into the vaporization device. The vaporization device is connected to the inlet end of the sample tube and is used to vaporize the reaction liquid and introduce it into the sample tube. The vaporization device is a vaporization tank, and the flow meter is connected to the vaporization tank to realize the confluence of the high-pressure gas and the vaporized reaction liquid. Heating tapes are wound around the outside of the vaporization tank and on the pipeline between the vaporization tank and the sample tube to heat the high-pressure gas and the vaporized reaction liquid. A reaction product cooling device, which includes a cold trap and a back pressure valve connected in sequence through a pipeline. The cold trap is connected to the outlet end of the sample tube. A control system, which is communicatively connected to the temperature detection device, the sample heating device, and the flow meter.

2. The in-situ test device for catalyst reaction according to claim 1, wherein The sample stage is a stainless steel sample stage or a pure copper sample stage; the temperature detection device and the sample heating device are a thermocouple and a heating rod respectively, and both the thermocouple and the heating rod are inserted into the sample stage.

3. The in-situ test device for catalyst reaction according to claim 1, wherein, The sample tube is a polyimide tube or a beryllium tube; the outer diameter of the sample tube is 0.4 mm to 3 mm, and the wall thickness is 0.08 mm to 0.6 mm.

4. The in-situ test device for catalyst reaction according to claim 1, wherein, There are two pipeline plugging members arranged at intervals in the sample tube. A sample reaction zone is formed between the two pipeline plugging members. The catalyst powder sample is placed in the sample reaction zone, and the sample reaction zone is used to be exposed to the exposure zone. Among them, the pipeline plugging member includes a liner tube and quartz wool.

5. The in-situ test device for catalyst reaction according to claim 1, characterized in that, The X-ray emission device is detected by an amorphous silicon flat panel detector.

6. A catalyst reaction in-situ testing method implemented by using the catalyst reaction in-situ testing device described in any one of claims 1 to 5, characterized in that, Including: Load the catalyst powder sample to be tested into the sample tube and install the sample tube on the sample stage; Start the X-ray emission device, the temperature detection device and the sample heating device; Pump the reaction liquid into the vaporization device through the liquid chromatography feed pump. The vaporization device vaporizes the reaction liquid and introduces it into the sample tube. At the same time, hydrogen is introduced into the sample tube from the gas storage bottle; Change the heating temperature of the sample heating device to test the XAFS data and XRD spectrum data under different temperature conditions.

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