CN113702413B - Heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and use method - Google Patents
Heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and use method Download PDFInfo
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Abstract
The invention discloses a heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research, which consists of a vacuum pump, a cooling device, a connecting pipeline and a reaction tank: the cooling device consists of a cold hydrazine and a liquid nitrogen tank; the reaction tank consists of a double-layer glass sleeve and a heating furnace, the double-layer glass sleeve is convenient to detach, and the double-layer glass sleeve can be directly placed in a resonant cavity of the electron paramagnetic resonance spectrometer for characterization test; the connecting pipeline comprises a vacuum gauge, a three-way valve, a ball valve, a filter and a back pressure valve, and can directly connect the reaction tank with the activation/reaction device and simultaneously meet the activation/reaction requirements of the catalyst. The device can be used in combination with various characterization instruments, and provides powerful support for activating the catalyst and performing in-situ/quasi-in-situ characterization of the catalytic reaction.
Description
Technical Field
The invention relates to the technical field of heterogeneous catalyst activation/reaction, in particular to a heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research and a use method thereof, which can be applied to in-situ and quasi-in-situ characterization of a heterogeneous catalyst.
Background
Catalysts are widely used in the fields of modern chemical industry, petroleum processing industry, energy, pharmaceutical industry, environmental protection, and the like. In chemical industry, the catalytic process accounts for more than 80% of the total chemical processes. Heterogeneous catalysts are dominant in the manufacture of chemical products because of their easy separation from the products. The supported heterogeneous catalyst usually needs to be activated in the practical application process to remove surface adsorption substances, reduce metal valence states and the like so as to achieve the effect of exposing active sites and improve the reaction activity.
The catalyst activation method commonly used in the industry is to bake or further reduce, oxidize, sulfide, hydroxylate, dehydroxylate the catalyst at a higher temperature, thereby converting the passive catalyst or catalyst precursor into an active catalyst. For partial catalysts, the activation process only needs to remove substances adsorbed on the surface and expose active sites, and the method of heating and activating by introducing gas has high cost and is easy to generate waste gas, which is not a preferable scheme. In addition, if the activated catalyst needs to be prevented from contacting air in the process of transferring to the reaction device, the operation in a glove box is required, the operation is complex, the effect is difficult to ensure, and the catalyst activation/reaction integrated device can effectively solve the problem.
Disclosure of Invention
The technical problems to be solved are as follows:
the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research, designed by the invention, meets two activation approaches of vacuum activation and gas heating activation at the same time, and is suitable for the activation requirements of various catalysts; the catalyst can directly participate in the reaction process after being activated, and the reaction tank can perform electron paramagnetic resonance in-situ/quasi-in-situ test. The device can be connected with an online testing instrument, such as a Gas Chromatograph (GC) or an online Mass Spectrometer (MS), and can directly characterize the reacted product to complete a whole set of catalyst activation, reaction and characterization processes, so that the time required by experiments is greatly shortened, the operation steps are simplified, and the reduction or inactivation of the catalytic performance caused by repeated contact of the catalyst with air is avoided.
The technical scheme is as follows:
a heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research, characterized in that: the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research consists of a vacuum pump, a cooling device, a connecting pipeline and a reaction tank. The cooling device consists of a liquid nitrogen tank and a cold trap, and the upper part of the pipe is provided with a deflation valve for balancing the air pressure in the pipe after vacuum activation; the adsorbed gas and water removed in the vacuum activation process of the catalyst are condensed into the glass tube through the cooling device, so that volatile substances are prevented from entering the vacuum pump to damage the pump body. The connecting pipeline consists of a needle valve, a ball valve, a vacuum gauge, a three-way valve, a one-way valve, a filter, a back pressure valve and a temperature measuring point, and part of the pipeline needs to be insulated to ensure that the reaction gas and the product cannot be condensed in the pipeline. The connecting pipeline connects the gas distribution system, the vacuum pump and the reaction tank, and can be flexibly switched to a catalyst activation or reaction path by using a three-way valve. The main body of the reaction tank is a double-layer glass sleeve, and a heating furnace with a quartz window is configured, so that different requirements of the catalyst on photo/thermal catalytic reaction characterization under vacuum activation, ventilation body activation and quasi-in-situ conditions and photo/thermal catalytic reaction characterization under in-situ conditions can be met.
As a preferred embodiment of the present invention, the electron paramagnetic resonance research multiphase catalyst activation/reaction apparatus has two operation modes when used for catalyst activation: a vacuum activation mode and a vent activation mode. The vacuum activation mode is to remove adsorbate on the surface of the catalyst to expose active sites by using high vacuum condition and high temperature as assistance, thereby realizing the activation of the catalyst; the aeration body activation is to connect the gas distribution system with the reaction tank, and the target gas is assisted with high temperature condition to meet the specific gas activation mode requirement required by certain catalysts; meanwhile, the gas distribution system is connected with the reaction tank, and can be used as a reaction device required by in-situ/quasi-in-situ characterization of the catalyst, a double-layer glass sleeve in the reaction tank can be directly placed in a resonant cavity of an electron paramagnetic resonance spectrometer for catalyst characterization, and an evacuation pipeline can be connected with other characterization instruments, such as Gas Chromatography (GC) or online Mass Spectrometer (MS) for online testing of reaction products.
As a preferred technical scheme of the invention: the cooling device is made of high borosilicate glass, two ends of the cooling device are connected with a vacuum pump and a three-way valve through vacuum bellows, and a vacuum gauge is connected to the right side of the cooling device to observe the vacuum degree in the system; the air release valve is used for balancing the system air pressure after the vacuum activation operation is finished, so that the device is conveniently switched to a catalyst reaction path, and the activated catalyst is directly subjected to in-situ/quasi-in-situ characterization.
As a preferred technical scheme of the invention: in the reaction tank, the double-layer glass sleeve serving as the main body of the reaction tank is made of quartz, so that illumination is convenient, the outer diameter is less than or equal to 10mm, and the double-layer glass sleeve can be directly placed in a resonant cavity of an electron paramagnetic resonance spectrometer for characterization; the wall thickness of the glass sleeve is adjusted according to the internal pressure of an actual system. The two ends of the double-layer glass sleeve are provided with filters to prevent the catalyst in the tube from being blown out along with the air flow to block the pipeline and the valve, and meanwhile, the ball valve is additionally arranged, so that the disassembly of the reaction tank is convenient, and the vacuum or gas environment in the reaction tube is kept. The back end of the air outlet pipeline is provided with a one-way valve to prevent the gas from flowing back and polluting the catalyst. The heating furnace with the quartz window, which is equipped with the reaction tank, can be manufactured into an independent heating furnace for respectively heating the double-layer glass sleeve; the furnace can also be manufactured into an integral furnace, and simultaneously, a plurality of glass sleeves are heated, and the design can be specifically selected according to experimental requirements.
As a preferred embodiment of the present invention, the connecting line is characterized in that: the three-way valve is connected with the cooling device and the reaction tank, the ball valve is assembled at the outlet of the gas distribution system, so that the gas flow generated by the gas distribution system can be controlled to slowly enter the reaction tank in a vacuum state, and the catalyst is prevented from being blown away from the detection area from the bottom of the double-layer glass sleeve by overlarge gas flow when the valve 1-2 is opened. In addition, a three-way valve is additionally arranged at the front end of the reaction tank and is directly communicated with an emptying pipeline, so that the gas distribution proportion can be conveniently checked before the reaction starts by a gas chromatograph analytical instrument. Filters are designed at two ends of the back pressure valve with the temperature measuring points so as to prevent solid particles from entering the back pressure valve or downstream detection equipment to cause damage to accessories; the ball valve and the needle valve of the back pressure valve bypass are used for rapidly discharging the gas in the system.
As a preferred embodiment of the present invention, the connecting line is characterized in that: the gas path of the evacuation pipeline is connected with the reaction tank by the gas distribution system, and the temperature is not lower than 130 ℃, so that the gas path is connected with the reaction tank by the gas distribution system, and the gas path is convenient for preheating the contact catalyst gas in order to prevent the condensation of part of low-boiling-point raw material gas or products.
As a preferred technical scheme of the invention: the vacuum degree of the vacuum pump can reach < -0.01 mbar; the double-layer glass sleeve in the reaction tank can bear 5MPa pressure at maximum, and the sealing joint is made of nonmagnetic materials; the heating furnace adopts temperature programming, and can meet the heating condition from room temperature to 800 ℃.
The application method of the heterogeneous catalyst vacuum activation/reaction device for electron paramagnetic resonance research is characterized by comprising the following steps:
the first step: adding a catalyst into the double-layer glass sleeve, and if an electron paramagnetic resonance test is required, filling the sample within 4.0 cm; the pipelines are connected in sequence, and the double-layer glass sleeve filled with the catalyst is placed in a heating furnace.
And a second step of: switching the three-way valve 4-1 to a cooling device to be communicated with the reaction tank, and switching the three-way valve 4-2 to an air inlet pipeline to be communicated with the reaction tank; and closing the ball valve 1-4 at the rear part of the reaction tank, under the condition of ensuring that a gas release valve on the cooling device is closed, firstly opening a vacuum pump, then opening the ball valve 1-1, slowly opening the ball valve 1-3, vacuumizing, checking a vacuum gauge to show that a system of the device has no gas leakage phenomenon, and activating the vacuum for a certain time.
And a third step of: under the condition that the ball valve 1-2 behind the gas distribution system is closed, the three-way ball valve 4-1 is switched to be communicated with the reaction tank, the air release valve is opened to balance the air pressure of the pipeline, the vacuum pump is closed, and the subsequent catalyst reaction process is carried out.
Fourth step: under the condition that the three-way valve 4-2 is directly communicated with the gas distribution system and the rear evacuation pipe, preparing gas according to experimental requirements, opening the ball valve 1-2, flushing a pipeline with a small amount of gas, closing the ball valve 1-5 and the back pressure valve after flushing, closing the ball valve 1-2, and switching the three-way valve 4-2 to be communicated with the gas distribution system and the reaction tank.
Fifth step: sequentially opening ball valves 1-2, 1-3 and 1-4, regulating back pressure valve to a required pressure, enabling gas to flow through the reaction cell, setting the temperature of the heating furnace to be a temperature required by experiments, and carrying out catalytic reaction.
Sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is to be carried out, the double-layer glass sleeve is placed in a heating furnace for reaction, after the reaction is finished, the ball valves 1-3 and 1-4 are closed, the connecting parts at the upper ends of the ball valves 1-3 and 1-4 are disconnected, and then the double-layer glass sleeve is taken out and placed in a resonant cavity for test. The rear end of the evacuation tube can be connected with a Gas Chromatograph (GC) or an online Mass Spectrometer (MS) to test the reaction product.
The application method of the catalyst gas heating activation/reaction device is characterized by comprising the following steps:
the first step: adding a catalyst into the double-layer glass sleeve, and if an electron paramagnetic resonance test is required, filling the sample within 4.0 cm; and (5) connecting the pipelines in sequence, and placing the double-layer glass sleeve filled with the catalyst into a heating furnace.
And a second step of: the three-way valves 4-1 and 4-2 are communicated with the gas distribution device and the reaction tank, the ball valves 1-3 and 1-4 are opened, the valves 1-5 and 14 are opened, and the back pressure valve is opened to enable the required gas to flow through the reaction tank. And setting the temperature of the heating furnace according to the activation requirement, and activating the catalyst.
And a third step of: and after the activation is finished, sequentially closing the back pressure valve, the ball valve 1-5, the ball valve 1-4, the ball valve 1-3 and the ball valve 1-2, and preparing gas for catalytic reaction test. If the gas distribution system needs to be replaced, the three-way valve 4-2 is switched to the gas distribution system to be directly communicated with the emptying pipeline, the ball valve 1-2, the back pressure valve and the valves 1-5 and 14 are opened, the reaction gas is utilized to purge the pipeline for a plurality of times, and then subsequent catalytic reaction and related characterization tests are carried out.
Fourth step: after the purging is finished, the valve 1-5 and the back pressure valve are closed, the ball valve 1-2 is closed, and the three-way valve 4-2 is switched to be communicated with the gas distribution system and the reaction tank.
Fifth step: sequentially opening ball valves 1-2, 1-3 and 1-4, regulating back pressure valve to required pressure, enabling gas to flow through the reaction cell, setting the temperature of the heating furnace to be required by experiments, and carrying out catalytic reaction.
Sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is to be carried out, the double-layer glass sleeve is placed in a heating furnace for reaction, after the reaction is finished, the ball valves 1-3 and 1-4 are closed, the connection of the upper ends of the ball valves 1-3 and 1-4 is disconnected, and then the double-layer glass sleeve is taken out and placed in a resonant cavity for test. The rear end of the evacuation tube can be connected with a Gas Chromatograph (GC) or an online Mass Spectrometer (MS) to test the reaction product.
The beneficial effects are that:
1. the invention combines the vacuum activation operation and the gas heating activation operation of the catalyst, avoids the problem of higher cost of gas heating activation of partial catalyst, and improves the operation cost performance while simplifying the operation.
2. The invention can directly introduce the reaction gas to the catalyst for reaction after the catalyst is activated, avoids the complicated step of transferring the catalyst to the reaction tank after the catalyst is activated, and simplifies the catalytic reaction process.
3. The invention can be used for in-situ/quasi-in-situ electron paramagnetic resonance test, and overcomes the defects that the electron paramagnetic resonance spectrometer cannot be filled with gas and has insufficient pressure resistance in the in-situ characterization process.
4. The invention can test the catalytic reaction products on line by connecting with other characterization instruments, and is a set of complete catalytic activation/reaction/testing device.
Drawings
Fig. 1: the invention provides a schematic structural diagram of a heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research.
Reference numerals illustrate: 1. ball valve, 2, bleed valve, 3, vacuum gauge, 4, three-way valve, 5, cold trap, 6, liquid nitrogen tank, 7, filter, 8, catalyst, 9, check valve, 10, double-layer glass sleeve, 11, heating furnace with quartz window, 12, back pressure valve, 13, temperature measuring point, 14, needle valve.
Detailed Description
The following examples illustrate the invention in detail, but are not to be construed as limiting the invention, as alternatives and modifications of the method, steps or conditions of the invention are within the scope of the invention without departing from the spirit and nature of the invention.
Furthermore, those of ordinary skill in the art will appreciate that the drawings are provided solely for the purposes of illustrating the objects, features, and advantages of the invention and that the drawings do not contain all of the component configurations and attachment means of the invention.
As shown in FIG. 1, the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research consists of a vacuum pump, a cooling device, a connecting pipeline and a reaction tank. The cooling device consists of a liquid nitrogen tank 6 and a cold trap 5, and the upper part of the pipe is provided with a deflation valve 2 for balancing the air pressure in the pipe after the vacuum activation is finished; the gas and water adsorbed on the catalyst removed in the vacuum activation process are condensed in the cold trap by the cooling device, so that volatile substances are prevented from entering the vacuum pump to damage the pump body. The connecting pipeline consists of a ball valve 1, a vacuum gauge 3, a three-way valve 4, a filter 7, a one-way valve 9, a back pressure valve 12, a temperature measuring point 13 and a needle valve 14, and part of the pipeline needs to be insulated to ensure that gas cannot be condensed in the pipeline. The connecting pipeline connects the gas distribution system, the vacuum pump and the reaction tank, and the three-way valve 4 can be utilized to flexibly switch to a catalyst activation or reaction path. The main body of the reaction tank is a double-layer glass sleeve 10, and a heating furnace 11 with a quartz window is configured, so that different requirements of the photo/thermal catalytic reaction characterization of the catalyst under the conditions of vacuum activation, ventilation activation and quasi-in-situ and the photo/thermal catalytic reaction characterization under the in-situ conditions can be met.
The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research has two operation modes when used for catalyst activation: a vacuum activation mode and a vent body heating activation mode. The vacuum activation mode is to remove adsorbate on the surface of the catalyst to expose active sites by using high vacuum condition and high temperature as assistance, thereby realizing the activation of the catalyst; the aeration body is heated and activated, namely the gas distribution system is connected with the reaction tank part, and the target gas is assisted by high temperature conditions, so that the specific gas activation mode requirement required by certain catalysts is met; meanwhile, the gas distribution system is connected with the reaction tank and can be used as a reaction device required by in-situ/quasi-in-situ characterization of the catalyst, and the double-layer glass sleeve 10 in the reaction tank can be directly placed in the resonant cavity of the electron paramagnetic resonance spectrometer for catalyst characterization; in addition, the evacuation line may be connected to other analytical instrumentation, such as in situ characterization of the reaction gas product in combination with Gas Chromatography (GC) or on-line Mass Spectrometry (MS), and the like.
The cooling device is characterized in that: high borosilicate glass is selected as a cold trap 5 material, two ends of the high borosilicate glass are connected with a vacuum pump and a three-way valve 4-1 through vacuum bellows, and a vacuum gauge 3 is connected to the right side of the high borosilicate glass so as to observe the vacuum degree in the system; the air release valve 2 is used for balancing the system air pressure (the device connection mode is switched to the catalyst reaction way firstly) after the vacuum activation operation is finished, so that the oil pumping back suction is avoided.
The reaction tank is characterized in that: the double-layer glass sleeve 10 serving as the main body of the reaction tank is made of quartz, is convenient for illumination, has the outer diameter less than or equal to 10mm, and can be directly placed in a resonant cavity of an electron paramagnetic resonance spectrometer for catalyst characterization; the wall thickness of the glass sleeve is adjusted according to the internal pressure of an actual system. The two ends of the double-layer glass sleeve 10 are provided with filters 7-1 and 7-2 to prevent the catalyst in the tube from being blown out along with the air flow to block the pipeline and the valve, and meanwhile, the ball valves 1-3 and 1-4 are additionally arranged to facilitate the disassembly of the reaction tank and maintain the vacuum or gas environment in the reaction tube. The back end of the air outlet pipeline is provided with a one-way valve 9 to prevent the gas from flowing back and polluting the catalyst. The heating furnace 11 having the quartz window may be manufactured as an independent heating furnace, respectively heating the double glass sleeve 10; the furnace can also be manufactured into an integral furnace, and simultaneously, a plurality of glass sleeves are heated, and the design can be specifically selected according to experimental requirements.
The connecting pipeline is characterized in that: the three-way valve 4-1 is connected with the cooling device and the reaction tank, the ball valve 1-2 is assembled at the outlet of the air distribution system, so that air flow generated by the air distribution system can be controlled to slowly enter the reaction tank in a vacuum state, and the catalyst is prevented from being blown away from the detection area from the bottom of the double-layer glass sleeve by overlarge air flow when the valve 1-2 is opened. In addition, a three-way valve 4-2 is additionally arranged at the front end of the reaction tank and is directly communicated with an evacuation pipeline, so that the gas proportion can be conveniently checked before the reaction starts (through on-line gas chromatography and other on-line detection instruments). Filters 7-3 and 7-4 are designed at two ends of the back pressure valve 12 with the temperature measuring point 13 so as to prevent solid particles from entering the back pressure valve or a downstream detecting instrument to cause the damage of accessories; ball valves 1-5 bypassed by back pressure valve 12 and needle valve 14 are used for rapid pressure relief of the reaction system. The gas path of the evacuation pipeline is connected with the reaction tank by the gas distribution system, and the temperature is not lower than 130 ℃, so that the reaction gas can be preheated conveniently to prevent the condensation of partial low-boiling-point raw material gas or product.
The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research has the following characteristic parameters: the vacuum degree of the vacuum pump can reach < -0.01 mbar; the double-layer glass sleeve 10 in the reaction tank can bear 5MPa pressure at maximum, and the sealing joint is made of nonmagnetic materials; the heating furnace 11 is programmed to raise the temperature, and can satisfy the heating condition from room temperature to 800 ℃.
The using method of the catalyst vacuum activation/reaction device comprises the following steps:
the first step: adding a catalyst into the double-layer glass sleeve, and if an electron paramagnetic resonance test is required, filling the sample within 4.0 cm; the pipelines are connected in sequence, and the double-layer glass sleeve filled with the catalyst is placed in a heating furnace.
And a second step of: switching the three-way valve 4-1 to a cooling device to be communicated with the reaction tank, and switching the three-way valve 4-2 to an air inlet pipeline to be communicated with the reaction tank; and closing the ball valve 1-4 at the rear part of the reaction tank, under the condition of ensuring that a gas release valve on the cooling device is closed, firstly opening a vacuum pump, then opening the ball valve 1-1, slowly opening the ball valve 1-3, vacuumizing, checking a vacuum gauge to show that a system of the device has no gas leakage phenomenon, and activating the vacuum for a certain time.
And a third step of: under the condition that the ball valve 1-2 behind the gas distribution system is closed, the three-way ball valve 4-1 is switched to be communicated with the reaction tank, the air release valve is opened to balance the air pressure of the pipeline, the vacuum pump is closed, and the subsequent catalyst reaction process is carried out.
Fourth step: under the condition that the three-way valve 4-2 is directly communicated with the gas distribution system and the rear evacuation pipe, pipeline purging is carried out when experiment needs to be carried out, the ball valve 1-2 is opened, a small amount of gas is used for flushing a pipeline (wherein the needle valve 14 keeps a small opening degree all the time), the ball valve 1-5 and the back pressure valve are closed after flushing is finished, the ball valve 1-2 is closed, and the three-way valve 4-2 is switched to be communicated with the gas distribution system and the reaction tank.
Fifth step: sequentially opening ball valves 1-2, 1-3 and 1-4, regulating back pressure valve to a required pressure, enabling gas to flow through the reaction cell, setting the temperature of the heating furnace to be a temperature required by experiments, and carrying out catalytic reaction.
Sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is to be carried out, the double-layer glass sleeve is placed in a heating furnace for reaction, after the reaction is finished, the ball valves 1-3 and 1-4 are closed, the connecting parts at the upper ends of the ball valves 1-3 and 1-4 are disconnected, and then the double-layer glass sleeve is taken out and placed in a resonant cavity for test. The rear end of the evacuation tube can be connected with a Gas Chromatograph (GC) or an online Mass Spectrometer (MS) to test the reaction product.
The using method of the catalyst gas heating activation/reaction device comprises the following steps:
the first step: adding a catalyst into the double-layer glass sleeve, and if an electron paramagnetic resonance test is required, filling the sample within 4.0 cm; and (5) connecting the pipelines in sequence, and placing the double-layer glass sleeve filled with the catalyst into a heating furnace.
And a second step of: the three-way valves 4-1 and 4-2 are communicated with the gas distribution device and the reaction tank, the ball valves 1-3 and 1-4 are opened, the valves 1-5 and 14 are opened (wherein the needle valve 14 keeps a smaller opening degree all the time), and the back pressure valve is opened to enable the needed gas to flow through the reaction tank. And setting the temperature of the heating furnace according to the activation requirement, and activating the catalyst.
And a third step of: and after the activation is finished, sequentially closing the back pressure valve, the ball valve 1-5, the ball valve 1-4, the ball valve 1-3 and the ball valve 1-2, and preparing gas for catalytic reaction test. If the pipeline is required to be purged, the three-way valve 4-2 is switched to the gas distribution system to be directly communicated with the emptying pipeline, the ball valve 1-2, the back pressure valve and the valves 1-5 and 14 are opened, the reaction gas is utilized to purge the pipeline for a plurality of times, and then the subsequent catalytic reaction and related characterization test are carried out.
Fourth step: after purging, the valve 1-5 and the back pressure valve are closed, the ball valve 1-2 is closed, and the three-way valve 4-2 is switched to be communicated with the gas distribution system and the reaction tank.
Fifth step: sequentially opening ball valves 1-2, 1-3 and 1-4, regulating back pressure valve to required pressure, enabling gas to flow through the reaction cell, setting the temperature of the heating furnace to be required by experiments, and carrying out catalytic reaction.
Sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is to be carried out, the double-layer glass sleeve is placed in a heating furnace for reaction, after the reaction is finished, the ball valves 1-3 and 1-4 are closed, the connecting parts at the upper ends of the ball valves 1-3 and 1-4 are disconnected, and then the double-layer glass sleeve is taken out and placed in a resonant cavity for test. The rear end of the evacuation tube can be connected with a Gas Chromatograph (GC) or an online Mass Spectrometer (MS) to test the reaction product.
Claims (7)
1. A heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research, characterized in that: the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research consists of a vacuum pump, a cooling device, a connecting pipeline and a reaction tank;
the cooling device consists of a liquid nitrogen tank (6) and a cold trap (5), and the upper part of the pipe is provided with a deflation valve (2) for balancing the air pressure in the pipe after the vacuum activation is finished; the gas and water adsorbed on the catalyst removed in the vacuum activation process are condensed in the cold trap through the cooling device, so that volatile substances are prevented from entering the vacuum pump to damage the pump body;
the connecting pipeline consists of a ball valve (1), a vacuum gauge (3), a three-way valve (4), a filter (7), a one-way valve (9), a back pressure valve (12), a temperature measuring point (13) and a needle valve (14), and part of the pipeline needs to be insulated to ensure that gas cannot be condensed in the pipeline;
the connecting pipeline connects the gas distribution system, the vacuum pump and the reaction tank, and the three-way valve (4) can be utilized to flexibly switch to a catalyst activation or reaction path;
the main body of the reaction tank is a double-layer glass sleeve (10), and a heating furnace (11) with a quartz window is arranged, so that different requirements of the photo/thermal catalytic reaction characterization of the catalyst under the conditions of vacuum activation, ventilation activation and quasi-in-situ and the photo/thermal catalytic reaction characterization under the in-situ conditions can be met;
in the cooling device, high borosilicate glass is selected as a cold trap (5) material, two ends of the cooling device are connected with a vacuum pump and a first three-way valve (4-1) through vacuum bellows, and a vacuum gauge (3) is connected to the right side of the cooling device to observe the vacuum degree in the system; the air release valve (2) is used for balancing the system air pressure after the vacuum activation operation is finished, and the device connection mode is switched to a catalyst reaction path;
the first three-way valve (4-1) is connected with the cooling device and the reaction tank, the second ball valve (1-2) is arranged at the outlet of the air distribution system, so that air flow generated by the air distribution system can be controlled to slowly enter the reaction tank in a vacuum state, and the catalyst is prevented from being blown away from the detection area from the bottom of the double-layer glass sleeve by overlarge air flow when the second ball valve (1-2) is opened;
in addition, a second three-way valve (4-2) is additionally arranged at the front end of the reaction tank and is directly communicated with an emptying pipeline, so that the gas proportion can be conveniently checked before the reaction starts;
one end of the back pressure valve (12) with a temperature measuring point (13) is provided with a third filter (7-3), and the other end is provided with a fourth filter (7-4) so as to prevent solid particles from entering the back pressure valve or a downstream detecting instrument to cause the damage of accessories;
the fifth ball valve (1-5) and the needle valve (14) which bypass the back pressure valve (12) are used for quick pressure relief of the reaction system.
2. The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research according to claim 1, wherein: there are two modes of operation when used for catalyst activation: a vacuum activation mode and a vent heating activation mode;
the vacuum activation mode is to remove adsorbate on the surface of the catalyst to expose active sites by using high vacuum condition and high temperature as assistance, thereby realizing the activation of the catalyst;
the ventilation body is heated and activated, namely a gas distribution system is connected with a reaction tank part, and target gas is assisted with high-temperature conditions, so that the gas activation mode requirement of the catalyst is met; the gas distribution system is connected with the reaction tank and can be used as a reaction device required by in-situ/quasi-in-situ characterization of the catalyst, and a double-layer glass sleeve (10) in the reaction tank can be directly placed in a resonant cavity of the electron paramagnetic resonance spectrometer for catalyst characterization; optionally, the evacuation line is connected to other characterization instruments for in situ characterization of the reaction gas product.
3. The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research according to claim 1, wherein: the double-layer glass sleeve (10) serving as the main body of the reaction tank is made of quartz, is convenient for illumination, has the outer diameter of less than or equal to 10mm, and can be directly placed in a resonant cavity of an electron paramagnetic resonance spectrometer for catalyst characterization; the wall thickness of the glass sleeve is adjusted according to the internal pressure of an actual system;
one end of the double-layer glass sleeve (10) is provided with a first filter (7-1) and a third ball valve (1-3), and the other end is provided with a second filter (7-2) and a fourth ball valve (1-4), so that the catalyst in the pipe is prevented from being blown out along with air flow to block a pipeline and a valve, and the disassembly of the reaction tank and the maintenance of the vacuum or gas environment in the reaction pipe are facilitated;
the rear end of the air outlet pipeline is provided with a one-way valve (9) for preventing the gas from flowing back and polluting the catalyst;
the heating furnace (11) with the quartz window is manufactured as an independent heating furnace and respectively heats the double-layer glass sleeve (10); or a heating furnace (11) with a quartz window is manufactured into an integral hearth, and a plurality of glass sleeves are heated at the same time;
a first ball valve (1-1) is arranged between the vacuum pump and the air release valve (2).
4. The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research according to claim 1, wherein: the gas path of the evacuation pipeline is connected with the reaction tank by the gas distribution system, and the temperature is not lower than 130 ℃, so that the gas path is connected with the reaction tank by the gas distribution system, and the gas path is convenient for preheating the contact catalyst gas in order to prevent the condensation of part of low-boiling-point raw material gas or products.
5. The heterogeneous catalyst activation/reaction device for electron paramagnetic resonance research according to claim 1, wherein: the parameters are as follows: the vacuum degree of the vacuum pump can reach less than 0.01mbar; the maximum bearable pressure of the double-layer glass sleeve (10) in the reaction tank is 5MPa, and the sealing joint is made of nonmagnetic materials; the heating furnace (11) adopts temperature programming, and can meet the heating condition from room temperature to 800 ℃.
6. A method of using the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance study according to claim 3, comprising the steps of:
the first step: adding a catalyst (8) into the double-layer glass sleeve (10), and if an electron paramagnetic resonance test is required, filling the sample to a height of within 4.0 cm; sequentially connecting pipelines, and placing a double-layer glass sleeve (10) filled with a catalyst into a heating furnace (11);
and a second step of: the first three-way valve (4-1) is switched to the cooling device to be communicated with the reaction tank, and the second three-way valve (4-2) is switched to the air inlet pipeline to be communicated with the reaction tank; closing a fourth ball valve (1-4) at the rear part of the reaction tank, under the condition of ensuring that a deflation valve (2) on the cooling device is closed, firstly opening a vacuum pump, then opening the first ball valve (1-1), slowly opening a third ball valve (1-3), vacuumizing, checking a vacuum gauge to show that a device system has no gas leakage phenomenon, and activating the vacuum for a certain time;
and a third step of: under the condition that a second ball valve (1-2) behind the gas distribution system is closed, switching a first three-way valve (4-1) to the gas distribution system to be communicated with the reaction tank, opening a gas release valve (2) to balance the air pressure of a pipeline, and closing a vacuum pump to perform the subsequent catalyst reaction process;
fourth step: under the condition that the second three-way valve (4-2) is directly communicated with the gas distribution system and the rear emptying pipe, preparing gas according to experimental requirements, opening a gas flushing pipeline for the second ball valve (1-2), closing the fifth ball valve (1-5) and the back pressure valve (12) after flushing, closing the second ball valve (1-2), and switching the second three-way valve (4-2) to be communicated with the gas distribution system and the reaction tank;
fifth step: sequentially opening a second ball valve (1-2), a third ball valve (1-3) and a fourth ball valve (1-4), regulating a back pressure valve (12) to be the required pressure, enabling the gas to flow through the reaction cell, setting the temperature of a heating furnace (11) to be the temperature required by an experiment, and carrying out catalytic reaction;
sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve (10) in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is required, placing the double-layer glass sleeve (10) in a heating furnace (11) for reaction, closing the third ball valve (1-3) and the fourth ball valve (1-4) after the reaction is finished, disconnecting the upper ends of the third ball valve and the fourth ball valve, and taking out the double-layer glass sleeve (10) and placing in a resonant cavity for test;
the reaction products were tested by Gas Chromatography (GC) or on-line Mass Spectrometer (MS) at the rear end of the evacuation tube.
7. A method of using the heterogeneous catalyst activation/reaction device for electron paramagnetic resonance study according to claim 3, comprising the steps of:
the first step: adding a catalyst (8) into the double-layer glass sleeve (10), and if an electron paramagnetic resonance test is required, filling the sample to a height of within 4.0 cm; the double-layer glass sleeve (10) filled with the catalyst is arranged in a heating furnace (11) according to the connecting pipeline;
and a second step of: the first three-way valve (4-1) and the second three-way valve (4-2) are communicated with the gas distribution device and the reaction tank, the third ball valve (1-3) and the fourth ball valve (1-4) are opened, the fifth ball valve (1-5) and the needle valve (14) are opened, and the back pressure valve (12) is opened to enable the required gas to flow through the reaction tank; setting the temperature of a heating furnace (11) according to the activation requirement, and activating the catalyst; and a third step of: after activation, sequentially closing a back pressure valve (12), a fifth ball valve (1-5), a fourth ball valve (1-4), a third ball valve (1-3) and a second ball valve (1-2), and preparing gas for catalytic reaction test; if the gas distribution system needs to be replaced, switching the second three-way valve (4-2) to the gas distribution system to be directly communicated with an emptying pipeline, opening the second ball valve (1-2), the back pressure valve (12), the fifth ball valve (1-5) and the fourth ball valve (1-4), flushing the pipeline for a plurality of times by utilizing the reaction gas, and then carrying out subsequent catalytic reaction and related characterization test;
fourth step: after the purging is finished, closing the fifth ball valve (1-5) and the back pressure valve (12), closing the second ball valve (1-2), and switching the second three-way valve (4-2) to be communicated with the gas distribution system and the reaction tank;
fifth step: sequentially opening a second ball valve (1-2), a third ball valve (1-3) and a fourth ball valve (1-4), regulating a back pressure valve (12) to be the required pressure, enabling a gas to circulate in the reaction tank, setting the temperature of a heating furnace (11) to be the required temperature for experiments, and carrying out catalytic reaction;
sixth step: if in-situ electron paramagnetic resonance test is to be carried out, directly placing a double-layer glass sleeve (10) in the reaction tank into a resonant cavity of an electron paramagnetic resonance spectrometer, and carrying out in-situ test by utilizing a self-contained heating device of the instrument; if quasi-in-situ electron paramagnetic resonance test is required, placing the double-layer glass sleeve (10) in a heating furnace (11) for reaction, closing the third ball valve (1-3) and the fourth ball valve (1-4) after the reaction is finished, disconnecting the upper ends of the third ball valve (1-3) and the fourth ball valve (1-4), and taking out the double-layer glass sleeve (10) and placing the double-layer glass sleeve in a resonant cavity for test;
the reaction product is tested by gas chromatography or on-line mass spectrometer after the evacuation tube is connected.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB849929A (en) * | 1956-08-20 | 1960-09-28 | Phillips Petroleum Co | Improved method and apparatus for catalyst activation |
| US6306349B1 (en) * | 1997-03-21 | 2001-10-23 | Korea Institute Of Science And Technology | Catalyst characterization apparatus |
| CN108760867A (en) * | 2018-03-13 | 2018-11-06 | 上海科技大学 | The combination structure in the reaction in-situ pond and built-in mass spectrum electric quadrupole bar of the interconnection of UHV equipment |
| CN112697832A (en) * | 2020-12-18 | 2021-04-23 | 兰州大学 | In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and using method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ES2187387B1 (en) * | 2001-11-20 | 2004-04-16 | Universidad Politecnica De Valencia. | A TEST UNIT FOR THE STUDY OF CATALYSTS IN SHORT REACTIONS CONTACT TIME BETWEEN THE CATALYST AND THE REAGENTS. |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB849929A (en) * | 1956-08-20 | 1960-09-28 | Phillips Petroleum Co | Improved method and apparatus for catalyst activation |
| US6306349B1 (en) * | 1997-03-21 | 2001-10-23 | Korea Institute Of Science And Technology | Catalyst characterization apparatus |
| CN108760867A (en) * | 2018-03-13 | 2018-11-06 | 上海科技大学 | The combination structure in the reaction in-situ pond and built-in mass spectrum electric quadrupole bar of the interconnection of UHV equipment |
| CN112697832A (en) * | 2020-12-18 | 2021-04-23 | 兰州大学 | In-situ and quasi-in-situ heterogeneous catalysis electron paramagnetic resonance platform and using method |
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