An in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediate product

Abstract

The application relates to an in-situ detection device for lateral high-temperature electro-catalytic reaction gas-phase intermediate products, which comprises a high-temperature electro-catalytic reactor, an ionization chamber and a mass spectrometer which are sequentially connected; the high-temperature electro-catalytic reactor comprises a reactor flange connected with the bottom of the ionization chamber, a glass outer sleeve pipe connected with the reactor flange, an electrode reaction pipe arranged in the glass outer sleeve pipe, a heating assembly arranged outside the glass outer sleeve pipe and a glass pipe clamping sleeve fixedly sleeved at both ends of the glass outer sleeve pipe. The glass outer sleeve pipe is heated by the heating assembly, the two tail ends of the glass outer sleeve pipe and the electrode reaction pipe are isolated by ceramic gaskets, the annular electrode plate can perform ionization reaction on the reactants under high-temperature conditions, the electrode reaction pipe can be fully combined with the reactants, the reactants can be fully reacted in high-temperature catalysis, and the measured substances of the reactants after heating can fully enter the mass spectrometer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalytic reaction detection, and particularly relates to an in-situ detection device for gaseous intermediate products of lateral high-temperature electrocatalytic reaction. BACKGROUND

[0002] Catalytic technology is an important industrial application technology in modern chemical production. Traditional catalysis, new catalysis such as electrocatalysis, photocatalysis and magnetic catalysis, etc. greatly reduce the production difficulty, improve the production efficiency, are conducive to energy saving and environmental protection, and are one of the current research hotspots. In recent years, solid oxide electrolysis cells have attracted much attention due to their potential for direct conversion of electrical energy and chemical energy at high temperature. High-temperature electrochemical reactions involve electron (charge) and ion (mass) transfer at the solid / gas interface, and the reaction path is complex, making it difficult to analyze the reaction mechanism. At present, through in-situ real-time online qualitative and quantitative detection of intermediates, especially free radicals, the microstructure information of intermediates is analyzed, which provides the most direct observation data and structural information for in-depth exploration of the molecular mechanism of the microcosmic level of the catalytic reaction mechanism and reveals the key mechanism of the dynamic evolution process of the catalytic reaction kinetics.

[0003] In the prior art, a Chinese invention patent with the patent number CN116448863A discloses an in-situ detection device for gaseous intermediate products of high-temperature electrocatalytic reaction. The patent is based on the synchrotron radiation photoionization mass spectrometry technology, and adopts the electrode sheet ionization heating mode in the tube, which can realize in-situ detection of gaseous intermediate products at different diffusion heights from the catalyst surface. However, due to the particularity of the solid oxide electrolysis cell research system, in-situ detection needs to be realized under the conditions of meeting a higher temperature and vacuum isolation of both ends of the electrode sheet. Therefore, the in-situ detection device still has defects in use, specifically: first, the electrode sheet ionization heating in the tube generally cannot reach or stably maintain at 800-900 DEG C, which cannot meet the high-temperature demand (generally at 800-900 DEG C) of the electrocatalytic reaction; second, the electrode sheet cannot well isolate the reactants, and when the reactants are heated, the measured substances of the reactants may be taken away with the carrier gas, which cannot fully enter the mass spectrometer, thereby causing a large deviation between the detection results and the actual situation. SUMMARY

[0004] The purpose of the present application is to provide an in-situ detection device for gaseous intermediate products of lateral high-temperature electrocatalytic reaction to solve the above problems.

[0005] The present application achieves the above-mentioned purposes through the following technical solutions:

[0006] A kind of in-situ detection device of lateral high-temperature electrocatalytic reaction gas-phase intermediate product, including high-temperature electrocatalytic reactor, ionization chamber, mass spectrometer connected in turn;

[0007] The high-temperature electrocatalytic reactor includes reactor flange connected with the bottom of ionization chamber, glass outer sleeve tube connected with the reactor flange, electrode reaction tube arranged in the glass outer sleeve tube, heating assembly arranged outside the glass outer sleeve tube, glass tube sleeve fixedly sleeved at both ends of the glass outer sleeve tube, two gas delivery pipelines respectively clamped outside both ends of the electrode reaction tube and connected with the electrode reaction tube, the inlet end of the electrode reaction tube and the glass outer sleeve tube are connected with straight-through connector, the outlet end of the electrode reaction tube and the glass outer sleeve tube are connected with three-way connector, and the reactor flange and both ends of the glass outer sleeve tube are provided with water cooling assembly;

[0008] The ionization chamber is provided with heating electrode sheet group inside and sampling cone at the bottom, the glass outer sleeve tube is formed with sampling bucket with narrow bottom and wide top at the middle top, and the sampling cone extends into the sampling bucket.

[0009] Two ceramic gaskets are arranged between the glass outer sleeve tube and the electrode reaction tube on both sides of the sampling bucket, and annular electrode plates are arranged on the inner and outer walls of the electrode reaction tube between the two ceramic gaskets.

[0010] As a further optimization scheme of the application, a water cooling cavity one is formed in the inner bottom of the reactor flange, a water cooling cavity sealing gasket is sealingly connected to the top of the water cooling cavity one, and the water cooling assembly includes water cooling inlet pipe and water cooling outlet pipe connected with the water cooling cavity one.

[0011] As a further optimization scheme of the application, a regulation outlet is connected to the reactor flange above the water cooling cavity sealing gasket.

[0012] As a further optimization scheme of the application, the water cooling assembly further includes two glass tube water jackets respectively sleeved at both ends of the glass outer sleeve tube, a water cooling cavity two formed in the glass tube water jacket, a water jacket cover for sealing the water cooling cavity two, and water cooling input pipe and water cooling output pipe connected with the water cooling cavity two.

[0013] As a further optimization scheme of the application, the glass tube water jacket and the glass tube sleeve are fixedly connected by bolts, and a sealing ring one is arranged at the connection of the glass tube water jacket, the glass tube sleeve and the glass outer sleeve tube.

[0014] As a further optimization scheme of the application, the glass tube sleeve and the gas delivery pipeline are fixedly connected by bolts, and a sealing ring two is arranged at the connection of the glass tube sleeve, the gas delivery pipeline and the electrode reaction tube.

[0015] As a further optimization scheme of the present application, the heating assembly comprises an outer protective seat sleeved outside the glass outer sleeve pipe and a plurality of electric heating rods arranged inside the outer protective seat and evenly distributed around the glass outer sleeve pipe.

[0016] As a further optimization scheme of the present application, a pressing plate is arranged between the reactor flange and the outer protective seat, a fluorine pad is arranged between the top of the pressing plate and the bottom of the sampling bucket, and a silica gel pad is arranged between the top of the sampling bucket and the connecting portion of the reactor flange.

[0017] The present application has the following beneficial effects:

[0018] 1) The present application heats the glass outer sleeve pipe through the heating assembly, and isolates the two tail ends of the glass outer sleeve pipe and the electrode reaction pipe through the ceramic gasket, so that the annular electrode plate can perform ionization reaction on the reactants under high temperature conditions, the electrode reaction pipe can be fully attached to the reactants, and the reactants can fully react in high-temperature catalysis, and the measured substances of the reactants after heating can fully enter the mass spectrometer;

[0019] 2) The sampling cone at the bottom of the ionization chamber in the present application extends into the interior of the sampling bucket, and the sampling bucket is located at the top of the middle position of the electrode reaction pipe, so that the molecular beam of the heated reactants can fully enter the interior of the ionization chamber;

[0020] 3) The present application continuously heats the glass outer sleeve pipe through the electric heating rods, and isolates the two tail ends of the glass outer sleeve pipe and the electrode reaction pipe through the ceramic gasket, so that the annular electrode plate can perform ionization reaction on the reactants under high temperature conditions, wherein the heating temperature is easily reached and maintained at 800-900℃, which can fully meet the high-temperature requirement of the electro-catalytic reaction, thereby ensuring the continuous performance of the electro-catalytic reaction, and the increase of the temperature can make the reactants fully react in high-temperature catalysis, and ensure more measured substances to overflow. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is the overall structure schematic diagram of the present application.

[0022] Figure 2 is the front view of the present application. Figure 1 is the front view of the present application.

[0023] Figure 3 is the overall structure schematic diagram of the high-temperature electro-catalytic reactor of the present application.

[0024] Figure 4 is the overall structure schematic diagram of the high-temperature electro-catalytic reactor of the present application.

[0025] Figure 5This is a perspective view of a portion of the structure of the high-temperature electrocatalytic reactor of the present invention (without the water-cooled inlet pipe 6 and water-cooled outlet pipe 7 installed).

[0026] Figure 6 This is the invention Figure 2 Front sectional view.

[0027] In the diagram: 1. Ionization chamber; 101. Electrode assembly; 102. Sampling cone; 2. Mass spectrometer; 3. High-temperature electrocatalytic reactor; 4. Reactor flange; 5. Water-cooled chamber sealing gasket; 61. Water-cooled inlet pipe; 62. Water-cooled outlet pipe; 7. Gauge outlet; 81. Electric heating rod; 82. Outer protective seat; 9. Pressure plate; 10. Silicone gasket; 11. Fluorine gasket; 12. Glass tube water jacket; 131. Glass outer tube; 132. Electrode reaction tube; 1310. Sampling hopper; 14. Water jacket cover; 15. Water-cooled chamber two; 161. Water-cooled input pipe; 162. Water-cooled output pipe; 17. Glass tube clamp; 18. Sealing ring one; 19. Gas delivery pipe; 20. Sealing ring two; 21. Straight connector; 22. T-connector; 23. Ceramic gasket; 24. Annular electrode plate. Detailed Implementation

[0028] The present application will now be described in further detail with reference to the accompanying drawings. It should be noted that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0029] like Figures 1-6 As shown, an in-situ detection device for gas-phase intermediate products of transverse high-temperature electrocatalytic reaction includes a high-temperature electrocatalytic reactor 3, an ionization chamber 1, and a mass spectrometer 2 connected in sequence.

[0030] The high-temperature electrocatalytic reactor 3 includes a reactor flange 4 connected to the bottom of the ionization chamber 1, a glass outer tube 131 connected to the reactor flange 4, an electrode reaction tube 132 disposed inside the glass outer tube 131, a heating assembly disposed outside the glass outer tube 131, glass tube clamps 17 fixedly sleeved on both ends of the glass outer tube 131, and two gas delivery pipes 19 respectively clamped to the outside of both ends of the electrode reaction tube 132 and connected to the electrode reaction tube 132. The inlet ends of the electrode reaction tube 132 and the glass outer tube 131 are both connected to straight connectors 21, and the outlet ends of the electrode reaction tube 132 and the glass outer tube 131 are both connected to tee connectors 22. Water cooling assemblies are provided on the reactor flange 4 and both ends of the glass outer tube 131.

[0031] The ionization chamber 1 is internally provided with a heating electrode sheet group 101, and is externally provided with a sampling cone 102, the glass outer sleeve pipe 131 is internally provided with a sampling hopper 1310 which is narrow at the bottom and wide at the top, and the sampling cone 102 extends into the sampling hopper 1310.

[0032] Two ceramic gaskets 23 are respectively arranged on both sides of the sampling hopper 1310 between the glass outer sleeve pipe 131 and the electrode reaction pipe 132, and the electrode reaction pipe 132 is internally and externally provided with annular electrode plates 24 between the two ceramic gaskets 23.

[0033] It should be noted that, in the embodiment, the annular electrode plate 24 arranged on the inner wall of the electrode reaction pipe 132 serves as a negative electrode, and the annular electrode plate 24 arranged on the outer wall of the electrode reaction pipe 132 serves as a positive electrode, and the lead wires of the annular electrode plates 24 of the positive and negative electrodes are led out from the two straight-through connectors 21.

[0034] Preferably, the reactor flange 4 is internally provided with a water-cooling cavity one, the water-cooling cavity one is sealingly connected with a water-cooling cavity sealing gasket 5 at the top, and the water-cooling assembly comprises a water-cooling inlet pipe 61 and a water-cooling outlet pipe 62 connected with the water-cooling cavity one, and the water-cooling function of the reactor flange 4 is to protect the reactor flange 4 connected with the high-temperature electro-catalytic reactor 3 and the ionization chamber 1 from being deformed so as to maintain a good vacuum degree in the high-temperature electro-catalytic reactor 3.

[0035] Preferably, the reactor flange 4 is connected with a gauge outlet 7 above the water-cooling cavity sealing gasket 5, which can be connected with an external vacuum degree monitor, i.e. a vacuum gauge, so as to monitor the vacuum degree of the high-temperature electro-catalytic reactor 3 in real time.

[0036] Preferably, the water-cooling assembly further comprises two glass pipe water jackets 12 respectively sleeved on both ends of the glass outer sleeve pipe 131, a water-cooling cavity two 15 arranged in the glass pipe water jacket 12, a water jacket cover 14 for sealing the water-cooling cavity two 15, a water-cooling input pipe 161 and a water-cooling output pipe 162 connected with the water-cooling cavity two 15, and the water-cooling function of the glass outer sleeve pipe 131 and the electrode reaction pipe 132 is to protect both ends of the glass outer sleeve pipe 131 and the electrode reaction pipe 132 from being deformed so as to maintain a stable internal pressure and enable the reactants to fully react under suitable vacuum conditions.

[0037] Preferably, the glass pipe water jacket 12 and the glass pipe clamping sleeve 17 are fixedly connected by bolts, and the connection positions of the glass pipe water jacket 12, the glass pipe clamping sleeve 17 and the glass outer sleeve pipe 131 are provided with a sealing ring one 18 to enhance the sealing property.

[0038] Preferably, the glass tube sleeve 17 is fixed by bolt connection with the gas delivery pipeline 19, and a sealing ring 20 is arranged at the connection of the glass tube sleeve 17, the gas delivery pipeline 19 and the electrode reaction tube 132, so as to enhance the sealing property of the connection.

[0039] Preferably, the heating assembly comprises an outer protective seat 82 sleeved outside the glass outer sleeve 131 and a plurality of electric heating rods 81 arranged inside the outer protective seat 82 and uniformly dispersed around the glass outer sleeve 131.

[0040] Preferably, a pressing plate 9 is arranged between the reactor flange 4 and the outer protective seat 82, a fluorine pad 11 is arranged between the top of the pressing plate 9 and the bottom of the sampling cup 1310, and a silica gel pad 10 is arranged between the top of the sampling cup 1310 and the connection of the reactor flange 4, so as to stabilize the connection between the reactor flange 4 and the sampling cup 1310 or the glass outer sleeve 131 and the connection between the reactor flange 4 and the outer protective seat 82.

[0041] In use, the carrier gas is input through the straight-through connector 21 connected with the electrode reaction tube 132 and is output through the three-way connector 22 connected with the electrode reaction tube 132, wherein one of the interfaces of the three-way connector 22 connected with the electrode reaction tube 132 is an air extraction port connected with an air pump.

[0042] In operation, the carrier gas is input into the glass outer sleeve 131 and the electrode reaction tube 132 through the straight-through connector 21 connected with the electrode reaction tube 132, the glass outer sleeve 131 is heated by the heating assembly, the reactant is located in the glass outer sleeve 131 between the two ceramic gaskets 23, the electrode reaction tube 132 can be fully attached to the reactant, the reactant enters the ionization chamber 1 through the sampling cone 102, is heated and ionized again by the electrode sheet group 101, the vacuum degree is monitored in real time by the vacuum gauge 7 and the connected vacuum gauge, and the internal air pressure condition is adjusted by the air extraction port and the connected air pump.

[0043] The carrier gas nitrogen flows into the glass outer sleeve 131 and the electrode reaction tube 132, the glass outer sleeve 131 is heated by the heating assembly, the two tail ends of the glass outer sleeve 131 and the electrode reaction tube 132 are isolated by the ceramic gaskets 23, the reactant is located in the glass outer sleeve 131 between the two ceramic gaskets 23, the annular electrode plate 24 can ionize the reactant under high temperature condition, the electrode reaction tube 132 can be fully attached to the reactant, the reactant can be fully reacted under high temperature catalysis, and the measured substance of the reactant after heating can fully enter the mass spectrometer 2.

[0044] The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the patent scope of the present application. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are within the protection scope of the present application.

Claims

1. An in-situ probe for lateral high temperature electrocatalytic reaction gas phase intermediates, characterized by: The device comprises a high-temperature electro-catalytic reactor (3), an ionization chamber (1) and a mass spectrometer (2) connected in sequence. The high-temperature electro-catalytic reactor (3) comprises a reactor flange (4) connected with the bottom of the ionization chamber (1), a glass outer sleeve tube (131) connected with the reactor flange (4), an electrode reaction tube (132) arranged in the glass outer sleeve tube (131), a heating assembly arranged outside the glass outer sleeve tube (131), a glass tube sleeve (17) fixedly sleeved on both ends of the glass outer sleeve tube (131), and two gas delivery pipelines (19) respectively clamped outside both ends of the electrode reaction tube (132) and connected with the electrode reaction tube (132). The electrode reaction tube (132) and the glass outer sleeve tube (131) are both connected with a straight-through connector (21) at the inlet end, and both are connected with a three-way connector (22) at the outlet end. The reactor flange (4) and both ends of the glass outer sleeve tube (131) are provided with a water cooling assembly. The ionization chamber (1) is internally provided with a heating electrode sheet group (101) and is provided with a sampling cone (102) at the bottom. The middle top of the glass outer sleeve tube (131) is formed with a sampling hopper (1310) with a narrow bottom and a wide top. The sampling cone (102) extends into the sampling hopper (1310). Two ceramic gaskets (23) are arranged on both sides of the sampling hopper (1310) between the glass outer sleeve tube (131) and the electrode reaction tube (132). The inner and outer walls of the electrode reaction tube (132) between the two ceramic gaskets (23) are both provided with an annular electrode plate (24).

2. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediate product according to claim 1, characterized in that: A water cooling cavity one is formed in the inner bottom of the reactor flange (4). The top of the water cooling cavity one is sealingly connected with a water cooling cavity sealing gasket (5). The water cooling assembly comprises a water cooling inlet pipe (61) and a water cooling outlet pipe (62) connected with the water cooling cavity one.

3. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 2, characterized in that: A regulation outlet (7) is connected above the water cooling cavity sealing gasket (5) on the reactor flange (4).

4. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 1, characterized in that: The water cooling assembly further comprises two glass tube water jackets (12) respectively sleeved on both ends of the glass outer sleeve tube (131), a water cooling cavity two (15) formed in the glass tube water jacket (12), a water jacket cover (14) for sealing the water cooling cavity two (15), a water cooling input pipe (161) and a water cooling output pipe (162) connected with the water cooling cavity two (15).

5. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 4, characterized in that: The glass tube water jacket (12) and the glass tube sleeve (17) are fixedly connected by bolts. Sealing rings one (18) are arranged at the connection positions of the glass tube water jacket (12), the glass tube sleeve (17) and the glass outer sleeve tube (131).

6. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 1, characterized in that: The glass tube sleeve (17) and the gas delivery pipeline (19) are fixedly connected by bolts. Sealing rings two (20) are arranged at the connection positions of the glass tube sleeve (17), the gas delivery pipeline (19) and the electrode reaction tube (132).

7. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 1, characterized in that: The heating assembly comprises an outer protective seat (82) sleeved outside a glass outer sleeve (131) and a plurality of electric heating rods (81) arranged inside the outer protective seat (82) and uniformly dispersed around the glass outer sleeve (131).

8. The in-situ detection device for lateral high-temperature electrocatalytic reaction gas-phase intermediates according to claim 1, characterized in that: A pressing plate (9) is arranged between the reactor flange (4) and the outer protective seat (82), a fluorine pad (11) is arranged between the top of the pressing plate (9) and the bottom of a sampling bucket (1310), and a silica gel pad (10) is arranged between the top of the sampling bucket (1310) and the connecting portion of the reactor flange (4).

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