Device and method for catalyst deactivation under simulatable working condition

Abstract

The invention discloses a device and a method for catalyst deactivation under a simulatable working condition. The device comprises a fixed bed reactor, an atomizer and a gas pump, and a quartz reaction tube is arranged in the fixed bed reactor and used for being filled with a solid catalyst; the atomizer is filled with deionized water or a precursor solution of toxic metal ions; the top of the quartz reaction tube is connected with an atomizer and a plurality of gas channels, and the bottom is connected with a gas pump; the method is used for simulating the conditions of inactivation of the solid catalyst caused by the following conditions: hydrothermal aging, acid gas and toxic metal ions. According to the invention, various catalyst inactivation conditions can be simulated, conditions of catalyst inactivation caused by hydrothermal aging, acid gases, toxic metals and the like can be successfully simulated, meanwhile, the catalyst inactivation conditions when various adverse factors exist at the same time can be simulated, and the inactivation path of the catalyst is explored from the molecular level; the purpose of improving the economic benefit of the catalyst is achieved, and the operation is simple and efficient.

Description

TECHNICAL FIELD

[0001] The present application relates to a device and method for simulating catalyst deactivation under working conditions, belonging to the technical field of multiphase catalyst deactivation research. BACKGROUND

[0002] Multiphase catalyst deactivation is a common problem in industrial production and pollutant removal processes. Catalyst deactivation can lead to low industrial production efficiency, excessive pollutant discharge, and decline in catalyst economic benefits. However, in the laboratory, the current analysis of catalyst deactivation cannot simulate the real working conditions of the catalyst, which makes the simulated poisoned catalyst in the laboratory not referenceable, and further leads to the conclusion that the related experiments are not applicable to the improvement of related catalysts. Studies have shown that catalysts mainly face deactivation caused by factors such as hydrothermal aging, acid deposition, and toxic metal ion deposition during actual use. In view of the above factors causing catalyst deactivation, it is necessary to design a special device for simulating catalyst deactivation in actual use to achieve a high degree of reduction of different types of catalyst working environments. SUMMARY

[0003] The purpose of the present application is to provide a device and method for simulating catalyst deactivation in actual use, which can achieve the purpose of regulating the working temperature, reaction atmosphere, and poisoning time of the catalyst, and further simulate the deactivation of the catalyst when factors such as hydrothermal aging, acid deposition, and toxic metal ion deposition exist alone or simultaneously.

[0004] The device of the present application can simulate the deactivation of the catalyst caused by factors such as hydrothermal aging (H2O: 0-30%), acid deposition (SO2, HCl, HBr), and toxic metal ion (alkali metal, alkaline earth metal, heavy metal) deposition alone or simultaneously.

[0005] The device for simulating catalyst deactivation under working conditions provided by the present application comprises a fixed bed reactor, an atomizer, and a gas pump, wherein the fixed bed reactor is provided with a quartz reaction tube for loading solid catalyst; The atomizer is filled with deionized water or a precursor solution of toxic metal ions; The top of the quartz reaction tube is connected with the atomizer and a plurality of gas channels, and the bottom is connected with the gas pump; The device is used to simulate the deactivation of the solid catalyst caused by the following conditions: Hydrothermal aging, acid gas, and toxic metal ions.

[0006] In the device of the present invention, the atomizer can atomize the precursor solution of toxic substances and has certain acid resistance characteristics; the atomizer can adjust the atomization amount to adapt to the simulation of working conditions with different water flow rates.

[0007] In the device of the present invention, the top of the quartz reaction tube is provided with a top ventilation inlet and a side wall atomizing gas inlet; The vent extends to the bottom of the quartz reaction tube near the solid catalyst, allowing the gas pressure drop and water mist to mix thoroughly before contacting the catalyst.

[0008] In the device of the present invention, several gas channels are connected in parallel and then connected to a mixing tank; The gas passage is equipped with a flow meter and a gas throttle valve.

[0009] In the device of the present invention, a gas washing bottle is provided at the inlet end of the gas pump; The flow rate of the gas pump is adjustable.

[0010] In the device of the present invention, the fixed bed reactor is equipped with an adjustable temperature constant temperature electric heating furnace, which can achieve constant temperature at any temperature below 900℃.

[0011] The device of this invention simulates the deactivation process of various catalysts in actual use in a laboratory setting by adjusting conditions such as fixed-bed reaction temperature, type of toxic precursor, atomizing liquid content, and gas flow rate.

[0012] When simulating catalyst deactivation under operating conditions using the device of the present invention, the process can be carried out according to the following steps: S1. A solid catalyst is loaded into the quartz reaction tube; S2. A reaction gas, including N2, O2, NH3, and NO, is introduced into the quartz reaction tube through the gas channel. x And select SO2 to be introduced according to the specific circumstances; S3. Injecting atomizing liquid into the quartz reaction tube through the atomizer, wherein the atomizing liquid is deionized water or a toxic substance precursor solution; S4. Adjust the flow rate of the gas pump to control the gas flow rate, so that the reaction gas and the atomized liquid are mixed in the quartz reaction tube and come into contact with the solid catalyst to simulate catalyst deactivation.

[0013] Preferably, the atomizing liquid is deionized water, and the proportion of water introduced into the quartz reaction tube can be adjusted to 0-30% of the total gas volume to simulate deactivation caused by hydrothermal aging.

[0014] Preferably, the reaction gas introduced into the quartz reaction tube includes SO2, HCl or HBr to simulate deactivation caused by the deposition of acidic substances.

[0015] Preferably, the atomizing liquid is a nitrate solution of alkali metal, alkaline earth metal, or heavy metal, with a concentration range of 0.01-0.2 mol·L⁻¹. -1 To simulate the deactivation caused by the deposition of toxic metal ions.

[0016] More preferably, the method of the present invention includes at least two aging simulations from 1) to 3) below: 1) The atomizing liquid is deionized water, and the proportion of water introduced into the quartz reaction tube can be adjusted to 0-30% of the total gas volume to simulate deactivation caused by hydrothermal aging. 2) The reaction gas introduced into the quartz reaction tube includes SO2, HCl or HBr, to simulate the deactivation caused by the deposition of acidic substances; 3) The atomizing liquid is a nitrate solution of alkali metal, alkaline earth metal, or heavy metal, with a concentration range of 0.01-0.2 mol·L⁻¹. -1 To simulate the deactivation caused by the deposition of toxic metal ions.

[0017] In the method of this invention, residual acidic gas or ammonia is absorbed by a gas washing bottle; The catalysts applicable to this invention include a variety of molecular sieve catalysts and a variety of metal oxide catalysts.

[0018] The method of this invention can simulate various catalyst deactivation conditions, successfully simulating deactivation caused by hydrothermal aging, acidic gases, toxic metals, etc. It can also simulate catalyst deactivation when multiple adverse factors coexist, exploring the deactivation pathway of catalysts at the molecular level, thereby improving the economic benefits of catalysts. Moreover, the device is simple and efficient to operate.

[0019] By flexibly adjusting parameters (temperature, gas, atomization rate), this invention efficiently simulates catalyst deactivation (such as hydrothermal aging or heavy metal poisoning) under real-world conditions in a laboratory environment, and can also simulate multiple factors in combination. The method is simple to operate.

[0020] This invention first mixes the reaction gas components of the relevant catalyst in a mixing tank and then introduces them into a quartz tube reaction tube. The mixture is atomized by an atomizer to obtain water mist, which carries the relevant toxic metal precursors along with the mixed reaction gas to the location where fresh catalyst is loaded in the quartz tube. The fixed-bed reactor is kept at a constant temperature according to the corresponding reaction temperature, and a gas pump continuously pumps out the mixed gas to simulate the working conditions of a real catalyst. Furthermore, by changing the reaction gas components, reaction temperature, type of toxic precursor, and gas flow rate, the catalyst operating conditions under different reaction conditions can be simulated, enabling the reproduction of the deactivation process of catalysts in various catalytic reactions. This facilitates the study of catalyst deactivation mechanisms and regeneration. The device is also simple and efficient to operate. Attached Figure Description

[0021] Figure 1 This is an overall schematic diagram of the device of the present invention; The markings in the diagram are as follows: 1-Flow meter, 2-Gas passage, 3-Gas throttle valve, 4-Mixer, 5-Atomizer, 6-Quartz reaction tube, 7-Fixed bed reactor, 8-Gas washing bottle, 9-Gas pump.

[0022] Figure 2 This refers to the SCR activity of the catalyst before and after deactivation in Example 1 of the present invention.

[0023] Figure 3 This refers to the SCR activity of the catalyst before and after deactivation in Example 2 of the present invention.

[0024] Figure 4 This refers to the SCR activity of the catalyst before and after deactivation in Example 3 of the present invention.

[0025] Figure 5 This refers to the SCR activity of the catalyst before and after deactivation in Example 4 of the present invention.

[0026] Figure 6 This refers to the SCR activity of the catalyst before and after deactivation in Example 5 of the present invention.

[0027] Figure 7 This refers to the SCR activity of the catalyst before and after deactivation in Example 6 of the present invention.

[0028] Figure 8 This refers to the SCR activity of the catalyst before and after deactivation in Example 7 of the present invention. Detailed Implementation

[0029] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0030] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0031] The present invention provides an apparatus for simulating catalyst deactivation under operating conditions. By adjusting parameters such as temperature, gas flow rate, and type of toxic substance, it simulates the actual deactivation process of catalysts in a laboratory setting. Specifically, it includes: exploring deactivation pathways at the molecular level (such as hydrothermal aging leading to changes in catalyst structure); improving the economic efficiency and industrial applicability of catalysts; and supporting standardized experiments for heterogeneous catalysis research.

[0032] The device of this invention for simulating catalyst deactivation under operating conditions includes a fixed-bed reactor, an atomizer, a gas pump, etc., and the key structures include: Quartz reaction tube: filled with solid catalyst, with two inlets (gas inlet and atomizing liquid side inlet) to ensure thorough mixing of gas and atomizing liquid.

[0033] Gas passage: can be used for N2, O2, NH3, SO2, NO x Gases such as these are equipped with flow meters and gas valves for precise flow control.

[0034] Nebulizer: Connects to the side port of the quartz reaction tube, and can atomize toxic precursor solutions (such as metal salts) or deionized water, supporting adjustment of atomization volume.

[0035] Fixed-bed reactor: Integrated adjustable temperature constant temperature electric heating furnace, which can maintain a constant temperature at any temperature below 900℃.

[0036] Auxiliary systems: a gas pump regulates the flow rate, and a gas washing bottle is used to absorb harmful gases (such as SO2).

[0037] The overall structural layout of the device is as follows Figure 1 As shown, the connection methods and workflows of each component (such as the mixing tank and the quartz reaction tube) are illustrated.

[0038] The device of this invention has the following functions and simulation capabilities: Single-factor inactivation simulation: Hydrothermal aging: A high-temperature and high-humidity environment is simulated by atomizing deionized water (H2O content 0-30%).

[0039] Acidic substance deposition: SO2, HCl or HBr gas is introduced to simulate acidic gas poisoning.

[0040] Toxic metal ion deposition: atomized alkali metal, alkaline earth metal, or heavy metal solution (concentration 0.01-0.2 mol·L⁻¹). -1 (This simulates metal ion poisoning.)

[0041] Multi-factor synergistic inactivation simulation: Two-factor combinations: such as simultaneously simulating hydrothermal aging + acidic substances, hydrothermal aging + toxic metals, or acidic substances + toxic metals.

[0042] The three-factor combination simultaneously simulates hydrothermal aging, acidic substances, and toxic metal ions to recreate the most demanding operating conditions.

[0043] Adjustable parameters: Supports flexible adjustment of reaction temperature (200-800℃), gas flow rate (adjusted by gas pump), atomizing liquid content, etc., to adapt to different catalysts (such as Cu / SSZ-13 or V2O5-WO3 / TiO2) and operating conditions.

[0044] The principle by which this invention achieves the above-mentioned functional simulation is as follows: the reaction gas is mixed in a mixing tank and then enters a quartz reaction tube, where it combines with the atomizing liquid (water or precursor). Under constant temperature conditions, the mixed gas contacts the catalyst, and a gas pump maintains the flow, simulating an actual reaction.

[0045] The apparatus and method of the present invention have the following advantages: High efficiency: The device is easy to operate and has a short experimental cycle (e.g., simulation can be completed in 12 hours), which improves research efficiency.

[0046] Accuracy: Precise parameter control is achieved through flow meters, valves, etc., ensuring reliable simulation results.

[0047] Economic efficiency: By exploring deactivation pathways at the molecular level, catalyst design can be optimized to improve the lifespan and efficiency of industrial applications.

[0048] Example 1: Simulation of hydrothermal aging and deactivation of Cu / SSZ-13 catalyst for NH3-SCR reaction by Figure 1 For reference, the hydrothermal aging deactivation simulation device used in this embodiment includes four gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. Deionized water is connected to quartz reaction tube 6 via atomizer 5 and undergoes isothermal treatment through fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump the gas out. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains deionized water, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, and gas washing bottle 8 contains a solution to remove the reaction gas to protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate. The atomization rate of atomizer 5 and the flow rate of gas pump 9 are adjustable.

[0049] Perform hydrothermal aging and deactivation simulation of the Cu / SSZ-13 catalyst according to the following steps: Quartz reaction tube 6 is filled with 0.5-1 g of Cu / SSZ-13 solid, atomizer 5 is filled with 80-100 mL of deionized water, and gas washing bottle 8 is filled with deionized water. Four reaction gases, N2, O2, NH3, and NO, are introduced respectively. During operation, the electric heater in fixed-bed reactor 7 is first set to 700-800 ℃. Gas pump 9 is turned on, and the total gas flow rate is set to 1 L / min using the flow meter display. -1 The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6, carrying water vapor. Deionized water mist comes into contact with the catalyst along with the reactant gas. The remaining reactant gas enters the gas washing bottle 8, where H2O and NH3 are absorbed by the deionized water, and the remaining gas is extracted and vented by gas pump 9. After maintaining this for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the Cu / SSZ-13 catalyst is removed and analyzed. The SCR activity of the catalyst before and after deactivation is as follows: Figure 2 As shown.

[0050] analyze Figure 2 It can be seen that the SCR activity of Cu / SSZ-13 catalyst decreased significantly after hydrothermal aging treatment using this poisoning device, ranging from 2% to 13% across the entire temperature range, with the most significant decrease occurring between 200 and 400 °C. This indicates that the device effectively simulates the hydrothermal aging of the catalyst, achieving simulation of catalyst deactivation within the laboratory setting, and the experimental results are of reference value.

[0051] Example 2: Simulation of SO2 poisoning and deactivation of V2O5-WO3 / TiO2 catalyst used in NH3-SCR reaction by Figure 1 For reference, the SO2 poisoning inactivation simulation device used in this embodiment includes five gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttling valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. The mixture is then subjected to constant temperature treatment in fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump the gas out. Quartz reaction tube 6 is filled with solid catalyst. Fixed-bed reactor 7 is equipped with a temperature-controlled electric heater. Gas washing bottle 8 contains a solution to remove the reactant gas and protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttling valve 3 for observing gas flow rate. The flow rate of gas pump 9 is adjustable.

[0052] Simulate SO2 poisoning and deactivation of the V2O5-WO3 / TiO2 catalyst according to the following steps: Quartz reaction tube 6 is filled with 0.5-1 g of V₂O₅-WO₃ / TiO₂ solid, and gas washing bottle 8 is filled with NaHCO₃ solution. Five reaction gases, namely N₂, O₂, NH₃, NO, and SO₂, are introduced respectively. During operation, the electric heater in fixed-bed reactor 7 is first set to 200-400℃. Gas pump 9 is turned on, and the total gas flow rate is set to 1 L / min using the flow meter display. -1 The mixed gas enters the quartz reaction tube 6. The remaining reactant gas enters the gas washing bottle 8, where SO2 and NH3 are absorbed by the NaHCO3 solution, and the remaining gas is extracted and vented by the gas pump 9. After maintaining this state for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, the gas pump 9 is turned off. After cooling to room temperature, the V2O5-WO3 / TiO2 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 3 As shown.

[0053] analyze Figure 3 It can be seen that the SCR activity of the V2O5-WO3 / TiO2 catalyst decreased most significantly in the range of 100-300 °C after SO2 poisoning using this poisoning device, with an 85% decrease in activity at 250 °C. This indicates that the presence of SO2 has a significant poisoning effect on the V2O5-WO3 / TiO2 catalyst, and further confirms that the device effectively simulates the deposition of acidic substances on the catalyst. It achieves the simulation of catalyst poisoning in the laboratory, and the experimental results are of reference value.

[0054] Example 3: Simulation of alkali metal poisoning and deactivation of V2O5-WO3 / TiO2 catalyst for NH3-SCR reaction by Figure 1 For reference, the alkali metal poisoning inactivation simulation device used in this embodiment includes four gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. The precursor solution of the toxic substance is connected to quartz reaction tube 6 via atomizer 5 and subjected to constant-temperature treatment in fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump out the gas. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains toxic metal precursor solution, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, and gas washing bottle 8 contains deionized water to protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate, and the flow rate of gas pump 9 is adjustable.

[0055] Simulate alkali metal poisoning and deactivation of V2O5-WO3 / TiO2 catalysts according to the following steps: The quartz reaction tube 7 is filled with 0.5-1 g of V₂O₅-WO₃ / TiO₂ solid, and the atomizer 5 is filled with 0.01-0.2 mol L⁻¹. -1 Add 50-100 mL of KNO3 solution, deionized water to gas washing bottle 8, and introduce N2, O2, NH3, and NO into the four reaction gas streams respectively. During operation, first set the electric heater in fixed-bed reactor 7 to 200-400 ℃. Turn on gas pump 9, and set the total gas flow rate to 1 L / min using the flow meter display. -1 The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6. KNO3 mist, along with the reactant gas, contacts the catalyst, and some KNO3 deposits on the catalyst surface. The remaining KNO3 enters the gas washing bottle 8 with the reactant gas; KNO3, H2O, and NH3 are absorbed by the deionized water in the gas washing bottle, and the remaining gas is extracted and vented by gas pump 9. After maintaining this for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the V2O5-WO3 / TiO2 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 4 As shown.

[0056] analyze Figure 4 It can be seen that the SCR activity of the V2O5-WO3 / TiO2 catalyst decreased significantly after alkali metal poisoning using this poisoning device. The NOx conversion rate of the catalyst decreased most significantly in the range of 200-400℃, and the catalyst activity was most significantly reduced at 250℃, decreasing by 37.3%. This indicates that the device effectively simulates the deposition of toxic metal substances on the catalyst, realizes the simulation of catalyst deactivation in the laboratory, and the experimental results are of reference value.

[0057] Example 4: Simulation of simultaneous hydrothermal aging and SO2 poisoning deactivation of Cu / SSZ-13 catalyst used in NH3-SCR reaction by Figure 1 For reference, the hydrothermal aging and SO2 poisoning simultaneous deactivation simulation device used in this embodiment includes five gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. Deionized water is connected to quartz reaction tube 6 via atomizer 5 and undergoes isothermal treatment through fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump out the gas. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains deionized water, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, and gas washing bottle 8 contains a solution to remove the reaction gas to protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate, and the flow rate of gas pump 9 is adjustable.

[0058] Simulated hydrothermal aging and simultaneous deactivation due to SO2 poisoning of Cu / SSZ-13 catalyst were performed according to the following steps: Quartz reaction tube 6 is filled with 0.5-1 g of Cu / SSZ-13 solid, atomizer 5 is filled with 50-100 mL of deionized water, and gas washing bottle 8 is filled with NaHCO3 solution. Five reaction gases, namely N2, O2, NH3, NO, and SO2, are introduced respectively. During operation, the electric heater in fixed-bed reactor 7 is first set to 700-800 ℃. Gas pump 9 is turned on, and the total gas flow rate is set to 1 L / min using the flow meter display. -1 The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6. The mist, along with the reactant gas, contacts the catalyst. The remaining reactant gas enters the gas washing bottle 8, where H2O, SO2, and NH3 are absorbed by the NaHCO3 solution. The remaining gas is extracted and vented by gas pump 9. After maintaining this state for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the poisoned Cu / SSZ-13 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 5 As shown.

[0059] analyze Figure 5 It can be seen that the SCR activity of the Cu / SSZ-13 catalyst decreased significantly after hydrothermal aging and simultaneous SO2 deactivation treatment using this poisoning device. Compared with hydrothermal aging alone, the simultaneous hydrothermal aging and SO2 treatment resulted in more NO production in the catalyst. x The decrease in conversion rate is most pronounced in the temperature range of 200-550 °C, and within this range, the catalyst's NO content also decreases. x The conversion rates all exceeded 13%, indicating that the method of simulating hydrothermal aging and acidic substance deposition for simultaneous deactivation is feasible. This method enables the simulation of catalyst deactivation in the laboratory, and the experimental results are of reference value.

[0060] Example 5: Simulation of hydrothermal aging and heavy metal poisoning-induced deactivation of V2O5-WO3 / TiO2 catalyst for NH3-SCR reaction by Figure 1For reference, the hydrothermal aging and heavy metal poisoning simultaneous inactivation simulation device used in this embodiment includes four gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. The precursor solution of the toxic substance is connected to quartz reaction tube 6 via atomizer 5 and undergoes isothermal treatment through fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump out the gas. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains toxic metal precursor solution, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, and gas washing bottle 8 contains deionized water to protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate, and the flow rate of gas pump 9 is adjustable.

[0061] Simulated hydrothermal aging and simultaneous deactivation due to heavy metal poisoning of V2O5-WO3 / TiO2 catalyst were performed according to the following steps: The quartz reaction tube 6 is filled with 0.5-1 g of V₂O₅-WO₃ / TiO₂ solid, and the atomizer 5 is filled with 0.01-0.2 mol L⁻¹. -1 50-100 mL of Pb(NO3)2 solution was added, and deionized water was placed in gas washing bottle 8. The four reaction gases—N2, O2, NH3, and NO—were introduced respectively. During operation, the electric heater in fixed-bed reactor 7 was first set to 700-800 ℃. Gas pump 9 was turned on, and the total gas flow rate was set to 1 L / min based on the flow meter display. -1 The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6. Pb(NO3)2 mist, along with the reactant gas, contacts the catalyst, and some Pb(NO3)2 is deposited on the catalyst surface. The remaining Pb(NO3)2 enters the gas washing bottle 8 with the reactant gas. Pb(NO3)2, H2O, and NH3 are absorbed by the deionized water in the gas washing bottle, and the remaining gas is extracted and vented by gas pump 9. After maintaining this for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the poisoned V2O5-WO3 / TiO2 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 6 As shown.

[0062] analyze Figure 6It can be seen that the SCR activity of the V2O5-WO3 / TiO2 catalyst decreased significantly after hydrothermal aging and simultaneous deactivation by heavy metals using this poisoning device. The NOx conversion rate of the catalyst decreased by more than 37.8% in the range of 200-400 °C, which confirms that the simultaneous action of hydrothermal aging and heavy metals on the catalyst will cause severe deactivation. This indicates that the method of simulating hydrothermal aging and simultaneous deactivation by toxic metal ion deposition using this device is feasible, realizes the simulation of catalyst deactivation in the laboratory, and the experimental results are of reference value.

[0063] Example 6: Simulation of simultaneous deactivation of Cu / SSZ-13 catalyst for NH3-SCR reaction due to SO2 poisoning and alkali metal poisoning by Figure 1 For reference, the simultaneous deactivation simulation device for SO2 poisoning and alkali metal poisoning used in this embodiment includes five gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. The precursor solution of the toxic substance is connected to quartz reaction tube 6 via atomizer 5 and subjected to constant-temperature treatment in fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump out the gas. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains toxic metal precursor solution, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, gas washing bottle 8 contains a solution to remove the reaction gas to protect gas pump 9, and gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate. The flow rate of gas pump 9 is adjustable.

[0064] Simulated deactivation of Cu / SSZ-13 catalyst under both SO2 poisoning and alkali metal poisoning was performed according to the following steps: The quartz reaction tube 6 is filled with 0.5-1 g of Cu / SSZ-13 solid, and the nebulizer 5 is filled with 0.01-0.2 mol / L. -1 Add 50-100 mL of KNO3 solution, deionized water to gas washing bottle 8, and introduce N2, O2, NH3, NO, and SO2 into the five reaction gas streams respectively. During operation, first set the electric heater in fixed-bed reactor 7 to 200-400 ℃. Turn on gas pump 9, and set the total gas flow rate to 1 L / min using the flow meter display. -1The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6. KNO3 mist, along with the reactant gas, contacts the catalyst, and some KNO3 deposits on the catalyst surface. The remaining KNO3 enters the gas washing bottle 8 with the reactant gas; KNO3, H2O, SO2, and NH3 are absorbed by the NaHCO3 solution in the gas washing bottle, and the remaining gas is extracted and vented by gas pump 9. After maintaining this for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the poisoned Cu / SSZ-13 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 7 As shown.

[0065] analyze Figure 7 It can be seen that the SCR activity of the Cu / SSZ-13 catalyst decreased significantly after simultaneous deactivation treatment with SO2 and alkali metal deposition using this poisoning device. The catalyst exhibited a marked decrease in activity across the entire temperature range, with this phenomenon concentrated in the 150-300℃ and 450-550℃ ranges. Within these ranges, the catalyst's highest NO content... x The conversion rate loss reached 46.4%, indicating that the method of simulating the simultaneous deactivation treatment of acidic substances and toxic metal ions by the device is feasible. It realizes the simulation of catalyst deactivation in the laboratory and the experimental results are of reference value.

[0066] Example 7: Simulation of hydrothermal aging, SO2 poisoning, and heavy metal poisoning simultaneous deactivation of V2O5-WO3 / TiO2 catalyst used in NH3-SCR reaction by Figure 1 For reference, the simultaneous deactivation simulation device for hydrothermal aging, SO2 poisoning, and heavy metal poisoning used in this embodiment includes five gas paths. Gas flows through gas channel 2, passing through flow meter 1 and gas throttle valve 3, then through mixing tank 4 for mixing, and is connected to quartz reaction tube 6. The precursor solution of the toxic substance is connected to quartz reaction tube 6 via atomizer 5 and undergoes isothermal treatment in fixed-bed reactor 7. The tail end of quartz reaction tube 6 is connected to gas pump 9 via gas washing bottle 8 to pump out the gas. Quartz reaction tube 6 is filled with solid catalyst, atomizer 5 contains toxic metal precursor solution, fixed-bed reactor 7 is equipped with a temperature-controlled electric heater, and gas washing bottle 8 contains a solution to remove the reaction gas and protect gas pump 9. Gas channel 2 is equipped with flow meter 1 and gas throttle valve 3 for observing gas flow rate, and the flow rate of gas pump 9 is adjustable.

[0067] Simulated hydrothermal aging, SO2 poisoning, and simultaneous deactivation of heavy metal poisoning of V2O5-WO3 / TiO2 catalyst were performed according to the following steps: The quartz reaction tube 6 is filled with 0.5-1 g of V₂O₅-WO₃ / TiO₂ solid, and the atomizer 5 is filled with 0.01-0.2 mol L⁻¹.-1 50-100 mL of Pb(NO3)2 solution was added, and NaHCO3 solution was added to gas washing bottle 8. Five reaction gases, namely N2, O2, NH3, NO, and SO2, were introduced respectively. During operation, the electric heater in fixed-bed reactor 7 was first set to 700-800 ℃. Gas pump 9 was turned on, and the total gas flow rate was set to 1 L / min using the flow meter display. -1 The mixed gas and water mist generated by atomizer 5 enter the quartz reaction tube 6. Pb(NO3)2 mist, along with the reactant gas, contacts the catalyst, and some Pb(NO3)2 is deposited on the catalyst surface. The remaining Pb(NO3)2 enters the gas washing bottle 8 with the reactant gas. Pb(NO3)2, H2O, SO2, and NH3 are absorbed by the NaHCO3 solution in the gas washing bottle, and the remaining gas is extracted and vented by gas pump 9. After maintaining this state for 12 hours, all gas throttling valves 3 are closed, the electric heater of the fixed-bed reactor 7 is shut off, and finally, gas pump 9 is turned off. After cooling to room temperature, the poisoned V2O5-WO3 / TiO2 catalyst is removed for analysis and testing. The SCR activity of the catalyst before and after deactivation is as follows: Figure 8 As shown.

[0068] analyze Figure 8 It can be seen that the SCR activity of the V2O5-WO3 / TiO2 catalyst after hydrothermal aging and simultaneous deactivation by SO2 and heavy metals using this poisoning device decreased significantly. Compared with the catalyst after simultaneous deactivation by SO2 and heavy metals, the SCR activity of the catalyst after hydrothermal aging and simultaneous deactivation by SO2 and heavy metals decreased more significantly, with NO showing a more pronounced decrease across the entire temperature range. x The highest decrease in conversion rate reached 84.3%, indicating that the method of simulating hydrothermal aging, acidic substances and toxic metal ion deposition for simultaneous deactivation is feasible. It realizes the simulation of catalyst deactivation in the laboratory and the experimental results are of reference value.

[0069] The applicant declares that the present invention is illustrated through the above embodiments, but the present invention is not limited to the above detailed methods, that is, it does not mean that the present invention must rely on the above detailed methods to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions for the product device of the present invention, additions of auxiliary devices, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An apparatus for simulating catalyst deactivation under operating conditions, comprising a fixed-bed reactor, an atomizer, and a gas pump, wherein the fixed-bed reactor is provided with a quartz reaction tube for loading a solid catalyst; The atomizer is filled with deionized water or a precursor solution of toxic metal ions. The top of the quartz reaction tube is connected to the atomizer and several gas channels, and the bottom is connected to the gas pump. The device is used to simulate the following conditions that cause deactivation of the solid catalyst: Hydrothermal aging, acidic gases, and toxic metal ions.

2. The apparatus according to claim 1, characterized in that: The quartz reaction tube is provided with a top ventilation inlet and a side wall atomizing gas inlet. The vent extends to the bottom of the quartz reaction tube near the solid catalyst.

3. The apparatus according to claim 1 or 2, characterized in that: Several of the gas channels are connected in parallel and then connected to a mixing tank; The gas passage is equipped with a flow meter and a gas throttle valve.

4. The apparatus according to claim 1 or 2, characterized in that: The gas pump is equipped with a gas washing bottle at its inlet.

5. The apparatus according to claim 1 or 2, characterized in that: The fixed-bed reactor is equipped with an adjustable temperature constant-temperature electric heater.

6. A method for simulating catalyst deactivation under operating conditions, comprising the following steps performed in the apparatus of any one of claims 1-5: S1. A solid catalyst is loaded into the quartz reaction tube; S2. A reaction gas, including N2, O2, NH3, and NO, is introduced into the quartz reaction tube through the gas channel. x And select SO2 to be introduced according to the specific circumstances; S3. Injecting atomizing liquid into the quartz reaction tube through the atomizer, wherein the atomizing liquid is deionized water or a toxic substance precursor solution; S4. Adjust the flow rate of the gas pump to control the gas flow rate, so that the reaction gas and the atomized liquid are mixed in the quartz reaction tube and come into contact with the solid catalyst to simulate catalyst deactivation.

7. The method according to claim 6, characterized in that: The atomizing liquid is deionized water, and the amount of water introduced into the quartz reaction tube can be adjusted to be 0-30% of the total gas volume to simulate deactivation caused by hydrothermal aging.

8. The method according to claim 6, characterized in that: The reaction gas introduced into the quartz reaction tube includes SO2, HCl, or HBr to simulate deactivation caused by the deposition of acidic substances.

9. The method according to claim 6, characterized in that: The atomizing fluid is a nitrate solution of alkali metal, alkaline earth metal, or heavy metal, with a concentration range of 0.01-0.2 mol·L⁻¹. -1 To simulate the deactivation caused by the deposition of toxic metal ions.

10. The method according to claim 6, characterized in that: The method includes at least two of the following aging simulations: 1)-3) below: 1) The atomizing liquid is deionized water, and the proportion of water introduced into the quartz reaction tube can be adjusted to 0-30% of the total gas volume to simulate deactivation caused by hydrothermal aging. 2) The reaction gas introduced into the quartz reaction tube includes SO2, HCl or HBr, to simulate the deactivation caused by the deposition of acidic substances; 3) The atomizing liquid is a nitrate solution of alkali metal, alkaline earth metal, or heavy metal, with a concentration range of 0.01-0.2 mol·L⁻¹. -1 To simulate the deactivation caused by the deposition of toxic metal ions.

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