CN111437890B

CN111437890B - Microwave-assisted regeneration method and system for three-way catalyst

Info

Publication number: CN111437890B
Application number: CN202010420017.8A
Authority: CN
Inventors: 宋占龙; 吴振豪; 孙伟婷; 赵希强; 孙静; 毛岩鹏; 王文龙
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2020-05-18
Filing date: 2020-05-18
Publication date: 2021-06-22
Anticipated expiration: 2040-05-18
Also published as: CN111437890A

Abstract

The invention relates to a method and a system for microwave-assisted regeneration of a three-way catalyst, and the activity of the regenerated catalyst. The microwave technology is applied to a catalyst regeneration process, and the active regeneration is realized through links such as pretreatment, classification regeneration, active component supplement, microwave activation treatment and the like. The method is used for detecting the active sites of the catalyst, and has the regeneration value of respectively eliminating inactivation factors by microwave assistance according to three types of inactivation factors of heat inactivation, poisoning inactivation and carbon deposition inactivation, sequentially loading a coating, an auxiliary agent and an active component in a microwave field environment selectivity mode, and activating the active sites of the catalyst by microwave radiation. According to the method, microwave-assisted regeneration is utilized, the absorbent is supplemented to strengthen the microwave absorption characteristic of the inactivated target site, the microwave field is used for assisting in eliminating the inactivation factor in a targeted manner, the activation of the active site precursor is promoted at a fixed point, the regeneration process does not need to be broken, the regeneration efficiency of the catalyst is greatly improved, the loss rate of active components is reduced, the damage of a mechanical structure is reduced, the multiple regeneration of the catalyst is facilitated, the service life of the catalyst is prolonged, and the overall energy consumption.

Description

Microwave-assisted regeneration method and system for three-way catalyst

Technical Field

The invention belongs to the technical field of catalyst regeneration, and particularly relates to a method and a system for microwave-assisted regeneration of a three-way catalyst.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

The catalyst maintains high catalytic activity while reducing the catalytic conversion temperature of the polluted gas, and is widely applied to the purification of the polluted gas of an automobile exhaust conversion system. The three-way catalyst consists of carrier, coating, assistant and active component, and has platinum, palladium, rhodium and other noble metals as the active component, with platinum and palladium being used mainly in the oxidation of CO and hydrocarbon, and rhodium providing mainly the reducing activity of NOx and the oxidation activity of hydrocarbon.

After the catalyst participates in the gas purification reaction of the automobile exhaust conversion system, the physical and chemical properties of part of the three-way catalyst are changed, the activity and the selectivity of the catalyst are reduced, and the conversion activity of the polluted gas of the exhaust conversion system shows a trend from reduction to inactivation. The main deactivation modes of the three-way catalyst are heat deactivation, poisoning deactivation, carbon deposition deactivation, mechanical damage and the like. The method has the advantages that the brand-new three-way catalyst is simply replaced to ensure the emission of the automobile exhaust conversion system to reach the standard, so that the activity of the catalyst can be fundamentally improved, but the problems of low-efficiency utilization of resources, increase of environment supply pressure and the like are caused. In addition, the mechanical life of the three-way catalyst is usually 2-3 times of the chemical life of the three-way catalyst, on the premise that the mechanical structure still meets the use standard, the activity and selectivity of the catalyst are influenced by partial physical or chemical reasons, the reversible regeneration activity is achieved, the activity and selectivity of the regenerated three-way catalyst can be recovered to 80% or even completely recovered of a new three-way catalyst, the regeneration cost is half or even lower than that of the new catalyst, and the requirements of national sustainable and circular economy development are met.

The method is characterized in that the regeneration and utilization value of the three-way catalyst is evaluated aiming at the inactivation type of the three-way catalyst, the three-way catalyst with the regeneration and utilization value is regenerated by combining various physical and chemical methods, toxic substances remained on the catalyst, dust covering the surface, sediments generated on the surface and in the pores of the catalyst due to side reactions and the like are removed, the structure of the catalyst is adjusted and improved, active substances are supplemented to increase the active site of the three-way catalyst, the inherent composition and structure of the catalyst are recovered, the activity and the selectivity of the three-way catalyst can be recovered to a certain degree, and the standard requirement of the purification.

The existing three-way catalyst regeneration method and related matched technology have the following defects in the catalyst regeneration process:

(1) heat is gradually transferred from the outside to the inside of the catalyst, temperature gradients with high outside and low inside are generated, and the generated thermal stress damages the overall structural strength of the catalyst and is not beneficial to multiple regeneration;

(2) the penetrability is poor, and heat is difficult to penetrate into the catalyst;

(3) the heating rate is slow during heating, the energy consumption of ineffective action is high, and the product quality is low;

(4) the controllability of the temperature field is poor, which is not beneficial to configuring a control system for automatic management;

(5) the active component has low dispersion uniformity and poor regeneration effect uniformity;

(6) the loss rate of active components is high, and the supplement impregnation amount of regenerated active components is large;

(7) the regeneration method is single, the regeneration is not classified according to the inactivation reason, and the regeneration effect is poor.

The microwave radiation is introduced into the catalyst regeneration process, so that the catalyst is rapidly heated from inside to outside at a low temperature gradient, the catalyst module is prevented from being crushed or cracked due to nonuniform heating, the conventional catalyst regeneration process by microwave radiation is simply replaced by microwave selective rapid heating characteristics, the three-way catalyst regeneration is assisted by the unique advantage of microwave action characteristics without pertinence according to the catalyst inactivation reason, and the mechanical structure damage is reduced, so that the catalyst is repeatedly regenerated; in addition, because a proper amount of active components and a specific wave-absorbing medium are not added in a targeted manner for evaluating the activity of the catalyst, the wave-absorbing performance of the catalyst material is weak, the loss rate of the active components is high, the activation rate of active sites of the catalyst is low, and the improvement of the regeneration efficiency of the catalyst assisted by a microwave field is not obvious.

Disclosure of Invention

In view of the above problems in the prior art, the present invention is directed to a method and system for microwave-assisted regeneration of a three-way catalyst.

In order to solve the technical problems, the technical scheme of the invention is as follows:

a microwave-assisted regeneration method of a three-way catalyst comprises the following specific steps:

detecting active sites of the catalyst, and dividing the catalyst with regeneration value into three categories of heat inactivation, poisoning inactivation and carbon deposition inactivation according to inactivation reasons;

the three catalysts are respectively subjected to microwave treatment to supplement an absorbent to enhance the microwave absorption characteristic;

after the absorbent is supplemented, the three catalysts are respectively subjected to inactivation regeneration treatment, and the microwave field assists in eliminating inactivation factors in a targeted manner;

after the inactivation regeneration treatment, sequentially carrying a coating component, an auxiliary agent component and an active component in a microwave field environment selective manner;

after loading, microwave radiation is carried out to activate the active sites of the catalyst at fixed points.

Microwave, a limited frequency band in radio waves, a frequency range of 300 MHz-300 GHz, and a wavelength of 1 mm-1 m. The microwave heating mode is that electromagnetic energy is converted into internal storage energy of the catalyst component, the atomic outer orbital dipole rotates rapidly, molecules rub against each other to heat the whole catalyst, the inside and the surface of the catalyst generate heat under microwave radiation, and the heating part required by the catalyst is heated to proper temperature in a short time.

The inventor finds that the microwave directly acts on the active site to have a better regeneration effect, and the principle is as follows: by utilizing the characteristic of microwave selective heating, the target site is selectively and directly deactivated, the layered structure is adjusted layer by layer through microwave radiation, the structural resistance of the catalyst is improved, and the catalyst is beneficial to multiple regeneration; the heated target spot of the microwave radiation catalyst is heated uniformly, so that active substances re-impregnated in the regeneration liquid of the catalyst are uniformly attached to the active sites of the catalyst, precursors on the surface of the catalyst are promoted to be converted into active components under microwave radiation, and meanwhile, the heat treatment part is heated uniformly to generate uniform thermal stress, so that the mechanical strength of the regenerated catalyst carrier can be effectively improved.

In a second aspect, the three-way catalyst microwave-assisted regeneration system comprises an absorbent supplementing device, a microwave activating device, a component loading device and a catalytic activity activating device, wherein the absorbent supplementing device is sequentially connected with the microwave activating device, the component loading device and the catalytic activity activating device, the microwave activating device comprises a heat inactivation regeneration responding device, a poisoning inactivation regeneration responding device and a carbon deposition inactivation regeneration responding device, the absorbent supplementing device supplements an absorbent to strengthen the microwave absorption characteristic of the catalyst, the component loading device comprises a coating loading area, an auxiliary agent loading area and an active component loading area, and the component loading areas are independent of one another.

The invention has the beneficial effects that:

(1) the microwave selectivity is strong, the heated substances have different dielectric properties, the selective action on the surface of the catalyst and the pollutant deposition positions in pores, especially the carbon deposition generated on the surface of the catalyst has the characteristic of efficiently absorbing microwaves, the microwave directional action carbon deposition is realized under the action of microwaves, the desorption of the deposited substances is accelerated, the active sites are activated, and the energy utilization rate is improved.

(2) The microwave penetrability is strong, and rate of rise is fast, direct action inside dielectric constant high value position, and the catalyst is heated evenly, effectively reduces thermal regeneration bulk temperature to reduce the energy consumption, improve regeneration efficiency.

(3) The microwave controllability is strong, the thermal inertia is low, and the control system is convenient to configure for automatic management of radiation conditions.

(4) Microwave radiation reduces thermal stress uneven damage and improves catalyst structure resistance by adjusting the layered structure.

(5) The pore-enlarging operation of the three-way catalyst is assisted by microwaves, the pore-enlarging solution expands by heated volume, is gasified and escapes from the surface of the catalyst, and etches the catalyst to form a new porous structure, so that the pore structure of the inactivated catalyst is improved, and the specific surface area of the catalyst is increased.

(6) The microwave radiation enhances the dispersion uniformity of the surface active component of the three-way catalyst and improves the regeneration activity.

(7) The microwave radiation heating temperature is uniform, the loss rate of active components and the sintering deactivation rate are effectively reduced, and the supplement amount of regenerated active components is reduced.

(8) Supplementing high dielectric constant absorbent components and strengthening the microwave absorption characteristic of the catalyst in a targeted manner.

(9) The microwave radiation can realize the integral regeneration of the catalyst without breaking, has low damage strength to the mechanical structure and is beneficial to multiple regeneration.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.

FIG. 1 is a schematic structural diagram of a three-way catalyst regeneration system of a microwave-assisted fuel automobile according to the invention;

the device comprises a vacuum pump 1, a vacuum pump 2, an air inlet pump 3, a pretreatment device 4, a dispensing device 5, an ultrasonic microwave chemical reactor 6, a first microwave controller component 7, a magnetron microwave emission source 8, a transmission line 9, a waveguide tube 10, an ultrasonic controller component 11, an ultrasonic amplitude transformer 12, a temperature control component 13, a first catalytic evaluation component 14, a first regeneration value evaluation device 15, a recycling device 16, an absorbent supplement device 17, a second microwave controller component 18, a heat inactivation regeneration response device 19, a first liquid inlet 20, a second liquid inlet 21, a third microwave controller component 22, a microwave hole expanding region 23, a structure strengthening region 24, a heat inactivation regeneration stabilizing region 25, a poisoning inactivation regeneration response device 26, a chemical repair region 27, a catalytic oxidation region 28, a second liquid inlet 28, a third microwave controller component, a microwave hole region 23, a structure strengthening region 24, a heat inactivation regeneration stabilizing region 25, a poisoning inactivation regeneration response device 26, a chemical repair region 27, a catalytic oxidation, A poisoning inactivation regeneration stabilizing zone, 29, a carbon deposition inactivation regeneration responding device, 30, a carbon removal zone, 31, a cleaning zone, 32, a carbon deposition inactivation regeneration stabilizing zone, 33, a component loading device, 34, a fourth microwave controller component, 35, a coating loading zone, 36, an auxiliary agent loading zone, 37, an active component loading zone, 38, a catalytic activity activating device, 39, a fifth microwave controller component, 40, a first activating zone, 41, a second activating zone, 42, an activation stabilizing zone, 43, a second catalytic evaluation component, 44 and a second regeneration quality evaluation device.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

The active site is a value artificially set and is comprehensively determined according to the distribution condition of the active site of the catalyst, the emission standard of automobile exhaust and the regeneration economy of the catalyst.

As described in the background art, the existing catalyst regeneration method needs to crush the catalyst and destroy the structural strength of the catalyst. The invention does not break the regenerated catalyst and avoids damaging the structural strength of the catalyst. The microwave radiation catalyst uniformly heats the target part, the active substances impregnated by the regeneration liquid are uniformly attached to the catalyst, the microwave radiation promotes the surface precursor of the catalyst to be converted into active components, the impregnation efficiency of the regeneration liquid of the catalyst is improved, and meanwhile, the heat treatment part generates uniform thermal stress due to uniform heating, so that the mechanical strength of the regenerated catalyst carrier can be effectively improved.

In the background technology, the existing microwave regeneration method has poor penetration characteristic and high ineffective energy consumption, the catalyst is loaded with active substances, the absorbent is supplemented to enhance the wave absorbing capacity, the microwave field assists in eliminating inactivation factors in a targeted mode, the activation of the active site precursor is promoted in a fixed point mode, the action effect and the action efficiency of microwaves are improved, and the problem of poor radiation penetration characteristic when the microwaves act independently is solved.

In the background technology, the existing microwave regeneration method has poor repeated regeneration effect, microwaves selectively and directly act on deactivated target spot parts, the layered structure is adjusted layer by layer through microwave radiation, the structural resistance of the catalyst is improved, and the repeated regeneration of the catalyst is facilitated.

In some embodiments of the invention, the coating composition comprises Al₂O₃One or more of a base material, a cordierite-based material, a zeolite-based material, a vanadium-based material, an MgO material, and an SiC material.

In some embodiments of the invention, the adjunct component is one or more of a rare earth metal oxide and an alkali metal oxide; preferably, the metal element of the rare earth metal oxide is one or more of Ce, Zr, La, Sn, Mo and Ti; preferably, the alkali metal oxide is one or more of BaO, CaO and SrO; preferably, the auxiliary agent component is a rare earth metal oxide, the metal of the rare earth metal oxide is Ce, Zr and La, and the mass ratio of Ce, Zr and La is 3: 1: 1.

in some embodiments of the invention, the active component is one or more of a noble metal and a non-noble metal; further, the noble metal is one or more of Pt, Pd and Rh, and the non-noble metal is one or more of Mn, Co, Fe, Sr, Cu, Ni and Bi; furthermore, the active components are precious metals of Pt, Pd and Rh, and the mass ratio of Pt, Pd and Rh is 5: 2: 1.

in some embodiments of the present invention, the method for supporting the active material is one or more of impregnation, adsorption, precipitation, ion exchange, and chemical vapor deposition.

In some embodiments of the invention, the method for detecting the active site of the catalyst is one or more of inductively coupled plasma mass spectrometry, spectroscopic analysis, chemical titration, and spectrophotometry.

In some embodiments of the invention, the microwave action time can be adjusted to 10-30 min, the microwave energy can be adjusted to 30-60W/kg, and the microwave frequency can be adjusted to 2000-4000 MHz in the loaded active substance treatment process.

In some embodiments of the present invention, the microwave activation process is divided into three processes, namely a first activation process, a second activation process and an activation stabilization process, and the microwave conditions of the three processes are the same.

In some embodiments of the invention, the conditions of microwave activation after active loading are: the microwave action time can be adjusted to 10-60 min, the microwave energy can be adjusted to 50-100W/kg, and the microwave frequency can be adjusted to 1000-4000 MHz.

In some embodiments of the invention, the catalyst is pretreated before loading the catalyst with the active material, and the pretreatment comprises the following steps: and (3) blowing the catalyst by using gas, and cleaning and drying the catalyst by using ultrasonic waves and microwaves in a synergistic manner.

The pretreatment can remove deposited adhesion matters such as carbon deposition with low adhesion degree on the surface and/or in the pores, and toxic substances which are easy to dissolve in a cleaning agent.

Further, the gas is compressed gas, and the gas comprises one or more of air, oxygen and nitrogen. Further, the gas pressure is 0.1-2 MPa, and the purging time is 10-30 min. Further, the cleaning agent in the pretreatment process is one or more of acid, alkali, salt solution, complexing agent, oxidant, surfactant and deionized water; further, the volume ratio of the cleaning agent to the pretreated three-way catalyst is 2: 1-5: 1, the cleaning temperature is 30-50 ℃, the cleaning time is 30-60 min, and the cleaning times are 2-3. Furthermore, the ultrasonic power can be adjusted to 0-500W (not 0), the pulse width is 5-20 ms, and the power density can be adjusted to 0.3-0.4W/cm². Furthermore, the microwave condition is that the acting time is 10-60 min, the microwave energy is 10-100W/kg, and the microwave frequency is 100-4000 MHz.

The acid is hydrochloric acid, nitric acid, etc., the alkali is sodium hydroxide, ammonia water, etc., the salt solution is sodium chloride solution, etc., the complexing agent is sodium tripolyphosphate, sodium hexametaphosphate, the oxidant is hydrogen peroxide solution, sodium peroxide solution, and the surfactant is sodium dodecyl benzene sulfonate, sodium dioctyl succinate.

In some embodiments of the invention, the process of detecting the active sites of the catalyst is: before the catalyst is loaded with active substances, the performance of the three-way catalyst is detected according to the GBT3428-2017 standard, and the inactivation reason and the predicted service life of the catalyst are obtained according to the morphological characteristics and the physicochemical characteristics of the catalyst.

Further, the evaluation parameters of the morphological characteristics and the physicochemical characteristics include surface wear degree, crystalline phase structure, compressive strength, specific surface area, active components, elemental composition and conversion efficiency.

In some embodiments of the invention, the process of regeneration value evaluation is: after the performance of the catalyst is tested according to the GBT3428-2017 three-way catalyst performance detection standard, the regeneration value of the catalyst is judged in advance, a system regeneration value threshold is set as a judgment condition according to the morphological characteristics and the physicochemical characteristic requirements of the catalyst, the catalyst is divided into a catalyst with the regeneration value and a catalyst without the regeneration value, and the catalysts without the regeneration value are recycled and processed uniformly. Has regeneration value, and supplements the active components of the regenerated catalyst for regeneration treatment.

The requirements of the morphological characteristics are as follows: the wear area is less than or equal to 2 percent, the number of the through holes is less than or equal to 5, the number of the cracks is less than or equal to 5, the wear rate of the windward end is less than or equal to 5 percent, and the wear rate of the non-windward end is less than or equal to 2 percent.

Physical and chemical property requirements are as follows: the degree of structural change of the crystalline phase is less than or equal to 10 percent, the axial compressive strength is not less than 0.5MPa, the radial compressive strength is not less than 0.1MPa, and the specific surface area is not less than 20m²The content of active components is equal to or more than 80 percent, the hot sintering area is less than or equal to 5 percent, the poisoning area is less than or equal to 5 percent, the carbon deposition area is less than or equal to 30 percent,the gas conversion efficiency is larger than or equal to 80% of the gas conversion efficiency of the new catalyst.

In some embodiments of the invention, the microwave treatment of the supplemental absorbent is by: the catalyst with regeneration value is supplemented with an absorbent by microwave treatment, the microwave absorption characteristic of the catalyst is enhanced, and the active sites of the catalyst are radiated by microwaves and are transferred with energy to activate the active sites of the catalyst. By supplementing the absorbent, the content of the absorbent with high dielectric constant is increased, the wave-absorbing property of the deactivated target site of the catalyst is enhanced, and the regeneration advantage of the catalyst in the microwave field is fully exerted.

Further, the absorbent comprises one or more of ferrite powder, carbonyl iron powder, ultrafine metal powder, silicon carbide powder, carbon fiber, metal oxide powder and organic high molecular polymer; further, the active substance comprises the following substances in parts by mass: 10-20 parts of ferrite powder, 5-10 parts of ultrafine metal powder, 20-40 parts of aluminum oxide and 10-30 parts of magnesium oxide.

The kind of substance and its dielectric characteristics all have a certain influence on the amount of heat generated by the substance absorbing microwaves in a microwave field, and mainly depend on its dielectric loss factor, that is, the microwave has the characteristic of selectively heating the substance. The microwave absorption capacity of the substance with large dielectric loss factor is strong, otherwise, the microwave absorption capacity is weak.

Further, the microwave conditions were: the action time can be adjusted for 10-20 min, the microwave energy can be adjusted for 50-100W/kg, and the microwave frequency can be adjusted for 2000-4000 MHz.

In some embodiments of the invention, the method for recovering and treating the catalyst without regeneration value comprises: comprises a smelting enrichment method, a chlorination and dry distillation method, a selective dissolution method and a high-temperature volatilization method, and the purification method comprises an electrolysis method, a solvent extraction method and an ion exchange method. Extracting effective active components in the three-way catalyst which does not have regeneration value, and acting on the active substance loading and active substance activating stage of the three-way catalyst.

In some embodiments of the present invention, the microwave activation treatment process for the heat-deactivated catalyst comprises a microwave pore-enlarging treatment, a microwave structure-strengthening treatment, and a regeneration stabilizing treatment.

The microwave special heating technology assists the heat inactivation regeneration of the three-way catalyst of the fuel automobile, microwave electromagnetic energy is converted into internal stored energy of the catalyst, an atomic outer orbital dipole rotates rapidly, molecules rub with each other to heat the whole catalyst, the internal energy is generated in the catalyst and on the surface of the catalyst under the microwave radiation, and the heating part of the catalyst is heated to a proper temperature in a short time; under the action of microwave, the special reaming solution is rapidly heated to generate large steam pressure, the volume expansion is extremely violent, a new porous structure impacts and etches the pore canal formation in the catalyst in the gasification process, the specific surface area of the catalyst is improved, and the microscopic pore diameter is enlarged; by utilizing the characteristic of microwave selective heating, the target site is selectively and directly deactivated, the layered structure is adjusted layer by layer through microwave radiation, the structural resistance of the catalyst is improved, and the catalyst is beneficial to multiple regeneration; the heated target spot of the microwave radiation catalyst is heated uniformly, so that active substances re-impregnated in the regeneration liquid of the catalyst are uniformly attached to the active sites of the catalyst, precursors on the surface of the catalyst are promoted to be converted into active components under microwave radiation, and meanwhile, the heat treatment part is heated uniformly to generate uniform thermal stress, so that the mechanical strength of the regenerated catalyst carrier can be effectively improved.

Furthermore, the reaming liquid used in the microwave reaming area comprises formic acid, acetic acid, ethanol and the like, has higher loss tangent value and effectively absorbs microwaves; preferably, the pore-expanding liquid is 20% ethanol, so that a good pore-expanding effect is achieved.

Further, the structural reinforcement region is impregnated with a coating composition comprising Al₂O₃One or more of a base material, a cordierite-based material, a zeolite-based material, a vanadium-based material, an MgO material, and an SiC material. The microwave radiation adjusts the layered structure layer by layer, and the structural resistance of the catalyst is improved.

Furthermore, an auxiliary agent component is coated on the heat inactivation regeneration stabilizing zone, and the auxiliary agent component is one or more of rare earth metal oxide and alkali metal oxide; preferably, the metal element of the rare earth metal oxide is one or more of Ce, Zr, La, Sn, Mo and Ti; preferably, the alkali metal oxide is one or more of BaO, CaO and SrO; further preferably, the mass ratio of BaO, CaO and SrO is 3: 1: 1. the microwave radiation promotes the surface precursor of the catalyst to be converted into active components which are uniformly attached to the active sites of the catalyst.

Furthermore, the microwave action time of the heat inactivation regeneration response device can be adjusted by 10-20 min, the microwave energy can be adjusted by 20-50W/kg, the microwave frequency can be adjusted by 1000-3000 MHz, and the microwave heating temperature is 150-250 ℃.

In some embodiments of the present invention, the microwave activation treatment process for the poisoned deactivated catalyst includes a chemical remediation treatment, a catalytic oxidation treatment, a regeneration stabilization treatment.

The method comprises the steps of performing poisoning inactivation regeneration on a three-way catalyst by microwave assistance, converting microwave electromagnetic energy into internal stored energy consisting of the catalyst, generating heat energy in the catalyst and on the surface of the catalyst under microwave radiation, heating a heating part required by the catalyst to a proper temperature in a short time, assisting a chemical reagent or electrochemically repairing the poisoning inactivation part, reducing the loss rate of active components and reducing the supplement amount of regenerated active components; by utilizing the microwave selective heating characteristic, the inactive target site is selectively and directly acted with the coating auxiliary agent components of rare earth metal oxide and alkali metal oxide, the surface precursor of the catalyst is promoted to be converted into an active component by microwave radiation, and an oxidizing reagent is added for rapid activation and regeneration.

Furthermore, the solid-liquid ratio (catalyst mass/repair agent mass) of the repair agent in the chemical repair area is 10-30: 1, the catalyst is soaked in the repair agent solution, and the poisoned and inactivated part is repaired under microwave heating.

Furthermore, the repairing agent is a microwave-assisted chemical agent or an electrochemical repairing poisoning inactivation site in the catalytic oxidation process, and the chemical agent comprises one or more of acid, alkali, a salt solution, an oxidizing agent and a surfactant; preferably an iron oxide desulphurizing agent.

Further, during the process of stabilizing the poisoning deactivation regeneration, the catalyst is soaked in an oxidizing solution under the microwave environment, wherein the oxidizing solution comprises a hydrogen peroxide solution, nitric acid and a manganese dioxide solution, and preferably, the hydrogen peroxide solution has better oxidation characteristics.

Furthermore, an antitoxic is added into the poisoning inactivation regeneration stabilizing zone, the solid-to-liquid ratio (the mass of the catalyst/the mass of the antitoxic) of the antitoxic is 10-30: 1, and the antitoxic comprises 0.1-5 wt% of titanium nitrate, 0.1-5 wt% of vanadium nitrate and deionized water. The antitoxic property of the catalyst is strengthened.

Furthermore, the poisoning inactivation regeneration stabilization zone is coated with auxiliary agent components of rare earth metal oxide and alkali metal oxide, preferably, the metal element of the rare earth metal oxide is one or more of Ce, Zr, La, Sn, Mo and Ti; preferably, the alkali metal oxide is one or more of BaO, CaO and SrO; further preferably, the mass ratio of BaO to CaO is 1: 1. the microwave radiation promotes the surface precursor of the catalyst to be converted into active components which are uniformly attached to the active sites of the catalyst.

Furthermore, the microwave action time of the poisoning inactivation regeneration response device can be adjusted by 10-30 min, the microwave energy can be adjusted by 40-80W/kg, the microwave frequency can be adjusted by 2000-4000 MHz, and the microwave heating temperature is 350-450 ℃.

In some embodiments of the present invention, the microwave activation treatment process for the soot deactivated catalyst comprises a carbon elimination treatment, a cleaning treatment, and a regeneration stabilization treatment.

The microwave-assisted deactivation regeneration of the carbon deposition of the three-way catalyst of the fuel automobile is based on the characteristic that the comprehensive dielectric constant of the carbon deposition and the noble metal in a three-way catalyst carrier is higher, under the condition of not damaging the internal structure of the three-way catalyst, by utilizing the characteristics that the microwave radiation penetrating power is strong, the temperature rising rate is high, the microwave radiation penetrating the inside of an object directly acts on a target site, under the action of microwave, an external orbital dipole of a polar adsorption substance rapidly rotates under the action of microwave radiation energy, the microwave uniformly heats the porous medium noble metal catalyst and assists in oxidizing or washing the carbon deposition on the surface of the catalyst by gas cyclone, the substance adsorbed on the catalyst is heated and oxidized into gas to escape or fall off under the disturbance of the gas, the pollution adsorbate which is difficult to desorb on the catalyst is volatilized or decomposed, the organic pollutant is promoted to be fully degraded, the auxiliary cleaning agent is coated with, microwave radiation promotes the precursor on the surface of the catalyst to be converted into active components, and the carbon adsorption performance on the surface of the catalyst is weakened.

Furthermore, in the microwave carbon elimination treatment process, the catalyst is subjected to microwave heating treatment to assist in gas rotational flow oxidation or washing carbon deposition on the surface of the catalyst.

Further, the mass portion of the gas rotational flow is set to 1 to 10 portions of O₂1 to 10 parts of H₂O (steam) and 60 to 90 parts by weight of N₂The mixed atmosphere of (3); preferably 4 parts of O₂Gas, 5 parts H₂O (steam), 70 parts of N₂The mixed atmosphere of (3).

Furthermore, the carbon deposition inactivation regeneration stabilization zone is coated with auxiliary agent components of rare earth metal oxide and alkali metal oxide, microwave radiation promotes the surface precursor of the catalyst to be converted into active components, and the carbon adsorption performance on the surface of the catalyst is weakened.

Furthermore, the microwave action time of the carbon deposition inactivation regeneration response device can be adjusted by 10-45 min, the microwave energy can be adjusted by 20-100W/kg, the microwave frequency can be adjusted by 1000-4000 MHz, and the microwave heating treatment temperature range is 300-500 ℃; preferably, the heating treatment time is 10-20 min, and the heating temperature is 400 ℃.

In some embodiments of the present invention, the regeneration value evaluation is performed after the microwave radiation site-specific activation of the catalyst active sites, and the regeneration value evaluation is performed by the following process: after the catalyst is subjected to microwave activation treatment, the regeneration quality of the catalyst is evaluated according to the performance detection standard of the GBT3428-2017 three-way catalyst.

And setting system regeneration quality evaluation conditions according to the morphology characteristics and physicochemical property requirements of the catalyst, wherein the evaluation parameters comprise surface wear degree, crystalline phase structure, compressive strength, specific surface area, active components, element composition and conversion efficiency.

The requirements of the morphological characteristics are as follows: the abrasion area is less than or equal to 5 percent, the abrasion rate of the windward end is less than or equal to 2 percent, and the abrasion rate of the non-windward end is less than or equal to 2 percent.

Physical and chemical property requirements are as follows: the structural change degree of the crystal phase is less than or equal to 5 percent, the axial compressive strength is not less than 0.5MPa, the radial compressive strength is not less than 0.1MPa, and the specific surface area is not less than 20m²The content of active components is not less than 90 percent of that of the active components of the new catalyst, the hot sintering area is not more than 2 percent, the poisoning area is not more than 2 percent, the carbon deposition area is not more than 10 percent, and the gas conversion efficiency is not less than that of the new catalystThe efficiency is 90%.

The catalyst without regeneration value is used for recovering effective active components by a smelting enrichment method, a chlorination and dry distillation method, a selective dissolution method and a high-temperature volatilization method, and the purification method comprises an electrolysis method, a solvent extraction method and an ion exchange method.

A three-way catalyst microwave-assisted regeneration system comprises an absorbent supplementing device 16, a microwave activating device, a component loading device 33 and a catalytic activity activating device 38, wherein the absorbent supplementing device 16 is sequentially connected with the microwave activating device, the component loading device 33 and the catalytic activity activating device 38, the microwave activating device comprises a heat inactivation regeneration responding device 18, a poisoning inactivation regeneration responding device 25 and a carbon deposition inactivation regeneration responding device 29, the absorbent supplementing device 16 supplements an absorbent to strengthen the microwave absorption characteristic of a catalyst, and the component loading device 33 comprises a coating loading area 35, an auxiliary agent loading area 36 and an active component loading area 37.

It will be appreciated that the loading zones of the respective active components of the component loading means are spaced from each other, and that loading and microwave irradiation may be carried out separately. The absorbent supplementing device 16 is respectively connected with the heat inactivation regeneration responding device 18, the poisoning inactivation regeneration responding device 25 and the carbon deposition inactivation regeneration responding device 29.

In some embodiments of the present invention, the catalytically active activation device 38 comprises a first activation zone 40, a second activation zone 41, and an activation stabilization zone 42, the three activation zones being independent of each other.

In some embodiments of the present invention, the device further comprises a pretreatment device 3, an ultrasonic microwave chemical reactor 5 is arranged inside the pretreatment device 3, the ultrasonic microwave chemical reactor 5 is provided with a first microwave controller component 6, an ultrasonic controller component 10 and a temperature control component 12, and the pretreatment device is connected with the air inlet device, the dispensing device and the vacuum device.

As shown in fig. 1, the pretreatment of the catalyst is performed in a pretreatment device. The temperature control assembly 12 monitors and controls the reactor temperature in real time by means of a high-precision non-contact infrared sensor. The vacuum device is mainly realized through equipment such as a vacuum pump 1, the air inlet device mainly leads gas into the pretreatment device 3 through an air inlet pipe through an air inlet pump 2, the vacuum pump and the air inlet pump realize the entrance of compressed gas and the suction filtration of cleaning liquid, and the top end of the pretreatment device 3 is provided with a dispensing device 4 for preparing reagents required by the pretreatment process. The ultrasonic controller component 10 comprises an ultrasonic amplitude transformer 11, the ultrasonic controller component 10 sends out a high-frequency vibration signal by an ultrasonic generator, the high-frequency vibration signal is converted into high-frequency mechanical vibration by the ultrasonic amplitude transformer 11 through a transducer and is transmitted to the cleaning agent, and the ultrasonic density is transmitted at intervals.

In some embodiments of the invention, a first catalytic evaluation assembly 13 is also included, the first catalytic evaluation assembly 13 being located downstream of the pretreatment device 3. The first catalytic evaluation assembly 13 is used for evaluating the morphological characteristics and physicochemical characteristics of the catalyst. The method is realized by a scanning electron microscope, an element analyzer, a spectrum analyzer, a chemical adsorption instrument, a physical adsorption instrument and the like. Samples can be taken from different beds of catalyst.

In some embodiments of the present invention, the system further includes a first regeneration value evaluation device 14, the first regeneration value evaluation device 14 is a PC terminal, and the first regeneration value evaluation device 14 is electrically connected to the first catalyst evaluation assembly 13.

The performance characteristics of the catalyst obtained by the first catalytic evaluation component are input into the PC terminal, and the catalyst is classified by analyzing data at the PC terminal. After the catalyst is evaluated by the first regeneration value evaluation device, the catalyst having the regeneration value is sent to the absorbent replenishment device.

The first regeneration value evaluation device 14 sets a catalyst regeneration value evaluation parameter for determining the regeneration value of the catalyst. Samples can be taken from different beds of catalyst.

In some embodiments of the invention, the sorbent replenishment means 16 is provided with the second microwave controller assembly 17, the thermal deactivation regeneration response means 18, the poisoning deactivation regeneration response means 25, the soot deactivation regeneration response means 29, the third microwave controller assembly 21, the component loading means 33 is provided with the fourth microwave controller assembly 34, and the catalytic activity activation means 38 is provided with the fifth microwave controller assembly 39, respectively.

In some embodiments of the present invention, the heat-inactivation regeneration device comprises a microwave-porous region 22, a structure-enhancement region 23, and a heat-inactivation regeneration-stabilization region 24, which are independent of each other.

In some embodiments of the present invention, the poisoning deactivation regeneration device comprises a chemical remediation zone 26, a catalytic oxidation zone 27, and a poisoning deactivation regeneration stabilization zone 28, which are independent of each other.

In some embodiments of the present invention, the soot deactivation regeneration device comprises a carbon elimination zone 30, a cleaning zone 31, and a soot deactivation regeneration stabilization zone 32, which are independent of each other.

In some embodiments of the present invention, the recycling device 15 is further included, the recycling device is connected to the first regeneration value evaluation device 14, and the recycling device 15 is respectively connected to the thermal deactivation regeneration device, the poisoning deactivation regeneration device, the carbon deposition deactivation regeneration device, the component loading device, and the catalytic activity activation device.

Further, the recycling device 15 is respectively communicated with the microwave hole expanding area 22, the structure strengthening area 23, the chemical repairing area 26 of the poisoning inactivation regeneration device, the catalytic oxidation area 27, the carbon eliminating area 30 of the carbon deposit inactivation regeneration device, the cleaning area 31, the coating loading area 35 of the component loading device, the auxiliary agent loading area 36, the first activation area 40 of the catalytic activity activation device and the second activation area 41 of the thermal inactivation regeneration device 18.

As shown in FIG. 1, the recycling device 15 is connected to a first inlet 19 of a microwave-expanded region 22 of a heat-inactivation regeneration device 18 and to a second inlet 20 of a structure-strengthening region 23.

The recovery device is used for recovering and treating the catalyst without regeneration value, and the device realizes the smelting enrichment method, the chlorination and dry distillation method, the selective dissolution method, the high-temperature volatilization method and the like of the catalyst. The content of the effective active components is detected by one or more methods of inductively coupled plasma mass spectrometry (ICP-MS), X fluorescence spectroscopy (XRF), spectrum analysis (PMI), chemical titration method and spectrophotometer method.

In some embodiments of the invention, a second catalytic evaluation assembly 43 is also included, the second catalytic evaluation assembly 43 being located downstream of the catalytic activity activation device 38. The material from the catalytically active activation device 38 is sent to the second catalytic evaluation component for testing by recognition or by a transfer cart or the like.

In some embodiments of the present invention, a second regeneration quality evaluation device 44 is further included, the second regeneration value evaluation device 44 is a PC terminal, and the second regeneration quality evaluation device 44 is electrically connected to the second catalytic evaluation component 43; catalysts that did not meet the evaluation requirements were returned (considered returned and transported) to the heat-deactivated regeneration unit, the poisoning-deactivated regeneration unit, the soot-deactivated regeneration unit.

In the device, the material is fixed in the device through the fixing component or the material is arranged on the bottom plate of the device.

The pretreatment device, the absorbent supplement device, the thermal deactivation regeneration device, the poisoning deactivation regeneration device, the carbon deposition deactivation regeneration device, the component loading device and the catalytic activity activation device can be seen as a closed box body, and the catalyst is correspondingly treated in the box body.

In the invention, the mutually independent devices or areas can independently process the materials, and the materials can be put into the devices or areas for processing and then can be taken out for transferring and other operations.

The microwave control assembly comprises a magnetron microwave emission source 7, a waveguide tube 9 and a transmission line 9, wherein the magnetron microwave emission source 7 is communicated with a reactor in a box body through the waveguide tube 9, the microwave emission sources are arranged in a staggered mode to reduce microwave interference influence, the waveguide tubes 9 are uniformly arranged on the wall of the reactor in a staggered mode, alternating current is converted into microwave vibration through a semiconductor device and transmitted into the reactor, and the effect of the microwave is enhanced through the reflection of a wall panel.

As shown in fig. 1, the air intake means is mainly realized by an intake pump and some other means, and the vacuum means is mainly realized by a vacuum pump and some other means.

Example 1

The test material selects a same model seven-generation Acura 2.4 vehicle-mounted fresh three-way catalyst and an inactivated three-way catalyst, and the microwave-assisted regeneration of the three-way catalyst of the fuel automobile is carried out as follows:

firstly, after the catalyst is fixed in a pretreatment device and the surface and the inside of the three-way catalyst are purged by nitrogen with the pressure of 0.2MPa for 20min,the volume ratio of the addition of the dispensing device to the pretreated three-way catalyst is 2:1 sodium dodecyl benzene sulfonate to a pretreatment device, and an ultrasonic controller component adjusts the ultrasonic power to 200W, the pulse width to 10ms and the power density to 0.30W/cm at the temperature of 30 DEG C²The first microwave control component adjusts the microwave energy to be 20W/kg and the microwave frequency to be 1000MHz, the ultrasonic microwave chemical reactor cooperates with the sodium dodecyl benzene sulfonate to deeply clean the catalyst for 60min, the ultrasonic controller component has the ultrasonic power of 500W, the pulse width of 20ms and the power density of 0.40W/cm at the temperature of 50 DEG C²The first microwave control assembly adjusts the microwave energy to be 20W/kg, the microwave frequency is 1000MHz, the ultrasonic microwave chemical reactor is deeply dried for 30min, and the cleaning operation is repeated once.

And secondly, detecting the morphological characteristics and the physicochemical characteristics of the pretreated three-way catalyst by using a first catalytic evaluation component, selectively dissolving and recovering active components without regeneration value, purifying the active components by ion exchange, dividing the regeneration value into three types, namely heat inactivation regeneration, poisoning inactivation regeneration and carbon deposition inactivation regeneration, according to inactivation reasons, setting the number 1 and the number 2 of regenerated catalysts for each type, supplementing 10 parts of microwave absorbent ferrite powder, 5 parts of ultrafine metal powder, 20 parts of aluminum oxide and 10 parts of magnesium oxide for the number 2 of regenerated catalysts, and strengthening the microwave absorption characteristics of deactivated parts of the catalysts.

The microwave action time of the second microwave control assembly can be adjusted by 10min, the microwave energy can be adjusted by 50W/kg, and the microwave frequency can be adjusted by 2000 MHz.

Thirdly, microwave-assisted three-way catalyst thermal inactivation regeneration: detecting the crystal phase of the catalyst by fluorescence spectrum, fusing and aggregating the active component crystal grains, calibrating the hot sintering target site of the catalyst, and activating the hot inactivation regeneration area. Firstly, the microwave radiation catalyst is heated to 200 ℃ to act on a heat inactivation target spot part, the 20% ethanol pore-expanding agent is assisted to soak the catalyst for rapid gasification, pore channels in the catalyst are impacted and etched to form a new porous structure, the specific surface area of the catalyst is improved, and the microscopic pore diameter is enlarged. Secondly, the heat inactivation part of the microwave radiation catalyst accelerates the uniform coating of cordierite-based material coating components, the layered structure is adjusted layer by layer, and the structural resistance of the catalyst is improved. Then, coating an auxiliary component BaO, CaO and SrO precursor mixed solution (the mass ratio of BaO, CaO and SrO is 3: 1: 1), and promoting the conversion of the catalyst surface precursor into an active component by microwave radiation to enhance the high-temperature resistance of the catalyst.

Heat inactivation: the action time of the third microwave component can be adjusted by 10min, the microwave energy can be adjusted by 20W/kg, and the microwave frequency can be adjusted by 1000 MHz.

Carrying out microwave-assisted three-way catalyst poisoning inactivation regeneration: detecting the composition of catalyst elements by spectral analysis, calibrating the excessive part of the sulfur element content when the sulfur element content of the deactivated catalyst exceeds a threshold value, and activating a poisoning deactivation regeneration area. Firstly, heating a microwave radiation catalyst to 400 ℃ to act on a part with excessive sulfur element content, soaking an auxiliary repairing agent iron oxide (the mass of the catalyst/the mass of the repairing agent is 10: 1) in the catalyst to remove excessive sulfur element, and soaking a hydrogen peroxide solution to restore the oxidation activity of the catalyst. Secondly, adding 1 wt% of titanium nitrate, 0.5 wt% of vanadium nitrate and an antitoxic agent of deionized water in a microwave-assisted manner (the mass of the catalyst/the mass of the antitoxic agent is 10: 1). Then, coating an auxiliary component BaO and CaO precursor mixed solution (the mass ratio of BaO to CaO is 1: 1), promoting the conversion of the catalyst surface precursor into an active component by microwave radiation, and strengthening the antitoxic property of the catalyst.

And (3) poisoning and inactivation: the microwave action time of the third microwave component can be adjusted by 20min, the microwave energy can be adjusted by 40W/kg, and the microwave frequency can be adjusted by 2000 MHz.

Microwave-assisted carbon deposition inactivation regeneration of three-way catalyst O₂And detecting the oxygen consumption area by TPO to represent the carbon deposition content of the catalyst, calibrating the carbon deposition deactivation part when the carbon deposition amount of the deactivated catalyst exceeds a threshold value, and activating a carbon deposition deactivation regeneration area. Firstly, microwave radiation catalyst is heated to 400 ℃ for targeting carbon deposition, and 4 parts of O is assisted₂5 parts of H₂O (steam), 70 parts of N₂The mixed atmosphere of (3). The cyclone flushes carbon deposit on the surface of the catalyst. Secondly, the microwave-assisted surfactant ethylene diamine tetraacetate solution cleans carbon on the surface of the catalyst disturbed by the gas rotational flow. Then, coating an auxiliary component BaO and SrO precursor mixed solution (the ratio of BaO to SrO is 3: 1), and promoting the conversion of the catalyst surface precursor into an active component by microwave radiation to weaken the carbon adsorption performance of the catalyst surface.

Carbon deposition inactivation: the microwave action time of the third microwave component can be adjusted for 30min, the microwave energy can be adjusted for 60W/kg, and the microwave frequency can be adjusted for 3000 MHz.

The fourth step of applying a coating component Al₂O₃The catalyst is prepared by coating an auxiliary component Ce, Zr and La precursor mixed solution (mass ratio of Ce, Zr and La is 3: 1: 1) and a loaded catalyst active component Pt, Pd and Rh precursor mixed solution (mass ratio of Pt, Pd and Rh is 5: 2: 1), heating the catalyst to 400 ℃ by microwave radiation to act on a target part, promoting the conversion of the precursor on the surface of the catalyst into the active component, transferring energy to activate the pore active component and the surface active component of the three-way catalyst, and improving the catalytic conversion efficiency of the three-way catalyst.

The microwave action time of the fourth microwave control assembly can be adjusted by 20min, the microwave energy can be adjusted by 50W/kg, and the microwave frequency can be adjusted by 3000 MHz.

The microwave action time of the fifth microwave control assembly can be adjusted for 30min, the microwave energy can be adjusted for 60W/kg, and the microwave frequency can be adjusted for 2500 MHz.

And fifthly, evaluating the morphological characteristics and the physicochemical characteristics of the regenerated three-way catalyst of the fuel automobile by the second catalytic evaluation component, and obtaining a qualified regenerated three-way catalyst product of the fuel automobile according to the parameter threshold requirement.

The method is characterized in that a laboratory simulates the working environment of the exhaust conversion system of the fuel automobile to detect the activity of the catalyst, detects the gas conversion efficiency of the catalyst according to the performance detection standard of the GBT3428-2017 three-way catalyst, represents the regeneration activity of three types of deactivated catalysts, and compares the influence of the presence or absence of the added microwave absorbent on the regeneration activity of the three-way catalyst of the fuel automobile. The gas conversion rate is detected by selecting rich combustion (oxygen sufficiency) and lean combustion (oxygen insufficiency) conditions, and the gas distribution composition under the rich combustion condition is O₂Volume fraction of 6%, volume fraction of CO of 5%, C₃H₈1500ppm、NO_X1000ppm，N₂The gas distribution component under the condition of balancing and lean combustion is O₂Volume fraction of 4.5%, volume fraction of CO 5%, C₃H₈1500ppm、NO_X1000ppm，N₂The temperature was 400 ℃ for both the trim and test. Detecting NO by ultraviolet flue gas analyzer_XContent, gas chromatography two-channel detection of CO and C₃H₈And (4) content.The effect of gas conversion is shown in table 1.

TABLE 1 results for gas conversion efficiency of three-way catalyst for fuel-powered automobile

According to the results of the gas conversion efficiency of the three-way catalyst of the fuel automobile, the gas conversion efficiency of the three regenerated catalysts is improved after the three-way catalyst of the fuel automobile is regenerated by microwave assistance, but the improvement degree of the gas conversion efficiency of the regenerated catalyst No. 2 added with the absorbent is better than that of the regenerated catalyst No. 1, the absorbent enhances the microwave absorption characteristic of the catalyst material, and the regeneration advantage of the microwave field auxiliary agent is fully exerted.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A microwave-assisted regeneration method for a three-way catalyst of a fuel automobile is characterized by comprising the following steps: the method comprises the following specific steps:

carrying out microwave radiation fixed-point activation on the catalyst active site after loading;

the microwave activation treatment process of the heat inactivation catalyst comprises microwave reaming treatment, microwave structure strengthening treatment and regeneration stabilizing treatment;

the pore-expanding liquid used in the microwave pore-expanding area comprises formic acid, acetic acid or ethanol with a high loss tangent value, and can effectively absorb microwaves;

the structural strengthening region is impregnated with a coating composition comprising Al₂O₃One or more of a base material, a cordierite-based material, a zeolite-based material, a vanadium-based material, an MgO material, and an SiC material;

the heat inactivation regeneration stabilizing zone is coated with auxiliary agent components of rare earth metal oxide and alkali metal oxide, or the auxiliary agent components are one or more of rare earth metal oxide and alkali metal oxide.

2. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the active component is one or more of noble metal and non-noble metal.

3. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the coating component comprises Al₂O₃One or more of a base material, a cordierite-based material, a zeolite-based material, a vanadium-based material, an MgO material, and an SiC material.

4. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the method for detecting the active sites of the catalyst is one or more of inductively coupled plasma mass spectrometry, spectroscopic analysis, chemical titration and spectrophotometer.

5. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: in the process of loading the active components, the microwave action time can be adjusted for 10-30 min, the microwave energy can be adjusted for 30-60W/kg, and the microwave frequency can be adjusted for 2000-4000 MHz.

6. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the microwave activation treatment process is divided into three processes, namely a first activation treatment process, a second activation treatment process and an activation stabilization treatment process, and the microwave conditions of the three processes are the same.

7. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the microwave activation condition after the active component is loaded is as follows: the microwave action time can be adjusted to 10-60 min, the microwave energy can be adjusted to 50-100W/kg, and the microwave frequency can be adjusted to 1000-4000 MHz.

8. The method for microwave-assisted regeneration of a three-way catalyst according to claim 2, wherein: the noble metal is Pt, Pd, Rh.

9. The method for microwave-assisted regeneration of a three-way catalyst according to claim 2, wherein: the non-noble metal is Mn, Co, Fe, Sr, Cu, Ni, Bi.

10. The method for microwave-assisted regeneration of a three-way catalyst according to claim 2, wherein: the metal element of the rare earth metal oxide is one or more of Ce and La.

11. The method for microwave-assisted regeneration of a three-way catalyst according to claim 2, wherein: the alkali metal oxide is BaO, CaO and SrO.

12. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: before loading active components on the catalyst, pretreating the catalyst, blowing the catalyst by using gas, and cleaning and drying the catalyst by using ultrasonic waves and microwaves in a synergistic manner.

13. The method for microwave-assisted regeneration of a three-way catalyst according to claim 12, wherein: the gas is compressed gas, and the gas comprises one or more of air, oxygen and nitrogen.

14. The method for microwave-assisted regeneration of a three-way catalyst according to claim 12, wherein: the pressure of the gas is 0.1-2 MPa, and the purging time is 10-30 min.

15. The method for microwave-assisted regeneration of a three-way catalyst according to claim 12, wherein: the cleaning agent in the pretreatment process is one or more of acid, alkali, salt solution, complexing agent, oxidant, surfactant and deionized water.

16. The method for microwave-assisted regeneration of a three-way catalyst according to claim 15, wherein: the volume ratio of the cleaning agent to the pretreated three-way catalyst is 2: 1-5: 1, the cleaning temperature is 30-50 ℃, the cleaning time is 30-60 min, and the cleaning times are 2-3.

17. The method for microwave-assisted regeneration of a three-way catalyst according to claim 12, wherein: the ultrasonic power can be adjusted to 0-500W, the pulse width is 5-20 ms, and the power density can be adjusted to 0.3-0.4W/cm²。

18. The method for microwave-assisted regeneration of a three-way catalyst according to claim 12, wherein: the microwave condition is that the acting time is 10-60 min, the microwave energy is 10-100W/kg, and the microwave frequency is 100-4000 MHz.

19. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: before the catalyst is loaded with active components, the performance of the three-way catalyst is detected according to the GBT3428-2017 standard, and the inactivation reason and the predicted service life of the catalyst are obtained according to the morphological characteristics and the physicochemical characteristics of the catalyst.

20. The method for microwave-assisted regeneration of a three-way catalyst according to claim 19, wherein: the evaluation parameters of the morphological characteristics and the physicochemical characteristics comprise surface wear degree, crystalline phase structure, compressive strength, specific surface area, active components, element composition and conversion efficiency.

21. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the regeneration value evaluation process comprises the following steps: after the performance of the catalyst is tested according to the performance detection standard of the GBT3428-2017 three-way catalyst, the regeneration value of the catalyst is judged in advance, a system regeneration value threshold is set as a judgment condition according to the morphological characteristics and the physicochemical characteristic requirements of the catalyst, and the catalyst is divided into a catalyst with the regeneration value and a catalyst without the regeneration value.

22. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the process of supplementing the absorbent by microwave treatment comprises the following steps: the catalyst with regeneration value is supplemented with an absorbent by microwave treatment, the microwave absorption characteristic of the catalyst is enhanced, and the active sites of the catalyst are radiated by microwaves and are transferred with energy to activate the active sites of the catalyst.

23. The method for microwave-assisted regeneration of a three-way catalyst according to claim 22, wherein: the absorbent comprises one or more of ferrite powder, carbonyl iron powder, ultramicro metal powder, silicon carbide powder, carbon fiber, metal oxide powder and organic high molecular polymer.

24. The method for microwave-assisted regeneration of a three-way catalyst according to claim 22, wherein: the active components comprise the following substances in parts by mass: 10-20 parts of ferrite powder, 5-10 parts of ultrafine metal powder, 20-40 parts of aluminum oxide and 10-30 parts of magnesium oxide.

25. The method for microwave-assisted regeneration of a three-way catalyst according to claim 18, wherein: the microwave action time can be adjusted by 10-20 min, the microwave energy can be adjusted by 50-100W/kg, and the microwave frequency can be adjusted by 2000-4000 MHz.

26. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the pore-enlarging liquid is 20% ethanol, so that the pore-enlarging effect is better.

27. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the metal element of the rare earth metal oxide is one or more of Ce and La.

28. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the alkali metal oxide is one or more of BaO, CaO and SrO.

29. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the microwave action time of the heat inactivation regeneration response device can be adjusted by 10-20 min, the microwave energy can be adjusted by 20-50W/kg, and the microwave frequency can be adjusted by 1000-3000 MHz.

30. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the microwave activation treatment process for the poisoning deactivated catalyst comprises chemical repair treatment, catalytic oxidation treatment and regeneration stabilization treatment.

31. The method for microwave-assisted regeneration of a three-way catalyst according to claim 30, wherein: the solid-liquid ratio of a repairing agent used for the chemical repairing area treatment is 10-30: 1, and a catalyst is soaked in the repairing agent solution.

32. The method for microwave-assisted regeneration of a three-way catalyst according to claim 31, wherein: the repairing agent is a microwave-assisted chemical agent or an electrochemical repairing poisoning inactivation site in the catalytic oxidation process, and the chemical agent comprises one or more of acid, alkali, salt solution, oxidant and surfactant.

33. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: in the process of stabilizing the poisoning inactivation regeneration, the catalyst is soaked in an oxidizing solution under the microwave environment, wherein the oxidizing solution comprises a hydrogen peroxide solution, nitric acid and a manganese dioxide solution.

34. The method for microwave-assisted regeneration of a three-way catalyst according to claim 33, wherein: the hydrogen peroxide solution has better oxidation characteristics.

35. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: and adding an antitoxic agent into the poisoning inactivation regeneration stabilizing zone, wherein the solid-to-liquid ratio of the antitoxic agent is 10-30: 1, and the antitoxic agent comprises 0.1-5 wt% of titanium nitrate, 0.1-5 wt% of vanadium nitrate and deionized water, so that the antitoxic property of the catalyst is enhanced.

36. The method for microwave-assisted regeneration of a three-way catalyst according to claim 35, wherein: and the poisoning inactivation regeneration stabilizing zone is coated with auxiliary agent components of rare earth metal oxide and alkali metal oxide, or the auxiliary agent components are one or more of rare earth metal oxide and alkali metal oxide.

37. The method for microwave-assisted regeneration of a three-way catalyst according to claim 36, wherein: the metal element of the rare earth metal oxide is one or more of Ce and La.

38. The method for microwave-assisted regeneration of a three-way catalyst according to claim 36, wherein: the alkali metal oxide is one or more of BaO, CaO and SrO.

39. The method for microwave-assisted regeneration of a three-way catalyst according to claim 38, wherein: the microwave action time of the poisoning inactivation regeneration response device can be adjusted by 10-30 min, the microwave energy can be adjusted by 40-80W/kg, and the microwave frequency can be adjusted by 2000-4000 MHz.

40. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: the microwave activation treatment process of the carbon deposition inactivation catalyst comprises carbon removal treatment, cleaning treatment and regeneration stabilization treatment.

41. The method for microwave-assisted regeneration of a three-way catalyst according to claim 40, wherein: in the microwave carbon elimination treatment process, the catalyst is subjected to microwave heating treatment, and gas rotational flow oxidation or carbon deposition on the surface of the catalyst is assisted to be washed.

42. The method for microwave-assisted regeneration of a three-way catalyst according to claim 41, wherein: the gas rotational flow is 1-10 parts of O₂1 to 10 parts of H₂O, 60-90 parts of N₂The mixed atmosphere of (3).

43. The method for microwave-assisted regeneration of a three-way catalyst according to claim 42, wherein: the gas rotational flow is 4 parts of O₂Gas, 5 parts H₂O, 70 parts of N₂The mixed atmosphere of (3).

44. The method for microwave-assisted regeneration of a three-way catalyst according to claim 43, wherein: the microwave action time of the carbon deposition inactivation regeneration response device can be adjusted by 10-45 min, the microwave energy can be adjusted by 20-100W/kg, the microwave frequency can be adjusted by 1000-4000 MHz, and the microwave heating treatment temperature range is 300-500 ℃.

45. The method for microwave-assisted regeneration of a three-way catalyst according to claim 44, wherein: the heating treatment time is 10-20 min, and the heating temperature is 400 ℃.

46. The method for microwave-assisted regeneration of a three-way catalyst according to claim 1, wherein: carrying out regeneration value evaluation after activating the catalyst active site at fixed point by microwave radiation, wherein the regeneration value evaluation process comprises the following steps: after the catalyst is subjected to microwave activation treatment, the regeneration quality of the catalyst is evaluated according to the performance detection standard of the GBT3428-2017 three-way catalyst.

47. The method for microwave-assisted regeneration of a three-way catalyst according to any one of claims 1-46, wherein: the three-way catalyst microwave-assisted regeneration system comprises an absorbent supplementing device, a microwave activating device, a component loading device and a catalytic activity activating device, wherein the absorbent supplementing device is sequentially connected with the microwave activating device, the component loading device and the catalytic activity activating device, the microwave activating device comprises a heat inactivation regeneration responding device, a poisoning inactivation regeneration responding device and a carbon deposition inactivation regeneration responding device, the absorbent supplementing device supplements an absorbent to strengthen the microwave absorption characteristic of a catalyst, and the component loading device comprises a coating loading area, an auxiliary agent loading area and an active component loading area.

48. The method for microwave-assisted regeneration of a three-way catalyst according to claim 47, wherein: the catalytic activity activation device comprises a first activation area, a second activation area and an activation stable area, wherein the three activation areas are independent from each other.

49. The method for microwave-assisted regeneration of a three-way catalyst according to claim 48, wherein: the device is characterized by further comprising a pretreatment device, wherein an ultrasonic microwave chemical reactor is arranged in the pretreatment device, the ultrasonic microwave chemical reactor is provided with a first microwave controller component, an ultrasonic controller component and a temperature control component, and the pretreatment device is connected with an air inlet device, a dispensing device and a vacuum device.

50. The method for microwave-assisted regeneration of a three-way catalyst according to claim 49, wherein: also included is a first catalytic evaluation assembly located downstream of the pretreatment device.

51. The method for microwave-assisted regeneration of a three-way catalyst according to claim 49, wherein: the first regeneration value evaluation device is a PC end and is electrically connected with the first catalytic evaluation assembly.

52. The method for microwave-assisted regeneration of a three-way catalyst according to claim 47, wherein: the absorbent supplementing device is provided with a second microwave controller component, the heat inactivation regeneration responding device, the poisoning inactivation regeneration responding device and the carbon deposition inactivation regeneration responding device are respectively provided with a third microwave controller component, the component loading device is provided with a fourth microwave controller component, and the catalytic activity activating device is provided with a fifth microwave controller component.

53. The method for microwave-assisted regeneration of a three-way catalyst according to claim 52, wherein: the heat inactivation regeneration device comprises a microwave hole expanding area, a structure strengthening area and a heat inactivation regeneration stabilizing area which are mutually independent.

54. The method for microwave-assisted regeneration of a three-way catalyst according to claim 52, wherein: the poisoning inactivation regeneration device comprises a chemical repair area, a catalytic oxidation area and a poisoning inactivation regeneration stabilizing area which are mutually independent.

55. The method for microwave-assisted regeneration of a three-way catalyst according to claim 52, wherein: the carbon deposition inactivation regeneration device comprises a carbon removal area, a cleaning area and a carbon deposition inactivation regeneration stabilizing area which are mutually independent.

56. The method for microwave-assisted regeneration of a three-way catalyst according to claim 47, wherein: the device also comprises a recycling device, the recycling device is connected with the regeneration value evaluation assembly, and the recycling device is respectively connected with the absorbent supplementing device, the heat inactivation regeneration device, the poisoning inactivation regeneration device, the carbon deposition inactivation regeneration device, the component loading device and the catalytic activity activation device.

57. The method for microwave-assisted regeneration of a three-way catalyst according to claim 55, wherein: the carbon deposition inactivation regeneration stabilization zone is coated with auxiliary agent components of rare earth metal oxide and alkali metal oxide, and the precursor on the surface of the catalyst is promoted to be converted into an active component under microwave radiation, so that the carbon adsorption performance on the surface of the catalyst is weakened.

58. The method for microwave-assisted regeneration of a three-way catalyst according to claim 57, wherein: the recycling device is respectively communicated with a microwave hole expanding area, a structure strengthening area, a chemical repairing area, a catalytic oxidation area, a carbon eliminating area, a cleaning area, a coating loading area, an auxiliary agent loading area, a first activation area and a second activation area of the catalytic activity activation device.

59. The method for microwave-assisted regeneration of a three-way catalyst according to claim 47, wherein: the catalytic activity activation device further comprises a second catalytic evaluation assembly and a second catalytic evaluation assembly, wherein the second catalytic evaluation assembly is positioned at the downstream of the catalytic activity activation device.

60. The method for microwave-assisted regeneration of a three-way catalyst according to claim 47, wherein: the device also comprises a second regeneration quality evaluation device and a second regeneration quality evaluation device, wherein the second regeneration value evaluation device is a PC (personal computer) end, and the second regeneration quality evaluation device is electrically connected with the second catalytic evaluation component.