CN114535245B

CN114535245B - Method for comprehensively utilizing all components of waste denitration catalyst module

Info

Publication number: CN114535245B
Application number: CN202210057123.3A
Authority: CN
Inventors: 张深根; 张柏林
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 2022-01-17
Filing date: 2022-01-17
Publication date: 2023-04-07
Anticipated expiration: 2042-01-17
Also published as: CN114535245A

Abstract

A method for comprehensively utilizing all components of a waste denitration catalyst module belongs to the field of flue gas denitration and material recycling, and comprises iron frame regeneration, ceramic fiber recycling and regeneration of a renewable catalyst, non-renewable catalyst resource recovery and dust resource preparation microcrystalline glass 5 resource recycling routes, so that comprehensive recycling of all components of the waste denitration catalyst module is realized. The iron frame regeneration is to carry out heat treatment, derusting and assembling on the disassembled iron frame to obtain the regenerated iron frame. The ceramic fiber recycling is to wash and regenerate the removed ceramic fiber to prepare the ceramic fiber blanket again. The regenerated denitration catalyst is obtained by cleaning and active implanting the renewable catalyst. The non-renewable catalyst is recovered through the steps of pretreatment, grinding, cleaning, drying and air separation. And the dust is subjected to component blending, melting, rolling and annealing to obtain the microcrystalline glass. The invention fully utilizes the valuable components of the waste denitration catalyst module and realizes the comprehensive utilization of all the components of the waste denitration catalyst module.

Description

Method for comprehensively utilizing all components of waste denitration catalyst module

Technical Field

The invention relates to a method for comprehensively utilizing all components of a waste denitration catalyst module, and belongs to the field of flue gas denitration and material recycling.

Background

The Selective Catalytic Reduction (SCR) technology is used for realizing NO in industrial flue gas _x The denitration catalyst used by the important technology with ultra-low emission is easy to be deactivated by being washed by flue gas and poisoned by harmful components, so that the service life of the catalyst is short. The inactivated waste denitration catalyst is a hazardous waste specified in national hazardous waste entry, has great environmental risk, but has extremely high recycling value. In 2014, the department of ecological environment issued "notice on the supervision and control work of waste flue gas denitration catalyst reinforcement", and required to improve the regeneration and utilization and disposal capabilities of the waste flue gas denitration catalyst, encourage the preferential regeneration, and perform safe treatment on the waste denitration catalyst which cannot be regenerated.

The existing waste denitration catalyst regeneration and resource recycling technology can only regenerate the denitration catalyst with good mechanical strength and not serious inactivation, and the resource recycling technology can only recycle vanadium, tungsten and titanium components, and can not recycle iron frames, ceramic fiber paper and other parts. Specifically, for resource recovery of the waste denitration catalyst, a complex alkali fusion process is usually adopted to convert vanadium, tungsten and titanium oxides into salts, and then the salts are dissolved in a solution to separate vanadium, tungsten and titanium components step by step to prepare ammonium metavanadate, sodium tungstate and titanium dioxide products, or simple water washing, pulping and drying are adopted or powder materials are directly recycled. The process of adopting alkali fusion is complex and has high energy consumption, and the product quality is poor when the alkali fusion is simply washed and recycled.

Patent CN109536721A discloses a resource comprehensive utilization method of a waste SCR denitration catalyst, which comprises pretreatment, crushing, grinding, ultrasonic-enhanced alkaline leaching, liquid-solid separation, ion exchange, desorption, chemical precipitation and flood drying cleaning, wherein vanadium, tungsten and titanium can be selectively recovered as raw materials of related industries, but the process of recovering vanadium and tungsten is very complicated, and the recovered products are mainly calcium salts and magnesium salts, and cannot be recycled for preparation of the denitration catalyst in a grade-preserving manner. Patent CN108687105A discloses a comprehensive utilization method of a waste SCR denitration catalyst, which comprises pretreatment, pulverization, vanadium extraction, tungsten extraction and insoluble slag drying, wherein the recovered raw materials can be directly used for the production of a new catalyst, but the process for recovering vanadium and tungsten is complex and has large water consumption.

Disclosure of Invention

In order to solve the problems, the invention provides a method for comprehensively utilizing all components of a waste denitration catalyst module, which is used for disassembling the waste denitration catalyst module and respectively utilizing an iron frame, ceramic fibers, a denitration catalyst and dust in a resource manner. Wherein the iron frame material recovers the mechanical property through quenching and tempering, and is assembled into a regenerated iron frame again, and the ceramic fiber is regenerated and recycled; the catalyst is respectively regenerated and recycled through separation. The catalyst with good mechanical strength is regenerated into a regenerated catalyst, the catalyst with serious damage removes harmful components through acid leaching and wet milling, simultaneously improves the specific surface area, and divides the recovered powder into two quality grades of low density and high density through air separation; the microcrystalline glass is prepared by utilizing the dust resource, and finally the comprehensive utilization of all components of the waste denitration catalyst module is realized.

The invention is realized by the following technical scheme:

a method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module.

The iron frame regeneration is to carry out heat treatment, rust removal and assembly on the disassembled iron frame to obtain a regenerated iron frame, and the ceramic fiber recycling is to carry out cleaning and reconstruction on the disassembled ceramic fiber to obtain a regenerated ceramic fiber blanket. The regeneration of the renewable catalyst is to detoxify and reactivate the sorted catalyst with good mechanical property to obtain a regenerated denitration catalyst; the sorting standard is that the denitration catalyst is sorted into renewable and non-renewable catalysts according to the damage condition of the denitration catalyst; the sorting condition is that the average abrasion depth of the windward end of the honeycomb catalyst is less than or equal to 30mm, and the number of penetrating holes is less than or equal to 5, the honeycomb catalyst is a renewable catalyst, otherwise, the honeycomb catalyst is a non-renewable catalyst; the abrasion length of the paste material at the windward end of the flat plate type catalyst is less than or equal to 50mm, the abrasion area of the single plate is less than 10% of the whole single plate area, the catalyst is a renewable catalyst, and the catalyst is not renewable catalyst otherwise. The dust-prepared microcrystalline glass is prepared by collecting dust of a waste denitration catalyst module, and preparing a microcrystalline glass plate through component preparation, melting, rolling and annealing.

Further, the iron frame is disassembled, namely, firstly, steel strips on the windward side and the leeward side of the iron frame of the waste denitration catalyst module are disassembled, and then, the steel plates on the periphery are cut along welding seams; the denitration catalyst can be taken out after the steel plate strips on the windward side or the leeward side are removed, and the denitration catalyst can be directly reused after being repaired when the whole iron frame is well stored.

The heat treatment of the regenerated iron frame is to carry out quenching and tempering treatment on the disassembled iron frame material, wherein the quenching is to heat the iron frame material to 820-960 ℃, preserve heat for 15-60min and then carry out water quenching; the tempering treatment is to heat the quenched iron frame material to 450-550 ℃, preserve heat for 15-60min, and then air-cool the iron frame material to room temperature;

the rust removal is to firstly carry out quality detection on the iron frame material after heat treatment to ensure that the strength requirement of the iron frame of the denitration catalyst is met, and carry out surface rust removal on the iron frame material qualified through detection, wherein the rust removal method adopts one of injection, shot blasting and chemical rust removal methods;

and the assembling is to re-weld and assemble the derusted iron frame material to form the regenerated iron frame.

And further, removing the ceramic fiber, namely removing the iron frame, taking out the denitration catalyst, and removing the anti-seismic ceramic fiber blanket with the catalyst coated with the wind blocking layer. The step of cleaning the ceramic fiber comprises the step of washing the removed ceramic fiber with water to remove part of impurities;

the ceramic fiber reconstruction step is to take the cleaned ceramic fiber as a raw material, and prepare the regenerated ceramic fiber blanket through pulping, deslagging, molding and drying, so that the recycling of the ceramic fiber is realized.

Further, the catalyst regeneration is detoxified by placing the catalyst unit strips in 2-10wt.% NaOH solution, washing the solution at 40-90 ℃ for 20-60min, adding 25-35kHz ultrasonic waves along the 45-degree angle direction of the axial direction of the catalyst unit strips, then washing the catalyst unit strips in 0.5-2wt.% dilute sulfuric acid solution for 5-15min, and then drying the catalyst unit strips.

The reactivation is to dip the detoxified catalyst in a butyl titanate solution for 1-5min, then place the detoxified catalyst in a constant temperature and humidity room for 30-120min, dry the detoxified catalyst, dip the detoxified catalyst in an ammonium metavanadate solution to load active components, and roast the detoxified catalyst to obtain the regenerated denitration catalyst. The hydrolysis of the butyl titanate can be promoted to form TiO by putting the titanium dioxide into a constant temperature and humidity room ₂ The mechanical strength of the catalyst can be enhanced, the specific surface area of the surface material of the catalyst can be increased, and the loading capacity of the active component is increased.

Further, the step of recovering the non-renewable catalyst comprises the steps of pretreatment, grinding, cleaning, drying and air separation to obtain recovered powder.

The pretreatment comprises the steps of crushing, screening and washing, wherein the non-renewable catalyst is crushed to 2-150mm, the dust in the crushed materials is further screened and removed, the aperture of a screen mesh is controlled to be 1-10mm, and the crushed materials are washed after screening to remove the dust on the surface of the crushed materials. The size of the crushed materials is controlled to be 2-150mm in the crushing process, so that dust, sand grains and the like in the catalyst can be well removed in the screening process, the crushing process is simple, the dust on the surface of the crushed materials of the catalyst can be washed away by cleaning after screening, and the cleaning wastewater can be recycled.

Further, acid liquor is added into the waste denitration catalyst crushed material for wet grinding, the mass part ratio of sulfuric acid, nitric acid and water in the acid liquor is (5-40): 1-20): 100, the mass part ratio of the acid liquor and the catalyst material is (65-135): 100, and the material granularity is controlled to be D90 ≤ 15um by grinding. Adding acid liquor to grind and dissolve harmful metal ions such As Na, K, ca, mg, al, as, hg and the like in the waste catalyst, and heating the waste catalyst in the grinding process promotes the reaction of dissolving the harmful components. The vanadium, tungsten and titanium oxides are dissolved by acid with difficulty higher than that of the harmful metal ions, so impurity removal reaction can be ensured to occur first, and partial vanadium, tungsten oxides and TiO can be gradually dissolved in sequence along with the increase of the acid concentration ₂ Surface erosion and TiO enhancement ₂ Specific surface area, pore volume and pore size of the support.

Further, cleaning the ground slurry, adding 1-3 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 1-3 times, and finally filtering to obtain a material with the water content of less than or equal to 80%; and the drying is to dry the cleaned and filtered material, and the moisture content of the dried powder is less than or equal to 5%.

Further, the powder is subjected to air separation, the dried material is conveyed to an air separation system, the air speed is set to be 0.5-5m/s, a first discharge port and a second discharge port are arranged according to the difference of the final sedimentation speed, the first discharge port obtains heavy powder with high density and large particles, and the second discharge port obtains light powder with low density and small particles. The first discharge port powder is mainly used for preparing the catalyst with the hole number of less than 25 multiplied by 25 or the plate-type catalyst, and the second discharge port powder is mainly used for preparing the catalyst with the hole number of more than 25 multiplied by 25.

Further, the component preparation of the dust-prepared glass ceramics is to mix the waste catalyst pore canal, the dust with rich Si, na and Ca on the surface and the component with rich Fe generated by the iron frame derusting to form the easily meltable glass component and the easily nucleated and crystallized microcrystal component; the melting is to heat the dust system to 1000-1400 ℃ for melting to obtain a melting system; the calendering is to cool the melting system to 600-1000 ℃ and press the melting system by a calendering roller to obtain a glass plate blank; and in the annealing step, the plate blank is subjected to heat preservation at 400-600 ℃ for 1-4 hours, and air cooling is carried out to room temperature to obtain the microcrystalline glass plate. The dust in the waste denitration catalyst mainly comprises components such as Si, na and the like, and can form a good glass network system, the rust waste in the iron frame rust removing process is a good nucleating agent, and the two waste are combined and blended to form a good raw material for preparing the microcrystalline glass.

The powder recovered by the process does not adopt a complex process to separate vanadium, tungsten and titanium, but effectively removes impurities by adjusting the using amount of acid and keeps valuable components to realize cyclic utilization.

The beneficial technical effects of the invention are as follows:

(1) All valuable components of the waste denitration catalyst module are recycled, and all components can be comprehensively utilized by combining with high-value utilization of dust and sludge screened and cleaned in the comprehensive utilization process;

(2) The acid leaching grinding process is adopted for recovering the powder, so that impurities can be effectively removed, valuable components of vanadium, tungsten and titanium are reserved, and the specific surface area of the recovered powder is increased;

(3) The iron frame material is recycled and quenched and tempered by adopting a quenching and tempering process, the mechanical property of the material is recovered, and the use safety of the regenerated iron frame is guaranteed;

(4) The catalyst in the waste catalyst module is sorted, and the reproducible unit preferentially regenerates to avoid crushing and recycling without distinguishing.

Drawings

FIG. 1 is a process flow diagram of the method of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to specific embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present invention, as will be readily apparent to those of ordinary skill in the art upon the description of the specific embodiments. The invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims.

Example 1

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 820 ℃, preserving heat for 60min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 450 ℃, preserving heat for 60min, then air cooling to room temperature, one of jet rust removal methods is adopted for rust removal, and the rust-removed iron frame material is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 2wt.% NaOH solution, washing the solution at 90 ℃ for 40min, adding 25kHz ultrasonic waves in the direction of 45-degree angle along the axial direction of the catalyst unit strip, then placing the catalyst unit strip in 0.5wt.% dilute sulfuric acid solution, washing for 15min, and then drying; and further soaking the catalyst in a butyl titanate solution for 1min, then placing the catalyst in a constant temperature and humidity room for 30min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load an active component, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 2-10mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 1mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 5. And further adding water with the mass being 1 time that of the ground slurry, fully stirring, filtering, repeating the steps for 3 times, and finally drying to obtain the powder with the water content being less than or equal to 80 percent. And further performing air separation, setting the air speed to be 5m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is characterized in that dust in a waste denitration catalyst module is collected and mixed with rust slag generated by rust removal, the mixture is heated to 1000 ℃ for melting, the mixture is cooled to 600 ℃ and pressed by a calendering roller to obtain a glass plate blank, the temperature is further kept at 400 ℃ for 4 hours, and the glass plate is obtained by air cooling to room temperature.

Example 2

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 830 ℃, preserving heat for 55min, then performing water quenching, tempering by heating the quenched iron frame material to 460 ℃, preserving heat for 55min, then performing air cooling to room temperature, performing rust removal by adopting one of shot blasting rust removal methods, and re-welding and assembling the rust-removed iron frame material to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in a 3wt.% NaOH solution, washing the renewable catalyst unit strip for 45min at the solution temperature of 85 ℃, adding 26kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in a 0.6wt.% dilute sulfuric acid solution, washing for 14min, and then drying; and further soaking the catalyst in a butyl titanate solution for 2min, then placing the catalyst in a constant temperature and humidity room for 50min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load an active component, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 2-50mm, further screening to remove dust in the crushed material, controlling the aperture of a screen mesh to be 1mm, washing with water after screening to remove dust on the surface of the crushed material, and further adding acid liquor for wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 10. And further adding water with the mass of 1 time into the ground slurry, fully stirring, filtering, repeating the steps for 3 times, and finally, filtering to obtain a material with the water content of less than or equal to 80%, and further drying to obtain a powder with the water content of less than or equal to 5%. And further performing air separation, setting the air speed to be 4.5m/s, obtaining heavy powder with larger density and larger particles from a first discharge port, and obtaining light powder with smaller density and smaller particles from a second discharge port.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1000 ℃ for melting, cooling to 800 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 450 ℃ for 3 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Embodiment 3

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The iron frame regeneration quenching is to heat the iron frame material to 840 ℃, preserve heat for 50min, then carry on water quenching, the tempering is to heat the iron frame material after quenching to 470 ℃, preserve heat for 50min, then air cool to room temperature, the derusting adopts one of chemical derusting methods, the iron frame material after derusting is welded again, assembled to form the regeneration iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in a 4wt.% NaOH solution, washing the renewable catalyst unit strip for 50min at the solution temperature of 80 ℃, adding 27kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in a 0.8wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 13min, and then drying the renewable catalyst unit strip; further soaking the catalyst in a butyl titanate solution for 3min, then placing the catalyst in a constant temperature and humidity room for 70min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 2-100mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 2mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 10. And further adding water with the mass being 1.5 times of that of the ground slurry, fully stirring, filtering, repeating for 2 times, and finally drying to obtain the powder with the water content of less than or equal to 80 percent. And further performing air separation, setting the air speed to be 4m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is characterized in that dust in a waste denitration catalyst module is collected and mixed with rust slag generated by rust removal, the mixture is heated to 1000 ℃ for melting, the mixture is cooled to 1000 ℃ and pressed by a calendering roller to obtain a glass plate blank, the temperature is further kept at 500 ℃ for 2 hours, and the glass plate is obtained by air cooling to room temperature.

Example 4

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 recycling routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 850 ℃, preserving heat for 45min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 480 ℃, preserving heat for 45min, then air cooling to room temperature, one of jet rust removal methods is adopted for rust removal, and the rust-removed iron frame material is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strips in 5wt.% NaOH solution, washing at 75 ℃ for 55min, adding 28kHz ultrasonic waves in the direction of 45-degree angle along the axial direction of the catalyst unit strips, then placing in 1wt.% dilute sulfuric acid solution, washing for 12min, and then drying; and further soaking the catalyst in a butyl titanate solution for 4min, then placing the catalyst in a constant temperature and humidity room for 90min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load an active component, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 2-150mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 2mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 15. And further adding water with the mass being 1.5 times of that of the ground slurry, fully stirring, filtering, repeating for 2 times, and finally drying to obtain the powder with the water content being less than or equal to 75 percent. And further performing air separation, wherein the air speed is set to be 3.5m/s, the first discharge port obtains heavy powder with higher density and larger particles, and the second discharge port obtains light powder with lower density and smaller particles.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1100 ℃ for melting, cooling to 700 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 500 ℃ for 2 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 5

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 860 ℃, preserving heat for 40min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 490 ℃, preserving heat for 40min, then air cooling to room temperature, one of shot blasting rust removal methods is adopted for rust removal, and the rust-removed iron frame material is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 6wt.% NaOH solution, washing the renewable catalyst unit strip for 60min at the solution temperature of 70 ℃, adding 29kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 1.2wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 11min, and then drying the renewable catalyst unit strip; further soaking the catalyst in a butyl titanate solution for 5min, then placing the catalyst in a constant temperature and humidity room for 120min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 5-50mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 3mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 20. And further adding water with the mass being 1.5 times of that of the ground slurry, fully stirring, filtering, repeating for 2 times, and finally drying to obtain the powder with the water content being less than or equal to 75 percent. And further performing air separation, setting the air speed to be 3m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is prepared by mixing dust in a waste denitration catalyst module with rust slag generated by rust removal, heating to 1100 ℃ for melting, cooling to 900 ℃ for pressing through a calendering roller to obtain a glass plate blank, further preserving heat at 550 ℃ for 1 hour, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 6

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The iron frame regeneration quenching is to heat the iron frame material to 870 ℃, preserve heat for 35min, then carry on water quenching, the tempering is to heat the iron frame material after quenching to 500 ℃, preserve heat for 35min, then air cool to room temperature, the derusting adopts one of the chemical derusting methods, the iron frame material after derusting is welded again, assembled to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in a 7wt.% NaOH solution, washing the renewable catalyst unit strip for 20min at the solution temperature of 65 ℃, adding 30kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in a 1.4wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 10min, and then drying the renewable catalyst unit strip; and further soaking the catalyst in a butyl titanate solution for 1min, then placing the catalyst in a constant temperature and humidity room for 40min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load an active component, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 5-100mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 4mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 25. And further adding 2 times of water by mass into the ground slurry, fully stirring, filtering, repeating for 2 times, and finally drying to obtain the powder with the water content of less than or equal to 75 percent and the powder with the water content of less than or equal to 4 percent. And further performing air separation, setting the air speed to be 2.5m/s, obtaining heavy powder with larger density and larger particles by a first discharge port, and obtaining light powder with smaller density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is prepared by mixing dust in a waste denitration catalyst module with rust slag generated by rust removal, heating to 1100 ℃ for melting, cooling to 1000 ℃, pressing through a calendering roller to obtain a glass plate blank, further keeping the temperature at 600 ℃ for 1 hour, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 7

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 880 ℃, preserving heat for 30min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 510 ℃, preserving heat for 30min, then air cooling to room temperature, one of jet rust removal methods is adopted for rust removal, and the rust-removed iron frame material is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 8wt.% NaOH solution, washing the renewable catalyst unit strip for 25min at the solution temperature of 60 ℃, adding 31kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 1.6wt.% dilute sulfuric acid solution, washing for 9min, and then drying; further soaking the catalyst in a butyl titanate solution for 2min, then placing the catalyst in a constant temperature and humidity room for 60min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 5-150mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 5mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 25. And further adding 2 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 2 times, and finally, filtering to obtain a material with the water content of less than or equal to 70%, and further drying to obtain a powder with the water content of less than or equal to 4%. And further performing air separation, setting the air speed to be 2m/s, obtaining heavy powder with higher density and larger particles from a first discharge port, and obtaining light powder with lower density and smaller particles from a second discharge port.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1200 ℃ for melting, cooling to 650 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 600 ℃ for 1 hour, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 8

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 890 ℃, preserving heat for 25min, then carrying out water quenching, tempering by heating the quenched iron frame material to 520 ℃, preserving heat for 25min, then air cooling to room temperature, carrying out rust removal by adopting one of jet rust removal methods, and re-welding and assembling the rust-removed iron frame material to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 9wt.% NaOH solution, washing the renewable catalyst unit strip for 30min at 55 ℃, increasing 32kHz ultrasonic waves along the 45-degree angle direction of the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 1.8wt.% dilute sulfuric acid solution, washing for 8min, and then drying; further soaking the catalyst in a butyl titanate solution for 3min, then placing the catalyst in a constant temperature and humidity room for 80min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 10-50mm, further screening to remove dust in the crushed material, controlling the aperture of a screen mesh to be 5mm, washing with water after screening to remove dust on the surface of the crushed material, and further adding acid liquor for wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 25 to 100, the mass part ratio of the acid solution to the catalyst material is 100, and the grinding is performed to control the material granularity to be D90 less than or equal to 8um. And further adding 2 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 2 times, and finally, filtering to obtain a material with the water content of less than or equal to 70%, and further drying to obtain a powder with the water content of less than or equal to 4%. And further performing air separation, setting the air speed to be 1.5m/s, obtaining heavy powder with larger density and larger particles from a first discharge port, and obtaining light powder with smaller density and smaller particles from a second discharge port.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1200 ℃ for melting, cooling to 750 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 500 ℃ for 3 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 9

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 900 ℃, preserving heat for 20min, then performing water quenching, tempering by heating the quenched iron frame material to 530 ℃, preserving heat for 20min, then air cooling to room temperature, derusting by one of shot blasting derusting methods, and re-welding and assembling the derusted iron frame material to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strips in 10wt.% NaOH solution, washing the renewable catalyst unit strips for 35min at the solution temperature of 50 ℃, adding 33kHz ultrasonic waves in the direction of 45-degree angle along the axial direction of the catalyst unit strips, then placing the renewable catalyst unit strips in 2wt.% dilute sulfuric acid solution, washing for 7min, and then drying; further soaking the catalyst in a butyl titanate solution for 4min, then placing the catalyst in a constant temperature and humidity room for 100min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 10-100mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 6mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 30. And further adding water with the mass of 2.5 times of that of the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 70%, and further drying to obtain a powder with the water content of less than or equal to 4%. And further performing air separation, setting the air speed to be 1m/s, obtaining heavy powder with higher density and larger particles from a first discharge port, and obtaining light powder with lower density and smaller particles from a second discharge port.

The dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the collected dust with rust slag generated by rust removal, heating to 1200 ℃ for melting, cooling to 850 ℃ for pressing through a calendering roller to obtain a glass plate blank, further keeping the temperature at 520 ℃ for 4 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Embodiment 10

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 910 ℃, preserving heat for 15min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 540 ℃, preserving heat for 15min, then air cooling to room temperature, one of chemical rust removal methods is adopted for rust removal, and the iron frame material after rust removal is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 2.5wt.% NaOH solution, washing the renewable catalyst unit strip for 40min at the solution temperature of 45 ℃, increasing ultrasonic waves of 34kHz along the 45-degree angle direction of the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 0.5wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 6min, and then drying the renewable catalyst unit strip; further soaking the catalyst in a butyl titanate solution for 5min, then placing the catalyst in a constant temperature and humidity room for 110min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 10-150mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 6mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 30. And further adding water with the mass of 2.5 times of that of the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 65 percent and further drying to obtain a powder with the water content of less than or equal to 4 percent. And further performing air separation, wherein the air speed is set to be 0.5m/s, the first discharge port obtains heavy powder with higher density and larger particles, and the second discharge port obtains light powder with lower density and smaller particles.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1300 ℃ for melting, cooling to 950 ℃ and pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 540 ℃ for 2 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 11

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The iron frame regeneration quenching is to heat the iron frame material to 920 ℃, preserve heat for 15min, then carry out water quenching, the tempering is to heat the quenched iron frame material to 550 ℃, preserve heat for 15min, then air cool to room temperature, one of spray rust removal methods is adopted for rust removal, and the iron frame material after rust removal is welded and assembled again to form the regeneration iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strips in a 3.5wt.% NaOH solution, washing for 45min at the temperature of 40 ℃, adding 35kHz ultrasonic waves in the direction of an angle of 45 degrees along the axial direction of the catalyst unit strips, then placing the renewable catalyst unit strips in a 0.7wt.% dilute sulfuric acid solution, washing for 5min, and then drying; further soaking the catalyst in a butyl titanate solution for 1min, then placing the catalyst in a constant temperature and humidity room for 35min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 20-100mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 7mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 30. And further adding water with the mass of 2.5 times of that of the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 65 percent and further drying to obtain a powder with the water content of less than or equal to 3 percent. And further performing air separation, setting the air speed to be 1m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is characterized in that dust in a waste denitration catalyst module is collected and mixed with rust slag generated by rust removal, the mixture is heated to 1300 ℃ for melting, the mixture is cooled to 1000 ℃ and pressed by a calendering roller to obtain a glass plate blank, the temperature is further kept at 560 ℃ for 1 hour, and the glass plate is obtained by air cooling to room temperature.

Example 12

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The iron frame regeneration quenching is to heat the iron frame material to 930 ℃, preserve heat for 35min, then carry on water quenching, the tempering is to heat the iron frame material after quenching to 485 ℃, preserve heat for 35min, then air cool to room temperature, the derusting adopts one of the shot blasting derusting methods, the iron frame material after derusting is welded again, assembled to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 4.5wt.% NaOH solution, washing the renewable catalyst unit strip for 50min at the solution temperature of 50 ℃, adding 26kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 0.9wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 12min, and then drying the renewable catalyst unit strip; further soaking the catalyst in a butyl titanate solution for 2min, then placing the catalyst in a constant temperature and humidity room for 55min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 30-80mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 8mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 35. And further adding water with the mass of 2.5 times of that of the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 65 percent and further drying to obtain a powder with the water content of less than or equal to 3 percent. And further performing air separation, wherein the air speed is set to be 1.5m/s, the first discharge port obtains heavy powder with higher density and larger particles, and the second discharge port obtains light powder with lower density and smaller particles.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1300 ℃ for melting, cooling to 800 ℃, pressing by a calendering roller to obtain a glass plate blank, further preserving heat at 550 ℃ for 1 hour, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 13

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The iron frame regeneration quenching is to heat the iron frame material to 940 ℃, preserve heat for 30min, then carry out water quenching, the tempering is to heat the quenched iron frame material to 495 ℃, preserve heat for 30min, then air-cool to room temperature, one of chemical rust removal methods is adopted for rust removal, and the iron frame material after rust removal is welded and assembled again to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in a 5.5wt.% NaOH solution, washing the renewable catalyst unit strip for 55min at the solution temperature of 60 ℃, adding 27kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in a 1.1wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strip for 13min, and then drying the renewable catalyst unit strip; further soaking the catalyst in a butyl titanate solution for 3min, then placing the catalyst in a constant temperature and humidity room for 75min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 40-120mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 9mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 35. And further adding 3 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 60%, and further drying to obtain a powder with the water content of less than or equal to 3%. And further performing air separation, setting the air speed to be 2m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the collected dust with rust slag generated by rust removal, heating to 1400 ℃ for melting, cooling to 600 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 530 ℃ for 2 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Embodiment 14

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 950 ℃, preserving heat for 25min, then water quenching is carried out, tempering is carried out by heating the quenched iron frame material to 505 ℃, preserving heat for 25min, then air cooling to room temperature, one of jet rust removal methods is adopted for rust removal, and the rust-removed iron frame material is welded and assembled again to form the regenerated iron frame. The ceramic fiber is washed, and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in 6.5wt.% NaOH solution, washing the renewable catalyst unit strip for 60min at the solution temperature of 70 ℃, adding 28kHz ultrasonic waves in the 45-degree angle direction along the axial direction of the catalyst unit strip, then placing the renewable catalyst unit strip in 1.3wt.% dilute sulfuric acid solution, washing for 14min, and then drying; further soaking the catalyst in a butyl titanate solution for 4min, then placing the catalyst in a constant temperature and humidity room for 95min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 50-100mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 9mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 40. And further adding 3 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 1 time, and finally, filtering to obtain a material with the water content of less than or equal to 60%, and further drying to obtain a powder with the water content of less than or equal to 3%. And further performing air separation, setting the air speed to be 1.5m/s, obtaining heavy powder with larger density and larger particles from a first discharge port, and obtaining light powder with smaller density and smaller particles from a second discharge port.

Dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the dust with rust slag generated by rust removal, heating to 1400 ℃ for melting, cooling to 1000 ℃, pressing through a calendering roller to obtain a glass plate blank, further keeping the temperature at 520 ℃ for 3 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 15

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 960 ℃, preserving heat for 20min, then performing water quenching, tempering by heating the quenched iron frame material to 515 ℃, preserving heat for 20min, then air cooling to room temperature, performing rust removal by adopting one of jet rust removal methods, and re-welding and assembling the rust-removed iron frame material to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strip in a 7.5wt.% NaOH solution, washing the solution at the temperature of 80 ℃ for 20min, adding 29kHz ultrasonic waves in the direction of an angle of 45 degrees along the axial direction of the catalyst unit strip, then placing the catalyst unit strip in a 1.5wt.% dilute sulfuric acid solution, washing the catalyst unit strip for 15min, and then drying the catalyst unit strip; and further soaking the catalyst in a butyl titanate solution for 5min, then placing the catalyst in a constant temperature and humidity room for 115min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load an active component, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 50-150mm, further screening to remove dust in the crushed materials, controlling the aperture of a screen to be 10mm, washing with water after screening to remove dust on the surface of the crushed materials, and further adding acid liquor to carry out wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 40. And further adding 3 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 2 times, and finally, filtering to obtain a material with the water content of less than or equal to 60%, and further drying to obtain a powder with the water content of less than or equal to 3%. And further performing air separation, setting the air speed to be 3m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is prepared by collecting dust in a waste denitration catalyst module, mixing the collected dust with rust slag generated by rust removal, heating to 1400 ℃ for melting, cooling to 750 ℃, pressing by a calendering roller to obtain a glass plate blank, further keeping the temperature at 510 ℃ for 4 hours, and air-cooling to room temperature to obtain the microcrystalline glass plate.

Example 16

A method for comprehensively utilizing all components of a waste denitration catalyst module comprises 5 recycling routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, and realizes comprehensive recycling of all components of the waste denitration catalyst module. The regenerated iron frame is quenched by heating the iron frame material to 915 ℃, preserving heat for 15min, then performing water quenching, tempering by heating the quenched iron frame material to 525 ℃, preserving heat for 15min, then air cooling to room temperature, performing rust removal by one of shot blasting rust removal methods, and re-welding and assembling the rust-removed iron frame material to form the regenerated iron frame. The ceramic fiber is cleaned and then is pulped, deslagged, formed and dried to prepare the regenerated ceramic fiber blanket, thereby realizing the recycling of the ceramic fiber.

Placing the renewable catalyst unit strips in 8.5wt.% NaOH solution, washing the renewable catalyst unit strips for 20min at the temperature of 90 ℃, adding 35kHz ultrasonic waves in the direction of an angle of 45 degrees along the axial direction of the catalyst unit strips, then placing the renewable catalyst unit strips in 1.7wt.% dilute sulfuric acid solution, washing the renewable catalyst unit strips for 10min, and then drying the renewable catalyst unit strips; further soaking the catalyst in a butyl titanate solution for 3min, then placing the catalyst in a constant temperature and humidity room for 60min, drying the catalyst, soaking the dried catalyst in an ammonium metavanadate solution to load active components, and roasting the catalyst to obtain the regenerated denitration catalyst. Crushing the non-renewable catalyst to 100-150mm, further screening to remove dust in the crushed material, controlling the aperture of a screen mesh to be 10mm, washing with water after screening to remove dust on the surface of the crushed material, and further adding acid liquor for wet grinding. The mass part ratio of sulfuric acid, nitric acid and water in the acid solution is 40. And further adding 3 times of water by mass into the ground slurry, fully stirring, filtering, repeating the steps for 3 times, and finally, filtering to obtain a material with the water content of less than or equal to 80%, and further drying to obtain a powder with the water content of less than or equal to 3%. And further performing air separation, setting the air speed to be 3m/s, obtaining heavy powder with higher density and larger particles by a first discharge port, and obtaining light powder with lower density and smaller particles by a second discharge port.

The dust preparation microcrystalline glass is characterized in that dust in a waste denitration catalyst module is collected and mixed with rust slag generated by rust removal, the mixture is heated to 1000 ℃ for melting, the mixture is cooled to 650 ℃ and pressed by a calendering roller to obtain a glass plate blank, the glass plate blank is further subjected to heat preservation at 490 ℃ for 4 hours, and the glass plate blank is obtained by air cooling to room temperature.

Claims

1. A method for comprehensively utilizing all components of a waste denitration catalyst module is characterized by comprising 5 resource routes of iron frame regeneration, ceramic fiber recycling, regeneration of a renewable catalyst, recycling of a non-renewable catalyst and preparation of microcrystalline glass by dust, so that the comprehensive recycling of all components of the waste denitration catalyst module is realized;

the iron frame regeneration is to disassemble the iron frame, and then carry out heat treatment, rust removal and assembly to obtain a regenerated iron frame; the iron frame is disassembled by firstly disassembling steel strips on the windward side and the leeward side of the iron frame of the waste denitration catalyst module and then cutting the steel plates on the periphery along a welding line; the denitration catalyst can be taken out after the steel plate strips on the windward side or the leeward side are removed, and the denitration catalyst can be directly reused after being repaired when the whole iron frame is well stored;

the ceramic fiber is recycled by dismantling the ceramic fiber, and then cleaning and regenerating to obtain a regenerated ceramic fiber blanket; the ceramic fiber is dismantled, the denitration catalyst is taken out after the iron frame is dismantled, and the catalyst is externally coated with wind blocking and the anti-seismic ceramic fiber blanket is dismantled;

the regeneration of the renewable catalyst is to detoxify and reactivate the sorted catalyst with good mechanical properties to obtain a regenerated denitration catalyst; the sorting standard is that the denitration catalyst is sorted into renewable and non-renewable catalysts according to the damage condition of the denitration catalyst; the sorting condition is that the average abrasion depth of the windward end of the honeycomb catalyst is less than or equal to 30mm, and the number of penetrating holes is less than or equal to 5, the honeycomb catalyst is a renewable catalyst, otherwise, the honeycomb catalyst is a non-renewable catalyst; the paste abrasion length of the windward end of the flat plate type catalyst is less than or equal to 50mm, the abrasion area of the single plate is less than 10% of the whole single plate area, the catalyst is a renewable catalyst, otherwise, the catalyst is a non-renewable catalyst;

the catalyst regeneration detoxification method comprises the steps of placing a catalyst unit strip in 2-10wt.% NaOH solution, washing the catalyst unit strip for 20-60min at the temperature of 40-90 ℃, adding 25-35kHz ultrasonic waves in the 45-degree axial direction of the catalyst unit strip, then washing the catalyst unit strip in 0.5-2wt.% dilute sulfuric acid solution for 5-15min, and then drying the catalyst unit strip;

the reactivation of the catalyst regeneration is to dip the detoxified catalyst in a butyl titanate solution for 1-5min, then place the detoxified catalyst in a constant temperature and humidity room for 30-120min, dip the detoxified catalyst in an ammonium metavanadate solution after drying to load active components, and obtain a regenerated denitration catalyst after roasting;

the step of recovering the non-renewable catalyst comprises the steps of pretreatment, grinding, cleaning, drying and air separation to obtain recovered powder; the air separation is to convey the dried material to an air separation system, set the air speed to be 0.5-5m/s, and set a first discharge port and a second discharge port according to the difference of the final sedimentation speed, wherein the first discharge port obtains heavy powder with larger density and larger particles, and the second discharge port obtains light powder with smaller density and smaller particles; the first discharge port powder is mainly used for preparing a catalyst with the hole number of less than 25 multiplied by 25 or a plate-type catalyst, and the second discharge port powder is mainly used for preparing a catalyst with the hole number of more than 25 multiplied by 25.

The dust-prepared glass ceramics is prepared by collecting dust of a waste denitration catalyst module, and preparing a glass ceramics plate through component preparation, melting, rolling and annealing.

2. The method for comprehensive utilization of all components of the waste denitration catalyst module as claimed in claim 1, wherein the method is characterized in that

The heat treatment of the iron frame regeneration is to carry out quenching and tempering treatment on the disassembled iron frame material, wherein the quenching is to heat the iron frame material to 820-960 ℃, preserve heat for 15-60min and then carry out water quenching; the tempering treatment is to heat the quenched iron frame material to 450-550 ℃, preserve heat for 15-60min, and then cool the iron frame material to room temperature in air;

3. The method for comprehensive utilization of all components of the waste denitration catalyst module as claimed in claim 1, wherein the method is characterized in that

The step of cleaning the ceramic fiber comprises the steps of washing the removed ceramic fiber with water to remove part of impurities;

4. The method for comprehensive utilization of all components of a spent denitration catalyst module as set forth in claim 1, wherein the pretreatment for recycling the non-renewable catalyst includes the steps of crushing, screening, and washing, wherein the non-renewable catalyst is crushed to 2-150mm, the crushed material is further screened to remove dust in the crushed material, the aperture of the screen is controlled to 1-10mm, and the crushed material is washed with water after screening to remove dust on the surface of the crushed material.

5. The method for comprehensive utilization of all components of the waste denitration catalyst module as claimed in claim 1, wherein the grinding for recycling the non-renewable catalyst is wet grinding by adding acid solution to the crushed waste denitration catalyst, the ratio of the mass parts of sulfuric acid, nitric acid and water in the acid solution is (5-40): 1-20): 100, the ratio of the mass parts of the acid solution and the catalyst material is (65-135): 100, and the grinding controls the particle size of the material to D90 ≤ 15um.

6. The method for comprehensive utilization of all components of the waste denitration catalyst module as claimed in claim 1, wherein the cleaning for recycling the non-renewable catalyst is to add water with 1-3 times of the mass of the ground slurry, fully stir the mixture, filter the mixture, repeat the process for 1-3 times, and finally filter the mixture until the water content of the filtered material is less than or equal to 80%; and the drying is to dry the cleaned and filtered material, and the moisture content of the dried powder is less than or equal to 5%.

7. The method for comprehensive utilization of all components of the waste denitration catalyst module as claimed in claim 1, wherein the component preparation of the dust-prepared microcrystalline glass is to mix the dust rich in Si, na and Ca on the channel and surface of the waste catalyst with the Fe-rich component generated by derusting the iron frame to form a fusible glass component and a microcrystalline component easy to form and nucleate and crystallize; the melting is to heat the dust system to 1000-1400 ℃ for melting to obtain a melting system; the calendering is to cool the melting system to 600-1000 ℃ and press the melting system by a calendering roller to obtain a glass plate blank; and in the annealing step, the plate blank is subjected to heat preservation at 400-600 ℃ for 1-4 hours, and air cooling is carried out to room temperature to obtain the microcrystalline glass plate.