CN105536884B - Regeneration method of waste denitration catalyst selectively implanted with active ingredients - Google Patents

Regeneration method of waste denitration catalyst selectively implanted with active ingredients Download PDF

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CN105536884B
CN105536884B CN201610031071.7A CN201610031071A CN105536884B CN 105536884 B CN105536884 B CN 105536884B CN 201610031071 A CN201610031071 A CN 201610031071A CN 105536884 B CN105536884 B CN 105536884B
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catalyst
temperature
drying
denitration catalyst
denitration
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CN105536884A (en
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杨建辉
路光杰
肖雨亭
白伟
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Guoneng Shandong Energy Environment Co ltd
Guoneng Longyuan Environmental Protection Co Ltd
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Beijing Guodian Longyuan Environmental Engineering Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/02Heat treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation
    • B01J23/92Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J35/56
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/48Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/485Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention relates to a regeneration method of a waste denitration catalyst selectively implanted with active ingredients. And disturbing the solution by using ultrasonic waves or bubbling, drying the catalyst after soaking, putting the catalyst into the prepared active ingredient precursor solution when the drying weight loss is about half of the mass increment of the catalyst, quickly drying and roasting the catalyst after soaking, cooling along with a furnace, and taking out the catalyst. The invention relates to a2O5And/or WO3Selectively loaded to a denitration reaction area within 200 mu m away from the micropores of the catalyst, effectively improves the denitration activity of the catalyst, and simultaneously controls the increase of vanadium and/or tungsten to the SO of the catalyst2The acceleration of the oxidation rate. The regeneration process disclosed by the invention is simple to operate and has an outstanding effect, the recycling frequency of the catalyst is effectively prolonged, the cost is greatly reduced, the emission of the waste denitration catalyst can be reduced, and the environmental hazard of solid waste is reduced.

Description

Regeneration method of waste denitration catalyst selectively implanted with active ingredients
Technical Field
The invention relates to the technical field of regeneration of waste denitration catalysts, in particular to a regeneration method of a waste denitration catalyst selectively implanted with active ingredients.
Background
The Selective Catalytic Reduction (SCR) denitration technology is an efficient, reliable and mature flue gas denitration technology and is widely applied to a boiler flue gas denitration system of a coal-fired power plant in China, an SCR denitration catalyst is the core of the technology, and a honeycomb type V is adopted2O5-WO3(MoO3)/TiO2The catalyst is one of the most widely used catalysts in the world at present. Recently, the rapid increase of flue gas denitration devices of coal-fired power plants has resulted in the explosive demand and on-line operation of denitration catalystsAnd (4) increasing. Because the service life of the denitration catalyst is generally 3 years, according to the operation replacement rule of the denitration catalyst, the invalid denitration catalyst is expected to appear in a well-blowout manner from 2016 and increase year by year, and the amount of the waste denitration catalyst is expected to be stabilized at 25-30 million cubic meters per year after 2020. Because V is removed from the waste denitration catalyst2O5、WO3Besides heavy metal components, harmful components such As As, Hg, Pb and the like are adsorbed from coal-fired flue gas, and the method belongs to the national recognized dangerous solid waste. If a large amount of waste catalysts are eliminated every year without proper treatment, huge secondary pollution to the environment is caused, and meanwhile, the waste of precious metal resources in the catalysts is caused. As the domestic denitration market starts late, the treatment of the dangerous wastes has no mature experience at present. In view of the fact that the denitration catalyst is expensive and is the largest part of investment and operation cost of a denitration device, in order to save resources and reduce cost, the waste catalyst is considered to be regenerated at first in China, and the catalyst which cannot be regenerated is recycled through chemical metallurgy or other methods.
According to the application experience at foreign countries and the current situation of research at home, the regeneration process of the universal waste denitration catalyst is mainly divided into four procedures: ash removal, blockage removal, active ingredient implantation and heat treatment (drying and roasting). In the four steps, the ash removal, the blockage removal and the heat treatment are physical treatment means which are carried out on the catalyst under the condition of not changing the structure and the components of the catalyst, and are recovery treatment modes of the activity and other various performances of the catalyst, and the implantation of the active component is a chemical treatment method which adds a new active component or an active auxiliary component into the catalyst and further improves various performances of the activity and the like of the catalyst on the basis of changing the structure of the original catalyst component. The active ingredient implantation step determines the final activity, ammonia slip rate, and SO of the regenerated catalyst as compared with the physical treatment means2Oxidation rate and the like, and thus, the implantation of the active ingredient is a key process in the regeneration process of the catalyst.
At present, although domestic reports exist on the active impregnation process of the waste denitration catalyst, most of the processes only relate to the pretreatmentAnd soaking the treated waste denitration catalyst in a regeneration liquid containing an active ingredient precursor for a certain time, namely directly loading the active ingredient precursor on the surface of the catalyst. When is expressed as V2O5SO of the catalyst when the active component is indiscriminately loaded on the surface of the catalyst2The oxidation rate is easy to exceed 1 percent, so that the ammonium sulfate in the flue gas blocks the coal economizer, the pressure drop of the flue is increased, and the normal operation of downstream equipment of the flue is not facilitated.
According to the report of foreign research data, the open pores on the surface of the catalyst mainly generate denitration reaction in the area extending from the pore opening to the inside by about 200 microns, and the area from 200 microns to the inside mainly generates SO2Oxidation reaction, thus, converting V2O5Selectively loading the catalyst into the area within 200 μm of the opening, thereby effectively improving the denitration reaction in the catalyst micropores without increasing the SO of the catalyst2The oxidation rate. Thus, V is selectively supported on the surface of the catalyst2O5The method is a novel regeneration method with half the effort, and is recently reported at home and abroad.
Disclosure of Invention
The invention aims to solve the problem that SO is caused by active ingredient implantation in the regeneration process of the waste denitration catalyst2The problem of the oxidation rate is increased, and a method for regenerating a waste denitration catalyst by selectively implanting active ingredients is provided, so that the existing problems are solved.
The method for regenerating the waste denitration catalyst selectively implanted with the active ingredients comprises the following specific steps:
1) pretreatment: performing ash removal, cleaning and drying pretreatment on the waste denitration catalyst in sequence by adopting compressed air soot blowing, ultrasonic cleaning and blowing type drying box heat treatment means;
2) primary impregnation: soaking the waste denitration catalyst which is processed in the step 1) and forms a block shape in a container containing a blocking liquid, and carrying out disturbance treatment on the blocking liquid;
3) partial drying: placing the catalyst block treated in the step 2) in a room temperature or negative pressure drying system, drying until the mass is reduced to 50% of the increased weight, and taking out the catalyst;
4) secondary impregnation: putting the catalyst treated in the step 3) into active liquid with a certain concentration, and soaking for 90-240 min at normal temperature;
5) and (3) completely drying: putting the catalyst treated in the step 4) into a blast type drying oven, quickly heating the temperature to 100-110 ℃ from room temperature, and preserving the temperature for 60-120 min;
6) roasting: and (3) quickly putting the catalyst treated in the step 5) into a muffle furnace, heating to a certain temperature at the speed of 4-6 ℃/min, roasting for a certain time, and cooling to room temperature along with the furnace. After regeneration, the active ingredient is selectively implanted in a region within 200 μm from the orifice or pore passage of the denitration catalyst.
In the step 1), the waste denitration catalyst is a honeycomb type vanadium series or honeycomb type iron series waste denitration catalyst.
In the step 1), through the pretreatment, the channel dredging rate of the catalyst is more than 95%, the mass of the carried ash is less than 10% of the mass of the catalyst, and the moisture content is less than 1% of the mass of the catalyst.
In the step 2), the soaking temperature is 20-60 ℃, and the soaking time is 10-120 min.
In the step 2), the blocking solution is a solution with the concentration of less than 0.1%, the room-temperature viscosity of 5-10 mPa & s and V2O5Aqueous solution immiscible aqueous solution.
In the step 2), the disturbance treatment is ultrasonic wave addition or aeration bubbling or vacuum pumping.
In the step 3), the negative pressure drying system is a closed space with the temperature of more than 20 ℃ and the pressure of less than 101.325 kPa.
In the step 3), the weight gain is the difference between the mass of the catalyst after primary impregnation and the mass of the catalyst before primary impregnation.
In the step 4), the active liquid is a precursor solution containing vanadium, tungsten or a mixture of the two elements.
In the step 4), the concentration of the active liquid refers to that the mass fraction of the vanadium-containing precursor in the precursor solution is less than 1% and/or the mass fraction of the tungsten-containing precursor is less than 5%.
In the step 5), the temperature rise speed of the rapid temperature rise is 4 ℃/min.
In the step 5), the complete drying means that the mass fraction of the moisture in the dried catalyst is less than 1%.
In the step 6), the roasting temperature is 500-600 ℃, and the heat preservation time is 120-240 min.
Compared with the prior art, the invention has the advantages and beneficial effects as follows:
(1) the method selectively loads vanadium or tungsten components to a denitration reaction area of catalyst micropores, and V is enabled to be realized through processes of primary impregnation, partial drying, secondary impregnation, complete drying, baking and the like2O5And/or WO3Selectively loaded in a region which is more than 200 mu m away from the orifice or pore canal of the denitration catalyst, thereby improving the denitration activity of the catalyst and strictly controlling the increase of vanadium and/or tungsten to the SO of the catalyst2The acceleration of the oxidation rate.
(2) The regeneration process disclosed by the invention is simple to operate, low in cost, remarkable in effect and wide in application range, and can not block coal devices and flues, so that the safe production operation of the process flow is ensured.
(3) The invention can effectively prolong the recycling frequency of the catalyst, not only can greatly reduce the use cost of the catalyst, but also can reduce the discharge amount of denitration catalyst wastes and reduce the environmental hazard of solid wastes.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Fig. 2 is an SEM picture of the denitration catalyst before regeneration in example 1.
Fig. 3 is an SEM picture after the denitration catalyst of example 1 was regenerated.
Fig. 4 is an EDS spectrum of the region labeled 3 in fig. 3.
Reference numbers in the figures: 1-catalyst bulk part not implanted with active ingredient, 2-calcined catalyst containing selectively implanted V2O5The particulate agglomerate portion of the internal structure of the catalyst of (a).
Detailed Description
For the purpose of promoting an understanding of the invention, reference will now be made to the following descriptions taken in conjunction with the accompanying drawings and specific examples, in which:
example 1
Taking a waste honeycomb type SCR denitration catalyst (68cm multiplied by 15 cm; about 21 months of use; complete integral structure), blowing the surface and the pore channels by a compressed air gun, and then blowing the catalyst pore channels by a high-pressure water gun in a direction from the air inlet end. And after all pore channels of the catalyst are dredged, putting the catalyst into a blast type drying oven, drying at 105 ℃ for more than 4h, cooling the catalyst to room temperature, and weighing the mass as M1. Through the pretreatment, the channel dredging rate of the treated catalyst is more than 95%, the mass of the carried ash is less than 10% of the mass of the catalyst, and the moisture content is less than 1% of the mass of the catalyst.
And putting the weighed catalyst into a container containing a blocking solution, starting ultrasonic waves to disturb, soaking at the temperature of 20 ℃ for 10min, taking out the catalyst, sucking surface liquid, and weighing as M2. The weighed catalyst is placed at room temperature, when the mass M3 of the catalyst is 50 percent of (M2-M1), the catalyst is placed into a vanadium-containing precursor solution prepared in advance, the mass fraction of the vanadium-containing precursor in the solution is less than 1 percent, and the solution is kept still at room temperature and soaked for about 90min under the condition that the liquid is not disturbed. Taking out, placing into a blast type drying oven, heating to 100 deg.C at a temperature rise rate of 4 deg.C/min, maintaining for 60min, placing the catalyst into a muffle furnace, heating to 500 deg.C at a temperature rise rate of 4 deg.C/min, calcining, maintaining for 120min, turning off the heating power supply, opening the furnace to take out the catalyst when the temperature in the muffle furnace reaches room temperature, regenerating, and recovering V2O5And is supported in a region of 200 μm away from the denitration catalyst openings or channels. The SEM pictures of the waste denitration catalyst before the selective active ingredient was implanted are shown in fig. 2, the particle size was uniform on the entire surface inside the orifice of the catalyst before regeneration, the SEM pictures of the waste denitration catalyst after regeneration are shown in fig. 3, the internal structure of the catalyst after regeneration was regionalized, and the partially sintered particles were V in the catalyst body2O5I.e. the region marked 1 in fig. 3, is a bulk portion of the procatalyst of uniform particle size, which is not implanted with active ingredient; the area of reference number 2 is an agglomerate of particles of the internal structure of the calcined and sintered catalyst, which is formed by the agglomeration of particles and has uneven granularity, and the particles with lower sintering degree are V of subsequent implantation2O5I.e. the area marked 2 in fig. 3 is implanted with a new V after the regeneration treatment2O5And due to the supported V2O5Are on the surface of the catalyst internal structure, so that the distance between the newly implanted active ingredient substance and the catalyst internal pore opening is within 200 μm as shown by the scale in the figure. EDS analysis results show that the components of the single particles in FIG. 4 are mainly V and O, wherein the lower energy level at the left side of FIG. 4 is V contained in the catalyst body before regeneration2O5V and O in the figure 4, the higher energy level at the right side of the figure is the implanted active component V after regeneration treatment2O5V and O in (1), and the implanted active ingredient V after regeneration can be obtained from the peak intensity2O5The peak value of V in the process is more prominent, which shows that the treatment of the implanted active ingredients has very obvious loading effect on the waste denitration catalyst; the particles are partially impregnated with TiO as a result of sintering2Therefore, the EDS chart contains a characteristic peak of Ti. As can be seen from comparison and comprehensive analysis of the previous and subsequent figures, the regeneration method successfully and selectively implants the active ingredient vanadium-containing substance V into the waste denitration catalyst after treatment2O5
Example 2
Taking a waste honeycomb type SCR catalyst (68cm multiplied by 15 cm; about 21 months of use; complete integral structure), blowing the surface and the pore channels by a compressed air gun, and then blowing the catalyst pore channels by a high-pressure water gun in a direction from the air inlet end. And after all pore channels of the catalyst are dredged, putting the catalyst into a blast type drying oven, drying at 105 ℃ for more than 4h, cooling the catalyst to room temperature, and weighing the mass as M1. Through the pretreatment, the channel dredging rate of the treated catalyst is more than 95%, the mass of the carried ash is less than 10% of the mass of the catalyst, and the moisture content is less than 1% of the mass of the catalyst.
And putting the weighed catalyst into a container containing a blocking liquid, starting a bubbling machine to bubble and disturb, soaking at the temperature of 40 ℃ for 120min, taking out the catalyst, sucking the surface liquid, weighing, and recording as M2. The weighed catalyst is placed in a negative pressure drying system, wherein the negative pressure drying system is preferably a closed space with a drying temperature of more than 20 ℃ and a pressure of less than 101.325kPa or a vacuum drying oven with a drying temperature of 40 ℃ and a pressure of 80 kPa. When the mass M3 of the catalyst is 50% of (M2-M1), putting the catalyst into a tungsten-containing precursor solution prepared in advance, wherein the mass fraction of the tungsten-containing precursor in the solution is less than 5%, and standing and soaking at normal temperature for about 240min under the condition that the liquid is not disturbed. Taking out, placing into a blast type drying oven, heating to 100 deg.C at a temperature rise rate of 4 deg.C/min, maintaining for 60min, placing the catalyst into a muffle furnace, heating to 600 deg.C at a temperature rise rate of 6 deg.C/min, calcining, maintaining for 120min, turning off the heating power supply, opening the furnace to take out the catalyst when the temperature in the muffle furnace reaches room temperature, regenerating, and then WO3And is supported in a region of 200 μm away from the denitration catalyst openings or channels.
Example 3
Taking a waste honeycomb type SCR catalyst (68cm multiplied by 15 cm; about 21 months of use; complete integral structure), blowing the surface and the pore channels by a compressed air gun, and then blowing the catalyst pore channels by a high-pressure water gun in a direction from the air inlet end. And after all pore channels of the catalyst are dredged, putting the catalyst into a blast type drying oven, drying at 105 ℃ for more than 4h, cooling the catalyst to room temperature, and weighing the mass as M1. Through the pretreatment, the channel dredging rate of the treated catalyst is more than 95%, the mass of the carried ash is less than 10% of the mass of the catalyst, and the moisture content is less than 1% of the mass of the catalyst.
And putting the weighed catalyst into a container containing a blocking solution, starting a vacuum pump to vacuumize for disturbance, soaking at the temperature of 60 ℃ for 60min, taking out the catalyst, sucking surface liquid, weighing, and recording as M2. The weighed catalyst is placed at room temperature, and when the catalyst mass M3 is 50% of (M2-M1), the catalyst will catalyzeThe agent is put into a prepared vanadium-containing precursor solution and a tungsten-containing precursor solution, the mass fraction of the vanadium-containing precursor in the solution is less than 1 percent, and the mass fraction of the tungsten-containing precursor in the solution is less than 5 percent, and the solution is stood and soaked for about 180min at normal temperature under the condition that the liquid is not disturbed. Taking out, placing into a blast type drying oven, heating to 110 deg.C at a temperature rise rate of 4 deg.C/min, maintaining for 120min, placing the catalyst into a muffle furnace, heating to 600 deg.C at a temperature rise rate of 6 deg.C/min, calcining, maintaining for 240min, turning off the heating power supply, opening the furnace to take out the catalyst when the temperature in the muffle furnace reaches room temperature, regenerating, and recovering V2O5And WO3And at the same time, in a region of 200 μm away from the denitration catalyst orifice or pore channel.
The present invention and the embodiments thereof have been described above without limitation, and it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principle and spirit of the invention, and it is intended that all structural devices or products and methods of use thereof which are not inventive to design the same or similar to the technical solution of the present invention shall fall within the protection scope of the present invention.

Claims (2)

1. A regeneration method of a waste denitration catalyst selectively implanted with active ingredients is characterized by comprising the following steps: the method comprises the following specific steps:
1) pretreatment: performing ash removal, cleaning and drying pretreatment on the waste denitration catalyst in sequence by adopting compressed air soot blowing, ultrasonic cleaning and blowing type drying box heat treatment means;
2) primary impregnation: soaking the waste denitration catalyst which is processed in the step 1) and forms a block shape in a container containing a blocking liquid, and carrying out disturbance treatment on the blocking liquid;
3) partial drying: placing the catalyst block treated in the step 2) in a room temperature or negative pressure drying system, drying until the mass is reduced to 50% of the increased weight, and taking out the catalyst; the weight gain is the difference between the mass of the catalyst after primary impregnation and the mass of the catalyst before primary impregnation;
4) secondary impregnation: putting the catalyst treated in the step 3) into active liquid with a certain concentration, and soaking for 90-240 min at normal temperature;
5) and (3) completely drying: putting the catalyst treated in the step 4) into a blast type drying oven, quickly heating the temperature to 100-110 ℃ from room temperature, and preserving the temperature for 60-120 min;
6) roasting: quickly putting the catalyst treated in the step 5) into a muffle furnace, heating to a certain temperature at the speed of 4-6 ℃/min, roasting for a certain time, and cooling to room temperature along with the furnace;
wherein the waste denitration catalyst in the step 1) is a honeycomb type vanadium-series or honeycomb type iron-series waste denitration catalyst; the blocking solution in the step 2) has a concentration of less than 0.1%, a room-temperature viscosity of 5-10 mPa.s and a viscosity of V2O5The water solution is immiscible, the soaking temperature in the step 2) is 20-60 ℃, and the soaking time is 10-120 min; the active solution in the step 4) is a precursor solution containing vanadium, tungsten or a mixture of the two elements, and the concentration of the active solution in the step 4) is that the mass fraction of the vanadium-containing precursor in the precursor solution is less than 1% and/or the mass fraction of the tungsten-containing precursor is less than 5%; the temperature rise speed of the rapid temperature rise in the step 5) is 4 ℃/min, and the complete drying in the step 5) means that the mass fraction of water in the dried catalyst is less than 1%; the roasting temperature in the step 6) is 500-600 ℃, and the heat preservation time is 120-240 min.
2. The method for regenerating a spent denitration catalyst by selective implantation of an active ingredient as set forth in claim 1, wherein: the negative pressure drying system in the step 3) is a closed space with the temperature of more than 20 ℃ and the pressure of less than 101.325 kPa.
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CN106215980B (en) * 2016-07-06 2018-09-07 神华集团有限责任公司 A kind of regeneration method of denitrating catalyst
CN106732526A (en) * 2016-12-20 2017-05-31 浙江德创环保科技股份有限公司 The method of the denitrating catalyst regeneration duties vanadic anhydride based on curve matching
CN107999147B (en) * 2017-11-28 2020-04-24 武汉大学 Method for preparing catalyst capable of simultaneously performing denitration and dearsenification by modifying waste SCR catalyst
CN110013885B (en) * 2018-01-08 2022-12-09 国家能源投资集团有限责任公司 Regeneration method of denitration catalyst
CN112481507A (en) * 2020-12-15 2021-03-12 江苏龙源催化剂有限公司 Method for recovering metallic lead and thallium components from waste denitration catalyst

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JP6205153B2 (en) * 2013-03-29 2017-09-27 日立造船株式会社 On-site regeneration method of denitration catalyst in exhaust gas purification system
CN104888806B (en) * 2015-05-07 2018-11-09 中国华能集团清洁能源技术研究院有限公司 A kind of regeneration method that inactivation vanadium titanium-based Faveolate denitration catalyst combined denitration demercuration is modified

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