CN110769933A - Regeneration method and regeneration system of denitration catalyst - Google Patents
Regeneration method and regeneration system of denitration catalyst Download PDFInfo
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- CN110769933A CN110769933A CN201880038532.0A CN201880038532A CN110769933A CN 110769933 A CN110769933 A CN 110769933A CN 201880038532 A CN201880038532 A CN 201880038532A CN 110769933 A CN110769933 A CN 110769933A
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Abstract
The invention provides a method and a system for regenerating a denitration catalyst, which can remove coarse particles blocked in the denitration catalyst and poisoning substances attached to the denitration catalyst. The regeneration method of the denitration catalyst at least comprises the following steps: a chemical cleaning step of immersing the denitration catalyst in a chemical containing a fluorine compound, an inorganic acid, and a surfactant in a dry state to perform chemical cleaning.
Description
Technical Field
The present invention relates to a method and a system for regenerating a denitration catalyst, and particularly to a method and a system for regenerating a denitration catalyst for a coal-fired boiler.
Background
An apparatus for burning a fuel such as a fossil fuel or biomass is provided with a denitration apparatus for removing nitrogen oxides contained in an exhaust gas generated by burning the fuel. Such a denitration facility is provided with a denitration catalyst that promotes the removal of nitrogen oxides. Since the denitration catalyst deteriorates in performance when used, the denitration catalyst is replaced or added during maintenance in the denitration plant equipped with the denitration catalyst. Further, it has been proposed to perform a regeneration treatment for recovering the performance of the denitration catalyst in order to reuse the denitration catalyst.
As such a regeneration treatment, the following methods and apparatuses are known: a denitration catalyst whose activity is lowered by a poisoning substance of silica, alumina, and calcium sulfate is preliminarily washed with water to contain water, and then the substance is washed and removed at normal temperature using a mixed solution of an organic acid and a fluoride (patent document 1). Further, the following methods and systems are known: the denitration catalyst is washed with water and then immersed in a chemical solution containing a fluorine compound and an inorganic acid to remove deposits such as calcium adhering to the surface of the catalyst (patent document 2).
Prior art documents
Patent document
Patent document 1: japanese patent application laid-open No. 2011-31237
Patent document 2: international publication No. 2017/010402
Disclosure of Invention
Technical problem to be solved by the invention
In the above example, even if the regeneration treatment is performed, coarse particles clogged in the gas passage holes of the denitration catalyst cannot be sufficiently removed. Further, it may be necessary to perform a treatment for removing such coarse particles. In the above example, although the pre-washing with water was followed by the chemical washing with a fluorine compound and an acid, the deposited material such as coarse particles could not be removed effectively, and the effect of catalyst regeneration was reduced. One of the reasons for this is that the effect of the fluorine compound and the acid is reduced by the water content of the catalyst due to the prewashing with water. As a countermeasure, it is conceivable to increase the concentration of the fluorine compound, but this countermeasure may have an influence on the components of the catalyst. Further, when the used denitration catalyst is washed with water and then dried again, the deposits accumulated in the gas passage holes of the denitration catalyst aggregate into coarse particles, and cannot be removed.
The purpose of the present invention is to provide a method for regenerating a denitration catalyst and a system for regenerating a denitration catalyst, which are capable of removing a poisoning substance attached to the denitration catalyst and removing coarse particles clogged in gas passage holes of the denitration catalyst.
Means for solving the technical problem
In order to achieve the above object, a method for regenerating a denitration catalyst according to an aspect of the present invention includes at least: a chemical cleaning step of immersing the denitration catalyst in a chemical containing a fluorine compound, an inorganic acid, and a surfactant in a dry state to perform chemical cleaning.
A method for regenerating a denitration catalyst according to an aspect of the present invention includes at least: and a final cleaning step of immersing the denitration catalyst taken out of the chemical solution in water in a vacuum tank, and sealing the tank to suck air in the tank.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the fluorine compound is ammonium bifluoride, the amount of the fluorine compound is 1 to 10% by mass based on the entire chemical solution, the amount of the inorganic acid is added so that the pH of the chemical solution falls within a range of pH1 to 6, and the amount of the surfactant is 0.001 to 10% by mass based on the entire chemical solution.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the final cleaning step further includes: and a final washing step of washing the denitration catalyst taken out from the vacuum tank with water or water containing a sulfonamide as a washing liquid after the washing in the vacuum tank.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the denitration catalyst removed from the denitration device is directly immersed in the chemical solution washing step to be washed.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the surfactant is a nonionic surfactant containing a polyoxyethylene polyoxypropylene glycol, a polyoxyethylene derivative or a polyalkylene glycol derivative as a main component, or an anionic surfactant containing a polyoxyethylene alkyl ether phosphate as a main component.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the fluorine compound is ammonium bifluoride, the inorganic acid is sulfamic acid, and the surfactant is a nonionic surfactant containing polyoxyethylene polyoxypropylene glycol as a main component.
In the method for regenerating a denitration catalyst according to one aspect of the present invention, the chemical solution is repeatedly used in the chemical solution cleaning step.
In order to achieve the above object, a denitration catalyst regeneration system according to an aspect of the present invention includes at least: the chemical cleaning section is configured to perform chemical cleaning by immersing the denitration catalyst in a dry state in a chemical containing a fluorine compound, an inorganic acid, and a surfactant.
Furthermore, a system for regenerating a denitration catalyst according to an aspect of the present invention further includes: and a vacuuming tank configured to immerse the denitration catalyst taken out of the chemical solution in water in the vacuuming tank, and to seal the tank to suck air in the tank.
In the regeneration system for a denitration catalyst according to one aspect of the present invention, the fluorine compound is ammonium bifluoride in an amount of 1 to 10% by mass based on the entire chemical solution, the inorganic acid is added in an amount such that the pH of the chemical solution falls within a range of pH1 to 6, and the surfactant is in an amount of 0.001 to 10% by mass based on the entire chemical solution.
Furthermore, a system for regenerating a denitration catalyst according to an aspect of the present invention further includes: and a final washing tank for finally washing the denitration catalyst taken out of the vacuum tank with water or water containing sulfamic acid as a final washing liquid.
In the regeneration system of a denitration catalyst according to one aspect of the present invention, the chemical solution cleaning unit is configured to clean the denitration catalyst removed from the denitration device by directly immersing the denitration catalyst in the chemical solution washing tank.
Effects of the invention
According to the present invention, it is possible to provide a method for regenerating a denitration catalyst and a system for regenerating a denitration catalyst, which can remove a poisoning substance attached to the denitration catalyst and remove coarse particles clogged in gas passage holes of the denitration catalyst.
Drawings
Fig. 1 is a schematic diagram showing a schematic configuration of a denitration catalyst regeneration system according to a first embodiment.
Fig. 2 is a flowchart illustrating an example of the method for regenerating the denitration catalyst according to the first embodiment.
Fig. 3 is a schematic diagram showing a schematic configuration of a denitration catalyst regeneration system according to a second embodiment.
Fig. 4 is a flowchart showing an example of the method for regenerating the denitration catalyst according to the second embodiment.
Fig. 5 is a graph showing the measurement results of the clogging rate of the denitration catalyst according to the example.
Fig. 6 is a graph showing the calculation result of the clogging removal rate of the denitration catalyst according to the example.
Fig. 7 is a graph showing the measurement results of the denitration reaction rate constant ratio of the denitration catalyst according to the example.
Fig. 8 is a graph showing the measurement results of the amount of silica eluted from the denitration catalyst according to the example.
Detailed Description
Hereinafter, embodiments of a method for regenerating a denitration catalyst and a system for regenerating a denitration catalyst according to the present invention will be described in detail with reference to the drawings. The present invention is not limited to these embodiments. The drawings are for explaining the outline of the embodiments, and some of the attached devices are omitted. In addition, when there are a plurality of embodiments, a configuration in which each embodiment is combined or partially replaced is also included in the technical scope of the present invention.
1. First embodiment
1.1. Regeneration system
A system for regenerating a denitration catalyst according to a first embodiment will be described with reference to fig. 1. As shown in fig. 1, the denitration catalyst regeneration system 100 includes a chemical cleaning unit 102, a final cleaning unit 104, and a drying unit 106, and is configured to execute a regeneration process for recovering the denitration performance of the denitration catalyst.
The denitration catalyst to be subjected to the regeneration treatment is, for example, a catalyst containing Silica (SiO) generated in a coal-fired boiler2) And poisoning substances such As silicon (Si), aluminum (a1), calcium (Ca), phosphorus (P), arsenic (As), sodium (Na), and potassium (K) used for denitration of exhaust gas, and the like, and thus the denitration performance thereof is lowered (hereinafter,also referred to as used denitration catalyst. ). Such a denitration catalyst is, for example, a catalyst having at least 1 through hole for exhaust gas (hereinafter, also referred to as a gas through hole), and having a lattice (honeycomb), plate, corrugated (corrugated) or other shape, and is used for titanium dioxide (TiO)2) The carrier is one in which at least 1 active ingredient selected from the group consisting of vanadium (V), tungsten (W) and molybdenum (Mo) is supported. In addition, such a denitration catalyst is a target of a regeneration treatment in a dry state.
The dry state described in the present specification is not limited to an absolute dry state in which moisture is not contained, and includes a state in which moisture in the air is adsorbed. The catalyst such as a denitration catalyst has small pores, and even when the catalyst is left in a room, moisture in the air is adsorbed on the catalyst. The catalyst placed under high humidity conditions becomes in a wet state, which is also included in the dry state of the present invention. Further, the catalyst may be dried after water washing. The dry state described in the present specification is not limited to such a completely dry state, and refers to a state of the catalyst in which the denitration catalyst is not subjected to treatment for the purpose of washing with water after being taken out from the inside of the denitration facility or the apparatus. Examples of such treatment include washing treatment such as impregnation of the catalyst in water or pre-washing of the catalyst with water. The regeneration treatment in a dry state described in the present specification refers to a treatment in which the denitration catalyst is directly immersed in the chemical solution tank to clean the denitration catalyst without performing a cleaning treatment such as pre-washing after the denitration catalyst is taken out from the inside of the denitration plant and the apparatus, and a treatment in which the catalyst is dried again after the cleaning treatment and then the chemical solution cleaning is performed. Therefore, the denitration catalyst can be subjected to dust removal treatment such as air blowing after the denitration catalyst is taken out from the inside of the denitration equipment and the device and before the denitration catalyst is cleaned with the chemical solution.
The chemical cleaning section 102 includes at least a chemical cleaning tank for cleaning the denitration catalyst and a mechanism for supplying a chemical into the chemical cleaning tank. The chemical washing tank is a container which is larger than the denitration catalyst to be regenerated and can store the chemical. The chemical cleaning section 102 is configured to introduce a dried denitration catalyst into a chemical cleaning tank in which a chemical is stored, and immerse the denitration catalyst in the chemical. The chemical cleaning section 102 is configured to be able to prevent active components such as vanadium from dissolving out of the denitration catalyst by immersing the denitration catalyst in the chemical, to dissolve out poisoning substances such as silica that are hardly soluble from the denitration catalyst, and to dissolve particles that are clogged inside the denitration catalyst, particularly coarse particles that are clogged in the exhaust gas passage holes, to reduce the particle diameter thereof. As the chemical cleaning unit 102, a device having a shower nozzle or the like and applying a chemical to the denitration catalyst to impregnate the denitration catalyst with the chemical may be used. In the present specification, the "coarse particles" are particles having a diameter substantially equal to that of the gas passage holes of the denitration catalyst, and for example, are particles having a diameter substantially equal to that of the honeycomb holes of the denitration catalyst having a honeycomb shape. The coarse particles have a diameter of, for example, about 5.0mm, and are presumably formed mainly of silica, aluminum, or the like.
The final cleaning unit 104 includes at least a vacuuming tank having a water tank for cleaning the denitration catalyst, a mechanism for supplying water into the water tank, and a vacuum pump for sucking air in the water tank. The evacuation tank is a container which is larger than the denitration catalyst to be regenerated and can store water, and is configured to be capable of taking out and putting in the denitration catalyst by having a lid or the like and to be capable of sealing the inside thereof. The final cleaning unit 104 is configured to suck and remove particles clogged in the denitration catalyst, particularly coarse particles clogged in the exhaust gas passage holes, by sucking air while setting the inside thereof in a sealed state to a vacuum state.
The drying section 106 is configured to remove water from the denitration catalyst cleaned with the chemical solution in the chemical solution cleaning section 102 or the denitration catalyst cleaned with the final cleaning section 104. The drying section 106 is configured to introduce a gas heated to 100 ℃ or higher, for example, a gas at 130 ℃ into the denitration catalyst to remove moisture adhering to the denitration catalyst. The drying section 106 may be configured to remove moisture from the denitration catalyst, and may be configured to blow moisture off the denitration catalyst by sending dried air to the denitration catalyst, or may be configured to evaporate moisture from the denitration catalyst in a space heated to 100 ℃.
The final cleaning unit 104 of the regeneration system 100 according to the present embodiment may optionally further include a water jet washing tank, not shown, for performing water jet washing. The water jet washing tank is provided with at least a water tank for washing the denitration catalyst and a water supply device, and is configured to supply washing water to the gas vent holes of the denitration catalyst by spraying high-pressure water assisted by compressed air.
1.2. Regeneration method
Fig. 2 is a flowchart showing an example of the method for regenerating the denitration catalyst according to the first embodiment. As shown in fig. 1 and 2, the method for regenerating a denitration catalyst according to the present embodiment can be realized by executing processes by each part of the denitration catalyst regeneration system 100. The method for regenerating a denitration catalyst according to the present embodiment includes at least a chemical cleaning step and a final cleaning step. As described above, the dust removal step in which the catalyst does not absorb water, such as air blowing, can be performed before the chemical cleaning step after being taken out from the inside of the denitration facility and the apparatus. Further, the chemical cleaning step may be performed after the water washing and drying.
As shown in fig. 1 and 2, in the chemical cleaning step (step S12), a chemical containing a fluorine compound, an inorganic acid, and a surfactant is used, and the denitration catalyst is impregnated in the chemical cleaning portion 102 filled with the chemical in a dry state. The immersion time can be set to 15 minutes to 60 minutes, for example. After the liquid medicine is cleaned, the denitration catalyst is taken out of the liquid medicine. In order to clean the denitration catalyst in another dry state, it is preferable to use a chemical solution remaining in the chemical solution cleaning tank after the chemical solution cleaning.
As the fluorine compound of the chemical solution, ammonium hydrogen fluoride (NH) can be exemplified4HF2) Ammonium fluoride (NH)4F) In that respect The fluorine compound is preferably ammonium bifluoride. The amount of the fluorine compound can be, for example, 1 to 10% by mass, preferably 1 to 5% by mass, based on the entire chemical solution.
As the inorganic acid of the chemical solution, sulfamic acid can be exemplifiedAcid (H)3NSO3) Hydrochloric acid (HCl), sulfuric acid (H)2SO4) Boric acid (H)3BO3). The mineral acid is preferably hydrochloric acid or hydrochloric acid and boric acid. Boric acid can also function as a rust inhibitor. The amount of boric acid can be set to 0.001 to 10% by mass, for example, relative to the chemical solution. Also, the inorganic acid is preferably sulfamic acid. The amount of the inorganic acid is preferably added so that the pH of the chemical solution is in the range of 1 to 6, and more preferably in the range of 1 to 3, for example. If the amount of the acid is such that the pH of the chemical solution is within the above range, an acid other than the inorganic acid may be added.
The surfactant of the chemical solution is preferably a nonionic surfactant or an anionic surfactant. The nonionic surfactant is preferably a non-phosphoric acid surfactant containing a polyoxyethylene polyoxypropylene glycol, a polyoxyethylene derivative, or a polyalkylene glycol derivative as a main component. The Ethylene Oxide (EO) content of the polyoxyethylene polyoxypropylene glycol can be set to 39 mass%, for example. Examples of the non-phosphoric acid-based surfactant containing a polyoxyethylene polyoxypropylene glycol as a main component include BLANON P-101M (AOKI OIL INDUSTROL IAL Co., manufactured by Ltd.), EMULGEN PP-220 (manufactured by Kao corporation), NEWPOL PE-61, NEWPOL PE-62, NEWPOL PE-64, NEWPOL PE-68, NEWPOLPE-71, NEWPOLPE-74, NEWPOL PE-75, NEWPOL PE-78, NEWPOL PE-108, etc. (manufactured by Sanyo chemical industries, Ltd.), EPAN 410, EPAN 420, EPAN 450, EPAN 485, EPAN 680, EPAN 710, EPAN 720, EPAN 740, EPAN 750, EPAN 785, EPAN U-103, EP AN U-105, EPAN-108, etc. (manufactured by Ltd.), PLON #101, PLON #188, PLON #056, EPAN # 3583, PLON # 85P #124, EPAN # PLON # 8580, EPAN # 108, EPAN # P # 3, and the like (manufactured by Ltd.), PLON #188, PLON # 3, PLON # and the like, PLONON #201, PLONON #202, PLONON #204, PLONON #208, PLONON #235P, PLONON #237P, PLONON #238, PLONON #407P, Unilube (registered trademark) 70DP-950B, Unilube 75DE-2620R and the like (manufactured by NOF CORPORATION), Presstall EM-440, Presstall EM-640, Presstall RM-183 and the like (manufactured by MIYOSHIOL OIL & FAT CO., LTD.). Examples of the non-phosphate surfactant containing a polyalkylene glycol derivative as a main component include Master Air404 (manufactured by BASF corporation), FoamKil1er M-14 (manufactured by AOKI OILI NDUSTRIAL Co., Ltd.), DISPANOL WI-115 (manufactured by NOFCORPORATION), Un ilebe 50MB-2, Unilube 50MB-5, Unilube 50MB-11, Unilube 50MB-26, Unilube 50MB-72, Unilube 60MB-2B, Unilube 60MB-16, Unilube 60MB-26, Unilube 75DE-15, Unilube 75-25, Unilube 75DE-60, Unilube 75DE-170, Unilube 75DE-2620, Unilube 75-3800, Unilube 80-40, SAF 75-60, Unilube 7-MB-700, Unilube 7-700 MB-19, Unilube 7-700, Unilube 7-MB-2 MB-16, Unilube, Unilube MB-11X, Unilube 10MS-250KB, et al (manufactured by NOFCORPORATION), Trimming DF-300, Trimming 610, et al (manufactured by MIYOSHI OIL & FAT CO., LTD.), RIKEI RK-95 (manufactured by RI CHEMICALINDUSTRIRY CO., LTD.). The anionic surfactant is preferably a phosphate ester surfactant containing a phosphate ester such as polyoxyethylene alkyl ether phosphate or a salt thereof as a main component. The phosphate ester surfactant is preferably a surfactant containing a phosphate ester such as polyoxyethylene alkyl ether phosphate as a main component, and more preferably a surfactant containing polyoxyethylene alkyl (C8) ether phosphate ester or monoethanolamine salt as a main component. Examples of the phosphate ester-based surfactant containing a phosphate ester or a salt thereof as a main component include Antox EHD-PNA, Newcol 100-FCP, AntoxEHD-400 (NIPPON NYUKAZAI C0., manufactured by LTD.), Plusturf A208F, Plusturf A208N, Plusturf A210D, and Plusturf M208F (DKS Co., manufactured by Ltd.). The amount of the surfactant can be set to 0.001 to 10% by mass, for example, with respect to the entire chemical solution.
In the final cleaning step (step S14), the denitration catalyst taken out after the chemical cleaning is moved to the vacuuming tank of the final cleaning unit 104 as vacuuming cleaning. In the vacuum tank, the denitration catalyst is immersed in water, and the vacuum tank is sealed to suck air from the tank, thereby achieving a vacuum state. In the final cleaning step, the inside of the evacuation tank is brought into a vacuum state, whereby particles inside the denitration catalyst, particularly coarse particles clogged in the gas passage holes, can be suctioned and removed. After this final cleaning, the evacuated cell was opened to atmospheric pressure and the denitration catalyst was removed from the evacuated cell.
In the final cleaning step (step S14), the air pressure in the evacuation tank of the final cleaning unit 104 is preferably reduced to-600 mmHg or less. By reducing the air pressure in the water tank to-600 mmHg or less, coarse particles that clog the gas passage holes of the denitration catalyst can be effectively removed, and all regions of the denitration catalyst can be immersed in water.
In the drying step (step S16), the denitration catalyst taken out after the chemical cleaning or after the final cleaning is moved to the drying section 106. In the drying section 106, water adhering to the denitration catalyst is evaporated to dry the denitration catalyst.
Also, the final cleaning step (step S14) can further include spray cleaning after the vacuum cleaning and before the drying step. In the spray cleaning, the final cleaning unit 104 or a spray water tank provided in the final cleaning unit 104 sprays high-pressure water assisted by compressed air to supply cleaning water to the gas passage holes. This makes it possible to wash out particles remaining inside the denitration catalyst.
According to the present embodiment, it is possible to remove the poisoning substances such as silica (Si) adhering to the surface of the denitration catalyst and the gas passage holes and to remove almost all the coarse particles clogged in the gas passage holes of the used denitration catalyst. As one of the reasons for this, it is presumed that the effect of the chemical solution at the time of the chemical solution cleaning step is prevented from being lowered by performing the chemical solution cleaning step on the denitration catalyst in a dry state. Further, it is presumed that the strength of the denitration catalyst can be maintained as described later even if the denitration catalyst used is not subjected to pre-washing with water before the chemical cleaning step. Since the pre-washing can be omitted, the amount of water required for the pre-washing, the equipment for the pre-washing, the treatment time, and the like can be reduced. As a result, the facility and processing costs can be reduced.
Further, as one of the reasons why the coarse particles can be effectively removed, it is presumed that the coarse particles clogged in the gas passage holes of the denitration catalyst are dissolved and the particle diameter thereof is reduced by the chemical cleaning, and the gas of the denitration catalyst is sucked out through the bubbles in the gas passage holes by the final cleaning, and the coarse particles whose particle diameter is reduced in the gas passage holes and the poisoning material accumulated in the gas passage holes are removed. On the other hand, even if chemical cleaning is performed after vacuuming cleaning, it is difficult to remove coarse particles in the gas passage holes. This is presumably because, for example, by performing only vacuuming cleaning, the gas of the denitration catalyst is taken out through the bubbles in the pores and the small particles accumulated in the gas passing pores are removed, but the particle diameter of the coarse particles clogged in the gas passing pores does not change greatly. Further, it is presumed that even if the chemical cleaning is performed after the evacuation cleaning, since the treatment of forcibly sucking out the coarse particles in the gas passage holes is not performed, the coarse particles in the gas passage holes remain.
Further, according to the present embodiment, even when the chemical liquid used in the chemical liquid cleaning step is repeatedly used for a plurality of used denitration catalysts, almost all of the coarse particles clogged in the gas passage holes of the used denitration catalysts can be removed. In addition, since the chemical solution containing the fluorine compound, the inorganic acid, and the surfactant is used in the chemical solution cleaning step, the strength of the denitration catalyst can be prevented from being lowered by the regeneration treatment.
2. Second embodiment
2.1. Regeneration system
Fig. 3 shows a schematic configuration of a denitration catalyst regeneration system according to a second embodiment. As shown in fig. 3, the denitration catalyst regeneration system 100a according to the present embodiment includes at least a chemical cleaning unit 102a, final cleaning units 104a and 104c, a drying unit 106, and a denitration catalyst conveyance device 112. The denitration catalyst transfer device 112 is a device that removes a denitration catalyst from a denitration apparatus provided with the denitration catalyst and transfers the removed denitration catalyst. The denitration catalyst transfer device 112 may include a crane, a vehicle, a manually movable cart, and the like that transfer the denitration catalyst.
The chemical cleaning section 102a includes at least a chemical cleaning tank 114, a chemical supply device 116, and a waste liquid tank 119. The chemical washing tank 114 is a container which is larger than the denitration catalyst to be regenerated and can store liquid. The chemical liquid supply device 116 is configured to have a tank for storing the chemical liquid described in this specification, a valve for controlling the supply of the chemical liquid, and the like, and to supply the chemical liquid used for chemical liquid cleaning to the chemical tank 114. The chemical cleaning section 102a is configured to inject the denitration catalyst into the chemical cleaning tank 114 in which the chemical is accumulated, and immerse the denitration catalyst in the chemical. The chemical cleaning section 102a is configured to be able to suppress elution of active components such as vanadium from the denitration catalyst by immersing the denitration catalyst in the chemical cleaning tank 114, to elute poisoning substances such as silica that is hardly soluble from the denitration catalyst, and to dissolve particles that block the inside of the denitration catalyst, particularly coarse particles that block the exhaust gas passage holes, to reduce the particle diameter. The waste liquid tank 119 is a container that stores the liquid medicine discharged from the medicine washing tank 114.
The final cleaning unit 104a includes at least a vacuum pump 120, a vacuum tank 124a, a water supply device 126a, and a waste liquid tank 129 a. The vacuuming tank 124a is a container which is larger than the denitration catalyst to be regenerated and can store liquid. The evacuation tank 124a is configured to have a lid or the like so that the denitration catalyst can be taken out and put in, and the inside thereof can be sealed by the vacuum pump 120. The water supply device 126a is configured to have a tank for storing water, a valve for controlling the supply of water, and the like, and is capable of supplying water used for evacuation to the evacuation tank 124 a. The waste liquid tank 129a is a container for storing the waste liquid discharged from the vacuum tank 124 a.
The final cleaning unit 104c includes at least a final rinsing bath 124c, a final rinsing liquid supply device 126c, and a waste liquid tank 129 c. The final rinsing bath 124c is a container that is larger than the denitration catalyst to be subjected to the regeneration treatment and can store a liquid. The final rinse liquid supply device 126c is configured to have a tank for storing the final rinse liquid described in this specification, a valve for controlling supply of the final rinse liquid, and the like, and to be capable of supplying the final rinse liquid to the final rinse tank 124 c. The waste liquid tank 129c is a container that stores the final water-washing liquid discharged from the final water-washing tank 124 c.
The drying section 106 can preferably have the same configuration as the drying section 106 of the first embodiment.
Further, the denitration catalyst regeneration system 100a according to the present embodiment may further include a water jet washing tank, not shown, for performing water jet washing between the final washing unit 104a and the final washing unit 104 c. The spray water washing tank is configured to include a water tank for receiving washing water and a water supply device, and to be able to wash out particles remaining inside the denitration catalyst by spraying high-pressure water assisted with compressed air.
2.2. Regeneration method
Fig. 4 is a flowchart showing an example of a method for regenerating a denitration catalyst according to a second embodiment. The method of regenerating the denitration catalyst shown in fig. 4 can be realized by executing the processing by each part of the denitration catalyst regeneration system 100 a. The method for regenerating a denitration catalyst according to the present embodiment includes at least a chemical cleaning step and a final cleaning step.
As shown in fig. 4, in the chemical cleaning step, first, the denitration catalyst is taken out of the denitration device by the denitration catalyst transfer device 112, and the taken-out denitration catalyst is moved to the chemical cleaning tank 114 (step S22). After the denitration catalyst is moved to the chemical bath 114, the denitration catalyst is immersed in the chemical liquid supplied from the chemical liquid supply device 116 in the chemical bath 114 (step S24). After the chemical cleaning step, the chemical remaining in the chemical washing tank 114 may be discharged to the waste liquid tank 119, or may be repeatedly used for cleaning another denitration catalyst while maintaining the state of being stored in the chemical washing tank 114. In the chemical cleaning step, the denitration catalyst disposed in the chemical washing tank 114 may be immersed in the chemical by supplying the chemical into the chemical washing tank 114 after the denitration catalyst is moved to the chemical washing tank 114, or the denitration catalyst disposed in the chemical washing tank 114 may be immersed in the chemical by moving the denitration catalyst to the chemical washing tank 114 in which the chemical is stored.
In the next final cleaning step, after the denitration catalyst is cleaned in the chemical washing tank 114, the denitration catalyst is moved to the vacuuming tank 124a by the denitration catalyst transfer device 112 for vacuuming cleaning (step S30). The denitration catalyst is immersed in water in the vacuumized tank 124a by moving the denitration catalyst to the vacuumized tank 124 a. After the vacuuming groove 124a is sealed, the vacuum pump 120 sucks the air in the vacuuming groove 124a, thereby setting the interior of the vacuuming groove 124a in a vacuum state (step S32). By setting the interior of the vacuuming tank 124a to a vacuum state, foreign matter blocking the interior of the denitration catalyst, particularly coarse particles blocking the gas vent holes, can be sucked and removed. After the interior of the vacuuming tank 124a is set to a vacuum state, the vacuuming tank 124a is opened to atmospheric pressure.
In the final washing step, the denitration catalyst is transferred from the vacuuming tank 124a to the final rinsing tank 124c by the denitration catalyst transfer device 112 for the final rinsing step (step S34). After the denitration catalyst is moved to the final water rinse tank 124c, the final water rinse is supplied from the final water rinse supply device 126c into the final water rinse tank 124c, and the denitration catalyst is immersed in the final water rinse tank 124c, thereby cleaning the denitration catalyst (step S36). At this time, the final rinsing liquid in the final rinsing bath 124c may be discharged and treated, or the final rinsing liquid may be stored in the final rinsing bath 124c and then treated.
As the final water-washing liquid, water (H) can be exemplified2O), sulfamic acid (H)3NSO3) And a mixture thereof. The final aqueous wash preferably contains sulfamic acid. That is, the final water-washing liquid is preferably a mixed liquid of water and sulfamic acid of a predetermined concentration (hereinafter, also referred to as sulfamic acid-containing water). The amount of sulfamic acid can be set, for example, from 0.5mol/l to 5mol/l with respect to water.
Next, as a drying step, the process moves to the drying section 106 and the denitration catalyst is dried in the drying section 106 (step S38).
The final cleaning step according to the present embodiment may further include a spray cleaning step after the vacuuming cleaning and before the final water washing step. In the spray cleaning step, cleaning water is supplied to the gas passage holes by spraying high-pressure water assisted by compressed air in the vacuuming tank 124a or a spray water washing tank, not shown. This makes it possible to wash out particles remaining inside the denitration catalyst. Further, the method for regenerating the denitration catalyst according to the present embodiment can further include the same drying process as the drying step by moving the denitration catalyst to the drying section 106 after the vacuuming and cleaning and before the final water washing step.
According to the present embodiment, almost all of coarse particles clogged in the gas passage holes of the used denitration catalyst can be removed, and the poisoning substance such as silica adsorbed and accumulated on the surface of the denitration catalyst and in the gas passage holes can be removed, as in the first embodiment. In addition, the same effects as those of the first embodiment are exhibited, and the denitration performance of the used denitration catalyst can be restored to almost the same level as that of the unused denitration catalyst by the final cleaning step.
Further, according to the present embodiment, as in the first embodiment, the amount of water used can be reduced by omitting the pre-washing. Further, by repeatedly using water used for evacuation, water can be used efficiently. By efficiently utilizing water, the amount of waste liquid can be reduced. Specifically, after the denitration catalyst is taken out from the vacuuming tank 124a, the next denitration catalyst can be moved to be vacuumed and cleaned while maintaining the state of water stored in the vacuuming tank 124 a. Further, a tank for temporarily storing water or a circulation mechanism for circulating water may be provided in the vacuuming tank 124a, and water may be once discharged from the vacuuming tank 124a into the tank and may be again introduced from the tank into the vacuuming tank 124a through the circulation mechanism when in use. This makes it possible to repeatedly use water used once for vacuum cleaning in the next vacuum cleaning of the denitration catalyst. In this case, the circulation mechanism may be provided with a filter or the like to remove foreign matter contained in the water. Further, when the final water-washing liquid used in the final water-washing step is water, water can be efficiently used by adopting the same configuration and method as in the vacuum cleaning, and the amount of waste liquid can be reduced. When the final water-washing liquid used in the final water-washing step is water containing sulfamic acid with importance placed on the recovery of the denitration performance of the chemical liquid, a tank for temporarily storing the water containing sulfamic acid or a circulation mechanism for circulating the water containing sulfamic acid may be provided only for the final water-washing tank 124c, the water containing sulfamic acid may be temporarily discharged from the final water-washing tank 124c to the tank, and the water containing sulfamic acid may be again fed from the tank to the final water-washing tank 124c by the circulation mechanism when in use. In this case, the circulation mechanism may be provided with a filter or the like to remove foreign matter contained in the sulfamic acid-containing water, or the circulation mechanism may be provided with a concentration meter and/or a pH meter to add sulfamic acid-containing water in accordance with the concentration and/or pH of sulfamic acid in the final water-washing liquid.
Further, according to the present embodiment, after the denitration catalyst is taken out from the chemical solution, the chemical solution is kept in a stored state without being discharged from the chemical solution rinse tank 114 to the waste liquid tank 119, and the next denitration catalyst is put in, whereby the chemical solution can be repeatedly used. The chemical solution described in the present specification can be used efficiently without reducing the regeneration effect even when used repeatedly. Therefore, the amount of waste liquid can be reduced by efficiently using the chemical liquid. The present invention is not limited to the structure and method for repeatedly using the chemical solution. The chemical cleaning part 102a may be provided with a tank for temporarily storing the chemical or a circulation mechanism for circulating the chemical, and the chemical may be temporarily discharged from the chemical tank 114 into the tank and may be introduced from the tank into the chemical tank 114 again by the circulation mechanism when in use. In this case, the circulation mechanism may be provided with a filter or the like to remove foreign matter in the chemical solution. Thus, the chemical solution used once can be repeatedly used to clean the other denitration catalyst. The circulation mechanism may be provided with a concentration meter and/or a pH meter, and the chemical solution may be added depending on the concentration and/or pH of sulfamic acid in the final washing liquid. In addition, the chemical cleaning part 102a shown in the second embodiment can be preferably used in the chemical cleaning part 102 shown in the first embodiment.
In the present embodiment, a configuration and a method of providing separate tanks for performing at least vacuum cleaning and final water cleaning are exemplified as the final cleaning step. The present invention is not limited thereto. The final cleaning step can be performed by providing 1 tank capable of performing the cleaning. Further, when the final cleaning step includes the spray cleaning step, the spray cleaning step can be performed in the 1 tank.
In addition, the present embodiment exemplifies a structure and a method for performing regeneration treatment by removing the denitration catalyst from the denitration plant. The present invention is not limited thereto. The denitration catalyst may be regenerated in a state where the denitration catalyst is installed in the denitration facility. In this case, the chemical liquid and water are supplied to the denitration device, and the waste liquid is recovered from the denitration device.
In the above embodiment, the denitration catalyst regeneration system 100 or 100a may be provided with a chemical solution temperature adjustment mechanism for adjusting the temperature of the chemical solution in the chemical bath 114. By providing the chemical liquid temperature adjusting mechanism, the temperature at which the chemical liquid immersed in the denitration catalyst is washed can be controlled. Thus, the temperature of the chemical solution impregnated in the denitration catalyst can be maintained at normal temperature by the chemical solution temperature adjustment mechanism, and the chemical solution can be heated to be higher than normal temperature.
In the present embodiment, a system including the chemical cleaning unit 102 or the chemical cleaning tank 102a and the final cleaning unit 104 or the vacuuming tank 104a, and a method including the chemical cleaning step and the final cleaning step, which are performed for the denitration catalyst in a dry state, are described as examples. The present invention is not limited thereto. As described above, as one of the reasons why the coarse particles can be effectively removed, it is presumed that the coarse particles and the poisoning material can be effectively removed by reducing the particle diameter of the coarse particles clogged in the gas passage holes of the denitration catalyst by chemical cleaning and then performing vacuum cleaning as the final cleaning step. Therefore, in another embodiment, the present invention can employ a system and a method for regenerating a denitration catalyst that can be subjected to chemical cleaning before vacuuming and cleaning, with the denitration catalyst being the target. For example, in another embodiment according to the present invention, a denitration catalyst regeneration system including a chemical cleaning unit configured to perform chemical cleaning by immersing a denitration catalyst in a chemical containing a fluorine compound, an inorganic acid, and a surfactant, and an evacuation tank configured to immerse a denitration catalyst taken out of the chemical in water in an evacuation tank, seal the tank, and evacuate air in the tank can be employed. Further, a regeneration method may be adopted which includes a chemical cleaning step of immersing the denitration catalyst in a chemical containing a fluorine compound, an inorganic acid, and a surfactant to perform chemical cleaning, and a final cleaning step of immersing the denitration catalyst taken out of the chemical in water in a vacuum tank, sealing the tank, and sucking air in the tank.
In the regeneration system and the regeneration method according to another embodiment of the present invention, by using the chemical solution described in the present specification in the final cleaning step such as the evacuation tank and the evacuation cleaning, it is possible to adopt a regeneration system including an evacuation tank configured to immerse the denitration catalyst in the chemical solution in the evacuation tank and seal the tank to suck the air in the tank, and a regeneration method including the final cleaning step to immerse the denitration catalyst in the chemical solution in the evacuation tank and seal the tank to suck the air in the tank. Thus, the chemical cleaning unit and the chemical cleaning step are omitted, and a more efficient catalyst regeneration system and regeneration method can be provided.
Examples
The present invention will be described in more detail with reference to examples. The method and system for regenerating a denitration catalyst according to the present invention are not limited to the following examples.
1. Verification of the Effect of regeneration I
As example 1, the method for regenerating a denitration catalyst according to the above embodiment was performed on a used denitration catalyst taken out of an actual machine, and as one of the regeneration effects, a change in the clogging rate of the denitration catalyst was examined.
The chemical used for chemical cleaning is prepared by adding ammonium bifluoride (NH) as fluorine compound4HF2) The hydrogen fluoride component (C) was 1.75% by mass, and sulfamic acid (H) as an inorganic acid3NSO3) 3.2% by mass of polyoxyethylene polyoxypropylene glycol as a main componentThe commercially available nonionic surfactant (2) was mixed in an amount of 0.05% by mass to prepare a chemical solution.
1.1. Measurement of the blockage Rate I
The used denitration catalyst was taken out from the actual equipment, and the number of clogged gas vents (cells) was counted by visual observation, whereby the clogging rate of the taken-out denitration catalyst was measured. The blocking rate (%) is calculated using an expression of the number of blocked units/total number of units × 100. As the denitration catalyst, a honeycomb-shaped denitration catalyst (honeycomb denitration catalyst) having gas holes (honeycomb holes) of 5mm square and having a size of 150mm × 150mm × 600mm was used. Next, the denitration catalyst in a dry state was immersed in the chemical solution for 60 minutes at room temperature in the chemical bath. After the chemical cleaning, the denitration catalyst was immersed in water in a vacuum tank, and the air in the tank was sucked at room temperature for 60 minutes while sealing the tank, thereby performing vacuum cleaning. This vacuum cleaning was repeated one more time under the same conditions, and was performed 2 times in total. After vacuum cleaning, the denitration catalyst taken out of the tank was dried at 110 ℃ for 4 hours or more. The clogging ratio of the dried denitration catalyst was measured in the same manner as described above.
Next, the 2 nd used denitration catalyst was taken out from the actual equipment, and the same regeneration treatment and clogging rate measurement were performed on the denitration catalyst in a dry state by repeatedly using the chemical used for chemical cleaning of the 1 st denitration catalyst. As described above, the regeneration treatment was repeated 2 times using the same chemical solution for the 2 nd used denitration catalyst taken out of the actual equipment, and the change in the clogging rate was verified. As comparative example 1, the 3 rd used denitration catalyst was taken out from the actual equipment, and the denitration catalyst in a dry state was subjected to a regeneration treatment of a prewash using water instead of the chemical solution, and the clogging rate thereof was measured. Then, for each denitration catalyst, the blockage removal rate is calculated from the difference in the blockage rate before and after the regeneration treatment. In the calculation of the clogging removal rate, an expression of (1-the number of cells maintaining the clogging state after cleaning/the number of clogging cells before cleaning) × 100 is used. Table 1 below shows the contents of 1 regeneration treatment in example 1 and comparative example 1. The results of the clogging rate and the clogging removal rate are shown in fig. 5 and 6.
[ Table 1]
TABLE 1 regeneration treatment
| Example 1 | Comparative example 1 |
| Cleaning with medicinal liquid | Pre-washing |
| ↓ | ↓ |
| Vacuum pumping | Vacuum pumping |
| ↓ | ↓ |
| Drying | Drying |
1.2. Property I
As shown in fig. 5, the clogging rate was reduced from 17.1% to 0.5% by the 1 st regeneration treatment of the 1 st used denitration catalyst. The clogging rate was reduced from 16.3% to 1.4% by the 2 nd regeneration treatment of the 2 nd used denitration catalyst. On the other hand, the clogging rate of comparative example 1 using water instead of the chemical liquid was reduced from 19.7% to 2.4% only, although the 1 st regeneration treatment was performed. As shown in fig. 6, clogging was removed by 97.2% in the 1 st regeneration treatment and 91.2% in the 2 nd regeneration treatment. On the other hand, in comparative example 1 in which water was used instead of the chemical liquid, the blockage removal rate was 87.8% even though the 1 st regeneration treatment was performed.
From the results, it was found that almost all of coarse particles clogged in the denitration catalyst can be removed by cleaning the used denitration catalyst in a dry state taken out from the actual equipment with a chemical solution containing a fluorine compound, an inorganic acid, and a surfactant, and then performing vacuum cleaning. Further, it was found that even if the same chemical solution is repeatedly used, almost all coarse particles clogged in the 2 nd used denitration catalyst can be removed by cleaning the used denitration catalyst in a dry state taken out from the actual equipment with the chemical solution and by vacuuming the catalyst.
1.3. Measurement of the blockage Rate II
As example 2, in the same manner as in example 1, the used denitration catalyst taken out from the actual equipment was immersed in the chemical solution for 30 minutes at room temperature in the chemical washing tank. A fluorine-based chemical different from that used in example 1 was used as the chemical. After the chemical cleaning, the denitration catalyst was immersed in water in a vacuum tank, and the air in the tank was sucked at room temperature for 60 minutes while sealing the tank, thereby performing vacuum cleaning. This vacuum cleaning was repeated one more time under the same conditions, and was performed 2 times in total. After vacuum cleaning, the denitration catalyst taken out of the tank was dried at 110 ℃ for 4 hours or more. The clogging ratio of the dried denitration catalyst was measured in the same manner as described above. In comparative example 2, the 2 nd used denitration catalyst taken out of the actual equipment was immersed in water in a vacuum tank, and the air in the tank was sucked at room temperature for 60 minutes while sealing the tank, thereby performing vacuum cleaning. This vacuum cleaning was repeated one more time under the same conditions, and was performed 2 times in total. Next, the denitration catalyst was immersed in the same chemical solution as in example 2 for 60 minutes at room temperature in the chemical bath. After the chemical cleaning, the denitration catalyst taken out of the tank was dried at 110 ℃ for 4 hours or more. The clogging ratio of the dried denitration catalyst was measured in the same manner as described above. The contents of 1 regeneration treatment of example 2 and comparative example 2 are shown in table 2 below.
[ Table 2]
TABLE 2 regeneration treatment
| Example 2 | Comparative example 2 |
| Cleaning with medicinal liquid | Vacuum pumping |
| ↓ | ↓ |
| Vacuum pumping | Cleaning with medicinal liquid |
| ↓ | ↓ |
| Drying | Drying |
1.4. Property II
The clogging rate of example 2 was 4.7%, and the clogging rate of comparative example 2 was 7.8%. As a result, it was found that coarse particles clogged in the denitration catalyst can be removed more efficiently when the vacuum cleaning is performed after the chemical cleaning. It is presumed that the chemical liquid reacts with the coarse particles clogged in the denitration catalyst to reduce the size of the coarse particles, so that the subsequent evacuation can be efficiently performed.
2. Verification of the Effect of regeneration II
Next, as example 3, the method for regenerating a denitration catalyst according to the above embodiment was performed on a used denitration catalyst taken out of an actual machine, and as one of the regeneration effects, the degree of recovery of the denitration performance of the denitration catalyst was verified. As an index of the denitration performance of the denitration catalyst, the reaction rate constant of the denitration catalyst is used.
2.1. Measurement of denitration reaction rate constant ratio of denitration catalyst
The reaction rate constant K of an unused denitration catalyst (denitration catalyst in the case of a new product) was obtained in an actual machine0. Next, the 1 st used denitration catalyst in a dry state taken out of the actual equipment was cleaned with the same chemical solution as in example 1, evacuated, and dried, using the same chemical solution as in example 1. Then, the 2 nd used denitration catalyst in a dry state was taken out from the actual apparatus, and the reaction rate constant K was obtained. The denitration catalyst used in the 2 nd cycle was cleaned with the same chemical solution, evacuated, and dried in the same manner. Then, the dried denitration catalyst was finally washed with water at room temperature for 30 minutes using a final water washing liquid prepared so that the concentration of sulfamic acid became 1N, and was dried overnight at 110 ℃. The reaction rate constant K was obtained for the denitration catalyst performance of the dried denitration catalyst. According to the obtained K and K0The denitration reaction rate constant ratio (measured reaction rate constant of the denitration catalyst/reaction rate constant of the denitration catalyst in the case of a new product: K/K) was obtained as the value of (A)0). The reaction rate constant of each sample was measured using a tubular flow-through reaction test apparatus using gases having the properties shown in table 3 below. The results are shown in FIG. 7.
[ Table 3]
TABLE 3 gas behavior
2.2. Property III
As shown in fig. 7, when the denitration reaction rate constant ratio of the non-used denitration catalyst is 1.0, the denitration reaction rate constant ratio of the used denitration catalyst is about 0.5 immediately after the denitration catalyst is taken out from the actual equipment and before the denitration catalyst is cleaned, whereas the denitration reaction rate constant ratio is improved to the same degree as the non-used denitration catalyst after the denitration catalyst is cleaned. Therefore, it is found that the denitration performance of the used catalyst taken out from the actual equipment is restored to the same degree as that of the unused catalyst by the regeneration method according to the above embodiment.
From the results, it was found that by performing final water washing with sulfamic acid-containing water after vacuum washing and chemical liquid washing, the denitration performance of the used denitration catalyst in a dry state taken out from the actual equipment can be restored to the same degree as that of the denitration catalyst not used. It is also found that the 2 nd used denitration catalyst can be recovered to the same extent as the unused denitration catalyst.
3. Verification of strength of denitration catalyst
Next, as example 4, the influence of the regeneration method according to the foregoing embodiment on the strength of the denitration catalyst was estimated by examining the influence on the strength of the pre-washed denitration catalyst.
3.1. Measurement of silica elution amount
The used denitration catalyst taken out of the actual equipment is put into a chemical washing tank in which a chemical solution is stored in a dry state and immersed in the chemical solution. The amount of silica eluted with the time of impregnation was measured by measuring the silica concentration in the chemical solution while impregnating the denitration catalyst. The results are shown in FIG. 7.
3.2. Property IV
As shown in fig. 7, the elution amount of silica from the used denitration catalyst was saturated at a constant value. Generally, as a prewash before vacuuming and cleaning, a treatment is known in which a used denitration catalyst is immersed in water to fill the inside of the denitration catalyst with water. It is known that the chemical liquid is prevented from entering the inside of the denitration catalyst, and the silica in the glass fiber contained in the denitration catalyst can be prevented from dissolving, so that the strength of the denitration catalyst can be prevented (for example, japanese patent application laid-open No. 2011-31237). On the other hand, from the results of the present example, it was found that the concentration of silica eluted from the denitration catalyst was rapidly saturated by the chemical cleaning treatment using the chemical solution. Since the diffusion of the chemical liquid filled in the pores in the denitration catalyst is very slow, the dissolution of silica in the glass fiber rapidly reaches the saturation solubility. That is, from the results of the present example, it can be estimated that the strength of the denitration catalyst can be maintained even when the denitration catalyst in a dry state taken out from the actual apparatus is directly subjected to the chemical cleaning treatment without being subjected to the preliminary cleaning.
Industrial applicability
According to the method for regenerating a denitration catalyst and the system for regenerating a denitration catalyst according to the present invention, it is possible to remove a poisoning substance attached to the denitration catalyst. Further, particles clogged in the denitration catalyst, particularly coarse particles clogged in the gas passage holes of the denitration catalyst, can be removed.
Description of the symbols
100. 100 a-a denitration catalyst regeneration system, 102 a-a chemical liquid cleaning part, 104 a-a final cleaning part, 106-a drying part, 112-a denitration catalyst conveying device, 114-a chemical washing tank, 116-a chemical liquid supply device, 119, 129a, 129 c-a waste liquid tank, 120-a vacuum pump, 124 a-a vacuum-pumping tank, 126 a-a water supply device, 124 c-a final washing tank and 126 c-a final washing liquid supply.
Claims (13)
1. A method for regenerating a denitration catalyst, comprising:
a chemical cleaning step of immersing the denitration catalyst in a chemical containing a fluorine compound, an inorganic acid, and a surfactant in a dry state to perform chemical cleaning.
2. The method for regenerating a denitration catalyst according to claim 1, further comprising:
and a final cleaning step of immersing the denitration catalyst taken out of the chemical solution in water in a vacuum tank, and sealing the tank to suck air in the tank.
3. The method of regenerating a denitration catalyst according to claim 1 or 2,
the amount of the fluorine compound is 1 to 10% by mass relative to the entire chemical solution, the amount of the inorganic acid is added so that the pH value of the chemical solution is in the range of 1 to 6, and the amount of the surfactant is 0.001 to 10% by mass relative to the entire chemical solution.
4. The method of cleaning a denitration catalyst according to claim 2,
the final cleaning step further comprises: and a final washing step of washing the denitration catalyst taken out from the vacuum tank with water or water containing a sulfonamide as a washing liquid after the washing in the vacuum tank.
5. The method of regenerating a denitration catalyst according to any one of claims 1 to 4,
in the chemical cleaning step, the denitration catalyst removed from the denitration device is directly immersed in the chemical cleaning tank to be cleaned.
6. The method of regenerating a denitration catalyst according to any one of claims 1 to 5,
the surfactant is a nonionic surfactant containing polyoxyethylene polyoxypropylene glycol, a polyoxyethylene derivative or a polyalkylene glycol derivative as a main component, or an anionic surfactant containing polyoxyethylene alkyl ether phosphate as a main component.
7. The method of regenerating a denitration catalyst according to any one of claims 1 to 6,
the fluorine compound is ammonium bifluoride, the inorganic acid is sulfamic acid, and the surfactant is a nonionic surfactant with polyoxyethylene polyoxypropylene glycol as a main component.
8. The method of regenerating a denitration catalyst according to any one of claims 1 to 7,
in the chemical cleaning step, the chemical is repeatedly used.
9. A denitration catalyst regeneration system is characterized by at least comprising:
the chemical cleaning section is configured to perform chemical cleaning by immersing the denitration catalyst in a dry state in a chemical containing a fluorine compound, an inorganic acid, and a surfactant.
10. The denitration catalyst regeneration system according to claim 9, further comprising:
and a vacuuming tank configured to immerse the denitration catalyst taken out of the chemical solution in water in the vacuuming tank, and to seal the tank to suck air in the tank.
11. The regeneration system of a denitration catalyst according to claim 9 or 10,
the fluorine compound is ammonium bifluoride, the amount of the ammonium bifluoride is 1-10% by mass relative to the whole liquid medicine, the amount of the inorganic acid is added in a mode that the pH value of the liquid medicine is in a range of 1-6, and the amount of the surfactant is 0.001-10% by mass relative to the whole liquid medicine.
12. The denitration catalyst regeneration system according to claim 10, further comprising:
and a final washing tank for finally washing the denitration catalyst taken out of the vacuum tank with water or water containing sulfamic acid as a final washing liquid.
13. The regeneration system of a denitration catalyst according to any one of claims 9 to 12,
the chemical cleaning unit is configured to clean the denitration catalyst removed from the denitration device by directly immersing the denitration catalyst in the chemical washing tank.
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| JP2018011675A JP7013258B2 (en) | 2017-06-30 | 2018-01-26 | Denitration catalyst regeneration method and denitration catalyst regeneration system |
| PCT/JP2018/024004 WO2019004123A1 (en) | 2017-06-30 | 2018-06-25 | Regeneration method for denitration catalyst and regeneration system for denitration catalyst |
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| JP2020163242A (en) * | 2019-03-28 | 2020-10-08 | 三菱日立パワーシステムズ株式会社 | Regeneration process of denitration catalyst, and regeneration system of denitration catalyst |
| JP2021079341A (en) * | 2019-11-20 | 2021-05-27 | 三菱パワー株式会社 | Catalyst cleaning method, catalyst cleaning apparatus and program |
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