CN113842954A - Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof - Google Patents
Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof Download PDFInfo
- Publication number
- CN113842954A CN113842954A CN202010600214.8A CN202010600214A CN113842954A CN 113842954 A CN113842954 A CN 113842954A CN 202010600214 A CN202010600214 A CN 202010600214A CN 113842954 A CN113842954 A CN 113842954A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- desulfurization
- denitration
- carrier
- pure water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 172
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 71
- 230000023556 desulfurization Effects 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000011069 regeneration method Methods 0.000 title claims abstract description 23
- 230000004913 activation Effects 0.000 title claims abstract description 20
- 238000001994 activation Methods 0.000 title claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 63
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002994 raw material Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 42
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 42
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 21
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 21
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 21
- 239000002912 waste gas Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000919 ceramic Substances 0.000 claims description 13
- 239000000835 fiber Substances 0.000 claims description 13
- 239000000428 dust Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 239000011572 manganese Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910000616 Ferromanganese Inorganic materials 0.000 description 4
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 244000089742 Citrus aurantifolia Species 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The desulfurization and denitration catalyst comprises raw materials, wherein the raw materials comprise 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid, and the raw materials are calculated by taking the total weight as 100 wt%, and can remove sulfur dioxide and nitrogen oxides in waste gas with good efficiency in an environment with the temperature of below 250 ℃ and moisture. In addition, the invention also provides a preparation method, an activation method and a regeneration method of the desulfurization and denitration catalyst, and a device containing the desulfurization and denitration catalyst. The catalyst for desulfurization and denitration can be prepared by the preparation method, the waste gas can be treated by the catalyst device, and the desulfurization and denitration efficiency of the catalyst for desulfurization and denitration can be simply recovered by the activation method and the regeneration method along with the increase of the service time.
Description
Technical Field
The invention relates to a catalyst, a device containing the catalyst, and a preparation and treatment method of the catalyst, in particular to a catalyst for desulfurization and denitration, a catalyst device, and a preparation, activation and regeneration method of the catalyst.
Background
After the boiler in the factory is subjected to combustion operation, waste gas with a temperature as high as 200 ℃ to 1400 ℃ is generated, heat recovery is often performed on the waste gas in order to properly use heat energy in the waste gas, and the recovered heat energy is used for power generation. The temperature of the waste gas after heat recovery is usually reduced to below 200 ℃, and dust, sulfur dioxide and nitrogen oxides in the waste gas need to be removed before the waste gas is discharged, so that environmental and air pollution is avoided. Generally, limestone and alkaline agent are mostly used to remove sulfur dioxide in exhaust gas (i.e. lime method), which has the disadvantage of easily generating sludge, increasing the cost of subsequent treatment. In the aspect of removing nitrogen oxides, studies have been conducted to indicate that manganese (Mn) has a better denitration activity in a low-temperature environment of 250 ℃ or lower, and is a better catalyst.
Because the low temperature environment may contain moisture, manganese is easily occupied by moisture at the reaction position, and is easily poisoned by sulfur dioxide to reduce the denitration efficiency, the waste gas after heat recovery needs to be heated to more than 300 ℃ to avoid the influence of moisture on the catalyst. In addition, the denitration efficiency of the catalyst will decrease with the increase of the usage time, and the honeycomb carrier combined with the catalyst is required to be newly manufactured or calcined at a temperature higher than 300 ℃ to recover the denitration efficiency of the catalyst. However, the existing method will increase the maintenance cost and extra energy consumption, and make the desulfurization and denitration equipment more likely to be damaged by high temperature, and the improvement is needed.
Disclosure of Invention
The invention aims to provide a desulfurization and denitration catalyst which has desulfurization and denitration functions in a low-temperature environment with the temperature of below 250 ℃ and moisture.
The invention relates to a catalyst for desulfurization and denitration, which comprises: the raw material comprises, by taking the total weight as 100 wt%, 40-60 wt% of manganese acetate, 20-30 wt% of ferric nitrate and 20-30 wt% of oxalic acid.
The invention relates to a device of a desulfurization and denitration catalyst, which is suitable for removing dust, sulfur dioxide and nitrogen oxide in waste gas and comprises a carrier and the catalyst attached to the carrier. The catalyst comprises raw materials, wherein the raw materials comprise 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid, and when the waste gas passes through the carrier, the waste gas forms emission gas for removing dust, sulfur dioxide and nitrogen oxides.
The preparation method of the desulfurization and denitration catalyst comprises a preparation step, a mixing step and a stirring step. In the preparation step, a raw material is prepared, and the raw material contains 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate, and 20 wt% to 30 wt% of oxalic acid, based on the total weight of 100 wt%. In the mixing step, the raw material and pure water are mixed in a weight ratio of 1: 0.75 to 1: 1.5, mixing to form a mixed solution. In the stirring step, the mixed solution is stirred at normal temperature, so that the raw materials are completely dissolved in pure water to prepare the catalyst solution.
The invention relates to an activation method of a desulfurization and denitration catalyst, which is suitable for activating the catalyst of a catalyst device and comprises the steps of pre-processing, material preparation, leaching and drying. Preparing the catalyst device in the pre-step, wherein the catalyst device comprises a carrier and the catalyst attached to the carrier, and the catalyst is provided with raw materials, and the raw materials comprise 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid based on 100 wt% of the total weight. In the preparation step, pure water having the same weight as that of the catalyst device is prepared. In the leaching step, pure water is leached on the catalyst device, so that the catalyst device is fully contacted with the pure water. And in the drying step, drying the catalyst device.
The invention relates to a regeneration method of a desulfurization and denitration catalyst, which is suitable for regenerating the catalyst of a catalyst device and comprises a pretreatment step, a preparation step and an impregnation step. In the pretreatment step, the catalyst device including a carrier to which the catalyst is attached is prepared. In the preparation step, a raw material and pure water are prepared, the raw material contains 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate, and 20 wt% to 30 wt% of oxalic acid, based on the total weight of 100 wt%, and the raw material and pure water are mixed in a ratio of 1: 0.75 to 1: 1.5 by weight and stirred to form the catalyst liquid. In the impregnation step, the catalyst liquid is sprayed on the carrier, so that the catalyst liquid is uniformly attached to the carrier.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the catalyst for desulfurization and denitration further comprises pure water, and the weight ratio of the raw material to the pure water is 1: 0.75 to 1: 1.5.
preferably, in the device for preparing the desulfurization and denitration catalyst, the carrier is a honeycomb filter, a filter cloth, a ceramic fiber filter tube, or a ceramic fiber filter cake.
Preferably, in the step of mixing, the weight ratio of the raw material to pure water is 1: 1.
preferably, the method for activating a desulfurization/denitration catalyst further comprises a regeneration step after the drying step, wherein in the regeneration step, the ratio of the raw material to pure water is controlled in a range of 1: 0.75 to 1: 1.5, stirring into catalyst liquid, and spraying the catalyst liquid on the carrier to uniformly attach the catalyst liquid on the carrier.
The invention has the beneficial effects that: the desulfurization and denitration catalyst can remove sulfur dioxide and nitrogen oxide with good efficiency in an environment with the temperature of below 250 ℃ and moisture, can be prepared by the preparation method, and can treat the waste gas by the catalyst device. When the desulfurization and denitrification efficiency of the desulfurization and denitrification catalyst decreases with an increase in the operating time, the desulfurization and denitrification efficiency of the desulfurization and denitrification catalyst can be easily recovered by the activation method and the regeneration method. The waste gas can be more efficiently treated, the energy consumption can be reduced, the carrier of the catalyst device is prevented from being damaged by high temperature, and the equipment cost is further saved.
Drawings
FIG. 1 is a process flow diagram illustrating one embodiment of a process for preparing a desulfurization, nitration catalyst of the present invention;
FIG. 2 is a schematic cross-sectional view of one embodiment of a desulfurization and denitrification catalyst assembly in accordance with the present invention;
FIG. 3 is a plot illustrating the denitration efficiency of an embodiment of the apparatus in a moisture-containing environment;
FIG. 4 is a process flow diagram illustrating one embodiment of a method for activating a desulfurization/denitrification catalyst in accordance with the present invention;
FIG. 5 is a comparative graph illustrating the desulfurization efficiency of an embodiment of the apparatus after activation with multiple instances of an embodiment of the activation method; and
FIG. 6 is a process flow diagram illustrating an example of a method for regenerating a desulfurization/denitration catalyst according to the present invention.
Detailed Description
The invention is described in detail below with reference to the following figures and examples:
referring to fig. 1, an embodiment of a method for preparing the desulfurization/denitration catalyst of the present invention is an embodiment of an article suitable for preparing the desulfurization/denitration catalyst of the present invention. The catalyst for desulfurization and denitration is suitable for low-temperature environment with temperature below 250 ℃ and containing water vapor, and is matched with Selective Catalytic Reduction (SCR) to carry out desulfurization and denitration, SO as to remove sulfur dioxide (SO) in waste gas2) And Nitrogen Oxide (NO)x). It should be noted that the preferred usage of the desulfurization and denitration catalyst is to perform desulfurization first and then denitration to avoid the problem of desulfurizationThe catalyst for desulfurization and denitration is poisoned by sulfur dioxide, thereby reducing denitration efficiency.
The method for preparing the desulfurization and denitration catalyst comprises a preparation step S11, a mixing step S12, and a stirring step S13. The catalyst for desulfurization and denitration comprises a raw material and pure water, wherein the weight ratio of the raw material to the pure water is 1: 0.75 to 1: 1.5, the raw material comprises 40 to 60 weight percent of manganese acetate, 20 to 30 weight percent of ferric nitrate and 20 to 30 weight percent of oxalic acid, wherein the total weight of the raw material is 100 weight percent.
In the preparation step S11, the raw material is prepared, and the raw material contains 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate, and 20 wt% to 30 wt% of oxalic acid, based on the total weight of 100 wt%. In the mixing step S12, the raw material and pure water are mixed in a weight ratio of 1: 0.75 to 1: 1.5, mixing to form a mixed solution. In the stirring step S13, the mixed solution is stirred at room temperature to completely dissolve the raw material in pure water, thereby obtaining a catalyst solution.
In the preparation method example and the article example, the raw material includes 50 wt% of manganese acetate, 25 wt% of iron nitrate, and 25 wt% of oxalic acid, based on 100 wt% of the total weight, however, in other embodiments, the component ratio of the raw material is not limited thereto. Manganese is a main active component for desulfurization and denitration reaction in a low-temperature environment, and can effectively capture (combine) sulfur dioxide and nitrogen oxide in the waste gas. In addition, the oxalic acid can effectively dissolve the manganese acetate and can dissolve redundant metal deposits, so that the manganese can be uniformly distributed in the catalyst liquid, the desulfurization and denitration efficiency of the catalyst 2 can be improved, and the subsequent utilization of the embodiment of the article, such as spraying or regeneration, can be facilitated.
In the preparation method embodiment and the article embodiment, pure water with RO grade or above is adopted to avoid excessive impurities in the water and further influence the activity of the catalyst liquid. In addition, in each of the embodiments of the preparation method and the article embodiment, the user can adjust the weight ratio of the raw material to the pure water according to the use requirement (for example, the material or the type of the carrier to which the catalyst liquid is attached), so as to adjust the catalyst liquid with different concentrations. For example, when the weight ratio of the raw material to pure water is 1: at 0.75, the catalyst liquid is in a thick syrup state, and the weight ratio of the raw material to the pure water is 1: 1.5, the weight ratio of the raw material to pure water is 1: the catalyst liquid of 0.75% contains a higher proportion of the raw material, can exert better desulfurization and denitrification efficiency, and is helpful for the catalyst liquid to permeate into the pores of a carrier and stay therein.
Referring to FIG. 2, an embodiment of the desulfurization and denitration catalyst device of the present invention is suitable for removing dust, sulfur dioxide and nitrogen oxides from an exhaust gas. The desulfurization and denitration catalyst device comprises a carrier 1 and a catalyst 2 attached to the carrier 1. The catalyst 2 comprises a raw material, wherein the raw material comprises 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid, wherein the total weight is 100 wt%.
It should be noted that in the present embodiment of the apparatus, the article embodiment and the carrier 1 are treated by a wet impregnation method and then calcined to attach the article embodiment to the carrier 1, in the present embodiment of the apparatus, the carrier 1 is a ceramic fiber filter tube, however, in other embodiments, the carrier 1 may be in the form of a honeycomb filter, a filter cloth, or a ceramic fiber filter cake, and the like, and the invention is not limited thereto. It should be noted that, when the carrier 1 is a filter cloth, the applicable temperature of the carrier 1 is 150 ℃ to 220 ℃, and when the carrier 1 is a ceramic fiber filter tube, a honeycomb filter, or a ceramic fiber filter cake, the applicable temperature of the carrier 1 is 150 ℃ to 300 ℃, which is indeed effective to lower the applicable temperature of the embodiments of the apparatus and the embodiments of the article compared to the prior art that must be heated to 300 ℃ or higher.
In practical operation, the waste gas containing dust, sulfur dioxide and nitrogen oxide passes through the carrier 1, the dust is filtered by the porous material of the carrier 1, and the catalyst 2 has good capability of capturing sulfur dioxide, so that sulfur dioxide can be adsorbed on the carrier 1, subsequent elements are prevented from being poisoned by sulfur dioxide, the denitration efficiency of the catalyst 2 is reduced, and the denitration efficiency of the catalyst 2 can be prolongedThe time of use. The nitrogen oxide in the waste gas is catalyzed by the catalyst 2 and reduced into nontoxic nitrogen and water, so that the waste gas forms a discharge gas which can remove dust, sulfur dioxide and nitrogen oxide and meets the environmental protection discharge standard, namely the granular pollutant is lower than 30mg/Nm3Sulfur oxide concentrations below 50ppm (parts per million concentration), and nitrogen oxides below 100 ppm.
The embodiment of the device is applied to a low-temperature environment with the water-gas content of 0-15% and the temperature of 150-300 ℃, and the desulfurization and denitrification efficiency of the carrier 1 is tested. The desulfurization efficiency can reach 95 to 100 percent of excellent efficiency in a low-temperature environment with the water-gas content of 0 to 15 percent and the temperature of 150 to 300 ℃, and the denitration efficiency is shown in the following table I.
For a better understanding of the invention, the following examples are given by way of illustration and are not intended to limit the invention:
[ Experimental example ]
In this experimental example, a ceramic fiber filter tube was selected as the carrier 1, and the weight ratio of the raw material to pure water was selected to be 1: 0.75 example of the article was used as the catalyst 2, and the raw material of the catalyst 2 had 50 wt% of manganese acetate, 25 wt% of iron nitrate, and 25 wt% of oxalic acid. In this experimental example, the article example and the carrier 1 were treated by a wet impregnation method and calcined to attach the catalyst 2 to the carrier 1, and the denitration efficiency of the carrier 1 was tested in an environment having a moisture content of 5% to 15% and a temperature of 150 ℃ to 300 ℃.
Referring to FIG. 2 and FIG. 3, it can be seen that the ceramic fiber filter tube combined with ferromanganese catalyst is in [ O ]2]10%, and a space flow rate (0 deg.C) of 2,250h-1Under the test conditions of (1), when the operation temperature is 150 ℃, the denitration efficiency of the ceramic fiber filter tube combined with the ferromanganese catalyst can reach more than 80 percent and more than 10 percent in an environment containing 15 percent of water gasThe moisture content in the environment can reach more than 90 percent, and the moisture content in the environment containing 5 percent of moisture can reach more than 95 percent. The denitration efficiency of the ceramic fiber filter tube combined with the ferromanganese catalyst can reach 98 to 99 percent when the operation temperature is 200 to 300 ℃.
As the operation time of the article embodiment and the apparatus embodiment increases, the dust and the sulfur dioxide in the exhaust gas gradually deposit on the surfaces of the carrier 1 and the catalyst 2, and the contact area between the catalyst 2 and the exhaust gas is reduced, so that the desulfurization and denitration efficiency of the catalyst 2 is reduced, and the catalyst 2 of the apparatus embodiment is activated by an activation method embodiment of the desulfurization and denitration catalyst activation method of the present invention, so as to recover the desulfurization and denitration efficiency of the catalyst 2 and prolong the operation time of the catalyst 2.
Referring to fig. 2 and 4, an embodiment of the method for activating a denitration catalyst according to the present invention is suitable for activating the catalyst 2 of the apparatus embodiment, and includes a pre-step S21, a material preparation step S22, a rinsing step S23, and a drying step S24.
The catalyst device is prepared in the pre-step S21, the catalyst device includes a carrier 1, and the catalyst 2 attached to the carrier 1, the catalyst 2 has a raw material containing, by total weight of 100 wt%, 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate, and 20 wt% to 30 wt% of oxalic acid. In the preparation step S22, pure water having the same weight as that of the catalyst device is prepared. In the rinsing step S23, pure water is rinsed on the catalytic device, so that the catalytic device is fully contacted with the pure water. In the drying step S24, the catalyst device is dried. In the example of the activation method, the raw material includes 50 wt% of manganese acetate, 25 wt% of ferric nitrate, and 25 wt% of oxalic acid, based on 100 wt% of the total weight, however, in other embodiments, the component ratio of the raw material is not limited thereto.
It should be noted that, in the embodiment of the activation method, in the rinsing step S23, pure water with a RO grade or higher is slowly poured onto the catalyst device, so that both the carrier 1 and the catalyst 2 can sufficiently contact with RO water to remove dust deposited on the surface of the carrier 1, and remove sulfur dioxide and surface ammonium salts captured by the catalyst 2, thereby recovering the contact area between the catalyst device and the exhaust gas and recovering the desulfurization and denitration efficiency of the catalyst device. In addition, in another embodiment of the present activation method embodiment, a regeneration step S25 is further included after the drying step S24, and when the catalyst 2 is activated for a plurality of times and it is difficult to recover the desulfurization and denitration efficiency, the catalyst 2 can be regenerated in the regeneration step S25. In the regeneration step S25, the raw material and pure water are mixed in a ratio of 1: 0.75 to 1: 1.5 to form a catalyst liquid, and then spraying the catalyst liquid on the carrier 1 to make the catalyst liquid uniformly adhere to the carrier 1.
Referring to FIG. 2 and FIG. 5, it can be seen that2]10% and the space flow rate (0 ℃) 2,250h-1Under the test conditions that the operating temperature is 160 ℃ and the sulfur dioxide concentration is 200ppm, the ceramic fiber filter tube combined with the ferromanganese catalyst can effectively capture 200ppm of sulfur dioxide, and the sulfur dioxide concentration in the test environment can be kept below 50ppm within one hour after the test is started, namely, the standard meets the emission standard of the regulation. When the sulfur dioxide concentration in the test environment rises with the increase of the service time and finally reaches 200ppm, which means that the catalyst 2 has been temporarily inactivated due to the deposition of dust and sulfur dioxide, the sulfur dioxide capturing capacity of the catalyst 2 can be recovered by the embodiment of the activation method.
From the test results, it can be seen that, compared with the existing lime method, the catalyst 2 of the embodiment of the apparatus has better sulfur dioxide capturing ability, the capturing ability of the catalyst 2 can be easily recovered by the embodiment of the activation method, and after the activation by water washing, the capability of the catalyst 2 for capturing sulfur dioxide is not substantially different from that of the brand-new catalyst 2, so that the carrier 1 and the catalyst 2 of the embodiment of the apparatus can be reused for many times, the frequency of remanufacturing the embodiment of the apparatus can be effectively reduced, the maintenance or updating cost of the equipment can be greatly reduced, and the sludge treatment cost generated by the existing lime method can be greatly reduced. It is worth mentioning that the embodiment of the activation method can be directly operated on the site of desulfurization and denitrification equipment, and has the advantage of convenient operation.
Referring to fig. 2 and fig. 6, when the catalyst 2 of the device embodiment ages with the increase of the usage time and times and it is difficult to recover the desulfurization and denitration efficiency by the activation method embodiment, the catalyst 2 of the device embodiment can be regenerated by the regeneration method embodiment of the regeneration method of the desulfurization and denitration catalyst of the invention and the article embodiment, so that the carrier 1 can be coated with a new catalyst 2 again and the usage time of the carrier 1 is prolonged.
The regeneration method embodiment of the regeneration method of the desulfurization and denitration catalyst of the invention is suitable for regenerating the catalyst 2 of the device embodiment by the article embodiment, and comprises a pretreatment step S31, a preparation step S32 and an impregnation step S33. The catalyst device including a carrier 1 to which the catalyst 2 is attached is prepared in the preprocessing step S31. In the preparation step S32, a raw material and pure water are prepared, the raw material contains, based on 100 wt% of the total weight, 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate, and 20 wt% to 30 wt% of oxalic acid, and the raw material and pure water are mixed in a ratio of 1: 0.75 to 1: 1.5 by weight and stirred to form a catalyst liquid. In the impregnation step S33, the catalyst liquid is sprayed on the carrier 1 to uniformly adhere the catalyst liquid to the carrier 1. In the embodiment of the regeneration method, the raw material comprises 50 wt% of manganese acetate, 25 wt% of ferric nitrate, and 25 wt% of oxalic acid, based on 100 wt% of the total weight, however, in other embodiments, the component ratio of the raw material is not limited thereto.
That is, the example recycling method is the example article made by the example preparation method and the example article is sprayed onto the example apparatus. It is worth mentioning that the embodiment of the regeneration method can be directly operated on the site of the desulfurization and denitration device, which has the advantage of convenient operation, and the embodiment of the article does not need to be calcined, so long as the temperature of the tail gas in the device (about 200 ℃) is utilized, the manganese with the desulfurization and denitration functions in the embodiment of the article can be coated on the carrier 1 of the embodiment of the device again, the desulfurization and denitration efficiency of the embodiment of the article is recovered, and the carrier 1 of the embodiment of the device can be prevented from being damaged due to the influence of the high temperature higher than 300 ℃ in the calcining process.
Claims (9)
1. A catalyst for desulfurization and denitration; the method is characterized in that: the desulfurization and denitration catalyst comprises:
the raw material comprises, by taking the total weight as 100 wt%, 40-60 wt% of manganese acetate, 20-30 wt% of ferric nitrate and 20-30 wt% of oxalic acid.
2. The desulfurization/denitrification catalyst according to claim 1, wherein: the water-based paint also comprises pure water, wherein the weight ratio of the raw materials to the pure water is 1: 0.75 to 1: 1.5.
3. the device of a catalyst for desulfurization and denitration is suitable for removing dust, sulfur dioxide and nitrogen oxide in waste gas; the method is characterized in that: the device for the desulfurization and denitration catalyst comprises:
a carrier; and
and a catalyst attached to the carrier, the catalyst comprising a raw material having, based on 100 wt% of the total weight, 40 to 60 wt% of manganese acetate, 20 to 30 wt% of ferric nitrate, and 20 to 30 wt% of oxalic acid, such that when the exhaust gas passes through the carrier, an exhaust gas from which dust, sulfur dioxide, and nitrogen oxides are removed is formed.
4. The apparatus for desulfurizing and denitrating a catalyst as set forth in claim 3, wherein: the carrier is a honeycomb filter, a filter cloth, a ceramic fiber filter tube or a ceramic fiber filter cake.
5. A method for preparing a desulfurization and denitration catalyst; the method is characterized in that: the preparation method of the desulfurization and denitration catalyst comprises the following steps:
a preparation step of preparing a raw material, wherein the raw material contains 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid, based on the total weight of 100 wt%;
mixing, namely mixing the raw materials with pure water in a weight ratio of 1: 0.75 to 1: 1.5, mixing to form a mixed solution; and
and a stirring step of stirring the mixed solution at normal temperature to completely dissolve the raw materials in pure water to prepare the catalyst solution.
6. The method for preparing a desulfurization/denitrification catalyst as set forth in claim 5, wherein: in the mixing step, the weight ratio of the raw materials to pure water is 1: 1.
7. a method for activating a catalyst for desulfurization and denitration, which is suitable for activating the catalyst of a catalyst device; the method is characterized in that: the activation method of the desulfurization and denitration catalyst comprises the following steps:
a preliminary step of preparing the catalyst device including a carrier, and the catalyst attached to the carrier, the catalyst having a raw material containing, by total weight of 100 wt%, 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of iron nitrate, and 20 wt% to 30 wt% of oxalic acid;
a material preparation step, namely preparing pure water with the same weight as the catalyst device;
a leaching step, wherein pure water is poured on the catalyst device to make the catalyst device fully contact with the pure water; and
and a drying step, drying the catalyst device.
8. The method for activating a desulfurization/denitrification catalyst according to claim 7, wherein: further comprising a regeneration step after the drying step, wherein in the regeneration step, the raw material and pure water are mixed in a ratio of 1: 0.75 to 1: 1.5, stirring into catalyst liquid, and spraying the catalyst liquid on the carrier to uniformly attach the catalyst liquid on the carrier.
9. A regeneration method of a desulfurization and denitration catalyst is suitable for regenerating the catalyst of a catalyst device; the method is characterized in that: the regeneration method of the desulfurization and denitration catalyst comprises the following steps:
a pretreatment step of preparing the catalyst device including a carrier to which the catalyst is attached;
preparing raw materials and pure water, wherein the raw materials comprise 40 wt% to 60 wt% of manganese acetate, 20 wt% to 30 wt% of ferric nitrate and 20 wt% to 30 wt% of oxalic acid, and the weight ratio of the raw materials to the pure water is 1: 0.75 to 1: 1.5 weight ratio and stirring into catalyst liquid; and
and an impregnation step, namely spraying the catalyst liquid on the carrier to uniformly attach the catalyst liquid on the carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010600214.8A CN113842954A (en) | 2020-06-28 | 2020-06-28 | Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010600214.8A CN113842954A (en) | 2020-06-28 | 2020-06-28 | Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113842954A true CN113842954A (en) | 2021-12-28 |
Family
ID=78972765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010600214.8A Pending CN113842954A (en) | 2020-06-28 | 2020-06-28 | Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113842954A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200833419A (en) * | 2007-02-15 | 2008-08-16 | China Steel Corp | Regenerating method of plate-shaped catalyst for denitration and dedioxin |
| CN107921420A (en) * | 2015-07-10 | 2018-04-17 | 三菱日立电力系统株式会社 | The renovation process of denitrating catalyst and the cleaning agent of the regenerative system of denitrating catalyst and denitrating catalyst |
| CN109092323A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application |
| CN109833882A (en) * | 2017-11-27 | 2019-06-04 | 中国石油化工股份有限公司 | Catalyst for denitrating flue gas and preparation method thereof |
| TWM587563U (en) * | 2019-08-21 | 2019-12-11 | 富利康科技股份有限公司 | Ceramic fiber filter tube having low-temperature moisture-proof denitration catalyst |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN210278800U (en) * | 2019-02-02 | 2020-04-10 | 富利康科技股份有限公司 | Low-temperature catalyst denitration dust removal equipment with pottery fine filter tube |
-
2020
- 2020-06-28 CN CN202010600214.8A patent/CN113842954A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200833419A (en) * | 2007-02-15 | 2008-08-16 | China Steel Corp | Regenerating method of plate-shaped catalyst for denitration and dedioxin |
| CN107921420A (en) * | 2015-07-10 | 2018-04-17 | 三菱日立电力系统株式会社 | The renovation process of denitrating catalyst and the cleaning agent of the regenerative system of denitrating catalyst and denitrating catalyst |
| CN109092323A (en) * | 2017-06-20 | 2018-12-28 | 中国石油化工股份有限公司 | Low-temperature SCR catalyst for denitrating flue gas and its preparation method and application |
| CN109833882A (en) * | 2017-11-27 | 2019-06-04 | 中国石油化工股份有限公司 | Catalyst for denitrating flue gas and preparation method thereof |
| CN110605122A (en) * | 2018-06-14 | 2019-12-24 | 中国石油化工股份有限公司 | Low-temperature flue gas denitration catalyst and preparation method and application thereof |
| CN210278800U (en) * | 2019-02-02 | 2020-04-10 | 富利康科技股份有限公司 | Low-temperature catalyst denitration dust removal equipment with pottery fine filter tube |
| TWM587563U (en) * | 2019-08-21 | 2019-12-11 | 富利康科技股份有限公司 | Ceramic fiber filter tube having low-temperature moisture-proof denitration catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0159959B1 (en) | Method for recovering denitrating catalyst for ammonia catalytic reduction | |
| KR101271105B1 (en) | Methods of recycling a catalyst | |
| KR101345444B1 (en) | Remanufactured scr aged catalyst by in-situ technology | |
| WO2008012878A1 (en) | Apparatus for removing of trace of toxic substance from exhaust gas and method of operating the same | |
| CA2182331A1 (en) | Method and apparatus for treating combustion exhaust gases | |
| JP2002143685A (en) | Method for manufacturing catalyst for selective catalytic reduction of nitrogen oxides | |
| CN102974368A (en) | Deactivated SCR denitration catalyst regeneration method | |
| US9421525B2 (en) | Exhaust gas treatment catalyst | |
| CN106000100A (en) | Method for regenerating ineffective SCR catalyst under negative pressure condition | |
| JP2012024669A (en) | Method for regenerating denitration catalyst | |
| JP5386096B2 (en) | Exhaust gas treatment catalyst | |
| CN210278800U (en) | Low-temperature catalyst denitration dust removal equipment with pottery fine filter tube | |
| CN113842954A (en) | Catalyst and catalyst device for desulfurization and denitration, and preparation, activation and regeneration methods thereof | |
| US6814948B1 (en) | Exhaust gas treating systems | |
| CN103599816A (en) | Cleaning agent and cleaning method for off-line cleaning calcium-poisoned SCR (Selective Catalytic Reduction) denitration catalyst | |
| CN113477083B (en) | Regeneration method of inactivated denitration dedusting ceramic tube | |
| TWM603389U (en) | Ceramic fiber filter tube with desulfurization and de-nitration catalyst | |
| TWI771685B (en) | Desulfurization, nitrification catalyst and catalyst device, and preparation, activation and regeneration method thereof | |
| CN104826494A (en) | Regeneration method for flue gas SCR de-nitration catalyst filtering element | |
| CN111790363B (en) | TiO2Nanotube and preparation method thereof, denitration catalyst and preparation method and application thereof | |
| JPS58247A (en) | Regenerating method for denitrating catalyst | |
| JPH10156192A (en) | Activity regenerating method of catalyst for eliminating nitrogenoxides and device therefor | |
| KR100382051B1 (en) | Catalyst for Selective Catalytic Reduction of Nitrogen Oxides Including Sulfur Dioxide at Low Temperature | |
| JP2000024520A (en) | Regeneration of denitration catalyst and regenerated catalyst | |
| US20080248943A1 (en) | Method of Regenerating Thermally Deteriorated Catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |