CN112121872A - Forming process for low-temperature NOx rapid alternate adsorption-regeneration catalyst - Google Patents
Forming process for low-temperature NOx rapid alternate adsorption-regeneration catalyst Download PDFInfo
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- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
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- 239000002253 acid Substances 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
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- 238000007873 sieving Methods 0.000 claims description 5
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- 238000001125 extrusion Methods 0.000 claims description 4
- 239000002241 glass-ceramic Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
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- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 21
- 239000003546 flue gas Substances 0.000 abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 19
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
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- 230000009471 action Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
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Abstract
The invention relates to a catalyst forming technology for removing nitrogen oxides in flue gas, and particularly discloses a forming process for a low-temperature NOx rapid alternate adsorption-regeneration catalyst. Dissolving soluble copper salt or/and cobalt salt, soluble cerium salt, other metal salt, citric acid or/and propylene glycol and pore-forming agent in water, fully stirring, drying, extruding and forming, crushing to obtain raw catalyst particles, and roasting to prepare the composite metal oxide catalyst; extruding the fiber paper into a wavy shape, coating aluminum sol or silica gel on the fiber paper, and drying. Dispersing the catalyst into the aluminum sol, and brushing the surface of the fiber paper; the invention not only utilizes the good permeability of the porous catalyst to prevent the flue gas from blocking the catalyst pore channel when flowing through the catalyst, but also can effectively promote the catalyst to adsorb NOx in the flue gas and improve the NOx adsorption efficiency of the catalyst.
Description
Technical Field
The invention relates to a catalyst forming technology for removing nitrogen oxides in flue gas, in particular to a forming process for low-temperature NOx rapid alternate adsorption-regeneration catalyst.
Background
With the development of economy in China, the requirements of the quality of life of the nation are improved, the pressure brought by environmental pollution is increased day by day, and the treatment level of nitrogen oxide is closely related to the quality of the atmospheric environment in China as one of the main pollutants of the current atmospheric pollution. The coal-fired power plant is used as a main pollution source for concentrated emission of nitrogen oxides, emission reduction of the nitrogen oxides in the emitted flue gas becomes an important target for treatment at present, flue gas denitrification also becomes a necessary environment-friendly facility for the coal-fired power plant, and the facility usually adopts NH3Denitration by SCR (ammonia Selective catalytic reduction) denitration technology based on NH3Or urea is used as a reducing agent to reduce NOx into N under the action of a catalyst2Thereby achieving the purpose of removing nitrogen oxide. NH adopted by industrial coal-fired power plant at present3The SCR catalyst is generally a V-W-Ti catalyst, but the optimum reaction temperature of the catalyst needs to be about 350 ℃. At present, no mature technology exists for treating low-temperature flue gas. The most applied low-temperature flue gas is an active coke/active carbon method, the method adopts active coke/active carbon as a catalyst, NOx in the flue gas is reduced by spraying ammonia, but the reaction temperature of the method is low, so that the NOx reduction efficiency is very low and is generally lower than 40%, and the requirement of a flue gas emission standard cannot be met. And unreacted NH at low temperature3Except for SO in the flue gas2And the like, so that the ammonium sulfate salt is formed, the catalyst is blocked, and the haze can be formed after the ammonium sulfate salt escapes to the atmosphere.
The NOx adsorption method is widely applied to the treatment of tail gas produced by nitric acid as a technology with great development potential, but the NO ratio in the flue gas of a coal-fired power plant and the metallurgical industry is very high, so that the NOx adsorption method is often applied to the treatment of tail gas produced by nitric acidAbove 90% and NO2The proportion of the adsorbent/catalyst is very low, the adsorption capacity of the common adsorbent/catalyst to NO is weak, the adsorbent/catalyst can not meet the requirement of the emission standard of the NOx in flue gas, the adsorbent is difficult to regenerate after adsorbing the NOx, and two sets of equipment are needed for adsorption and regeneration of the adsorbent/catalyst, so that the denitration process can not be continuously carried out.
The traditional particle bed catalyst has higher NOx adsorption efficiency, but is seriously abraded in the using process, so that the service life of the catalyst is shorter, and although the service life of a honeycomb catalyst, a plate catalyst and the like is longer, the preparation process is mature, but the NOx adsorption efficiency is very low.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides the forming process for the low-temperature NOx rapid alternate adsorption-regeneration catalyst, which has high mechanical strength and good adsorption performance.
The invention is realized by the following technical scheme:
a molding process for a low-temperature NOx rapid alternate adsorption-regeneration catalyst comprises the following steps:
(1) dissolving a mixture of soluble copper salt or/and cobalt salt, soluble cerium salt, other metal salt, citric acid or/and propylene glycol and a pore-forming agent in water, fully stirring and adjusting the pH of the system to be less than or equal to 5 to prevent metal ions from forming insoluble matters, drying to obtain a solid, and performing extrusion forming, crushing and sieving to obtain raw catalyst particles;
(2) roasting the raw catalyst particles at the temperature of 150-300 ℃ for 2-5 hours to decompose the residual nitrate and the added acid, and then roasting at the temperature of 400-650 ℃ for 2-5 hours to prepare the composite metal oxide catalyst;
(3) extruding glass fiber or ceramic fiber paper into a wavy shape at the temperature of 200-700 ℃, coating an aluminum sol or silica gel solution with the mass concentration of 10-50%, and drying at the temperature of 100-350 ℃ to obtain wavy corrugated paper;
(4) dispersing the composite metal oxide catalyst into an alumina sol solution, and brushing the alumina sol solution on the surface of the corrugated paper in the step (3);
(5) and (3) alternately stacking the corrugated paper coated with the catalyst and the glass fiber or ceramic fiber paper not coated with the catalyst to form a multi-layer corrugated shape, and drying at the temperature of 100-300 ℃ to obtain the product.
The catalyst forming method provided by the invention not only utilizes the good permeability of the porous catalyst to prevent the flue gas from blocking the catalyst pore channels when the flue gas flows through the catalyst, but also can effectively promote the catalyst to adsorb nitrogen oxides in the flue gas and improve the NOx adsorption efficiency of the catalyst, the expected effect is 3-5 times of that of the conventional process, and the overall denitration efficiency can reach 90-100%.
The more preferable technical scheme of the invention is as follows:
in the step (1), the soluble cerium salt is one or more of cerium nitrate, cerium acetate or cerium chloride, and the other metal salt is one or more of nitrate, acetate or chloride.
Adding hydrogen peroxide or acid while stirring to regulate pH to less than or equal to 5, drying at 110 deg.c for 12 hr, extruding and forming the dried solid at 0.5-5MPa, crushing and sieving to obtain 20-120 mesh green catalyst particle.
In the mixture, the mass ratio of the liquid to the solid is 1: 0.5-1: 200, the molar ratio of cerium element to other primary metals is 9: 1-1: 9.
the pore-forming agent is one or more of alumina, herba Hyperici Japonici powder, starch, ammonium bicarbonate, urea, PVP, PEG, and PVA.
In the step (2), the green catalyst particles are calcined at the temperature of 200-250 ℃ and then at the temperature of 450-550 ℃.
In the step (3), the distance between two wave crests of the wave-shaped corrugated paper is 0.1-5cm, the peak height is 0.01-2cm, the mass concentration of the aluminum sol or silica gel solution is 20-40%, and the drying temperature is 200-300 ℃.
In the step (4), the mass concentration of the aluminum sol solution is 50-100%, and the molar ratio of the composite metal oxide catalyst to the aluminum sol is 0.1: 9.9-9.9: 0.1; the drying temperature is 120-280 ℃.
The corrugated catalyst prepared by the invention has high mechanical strength and good NOx adsorption performance, is combined with a denitration reactor, and is very suitable for removing NOx in low-temperature flue gas of coal-fired power plants, iron and steel plants, biomass power plants and the like.
The invention utilizes the good permeability of the porous catalyst to prevent the flue gas from blocking the catalyst pore channel when flowing through the catalyst, effectively promotes the catalyst to adsorb NOx in the flue gas, and improves the adsorption efficiency.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of the structure of a catalyst according to the present invention;
FIG. 2 is a partially enlarged schematic view of the catalyst of the present invention.
Detailed Description
The invention is further described with reference to the drawings and the detailed description. It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular is intended to include the plural unless the context clearly dictates otherwise, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
The invention provides a forming process for a low-temperature NOx rapid alternate adsorption-regeneration catalyst, which comprises the following steps:
(1) dissolving soluble copper salt or/and cobalt salt, soluble cerium salt, other metal salt, citric acid or/and propylene glycol and pore-forming agent in water according to a specific ratio, wherein the molar ratio of cerium element to other metal element is 9:1-5:5, the pore-forming agent is one or a mixture of more of alumina, sesbania powder, starch, ammonium bicarbonate, urea, PVP, PEG, PVA and the like, and the mass ratio of liquid to solid is 1: 0.5-1: 200, fully stirring, adding hydrogen peroxide or acid while stirring to ensure that the pH value of the system is less than or equal to 5, preventing metal ions from forming insoluble matters, then drying at 110 ℃ for 12 hours, carrying out extrusion forming on the dried solid under 0.5-5MPa, crushing, and sieving to obtain 20-120 mesh catalyst particles;
(2) roasting the particles obtained in the step (1) at the temperature of 150-300 ℃ for 2-5 hours to decompose the residual nitrate and the added acid, and finally roasting at the temperature of 400-650 ℃ for 2-5 hours to prepare the composite metal oxide catalyst;
(3) extruding the glass fiber paper or the ceramic fiber paper into a wavy shape at the temperature of 200-350 ℃, wherein the distance between two wave crests of the wavy corrugated paper is 0.1-5cm, the height of the wave crest is 0.01-2cm, coating 10-50% of aluminum sol or silica gel on the glass fiber paper or the ceramic fiber paper, and quickly drying at the temperature of 100-350 ℃;
(4) dispersing the catalyst obtained in the step (2) into 50-100% of aluminum sol, and brushing the catalyst on the surface of the glass fiber paper or the ceramic fiber paper in the step (3);
(5) stacking the wavy glass fiber paper or ceramic fiber paper coated with the catalyst obtained in the step (4) and glass fiber paper or ceramic fiber paper not coated with the catalyst at intervals to form a multi-layer corrugated shape;
(6) and (4) drying the multilayer corrugated paper loaded with the catalyst obtained in the step (5) at the temperature of 100 ℃ and 300 ℃.
The following is a specific example to further understand the present invention.
Example (b):
(1) dissolving 2g of copper nitrate, 10g of cerium nitrate, 10g of manganese nitrate, 10ml of citric acid and 0.5g of aluminum oxide in water, fully stirring, adding a proper amount of hydrogen peroxide to enable the pH value of the solution to be 4.5, then drying at 110 ℃ for 12 hours, carrying out extrusion forming on the dried solid under 2.5MPa, crushing, sieving to obtain 20-40-mesh catalyst particles, and finally roasting at 200 ℃ and 550 ℃ for 3 hours respectively;
(2) extruding glass fiber paper into a wavy shape at 500 ℃, wherein the distance between two wave crests of the wavy corrugated paper is 0.25cm, the peak height is 0.15cm, coating 30% aluminum sol on the glass fiber paper, and quickly drying at 300 ℃;
(3) dispersing the catalyst obtained in the step (1) into 50% of aluminum sol, wherein the molar ratio of the composite metal oxide catalyst to the aluminum sol is 3.5: 8.5, brushing the surface of the glass fiber paper in the step (2);
(4) stacking the wavy glass fiber paper coated with the catalyst obtained in the step (3) and the glass fiber paper not coated with the catalyst at intervals to form a multi-layer corrugated shape;
(5) and (4) drying the multilayer corrugated paper loaded with the catalyst obtained in the step (4) at 200 ℃ to obtain the catalyst for quickly and alternately adsorbing a regeneration at low temperature.
The prepared catalyst is jointly applied to a novel denitration reactor (a rotary denitration reactor, application publication No. CN 103908892A), and can remove more than 95% of NOx in flue gas at 150 ℃.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (9)
1. A molding process for a low-temperature NOx rapid alternate adsorption-regeneration catalyst is characterized by comprising the following steps: (1) dissolving a mixture of soluble copper salt or/and cobalt salt, soluble cerium salt, other metal salt, citric acid or/and propylene glycol and a pore-forming agent in water, fully stirring and adjusting the pH of the system to be less than or equal to 5, drying to obtain a solid, and performing extrusion forming, crushing and sieving to obtain raw catalyst particles; (2) roasting the raw catalyst particles at the temperature of 150-300 ℃ for 2-5 hours to decompose the residual nitrate and the added acid, and then roasting at the temperature of 400-650 ℃ for 2-5 hours to prepare the composite metal oxide catalyst; (3) extruding glass fiber or ceramic fiber paper into a wavy shape at the temperature of 200-700 ℃, coating an aluminum sol or silica gel solution with the mass concentration of 10-50%, and drying at the temperature of 100-350 ℃ to obtain wavy corrugated paper; (4) dispersing the composite metal oxide catalyst into an alumina sol solution, and brushing the alumina sol solution on the surface of the corrugated paper in the step (3); (5) and (3) alternately stacking the corrugated paper coated with the catalyst and the glass fiber or ceramic fiber paper not coated with the catalyst to form a multi-layer corrugated shape, and drying at the temperature of 100-300 ℃ to obtain the product.
2. The molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (1), the soluble cerium salt is one or more of cerium nitrate, cerium acetate or cerium chloride, and the other metal salt is one or more of nitrate, acetate or chloride.
3. The molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (1), hydrogen peroxide or acid is added during stirring to adjust the pH value of the system to be less than or equal to 5, then the system is dried for 12 hours at the temperature of 110 ℃, the dried solid is extruded and formed under the pressure of 0.5 to 5MPa and is crushed, and the crushed solid is sieved to obtain the 20 to 120-mesh green catalyst particles.
4. The molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (1), the mass ratio of liquid to solid in the mixture is 1: 0.5-1: 200, the molar ratio of cerium element to other primary metals is 9: 1-1: 9.
5. the molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (1), the pore-forming agent is one or more of alumina, sesbania powder, starch, ammonium bicarbonate, urea, PVP, PEG and PVA.
6. The molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (2), the green catalyst particles are calcined at the temperature of 200-250 ℃ and then at the temperature of 450-550 ℃.
7. The molding process for a low temperature NOx rapid alternate adsorption-regeneration catalyst according to claim 1, wherein: in the step (3), the distance between two wave crests of the wave-shaped corrugated paper is 0.1-5cm, the peak height is 0.01-2cm, the mass concentration of the aluminum sol or silica gel solution is 20-40%, and the drying temperature is 200-300 ℃.
8. The process of claim 1 for forming a low temperature NOx rapid alternate adsorption-regeneration catalyst, wherein: in the step (4), the mass concentration of the aluminum sol solution is 50-100%, and the molar ratio of the composite metal oxide catalyst to the aluminum sol is 0.1: 9.9-9.9: 0.1.
9. the process of claim 1 for forming a low temperature NOx rapid alternate adsorption-regeneration catalyst, wherein: in the step (4), the drying temperature is 120-280 ℃.
Priority Applications (1)
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