CN114849469A - Flue gas denitration preposed module and preparation method thereof - Google Patents

Flue gas denitration preposed module and preparation method thereof Download PDF

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CN114849469A
CN114849469A CN202210654401.3A CN202210654401A CN114849469A CN 114849469 A CN114849469 A CN 114849469A CN 202210654401 A CN202210654401 A CN 202210654401A CN 114849469 A CN114849469 A CN 114849469A
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equal
solution
flue gas
preparation
active component
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CN114849469B (en
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张肖肖
李斐斐
张倩
陈家豪
李建行
潘志勇
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Dezhou Vocational and Technical College
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8631Processes characterised by a specific device
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • B01D53/56Nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8603Removing sulfur compounds
    • B01D53/8609Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8621Removing nitrogen compounds
    • B01D53/8625Nitrogen oxides
    • B01D53/8628Processes characterised by a specific catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/88Handling or mounting catalysts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (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)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention discloses a flue gas denitration preposed module and a preparation method thereof, mainly relating to the technical field of atmospheric pollution control. The invention can greatly reduce the scouring of the fly ash to the SCR denitration catalyst, reduce the influence of substances such as sulfur, alkali metal, mercury, arsenic and the like on the activity of the SCR denitration catalyst, prolong the service life and the replacement period of the catalyst and greatly reduce the operation cost.

Description

Flue gas denitration preposed module and preparation method thereof
Technical Field
The invention belongs to the technical field of air pollution control, and particularly relates to a flue gas denitration preposed module of a power plant and a preparation method thereof.
Background
The atmospheric pollution problem caused by nitrogen oxides is increasingly serious, the harm to the environment is increasingly prominent, and the nitrogen oxidesThe elimination becomes a hot problem of environmental field research, and Selective Catalytic Reduction (SCR) is one of the most effective nitrogen oxide elimination technologies at present, and is widely applied to tail gas treatment of coal-fired enterprises such as power plants, cement plants and the like and industrial boilers. In practical application, the SCR denitration system catalyst is in fly ash and SO for a long time 2 /SO 3 And alkali metal substances such As Na/K and the like and toxic substances such As Hg, As and the like in the flue gas are main factors causing catalyst deactivation and efficiency and service life reduction.
The denitration catalyst of the W-V-Ti system used in the industry at present has an excellent denitration effect, but the performances of fly ash erosion resistance, sulfur resistance, alkali metal resistance, Hg and As poisoning resistance still need to be improved, the cost of the SCR denitration catalyst accounts for about 40-60% of the whole denitration system, frequent replacement greatly increases the operation cost, and the modified W-V-Ti system SCR denitration catalyst can slow down the catalyst poisoning and inactivation to a certain extent, but cannot completely avoid the influence of harmful substances in flue gas on the catalyst, so that a flue gas denitration prepositive module and a preparation method thereof are provided.
Disclosure of Invention
The invention provides a flue gas denitration front-end module and a preparation method thereof, which solve the technical problems mentioned in the background technology.
The technical scheme adopted by the invention for solving the technical problems is as follows: the flue gas denitration preposed module comprises a cuboid honeycomb ceramic, the honeycomb ceramic comprises a carrier component and an active component, and the carrier component comprises Al 2 O 3 And SiO 2 Or a mixture of the two substances, the carrier component having the formula Al x Si (1-x) O (1+0.5x) Wherein x is more than or equal to 0.3 and less than or equal to 0.5; the active component comprises Fe, Ce and V elements, and the chemical formula of the active component is Fe y Ce (1-2y) V y O 2 Wherein y is more than or equal to 0.2 and less than or equal to 0.3.
Preferably, the carrier component forms a solid solution with the active component, wherein the active component accounts for 3% -8% of the total mass, and the solid solution has the chemical formula Fe y Ce (1-2y) V y O 2 /Al x Si (1-x) O (1+0.5x) Wherein0≤x≤1,0.2≤y≤0.3。
A preparation method of honeycomb ceramics for a flue gas denitration front module comprises the following steps:
first step preparation of mixed solution: (1) diluting 1-x mol fraction acidic silica sol by 2-3 times, and dripping x mol fraction Al 2 O 3 Stirring the aluminum sol solution uniformly, wherein x is more than or equal to 0 and less than or equal to 1;
(2) FeCl with the molar fraction of 0.2-0.3 is added into the solution formed in the step (1) 3 ·9H 2 O and 0.4-0.6 mole fraction Ce (NO) 3 ) 4 ·6H 2 O, stirring and dissolving;
(3) adding hexadecyl ammonium bromide or polyethylene oxide-polypropylene oxide-polyethylene oxide which accounts for 10% -15% of the total mass of the solution into the solution formed in the step (2), and uniformly stirring for later use;
second step preparation of NH 3 VO 3 Solution: NH with the molar fraction of the active component of 0.2 to 0.3 3 VO 3 Dissolving in proper amount of ammonia water to form NH 3 VO 3 A solution;
third step the NH formed in the second step 3 VO 3 Adding the solution into the mixed solution formed in the first step, and uniformly stirring;
fourthly, adding a proper amount of kaolin, polyoxyethylene, glass fiber, carboxymethyl cellulose and tissue paper fiber serving as structural auxiliaries into the solution formed in the third step, and uniformly stirring;
and a fifth step of adjusting the viscosity of the mixture formed in the fourth step, extruding the mixture into a cuboid shape, drying the cuboid shape, and then roasting the cuboid shape in a roasting furnace at the temperature of 500 ℃ and 600 ℃ for 2 to 4 hours.
Preferably, SiO in the acidic silica sol in the first step 2 The content of (B) is 25%.
Preferably, Al is present in the aluminium sol in the first step 2 O 3 The content of (B) is 25%.
The invention adopts the structure and has the following advantages:
the method can greatly reduce the scouring of the fly ash to the SCR denitration catalyst, reduce the influence of substances such as sulfur, alkali metal, mercury, arsenic and the like on the activity of the SCR denitration catalyst, prolong the service life and the replacement period of the catalyst, and greatly reduce the operation cost.
Detailed Description
In order to clearly explain the technical features of the present invention, the present invention will be explained in detail by the embodiments.
The flue gas denitration preposed module comprises a cuboid honeycomb ceramic, the honeycomb ceramic comprises a carrier component and an active component, and the carrier component comprises Al 2 O 3 And SiO 2 Or a mixture of the two substances, the carrier component having the formula Al x Si (1-x) O (1+0.5x) Wherein x is more than or equal to 0.3 and less than or equal to 0.5; the active component comprises Fe, Ce and V elements, and the chemical formula of the active component is Fe y Ce (1-2y) V y O 2 Wherein y is more than or equal to 0.2 and less than or equal to 0.3.
The carrier component and the active component form a solid solution, wherein the active component accounts for 3-8% of the total mass, and the chemical formula of the solid solution is Fe y Ce (1-2y) V y O 2 /Al x Si (1-x) O (1+0.5x) Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0.2 and less than or equal to 0.3.
A preparation method of honeycomb ceramics for a flue gas denitration front module comprises the following steps:
first step preparation of mixed solution: (1) diluting 1-x mol fraction acidic silica sol by 2-3 times, and dripping x mol fraction Al 2 O 3 Stirring the aluminum sol solution uniformly, wherein x is more than or equal to 0 and less than or equal to 1;
(2) FeCl with the molar fraction of 0.2-0.3 is added into the solution formed in the step (1) 3 ·9H 2 O and Ce (NO) in a molar fraction of 0.4 to 0.6 3 ) 4 ·6H 2 O, stirring and dissolving;
(3) adding hexadecyl ammonium bromide or polyethylene oxide-polypropylene oxide-polyethylene oxide which accounts for 10% -15% of the total mass of the solution into the solution formed in the step (2), and uniformly stirring for later use;
second step preparation of NH 3 VO 3 Solution: NH with the active component mole fraction of 0.2-0.3 3 VO 3 Dissolving in proper amount of ammonia water to form NH 3 VO 3 A solution;
third step the NH formed in the second step 3 VO 3 Adding the solution into the mixed solution formed in the first step, and uniformly stirring;
fourthly, adding a proper amount of kaolin, polyoxyethylene, glass fiber, carboxymethyl cellulose and tissue paper fiber serving as structural auxiliaries into the solution formed in the third step, and uniformly stirring;
and a fifth step of adjusting the viscosity of the mixture formed in the fourth step, extruding the mixture into a cuboid shape, drying the cuboid shape, and then roasting the cuboid shape in a roasting furnace at the temperature of 500 ℃ and 600 ℃ for 2 to 4 hours.
SiO in acidic silica sol in the first step 2 The content of (B) is 25%.
In the first step Al is present in the aluminium sol 2 O 3 The content of (B) is 25%.
The front module made of the honeycomb ceramics prepared by the method has higher mechanical strength, is resistant to flying ash scouring, can intercept most flying ash and can rapidly catalyze SO 2 Formation of SO 3 And the flue gas enters the denitration catalyst module after being purified by the preposed module, most of toxic and harmful substances are intercepted, and chemicals used in the preparation of the honeycomb ceramics are common and cheap substances, so that the preposed module formed by the honeycomb ceramics has low cost and is convenient to replace, the denitration effect of the SCR denitration catalyst can be kept for a long time, the service life is greatly prolonged, and the operation cost is reduced.
The above mentioned devices are prior art.
The above-described embodiments should not be construed as limiting the scope of the invention, and any alternative modifications or alterations to the embodiments of the present invention will be apparent to those skilled in the art.
The present invention is not described in detail, but is known to those skilled in the art.

Claims (5)

1. The utility model provides a leading module of flue gas denitration which characterized in that: comprises a honeycomb ceramic in a cuboid shape, the honeycomb ceramic comprises a carrier component and an active component, the carrier component comprises Al 2 O 3 And SiO 2 Or a mixture of the two, the carrier component having the formula Al x Si (1-x) O (1+0.5x) Wherein x is more than or equal to 0.3 and less than or equal to 0.5; the active component comprises Fe, Ce and V elements, and the chemical formula of the active component is Fe y Ce (1-2y) V y O 2 Wherein y is more than or equal to 0.2 and less than or equal to 0.3.
2. The flue gas denitration front module of claim 1, characterized in that: the carrier component and the active component form a solid solution, wherein the active component accounts for 3-8% of the total mass, and the solid solution has a chemical formula of Fe y Ce (1-2y) V y O 2 /Al x Si (1-x) O (1+0.5x) Wherein x is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0.2 and less than or equal to 0.3.
3. The preparation method of the honeycomb ceramic for the flue gas denitration pre-module, according to claim 1, is characterized in that: the method comprises the following steps:
first step preparation of mixed solution: (1) diluting 1-x mol fraction acidic silica sol by 2-3 times, and dripping x mol fraction Al 2 O 3 Stirring the aluminum sol solution uniformly, wherein x is more than or equal to 0 and less than or equal to 1;
(2) FeCl with the molar fraction of 0.2-0.3 is added into the solution formed in the step (1) 3 ·9H 2 O and 0.4-0.6 mole fraction Ce (NO) 3 ) 4 ·6H 2 O, stirring and dissolving;
(3) adding hexadecyl ammonium bromide or polyethylene oxide-polypropylene oxide-polyethylene oxide which accounts for 10% -15% of the total mass of the solution into the solution formed in the step (2), and uniformly stirring for later use;
second step preparation of NH 3 VO 3 Solution: NH with the active component mole fraction of 0.2-0.3 3 VO 3 Dissolve in waterMeasuring the ammonia to form NH 3 VO 3 A solution;
third step of reacting NH formed in the second step 3 VO 3 Adding the solution into the mixed solution formed in the first step, and uniformly stirring;
fourthly, adding a proper amount of kaolin, polyoxyethylene, glass fiber, carboxymethyl cellulose and tissue paper fiber serving as structural auxiliaries into the solution formed in the third step, and uniformly stirring;
and a fifth step of adjusting the viscosity of the mixture formed in the fourth step, extruding the mixture into a cuboid shape, drying the cuboid shape, and then roasting the cuboid shape in a roasting furnace at the temperature of 500 ℃ and 600 ℃ for 2 to 4 hours.
4. The method for preparing the honeycomb ceramic for the flue gas denitration front module according to claim 3, wherein SiO in the acidic silica sol in the first step 2 The content of (B) is 25%.
5. The preparation method of the honeycomb ceramic for the flue gas denitration pre-module, according to claim 4, is characterized in that: al in the alumina sol in the first step 2 O 3 The content of (B) is 25%.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07275695A (en) * 1994-04-06 1995-10-24 Hitachi Zosen Corp So2 adsorbent
CN104162349A (en) * 2014-07-23 2014-11-26 浙江大学 Method for inhibiting low-temperature denitration catalyst poisoning caused by SO2
CN106391040A (en) * 2016-11-18 2017-02-15 河南福流环保科技有限公司 High-efficiency low temperature denitration composite catalyst and preparation method thereof
CN109248679A (en) * 2018-09-11 2019-01-22 上海化工研究院有限公司 A kind of VOCs room temperature degradation effective catalyst and its preparation and application
CN111715302A (en) * 2020-04-08 2020-09-29 上海大学 Anti-poisoning metal oxide denitration catalyst and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07275695A (en) * 1994-04-06 1995-10-24 Hitachi Zosen Corp So2 adsorbent
CN104162349A (en) * 2014-07-23 2014-11-26 浙江大学 Method for inhibiting low-temperature denitration catalyst poisoning caused by SO2
CN106391040A (en) * 2016-11-18 2017-02-15 河南福流环保科技有限公司 High-efficiency low temperature denitration composite catalyst and preparation method thereof
CN109248679A (en) * 2018-09-11 2019-01-22 上海化工研究院有限公司 A kind of VOCs room temperature degradation effective catalyst and its preparation and application
CN111715302A (en) * 2020-04-08 2020-09-29 上海大学 Anti-poisoning metal oxide denitration catalyst and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
刘玉荣: "《介孔碳材料的合成及应用》", 30 June 2012, 国防工业出版社, pages: 13 - 14 *
朱仁发等: "调变组分对流化催化裂化助剂脱硫性能的影响", 《华东理工大学学报》 *
朱仁发等: "调变组分对流化催化裂化助剂脱硫性能的影响", 《华东理工大学学报》, no. 2, 25 April 2000 (2000-04-25), pages 149 - 153 *

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