CN113289678A - Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof - Google Patents

Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof Download PDF

Info

Publication number
CN113289678A
CN113289678A CN202110600492.8A CN202110600492A CN113289678A CN 113289678 A CN113289678 A CN 113289678A CN 202110600492 A CN202110600492 A CN 202110600492A CN 113289678 A CN113289678 A CN 113289678A
Authority
CN
China
Prior art keywords
denitration catalyst
molecular sieve
zsm
powder
drying
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
Application number
CN202110600492.8A
Other languages
Chinese (zh)
Inventor
黄力
王虎
王力腾
纵宇浩
常峥峰
刘洋
高义博
李金珂
姚晔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Datang Environment Industry Group Co Ltd
Original Assignee
Datang Environment Industry Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Datang Environment Industry Group Co Ltd filed Critical Datang Environment Industry Group Co Ltd
Priority to CN202110600492.8A priority Critical patent/CN113289678A/en
Publication of CN113289678A publication Critical patent/CN113289678A/en
Pending legal-status Critical Current

Links

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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Crystallography & Structural Chemistry (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)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of denitration catalysts, in particular to a honeycomb type denitration catalyst suitable for high-temperature flue gas and a preparation method thereof, wherein the honeycomb type denitration catalyst comprises the following steps: adding TiO into the mixture2Soaking in aqueous solution of vanadium composite tungsten and/or molybdenum, drying, and calcining to obtain powder A; mixing silica sol, electrolyte and deionized water, adding concentrated sulfuric acid, aluminum salt, ferric salt and copper salt, stirring, adding a template agent for crystallization, filtering, drying and roasting filter residues to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu; mixing the powder A and ZSM-5 molecular sieve, adding forming assistant and glassAnd mixing the fibers and the deionized water to form a paste, extruding, drying and calcining the paste to obtain the honeycomb denitration catalyst. The honeycomb denitration catalyst prepared by the preparation method has high denitration efficiency, wide denitration active temperature window and strong hydrothermal stability, and simultaneously has excellent SO resistance2And resistance to alkali metal poisoning.

Description

Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof
Technical Field
The invention relates to the technical field of denitration catalysts, in particular to a honeycomb type denitration catalyst suitable for high-temperature flue gas and a preparation method thereof.
Background
Nitrogen Oxides (NO)X) Is one of the main substances causing air pollution, can cause acid rain, photochemical smog, greenhouse effect and ozone layer damage, is harmful to the health of people, has the national emission standard for NOx becoming stricter, and can use Selective Catalytic Reduction (SCR) technology to remove Nitrogen Oxides (NO) in the smokeX) Reduction to harmless N2And H2And O is widely applied to denitration engineering of coal-fired power plants and industrial boilers.
The denitration catalyst is a core part of an SCR denitration technology, the industrial denitration catalyst mainly takes vanadium-titanium as a main component and is divided into a honeycomb type, a flat plate type and a corrugated plate type according to the structure, the activity temperature range of the conventional industrial denitration catalyst is 320-420 ℃, and when the flue gas temperature is higher than 450 ℃, the denitration catalyst is easy to sinter and inactivate and cannot exert a good denitration effect. Therefore, further development of a denitration catalyst suitable for a high-temperature flue gas environment is required.
CN201210279289.6 discloses a preparation method of an SCR denitration catalyst suitable for high-temperature flue gas conditions, wherein modified starch of graft copolymerization is added in the preparation process of a vanadium-tungsten-titanium denitration catalyst, and a pore-expanding agent, an adhesive and the like are matched, so that the denitration catalyst has better NO at the flue gas temperature of 400-430 DEG CXRemoval rate and resistance to sinteringAnd (4) performance. However, the denitration efficiency of the denitration catalyst at 430 ℃ is only 75.8% at most.
CN201410765626.1 discloses a denitration catalyst applied to high-temperature flue gas conditions and a preparation method thereof, wherein the prepared denitration catalyst contains Fe2O3And TiO2/SiO2、TiO2/Al2O3And the composite carrier is suitable for a coal-fired power plant burning lignite or under the conditions of high-temperature and high-sulfur flue gas. However, the denitration temperature window of the catalyst is narrow, and the catalyst is resistant to SO2The properties and hydrothermal stability are not clear.
In conclusion, the denitration catalyst prepared by the prior art and applied to the high-temperature flue gas condition still has the defects of narrow denitration activity temperature window, low denitration efficiency, poor hydrothermal stability and SO resistance2Poor performance and alkali metal poisoning resistance, and the like.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas, and the honeycomb denitration catalyst prepared by the method has the advantages of high denitration efficiency, wide denitration activity temperature window and strong hydrothermal stability, and simultaneously has excellent SO resistance2Performance and alkali metal poisoning resistance; the second purpose of the invention is to provide a honeycomb type denitration catalyst prepared by the method.
The invention provides a preparation method of a honeycomb type denitration catalyst suitable for high-temperature flue gas, which comprises the following steps:
s1, adding TiO2Soaking in aqueous solution of vanadium composite tungsten and/or molybdenum, drying, and calcining to obtain powder A;
s2, mixing silica sol, electrolyte and deionized water, adding concentrated sulfuric acid, aluminum salt, ferric salt and copper salt, stirring, adding a template agent, crystallizing, filtering, drying filter residues, and roasting to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu;
and S3, mixing the powder A obtained in the step S1 with the ZSM-5 molecular sieve obtained in the step S2, adding a forming aid, glass fiber and deionized water, uniformly mixing to form a paste, extruding, drying and calcining the paste to obtain the honeycomb denitration catalyst.
Preferably, V in the honeycomb denitration catalyst2O50.5-3% by mass of WO3And/or MoO31-10% by mass of Fe2O31-5% of CuO and 1-5% of CuO.
Preferably, among the honeycomb denitration catalysts, WO3And MoO3In the presence of both, WO3And MoO3The mass ratio of (a) to (b) is an arbitrary ratio. The honeycomb denitration catalyst prepared by the preparation method has the advantages of high denitration efficiency, wide denitration active temperature window and strong hydrothermal stability, and simultaneously has excellent SO resistance2Performance and resistance to alkali metal poisoning.
Preferably, in step S2, the electrolyte is NaCl or KCl; the template agent is TPABr or TPAOH; the aluminum salt is aluminum sulfate; the ferric salt is ferric nitrate; the copper salt is copper nitrate.
Preferably, in step S2, the mass ratio of the silica sol, the electrolyte, the deionized water, the concentrated sulfuric acid, the iron salt, and the template agent is 100: (1-25): (100-300): (0.5-3): (1-30): (1-26), and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 25-180.
Preferably, in the step S2, the crystallization temperature is 150-200 ℃, and the crystallization time is 36-72 h; the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-5 h.
The invention adopts a hydrothermal synthesis method to prepare the ZSM-5 molecular sieve, SO that part of Fe and Cu elements enter the framework of the molecular sieve, and the Fe and Cu elements are prevented from being SO-coated2Sulfurizing to deactivate and improve SO resistance of molecular sieve2In addition, Fe and Cu elements are introduced into the molecular sieve to form a Si-O-Fe/Cu structure, so that the bond energy and the crystal structure of the molecular sieve are changed, the overall stability of the molecular sieve can be improved, and the thermal stability and the hydrothermal stability of the molecular sieve are improved.
Preferably, in step S1, TiO2Mass of and volume of aqueous solution of vanadium-composited tungsten and/or molybdenumThe ratio is 1: 2-1: 5;
TiO2is anatase type TiO2The aqueous solution of vanadium composite tungsten and/or molybdenum is one of an aqueous solution of ammonium metavanadate composite ammonium metatungstate, an aqueous solution of ammonium metavanadate composite ammonium heptamolybdate, an aqueous solution of ammonium metavanadate composite ammonium metatungstate and ammonium heptamolybdate.
Preferably, in the step S1, the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the calcining temperature is 400-550 ℃, and the calcining time is 1-3 h.
The invention uses anatase type TiO2As a carrier, V2O5As the main active ingredient, WO3And/or MoO3As an auxiliary agent, the obtained vanadium-titanium based catalyst has excellent medium-low temperature denitration activity.
Preferably, in step S3, the forming aid is hydroxyethyl cellulose, carboxymethyl cellulose or sesbania powder;
the mass ratio of the powder A to the ZSM-5 molecular sieve is 8: 2-5: 5; the addition amount of the forming auxiliary agent is 1-5% of the total mass of the powder A and the ZSM-5 molecular sieve; the adding amount of the glass fiber is 1-5% of the total mass of the powder A and the ZSM-5 molecular sieve; the addition amount of the deionized water is 20-40% of the total mass of the powder A and the ZSM-5 molecular sieve.
According to the invention, the specific surface area, porosity, specific pore volume and reasonable pore size distribution of the honeycomb denitration catalyst are increased by adding the forming auxiliary agent, so that the catalyst has higher catalytic activity, and the denitration efficiency of the catalyst is improved; the strength of the denitration catalyst is enhanced by adding the glass fiber, and the denitration catalyst is shaped by drying and calcining.
Preferably, in the step S3, the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the calcining temperature is 400-600 ℃, and the calcining time is 1-6 h.
The vanadium-titanium catalyst (powder A) prepared by the method has excellent medium-low temperature denitration activity, the ZSM-5 molecular sieve with the framework containing Fe and Cu has excellent high-temperature denitration activity, the vanadium-titanium-based catalyst and the ZSM-5 molecular sieve with the framework containing Fe and Cu are respectively prepared, then the vanadium-titanium-based catalyst and the ZSM-5 molecular sieve with the framework containing Fe and Cu are mixed and molded to prepare the honeycomb denitration catalyst, and if all raw materials are blended by a one-step method and then dried and calcined, the honeycomb denitration catalyst cannot be obtained.
The invention also provides the honeycomb denitration catalyst which is prepared by the preparation method and is suitable for high-temperature flue gas.
The invention has the beneficial effects that:
(1) the preparation method comprises the steps of respectively preparing a vanadium-titanium-based catalyst and a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the prepared vanadium-titanium-based catalyst has excellent medium-low temperature denitration activity, the prepared ZSM-5 molecular sieve with the framework containing Fe and Cu has excellent high-temperature denitration activity, the two molecular sieves are mixed and molded to prepare the honeycomb type denitration catalyst, the honeycomb type denitration catalyst can fully exert the medium-low temperature denitration activity of the vanadium-titanium-based catalyst and the high-temperature denitration activity of the molecular sieve, and has the advantages of high denitration efficiency, wide denitration activity temperature window and strong hydrothermal stability, and meanwhile, the honeycomb type denitration catalyst also has excellent SO resistance2Performance and resistance to alkali metal poisoning.
(2) The invention adopts a hydrothermal synthesis method to prepare the ZSM-5 molecular sieve with the framework containing Fe and Cu, SO that part of Fe and Cu elements enter the framework of the molecular sieve, and the Fe and Cu elements are prevented from being SO-coated2The sulfuration is carried out to inactivate, the introduction of Fe and Cu elements changes the structure of the molecular sieve from Si-O-Al to Si-O-Fe/Cu, and the stability of the whole molecular sieve is increased by changing the bond energy and the crystal structure, thereby increasing the thermal stability and the hydrothermal stability of the molecular sieve.
(3) The ZSM-5 molecular sieve prepared by the invention has excellent pore structure and surface acidity, and can realize the adsorption of the alkaline metal element in the catalytic reaction process, thereby reducing the poisoning effect of the alkaline metal element on the active component of the denitration catalyst and prolonging the service life of the denitration catalyst.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application 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 example embodiments according to the present application. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise, and further, it is 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 technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, subjecting anatase type TiO2Soaking in aqueous solution of ammonium metavanadate and ammonium metatungstate to obtain anatase type TiO2The mass ratio of the powder A to the aqueous solution of ammonium metavanadate and ammonium metatungstate is 1:2, the powder A is obtained after the powder A is uniformly stirred, dried for 16h at 110 ℃ and calcined for 3h at 400 ℃ in air atmosphere;
s2, adding silica sol, NaCl and deionized water into a reaction kettle, sequentially adding 98% concentrated sulfuric acid, aluminum sulfate, ferric nitrate and cupric nitrate while stirring, adding TPABr to crystallize for 48 hours at 180 ℃ after uniformly stirring, cooling to room temperature, filtering the mixture, washing filter residues, drying for 16 hours at 110 ℃, and roasting for 3 hours at 500 ℃ in an air atmosphere to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the mass ratio of the silica sol, the deionized water, the NaCl, the concentrated sulfuric acid, the ferric nitrate and the TPABr is 100:180:2: 10:3.5, and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 25;
s3, mixing the powder A obtained in the step S1 and the ZSM-5 molecular sieve obtained in the step S2 according to a mass ratio of 8:2, adding carboxymethyl cellulose, glass fiber and deionized water, mixing uniformly to form a paste, extruding and forming the paste, drying the paste at 110 ℃ for 16 hours, and calcining the paste at 500 ℃ for 3 hours to obtain the honeycomb denitration catalyst, wherein the addition amount of the carboxymethyl cellulose is 2% of the total mass of the powder A and the ZSM-5 molecular sieve, the addition amount of the glass fiber is 3% of the total mass of the powder A and the ZSM-5 molecular sieve, and the addition amount of the deionized water is 20% of the total mass of the powder A and the ZSM-5 molecular sieve.
In the honeycomb type denitration catalyst prepared by the preparation method, V2O5Is 1% by mass, WO3Is 3% by mass, Fe2O3The mass percent of (B) is 2%, and the mass percent of CuO is 3%.
Example 2
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, subjecting anatase type TiO2Soaking in aqueous solution of ammonium metavanadate and ammonium heptamolybdate to obtain anatase type TiO2The mass ratio of the ammonium metavanadate to the aqueous solution of ammonium heptamolybdate is 1:2, after uniform stirring, drying at 120 ℃ for 14h, and calcining at 550 ℃ for 1h in air atmosphere to obtain powder A;
s2, adding silica sol, KCl and deionized water into a reaction kettle, sequentially adding 98% concentrated sulfuric acid, aluminum sulfate, ferric nitrate and cupric nitrate while stirring, adding TPAOH (thermoplastic ammonium hydroxide) to crystallize at 200 ℃ for 36 hours after uniformly stirring, obtaining a mixture, cooling to room temperature, filtering the mixture, washing filter residues, drying at 120 ℃ for 14 hours, and roasting at 600 ℃ for 2 hours in an air atmosphere to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the mass ratio of the silica sol, the deionized water, the NaCl, the concentrated sulfuric acid, the ferric nitrate and the TPABr is 100:180:15:2:2, and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 120;
s3, mixing the powder A obtained in the step S1 and the ZSM-5 molecular sieve obtained in the step S2 according to a mass ratio of 5:5, adding hydroxyethyl cellulose, glass fiber and deionized water, mixing uniformly to form a paste, extruding and forming the paste, drying at 120 ℃ for 14h, and calcining at 400 ℃ for 6h to obtain the honeycomb denitration catalyst, wherein the addition amount of the hydroxyethyl cellulose is 2% of the total mass of the powder A and the ZSM-5 molecular sieve, the addition amount of the glass fiber is 3% of the total mass of the powder A and the ZSM-5 molecular sieve, and the addition amount of the deionized water is 25% of the total mass of the powder A and the ZSM-5 molecular sieve.
In the honeycomb type denitration catalyst prepared by the preparation method, V2O5Is 1% by mass, MoO3Is 5% by mass, Fe2O3Is 1% by mass, and CuO is 5% by mass.
Example 3
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, subjecting anatase type TiO2Soaking in aqueous solution of ammonium metavanadate and ammonium metatungstate to obtain anatase type TiO2The mass ratio of the powder A to the aqueous solution of ammonium metavanadate and ammonium metatungstate is 1:5, the powder A is obtained after the powder A is uniformly stirred, dried for 16h at 110 ℃, and calcined for 2h at 450 ℃ in air atmosphere;
s2, adding silica sol, NaCl and deionized water into a reaction kettle, sequentially adding 98% concentrated sulfuric acid, aluminum sulfate, ferric nitrate and cupric nitrate while stirring, adding TPABr to crystallize for 48 hours at 180 ℃ after uniformly stirring, cooling to room temperature, filtering the mixture, washing filter residues, drying for 16 hours at 110 ℃, and roasting for 3 hours at 500 ℃ in an air atmosphere to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the mass ratio of the silica sol, the deionized water, the NaCl, the concentrated sulfuric acid, the ferric nitrate and the TPABr is 100:240:11:3:12.5:19, and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 180;
s3, mixing the powder A obtained in the step S1 and the ZSM-5 molecular sieve obtained in the step S2 according to a mass ratio of 6:4, adding sesbania powder, glass fibers and deionized water, mixing uniformly to form a paste, extruding and forming the paste, drying the paste for 16 hours at 110 ℃, and calcining the paste for 1 hour at 600 ℃ to obtain the honeycomb denitration catalyst, wherein the addition amount of hydroxyethyl cellulose is 3% of the total mass of the powder A and the ZSM-5 molecular sieve, the addition amount of the glass fibers is 5% of the total mass of the powder A and the ZSM-5 molecular sieve, and the addition amount of the deionized water is 30% of the total mass of the powder A and the ZSM-5 molecular sieve.
In the honeycomb type denitration catalyst prepared by the preparation method, V2O5Is 3% by mass, WO3Is 3% by mass, Fe2O35% by mass of CuO and 1% by mass of CuO.
Example 4
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, subjecting anatase type TiO2Soaking in aqueous solution of ammonium metavanadate composite ammonium metatungstate and ammonium heptamolybdate to obtain anatase type TiO2The mass ratio of the ammonium metavanadate to the aqueous solution of the ammonium metatungstate and the ammonium heptamolybdate is 1:5, the mixture is uniformly stirred, dried for 16 hours at 110 ℃, and calcined for 2 hours at 500 ℃ in an air atmosphere to obtain powder A;
s2, adding silica sol, KCl and deionized water into a reaction kettle, sequentially adding 98% concentrated sulfuric acid, aluminum sulfate, ferric nitrate and cupric nitrate while stirring, adding TPAOH to crystallize for 48 hours at 160 ℃ after uniformly stirring, obtaining a mixture, cooling to room temperature, filtering the mixture, washing filter residues, drying for 16 hours at 110 ℃, roasting for 2.5 hours at 550 ℃ in an air atmosphere, and obtaining a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the mass ratio of the silica sol, the deionized water, the NaCl, the concentrated sulfuric acid, the ferric nitrate and the TPABr is 100:240:7.5:3:10:11, and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 160;
s3, mixing the powder A obtained in the step S1 and the ZSM-5 molecular sieve obtained in the step S2 according to a mass ratio of 7:3, adding hydroxyethyl cellulose, glass fiber and deionized water, mixing uniformly to form a paste, extruding and forming the paste, drying the paste at 110 ℃ for 16 hours, and calcining the paste at 550 ℃ for 2.5 hours to obtain the honeycomb denitration catalyst, wherein the addition amount of the hydroxyethyl cellulose is 5% of the total mass of the powder A and the ZSM-5 molecular sieve, the addition amount of the glass fiber is 3% of the total mass of the powder A and the ZSM-5 molecular sieve, and the addition amount of the deionized water is 40% of the total mass of the powder A and the ZSM-5 molecular sieve.
By usingIn the honeycomb type denitration catalyst prepared by the preparation method, V2O5In a mass percentage of 2%, WO3Is 5% by mass, MoO3Is 5% by mass, Fe2O3Is 3% by mass, and CuO is 2% by mass.
Comparative example 1
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, according to the mass ratio of 1:2, anatase type TiO2Soaking in aqueous solution of ammonium metavanadate and ammonium metatungstate, stirring, oven drying at 110 deg.C for 16h, calcining at 400 deg.C for 3h in air atmosphere to obtain powder A;
s2, uniformly mixing the powder A obtained in the step S1, carboxymethyl cellulose, glass fiber and deionized water to form a paste, extruding and molding the paste, drying the paste at 110 ℃ for 16 hours, and calcining the dried paste at 500 ℃ for 3 hours to obtain the honeycomb denitration catalyst, wherein the addition amount of the carboxymethyl cellulose is 2% of the mass of the powder A, the addition amount of the glass fiber is 3% of the mass of the powder A, and the addition amount of the deionized water is 20% of the total mass of the powder A.
In the honeycomb type denitration catalyst prepared by the preparation method, V2O5Is 1% by mass, WO3The mass percentage of (B) is 3%.
Comparative example 2
A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas comprises the following steps:
s1, adding silica sol, KCl and deionized water into a reaction kettle, sequentially adding 98% concentrated sulfuric acid, aluminum sulfate, ferric nitrate and cupric nitrate while stirring, adding TPAOH (thermoplastic ammonium hydroxide) to crystallize at 200 ℃ for 36 hours after uniformly stirring, obtaining a mixture, cooling to room temperature, filtering the mixture, washing filter residues, drying at 120 ℃ for 14 hours, and roasting at 600 ℃ for 2 hours in an air atmosphere to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu, wherein the mass ratio of the silica sol, the deionized water, the NaCl, the concentrated sulfuric acid, the ferric nitrate and the TPABr is 100:180:15:2:2, and the silica-alumina ratio of the ZSM-5 molecular sieve is 120;
s2, uniformly mixing the ZSM-5 molecular sieve obtained in the step S1, hydroxyethyl cellulose, glass fiber and deionized water to form a paste, extruding and molding the paste, drying the paste at 120 ℃ for 14h, and calcining the dried paste at 400 ℃ for 6h to obtain the honeycomb denitration catalyst, wherein the addition amount of the hydroxyethyl cellulose is 2% of the mass of the ZSM-5 molecular sieve, the addition amount of the glass fiber is 3% of the total mass of the ZSM-5 molecular sieve, and the addition amount of the deionized water is 25% of the total mass of the ZSM-5 molecular sieve.
In the honeycomb type denitration catalyst prepared by the preparation method, Fe2O3Is 1% by mass, and CuO is 5% by mass.
Test example
(I) denitration Performance test
The honeycomb type denitration catalysts prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to denitration performance tests at 250 ℃, 350 ℃, 450 ℃ and 550 ℃, and the denitration efficiency is shown in table 1.
And (3) testing conditions are as follows: NH (NH)3At a concentration of 500ppm, NH3Volume ratio of NO to 1, SO2Concentration 500ppm, H2O concentration is 8%, GHSV is 120000h-1。
TABLE 1
Figure BDA0003092528740000101
As can be seen from Table 1, the denitration catalyst was found to be superior in SO to the honeycomb-type denitration catalysts prepared in comparative examples 1 to 22Concentration 500ppm, H2Under the condition that the O concentration is 8%, the honeycomb denitration catalysts prepared in examples 1 to 4 still have good denitration efficiency within a wide temperature range of 250 to 550 ℃, the temperature window of denitration activity is widened, and the denitration efficiency can reach more than 90% after the honeycomb denitration catalysts operate at 550 ℃ for 100 hours, which shows that the honeycomb denitration catalysts have good thermal stability, hydrothermal stability and SO resistance2And (4) performance. In summary, the honeycomb-type denitration catalyst prepared in embodiments 1 to 4 of the present invention has high denitration efficiency, wide denitration active temperature window, strong thermal stability and hydrothermal stability, and SO resistance2The honeycomb type denitration catalyst prepared in example 4 has the advantages of high denitration efficiency, high hydrothermal stability and high SO resistance2The performance is the most excellent.
(II) test of alkali Metal poisoning resistance
K of 1% was loaded on the honeycomb type denitration catalysts prepared in examples 1 to 4 and comparative examples 1 to 2, respectively2And O, carrying out a denitration performance test at 350 ℃, analyzing the anti-poisoning performance of different honeycomb type denitration catalysts, and showing the denitration efficiency in table 2.
And (3) testing conditions are as follows: NH (NH)3At a concentration of 500ppm, NH3Volume ratio of NO to 1, SO2Concentration 500ppm, H2O concentration is 8%, GHSV is 120000h-1。
Sample (I) Denitration efficiency (%)
Example 1 54.1
Example 2 60.2
Example 3 71.7
Example 4 73.6
Comparative example 1 28.5
Comparative example 2 19.1
As can be seen from Table 2, K at a load of 1%2Under the condition of O, the denitration efficiency of the honeycomb type denitration catalysts prepared in examples 1-4 at 350 ℃ is higher than that of the honeycomb type denitration catalysts prepared in comparative examples 1-2, and the honeycomb type denitration catalysts prepared in examples 1-4 have good alkali poisoning resistance, wherein the denitration efficiency of the honeycomb type denitration catalyst prepared in example 4 is highest, and the alkali poisoning resistance is most excellent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a honeycomb denitration catalyst suitable for high-temperature flue gas is characterized by comprising the following steps:
s1, adding TiO2Soaking in aqueous solution of vanadium composite tungsten and/or molybdenum, drying, and calcining to obtain powder A;
s2, mixing silica sol, electrolyte and deionized water, adding concentrated sulfuric acid, aluminum salt, ferric salt and copper salt, stirring, adding a template agent, crystallizing, filtering, drying filter residues, and roasting to obtain a ZSM-5 molecular sieve with a framework containing Fe and Cu;
and S3, mixing the powder A obtained in the step S1 with the ZSM-5 molecular sieve obtained in the step S2, adding a forming aid, glass fiber and deionized water, uniformly mixing to form a paste, extruding, drying and calcining the paste to obtain the honeycomb denitration catalyst.
2. A method according to claim 1The preparation method of the honeycomb denitration catalyst for high-temperature flue gas is characterized in that V in the honeycomb denitration catalyst2O50.5-3% by mass of WO3And/or MoO31-10% by mass of Fe2O31-5% of CuO and 1-5% of CuO.
3. The method according to claim 1, wherein in step S2, the electrolyte is NaCl or KCl; the template agent is TPABr or TPAOH; the aluminum salt is aluminum sulfate; the ferric salt is ferric nitrate; the copper salt is copper nitrate.
4. The method according to claim 3, wherein in step S2, the mass ratio of silica sol, electrolyte, deionized water, concentrated sulfuric acid, ferric salt and the template agent is 100: (1-25): (100-300): (0.5-3): (1-30): (1-26), and the silica-alumina ratio of the obtained ZSM-5 molecular sieve is 25-180.
5. The preparation method of the honeycomb denitration catalyst suitable for the high-temperature flue gas according to claim 1, wherein in the step S2, the crystallization temperature is 150-200 ℃, and the crystallization time is 36-72 hours; the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-5 h.
6. The method according to claim 1, wherein in step S1, TiO is added to prepare the honeycomb denitration catalyst for high-temperature flue gas2The volume ratio of the mass of the vanadium-tungsten composite powder to the volume of the aqueous solution of the vanadium-tungsten composite powder and/or the molybdenum composite powder is 1: 2-1: 5;
TiO2is anatase type TiO2The aqueous solution of vanadium-tungsten and/or molybdenum is aqueous solution of ammonium metavanadate-ammonium metatungstate, aqueous solution of ammonium metavanadate-ammonium heptamolybdate, and aqueous solution of ammonium metavanadate-ammonium metatungstate and ammonium heptamolybdateOne of (1) and (b).
7. The preparation method of the honeycomb denitration catalyst suitable for the high-temperature flue gas according to claim 1, wherein in the step S1, the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the calcining temperature is 400-550 ℃, and the calcining time is 1-3 h.
8. The method for preparing the honeycomb denitration catalyst suitable for high-temperature flue gas according to claim 1, wherein in step S3, the forming aid is hydroxyethyl cellulose, carboxymethyl cellulose or sesbania powder;
the mass ratio of the powder A to the ZSM-5 molecular sieve is 8: 2-5: 5; the addition amount of the forming auxiliary agent is 1-5% of the total mass of the powder A and the ZSM-5 molecular sieve; the adding amount of the glass fiber is 1-5% of the total mass of the powder A and the ZSM-5 molecular sieve; the addition amount of the deionized water is 20-40% of the total mass of the powder A and the ZSM-5 molecular sieve.
9. The preparation method of the honeycomb denitration catalyst suitable for the high-temperature flue gas according to claim 1, wherein in the step S3, the drying temperature is 110-130 ℃, and the drying time is 12-16 h; the calcining temperature is 400-600 ℃, and the calcining time is 1-6 h.
10. A honeycomb denitration catalyst suitable for high-temperature flue gas prepared by the preparation method of any one of claims 1 to 9.
CN202110600492.8A 2021-05-31 2021-05-31 Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof Pending CN113289678A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110600492.8A CN113289678A (en) 2021-05-31 2021-05-31 Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110600492.8A CN113289678A (en) 2021-05-31 2021-05-31 Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113289678A true CN113289678A (en) 2021-08-24

Family

ID=77326340

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110600492.8A Pending CN113289678A (en) 2021-05-31 2021-05-31 Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113289678A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114377683A (en) * 2022-01-25 2022-04-22 大唐南京环保科技有限责任公司 Anti-arsenic poisoning denitration catalyst and preparation method thereof
CN115814843A (en) * 2022-12-16 2023-03-21 大唐南京环保科技有限责任公司 Alkali-resistant metal plate-type denitration catalyst and preparation method thereof
CN115869989A (en) * 2022-09-27 2023-03-31 中国船舶重工集团公司第七一八研究所 Preparation method of low-temperature denitration catalyst for tail gas of marine diesel engine
CN116116451A (en) * 2022-11-25 2023-05-16 光大环境科技（中国）有限公司 Preparation method of low-temperature synergistic denitration and dioxin removal composite catalyst
CN115814843B (en) * 2022-12-16 2024-05-28 大唐南京环保科技有限责任公司 Alkali metal resistant plate-type denitration catalyst and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104582845A (en) * 2012-08-17 2015-04-29 庄信万丰股份有限公司 Zeolite promoted V/Ti/W catalysts
US20170007990A1 (en) * 2014-04-24 2017-01-12 Tongji University Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method thereof
CN107626342A (en) * 2017-09-18 2018-01-26 中节能万润股份有限公司 A kind of iron copper modified molecular screen base honeycomb type denitrification catalyst and preparation method thereof
CN109499606A (en) * 2018-11-13 2019-03-22 中节能万润股份有限公司 A kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104582845A (en) * 2012-08-17 2015-04-29 庄信万丰股份有限公司 Zeolite promoted V/Ti/W catalysts
US20170007990A1 (en) * 2014-04-24 2017-01-12 Tongji University Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method thereof
CN107626342A (en) * 2017-09-18 2018-01-26 中节能万润股份有限公司 A kind of iron copper modified molecular screen base honeycomb type denitrification catalyst and preparation method thereof
CN109499606A (en) * 2018-11-13 2019-03-22 中节能万润股份有限公司 A kind of copper and iron composite SCR honeycomb type denitrification catalyst and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YUANYUAN YUE, ET AL: "Direct synthesis of hierarchical FeCu-ZSM-5 zeolite with wide temperature window in selective catalytic reduction of NO by NH3", vol. 11, no. 19, pages 4744 *
李守信等: "SCR脱硝催化剂制造中的技术问题", 原创力文档, pages 2 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114377683A (en) * 2022-01-25 2022-04-22 大唐南京环保科技有限责任公司 Anti-arsenic poisoning denitration catalyst and preparation method thereof
CN114377683B (en) * 2022-01-25 2023-11-14 大唐南京环保科技有限责任公司 Arsenic poisoning-resistant denitration catalyst and preparation method thereof
CN115869989A (en) * 2022-09-27 2023-03-31 中国船舶重工集团公司第七一八研究所 Preparation method of low-temperature denitration catalyst for tail gas of marine diesel engine
CN116116451A (en) * 2022-11-25 2023-05-16 光大环境科技（中国）有限公司 Preparation method of low-temperature synergistic denitration and dioxin removal composite catalyst
CN115814843A (en) * 2022-12-16 2023-03-21 大唐南京环保科技有限责任公司 Alkali-resistant metal plate-type denitration catalyst and preparation method thereof
CN115814843B (en) * 2022-12-16 2024-05-28 大唐南京环保科技有限责任公司 Alkali metal resistant plate-type denitration catalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
CN113289678A (en) Honeycomb type denitration catalyst suitable for high-temperature flue gas and preparation method thereof
CN109174173B (en) A kind of molecular sieve SCR catalyst preparation method and its catalyst of preparation
CN113413904B (en) g-C 3 N 4 Low-temperature NH of loaded manganese cerium composite oxide 3 -SCR catalyst, preparation method and application thereof
WO2015149499A1 (en) Low-temperature and highly efficient denitration catalyst and preparation method therefor
CN101428212B (en) Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof
CN111036280B (en) Preparation method of Fe/Cu-SSZ-13 molecular sieve
KR101308496B1 (en) Methods of manufacturing a honeycomb catalyst
CN113600168B (en) Low SO 2 Conversion rate honeycomb denitration catalyst and preparation method and application thereof
CN105833901A (en) PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof
CN109967069A (en) A kind of low-temperature SCR catalyst and preparation method thereof for cement kiln flue gas denitration
JP2016129885A (en) Exhaust gas treating honeycomb catalyst and method for producing the same
CN113289609A (en) High-wear-resistance wide-temperature denitration catalyst and preparation method and application thereof
CN109482065B (en) Denitration treatment method for exhaust gas of ethylene cracking furnace
JPH1099684A (en) Catalyst composition for reduction of nox, its production and reducing method for nox in exhaust combustion gas containing oxygen
CN111437878A (en) Cu-SAPO-34 molecular sieve, preparation method thereof and application thereof in selective catalytic reduction denitration
CN104607198A (en) Vanadium-free plate-like denitration catalyst and preparation method thereof
CN112973766B (en) Preparation method of ammonium bisulfate-resistant flat-plate denitration catalyst and catalyst obtained by preparation method
CN114260015A (en) Flue gas denitration molded catalyst and preparation method and application thereof
CN113289651A (en) Low SO2Oxidation rate denitration catalyst and preparation method and application thereof
CN104324728A (en) Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof
CN114289011B (en) Denitration catalyst with wide active temperature window, and preparation method and application thereof
CN108671965B (en) Semicoke low-temperature SCR denitration catalyst and preparation method thereof
CN110124727A (en) The method of fly ash base denitrating catalyst and preparation method thereof and denitration
CN114917898B (en) Flat-plate type denitration catalyst applicable to high-temperature flue gas as well as preparation method and application thereof
CN107913696B (en) Denitration catalyst capable of resisting sulfur dioxide oxidation and preparation method thereof

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