CN111715302B - Poisoning-resistant metal oxide denitration catalyst and preparation method thereof - Google Patents

Poisoning-resistant metal oxide denitration catalyst and preparation method thereof Download PDF

Info

Publication number
CN111715302B
CN111715302B CN202010277796.0A CN202010277796A CN111715302B CN 111715302 B CN111715302 B CN 111715302B CN 202010277796 A CN202010277796 A CN 202010277796A CN 111715302 B CN111715302 B CN 111715302B
Authority
CN
China
Prior art keywords
metal oxide
poisoning
catalyst
metal
trimethyl ammonium
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.)
Active
Application number
CN202010277796.0A
Other languages
Chinese (zh)
Other versions
CN111715302A (en
Inventor
张登松
王芃芦
沈志
颜婷婷
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.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
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 University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN202010277796.0A priority Critical patent/CN111715302B/en
Publication of CN111715302A publication Critical patent/CN111715302A/en
Application granted granted Critical
Publication of CN111715302B publication Critical patent/CN111715302B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/881—Molybdenum and iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
    • B01J29/0356—Iron group metals or copper
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/398—Egg yolk like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01D2258/0233—Other waste gases from cement factories
    • 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
    • B01D2258/0241—Other waste gases from glass manufacture plants
    • 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
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • B01D2258/0291—Flue gases from waste incineration plants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention discloses an anti-poisoning metal oxide denitration catalyst and a preparation method thereof. The catalyst mainly grows a shell layer on the surface of a metal oxide coprecipitation precursor in situ through a silicon source and an aluminum source, and the metal oxide catalyst coated with mesoporous aluminosilicate is formed through calcination. The catalyst of the invention has the advantages of excellent low-temperature denitration performance, simple preparation method, low requirement on synthesis equipment, extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance and the like, and can be suitable for alkali/alkaline earth metal containing catalystBelonging to fly ash and SO 2 Such as garbage incinerator, cement kiln, biomass fuel boiler, glass kiln, etc.

Description

Poisoning-resistant metal oxide denitration catalyst and preparation method thereof
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to a metal oxide denitration catalyst and a preparation method thereof, which are applied to the technical field of nitrogen oxide control and purification in environmental protection.
Background
Along with the rapid development of the economy in China, the problem of environmental pollution is also gradually highlighted. Nitrogen Oxides (NO) x ) As a major atmospheric contaminant, it can cause haze, acid rain, ozone voids and photochemical smog, damage the natural environment and cause injury to living beings. In order to control nitrogen oxides, the national regulations such as "emission standards for atmospheric pollutants in thermal power plants" (GB 16723-2011), emission standards for atmospheric pollutants in boilers (GB 16767-2014), and prevention and control of atmospheric pollution (2016) have been put under limits in recent years. Currently, ammonia selective catalytic reduction (NH 3 SCR) technology is widely used at home and abroad, but commercial V 2 O 5 -WO 3 (MoO 3 )/TiO 2 The catalyst has a certain problem in domestic fixed source denitration application.
Due to the complex composition of the flue gases of industrial boilers, alkali/alkaline earth oxides (K 2 O、Na 2 O, caO) and SO 2 And iso-poisons, resulting in the catalyst needing to be replaced or regenerated once for about 3 years. In the practical application conditions of denitration catalysts such as garbage incinerators, cement kilns, biomass fuel boilers and glass kilns, a great amount of alkali metal fly ash contained in the flue gas accelerates the deactivation of the catalyst. Although toxic substances in the flue gas are greatly reduced after the dust removal and desulfurization process, the residual alkali metal fly ash can cover the surface of the catalyst and be combined with the acid center on the catalytic surface, so that the acid amount on the surface of the catalyst is reduced, the adsorption of the reducing agent ammonia is influenced, the reduction of the ammonia by the active center of the catalyst is inhibited, and the activation of the ammonia is reduced. In addition, at lower temperatures, NH 3 SCR catalyst self-reactivity and SO 2 Tolerance is faced withSerious challenges, residual SO from desulfurization process 2 Inactive sulfate may be formed with the catalyst active component; in addition, at 300 ℃ or less, SO 2 Possibly with NH 3 The formed ammonium (hydrogen) sulfate covers the catalytic active sites and blocks the pore channel structure, thereby seriously affecting the activity of the denitration catalyst.
At present, the domestic and foreign patents mainly focus on the improvement and preparation of the activity of the denitration catalyst, the research on the resistance of the denitration catalyst is less, and in the work reported in the literature, only alkali resistance, alkaline earth metal resistance or SO resistance are concerned 2 Poisoning, there are few reports of improvement of resistance in its coexisting state.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide an anti-poisoning metal oxide denitration catalyst and a preparation method thereof, and the catalyst is a core-shell structure selective reduction denitration catalyst with good performance and can improve alkali/alkaline earth metals and SO (sulfur dioxide) 2 Poisoning effect in coexistence. The catalyst developed by the invention enhances the alkali/alkaline earth metal resistance and sulfur resistance of the catalyst on the basis of ensuring the excellent medium-low temperature activity of the catalyst, and can greatly prolong the service life of the catalyst in fixed source flue gas denitration.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
an anti-poisoning metal oxide denitration catalyst takes a metal active component and a metal auxiliary agent as cores, and a mesoporous aluminosilicate shell layer is constructed in situ in a liquid phase; the active component of the catalyst metal is at least one of oxides of manganese, vanadium, iron and cerium, and the metal auxiliary agent is at least one of oxides of titanium, cobalt, zirconium, molybdenum, tungsten and niobium.
As a preferable technical scheme of the invention, the metal oxide active component and the auxiliary component are combined in a coprecipitation mode to form a precursor, a shell layer grows on the surface of the metal oxide coprecipitation precursor in situ through a silicon source and an aluminum source, and the mesoporous aluminosilicate coated metal oxide catalyst is formed through calcination.
As a preferable technical scheme of the invention, the solvent used for synthesizing the mesoporous aluminosilicate shell layer is at least one of methanol, ethanol, isopropanol, ethylene glycol and water.
As a preferable technical scheme of the invention, the mass ratio of the mesoporous aluminosilicate shell to the catalyst precursor is (0.1-10): 1.
as a preferable technical scheme of the invention, the molar ratio of silicon to aluminum in the mesoporous aluminosilicate shell layer is (0.1-50): 1.
the preparation method of the poisoning-resistant metal oxide denitration catalyst comprises the following steps:
a. preparing a metal oxide precursor:
dissolving a metal active component and a metal auxiliary agent serving as raw materials in deionized water, adjusting the pH value of the mixed solution to be alkaline, coprecipitating the active component and the auxiliary agent to obtain metal oxide precursor sediment, filtering and drying a product to obtain a precursor for later use;
b. preparation of mesoporous aluminosilicate:
dispersing the metal oxide precursor obtained after drying in the step a in a mixed solvent of alcohol and water, adding a template agent, adjusting the pH to 8-10 by using ammonia water, then adding a silicon source and an aluminum source respectively, filtering and washing after fully stirring, and then calcining at 450-550 ℃ by using a muffle furnace to obtain a product, namely the poisoning-resistant metal oxide denitration catalyst.
In the step a, the mass ratio of the metal active component to the metal auxiliary agent is (1-3): (1.5-2.5).
As a preferred technical solution of the present invention, in the step a, a precursor salt of the metal active component is a soluble salt of a metal; the precursor salt of the auxiliary agent adopts soluble salt of metal.
In the step a, ammonia water is added to adjust the pH of the mixed solution to 8-10.
In the step b, at least one of tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride is adopted as the template agent.
As a preferred embodiment of the present invention, in said step b, calcination is performed for at least 4 hours.
In the preferred embodiment of the present invention, in the step b, the alcohol is at least one of methanol, ethanol, isopropanol, and ethylene glycol.
In the preferred embodiment of the present invention, in the step b, the silicon source is ethyl orthosilicate.
In the step b, the aluminum source is at least one of aluminum chloride, aluminum sulfate, aluminum nitrate and aluminum isopropoxide.
As a preferred technical scheme of the present invention, in the step b, the amount of the aluminum source and the mass ratio of the metal salt for preparing the metal active component are (1-3) calculated with respect to the mass of the metal salt for preparing the metal active component: (0.1-0.4).
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the denitration catalyst takes a metal oxide precursor as a core, and mesoporous aluminosilicate is constructed in situ as a shell layer; with the increase of the thickness of the shell layer and the quality of the aluminum source, the alkali/alkaline earth metal resistance of the catalyst is greatly improved, and the catalyst has better sulfur resistance;
2. the preparation method of the invention is simple, low in cost, low in requirement on synthesis equipment, and has the advantages of extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance, and is suitable for fly ash containing alkali/alkaline earth metal and SO 2 The service life of the catalyst in fixed source flue gas denitration can be greatly prolonged in the fields of garbage incinerators, cement kilns, biomass fuel boilers and glass kilns.
Drawings
FIG. 1 is a TEM image of mesoporous aluminosilicate coated manganese cobalt oxide prepared in example 1 of the present invention.
FIG. 2 is a graph showing the pore size distribution of the mesoporous aluminosilicate-coated manganese cobalt oxide prepared in example 1 of the present invention.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
embodiment one:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 1.5g of manganese nitrate tetrahydrate and 2g of cobalt nitrate hexahydrate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH value to 8, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 5ml of methanol and 55ml of deionized water to prepare a mixed solution, adding 1.5g of dodecyl trimethyl ammonium bromide and 0.5g of octadecyl trimethyl ammonium bromide, and adding 2ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 2ml of tetraethoxysilane, and then adding 0.2g of aluminum nitrate nonahydrate; and stirring for 1h, filtering and washing the product, drying, and calcining at 450 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 90-250 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, and N is at 150 DEG C 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of sodium nitrate and calcined at 500℃for 3 hours to give a poisoning-simulating catalyst, which was then tested for 20ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 90-250 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 85 percent and N is below 150 DEG C 2 The amount of O produced is small. Poisoning resistance prepared in this exampleThe metal oxide denitration catalyst was used as a sample for experimental tests, and referring to fig. 1-2, fig. 1 is a TEM image of mesoporous aluminosilicate coated manganese cobalt oxide prepared in this example. FIG. 2 is a graph showing the pore size distribution of the mesoporous aluminosilicate-coated manganese cobalt oxide prepared in this example. The poisoning-resistant metal oxide denitration catalyst prepared in the embodiment has smaller particle size, and mesoporous aluminosilicate coated manganese cobalt oxide particles have uniform pore diameter. The catalyst of the embodiment is a core-shell structure selective reduction denitration catalyst with good performance, and has high alkali/alkaline earth metal resistance and sulfur resistance, and the catalyst can improve alkali/alkaline earth metal and SO 2 Poisoning effect in coexistence. The catalyst of the embodiment enhances the alkali/alkaline earth metal resistance and sulfur resistance of the catalyst on the basis of ensuring the excellent medium-low temperature activity of the catalyst, and can greatly prolong the service life of the catalyst in fixed source flue gas denitration. The catalyst has the advantages of excellent medium-low temperature denitration performance, simple preparation method, low requirement on synthetic equipment, extremely strong alkali/alkaline earth metal poisoning resistance, sulfur poisoning resistance and the like, and is suitable for alkali/alkaline earth metal-containing fly ash and SO in garbage incinerators, cement kilns, biomass fuel boilers, glass kilns and the like 2 Is a fixed source denitrification requirement.
Example 2:
this embodiment is substantially the same as embodiment 1, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 3g of ferric nitrate nonahydrate and 1.5g of titanium sulfate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH value to 9, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 10ml of ethanol and 50ml of deionized water to prepare a mixed solution, adding 1g of tetradecyl trimethyl ammonium bromide and 1g of octadecyl trimethyl ammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 3ml of ethyl orthosilicate, and then adding 0.2g of aluminum sulfate; and stirring for 2 hours, filtering and washing the product, drying, and calcining at 550 ℃ for 4 hours to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 270-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of potassium nitrate and calcined at 500℃for 3 hours to give a poisoning-simulating catalyst, which was then tested for 1000ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 270-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 80 percent, N 2 The amount of O produced is small.
Example 3
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 1g of cerium nitrate hexahydrate and 2g of ammonium metatungstate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH to 10, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 30ml of isopropanol and 30ml of deionized water to prepare a mixed solution, adding 0.5g of cetyltrimethylammonium chloride and 1g of octadecyltrimethylammonium chloride, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 4ml of ethyl orthosilicate, and then adding 0.4g of aluminum chloride; and stirring for 1h, filtering and washing the product, drying, and calcining at 500 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selective testingThe reaction temperature is 210-450 ℃ and the space velocity is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 80 percent, N 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.2g of calcium nitrate and the poisoning-simulating catalyst obtained by calcining at 500℃for 3 hours was retested to a catalyst containing 100ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 270-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 80 percent, N 2 The amount of O produced is small.
Example 4
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 1g of manganese acetate tetrahydrate and 2g of phosphotungstic acid are weighed, dissolved in deionized water, added with ammonia water to adjust the pH value to 9, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: 40ml of ethylene glycol and 20ml of deionized water are measured to prepare a mixed solution, 0.5g of tetradecyltrimethylammonium chloride and 1g of hexadecyltrimethylammonium bromide are added, and 1ml of ammonia water is added; then adding a metal oxide precursor, stirring for 0.5h, adding 3ml of tetraethoxysilane, and then adding 0.3g of aluminum nitrate nonahydrate; and stirring for 1h, filtering and washing the product, drying, and calcining at 550 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 90-300 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, and N is at 180 DEG C 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: a catalyst was impregnated with 0.05g of potassium nitrate and 0.2g of calcium nitrate, and the resulting poisoning-simulating catalyst was calcined at 500℃for 3 hours, and tested again for 50ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 180-300 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 85 percent and N is below 180 DEG C 2 The amount of O produced is small.
Example 5
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 2g of cerium acetate and 2.5g of zirconium nitrate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH to 8, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 20ml of methanol, 20ml of isopropanol and 20ml of deionized water to prepare a mixed solution, adding 1g of tetradecyltrimethylammonium chloride and 2.5g of hexadecyltrimethylammonium bromide, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 5ml of ethyl orthosilicate, and then adding 0.2g of aluminum sulfate; and stirring for 1h, filtering and washing the product, drying, and calcining at 500 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 280-480 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent and N is below 450 DEG C 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: impregnating catalyst with 0.1g sodium nitrate and 0.2g calcium nitrate, calcining at 500 deg.C for 3 hr to obtain simulated poisoningCatalyst retest it at 200ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 280-480 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 85 percent, N 2 The amount of O produced is small.
Example 6
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 2g of ferrous ammonium sulfate hexahydrate and 2g of ammonium molybdate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH to 10, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: 10ml of ethanol, 30ml of ethylene glycol and 20ml of deionized water are measured to prepare a mixed solution, 0.5g of tetradecyltrimethylammonium chloride and 0.5g of hexadecyltrimethylammonium bromide are added, and 0.5ml of ammonia water is added; then adding a metal oxide precursor, stirring for 0.5h, adding 1ml of ethyl orthosilicate, and then adding 0.4g of aluminum sulfate; and stirring for 1h, filtering and washing the product, drying, and calcining at 550 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 270-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of potassium nitrate and 0.05g of sodium nitrate, and the poisoning-simulating catalyst obtained by calcining at 500℃for 3 hours was retested to contain 500ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 300-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 O production amountLess.
Example 7
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 2g of ferric chloride and 2g of ammonium metavanadate are weighed and dissolved in deionized water, ammonia water is added to adjust the pH to 10, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: 10ml of ethanol, 20ml of ethylene glycol and 30ml of deionized water are measured to prepare a mixed solution, 0.5g of tetradecyltrimethylammonium chloride and 1.5g of hexadecyltrimethylammonium bromide are added, and 1ml of ammonia water is added; then adding a metal oxide precursor, stirring for 0.5h, adding 1.5ml of tetraethoxysilane and then adding 0.2g of aluminum sulfate; and stirring for 1h, filtering and washing the product, drying, and calcining at 550 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 240-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm，N 2 Is a dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of potassium nitrate and the poisoning-simulating catalyst obtained by calcining at 450℃for 3 hours was retested to a catalyst containing 50ppm SO 2 Under the condition of SCR denitration activity, the reaction temperature is 265-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 The amount of O produced is small.
Example 8
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 2g of cerium nitrate hexahydrate and 2g of niobium oxalate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH to 10, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 5ml of ethanol, 20ml of ethylene glycol and 35ml of deionized water to prepare a mixed solution, adding 1g of tetradecyltrimethylammonium chloride and 0.5g of hexadecyltrimethylammonium bromide, and adding 1ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 2ml of tetraethoxysilane and then adding 0.1g of aluminum sulfate; and stirring for 1h, filtering and washing the product, drying, and calcining at 550 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 300-400 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, N 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of potassium nitrate and calcined at 500℃for 3 hours to give a poisoning-simulating catalyst, which was then tested for 100ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 300-450 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 70 percent, N 2 The amount of O produced is small.
Example 9
This embodiment is substantially identical to the previous embodiment, except that:
in this embodiment, a method for preparing an anti-poisoning metal oxide denitration catalyst includes the following steps:
preparing a metal oxide precursor: 2g of manganese nitrate and 2g of titanium sulfate are weighed, dissolved in deionized water, added with ammonia water to adjust the pH value to 10, and metal oxide precursor sediment is obtained, filtered and dried for standby.
Preparation of mesoporous aluminosilicate: weighing 5ml of ethanol, 10ml of ethylene glycol and 45ml of deionized water to prepare a mixed solution, adding 0.5g of tetradecyltrimethylammonium chloride and 1g of hexadecyltrimethylammonium bromide, and adding 0.5ml of ammonia water; then adding a metal oxide precursor, stirring for 0.5h, adding 1.5ml of tetraethoxysilane and then adding 0.4g of aluminum sulfate; and stirring for 1h, filtering and washing the product, drying, and calcining at 450 ℃ for 4h to obtain the anti-poisoning metal oxide denitration catalyst.
Denitration performance test of catalyst: granulating the prepared catalyst to 40-60 meshes, and placing into a reaction furnace for activity and N 2 Selectively testing, the reaction temperature is 100-250 ℃ and the airspeed is 50000h -1 Under the condition of (1) the denitration efficiency is stabilized to be more than 90 percent, and N is at 150 DEG C 2 O yield was less than 10ppm. Simulated flue gas is O 2 5％，NO 500ppm，NH 3 500ppm, N2 is the dilution gas.
Alkali/alkaline earth metal and sulfur resistance simultaneous poisoning performance test: the catalyst was impregnated with 0.1g of sodium nitrate and calcined at 500℃for 3 hours to give a poisoning-simulating catalyst, which was then tested for 20ppm SO 2 SCR denitration activity under the condition that the reaction temperature is 100-250 ℃ and the airspeed is 50000h -1 Under the condition of that the denitration efficiency is stabilized to be more than 80 percent, N is lower than 150 DEG C 2 The amount of O produced is small.
In summary, the poisoning-resistant metal oxide denitration catalyst of the present invention is a denitration catalyst having both high alkali/alkaline earth metal resistance and sulfur-resistant metal oxide. The catalyst mainly grows a shell layer on the surface of a metal oxide coprecipitation precursor in situ through a silicon source and an aluminum source, and the metal oxide catalyst coated with mesoporous aluminosilicate is formed through calcination. The catalyst of the invention has the advantages of excellent low-temperature denitration performance, simple preparation method, low requirement on synthesis equipment, extremely strong alkali/alkaline earth metal poisoning and sulfur poisoning resistance and the like, and can be suitable for fly ash containing alkali/alkaline earth metal and SO 2 Such as garbage incinerator, cement kiln, biomass fuel boiler and glass kiln.
The embodiment of the present invention has been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical scheme of the present invention can be made according to the purpose of the present invention, so long as the purpose of the present invention is met, and the technical principles and the inventive concept of the anti-poisoning metal oxide denitration catalyst and the preparation method thereof of the present invention are all within the scope of the present invention.

Claims (4)

1. An anti-poisoning metal oxide denitration catalyst, which is characterized in that: taking a metal active component and a metal auxiliary agent as cores, and constructing a mesoporous aluminosilicate shell layer in situ in a liquid phase; the metal active component of the catalyst is at least one of oxides of manganese, vanadium, iron and cerium, and the metal auxiliary agent is at least one of oxides of titanium, cobalt, zirconium, molybdenum, tungsten and niobium;
the metal oxide active component and the auxiliary agent component are combined in a coprecipitation mode to form a precursor, a shell layer grows in situ on the surface of the metal oxide coprecipitation precursor through a silicon source and an aluminum source, and the metal oxide catalyst coated with mesoporous aluminosilicate is formed through calcination;
the mass ratio of the mesoporous aluminosilicate shell to the precursor is (0.1-10): 1, a step of;
the molar ratio of silicon to aluminum in the mesoporous aluminosilicate shell layer is (0.1-50): 1, a step of;
the poisoning-resistant metal oxide denitration catalyst is prepared by adopting the following preparation method, and comprises the following steps:
a. preparing a metal oxide precursor:
dissolving a metal active component source and a metal auxiliary agent source in deionized water, adjusting the pH value of the mixed solution to be alkaline to obtain metal oxide precursor sediment, filtering and drying to obtain a precursor for later use; the mass ratio of the metal active component to the metal auxiliary agent is (1-3): (1.5-2.5);
b. preparation of mesoporous aluminosilicate:
dispersing the metal oxide precursor obtained after drying in the step a in a mixed solvent of alcohol and water, adding a template agent, adjusting the pH to 8-10 by using ammonia water, then adding a silicon source and an aluminum source respectively, filtering and washing after fully stirring, and then calcining at 450-550 ℃ by using a muffle furnace to obtain a product, namely the poisoning-resistant metal oxide denitration catalyst;
the template agent adopts at least one of tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride.
2. A method for preparing the poisoning-resistant metal oxide denitration catalyst as defined in claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
a. preparing a metal oxide precursor:
dissolving a metal active component source and a metal auxiliary agent source in deionized water, adjusting the pH value of the mixed solution to be alkaline to obtain metal oxide precursor sediment, filtering and drying to obtain a precursor for later use; the mass ratio of the metal active component to the metal auxiliary agent is (1-3): (1.5-2.5);
b. preparation of mesoporous aluminosilicate:
dispersing the metal oxide precursor obtained after drying in the step a in a mixed solvent of alcohol and water, adding a template agent, adjusting the pH to 8-10 by using ammonia water, then adding a silicon source and an aluminum source respectively, filtering and washing after fully stirring, and then calcining at 450-550 ℃ by using a muffle furnace to obtain a product, namely the poisoning-resistant metal oxide denitration catalyst;
the template agent adopts at least one of tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium chloride.
3. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 2, characterized by comprising the steps of: in the step a, ammonia water is added to adjust the pH value of the mixed solution to 8-10.
4. The method for preparing the poisoning-resistant metal oxide denitration catalyst according to claim 2, characterized by comprising the steps of: in said step b, calcination is carried out for at least 4 hours.
CN202010277796.0A 2020-04-08 2020-04-08 Poisoning-resistant metal oxide denitration catalyst and preparation method thereof Active CN111715302B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010277796.0A CN111715302B (en) 2020-04-08 2020-04-08 Poisoning-resistant metal oxide denitration catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010277796.0A CN111715302B (en) 2020-04-08 2020-04-08 Poisoning-resistant metal oxide denitration catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111715302A CN111715302A (en) 2020-09-29
CN111715302B true CN111715302B (en) 2023-06-13

Family

ID=72564111

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010277796.0A Active CN111715302B (en) 2020-04-08 2020-04-08 Poisoning-resistant metal oxide denitration catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111715302B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112675833A (en) * 2020-12-23 2021-04-20 浙江盛旺环境工程有限公司 SCR catalyst module and preparation method thereof
CN113318749B (en) * 2021-06-23 2023-05-09 贵州大学 High-efficiency medium-low temperature NH for resisting heavy metal poisoning 3 SCR denitration catalyst, and preparation method and application thereof
CN113368863A (en) * 2021-07-01 2021-09-10 大连瑞克科技股份有限公司 Preparation method of eggshell type iron-molybdenum catalyst containing silicon dioxide
CN114849469B (en) * 2022-06-10 2023-07-21 德州职业技术学院（德州市技师学院） Front-end module for flue gas denitration and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102091658A (en) * 2010-12-27 2011-06-15 北京工业大学 Dust adhesion-resistant coated denitration catalytic sphere and preparation method thereof
CN105854873A (en) * 2016-05-11 2016-08-17 四川大学 Low-temperature high-efficiency metal composite oxide denitration catalyst and preparation method thereof
CN108246350A (en) * 2018-01-10 2018-07-06 武汉理工大学 A kind of mesoporous molecular sieve catalyst material and its in-situ preparation method for coating noble metal
CN110152653A (en) * 2019-05-15 2019-08-23 南京师范大学 A kind of hollow Nano tubulose manganese-based low-temperature denitration catalyst and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102091658A (en) * 2010-12-27 2011-06-15 北京工业大学 Dust adhesion-resistant coated denitration catalytic sphere and preparation method thereof
CN105854873A (en) * 2016-05-11 2016-08-17 四川大学 Low-temperature high-efficiency metal composite oxide denitration catalyst and preparation method thereof
CN108246350A (en) * 2018-01-10 2018-07-06 武汉理工大学 A kind of mesoporous molecular sieve catalyst material and its in-situ preparation method for coating noble metal
CN110152653A (en) * 2019-05-15 2019-08-23 南京师范大学 A kind of hollow Nano tubulose manganese-based low-temperature denitration catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN111715302A (en) 2020-09-29

Similar Documents

Publication Publication Date Title
CN111715302B (en) Poisoning-resistant metal oxide denitration catalyst and preparation method thereof
CN108212146B (en) Metal integrally-structured denitration catalyst with core-shell structure and preparation method thereof
CA2756736C (en) Catalyst composition for selective catalytic reduction of exhaust gases
CN112547129B (en) Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method and application thereof
WO2020103848A1 (en) Environmentally-friendly high-temperature denitration catalyst and preparation method therefor
CN110052264B (en) Preparation method of SCR denitration catalyst used under low temperature condition
CN109876856B (en) Low-temperature flue gas denitration catalyst and preparation method thereof
CN110773153B (en) Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof
CN107552088B (en) Composite molecular sieve denitration catalyst and preparation method and application thereof
CN102861565A (en) Aluminum oxide-loaded cerium oxide catalyst and preparation method and application thereof
CN111659413A (en) Low-temperature rare earth-based sulfur-resistant water-resistant denitration catalyst and preparation method thereof
CN105833901A (en) PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof
CN112742413A (en) Low-temperature SCR denitration catalyst and preparation method and application thereof
CN114682297A (en) Low-temperature denitration catalyst and preparation method and application thereof
CN113694933A (en) High-entropy co-doped low-temperature SCR denitration catalyst and preparation method and application thereof
CN112495390A (en) Medium-low temperature low-vanadium desulfurization and denitrification catalyst and preparation method thereof
CN111889100A (en) Cryptomelane type mixed manganese oxide catalyst for removing soot of diesel vehicle through oxidation
AU2021103091A4 (en) An acid-redox dual sites synergistic nh3-scr catalyst, a preparation method, and an application thereof
CN111545188A (en) Amorphous aluminosilicate-based denitration catalyst and preparation method thereof
CN111085217A (en) Three-dimensional porous Mn-Co microspheres grown on cordierite, and preparation and application thereof
CN110404542A (en) A kind of core-shell structure copolymer ball CoFe2O4Catalyst and the preparation method and application thereof
CN109745995B (en) Wide-temperature-window SCR flue gas denitration catalyst and preparation method and application thereof
CN116422352B (en) Preparation method and application of phosphotungstic acid modified iron-based MOF derivative material
CN111111641B (en) Cerium dioxide-based catalyst and preparation method and application thereof
CN110548502B (en) Vanadium oxide modified manganese-based catalyst for low-temperature SCR denitration and preparation method and application 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
GR01 Patent grant
GR01 Patent grant