CN114011458A - Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst - Google Patents

Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst Download PDF

Info

Publication number
CN114011458A
CN114011458A CN202111301536.3A CN202111301536A CN114011458A CN 114011458 A CN114011458 A CN 114011458A CN 202111301536 A CN202111301536 A CN 202111301536A CN 114011458 A CN114011458 A CN 114011458A
Authority
CN
China
Prior art keywords
denitration catalyst
ultralow
resistant
water
temperature denitration
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.)
Withdrawn
Application number
CN202111301536.3A
Other languages
Chinese (zh)
Inventor
刘苏涛
潘有春
王光应
梁燕
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.)
Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
Original Assignee
Anhui Yuanchen Environmental Protection Science and Technology 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 Anhui Yuanchen Environmental Protection Science and Technology Co Ltd filed Critical Anhui Yuanchen Environmental Protection Science and Technology Co Ltd
Priority to CN202111301536.3A priority Critical patent/CN114011458A/en
Publication of CN114011458A publication Critical patent/CN114011458A/en
Withdrawn legal-status Critical Current

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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium

Landscapes

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

Abstract

The invention provides a preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst, which comprises the following steps of: (1) weighing V2O5、WO3、MoO3、MnOxDissolving the precursor substance in water, adding titanium dioxide, stirring in a water bath environment, drying, and calcining to obtain the ultralow-temperature denitration catalyst; (2) weighing the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in an organic solvent, and stirring and dispersing the ultralow-temperature denitration catalyst; then adding perfluorooctyl triethoxysilane dropwise, and stirring under condensation reflux; and after the reaction is finished, carrying out suction filtration and washing for multiple times by using an organic solvent, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst. The invention has the beneficial effects that: can be used forSo as to prepare the ultra-low temperature denitration catalyst which is stable and has the functions of water resistance and sulfur resistance.

Description

Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst
Technical Field
The invention relates to the technical field of industrial catalysts, in particular to a preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst and a denitration catalyst.
Background
Nitrogen Oxides (NO)x) Is one of the main pollutants of the atmosphere and is one of the important reasons for causing acid rain, photochemical smog and ozone layer damage; NO for coal-fired power plant, cement plant, steel plant and other industriesxThe major source of (c); in recent years, with the continuous improvement of national atmospheric pollution emission standards, especially the proposal of ultra-low emission standards of flue gas in the non-coal and electricity industry, research on denitration technology of low-temperature flue gas (below 200 ℃) is receiving wide attention.
At present, the industrial flue gas denitration mainly adopts a Selective Catalytic Reduction (SCR) denitration technology, wherein a catalyst is the key of the SCR technology; the service temperature of the conventional commercial vanadium-titanium-tungsten denitration catalyst is generally over 300 ℃, and the working condition of the flue gas temperature of 120-300 ℃ in the industries such as buildings, cement, steel and the like cannot be met, so that the development of the denitration catalyst with higher activity at low temperature has important significance; the common low-temperature denitration catalyst at present comprises a vanadium-based catalyst, a manganese-based catalyst and an iron-based catalyst; if publication No. CN111530477A discloses a manganese-based ultra-low temperature denitration catalyst powder, which comprises the following components: MnO2：8-25wt.％，Fe2O3：0.5-10wt.％，WO3：0.5-10wt.％，TiO2：25-90.99wt.％，CeO2：0-10wt.％，Sm2O3：0-5wt.％，ZrO2：0-5wt.％，Y2O3：0-5wt.％，SnO2: 0-5 wt.%, which document uses manganese oxide, iron oxide and a large amount of rare earth oxide as active substances, titanium oxide as a carrier, SO that is usually contained in flue gas2Water vapor, etc., which readily react with the reactant NH under the action of the catalytically active material3The reaction generates ammonium bisulfate solid which is easily adhered to the surface of the catalyst, so that the denitration activity of the catalyst is reduced.
The development of a water-resistant and sulfur-resistant low-temperature denitration catalyst is of great significance, for example, the publication No. CN 106311213A discloses a sulfur-resistant and water-resistant low-temperature denitration catalyst, and the molecular formula of the low-temperature denitration catalyst is MV2O4Wherein M isFe. The low-temperature denitration catalyst is prepared by performing ball milling, acidification, calcination and other treatments on metal nitrate and vanadium pentoxide; the process uses metal salt and V2O5As a raw material, the acid sites of the catalyst are increased through acidification treatment to improve the water and sulfur resistance of the catalyst, but the added acid groups are easily affected by high-temperature treatment and are unstable.
Disclosure of Invention
The invention aims to solve the technical problem of providing an ultralow-temperature denitration catalyst which is stable and has water-resistant and sulfur-resistant functions.
The invention solves the technical problems through the following technical means:
a preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing V2O5、WO3、MoO3、MnOxDissolving the precursor substance in water, adding titanium dioxide, stirring in a water bath environment, drying, and calcining to obtain the ultralow-temperature denitration catalyst;
(2) weighing the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in an organic solvent, and stirring and dispersing the ultralow-temperature denitration catalyst; then adding perfluorooctyl triethoxysilane dropwise, and stirring under condensation reflux; and after the reaction is finished, carrying out suction filtration and washing for multiple times by using an organic solvent, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst.
Has the advantages that: the invention uses titanium dioxide as a carrier, V2O5、MoO3、WO3And MnOxIs an active substance, and is modified by perfluorooctyl triethoxysilane after high-temperature calcination to prepare the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the surface modification of the ultralow-temperature denitration catalyst prepared in the step (1) is performed through the perfluorooctyl triethoxysilane, so that the surface hydrophobicity of the denitration catalyst is improved, the contact between steam and the catalyst is reduced, and the sulfur resistance of the denitration catalyst is improved due to the introduced fluorine element; the water resistance and sulfur resistance of the denitration catalyst under low-temperature operation are improved under the synergistic effect.
Preferably, the concentration of said perfluorooctyltriethoxysilane in the organic solvent is 1-10%.
Preferably, V in the ultra-low temperature denitration catalyst prepared in the step (1)2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 1-5:1-5:1-5:1-5: 80-96.
Preferably, said V2O5The precursor substance of (2) comprises ammonium metavanadate; said WO3The precursor material of (1) comprises ammonium metatungstate; the MoO3The precursor material of (a) includes ammonium heptamolybdate; the MnOxThe precursor substance of (2) includes manganese nitrate.
Preferably, the organic solvent comprises isopropanol, toluene.
Preferably, the method comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
Preferably, the method comprises the following steps:
(1) weighing 3.28g of ammonium metavanadate, 2.94g of ammonium metatungstate, 2.88g of ammonium heptamolybdate and 12.61g of manganese nitrate solution (50%), respectively dissolving in water, then adding 40g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 5:5:5:5: 80;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
Preferably, the method comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in 200ml of isopropanol, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using isopropanol, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in isopropanol was 4%.
The invention also discloses a water-resistant sulfur-resistant ultralow-temperature denitration catalyst prepared by using the preparation method of any one of the technical schemes, which comprises V modified by perfluorooctyl triethoxysilane2O5、WO3、MoO3、MnOxAnd titanium dioxide.
Has the advantages that: the invention uses perfluorooctyl triethoxysilane to V2O5、WO3、MoO3、MnOxAnd V after modification by titanium dioxide2O5、WO3、MoO3、MnOxAnd the titanium dioxide not only has excellent denitration performance, but also has the water-resistant and sulfur-resistant capability under low-temperature operation.
Preferably, the titanium dioxide comprisesIn an amount of 80 to 96%, said V2O51-5% by mass of said WO3The mass content of (1-5%) of said MoO31-5% by mass of the MnOxThe mass content of (A) is 1-5%.
The invention has the advantages that:
the invention uses titanium dioxide as a carrier, V2O5、MoO3、WO3And MnOxIs an active substance, and is modified by perfluorooctyl triethoxysilane after high-temperature calcination to prepare the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the surface modification of the ultralow-temperature denitration catalyst prepared in the step (1) is performed through the perfluorooctyl triethoxysilane, so that the surface hydrophobicity of the denitration catalyst is improved, the contact between steam and the catalyst is reduced, and the sulfur resistance of the denitration catalyst is improved due to the introduced fluorine element; the water resistance and sulfur resistance of the denitration catalyst under low-temperature operation are improved under the synergistic effect.
The invention uses perfluorooctyl triethoxysilane to V2O5、WO3、MoO3、MnOxAnd V after modification by titanium dioxide2O5、WO3、MoO3、MnOxAnd the titanium dioxide not only has excellent denitration performance, but also has the water-resistant and sulfur-resistant capability under low-temperature operation.
Drawings
FIG. 1 is a graph showing the activity of a denitration catalyst according to the temperature in examples and comparative examples;
FIG. 2 shows H introduction into the denitration catalysts prepared in example 2 and comparative example 22O and SO2The change of the catalytic activity after the reaction.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 0.656g of ammonium metavanadate, 0.59g of ammonium metatungstate, 0.58g of ammonium heptamolybdate and 2.52g of manganese nitrate solution (50%), respectively dissolving in water, then adding 47g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 1:1:1:1: 96;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 2g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 1%.
Example 2
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
Example 3
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 3.28g of ammonium metavanadate, 2.94g of ammonium metatungstate, 2.88g of ammonium heptamolybdate and 12.61g of manganese nitrate solution (50%), respectively dissolving in water, then adding 40g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 5:5:5:5: 80;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
Example 4
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in 200ml of isopropanol, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using isopropanol, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in isopropanol was 4%.
Example 5
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in 200ml of isopropanol, and stirring and dispersing for 30 min; then 2g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using isopropanol, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in isopropanol was 1%.
Example 6
A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst comprises the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in 200ml of isopropanol, and stirring and dispersing for 30 min; then, 20g of perfluorooctyl triethoxysilane is dripped, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using isopropanol, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in isopropanol was 10%.
Comparative example 1
A preparation method of a denitration catalyst comprises the following steps:
weighing 1.97g of ammonium metavanadate and 1.76g of ammonium metatungstate, respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying, and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3And the mass ratio of the titanium dioxide is 3:3: 94.
Comparative example 2
A preparation method of a denitration catalyst comprises the following steps:
weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxAnd the mass ratio of the titanium dioxide is 3:3:3: 88.
The performance test method comprises the following steps:
the catalysts prepared in examples 1-6 and comparative examples 1 and 2 were put into a denitration experimental apparatus, temperature was controlled by programmed heating, and flow rate was controlled by a flow meter; the gas components at the inlet end are as follows: NO 500ppm, NH3 500ppm，H2O content 15%, SO2The content is 0.03 percent, and the space velocity is 20000h-1The reaction temperature is 120-240 ℃; and (4) after the mixed gas reacts with the catalyst, measuring the content of the residual NO by using a flue gas analyzer to obtain the catalytic efficiency.
FIGS. 1 and 2 are data measured by the above-described test method; FIG. 1 is a graph showing the change of denitration efficiency of the catalysts prepared in the examples and the comparative examples measured by the change of temperature, and it can be seen from FIG. 1 that the catalyst prepared in the examples of the present invention can be effectively denitrated in the low temperature environment of 120-240 ℃; FIG. 2 is a graph showing the denitration efficiency of catalysts prepared in examples and comparative examples measured by the change of time at a reaction temperature of 180 ℃ as shown in FIG. 2 by way of example 2 and comparative example 2; zone of example 2 and comparative example 2Other than that the catalyst prepared in comparative example 2 was not further modified by perfluorooctyltriethoxysilane, it can be seen from FIG. 2 that the denitration efficiency of example 2 was continuously maintained at a certain level with time, while the denitration efficiency of comparative example 2 was decreased with time and finally approached 30%, from the above test method, it is known that the H content in the measured gas is measured2O and SO2The catalyst prepared in example 2 was modified with perfluorooctyltriethoxysilane to have water and sulfur resistance, whereas the catalyst prepared in comparative example 2 did not have water and sulfur resistance, so that the denitration efficiency of comparative example 2 decreased with time.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a water-resistant sulfur-resistant ultralow-temperature denitration catalyst is characterized by comprising the following steps of:
(1) weighing V2O5、WO3、MoO3、MnOxDissolving the precursor substance in water, adding titanium dioxide, stirring in a water bath environment, drying, and calcining to obtain the ultralow-temperature denitration catalyst;
(2) weighing the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in an organic solvent, and stirring and dispersing the ultralow-temperature denitration catalyst; then adding perfluorooctyl triethoxysilane dropwise, and stirring under condensation reflux; and after the reaction is finished, carrying out suction filtration and washing for multiple times by using an organic solvent, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst.
2. The preparation method of the water-resistant sulfur-resistant ultralow temperature denitration catalyst as claimed in claim 1, wherein the concentration of the perfluorooctyltriethoxysilane in the organic solvent is 1-10%.
3. The preparation method of the water-resistant and sulfur-resistant ultralow-temperature denitration catalyst as claimed in claim 1, wherein V in the ultralow-temperature denitration catalyst prepared in the step (1)2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 1-5:1-5:1-5:1-5: 80-96.
4. The method for preparing the water-resistant sulfur-resistant ultra-low temperature denitration catalyst according to any one of claims 1 to 3, wherein V is2O5The precursor substance of (2) comprises ammonium metavanadate; said WO3The precursor material of (1) comprises ammonium metatungstate; the MoO3The precursor material of (a) includes ammonium heptamolybdate; the MnOxThe precursor substance of (2) includes manganese nitrate.
5. The method for preparing the water-resistant sulfur-resistant ultralow-temperature denitration catalyst according to any one of claims 1 to 3, wherein the organic solvent comprises isopropanol and toluene.
6. The preparation method of the water-resistant sulfur-resistant ultralow-temperature denitration catalyst according to claim 1, characterized by comprising the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
7. The preparation method of the water-resistant sulfur-resistant ultralow-temperature denitration catalyst according to claim 1, characterized by comprising the following steps:
(1) weighing 3.28g of ammonium metavanadate, 2.94g of ammonium metatungstate, 2.88g of ammonium heptamolybdate and 12.61g of manganese nitrate solution (50%), respectively dissolving in water, then adding 40g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 5:5:5:5: 80;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving in 200ml of toluene, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using methylbenzene, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in toluene was 4%.
8. The preparation method of the water-resistant sulfur-resistant ultralow-temperature denitration catalyst according to claim 1, characterized by comprising the following steps:
(1) weighing 1.97g of ammonium metavanadate, 1.76g of ammonium metatungstate, 1.73g of ammonium heptamolybdate and 7.57g of manganese nitrate solution (50%), respectively dissolving in water, then adding 44g of titanium dioxide, stirring in a water bath environment at 50 ℃, drying and calcining to obtain the ultralow-temperature denitration catalyst; wherein V2O5、WO3、MoO3、MnOxThe mass ratio of the titanium dioxide is 3:3:3: 88;
(2) weighing 20g of the ultralow-temperature denitration catalyst prepared in the step (1), dissolving the ultralow-temperature denitration catalyst in 200ml of isopropanol, and stirring and dispersing for 30 min; then 8g of perfluorooctyl triethoxysilane is dripped in the mixture, and the mixture is stirred for 8 hours under the reflux of condensation, wherein the condensation temperature is 80 ℃; after the reaction is finished, carrying out suction filtration and washing for 3 times by using isopropanol, and drying to obtain the water-resistant sulfur-resistant ultralow-temperature denitration catalyst; the concentration of perfluorooctyltriethoxysilane in isopropanol was 4%.
9. The water-resistant sulfur-resistant ultralow-temperature denitration catalyst prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising V modified by perfluorooctyltriethoxysilane2O5、WO3、MoO3、MnOxAnd titanium dioxide.
10. The water-resistant sulfur-resistant ultralow-temperature denitration catalyst as claimed in claim 9, wherein the mass content of the titanium dioxide is 80-96%, and the V is2O51-5% by mass of said WO3The mass content of (1-5%) of said MoO31-5% by mass of the MnOxThe mass content of (A) is 1-5%.
CN202111301536.3A 2021-11-04 2021-11-04 Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst Withdrawn CN114011458A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111301536.3A CN114011458A (en) 2021-11-04 2021-11-04 Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111301536.3A CN114011458A (en) 2021-11-04 2021-11-04 Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst

Publications (1)

Publication Number Publication Date
CN114011458A true CN114011458A (en) 2022-02-08

Family

ID=80060878

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111301536.3A Withdrawn CN114011458A (en) 2021-11-04 2021-11-04 Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst

Country Status (1)

Country Link
CN (1) CN114011458A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427628A (en) * 2023-10-12 2024-01-23 杭州玺富环保科技有限公司 Catalytic slurry for anti-falling water-resistant ceramic fiber filter tube, preparation method and application

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117427628A (en) * 2023-10-12 2024-01-23 杭州玺富环保科技有限公司 Catalytic slurry for anti-falling water-resistant ceramic fiber filter tube, preparation method and application

Similar Documents

Publication Publication Date Title
CN102500358B (en) Denitration catalyst with excellent alkali metal and alkaline-earth metal poisoning resistance
CN110773153B (en) Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof
KR101798713B1 (en) SCR Catalyst for Nitrogen Oxide Removal and Manufacturing method thereof
CN111167475B (en) Catalyst for simultaneously denitrifying, removing mercury and removing dioxin and preparation method thereof
CN112844366B (en) Multiple poisoning resistant NH 3 -SCR catalyst and method for producing the same
CN109999829A (en) A kind of bimetallic manganese iron low temperature SCR denitration catalyst, preparation method and applications
CN108465467B (en) High-efficiency NH applied to medium-low temperature flue gas3-SCR denitration catalyst, preparation method and application thereof
CN109351358A (en) A kind of transition metal oxide composite catalyst and its preparation method and application
CN105817233A (en) Preparation method of manganese series low-temperature SCR denitration catalyst
CN112657552B (en) Vanadium phosphorus oxygen low-temperature denitration catalyst and molding preparation method thereof
CN110947416B (en) For NH 3 Iron/molecular sieve catalyst of SCR (selective catalytic reduction), and preparation method and application thereof
CN114011458A (en) Preparation method of water-resistant sulfur-resistant ultralow-temperature denitration catalyst and denitration catalyst
KR20170126837A (en) SCR Catalyst for Nitrogen Oxide Removal and Manufacturing Method Thereof
CN108236943A (en) A kind of preparation method of vanadium oxide catalyst
CN110252317A (en) A kind of Ce-Fe base catalyst of Di Wen ﹑ efficient removal nitrogen oxides
CN111068709A (en) Preparation method of ferro-manganese catalyst
CN107803115A (en) The flue-gas denitration process that low-temperature denitration catalyst can be recycled
CN112121816A (en) Low-temperature catalyst special for waste incineration
CN108236944A (en) A kind of vanadium oxide catalyst and its application
CN112221488A (en) Novel core-shell structure catalyst for synergistic denitration and demercuration and preparation method thereof
CN109465007A (en) A kind of preparation method of ceria-based denitration catalyst
CN111389419B (en) Cerium dioxide loaded ferric sulfate catalyst and preparation method and application thereof
CN114471532A (en) Preparation method and application of flower-like samarium-manganese composite oxide denitration catalyst
CN110833827B (en) High nitrogen selectivity vanadium-based oxide catalyst and preparation method thereof
CN103055888B (en) Catalyst for selective catalytic reduction denitration of steam electric plant 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
WW01 Invention patent application withdrawn after publication

Application publication date: 20220208

WW01 Invention patent application withdrawn after publication