CN112973667A - Novel titanium dioxide doped modified layer columnar clay denitration catalyst and preparation method thereof - Google Patents
Novel titanium dioxide doped modified layer columnar clay denitration catalyst and preparation method thereof Download PDFInfo
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- CN112973667A CN112973667A CN202110247154.0A CN202110247154A CN112973667A CN 112973667 A CN112973667 A CN 112973667A CN 202110247154 A CN202110247154 A CN 202110247154A CN 112973667 A CN112973667 A CN 112973667A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 239000004927 clay Substances 0.000 title claims abstract description 110
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000011229 interlayer Substances 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 239000010410 layer Substances 0.000 claims abstract description 29
- 239000013543 active substance Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000004014 plasticizer Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 18
- 230000001070 adhesive effect Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000000440 bentonite Substances 0.000 claims description 7
- 229910000278 bentonite Inorganic materials 0.000 claims description 7
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 7
- -1 rectorite Chemical compound 0.000 claims description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920000742 Cotton Polymers 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910002339 La(NO3)3 Inorganic materials 0.000 claims description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 8
- 239000003546 flue gas Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 7
- 230000000607 poisoning effect Effects 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- B01J23/16—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
- B01J23/22—Vanadium
-
- 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
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
Abstract
The invention discloses a novel titanium dioxide doped modified pillared interlayer clay denitration catalyst which comprises a catalyst main body structure, wherein the catalyst main body structure comprises a catalyst carrier and a catalytic active substance, the catalyst carrier comprises titanium dioxide, the catalyst carrier also comprises at least one of Ti, Zr and Al modified pillared interlayer clay, wherein the Ti, Zr and Al are used as pillared agents of the pillared interlayer clay, and the catalytic active substance comprises at least one of oxides of V, Ce, Mn, Ho, La and Pr. The invention also discloses a simple and convenient preparation method of the composition. The invention provides a new typeThe titanium dioxide doped modified layer columnar clay denitration catalyst can effectively remove NO in flue gasXCan also effectively resist SO in flue gas2And H2And the poisoning action of O on the catalyst prolongs the service life of the catalyst, reduces the replacement times of the catalyst and reduces the enterprise cost.
Description
Technical Field
The invention belongs to the technical field of denitration catalysts, and particularly relates to a novel titanium dioxide doped modified layer columnar clay denitration catalyst and a preparation method thereof.
Background
Nitrogen Oxides (NO)X) Are the main pollutants released by human activities. Its discharge can lead to the formation of acid rain and haze. At present, NOXMainly from flue gases emitted from stationary sources (e.g. thermal power plants and industrial kilns), which are mainly driven by fossil fuel combustion, and secondly from automobile exhaust (mobile sources), while the cement industry becomes the third largest NO behind both thermal and automobile exhaustXA source of emissions. Currently, the reduction of NO in flue gasXIs to use NH3Selective Catalytic Reduction (SCR) technology as a reducing agent to reduce NOX。
Along with China's NOXThe emission standard is increasingly strict, and the SCR denitration technology is greatly developed in China. In the application process of the SCR technology, the preparation and production of the catalyst are the most important components, and the catalytic performance of the catalyst directly influences the overall denitration effect of an SCR system. Conventional commercial denitration catalysts are generally V2O5-WO3(MoO3)-TiO2The catalyst is applicable to the temperature range of 300-400 ℃, the temperature window is narrow, and TiO2The dosage is more and the cost is expensive.
Pillared Interlayer Clays (PILCs) are a new type of porous material, which is a new type of catalytic material being researched and developed internationally in recent years, and have very excellent catalytic performance. China has abundant bentonite resources, accounts for about 60% of the total world reserves, is a main raw material for preparing the pillared interlayer clay, and has low cost. And alsoThe catalyst of the pillared clay has good H resistance in the reduction of SCR by an ammonia process2O and SO2And (4) performance. If the TiO can be replaced or partially replaced by pillared clay2The denitration catalyst prepared by taking the denitration catalyst as a carrier can reduce the production cost to a great extent, bring greater profits for enterprises and improve the market competitiveness.
The invention aims to provide a high-efficiency, wide-temperature and low-cost flue gas denitration catalyst which is prepared on a carrier TiO2On the basis of titanium dioxide, pillared clay is used for partially replacing the titanium dioxide, different active components are adopted, the flue gas denitration performance of the pillared clay in a wide temperature range is inspected, a foundation is provided for the denitration catalyst industry, and the cost is reduced.
Disclosure of Invention
The invention aims to provide a novel titanium dioxide doped modified pillared layered clay denitration catalyst which is safe, effective and convenient to use, and a simple, convenient and practical preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a novel titanium dioxide doping modification layer column form clay denitration catalyst, denitration catalyst includes catalyst major structure, and catalyst major structure includes catalyst carrier and catalytic activity material, and catalyst carrier composition includes titanium white powder, and catalyst carrier composition still includes at least one in Ti, Zr and the Al modification layer column clay, and wherein Ti, Zr and Al are as the pillared agent of layer column clay, and catalytic activity material includes at least one in the oxide of V, Ce, Mn, Ho, La and Pr.
Further, the raw material component of the modified pillared interlayer clay is at least one of bentonite, montmorillonite, rectorite, bentonite, beidellite and hankt stone, and the particle size of the raw material of the modified pillared interlayer clay is 180-220 meshes.
Further, the precursor of the modified pillared interlayer clay Ti pillared agent is TiCl4Or Ti (OC)4H9)4The precursor of the Zr pillared agent is ZrCl4Or ZrO (NO)3)2·2H2The precursor of the O, Al pillared agent is AlCl3Or Al (NO)3)3·6H2O。
Further, the denitration catalyst is in a honeycomb structure, the catalyst carrier accounts for 95-99wt% of the main body structure of the catalyst, and the catalytic active substance accounts for 1-5wt% of the main body structure of the catalyst.
Further, the catalyst carrier also comprises a structural auxiliary agent, a binder and a plasticizer.
Further, the structural auxiliary agent is at least one of glass fiber and pulp cotton, the adhesive is at least one of polyacrylamide and methyl cellulose, and the plasticizer is polyethylene oxide.
Furthermore, the structural auxiliary agent accounts for 2-8% of the mass of the catalyst carrier, the adhesive accounts for 2-8% of the mass of the catalyst carrier, and the plasticizer accounts for 2-8% of the mass of the catalyst carrier.
A preparation method of a novel titanium dioxide doped modified layer columnar clay denitration catalyst comprises the following steps:
(1) preparing a modified pillared interlayer clay pillared agent;
(2) adding raw material components of the modified pillared interlayer clay into a solvent, adding a dispersing agent, and stirring until the raw material components are fully dispersed to obtain a clay suspension;
(3) dropwise adding the pillared agent in the step (1) into the clay suspension in the step (2), continuously stirring, washing with deionized water, adjusting the pH value to 6.5-7.5, drying, calcining and crushing to obtain modified pillared interlayer clay;
(4) and (3) uniformly mixing the modified pillared interlayer clay and the titanium dioxide in the step (3), adding a precursor solution of an active substance, adding a structural assistant, an adhesive and a plasticizer, fully and uniformly mixing, and ageing, pre-extruding, molding, drying and exercising to obtain the titanium dioxide doped modified pillared interlayer clay denitration catalyst.
Further, the pillared agent in the step (1) comprises a Ti pillared agent, a Zr pillared agent and an Al pillared agent, and the preparation method of the Ti pillared agent comprises the following steps: adding a Ti precursor into HCl under the condition of stirring, wherein the molar ratio of the Ti precursor to the HCl is 1-3:1, continuously stirring for 30-60 min, and standing for 2-6 h to obtain a Ti pillared agent; the preparation method of the Zr pillared agent comprises the following steps: adding the Zr precursor into deionized water to prepare a solution with the concentration of 0.1-0.5 mol/L, heating to 85 ℃, and continuously stirring for 4-8 h to obtain a Zr pillared agent; the preparation method of the Al pillared agent comprises the following steps: and adding the NaOH solution into the Al precursor solution, wherein the molar ratio of NaOH to the Al precursor is 1-2:1, continuously stirring for 8-16 h, and standing for 2-6 h to obtain the Al pillared agent.
Further, the solvent in the step (2) is deionized water, acetone, alcohol, deionized water + acetone or deionized water + alcohol, wherein the ratio of deionized water to acetone in deionized water + acetone is 1:0.5, 1:1, 1:2 or 1:4, the ratio of deionized water to alcohol in deionized water + alcohol is 1:0.5, 1:1, 1:2 or 1:4, the mass ratio of the raw material components of the modified pillared interlayer clay to the solvent is 0.4-1:100, and the dispersant is Na2P2O7、Na5P3O10、(NaPO3)6、Na2CO3Or at least one of NaCl, the concentration of the dispersant is 1-5 g/L, and the stirring time is 12-48 h after the dispersant is added;
the continuous stirring time in the step (3) is 12-36 h, the mass ratio of the pillared agent to the clay is 10-20 mmol:1 g, the drying temperature is 60-80 ℃, the calcining temperature is 450-;
the ratio of the modified pillared interlayer clay to the titanium dioxide in the step (4) is 5-40:100, and the precursor of the active substance is NH4VO3、Ce(NO3)3、Mn(NO3)2、Ho(NO3)3、La(NO3)3And Pr (NO)3)3The concentration of the precursor solution of the active substance is 1-5%.
The invention has the advantages that:
(1) the novel titanium dioxide doped modified layer columnar clay denitration catalyst provided by the invention can effectively remove NO in flue gasXCan also effectively resist SO in flue gas2And H2Poisoning behavior of O on catalyst, prolonging catalystThe service life of the catalyst is prolonged, the replacement times of the catalyst are reduced, and the enterprise cost is reduced.
(2) According to the novel titanium dioxide doped modified layer columnar clay denitration catalyst provided by the invention, the pillared agent can be uniformly distributed in a clay layer and is compact, the integral structure of the catalyst is more stable, the compression resistance and the abrasion resistance of the catalyst are improved, and the popularization of the catalyst in the field of flue gas treatment is facilitated.
(3) The novel titanium dioxide doped modified layer columnar clay denitration catalyst provided by the invention has the advantage of reducing the consumption of titanium dioxide which is the main raw material of the catalyst, increases the profit for reducing the cost of enterprises and has large market demand.
(4) The novel titanium dioxide doped modified layer columnar clay denitration catalyst provided by the invention improves the application prospect of the SCR denitration technology in the flue gas treatment direction, and has good economic and social benefits.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and the specific examples described herein are only for explaining the present invention and are not intended to limit the present invention.
Example 1
The utility model provides a novel titanium dioxide doping modified layer cylindric clay denitration catalyst, denitration catalyst include catalyst major structure, and catalyst major structure includes catalyst carrier and catalytic activity material, and catalyst carrier composition includes titanium white powder, and catalyst carrier composition still includes Ti modified layer post clay, and wherein Ti is as the pillared agent of layer post clay, and the precursor of modified layer post clay Ti pillared agent is TiCl4Or Ti (OC)4H9)4. The raw material components of the modified pillared interlayer clay comprise bentonite and montmorillonite, and the particle size of the raw material of the modified pillared interlayer clay is 180 meshes. The catalytically active material comprises V, Ce oxide.
The denitration catalyst is in a honeycomb structure, the mass fraction of the catalyst carrier in the main body structure of the catalyst is 95wt%, and the mass fraction of the catalytic active substance in the main body structure of the catalyst is 5 wt%. The catalyst support also includes a structural adjunct, a binder, and a plasticizer. The structural auxiliary agent is glass fiber, the adhesive is polyacrylamide, and the plasticizer is polyoxyethylene. The structural auxiliary agent accounts for 2% of the mass of the catalyst carrier, the adhesive accounts for 2% of the mass of the catalyst carrier, and the plasticizer accounts for 2% of the mass of the catalyst carrier.
A preparation method of a novel titanium dioxide doped modified layer columnar clay denitration catalyst comprises the following steps:
(1) preparing a modified pillared interlayer clay Ti pillared agent, adding a Ti precursor into HCl under the condition of stirring, wherein the molar ratio of the Ti precursor to the HCl is 1:1, continuously stirring for 30 min, and standing for 2 h to obtain the Ti pillared agent.
(2) Adding raw material components of modified pillared interlayer clay into solvent deionized water, wherein the mass ratio of the raw material components of the modified pillared interlayer clay to the solvent is 0.4:100, and adding 1 g/L dispersant Na2P2O7And stirring for 12 hours until the clay is fully dispersed to obtain the clay suspension.
(3) And (3) dropwise adding the pillared agent in the step (1) into the clay suspension in the step (2), continuously stirring for 12 h, cleaning with deionized water, adjusting the pH value to 6.5, drying, calcining, and crushing, wherein the drying temperature is 60 ℃, the calcining temperature is 450 ℃, the heating rate is 5 ℃/min, and the calcining time is 3 h, so that the modified pillared clay with the particle size of 40 meshes is obtained.
(4) Uniformly mixing the modified pillared interlayer clay and the titanium dioxide in the step (3) according to the ratio of 5:100, and adding a precursor NH of an active substance with the concentration of 1%4VO3、Ce(NO3)3Adding a structural assistant, an adhesive and a plasticizer into the solution, fully and uniformly mixing, and ageing, pre-extruding, molding, drying and exercising to obtain the titanium dioxide doped modified layer columnar clay denitration catalyst.
Example 2
Novel titanium dioxide doped modified layer columnar clay denitration catalyst comprises a catalyst main body structure which comprises a catalystCatalyst carrier and catalytic active substance, wherein the catalyst carrier comprises titanium dioxide, the catalyst carrier also comprises Zr modified pillared interlayer clay, Zr is used as pillared agent of pillared interlayer clay, and the precursor of the Zr pillared interlayer clay of the modified pillared interlayer clay is ZrCl4Or ZrO (NO)3)2·2H2And O. The raw material components of the modified pillared clay comprise montmorillonite and bentonite, and the particle size of the raw material of the modified pillared clay is 220 meshes. The catalytically active material comprises oxides of La and Pr.
The denitration catalyst is in a honeycomb structure, the catalyst carrier accounts for 99wt% of the main structure of the catalyst, and the catalytic active substance accounts for 1wt% of the main structure of the catalyst. The catalyst support also includes a structural adjunct, a binder, and a plasticizer. The structural auxiliary agent is pulp cotton, the adhesive is methyl cellulose, and the plasticizer is polyoxyethylene. The structural auxiliary agent accounts for 8% of the mass of the catalyst carrier, the adhesive accounts for 8% of the mass of the catalyst carrier, and the plasticizer accounts for 8% of the mass of the catalyst carrier.
A preparation method of a novel titanium dioxide doped modified layer columnar clay denitration catalyst comprises the following steps:
(1) preparing a modified pillared interlayer clay Zr pillared agent, adding a Zr precursor into deionized water to prepare a solution with the concentration of 0.5 mol/L, heating to 85 ℃, and continuously stirring for 8 hours to obtain the Zr pillared agent.
(2) Adding raw material components of modified pillared interlayer clay into solvent deionized water and acetone, wherein the ratio of the deionized water to the acetone is 1:1, and adding 5 g/L dispersant Na5P3O10And (NaPO)3)6And stirring for 48 hours until the clay is fully dispersed to obtain the clay suspension.
(3) Dropwise adding the pillared agent in the step (1) into the clay suspension in the step (2), wherein the mass ratio of the pillared agent to the clay is 20 mmol:1 g, continuously stirring for 36 h, cleaning with deionized water, adjusting the pH value to 7.5, drying, calcining, and crushing, wherein the drying temperature is 80 ℃, the calcining temperature is 600 ℃, and the heating rate is 10 DEG C/min, calcining for 8 h to obtain modified pillared interlayer clay with particle size of 80 mesh.
(4) Uniformly mixing the modified pillared interlayer clay and the titanium dioxide in the step (3) according to the ratio of 40:100, and adding a precursor La (NO) of an active substance with the concentration of 5%3)3、Pr(NO3)3Adding a structural assistant, an adhesive and a plasticizer into the solution, fully and uniformly mixing, and ageing, pre-extruding, molding, drying and exercising to obtain the titanium dioxide doped modified layer columnar clay denitration catalyst.
Example 3
The utility model provides a novel titanium dioxide doping modification layer cylindric clay denitration catalyst, denitration catalyst include catalyst major structure, and catalyst major structure includes catalyst carrier and catalytic activity material, and catalyst carrier composition includes titanium white powder, and catalyst carrier composition still includes Al modification layer post clay, and wherein Al is as the pillared agent of layer post clay, and the precursor of modification layer post clay Al pillared agent is AlCl3Or Al (NO)3)3·6H2And O. The raw material components of the modified pillared clay are montmorillonite and hankte stone, and the particle size of the raw material of the modified pillared clay is 200 meshes. The catalytic active material comprises oxides of Mn and Ho.
The denitration catalyst is in a honeycomb structure, the mass fraction of the catalyst carrier in the main body structure of the catalyst is 97wt%, and the mass fraction of the catalytic active substance in the main body structure of the catalyst is 3 wt%. The catalyst support also includes a structural adjunct, a binder, and a plasticizer. The structural auxiliary agent is glass fiber and pulp cotton, the adhesive is polyacrylamide and methyl cellulose, and the plasticizer is polyoxyethylene. The structural auxiliary agent accounts for 5% of the mass of the catalyst carrier, the adhesive accounts for 5% of the mass of the catalyst carrier, and the plasticizer accounts for 5% of the mass of the catalyst carrier.
A preparation method of a novel titanium dioxide doped modified layer columnar clay denitration catalyst comprises the following steps:
(1) preparing a modified pillared interlayer clay Al pillared agent, adding a NaOH solution into an Al precursor solution, continuously stirring for 16 h, and standing for 6 h to obtain the Al pillared agent, wherein the molar ratio of NaOH to the Al precursor is 2: 1.
(2) Will be provided withAdding raw material components of modified pillared interlayer clay into solvent deionized water and alcohol, wherein the ratio of the deionized water to the alcohol is 1:4, the mass ratio of the raw material components of the modified pillared interlayer clay to the solvent is 0.7:100, and adding a dispersing agent Na with the concentration of 3 g/L2CO3And NaCl, and stirring for 36 hours until the clay is fully dispersed to obtain the clay suspension.
(3) And (3) dropwise adding the pillared agent in the step (1) into the clay suspension in the step (2), continuously stirring for 24h, cleaning with deionized water, adjusting the pH value to 7.0, drying, calcining, and crushing, wherein the drying temperature is 70 ℃, the calcining temperature is 520 ℃, the heating rate is 7 ℃/min, and the calcining time is 6 h, so that the modified pillared clay with the particle size of 60 meshes is obtained.
(4) Uniformly mixing the modified pillared interlayer clay and the titanium dioxide in the step (3) according to the ratio of 20:100, and adding a precursor Mn (NO) of an active substance with the concentration of 3%3)2、Ho(NO3)3Adding a structural assistant, an adhesive and a plasticizer into the solution, fully and uniformly mixing, and ageing, pre-extruding, molding, drying and exercising to obtain the titanium dioxide doped modified layer columnar clay denitration catalyst.
Comparative example 1
The titanium dioxide denitration catalyst comprises a catalyst main body structure, the catalyst main body structure comprises a catalyst carrier and a catalytic active substance, the catalyst carrier comprises titanium dioxide, and the catalytic active substance comprises V, Ce oxide.
The denitration catalyst is in a honeycomb structure, the mass fraction of the catalyst carrier in the main body structure of the catalyst is 95wt%, and the mass fraction of the catalytic active substance in the main body structure of the catalyst is 5 wt%. The catalyst support also includes a structural adjunct, a binder, and a plasticizer. The structural auxiliary agent is glass fiber, the adhesive is polyacrylamide, and the plasticizer is polyoxyethylene. The structural auxiliary agent accounts for 2% of the mass of the catalyst carrier, the adhesive accounts for 2% of the mass of the catalyst carrier, and the plasticizer accounts for 2% of the mass of the catalyst carrier.
The preparation method of the denitration catalyst comprises the following steps:
adding 1 percent active substance precursor NH into titanium dioxide4VO3、Ce(NO3)3Adding a structural auxiliary agent, an adhesive and a plasticizer into the solution, fully and uniformly mixing, and ageing, pre-extruding, forming, drying and exercising to obtain the titanium dioxide denitration catalyst.
Comparison of the effects of examples and comparative examples
The test conditions were as follows:
total flow of flue gas: 20L/min; h2O：3%；NO：500 ppm；NH3：500 ppm；N2Is supplementary gas; and (3) testing temperature: 200 ℃ and 250 ℃.
The test results were as follows:
comparative example 1: the denitration efficiency is 92.1 percent, and the ammonia escapes by 1.6 ppm; example 1: the denitration efficiency is 95.3 percent, and the ammonia escapes by 1.3 ppm; example 2: the denitration efficiency is 93.0 percent, and the ammonia escapes by 1.6 ppm; example 3: the denitration efficiency is 94.8 percent, and the ammonia escape is 1.4 ppm.
According to the test result, the titanium dioxide doped modified layer columnar clay denitration catalyst has high denitration efficiency.
Claims (10)
1. The utility model provides a novel titanium dioxide doping modified layer cylindric clay denitration catalyst which characterized in that: the denitration catalyst comprises a catalyst main body structure, the catalyst main body structure comprises a catalyst carrier and a catalytic active substance, the catalyst carrier comprises titanium dioxide, the catalyst carrier also comprises at least one of Ti, Zr and Al modified pillared clay, wherein the Ti, Zr and Al are used as pillared agents of the pillared clay, and the catalytic active substance comprises at least one of oxides of V, Ce, Mn, Ho, La and Pr.
2. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 1, wherein: the raw material components of the modified pillared interlayer clay are at least one of bentonite, montmorillonite, rectorite, bentonite, beidellite and hanktite, and the particle size of the raw material of the modified pillared interlayer clay is 180-220 meshes.
3. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 1, wherein: the precursor of the modified pillared clay Ti pillared agent is TiCl4Or Ti (OC)4H9)4The precursor of the Zr pillared agent is ZrCl4Or ZrO (NO)3)2·2H2The precursor of the O, Al pillared agent is AlCl3Or Al (NO)3)3·6H2O。
4. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 1, wherein: the denitration catalyst is in a honeycomb structure, the catalyst carrier accounts for 95-99wt% of the main body structure of the catalyst, and the catalytic active substance accounts for 1-5wt% of the main body structure of the catalyst.
5. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 1, wherein: the catalyst carrier also comprises a structural assistant, a binder and a plasticizer.
6. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 5, wherein: the structural auxiliary agent is at least one of glass fiber and pulp cotton, the adhesive is at least one of polyacrylamide and methyl cellulose, and the plasticizer is polyoxyethylene.
7. The novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 5, wherein: the structural auxiliary agent accounts for 2-8% of the mass of the catalyst carrier, the adhesive accounts for 2-8% of the mass of the catalyst carrier, and the plasticizer accounts for 2-8% of the mass of the catalyst carrier.
8. The preparation method of the novel titanium dioxide doped modified pillared layered clay denitration catalyst according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing a modified pillared interlayer clay pillared agent;
(2) adding raw material components of the modified pillared interlayer clay into a solvent, adding a dispersing agent, and stirring until the raw material components are fully dispersed to obtain a clay suspension;
(3) dropwise adding the pillared agent in the step (1) into the clay suspension in the step (2), continuously stirring, washing with deionized water, adjusting the pH value to 6.5-7.5, drying, calcining and crushing to obtain modified pillared interlayer clay;
(4) and (3) uniformly mixing the modified pillared interlayer clay and the titanium dioxide in the step (3), adding a precursor solution of an active substance, adding a structural assistant, an adhesive and a plasticizer, fully and uniformly mixing, and ageing, pre-extruding, molding, drying and exercising to obtain the titanium dioxide doped modified pillared interlayer clay denitration catalyst.
9. The preparation method of the novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 8, wherein the preparation method comprises the following steps: the pillaring agent in the step (1) comprises a Ti pillaring agent, a Zr pillaring agent and an Al pillaring agent, and the preparation method of the Ti pillaring agent comprises the following steps: adding a Ti precursor into HCl under the condition of stirring, wherein the molar ratio of the Ti precursor to the HCl is 1-3:1, continuously stirring for 30-60 min, and standing for 2-6 h to obtain a Ti pillared agent; the preparation method of the Zr pillared agent comprises the following steps: adding the Zr precursor into deionized water to prepare a solution with the concentration of 0.1-0.5 mol/L, heating to 85 ℃, and continuously stirring for 4-8 h to obtain a Zr pillared agent; the preparation method of the Al pillared agent comprises the following steps: and adding the NaOH solution into the Al precursor solution, wherein the molar ratio of NaOH to the Al precursor is 1-2:1, continuously stirring for 8-16 h, and standing for 2-6 h to obtain the Al pillared agent.
10. The preparation method of the novel titanium dioxide-doped modified pillared clay denitration catalyst according to claim 8, wherein the preparation method comprises the following steps: the solvent in the step (2) is deionized water, acetone, alcohol, deionized water + acetone or deionized water + alcohol, wherein the deionized waterThe proportion of deionized water to acetone in acetone is 1:0.5, 1:1, 1:2 or 1:4, the proportion of deionized water to alcohol in deionized water and alcohol is 1:0.5, 1:1, 1:2 or 1:4, the mass ratio of raw material components of the modified pillared interlayer clay to the solvent is 0.4-1:100, and the dispersing agent is Na2P2O7、Na5P3O10、(NaPO3)6、Na2CO3Or at least one of NaCl, the concentration of the dispersant is 1-5 g/L, and the stirring time is 12-48 h after the dispersant is added;
the continuous stirring time in the step (3) is 12-36 h, the mass ratio of the pillared agent to the clay is 10-20 mmol:1 g, the drying temperature is 60-80 ℃, the calcining temperature is 450-;
the ratio of the modified pillared interlayer clay to the titanium dioxide in the step (4) is 5-40:100, and the precursor of the active substance is NH4VO3、Ce(NO3)3、Mn(NO3)2、Ho(NO3)3、La(NO3)3And Pr (NO)3)3The concentration of the precursor solution of the active substance is 1-5%.
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