CN118022757A - 3D ball chrysanthemum-shaped structure FeWAlxWater-resistant calcium sulfate denitration catalyst and preparation method and application thereof - Google Patents
3D ball chrysanthemum-shaped structure FeWAlxWater-resistant calcium sulfate denitration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 25
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- 239000012702 metal oxide precursor Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 241000723353 Chrysanthemum Species 0.000 claims description 6
- 235000007516 Chrysanthemum Nutrition 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- -1 iron-tungsten-aluminum Chemical compound 0.000 claims description 2
- 239000000693 micelle Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000859 sublimation Methods 0.000 abstract description 4
- 230000008022 sublimation Effects 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 229960000502 poloxamer Drugs 0.000 description 5
- 229920001983 poloxamer Polymers 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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Abstract
The invention discloses a water-resistant calcium sulfate denitration catalyst with a 3D (three-dimensional) ball chrysanthemum-shaped structure FeWAl x as well as a preparation method and application thereof. The catalyst is prepared from composite metal oxide of Fe 2O3 and WO 3 loaded by Al 2O3 by the combined action of PMMA colloidal crystal template microspheres and F127 to form a macroporous, mesoporous and microporous interweaved structure. The catalyst of the invention has a 3D (three-dimensional) ball chrysanthemum-shaped structure, the pore canal and the large pore volume and the pore diameter of the catalyst are communicated to accelerate the ammonium sulfate salt to reach the equilibrium state of generation and sublimation on the surface of the catalyst, the more dispersed active components are difficult to contact with SO 2 and H 2 O, the active sites are protected, the addition of Al 2O3 promotes the electron transfer between Fe-O-W, more active oxygen is generated, the removal capacity of NO x is improved, and meanwhile, enough acid sites are provided for the catalyst to neutralize the toxicity of CaO, SO that the efficient removal of NO x in complex industrial flue gas can be realized.
Description
Technical Field
The invention belongs to the field of denitration catalyst preparation, and particularly relates to a water-resistant calcium sulfate denitration catalyst with a 3D (three-dimensional) ball chrysanthemum-shaped structure FeWAl x, and a preparation method and application thereof.
Background
Attenuation of air pollution by ozone and particulates is an urgent need, and thus, more stringent control of NO x (including NO and NO 2), one of its primary precursors, is highly desirable. With the gradual completion of the implementation of Ultra Low Emission (ULE) in the power industry and the modification of Ultra Low Emission (ULE) in the China steel industry, the attention of efficient removal of NO x has been gradually transferred to the fixed emission sources of complex industrial flue gas in the cement industry. Currently, ammonia selective catalytic reduction (NH 3 -SCR) has been widely used for NO x treatment. However, the current commercial VWTi catalyst is subject to poisoning deactivation when facing to complex industrial flue gas containing SO 2、H2 O and alkali (earth) metals, and stable and efficient NO x removal is difficult to realize, SO that it is particularly important to develop an efficient denitration catalyst suitable for complex industrial flue gas containing SO 2、H2 O and alkali (earth) metals.
The SO 2 causes SCR catalyst poisoning and deactivation for two main reasons: one is sulfiding of the active site at higher temperatures, resulting in deactivation of the catalyst; the other is that ammonium sulfate salt substances formed by the reaction of sulfur oxide and ammonia at a lower temperature are deposited on the surface of the catalyst to cover the surface of the catalyst, so that the active molecules are prevented from contacting the catalyst, and the performance of the catalyst is affected. Therefore, if the deep vulcanization can be restrained, the deposition of ammonium sulfate salt substances on the surface of the catalyst can be reduced, and the problem of SO 2 poisoning can be solved. Researchers have generally recognized that deactivation of SCR catalysts by H 2 O involves competitive adsorption of H 2 O and NH 3 and catalyst deactivation by the formation of additional surface hydroxyl (-OH) groups on the catalyst. It has been reported that CaO content in complex industrial flue gas is as high as 80%, caO can block catalyst pores and reduce NH 3 adsorption on catalyst poresThe acidic sites reduce the redox activity of the catalyst. The 3D ball chrysanthemum structure has uniform macroporous and mesoporous structures, larger specific surface area and controllable aperture, and the special 3D ball chrysanthemum structure can highly disperse active components, increase the contact area of reactants and active sites and strengthen the interaction force of the active components and a carrier. The macroporous and mesoporous structures of the catalyst are beneficial to sublimation and decomposition of ammonium sulfate salt, so that the deposition of the ammonium sulfate salt is reduced; meanwhile, the larger pore diameter can prevent H 2 O on the catalyst from condensing, and ensure the capability of the catalyst for efficiently removing NO x.
Fe 2O3 based catalysts are of great interest because of their many advantages, such as adequate redox properties between Fe 3+ and Fe 2+ and low cost, good activity against SO 2 at medium and high temperatures. At the same time, the introduction of WO 3 into Fe 2O3 enhances the surface acidity and electronic properties and forms alpha-Fe 2O3 and FeWO 4 species by strong Fe-W interactions, thereby increasing SCR activity. Al 2O3 is a potential additive of an iron-based catalyst, is a catalyst accelerator, can provide neutral acidity for the catalyst, SO that adsorption of SO 2 and alkalinity of CaO are inhibited, the specific surface area of the catalyst can be increased, more surface adsorption oxygen is formed, the thermal stability of ABS is obviously reduced, the decomposition of the ABS is promoted, and the prepared 3D chrysanthemum-shaped structure FeWAl x denitration catalyst can face the complex flue gas environment of SO 2、H2 O and alkali (earth) metal to realize high-efficiency removal of NO x.
Disclosure of Invention
Aiming at the technical problems that the commercial VWTi catalyst faces to the poisoning of a denitration catalyst caused by water-sulfur-calcium components of complex industrial flue gas and the like, the invention provides a 3D (three-dimensional) chrysanthemum-shaped FeWAl x water-sulfur-calcium-resistant denitration catalyst, a preparation method and application thereof, wherein the catalyst is prepared by PMMA microspheres and F127 (poloxamer) in an auxiliary way and has a 3D porous structure with macropores, mesopores and micropores interwoven.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
A3D spherical chrysanthemum-shaped structure FeWAl x water-resistant sulfur-calcium denitration catalyst is composed of Al 2O3 loaded Fe 2O3 and a composite transition metal oxide of WO 3, which is recorded as FeWAl x, wherein x is the percentage of Al 2O3 in the total mass of the catalyst, and x is more than 5 and less than or equal to 50 percent.
Further, the catalyst comprises the following components in percentage by mass:
WO 3 -45% (preferably 5-40%, more preferably 30-35%), al 2O3 with a content of 5-50% (preferably 15-20%), fe 2O3 in balance, the sum of the mass percentages of the components being 100%.
Further, the catalyst has a Ping-Pong chrysanthemum-shaped 3D structure formed by interweaving macropores, mesopores and micropores, the specific surface area is 50-150 m 2/g, the total pore volume is 0.15-0.30 cm 3/g, and the average pore diameter is 2-20 nm.
The preparation method of the catalyst comprises the following steps:
(1) Synthesizing PMMA emulsion by adopting an improved soap-free emulsion polymerization method, and preparing PMMA colloidal crystal template microspheres by adopting a constant-temperature suspension film-forming method;
(2) Taking F127 (poloxamer) as a traction agent, and forming micelles through intermolecular forces with the metal precursor solution of iron-tungsten-aluminum to obtain a metal oxide precursor solution capable of forming mesopores;
(3) Immersing the PMMA microspheres prepared in the step (1) in the metal oxide precursor solution obtained in the step (2) until the metal oxide precursor solution completely fills gaps of the PMMA microspheres, and finally removing the PMMA colloidal crystal template through calcination to form the 3D porous metal oxide catalyst formed by interweaving macropores, mesopores and micropores, namely the 3D chrysanthemum-shaped structure FeWAl x denitration catalyst.
Further, in the step (1), the preparation method of the PMMA colloid template microsphere specifically comprises the following steps: continuously introducing inert gas into ultrapure water, heating to 60-75 ℃, adding methyl methacrylate into the ultrapure water, stirring for 30-50 min, reacting for 40-50 min by using a potassium persulfate initiator, wherein the dosage ratio of the potassium persulfate to the methyl methacrylate is 0.3-0.5 g: 100-120 mL, pouring the reaction product into ultrapure water with the temperature of 5-20 ℃ to prepare polymethyl methacrylate emulsion, subpackaging the prepared liquid, centrifuging to remove supernatant, adding ultrapure water into white precipitate for ultrasonic dispersion, and evaporating at constant temperature to form ordered PMMA microsphere crystals.
Further, the step (2) specifically comprises: f127 (poloxamer), absolute methanol, glycol, citric acid and absolute oxalic acid are stirred at 15-40 ℃ to form a uniform solution, then Fe(NO3)2·3H2O、(NH4)10[H2W12O42]·4H2O、Al(NO3)3·9H2O, is added and stirred at 35-65 ℃ for 2-4 hours to form a uniform colloid, and the dosage ratio of F127, absolute methanol, glycol, citric acid, absolute oxalic acid 、Fe(NO3)2·3H2O、(NH4)10[H2W12O42]·4H2O and Al (NO 3)3·9H2 O is 2-3 g:10-30 mL:5-20 mL:3-6 g:2-4 g:2-10 g:0.5-2 g:0.5-5 g).
Further, the step (3) specifically comprises: immersing a metal oxide precursor solution in PMMA microspheres for 5-10h, pumping out excessive precursor solution by a funnel, leaching by absolute methanol to obtain a filter cake, drying the filter cake in an oven, calcining by a muffle furnace, programming to 100-250 ℃ from room temperature, maintaining for 4-5 h, raising to 350-450 ℃ and maintaining for 4-6 h, and cooling to room temperature to obtain the 3D spherical chrysanthemum-shaped structure FeWAl x denitration catalyst.
The catalyst is used for denitration, can obtain good effect, is applied to industrial flue gas, has remarkable effect, and can still realize high-efficiency removal of NO x when facing complex industrial flue gas rich in SO 2、H2 O, alkali (earth) metal and other components.
The 3D ball chrysanthemum-shaped structure FeWAl x denitration catalyst with the interweaved macropores, mesopores and micropores is constructed by PMMA microspheres and F127 (poloxamer), has good denitration effect, is used for complex industrial flue gas rich in SO 2、H2 O, alkali (earth) metals and other components, and can realize high-efficiency removal of NO x. The 3D ball chrysanthemum-shaped structure of the catalyst has the advantages that the pore canal and the large pore volume and the pore diameter which are communicated with each other can accelerate the ammonium sulfate salt to reach the equilibrium state of generation and sublimation on the surface of the catalyst, more dispersed active components are difficult to contact with SO 2 and H 2 O, active sites are protected, the addition of a proper amount of Al 2O3 promotes the electron transfer between Fe-O-W, more active oxygen is generated, the removal capability of NO is improved, and meanwhile, enough acid sites are provided for the catalyst to neutralize the toxicity of CaO.
The invention has the beneficial effects that:
The catalyst prepared by the invention has a large number of 3D (three-dimensional) chrysanthemum-shaped special structures with interweaved macropores, mesopores and micropores, can promote good dispersion of surface active components and exposure of active sites, accelerate generation and sublimation of ammonium sulfate on the surface of the catalyst, inhibit SO 2 from adsorbing and neutralizing basicity of CaO, obviously improve the NO x removal capability of the catalyst, and can realize high-efficiency removal of NO x for complex industrial flue gas rich in SO 2、H2 O, alkali (earth) metals and other components.
Drawings
FIG. 1 is a graph of the test activity of the three-dimensional porous FeWAl x catalyst prepared in example 3.
FIG. 2 is a scanning electron microscope image of the three-dimensional porous FeWAl x catalyst prepared in example 2.
Fig. 3 is an N 2 adsorption-desorption curve and pore size distribution plot for the three-dimensional porous FeWAl x catalyst prepared in example 2.
Fig. 4 is an XRD pattern of the three-dimensional porous FeWAl x catalyst prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
The PMMA manufacturing steps are as follows:
Continuously introducing inert gas into ultrapure water and heating to 65 ℃, adding methyl methacrylate into the ultrapure water for stirring for 30-50 min, and reacting for 40-50 min by taking potassium persulfate as an initiator, wherein the dosage ratio of the potassium persulfate to the methyl methacrylate is 0.4g:115mL, pouring the mixture into ultrapure water with the temperature of 5-20 ℃ after the reaction is finished to prepare polymethyl methacrylate emulsion, subpackaging the prepared liquid, centrifuging to remove supernatant, adding ultrapure water into white precipitate for ultrasonic dispersion, and evaporating at constant temperature to form ordered PMMA microsphere crystals.
Example 2
The preparation method of the 3D ball chrysanthemum-shaped structure FeWAl x water-resistant sulfur-calcium denitration catalyst comprises the following steps:
(1) 2g of F127 (poloxamer), 2g of anhydrous oxalic acid and 4.8g of citric acid are dissolved in a mixed solution of 24mL of anhydrous methanol and 16mL of ethylene glycol under the water bath condition of 35 ℃ and stirred for 2h until the solution is transparent;
(2) Adding 5.0030g Fe(NO3)3·9H2O、0.5766g(NH4)10[H2W12O42]·4H2O、1.9843gAl(NO3)3·9H2O, to the solution obtained in the step (1) in sequence under the stirring condition, heating to 50 ℃, stirring for 2 hours until the solution is clear and sol-like, then cooling to 35 ℃ and continuing stirring for 1 hour;
(3) Immersing the metal oxide precursor solution obtained in the step (2) in 6g PMMA microspheres for 6h, pumping out excessive precursor solution by using a funnel, and leaching by using absolute methanol to obtain a filter cake;
(4) Drying the filter cake in a vacuum drying oven at 50 ℃ for 24 hours;
(5) And (3) placing the dried precursor into a muffle furnace, calcining at a speed of 3 ℃/min from room temperature to 250 ℃ and keeping for 5 hours, then at a speed of 1 ℃/min to 450 ℃ and keeping for 6 hours, cooling to room temperature to obtain the 3D chrysanthemum-shaped structure FeWAl x catalyst, and sieving the catalyst with a 40-60-mesh sieve for later use.
Example 3
The preparation method of the 3D ball chrysanthemum-shaped structure FeWAl x water-resistant sulfur-calcium denitration catalyst comprises the following steps:
(1) 20mL of deionized water was taken, to which 0.084g of Ca (NO 3)2·4H2 O was added with stirring until completely dissolved;
(2) Adding 2g of fresh catalyst into the aqueous solution prepared in the step (1), and fully stirring for 6h;
(3) Placing the stirred catalyst in a 105 ℃ oven for drying for 16 hours;
(4) And (3) placing the dried sample into a muffle furnace, heating from room temperature to 500 ℃ at a speed of 10 ℃/min, calcining for 5 hours, and cooling to room temperature to obtain the CaO-loaded 3D-spherical chrysanthemum-shaped structure FeWAl x catalyst for later use.
Example 4
Evaluation of water-resistant calcium sulfate denitration of the catalyst.
The catalyst of the alkali metal supported 3D-ball chrysanthemum FeWAl x prepared in example 3 of the present invention was targeted. 0.15g of catalyst was packed in a quartz tube and fixed in the reactor, the simulated reaction flue gas consisted of 500ppmNH 3、500ppmNO、400ppm SO2、6vol.％O2、10vol.％H2 O and balance gas N 2, the total gas flow rate was maintained at 200mL/min, and the volume space velocity (GHSV) was 100000h -1. The reaction temperature is controlled to be between 200 and 500 ℃, the capability of the catalyst for removing NOx by water resistant calcium sulfate is tested, the test result is shown in figure 1, and the result shows that the catalyst has the capability of efficiently removing NO by water resistant calcium sulfate at 300 to 500 ℃.
Example 5
SEM and BET testing of catalysts
Scanning Electron Microscope (SEM) analysis of the catalyst was carried out by using a JEOL JSM-6360LV electron scanning microscope of Hitachi. Specific surface area and pore structure were both determined using a model Micromeritics Tristar type i 3020 from the instrument company of USA Kang Da (Quantachrom, USA). Taking the test result of the product obtained in example 2 as an example, the test result is shown in fig. 2 and 3, and the result shows that FeWAl x catalyst prepared by the invention has a 3D ball chrysanthemum-like structure, the surface area of the catalyst is 124.46m 2/g, the total pore volume is 0.3cm 3/g, and the average pore diameter is 9.77nm.
Example 6
XRD testing of catalysts
The phase composition and crystal structure of the catalyst were tested by XRD using a powder X-ray diffractometer U1timaIV from Rigaku, japan. The test conditions were under Cu-ka radiation (λ=1.5406A), maximum operating voltage and current of 60KV and maximum operating current of 300mA experimental data were analyzed using the jade8.0 software. Taking the test result of the product of example 2 as an example, the obtained XRD pattern refers to JCPDS data to identify the crystal phase as shown in fig. 4. Three-dimensional, chrysanthemum-like, porous FeWAl x samples exhibited diffraction characteristic peaks at 2θ values of 30.24, 35.62, 54.62, 57.28, and 62.92 °, which can be attributed to the (220), (311), (430), (511), and (440) lattice planes of γ -Fe 2O3 (jcpds#39-1346) in typical spinel structures. gamma-Fe 2O3 is more active than alpha-Fe 2O3 in medium temperature SCR. In addition, no diffraction peak of Al 2O3 crystal phase was detected, indicating that Al 2O3 was in an amorphous state or highly dispersed on the surface of the composite oxide.
Claims (9)
1. A3D spherical chrysanthemum-shaped structure FeWAl x water-resistant sulfur-calcium denitration catalyst is characterized by comprising Al 2O3 loaded Fe 2O3 and a composite transition metal oxide of WO 3, wherein x is FeWAl x, and x is the percentage of Al 2O3 in the total mass of the catalyst, and is more than 5 and less than or equal to 50 percent.
2. The 3D-ball chrysanthemum-like structure FeWAl x water-resistant sulfur-calcium denitration catalyst according to claim 1, wherein the catalyst is composed of the following components in percentage by mass:
WO 3 0％～45％,Al2O3 -50%, the balance being Fe 2O3, the sum of the mass percentages of the components being 100%.
3. The 3D-ball chrysanthemum-like structure FeWAl x water-resistant sulfur-calcium denitration catalyst according to claim 1, wherein the catalyst is composed of the following components in percentage by mass:
WO 3 30％～35％,Al2O3 -20%, the balance being Fe 2O3, the sum of the mass percentages of the components being 100%.
4. The 3D ball chrysanthemum structure FeWAl x water-resistant sulfur-calcium denitration catalyst according to claim 1, wherein the catalyst has a 3D structure of table tennis chrysanthemum formed by interweaving macropores, mesopores and micropores, the specific surface area is 50-150 m 2/g, the total pore volume is 0.15-0.30 cm 3/g, and the average pore diameter is 2-20 nm.
5. The method for preparing the water-resistant calcium sulfate denitration catalyst for the 3D ball chrysanthemum-like structure FeWAl x according to any one of claims 1 to 4, comprising the steps of:
(1) Synthesizing PMMA emulsion by adopting an improved soap-free emulsion polymerization method, and preparing PMMA colloidal crystal template microspheres by adopting a constant-temperature suspension film-forming method;
(2) F127 is used as a traction agent, and micelles are formed through intermolecular forces with the metal precursor solution of iron-tungsten-aluminum, so that a metal oxide precursor solution capable of forming mesopores is obtained;
(3) Immersing the PMMA microspheres prepared in the step (1) in the metal oxide precursor solution obtained in the step (2) until the metal oxide precursor solution completely fills gaps of the PMMA microspheres, and finally removing the PMMA colloidal crystal template through calcination to form the 3D porous metal oxide catalyst formed by interweaving macropores, mesopores and micropores, namely the 3D chrysanthemum-shaped structure FeWAl x denitration catalyst.
6. The preparation method of claim 5, wherein in the step (1), the preparation method of the PMMA colloidal template microsphere specifically comprises the following steps: continuously introducing inert gas into ultrapure water, heating to 60-75 ℃, adding methyl methacrylate into the ultrapure water, stirring for 30-50 min, and reacting for 40-50 min by taking potassium persulfate as an initiator, wherein the dosage ratio of the potassium persulfate to the methyl methacrylate is 0.3-0.5 g: 100-120 mL, pouring the mixture into ultrapure water with the temperature of 5-20 ℃ after the reaction is finished to prepare polymethyl methacrylate emulsion, subpackaging the prepared liquid, centrifuging to remove supernatant, adding ultrapure water into white precipitate for ultrasonic dispersion, and evaporating at constant temperature to form ordered PMMA microsphere crystals.
7. The method according to claim 5, wherein the step (2) is specifically: f127, absolute methanol, ethylene glycol, citric acid and absolute oxalic acid are stirred at 15-40 ℃ to form a uniform solution, then Fe(NO3)2·3H2O、(NH4)10[H2W12O42]·4H2O、Al(NO3)3·9H2O, is added and stirred at 35-65 ℃ for 2-4 hours to form a uniform colloid, and the dosage ratio of F127, absolute methanol, ethylene glycol, citric acid, absolute oxalic acid 、Fe(NO3)2·3H2O、(NH4)10[H2W12O42]·4H2O and Al (NO 3)3·9H2 O is 2-3 g: 10-30 mL: 5-20 mL: 3-6 g: 2-4 g: 2-10 g: 0.5-2 g: 0.5-5 g).
8. The method according to claim 5, wherein the step (3) is specifically: immersing a metal oxide precursor solution in PMMA microspheres for 5-10h, pumping out excessive precursor solution by a funnel, leaching by absolute methanol to obtain a filter cake, drying the filter cake in an oven, calcining by a muffle furnace, programming to 100-250 ℃ from room temperature, maintaining for 4-5 h, raising to 350-450 ℃ and maintaining for 4-6 h, and cooling to room temperature to obtain the 3D spherical chrysanthemum-shaped structure FeWAl x denitration catalyst.
9. Use of the 3D ball chrysanthemum like structure FeWAl x water-resistant calcium sulfate denitration catalyst of any one of claims 1 to 4 in industrial flue gas denitration.
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