CN114849682A - High-sulfur-resistance zirconium-based pillared clay supported catalyst and preparation method and application thereof - Google Patents
High-sulfur-resistance zirconium-based pillared clay supported catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000004927 clay Substances 0.000 title claims abstract description 57
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 36
- 239000000440 bentonite Substances 0.000 claims abstract description 36
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 31
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 26
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003546 flue gas Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 230000002195 synergetic effect Effects 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000007598 dipping method Methods 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 15
- 230000032683 aging Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 10
- 229910052748 manganese Inorganic materials 0.000 abstract description 10
- 239000013543 active substance Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 6
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 82
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 13
- 229910052753 mercury Inorganic materials 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000011229 interlayer Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
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- 238000011056 performance test Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 230000007797 corrosion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000000891 luminescent agent Substances 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a high-sulfur-resistance zirconium-based pillared clay supported catalyst and a preparation method and application thereof, wherein a carrier Zr-PILC is prepared from a bentonite suspension and a zirconyl nitrate cross-linking agent; mn (NO) 3 ) 2 And Ce (NO) 3 ) 4 Dissolving in deionized water, adding a carrier Zr-PILC, stirring, dipping, drying, calcining and grinding the dipped product to obtain the high-sulfur-resistance zirconium-based pillared clay supported catalyst. In the preparation method, the prepared zirconium pillared clay (Zr-PILC) has high specific surface area and is beneficial to taking the zirconium pillared clay as a carrierThe catalyst is used for loading Ce and Mn active substances, and then the pillared clay supported catalyst is synthesized. On one hand, the pillared clay supported catalyst prepared by the preparation method realizes NO in coal-fired flue gas by utilizing the characteristic of strong catalytic capability of Ce and Mn active substances x 、Hg 0 The high-efficiency synergistic removal of the Zr-PILC on the other hand, the high sulfur resistance of the Zr-PILC is fully exerted, and the SO in the flue gas is greatly relieved 2 Poisoning effect on catalyst.
Description
Technical Field
The invention relates to the field of atmospheric pollution control, in particular to a high-sulfur-resistance zirconium-based pillared clay supported catalyst and a preparation method and application thereof.
Background
Coal-fired flue gas is considered an important man-made emission source for a variety of atmospheric pollutants. Mercury (Hg) pollution has become a global environmental problem due to its persistence, volatility, easy migration, and high bio-enrichment. The mercury in the coal-fired flue gas is mostly elemental mercury (Hg) 0 ) The existing pollutant control system of a coal-fired power plant is difficult to remove due to the characteristics of volatility, difficult water solubility and the like. Research shows that the SCR denitration system can remove Hg in coal-fired flue gas 0 Oxidation to Hg 2+ And then mercury in the flue gas is removed through a wet desulphurization device and a dust removal device to realize Nitrogen Oxide (NO) x ) And Hg 0 And (4) performing combined removal. However, conventional commercial catalysts are on Hg 0 The oxidation performance is limited.Therefore, the development of the catalyst with high catalytic oxidation performance and the combined removal of pollutants have important theoretical significance and practical significance. At present, various transition metal oxides such as Ce, Mn and the like have higher catalytic activity, so the transition metal oxides are used for flue gas NO x 、Hg 0 Combined removal studies of (a). However, a large amount of SO is present in the coal-fired flue gas 2 SO in flue gas 2 Can react with transition metal on the surface of the catalyst to generate sulfate, which causes irreversible deactivation of the catalyst. Therefore, the improvement of the sulfur resistance of the catalyst is the key to realize the synchronous denitration and demercuration of the coal-fired flue gas. Therefore, a catalyst is needed to realize the synergistic denitration and demercuration of the coal-fired flue gas.
Disclosure of Invention
The invention aims to provide a high-sulfur-resistance zirconium-based pillared clay supported catalyst, a preparation method thereof and application thereof in synergistic denitration and demercuration, and on one hand, the characteristic of strong catalytic capability of Ce and Mn active substances is utilized to realize NO in coal-fired flue gas x 、Hg 0 The high-efficiency synergistic removal of the Zr-PILC on the other hand, the high sulfur resistance of the Zr-PILC is fully exerted, and the SO in the flue gas is greatly relieved 2 Poisoning effect on catalyst.
The embodiment of the application provides a preparation method of a high-sulfur-resistance zirconium-based pillared clay supported catalyst on one hand, which comprises the following steps:
s1, preparing a bentonite suspension with the mass fraction of 0.5-2% and a zirconyl nitrate crosslinking agent with the mass fraction of 0.1-0.5 mol/L, dropwise adding the zirconyl nitrate crosslinking agent into the bentonite suspension to obtain a first mixed solution, stirring and standing, wherein the concentration of zirconyl nitrate in the first mixed solution is 10-30 mmol/g, centrifugally separating the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain a carrier Zr-PILC;
S2，Mn(NO 3 ) 2 and Ce (NO) 3 ) 4 Dissolving in deionized water to obtain a second mixed solution, and adding the carrier Zr-PILC (Zr-PILC) into the second mixed solution, wherein Mn (NO) 3 ) 2 With Ce (NO) 3 ) 4 The mass ratio of the total mass of the catalyst to deionized water and the carrier Zr-PILC is 2.6-2.8: 100: 10, stirring and dippingDrying, calcining and grinding the impregnated product to obtain alpha% MnO 2 -b％CeO 2 a/Zr-PILC catalyst, i.e. a high-sulfur-resistance zirconium-based pillared clay supported catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
In the preparation method, the prepared zirconium pillared clay (Zr-PILC) has high specific surface area, and is favorable for loading Ce and Mn active substances by taking the zirconium pillared clay as a carrier so as to synthesize the pillared clay supported catalyst.
On one hand, the pillared clay supported catalyst prepared by the preparation method realizes NO in coal-fired flue gas by utilizing the characteristic of strong catalytic capability of Ce and Mn active substances x 、Hg 0 The high-efficiency synergistic removal of the Zr-PILC on the other hand, the high sulfur resistance of the Zr-PILC is fully exerted, and the SO in the flue gas is greatly relieved 2 Poisoning effect on catalyst.
In some embodiments, in step S1, the method for preparing the zirconyl nitrate crosslinker is: aging 0.1-0.5 mol/L zirconyl nitrate in a constant-temperature water bath at 75-90 ℃ for 3-10 h, and then standing and cooling for 2-5 h.
In some embodiments, in the step S1, after the zirconyl nitrate crosslinking agent is added dropwise to the bentonite suspension, the mixture is stirred at room temperature for 3-8 hours and then left to stand for 8-16 hours.
In some embodiments, in the step S1, the precipitate is dried in a constant temperature water bath at 75-90 ℃ for 8-16 h.
In some embodiments, in the step S1, the calcination temperature of the precipitate is 400 to 600 ℃, and the calcination time is 2 to 5 hours.
In some embodiments, in the step S2, the dipping time is 8-16 h.
In some embodiments, in the step S2, the drying manner of the dipped product is constant temperature drying in a water bath at 75-90 ℃ for 8-16 h.
In some embodiments, in the step S2, the calcination temperature of the impregnation product is 400 to 600 ℃, the calcination time is 2 to 5 hours, and the impregnation product is ground and sieved by a 40-mesh sieve for later use.
On the other hand, the embodiment of the application provides a high-sulfur-resistance zirconium-based pillared clay supported catalyst prepared by the preparation method, and the high-sulfur-resistance zirconium-based pillared clay supported catalyst is alpha% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
The third aspect of the embodiment of the application provides an application of the high-sulfur-resistance zirconium-based pillared clay supported catalyst in synergistic denitration and demercuration in flue gas.
The beneficial effects of the invention are as follows:
(1) in the preparation method, the prepared zirconium pillared clay (Zr-PILC) has high specific surface area, and is favorable for loading Ce and Mn active substances by taking the zirconium pillared clay as a carrier so as to synthesize a pillared clay supported catalyst;
(2) on one hand, the pillared clay supported catalyst prepared by the preparation method realizes NO in coal-fired flue gas by utilizing the characteristic of strong catalytic capability of Ce and Mn active substances x 、Hg 0 The high-efficiency synergistic removal of the Zr-PILC on the other hand, the high sulfur resistance of the Zr-PILC is fully exerted, and the SO in the flue gas is greatly relieved 2 Poisoning effect on catalyst.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent from and readily appreciated by reference to the following description of the embodiments taken in conjunction with the accompanying drawings,
wherein:
FIG. 1 is a graph comparing the denitration efficiency curves of different high-sulfur-resistant zirconium-based pillared clay supported catalysts in examples 1 to 3 of the present application;
FIG. 2 is a comparison graph of mercury oxidation efficiency curves of different high sulfur-resistant zirconium-based pillared clay supported catalysts in examples 1 to 3 of the present application;
FIG. 3 is SO 2 A graph comparing the influence of the catalyst on the denitration efficiency of the catalysts used in examples 1 to 3 and comparative example 1;
FIG. 4 is SO 2 A graph comparing the effects of mercury oxidation efficiency on the catalysts used in examples 1 to 3 of the present application and comparative example 1, respectively;
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The high sulfur-resistant zirconium-based pillared clay supported catalyst, the preparation method and the application thereof according to the embodiments of the present invention are described below with reference to the accompanying drawings.
The embodiment of the application provides a preparation method of a high-sulfur-resistance zirconium-based pillared clay supported catalyst on one hand, which comprises the following steps:
s1, preparing bentonite suspension with the mass fraction of 0.5-2% and a zirconyl nitrate crosslinking agent with the concentration of 0.1-0.5 mol/L.
The preparation method of the bentonite suspension comprises the following steps: putting 5-20 g of bentonite into a 1L beaker, adding 980-995 g of deionized water as a solvent, and stirring at room temperature for 24 hours to obtain a bentonite suspension with the mass fraction of 0.5-2%.
The method for preparing the zirconyl nitrate crosslinking agent by taking zirconyl nitrate as a zirconium source comprises the following steps: aging 0.1mol/L zirconyl nitrate in a constant-temperature water bath at 75-90 ℃ for 3-10 h, and then standing and cooling for 2-5 h to obtain the 0.1-0.5 mol/L zirconyl nitrate crosslinking agent.
And dropwise and slowly adding the prepared zirconyl nitrate crosslinking agent into the fully dispersed bentonite turbid liquid to obtain a first mixed liquid, ensuring the concentration of zirconyl nitrate in the first mixed liquid to be 10-30 mmol/g, stirring for 3-8 h at room temperature, and standing for 8-16 h to perform full ion exchange between the zirconyl nitrate crosslinking agent and clay interlayer ions of the bentonite turbid liquid. And then, centrifugally separating the suspension of the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain the Zr-PILC carrier.
The drying mode of the precipitate is drying for 8-16 h at constant temperature in a water bath at 75-90 ℃. And calcining the precipitate in a muffle furnace at 400-600 ℃ for 2-5 h.
S2, adding Mn (NO) as precursor 3 ) 2 And Ce (NO) 3 ) 4 Dissolving in deionized water to obtain a second mixed solution. Adding the carrier Zr-PILC obtained in step S1 into the second mixed solution, wherein Mn (NO) 3 ) 2 With Ce (NO) 3 ) 4 The mass ratio of the total mass of the catalyst to deionized water and the carrier Zr-PILC is 2.6-2.8: 100: 10. uniformly stirring, dipping for 8-16 h to obtain a dipping product, drying, calcining and grinding the dipping product to obtain alpha% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
Specifically, 10g of Zr-PILC as a carrier was added to the second mixed solution.
In some specific examples, the impregnated product is dried in a constant temperature water bath.
Preferably, a constant-temperature water bath kettle is adopted for constant-temperature water bath drying, and the constant-temperature water bath kettle is widely used for drying, concentrating, distilling and dipping chemical reagents and can also be used for water bath warm heating and other temperature tests. The water tank inside the water tank is made of stainless steel, so that the water tank has excellent corrosion resistance, accurate temperature control and automatic temperature control. Magnetic stirring is adopted, so that the water temperature can quickly reach a uniform state.
Specifically, the drying mode of the dipping product is constant-temperature drying for 8-16 h in water bath at the temperature of 75-90 ℃. Calcining the impregnation product at 400-600 ℃ for 2-5 h, and grinding and sieving with a 40-mesh sieve for later use.
As a preferred embodiment:
the method comprises the following steps:
s1, preparing a bentonite suspension with the mass fraction of 1% and an zirconyl nitrate cross-linking agent with the concentration of 0.1 mol/L.
The preparation method of the bentonite suspension comprises the following steps: putting 10g of bentonite into a 1L beaker, adding 990g of deionized water as a solvent, and stirring for 24 hours at room temperature to obtain a bentonite suspension with the mass fraction of 1%.
The method for preparing the zirconyl nitrate crosslinking agent by taking zirconyl nitrate as a zirconium source comprises the following steps: aging 0.1mol/L zirconyl nitrate in a constant-temperature water bath at 85 ℃ for 5h, and standing for 3h for cooling to obtain the 0.1mol/L zirconyl nitrate crosslinking agent.
And dropwise and slowly adding the prepared zirconyl nitrate crosslinking agent into the fully dispersed bentonite suspension to obtain a first mixed solution, ensuring the concentration of zirconyl nitrate in the first mixed solution to be 15mmol/g, stirring for 6h at room temperature, and standing for 12h to ensure that the zirconyl nitrate crosslinking agent and clay interlayer ions of the bentonite suspension perform full ion exchange. And then, centrifugally separating the suspension of the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain the Zr-PILC carrier.
Wherein the precipitate is dried at constant temperature in 80 deg.C water bath for 12 hr. The calcination of the precipitate was carried out in a muffle furnace at a calcination temperature of 500 ℃ for a calcination time of 3 h.
S2, adding Mn (NO) as precursor 3 ) 2 And Ce (NO) 3 ) 4 Dissolving in deionized water to obtain a second mixed solution.
Specifically, 0.6366 g-1.9098 g of Mn (NO) is used as a precursor 3 ) 2 And 0.7012 g-2.1035 g of Ce (NO) 3 ) 4 Dissolved in 100ml of deionized water to obtain a second mixed solution.
10g of Zr-PILC as a carrier was added to the second mixture. Uniformly stirring, dipping for 12h to obtain a dipped product, drying, calcining and grinding the dipped product to obtain alpha% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
In some embodiments, the impregnated product is dried in a constant temperature water bath.
Preferably, a constant-temperature water bath kettle is adopted for constant-temperature water bath drying, and the constant-temperature water bath kettle is widely used for drying, concentrating, distilling and dipping chemical reagents and can also be used for water bath warm heating and other temperature tests. The water tank inside the water tank is made of stainless steel, so that the water tank has excellent corrosion resistance, accurate temperature control and automatic temperature control. Magnetic stirring is adopted, so that the water temperature can quickly reach a uniform state.
Specifically, the drying mode of the impregnated product is constant temperature drying for 12 hours at 85 ℃ in a water bath. Calcining the impregnated product at 500 ℃ for 5h, and sieving the ground impregnated product with a 40-mesh sieve for later use.
On the other hand, the embodiment of the present application provides a high sulfur-resistant zirconium-based pillared clay supported catalyst prepared by the above preparation method, wherein the high sulfur-resistant zirconium-based pillared clay supported catalyst is a% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 And a mass fraction of (c), wherein a is 3-9, b is 3-9, and a + b is 12.
The third aspect of the embodiment of the application provides an application of the high-sulfur-resistance zirconium-based pillared clay supported catalyst in synergistic denitration and demercuration in flue gas.
Pillared clay materials (i.e., pillared clay PILCs) are a particular material in which the exchangeable ions between the clay mineral layers are replaced, in whole or in part, by specific ions or groups of ions ("pillars") and are anchored in the interlamellar domains. The layer spread by the 'column' has two-dimensional channels, the maximum interlayer distance can reach 5.2nm, pore channel blockage is not easy to cause after coking, and the capability of resisting sulfur, nitrogen and heavy metal pollution is strong. At present, bentonite is the most mature.
Zirconyl nitrate is commonly used as a reagent for the determination of potassium and fluoride, and also for the preparation of luminescent agents and refractory materials. The solid zirconyl nitrate is white crystal or powder, easy to dissolve in water, and its water solution is acidic and oxidizing. The prior publications do not find a case of using zirconyl nitrate as a cross-linking agent, nor a case of doping pillared clay with zirconyl nitrate. The pillared clay doped with zirconyl nitrate has higher sulfur resistance, which is one of the innovative points of the invention.
It is noted that the pillared interlayer clay has a complex surface structure and an extremely large specific surface area, and is an ideal catalyst matrix, and in addition, the pillared interlayer clay doped with zirconium (Zr) oxide has high sulfur resistance. Therefore, the invention combines the strong catalytic activity of Ce and Mn oxides and the sulfur resistance of Zr pillared clay.
The invention is further illustrated by the following examples:
example 1:
6％MnO 2 -6％CeO 2 preparation and performance test of the/Zr-PILC catalyst.
Putting 10g of bentonite into a 1L beaker, adding 990g of deionized water as a solvent, and stirring for 24 hours at room temperature to obtain a bentonite suspension with the mass fraction of 1%.
Preparation of zirconyl nitrate cross-linking agent with zirconyl nitrate as zirconium source: preparing 0.1mol/L zirconyl nitrate solution, aging for 5h in a constant-temperature water bath at 85 ℃, and standing for 3h for cooling to obtain the 0.1mol/L zirconyl nitrate crosslinking agent.
And dropwise and slowly adding the prepared zirconyl nitrate crosslinking agent into the fully dispersed bentonite suspension to obtain a first mixed solution, ensuring the concentration of zirconyl nitrate in the first mixed solution to be 15mmol/g, stirring for 6h at room temperature, and standing for 12h to ensure that the zirconyl nitrate crosslinking agent and clay interlayer ions of the bentonite suspension perform full ion exchange. And then, centrifugally separating the suspension of the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain the Zr-PILC carrier.
1.2732g of Mn (NO) as a precursor 3 ) 2 And 1.4024g of Ce (NO) 3 ) 4 Dissolving in 100ml of deionized water to obtain a second mixed solution, then adding 10g of carrier Zr-PILC, stirring uniformly, dipping for 12h, drying the dipped product in a water bath at 85 ℃ for 12h at constant temperature, calcining for 5h at 500 ℃, grinding and sieving with a 40-mesh sieve for later use. To obtain 6% MnO 2 -6％CeO 2 A Zr-PILC catalyst.
In order to explore the support process and 6 percent MnO 2 -6％CeO 2 Influence of the pore structure of the/Zr-PILC catalyst by N 2 Adsorption-desorption characterization of Bentonite and 6% MnO 2 -6％CeO 2 The pore structure properties such as specific surface area, pore volume and average pore diameter of the/Zr-PILC sample. The BET specific surface area of the bentonite is 70.47m 2 /g，6％MnO 2 -6％CeO 2 The BET specific surface area of the/Zr-PILC sample is 120.70m 2 (ii) in terms of/g. After the bentonite is subjected to Zr pillared action, the specific surface area of the bentonite is 70.47m 2 g increase 120.70m 2 (ii) in terms of/g. Moreover, after the column bracing, the corresponding total pore volume is also obviously increased. This result indicates that the pillared clay material contains oxide pillars capable of supporting adjacent clay layers, thereby causing the clay layers to separate and finally to exist in a porous network structure of two-dimensional channels. The larger the specific surface area, the more favorable the reactants will be in full contact with the active sites of the catalyst, which is advantageous to some extent for the denitration and demercuration activity of the catalyst.
And (3) verifying the coordinated denitration and demercuration capability of the catalyst on a self-made experiment table. The basic components of the simulated smoke comprise 500ppm NO and 500ppm NH 3 ，5vol％O 2 ，50μg/m 3 Hg0，700ppm SO 2 ，3vol％H 2 O and high purity N 2 Balancing qi. Accurately controlling the flow of various gases by using a mass flow meter, wherein the total flow of the gases is 850ml/min, the loading amount of a catalyst in an experiment is 0.5g, the temperature of a catalytic reaction is controlled to be 250-400 ℃, and the space velocity is 50000h -1 。6％MnO 2 -6％CeO 2 The results of the test of the synergic denitration and demercuration performance of the/Zr-PILC sample are shown in figures 1 and 2. As can be seen in FIG. 1, 6% MnO 2 -6％CeO 2 the/Zr-PILC has higher denitration activity at various temperature points. The denitration rate at 250 ℃ is as high as 81.3%, and the denitration efficiency at 350 ℃ is 97.9% at most. The catalyst of the invention has excellent denitration capability when used for carrying out synergistic denitration and demercuration. FIG. 2 shows the results of mercury oxidation efficiency test with 6% MnO 2 -6％CeO 2 The Zr-PILC has higher mercury oxidation capacity at various temperature points and has the highest mercury oxidation efficiency of 96.2 percent at the temperature of 300 ℃. Thus, 6% MnO 2 -6％CeO 2 the/Zr-PILC has excellent synergistic denitration and demercuration capability.
The samples were further tested for sulfur resistance at 300 ℃. As shown in FIG. 3, as the reaction proceeds, the reaction proceeds inAfter running for 1h, 700ppm SO was added 2 Last, 6% MnO 2 -6％CeO 2 The denitration efficiency of the/Zr-PILC is slightly reduced to 89.9 percent from 92.9 percent, and the SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 87.5%. As shown in FIG. 4, 700ppm SO was added after 1h of operation 2 Last, 6% MnO 2 -6％CeO 2 The mercury oxidation efficiency of the/Zr-PILC is slightly reduced to 92.8 percent from 95.2 percent, and SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 89.1%. The catalyst is excellent in sulfur resistance in the process of synergetic denitration and demercuration, and the Zr-PILC has excellent sulfur resistance when being used as a catalyst carrier.
Example 2:
3% MnO 2-9% CeO2/Zr-PILC catalyst preparation and performance test.
Putting 10g of bentonite into a 1L beaker, adding 990g of deionized water as a solvent, and stirring for 24 hours at room temperature to obtain a bentonite suspension with the mass fraction of 1%.
Preparing a zirconyl nitrate crosslinking agent by taking zirconyl nitrate as a zirconium source: preparing 0.1mol/L zirconyl nitrate solution, aging for 5h in a constant-temperature water bath at 85 ℃, and standing for 3h for cooling to obtain the 0.1mol/L zirconyl nitrate crosslinking agent.
And dropwise and slowly adding the prepared zirconyl nitrate crosslinking agent into the fully dispersed bentonite suspension to obtain a first mixed solution, ensuring the concentration of zirconyl nitrate in the first mixed solution to be 15mmol/g, stirring for 6h at room temperature, and standing for 12h to ensure that the zirconyl nitrate crosslinking agent and clay interlayer ions of the bentonite suspension perform full ion exchange. And then, centrifugally separating the suspension of the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain the Zr-PILC carrier.
0.6366g of Mn (NO) as a precursor 3 ) 2 And 2.1036g of Ce (NO) 3 ) 4 Dissolving in 100ml of deionized water to obtain a second mixed solution, then adding 10g of carrier Zr-PILC, stirring uniformly, dipping for 12h, drying the dipped product in a water bath at 85 ℃ for 12h at constant temperature, calcining for 5h at 500 ℃, grinding and sieving with a 40-mesh sieve for later use. 3 percent of MnO2 to 9 percent of CeO2/Zr-PILC catalyst is prepared.
And (3) verifying the coordinated denitration and demercuration capability of the catalyst on a self-made experiment table. The basic components of the simulated smoke comprise 500ppm NO and 500ppm NH 3 ，5vol％O 2 ，50μg/m 3 Hg0，700ppm SO 2 ，3vol％H 2 O and high purity N 2 Balancing qi. Accurately controlling the flow of various gases by using a mass flow meter, wherein the total flow of the gases is 850ml/min, the loading amount of a catalyst in an experiment is 0.5g, the temperature of a catalytic reaction is controlled to be 250-400 ℃, and the space velocity is 50000h -1 。3％MnO 2 -9％CeO 2 The results of the test of the synergic denitration and demercuration performance of the/Zr-PILC sample are shown in figures 1 and 2. As can be seen in FIG. 1, 3% MnO 2 -9％CeO 2 The denitration efficiency of the/Zr-PILC at each temperature point is slightly lower than 6 percent MnO 2 -6％CeO 2 the/Zr-PILC still belongs to a higher level and has good synergistic denitration and demercuration capacity.
The samples were further tested for sulfur resistance at 300 ℃. As shown in FIG. 3, 700ppm SO was added after 1h of run as the reaction proceeded 2 Last, 3% MnO 2 -9％CeO 2 The denitration efficiency of the Zr-PILC is slightly reduced from 87.1 percent to 84.6 percent, and the SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 82.0%. As shown in FIG. 4, 700ppm SO was added after 1h of operation 2 Last, 3% MnO 2 -9％CeO 2 The mercury oxidation efficiency of the/Zr-PILC is slightly reduced to 81.6 percent from 85.8 percent, and the SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 78.7%. The catalyst is excellent in sulfur resistance in the process of synergetic denitration and demercuration, and the Zr-PILC has excellent sulfur resistance when being used as a catalyst carrier.
Example 3:
9% MnO 2-3% CeO2/Zr-PILC catalyst preparation and performance test.
Putting 10g of bentonite into a 1L beaker, adding 990g of deionized water as a solvent, and stirring for 24 hours at room temperature to obtain a bentonite suspension with the mass fraction of 1%.
Preparing a zirconyl nitrate crosslinking agent by taking zirconyl nitrate as a zirconium source: preparing 0.1mol/L zirconyl nitrate solution, aging for 5h in a constant-temperature water bath at 85 ℃, and standing for 3h for cooling to obtain the 0.1mol/L zirconyl nitrate crosslinking agent.
And dropwise and slowly adding the prepared zirconyl nitrate crosslinking agent into the fully dispersed bentonite suspension to obtain a first mixed solution, ensuring the concentration of zirconyl nitrate in the first mixed solution to be 15mmol/g, stirring for 6h at room temperature, and standing for 12h to ensure that the zirconyl nitrate crosslinking agent and clay interlayer ions of the bentonite suspension perform full ion exchange. And then, centrifugally separating the suspension of the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain the Zr-PILC carrier.
1.9098g of Mn (NO) from the precursor 3 ) 2 And 0.7012g of Ce (NO) 3 ) 4 Dissolving in 100ml of deionized water to obtain a second mixed solution, then adding 10g of carrier Zr-PILC, stirring uniformly, dipping for 12h, drying the dipped product in a water bath at 85 ℃ for 12h at constant temperature, calcining for 5h at 500 ℃, grinding and sieving with a 40-mesh sieve for later use. To obtain 9% MnO 2 -3％CeO 2 A Zr-PILC catalyst.
And (3) verifying the coordinated denitration and demercuration capability of the catalyst on a self-made experiment table. The basic components of the simulated smoke comprise 500ppm NO and 500ppm NH 3 ，5vol％O 2 ，50μg/m 3 Hg0，700ppm SO 2 ，3vol％H 2 O and high purity N 2 Balancing qi. Accurately controlling the flow of various gases by using a mass flow meter, wherein the total flow of the gases is 850ml/min, the loading amount of a catalyst in an experiment is 0.5g, the temperature of a catalytic reaction is controlled to be 250-400 ℃, and the space velocity is 50000h -1 。9％MnO 2 -3％CeO 2 The results of the test of the synergic denitration and demercuration performance of the/Zr-PILC sample are shown in figures 1 and 2. As can be seen in FIG. 1, 9% MnO 2 -3％CeO 2 The denitration efficiency of the/Zr-PILC at each temperature point is slightly lower than 6 percent MnO 2 -6％CeO 2 the/Zr-PILC still belongs to a higher level and has good synergistic denitration and demercuration capacity.
The samples were further tested for sulfur resistance at 300 ℃. As shown in FIG. 3, 700ppm SO was added after 1h of run as the reaction proceeded 2 Last, 9% MnO 2 -3％CeO 2 The denitration efficiency of the/Zr-PILC is slightly reduced to 85.3 percent from 90.3 percent, and the SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 83.3%. As shown in FIG. 4, 700ppm SO was added after 1h of operation 2 Last 9% MnO 2 -3％CeO 2 The mercury oxidation efficiency of the/Zr-PILC is slightly reduced to 89.4 percent from 94.3 percent, and the SO is continuously introduced 2 At 8h, the denitration efficiency only dropped to 83.2%. The catalyst is excellent in sulfur resistance in the process of synergetic denitration and demercuration, and the Zr-PILC has excellent sulfur resistance when being used as a catalyst carrier.
Comparative example 1:
to compare the sulfur resistance of the zirconium-based pillared clay supported catalyst, conventional P25 TiO was prepared 2 The catalyst is a Mn and Ce oxide catalyst of a carrier, and a sulfur resistance performance comparison test is carried out.
1.2732g of Mn (NO) as a precursor 3 ) 2 And 1.4024g of Ce (NO) 3 ) 4 Dissolving in 100ml deionized water to obtain a mixed solution, and adding 10g P25 TiO 2 The carrier is stirred uniformly, dipped for 12h, the dipped product is dried for 12h by water bath at 85 ℃ under constant temperature, then calcined for 5h at 500 ℃, and ground and sieved by a 40-mesh sieve for later use. To obtain 6% MnO 2 -6％CeO 2 An oxide catalyst.
Testing of 6% MnO at 300 deg.C 2 -6％CeO 2 The sulfur resistance of the oxide catalyst. As shown in FIG. 3, 700ppm SO was added after 1h of run as the reaction proceeded 2 Last, 6% MnO 2 -6％CeO 2 The denitration efficiency of the oxide catalyst is sharply reduced from 77.5 percent to 65.3 percent, and SO is continuously introduced 2 And the denitration efficiency is greatly reduced to 56.8% at the 8 h. As shown in FIG. 4, 700ppm SO was added after 1h of operation 2 Last 6% MnO 2 -6％CeO 2 The mercury oxidation efficiency of the oxide catalyst is sharply reduced from 80.4 percent to 70.4 percent, and SO is continuously introduced 2 And the denitration efficiency is greatly reduced to 60.7% at the 8 th hour. The comparison shows that the sulfur resistance of the catalyst taking the conventional P25 as the carrier is obviously better than that of 6 percent MnO taking Zr-PILC as the carrier 2 -6％CeO 2 The difference of Zr-PILC shows that the zirconium-based pillared clay supported catalyst has excellent sulfur resistance while ensuring excellent synergistic denitration and demercuration capability.
In the present invention, the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The preparation method of the high-sulfur-resistance zirconium-based pillared clay supported catalyst is characterized by comprising the following steps of:
s1, preparing a bentonite suspension with the mass fraction of 0.5-2% and a zirconyl nitrate crosslinking agent with the mass fraction of 0.1-0.5 mol/L, dropwise adding the zirconyl nitrate crosslinking agent into the bentonite suspension to obtain a first mixed solution, stirring and standing, wherein the concentration of zirconyl nitrate in the first mixed solution is 10-30 mmol/g, centrifugally separating the first mixed solution to obtain a precipitate, and drying and calcining the precipitate to obtain a carrier Zr-PILC;
S2，Mn(NO 3 ) 2 and Ce (NO) 3 ) 4 Dissolving in deionized water to obtain a second mixed solution, and adding the carrier Zr-PILC (Zr-PILC) into the second mixed solution, wherein Mn (NO) 3 ) 2 With Ce (NO) 3 ) 4 The mass ratio of the total mass of the catalyst to deionized water and the carrier Zr-PILC is 2.6-2.8: 100: 10, stirring and dipping, drying, calcining and grinding the dipped product to obtain alpha% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
2. The method for preparing the high sulfur-resistance zirconium-based pillared clay supported catalyst of claim 1, wherein in the step S1, the zirconium oxynitrate cross-linking agent is prepared by: aging 0.1-0.5 mol/L zirconyl nitrate in a constant-temperature water bath at 75-90 ℃ for 3-10 h, and then standing and cooling for 2-5 h.
3. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst of claim 1, wherein in the step S1, the zirconyl nitrate crosslinking agent is added dropwise to the bentonite suspension, stirred at room temperature for 3-8 h, and then left to stand for 8-16 h.
4. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst of claim 1, wherein in the step S1, the precipitate is dried in a constant temperature water bath at 75-90 ℃ for 8-16 h.
5. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst of claim 1, wherein in the step S1, the calcination temperature of the precipitate is 400-600 ℃ and the calcination time is 2-5 h.
6. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst of claim 1, wherein the impregnation time in step S2 is 8-16 h.
7. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst of claim 1, wherein in the step S2, the impregnated product is dried in a constant temperature water bath at 75-90 ℃ for 8-16 h.
8. The method for preparing the high sulfur resistance zirconium based pillared clay supported catalyst according to any one of claims 1 to 7, wherein in the step S2, the calcination temperature of the impregnated product is 400 to 600 ℃, the calcination time is 2 to 5 hours, and the impregnated product is ground and sieved by a 40-mesh sieve for later use.
9. The preparation method of any one of claims 1 to 8, wherein the high-sulfur-resistance zirconium-based pillared clay supported catalyst is a% MnO 2 -b％CeO 2 A Zr-PILC catalyst, wherein a and b are respectively MnO 2 And CeO 2 The mass fraction of (a) is 3 to 9, b is 3 to 9, and a + b is 12.
10. The use of the high sulfur resistance zirconium-based pillared clay supported catalyst of claim 9 in the synergistic denitration and demercuration of flue gas.
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| CN114733510A (en) * | 2022-04-11 | 2022-07-12 | 苏州西热节能环保技术有限公司 | High-strength marine SCR catalyst and preparation method and application thereof |
| WO2023226668A1 (en) * | 2022-05-23 | 2023-11-30 | 苏州西热节能环保技术有限公司 | High sulfur-resistant zirconium-based pillared clay supported catalyst and preparation method therefor and application thereof |
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| WO2016175706A1 (en) * | 2015-04-30 | 2016-11-03 | Nanyang Technological University | A pillared clay catalyst |
| CN107159191B (en) * | 2017-05-26 | 2020-01-24 | 四川大学 | Supported denitration catalyst based on pillared clay and preparation method thereof |
| CN109603808B (en) * | 2018-12-22 | 2022-02-15 | 北京工业大学 | Preparation method and application of zirconium pillared montmorillonite-loaded Ce-Nb composite catalyst |
| CN114849682A (en) * | 2022-05-23 | 2022-08-05 | 苏州西热节能环保技术有限公司 | High-sulfur-resistance zirconium-based pillared clay supported catalyst and preparation method and application thereof |
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| CN114733510A (en) * | 2022-04-11 | 2022-07-12 | 苏州西热节能环保技术有限公司 | High-strength marine SCR catalyst and preparation method and application thereof |
| CN114733510B (en) * | 2022-04-11 | 2024-04-05 | 苏州西热节能环保技术有限公司 | High-strength marine SCR catalyst and preparation method and application thereof |
| WO2023226668A1 (en) * | 2022-05-23 | 2023-11-30 | 苏州西热节能环保技术有限公司 | High sulfur-resistant zirconium-based pillared clay supported catalyst and preparation method therefor and application thereof |
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