CN113289613A - Preparation method of similar honeycomb manganese-based mullite catalyst for VOCs purification - Google Patents
Preparation method of similar honeycomb manganese-based mullite catalyst for VOCs purification Download PDFInfo
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- CN113289613A CN113289613A CN202110618287.4A CN202110618287A CN113289613A CN 113289613 A CN113289613 A CN 113289613A CN 202110618287 A CN202110618287 A CN 202110618287A CN 113289613 A CN113289613 A CN 113289613A
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- manganese
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- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 75
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 58
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 31
- 239000011572 manganese Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000000694 effects Effects 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 12
- -1 rare earth salt Chemical class 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 150000002696 manganese Chemical class 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 28
- 229940071125 manganese acetate Drugs 0.000 claims description 15
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 15
- 239000008247 solid mixture Substances 0.000 claims description 14
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Chemical class 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical class [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical class [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical class [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical class [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Chemical class 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 21
- 238000007254 oxidation reaction Methods 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 239000012467 final product Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 156
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 102
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 66
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 58
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 229940078552 o-xylene Drugs 0.000 description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 230000010718 Oxidation Activity Effects 0.000 description 14
- 229920006395 saturated elastomer Polymers 0.000 description 14
- ZRRNZPOIRAPEDF-UHFFFAOYSA-N [Mn].[Sm] Chemical compound [Mn].[Sm] ZRRNZPOIRAPEDF-UHFFFAOYSA-N 0.000 description 10
- 230000033558 biomineral tissue development Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001027 hydrothermal synthesis Methods 0.000 description 7
- 229960001484 edetic acid Drugs 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 229910016978 MnOx Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
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- 239000004071 soot Substances 0.000 description 1
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- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- 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
-
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- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
The invention relates to a preparation method of a honeycomb-like manganese-based mullite catalyst for purifying VOCs. The method comprises the following steps: directly mixing manganese salt, rare earth salt and self-polymerization monomers in a certain proportion in a solid state form, transferring the mixture into a crucible, and calcining the mixture in a muffle furnace at a certain temperature to obtain the manganese-based mullite catalyst for catalytic oxidation of high-activity VOCs. The process is simple, the final product can be obtained in one step, and the prepared mullite catalyst has better application prospect and economic benefit in the field of industrial VOCs flue gas purification.
Description
Technical Field
The invention relates to the field of industrial flue gas purification, in particular to a preparation method of a honeycomb-like manganese-based mullite catalyst for VOCs purification.
Background
Volatile Organic Compounds (VOC) are commonly found in tail gas of industries such as waste incineration, electric furnace steelmaking, iron ore sintering, metal smelting, coal burning, coking and the like, are one of main pushers for urban haze, photochemical smog, atmospheric toxicity and other composite atmospheric pollution phenomena, and bring serious influence on life and health of people. Catalytic oxidation technology has attracted much attention because it can rapidly convert VOCs into harmless substances such as carbon dioxide and water at low temperatures. The core of the catalytic oxidation technology is a catalyst, and the commonly used catalyst mainly comprises noble metal and transition metal oxides. Although noble metals have the advantage of high catalytic activity, they have the disadvantages of high price, high sintering temperature, high poisoning tendency, etc., which limits their further applications. Compared with noble metal catalysts, transition metal oxides have become hot catalysts for the research in the field of catalysis due to the advantages of wide sources, low cost, multiple valence states, strong structure adjustability, and the like. However, the common transition metal oxide has the defects of poor hydrothermal stability, insufficient activity in catalytic oxidation of complex multi-component VOCs and the like, so that the research on the high-activity transition metal oxide catalyst with high hydrothermal stability has good application prospect.
Manganese-based mullite, a member of the transition metal oxides, is of great interest because of its high hydrothermal stability in NO oxidation and soot removal [ CN104624184A, CN103801288A ]. In the prior art, mullite is also used as a catalyst for VOC oxidation, for example, Wangwang super reports that a SmMn2O5 mullite catalyst prepared by a hydrothermal method is used for catalyzing and converting VOC (CN 110433794A) such as toluene or benzene, but an amplified hydrothermal reaction kettle has explosion risk under high temperature and high pressure, and the mineralization efficiency of the manganese-based mullite catalyst prepared by the method is unknown. In addition, the manganese-based mullite catalyst is prepared by coprecipitation (Mixed-phaseoxide catalyst system Mn-mullite (Sm, Gd) Mn2O5forNOoxidinationselexioushaust. science,2012,337:832-835.) and sol-gel [ CN104624184A, CN103801288A ], but the preparation methods have complex operation and high energy consumption, are not suitable for the large-scale industrial production of the manganese-based mullite catalyst, and provide a preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs aiming at the problems.
Disclosure of Invention
The invention aims to overcome the defects of the background technology, prepare a low-temperature high-activity honeycomb-shaped manganese-based mullite catalyst by a simple and convenient method through a one-step calcination method, and provide the application of the catalyst in the catalytic oxidation of VOCs.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a similar honeycomb manganese-based mullite catalyst for purifying VOCs comprises the following steps:
the method comprises the following steps: directly mixing a solid self-polymerization monomer reagent, solid manganese salt and solid rare earth samarium salt without adding liquid solvents such as water and the like;
step two: putting the solid mixture in the step one into a crucible and placing the crucible into a muffle furnace;
step three: directly taking air as atmosphere, raising the temperature to a proper temperature at a certain temperature raising speed for reaction, maintaining the temperature for a period of time, and obtaining the samarium-manganese-mullite VOCs purification material after calcination.
Preferably, the solid self-polymerizing monomer reagent in the first step is one or more of citric acid, maleic acid and ethylenediamine tetraacetic acid.
Preferably, the manganese salt in the first step is solid metal salt such as manganese acetate, manganese sulfate, manganese chloride and the like.
Preferably, the rare earth samarium salt in the first step is solid samarium acetate, samarium sulfate, samarium chloride and samarium nitrate.
Preferably, the heating rate of the calcination in the third step is 1-10 ℃/min.
Preferably, the constant temperature maintained in the calcination in the third step is 650-900 ℃.
Preferably, the maintaining time of the calcining constant-temperature stage is 1-3 h.
Preferably, the molar ratio of the solid complexing agent to the total metal salt is 0.5: 1-5: 1.
Preferably, the method is also suitable for preparing the high-activity honeycomb-shaped manganese-based mullite catalyst by using solid rare earth salts such as lanthanum, praseodymium, neodymium, europium, gadolinium and the like.
Preferably, the method is also suitable for preparing a plurality of groups of classified honeycomb mullite catalysts by doping manganese-based mullite with solid transition metal salts such as iron, copper, nickel, cobalt, titanium and the like.
The preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs, provided by the invention, has the following beneficial effects:
firstly, directly mixing a solid self-polymerization monomer reagent, solid manganese salt and solid rare earth samarium salt without adding liquid solvents such as water and the like, putting the solid mixture obtained in the first step into a crucible and placing the crucible into a muffle furnace, directly taking air as atmosphere at the moment, raising the temperature to a proper temperature at a certain heating speed for reaction, maintaining the temperature for a period of time, and obtaining a samarium-manganese-mullite-VOCs purification material after calcination is finished, so that the aim of directly preparing the manganese-based mullite catalyst by calcining the solid mixture in one step is fulfilled, the raw materials are cheap and easy to obtain, the process operation is simple and convenient, and the production cost is saved;
secondly, by solid state self-polymerizing monomer reagents: one or more of citric acid, maleic acid and ethylene diamine tetraacetic acid are heated to generate a complex derivative polymer formed by self-polymerization reaction, so that the manganese-based mullite catalyst with a special structure can be formed;
thirdly, the manganese-based mullite catalyst shows more excellent performance of catalyzing and oxidizing complex multi-component VOCs at low temperature.
Drawings
FIG. 1 is a graph showing the yield of CO2 from the low temperature, high activity honeycomb-like manganese-based mullite catalyst made in example 1 for the long-term catalytic oxidation of 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene, and mixed VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene, 250ppm chlorobenzene.
FIG. 2 is a FESEM image of a low temperature highly active honeycomb-like manganese-based mullite catalyst made in example 1.
FIG. 3 is an XRD pattern of a low temperature highly active honeycomb-like manganese-based mullite catalyst (designated as SmMn2O5-MP) made in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium acetate and 22.5mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 750 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and maintaining the temperature for 2h to ensure that manganese acetate, samarium acetate and citric acid in the muffle furnace fully react to obtain a product, namely the samarium-manganese-mullite catalyst, so as to realize the preparation of the samarium-manganese-mullite catalyst.
Fig. 1 and fig. 2 are an XRD diagram and an FESEM diagram of the prepared samarium-manganese-mullite catalyst, respectively, and the prepared catalyst is SmMn2O5 mullite which presents a three-dimensional connected honeycomb-like structure of a porous structure, characterized by FESEM.
FIG. 2 is a graph showing the catalytic oxidation effect of the prepared SmMn2O5 mullite on 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm O-xylene, and a mixed component VOCs of 250ppm benzene, 250ppm toluene, 250ppm O-xylene and 250ppm chlorobenzene at 240 ℃, and the activity of the obtained SmMn2O5 mullite is stable after the obtained SmMn2O5 mullite is used for 120 hours for a long time.
The similar-honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for oxidizing benzene, toluene, chlorobenzene, o-xylene and mixed components thereof, so that high oxidation activity is obtained, and experimental results show that: under 10000h < -1 > airspeed and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized with 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene and 1000ppm o-xylene, and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90% at 200 ℃, 180 ℃, 330 ℃, 230 ℃ and 340 ℃, respectively, and the excellent VOCs mineralization activity is shown.
Example 2:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium acetate and 22.5mmol of maleic acid in a solid form;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 650 ℃ in a muffle furnace at the heating rate of 1 ℃/min, and maintaining the temperature for 3 hours to obtain the product, namely the samarium-manganese-mullite catalyst. The prepared similar honeycomb-shaped samarium-manganese-mullite catalyst is used for benzene oxidation, and obtains higher benzene oxidation activity, and experimental results show that: under 10000h < -1 > space velocity and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized to 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches to 90 percent at 205 ℃, 188 ℃, 335 ℃, 233 ℃ and 346 ℃, respectively, and the mineralized activity of the VOCs is excellent.
Example 3:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium acetate and 22.5mmol of ethylenediamine tetraacetic acid in a solid form;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 700 ℃ in a muffle furnace at the heating rate of 3 ℃/min, and maintaining the temperature for 3h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment example 3 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > space velocity and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized to 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene and 1000ppm o-xylene, and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches to 90% at 210 ℃, 193 ℃, 339 ℃, 236 ℃ and 352 ℃, and excellent VOCs mineralization activity is shown.
Example 4:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium nitrate, 7.5mmol of maleic acid, 7mmol of ethylene diamine tetraacetic acid and 8mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 800 ℃ in a muffle furnace at the heating rate of 4 ℃/min, and maintaining the temperature for 1.5h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 4 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h-1 airspeed and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized by 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene and 1000ppm o-xylene, and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90% at 212 ℃, 195 ℃, 343 ℃, 238 ℃ and 365 ℃, and the excellent mineralization activity of the VOCs is shown.
Example 5:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium sulfate, 14mmol of maleic acid and 8.5mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 850 ℃ in a muffle furnace at the heating rate of 5 ℃/min, maintaining the temperature for 3h, and washing and drying the obtained product to obtain the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h-1 airspeed and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized with 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene, and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90% at 220 ℃, 207 ℃, 351 ℃, 242 ℃ and 369 ℃, respectively, and the excellent VOCs mineralization activity is shown.
Example 6:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium chloride, 7.5mmol of maleic acid and 15mmol of ethylenediamine tetraacetic acid in a solid form;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: raising the temperature to 750 ℃ in a muffle furnace at the temperature raising speed of 6 ℃/min, and maintaining the temperature for 2h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > space velocity and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized to 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90 percent at 212 ℃, 188 ℃, 338 ℃, 239 ℃ and 346 ℃ respectively, and the excellent mineralization activity of the VOCs is shown.
Example 7:
the method comprises the following steps: directly mixing 10mmol of manganese sulfate, 5mmol of samarium sulfate and 7.5mmol of citric acid in a solid form;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 900 ℃ in a muffle furnace at the heating rate of 7 ℃/min, maintaining the temperature for 3h, and washing and drying the obtained product to obtain the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > airspeed and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized with 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene and 1000ppm o-xylene, and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90% at 240 ℃, 237 ℃, 368 ℃, 251 ℃ and 376 ℃, respectively, and the excellent mineralization activity of the VOCs is shown.
Example 8:
the method comprises the following steps: directly mixing 10mmol of manganese chloride, 5mmol of samarium acetate and 15mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 750 ℃ in a muffle furnace at the heating rate of 8 ℃/min, and maintaining the temperature for 1h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 8 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > space velocity and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized to 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches up to 90 percent at 219 ℃, 187 ℃, 346 ℃, 248 ℃ and 357 ℃ respectively, and the mineralization activity of the VOCs is excellent.
Example 9:
the method comprises the following steps: directly mixing 10mmol of manganese acetate, 5mmol of samarium acetate, 7.5mmol of maleic acid and 15mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 800 ℃ in a muffle furnace at the heating rate of 9 ℃/min, and maintaining the temperature for 1h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > airspeed and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized with 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches 90% at 214 ℃, 186 ℃, 340 ℃, 242 ℃ and 349 ℃, and the excellent mineralization activity of the VOCs is shown.
Example 10:
the method comprises the following steps: directly mixing 5mmol of manganese acetate, 5mmol of manganese chloride, 5mmol of samarium acetate and 22.5mmol of citric acid in a solid state;
step two: putting the solid mixture in the step one into a crucible and placing the crucible in a muffle furnace;
step three: heating to 900 ℃ in a muffle furnace at a heating rate of 10 ℃/min, and maintaining the temperature for 0.5h to obtain the product, namely the samarium-manganese-mullite catalyst. The similar honeycomb-shaped samarium-manganese-mullite catalyst prepared in the embodiment 1 is used for benzene oxidation, so that higher benzene oxidation activity is obtained, and experimental results show that: under 10000h < -1 > space velocity and saturated steam, the honeycomb-shaped samarium-manganese mullite is catalyzed and oxidized to 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, the yield of CO2 reaches to 90 percent at 219 ℃, 192 ℃, 341 ℃, 242 ℃ and 359 ℃, and the excellent mineralization activity of the VOCs is shown.
Comparative example 1: the preparation method of the manganese oxide comprises the following steps:
the method comprises the following steps: putting 10mmol of manganese acetate into a crucible and placing the crucible in a muffle furnace;
step two: heating to 750 ℃ at the heating rate of 2 ℃/min, maintaining the temperature for 2h, and obtaining the product MnOx after the reaction is finished.
When the MnOx catalyst prepared in the comparative example 1 is used for oxidizing VOCs, under 10000h < -1 > space velocity and saturated steam, the MnOx catalytically oxidizes 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm o-xylene and mixed components VOCs of 250ppm benzene, 250ppm toluene, 250ppm o-xylene and 250ppm chlorobenzene, and the CO2 yield reaches 90% at 349 ℃, 335 ℃, 481 ℃, 397 ℃ and 501 ℃ respectively, which indicates that the low-temperature catalytic oxidation activity is poor.
Comparative example 2: the preparation method for synthesizing the SmMn2O5 catalyst by the sol-gel method comprises the following steps:
the method comprises the following steps: dissolving 10mmol of manganese acetate, 5mmol of samarium acetate and 22.5mmol of citric acid in 100mL of deionized water, stirring and evaporating to remove excessive water, so that the solution is in a sol state;
step two: drying the sol obtained in the step one in an oven at 120 ℃ for 24 hours to form a gel state;
step three: and (3) putting the gel obtained in the step two into a crucible, placing the crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 2 ℃/min, maintaining the temperature for 2 hours, then heating to 850 ℃ again, maintaining for 3 hours, and obtaining a product after the reaction is finished, namely SmMn2O5 prepared by the sol-gel method.
When the SmMn2O5 catalyst prepared in the comparative example 2 is used for catalytic oxidation of VOCs, 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm O-xylene and VOCs of mixed components of 250ppm benzene, 250ppm toluene, 250ppm O-xylene and 250ppm chlorobenzene are catalytically oxidized by SmMn2O5 at 10000h-1 space velocity and saturated steam, and the CO2 yield reaches to 299 ℃, 292 ℃, 455 ℃, 341 ℃ and 464 ℃ to 90 percent respectively, which shows that the low-temperature catalytic oxidation activity is poor.
Comparative example 3: the preparation method of the SmMn2O5 by coprecipitation synthesis comprises the following steps:
the method comprises the following steps: putting 10mmol of manganese acetate and 5mmol of samarium acetate into 100mL of deionized water for full dissolution;
step two: dropwise adding a sodium hydroxide solution into the step one to adjust the pH value to 12-13, quickly stirring, and filtering to obtain filter residues;
step three: and (4) putting the filter residue obtained in the step two into a crucible, placing the crucible into a muffle furnace, heating to 850 ℃ at the heating speed of 2 ℃/min, maintaining the temperature for 3 hours, and obtaining a product after the reaction is finished, namely SmMn2O5 prepared by a coprecipitation method.
When the SmMn2O5 catalyst prepared in the comparative example 3 is used for catalytic oxidation of VOCs, 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm O-xylene and VOCs of mixed components of 250ppm benzene, 250ppm toluene, 250ppm O-xylene and 250ppm chlorobenzene are catalytically oxidized by SmMn2O5 at 10000h-1 space velocity and saturated steam, and the CO2 yield is up to 90% at 331 ℃, 327 ℃, 479 ℃, 358 ℃ and 485 ℃, respectively, which shows that the low-temperature catalytic oxidation activity is poor.
Comparative example 4: the preparation method for synthesizing SmMn2O5 by a hydrothermal method comprises the following steps:
the method comprises the following steps: putting 10mmol of manganese acetate and 5mmol of samarium acetate into 100mL of deionized water for full dissolution;
step two: adjusting the pH of the solution in the first step to 13 under the condition of continuous stirring;
step three: and D, transferring the mixed solution obtained in the step two into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 48 hours at 250 ℃, wherein the obtained product is the SmMn2O5 catalyst synthesized by the hydrothermal method.
When the SmMn2O5 catalyst prepared by the hydrothermal method in the comparative example 4 is used for catalytic oxidation of VOCs, under 10000h-1 space velocity and saturated steam, the SmMn2O5 catalytically oxidizes 1000ppm benzene, 1000ppm toluene, 1000ppm chlorobenzene, 1000ppm O-xylene, and VOCs with mixed components of 250ppm benzene, 250ppm toluene, 250ppm O-xylene and 250ppm chlorobenzene, and the CO2 yield reaches 319 ℃, 308 ℃, 462 ℃, 350 ℃ and 474 ℃ to 90 percent respectively, which shows that the low-temperature catalytic oxidation activity is poor.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a similar honeycomb manganese-based mullite catalyst for purifying VOCs is characterized by comprising the following steps:
the method comprises the following steps: directly mixing a solid self-polymerization monomer reagent, solid manganese salt and solid rare earth samarium salt without adding liquid solvents such as water and the like;
step two: putting the solid mixture in the step one into a crucible and placing the crucible into a muffle furnace;
step three: directly taking air as atmosphere, raising the temperature to a proper temperature at a certain temperature raising speed for reaction, maintaining the temperature for a period of time, and obtaining the samarium-manganese-mullite VOCs purification material after calcination.
2. The method of claim 1, wherein the solid self-polymerizing monomer reagent in step one is one or more selected from citric acid, maleic acid, and ethylenediaminetetraacetic acid.
3. The method as claimed in claim 1, wherein the manganese salt in the first step is solid metal salt such as manganese acetate, manganese sulfate, manganese chloride, etc.
4. The method for preparing a quasi-honeycomb-shaped manganese-based mullite catalyst for the purification of VOCs according to claim 1, wherein the rare earth samarium salt in the first step is solid samarium acetate, samarium sulfate, samarium chloride and samarium nitrate.
5. The preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs according to claim 1, wherein the heating rate of calcination in the third step is 1-10 ℃/min.
6. The preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs according to claim 1, wherein the constant temperature maintained during the calcination in the third step is 650-900 ℃.
7. The preparation method of the honeycomb-like manganese-based mullite catalyst for VOCs purification according to claim 1, wherein the maintaining time of the calcination constant temperature stage is 1-3 h.
8. The preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs according to claim 1, wherein the molar ratio of the solid complexing agent to the total metal salt is 0.5: 1-5: 1.
9. The method for preparing the honeycomb-like manganese-based mullite catalyst for purifying VOCs according to claim 1, wherein the method is also suitable for preparing high-activity honeycomb-like manganese-based mullite catalysts from solid rare earth salts of lanthanum, praseodymium, neodymium, europium, gadolinium and the like.
10. The preparation method of the honeycomb-like manganese-based mullite catalyst for purifying VOCs according to claim 1, wherein the method is also suitable for preparing a plurality of groups of classified honeycomb-like mullite catalysts by doping manganese-based mullite with solid transition metal salts of iron, copper, nickel, cobalt, titanium and the like.
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