CN113231057B - (001) Preparation and application of manganese-based mullite catalyst with oriented crystal face - Google Patents
(001) Preparation and application of manganese-based mullite catalyst with oriented crystal face Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 71
- 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 60
- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 60
- 239000013078 crystal Substances 0.000 title claims abstract description 57
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 24
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 239000000411 inducer Substances 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- BHVPEUGTPDJECS-UHFFFAOYSA-L manganese(2+);diformate Chemical compound [Mn+2].[O-]C=O.[O-]C=O BHVPEUGTPDJECS-UHFFFAOYSA-L 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000002912 waste gas Substances 0.000 abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002243 precursor Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- HDCOFJGRHQAIPE-UHFFFAOYSA-N samarium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HDCOFJGRHQAIPE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- SQWDGUOWCZUSAO-UHFFFAOYSA-L manganese(2+);diformate;dihydrate Chemical group O.O.[Mn+2].[O-]C=O.[O-]C=O SQWDGUOWCZUSAO-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- -1 PrNd Inorganic materials 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 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 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01D53/864—Removing carbon monoxide or hydrocarbons
-
- 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
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Abstract
The invention provides preparation and application of a manganese-based mullite catalyst with oriented (001) crystal face, namely, the manganese-based mullite oxidation catalyst with the advantage of exposed (001) crystal face is prepared by microwave irradiation on the basis of a hydrothermal synthesis method. The preparation method disclosed by the invention is simple in operation flow, short in preparation period and low in energy consumption, the exposure proportion of the crystal face of the obtained manganese-based mullite catalyst (001) is obviously increased, the low-temperature oxidation capability of the catalyst on hydrocarbon is greatly improved, hydrocarbon in the waste gas of a mobile source and a fixed source can be effectively removed, and the application prospect is good.
Description
Technical Field
The invention belongs to the technical field of oxidation catalyst materials and preparation, and particularly relates to preparation and application of a (001) crystal face oriented manganese-based mullite catalyst.
Background
China has rapidly developed economy and also has great pressure on environmental governance. The large-scale exploitation and use of coal, oil and natural gas and the wide-range application of diesel engines lead to the increasing emission of Hydrocarbons (HCs) in stationary source flue gas and mobile source tail gas, while HCs contain various alkanes, alkenes and aromatics, which can form aerosol after entering the atmosphere, cause photochemical smog and haze, cause serious environmental pollution and threaten human health. Among various waste gas treatment technologies, the catalytic combustion (oxidation) method has the advantages of wide application range, low energy consumption, high efficiency, no secondary pollution and the like, and has become an important waste gas purification technology and development direction at present. Noble metal (Pt, Pd, and the like) catalysts are still used as the leading factors in the field of exhaust gas purification in the current market, but the noble metal resources are limited, the price is high, and the noble metal catalysts are not beneficial to the implementation of the national sustainable development strategy. The development of a high-performance and low-cost oxidation catalyst is urgently needed, and the method has important significance for solving the current hydrocarbon emission control. In recent years, manganese-based mullite catalysts have great application value particularly in the field of automobile exhaust purification due to good redox activity, high hydrothermal stability and abundant and cheap raw materials. At present, the preparation of manganese-based mullite is mainly based on the traditional coprecipitation method, sol-gel method and hydrothermal method. For example, according to the reports of patents CN103801288B and CN104624184B, the precursor solution is first prepared into gel or precipitate, and then calcined at 800 ℃ for 5-10h to obtain the manganese-based mullite composite oxide. The process has the defects of complicated steps, long time consumption, high energy consumption and the like, and the surface structure of the catalyst can be damaged in the high-temperature calcination process. Patent CN108355647A discloses a hydrothermal synthesis method for preparing manganese-based mullite oxide, however, the conventional method has long reaction time (preferably 12-48h) and is a main energy-consuming process. Ma et al (Chemical Engineering Journal,2018,354,191-196) regulate and control the morphology of the manganese-based mullite based on a traditional hydrothermal method, but the obtained manganese-based mullite catalyst still has the problem of low exposure rate of a reactive crystal face. In the traditional hydrothermal synthesis, the temperature is transferred from outside to inside, the heating is not uniform, most of energy is absorbed by the wall of the reactor, the energy consumption is large, and the reaction rate is slow. The preparation of (001) active crystal face oriented manganese-based mullite by using a microwave hydrothermal technology is not reported so far, and only theoretical research on chemical behavior of oxygen with different crystal faces is shown, for example, Chen et al (ACS Catalysis,2015,5,4913-4926) prove that manganese-based mullite materials exposed by specific crystal faces of (001) and the like can be beneficial to catalytic oxidation reaction of nitric oxide through theoretical calculation.
Disclosure of Invention
Aiming at the problems of low specific crystal face exposure proportion, long catalyst preparation period, high energy consumption and the like of the existing manganese-based mullite catalyst, the invention aims to provide the manganese-based mullite with oriented (001) crystal face and the microwave hydrothermal synthesis method thereof, wherein the propane catalytic activity of the prepared manganese-based mullite catalyst with oriented (001) crystal face is obviously higher than that of the catalyst obtained by the traditional hydrothermal method, and the catalyst is suitable for catalytic oxidation removal of hydrocarbons in waste gas of a mobile source or a fixed source.
The molecular formula of the (001) crystal face oriented manganese-based mullite provided by the invention is LnMn2O5Wherein Ln is one or more of Sm, La, Ce, Pr, Nd, Gd and Y, and can be Sm or Y;
the molecular formula of the (001) crystal face oriented manganese-based mullite can be LnMn2O5- I001/I211Wherein Ln is one or the combination of more of Sm, La, Ce, Pr, Nd, Gd and Y, I001/I211The strength ratio of the (001) crystal face to the (211) crystal face of the mullite is shown as I001/I2110.30-0.94, specifically 0.3-0.90, 0.58-0.90, 0.31-0.89, 0.31, 0.58 or 0.89; the manganese-based mullite with the oriented (001) crystal face can be SmMn2O5-0.89、SmMn2O5-0.58 or YMn2O5-0.31；
The manganese-based mullite with the oriented (001) crystal face is prepared by a microwave hydrothermal method through the following steps:
and mixing the soluble Ln salt and the soluble divalent Mn salt solution, adding soluble heptavalent manganese salt, dropwise adding alkali liquor to adjust the pH value to 4-9, transferring to a hydrothermal reaction kettle, carrying out microwave hydrothermal reaction, and washing and drying to obtain the (001) crystal face oriented manganese-based mullite.
In the above method, the soluble Ln salt can be nitrate and/or chloride of Ln, specifically samarium chloride, samarium nitrate or yttrium nitrate;
the divalent Mn salt can be manganese nitrate, manganese acetate, manganese formate and/or manganese chloride, and the heptavalent manganese salt can be potassium permanganate and/or sodium permanganate;
the mol ratio of the soluble Ln salt to the divalent Mn salt and the heptavalent manganese salt can be 1: 1.4: 0.6;
a structure inducer can also be added into the reaction system,
the structure inducer can be any one or combination of more of formic acid, triethylamine, polyethylene glycol, ethanolamine, ethylene glycol, ethylene diamine tetraacetic acid, citric acid and sodium citrate, and specifically can be formic acid, citric acid and sodium citrate;
the structure inducer is citric acid, and the mol ratio of the soluble Ln salt to the divalent Mn salt to the heptavalent manganese salt to the structure inducer can be 1: 1.4: 0.6: 1-3; the method specifically comprises the following steps: 1: 1.4: 0.6: 1;
the alkali liquor is sodium hydroxide, potassium hydroxide or ammonia water solution;
the reaction temperature of the microwave hydrothermal reaction can be 120-260 ℃, specifically 180-240 ℃, more specifically 200 ℃, 210 ℃ or 220 ℃;
the reaction pressure of the microwave hydrothermal reaction can be 2-5 atm, specifically 2.9 atm, 3.2 atm or 3.6 atm, and the microwave power can be 200-1800W, specifically 800-1500W, more specifically 800W, 1200W or 1500W;
the microwave hydrothermal reaction time can be 0.2-1 hour, and specifically can be 30 min;
and after the reaction is finished, naturally cooling or cooling with the assistance of an exhaust fan, washing with water and washing with alcohol, and drying at normal pressure or in vacuum to obtain the (001) crystal face oriented manganese-based mullite, wherein the drying temperature can be 20-110 ℃.
The application of the manganese-based mullite with the oriented (001) crystal face as the oxidation catalyst also belongs to the protection scope of the invention.
The application specifically can be as follows: (001) the application of the manganese-based mullite with oriented crystal faces as an oxidation catalyst in the catalytic oxidation removal of Hydrocarbons (HCs) in exhaust gas discharged by a mobile source or a fixed source;
said Hydrocarbons (HCs) are replaced by propane (C)3H8) For example.
The present invention also provides a method for removing Hydrocarbons (HCs) from exhaust gas emitted from a mobile source or a stationary source.
The method for removing Hydrocarbons (HCs) in the exhaust gas discharged by a mobile source or a fixed source comprises the following steps: and (3) removing Hydrocarbons (HCs) in the exhaust gas discharged by a mobile source or a fixed source by catalytic oxidation by using the manganese-based mullite with the (001) crystal face orientation as a catalyst.
The manganese-based mullite oxidation catalyst with the (001) crystal face orientation is obtained by a microwave hydrothermal method. Compared with the prior art, the invention has the beneficial effects that:
(1) the manganese-based mullite catalyst obtained by the preparation process has (001) crystal face orientation, and the catalytic oxidation activity on hydrocarbon is obviously superior to that of a sample prepared by a traditional hydrothermal method;
(2) the preparation process is energy-saving and environment-friendly, greatly shortens the preparation period of the manganese-based mullite catalyst, and shortens the preparation period from several days of the traditional hydrothermal method to within 12 hours, wherein the hydrothermal treatment time is shortened from more than 12 hours of the traditional hydrothermal method to within 1 hour.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) and High Resolution Transmission Electron Microscope (HRTEM) image of manganese-based mullite prepared in example 1 of the present invention.
Fig. 2 is an XRD spectrum of the catalysts prepared in examples 1-3 of the present invention and comparative example 1.
FIG. 3 shows C of catalysts prepared in examples 1 to 3 of the present invention and comparative example 13H8Conversion is plotted.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The invention provides (001) crystal face oriented manganese-based mullite, and the molecular formula of the manganese-based mullite can be LnMn2O5-I001/I211Wherein Ln is La, Ce, PrNd, Gd and Y, I001/I211The strength ratio of the (001) crystal face to the (211) crystal face of the mullite is shown as I001/I211＝0.30-0.94；
The manganese-based mullite with the oriented (001) crystal face is prepared by a microwave hydrothermal method through the following steps:
and mixing the soluble Ln salt and the soluble divalent Mn salt solution, adding soluble heptavalent manganese salt, dropwise adding alkali liquor to adjust the pH value to 4-9, transferring to a hydrothermal reaction kettle, carrying out microwave hydrothermal reaction, and washing and drying to obtain the (001) crystal face oriented manganese-based mullite.
The application of the manganese-based mullite with the oriented (001) crystal face as the oxidation catalyst also belongs to the protection scope of the invention.
The application specifically can be as follows: (001) the application of the manganese-based mullite with oriented crystal faces as an oxidation catalyst in the catalytic oxidation removal of Hydrocarbons (HCs) in exhaust gas discharged by a mobile source or a fixed source.
The present invention also provides a method for removing Hydrocarbons (HCs) from exhaust gas emitted from a mobile source or a stationary source.
The method for removing Hydrocarbons (HCs) in the exhaust gas discharged by a mobile source or a fixed source comprises the following steps: and (3) removing Hydrocarbons (HCs) in the exhaust gas discharged by a mobile source or a fixed source by catalytic oxidation by using the manganese-based mullite with the (001) crystal face orientation as a catalyst.
The manganese-based mullite catalyst obtained by the preparation process has (001) crystal face orientation, and the catalytic oxidation activity on hydrocarbon is obviously superior to that of a sample prepared by a traditional hydrothermal method; the preparation process is energy-saving and environment-friendly, greatly shortens the preparation period of the manganese-based mullite catalyst, and shortens the preparation period from several days of the traditional hydrothermal method to within 12 hours, wherein the hydrothermal treatment time is shortened from more than 12 hours of the traditional hydrothermal method to within 1 hour.
Example 1
The Ln salt precursor used in this example is samarium nitrate hexahydrate (Sm (NO)3)3·6H2O), the precursor of the Mn salt is manganese nitrate (Mn (NO)3)2 50 wt.% aqueous solution) and potassium permanganate (KMnO)4) The structure inducer is citric acid, the adopted preparation method is a microwave hydrothermal method, the microwave power is 800W, the reaction condition is that the temperature is kept at 200 ℃ for 30 minutes, the drying mode is vacuum drying, and the drying temperature is 50 ℃.
The specific process is as follows: weighing 1mmol of samarium nitrate hexahydrate, 1.4mmol of manganese nitrate and 1mmol of citric acid, dissolving in 60mL of deionized water, adding weighed 0.6mmol of potassium permanganate, magnetically stirring for 20 minutes, then dropwise adding a 5mol/L NaOH aqueous solution into the solution, adjusting the pH value to 4, transferring the solution into a reaction kettle, placing the reaction kettle in a microwave hydrothermal synthesizer, heating to 200 ℃, controlling the microwave power to 800W, controlling the reaction pressure to be 3.2 atmospheres, and controlling the reaction time to be 30 minutes. The solid particles were washed (twice with deionized water and once with absolute ethanol) and then dried under vacuum at 50 ℃ for 2 hours. The obtained catalyst obtains the strength ratio (i.e. I) of the (001) crystal face and the (211) crystal face of the mullite by XRD test001/I211) Is 0.89 (by comparison, No.521096 card SmMn in JCPDS database2O5The XRD pattern of the standard sample has the (001) crystal face proportion of 0.20) and is named SmMn2O5-0.89. The catalyst was subjected to a propane catalytic oxidation performance test, and the light-off temperature (temperature corresponding to 50% conversion of propane) was 222 ℃.
Fig. 1 is a Scanning Electron Microscope (SEM) and High Resolution Transmission Electron Microscope (HRTEM) image of manganese-based mullite prepared in example 1.
As can be seen from fig. 1, the manganese-based mullite catalyst prepared by the microwave hydrothermal synthesis method provided by the present invention has a uniform morphology and a (001) crystal plane orientation, which proves the applicability of the method for preparing a manganese-based mullite catalyst with a (001) crystal plane orientation.
Example 2
The Ln salt precursor used in this example is samarium chloride (SmCl)3) The Mn salt precursor is manganese acetate tetrahydrate (Mn (CH)3COO)2·4H2O) and sodium permanganate (NaMnO)4) The adopted preparation method is a microwave hydrothermal method, the microwave power is 1500W, the reaction condition is that the temperature is kept at 210 ℃ for 30 minutes, and the drying mode is vacuum dryingThe drying temperature was 60 ℃.
The specific process is as follows: weighing 1mmol of samarium nitrate hexahydrate and 1.4mmol of manganese acetate tetrahydrate, dissolving in 70mL of deionized water, adding weighed 0.6mmol of sodium permanganate, magnetically stirring for 20 minutes, then dropwise adding a 5mol/L NaOH aqueous solution into the solution, adjusting the pH value to 9, transferring the solution into a reaction kettle, placing the reaction kettle in a microwave hydrothermal synthesizer, heating to 210 ℃, controlling the microwave power to 1500W, controlling the reaction pressure to 3.6 atmospheric pressures, and controlling the reaction time to be 30 minutes. The solid particles were washed (twice with deionized water and once with anhydrous methanol) and then dried under vacuum at 60 ℃ for 2 hours. The obtained catalyst obtains the strength ratio (i.e. I) of the (001) crystal face and the (211) crystal face of the mullite by XRD test001/I211) Is 0.58 and is named SmMn2O5-0.58. The test of the catalytic oxidation performance of the propane is carried out, and the ignition temperature is 240 ℃.
Example 3
The Ln salt precursor used in this example was yttrium nitrate (Y (NO)3)3) The Mn salt precursor is manganese formate dihydrate (Mn (HCOO)2·2H2O) and potassium permanganate (KMnO)4) The preparation method is a microwave hydrothermal method, the microwave power is 1200W, the reaction condition is that the temperature is kept at 220 ℃ for 30 minutes, the drying mode is vacuum drying, and the drying temperature is 50 ℃.
The specific process is as follows: weighing 1mmol of yttrium nitrate and 1.4mmol of manganese formate dihydrate, dissolving in 60mL of deionized water, adding weighed 0.6mmol of potassium permanganate, magnetically stirring for 20 minutes, then dropwise adding a 5mol/L KOH aqueous solution into the solution, adjusting the pH value to 7, transferring the solution into a reaction kettle, placing the reaction kettle in a microwave hydrothermal synthesizer, heating to 220 ℃, controlling the microwave power to 1200W, controlling the reaction pressure to be 2.9 atmospheres, and controlling the reaction time to be 30 minutes. The solid particles were washed (twice with deionized water and once with absolute ethanol) and then dried under vacuum at 50 ℃ for 2 hours. The obtained catalyst obtains the strength ratio (i.e. I) of the (001) crystal face and the (211) crystal face of the mullite by XRD test001/I211) Is 0.31 (for comparison, JCPDS database No.34667 card YMn2O5Standard sampleThe XRD pattern of (001) crystal face ratio of 0.08) was designated as YMn2O5-0.31. The test of the catalytic oxidation performance of the propane is carried out, and the ignition temperature is 226 ℃.
Comparative example 1
The Ln salt precursor is samarium nitrate hexahydrate (Sm (NO)3)3·6H2O), the precursor of the Mn salt is manganese nitrate (Mn (NO)3)250 wt.% aqueous solution) and potassium permanganate (KMnO)4) The structure inducer is citric acid, the adopted preparation method is a traditional hydrothermal method, the reaction conditions are that the temperature is kept at 200 ℃ for 24 hours, the pH value of reaction liquid is 4, the drying mode is vacuum drying, and the drying temperature is 50 ℃.
The specific process is as follows: weighing 1mmol of samarium nitrate hexahydrate, 1.4mmol of manganese nitrate and 1mmol of citric acid, dissolving in 60mL of deionized water, adding weighed 0.6mmol of potassium permanganate, magnetically stirring for 20 minutes, then dropwise adding a 5mol/L NaOH aqueous solution into the solution, adjusting the pH value to 4, then transferring the solution into a reaction kettle, placing the reaction kettle in an oven, heating to 200 ℃ and preserving the temperature for 24 hours, wherein the reaction pressure is 3.2 atmospheres. The solid particles were washed (twice with deionized water and once with absolute ethanol) and then dried under vacuum at 50 ℃ for 2 hours. The obtained catalyst obtains the strength ratio (i.e. I) of the (001) crystal face and the (211) crystal face of the mullite by XRD test001/I211) Is 0.27 and is named SmMn2O5-0.27. The test of the catalytic oxidation performance of the propane is carried out, and the ignition temperature is 284 ℃.
Fig. 2 is an XRD spectrum of the catalysts prepared in examples 1-3 of the present invention and comparative example 1.
As can be seen from fig. 2, the manganese-based mullite catalyst prepared by the microwave hydrothermal synthesis method provided by the present invention has a diffraction peak relative intensity corresponding to the (001) crystal plane significantly higher than that of a manganese-based mullite sample prepared by a conventional hydrothermal method, which proves the applicability of the method to the preparation of a manganese-based mullite catalyst with an oriented (001) crystal plane.
The catalysts are respectively subjected to a propane oxidation activity test under the condition of simulating the tail gas of a diesel engine.
C3H8The specific test method of the oxidation activity comprises the following steps: 100mg of catalyst particles are placed in a fixed bed reactor, and simulated diesel engine tail gas is introduced, wherein the simulated gas distribution contains 1000ppm of C3H8、10％O2，N2Equilibrium, volume space velocity 60,000h-1The testing temperature range is 30-500 ℃. On-line detection of C in tail gas by using Nicolet infrared gas analyzer3H8Concentration to obtain C3H8The conversion varied with the reaction temperature as shown in FIG. 1.
C3H8The conversion is defined as:
Claims (10)
1. manganese-based mullite with oriented (001) crystal face and molecular formula of LnMn2O5-I001/I211Wherein Ln is one or the combination of more of Sm, La, Ce, Pr, Nd, Gd and Y, I001/I211The strength ratio of the (001) crystal face to the (211) crystal face of the mullite is shown as I001/I211＝0.30-0.94；
The method for preparing the (001) crystal face oriented manganese-based mullite comprises the following steps: mixing soluble Ln salt and soluble divalent Mn salt solution, adding soluble heptavalent manganese salt, dropwise adding an alkali solution to adjust the pH value to 4-9, transferring to a hydrothermal reaction kettle, carrying out microwave hydrothermal reaction, and washing and drying to obtain (001) crystal face oriented manganese-based mullite;
the reaction temperature of the microwave hydrothermal reaction is 120-260 ℃;
the microwave power is 200-1800W.
2. A method for producing the (001) plane-oriented manganese-based mullite according to claim 1, comprising the steps of: mixing soluble Ln salt and soluble divalent Mn salt solution, adding soluble heptavalent manganese salt, dropwise adding an alkali solution to adjust the pH value to 4-9, transferring to a hydrothermal reaction kettle, carrying out microwave hydrothermal reaction, and washing and drying to obtain (001) crystal face oriented manganese-based mullite;
the reaction temperature of the microwave hydrothermal reaction is 120-260 ℃;
the microwave power is 200-1800W.
3. The method of claim 2, wherein: the soluble Ln salt is nitrate and/or chloride of Ln, wherein Ln is one or combination of more of Sm, La, Ce, Pr, Nd, Gd and Y;
the divalent Mn salt is manganese nitrate, manganese acetate, manganese formate and/or manganese chloride;
the heptavalent manganese salt is potassium permanganate and/or sodium permanganate.
4. A method according to claim 2 or 3, characterized in that: the mol ratio of the soluble Ln salt to the divalent Mn salt and the heptavalent manganese salt is 1: 1.4: 0.6.
5. a method according to claim 2 or 3, characterized in that: and a structure inducer is also added into the reaction system, and the structure inducer is any one or combination of more of formic acid, triethylamine, polyethylene glycol, ethanolamine, ethylene glycol, ethylene diamine tetraacetic acid, citric acid and sodium citrate.
6. The method of claim 5, wherein:
the structure inducer is citric acid, and the mol ratio of the soluble Ln salt to the divalent Mn salt to the heptavalent manganese salt to the structure inducer is 1: 1.4: 0.6: 1-3.
7. A method according to claim 2 or 3, characterized in that:
the reaction pressure of the microwave hydrothermal reaction is 2-5 atmospheric pressures;
the microwave hydrothermal reaction time is 0.2-1 hour.
8. Use of the (001) plane-oriented manganese-based mullite according to claim 1 as an oxidation catalyst.
9. Use according to claim 8, characterized in that: the application is as follows: (001) the application of the manganese-based mullite with oriented crystal face as an oxidation catalyst in catalytic oxidation removal of hydrocarbons in exhaust gas discharged by a mobile source or a fixed source.
10. A method for removing hydrocarbons in exhaust gas discharged by a mobile source or a fixed source comprises the following steps: the (001) crystal face oriented manganese-based mullite described in claim 1 is used as a catalyst for catalytic oxidation removal of hydrocarbons in exhaust gas discharged from a mobile source or a fixed source.
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