CN113368848A - Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof - Google Patents
Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof Download PDFInfo
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000015556 catabolic process Effects 0.000 title claims abstract description 13
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003245 coal Substances 0.000 claims abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000002910 solid waste Substances 0.000 claims abstract description 13
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000004480 active ingredient Substances 0.000 claims abstract description 9
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 9
- 239000000440 bentonite Substances 0.000 claims abstract description 9
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000004615 ingredient Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 4
- OQAYQCZNEFHEKE-UHFFFAOYSA-M [AlH](C)O Chemical compound [AlH](C)O OQAYQCZNEFHEKE-UHFFFAOYSA-M 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003546 flue gas Substances 0.000 abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- LQWKWJWJCDXKLK-UHFFFAOYSA-N cerium(3+) manganese(2+) oxygen(2-) Chemical compound [O--].[Mn++].[Ce+3] LQWKWJWJCDXKLK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004958 brain cell Anatomy 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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Abstract
The invention discloses a catalyst for catalytic oxidation degradation of chlorobenzene, a preparation method and a use method thereof. The catalyst takes manganese and cerium as active ingredients, coal-based solid wastes rich in alumina ingredients such as coal gangue, coal-based bentonite and kaolin as carrier raw materials, the alumina is separated and enriched through calcination and melting, and is compounded with carbon nanotubes to form a composite carrier, and finally the catalyst taking manganese and cerium oxides as the active ingredients is prepared, wherein the molar ratio of transition metal manganese to cerium atoms is 0.53-0.56, the loading capacity of the active ingredients is 10-20%, and the carbon nanotubes account for 5-10% of the mass of the composite carrier. The preparation method comprises the steps of mixing the oxidized carbon nanotube mixed acid with gangue, coal bentonite and alumina obtained by calcining, melting, separating and enriching kaolin to prepare a carrier, and soaking the carrier in a manganese nitrate solution and a cerium nitrate solution to prepare the catalyst. The catalyst is adopted to treat chlorobenzene in the flue gas, the chlorobenzene conversion rate at 350 ℃ is 100%, the catalytic activity is strong, and the chlorobenzene conversion rate is high; the raw materials used are coal-based solid wastes, and high-value utilization of the coal-based solid wastes can be effectively realized.
Description
Technical Field
The invention belongs to the technical field of resource utilization of solid wastes and control of flue gas pollutants, and particularly relates to a preparation method of a catalyst for degrading a flue gas pollutant chlorobenzene by resource utilization of coal-based solid wastes.
Background
Volatile Organic Compounds (VOCs) are important precursors for forming fine particulate matters and ozone, and as a large number of fine particulate matters are discharged in most areas to exceed the atmospheric circulation capacity and the bearing capacity, a large-scale haze weather occurs, the problem of overproof ozone is increasingly shown, and the pollution control of the VOCs is widely concerned by the society. Chlorobenzene is used as a chlorine-containing volatile organic compound, is released into the atmosphere through various industrial processes such as household garbage incineration and the like, and chlorobenzene in smoke gas can react with nitric oxide to generate photochemical smog, destroy the ozone layer and aggravate the greenhouse effect. In addition, chlorobenzene has inhibitory and anesthetic effects on the central nervous system of humans, and high content of chlorobenzene can cause brain cell damage and seriously threaten human health and ecological environment.
At present, chlorobenzene degradation technologies include photocatalytic oxidation, biodegradation, plasma degradation, direct combustion and the like. Photocatalytic oxidation is strongly dependent on light sources and the relatively low quantum efficiency leads to limited oxidation capabilities of the technology. Biodegradation only treats low-concentration pollutants, cannot control the treatment process and the pH value of the filler, and has large floor area and long retention time. The plasma technology has high requirements on power supply, easily produces toxic intermediate products, and is difficult to fix and easy to inactivate catalysts. The direct combustion has the advantages of high efficiency, complete degradation and the like, but the chlorobenzene is completely combusted by using high temperature of more than 1000 ℃, so that the energy consumption is high. The catalytic oxidation degradation of chlorobenzene has low temperature, low energy consumption and good purification effect, and has become a research hotspot at present. The development of a low-temperature, efficient, stable and cheap catalyst for catalytic oxidation degradation of chlorobenzene is a key problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a catalyst for catalytic oxidative degradation of chlorobenzene, a preparation method and a use method thereof.
The catalyst takes manganese cerium oxide as an active component, a small amount of cerium oxide is doped into the manganese oxide to enhance the active oxygen on the surface of the active component and the capability of desorbing chlorine species, and the carboxylated carbon nanotube modified alumina carrier is used for promoting the high dispersion of the active component, providing acid sites and surface active oxygen, promoting the adsorption/diffusion capability of reaction molecules and improving the activity of the catalyst.
The invention provides a catalyst for catalytic oxidative degradation of chlorobenzene, which is prepared from coal gangue, coal bentonite, coal-based solid wastes of kaolin rich in alumina components, and active components of manganese and cerium as catalyst preparation raw materials, wherein the active components are separated and enriched by alumina and prepared into a composite carrier with carbon nanotubes to obtain the catalyst with manganese-cerium oxide as an active component, the manganese-cerium atomic molar ratio is 0.53-0.56, the loading amount of the active components is 10-20%, and the carbon nanotubes account for 5-10% of the mass of the composite carrier.
The invention provides a preparation method of the catalyst for catalytic oxidative degradation of chlorobenzene, which comprises the following steps:
(1) separating and enriching coal gangue, coal bentonite and kaolin coal solid waste to obtain an alumina carrier;
(2) carrying out mixed acid oxidation treatment on the carbon nano tube to obtain a carboxylated carbon nano tube;
(3) dropwise adding the ethanol dispersion liquid of the carboxylated carbon nano tube into the ethanol dispersion liquid of the alumina to obtain alumina-carbon nano tube sol, and then drying and calcining to obtain the alumina-carbon nano tube composite carrier;
(4) and (3) impregnating the alumina-carbon nanotube carrier with manganese nitrate and cerium nitrate solution, drying and roasting.
The above preparation process is further illustrated as follows:
in the step (1), solid wastes such as coal gangue, coal-series bentonite, kaolin and the like are ground and then calcined and precipitated and dissolved for 4-6 times to form high-purity aluminum ammonium sulfate crystals, and alumina is formed after calcination. Calcining at 500-600W for 3-10 min.
In the step (2), the mixed acid is a mixed solution of concentrated nitric acid and concentrated sulfuric acid, and the ratio of the mixed acid to the carbon nano tubes is 40-60 mL/g.
In the step (3), the content of the carboxylated carbon nanotubes in the ethanol dispersion liquid of the carboxylated carbon nanotubes is 0.8-1 wt%, the content of the alumina in the ethanol dispersion liquid of the alumina is 20-30 wt%, the calcination temperature of the alumina-carbon nanotube sol is 400-600 ℃, and the calcination time is 3-5 hours.
The solution in the step (4) is soaked for 12-36 h, dried at 100-120 ℃ for 12-24 h, and roasted at 500-600 ℃ for 3-5 h.
The invention provides a use method of the catalyst for catalytic oxidative degradation of chlorobenzene, which adopts air as an oxidant and a fixed bed oxidation reactor to perform catalytic oxidative degradation on chlorobenzene, wherein the reaction temperature is 150-350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 11000-22000 h-1The chlorobenzene concentration was 500 ppm.
The catalyst of the invention adopts double carriers, thus enhancing the surface area and the acid strength of the catalyst, and the space velocity is as high as 11000 h-1Under the condition, the catalytic oxidation degradation activity of chlorobenzene at 350 ℃ can reach 100%, the chlorobenzene is not inactivated after continuous reaction for 4 hours, and the chlorobenzene conversion rate is always 100%.
The invention has the beneficial effects that:
(1) the catalyst obtained by the method has strong activity and high chlorobenzene conversion rate; the catalyst is adopted to treat chlorobenzene in flue gas, and the chlorobenzene conversion rate at 350 ℃ is 100 percent;
(2) the coal gangue, coal bentonite and kaolin coal solid waste are used as raw materials, so that high-value utilization of the coal solid waste can be effectively realized, and the coal solid waste has a good application prospect;
(3) the catalyst can completely degrade chlorobenzene into substances with low toxicity, even non-toxic and harmless, such as carbon dioxide, water and the like.
Drawings
FIG. 1 shows the reaction conditions of the catalyst activity test for catalytic oxidative degradation of chlorobenzene in application example 1;
FIG. 2 shows the reaction conditions of the catalyst activity test in application example 2 for the catalytic oxidative degradation of chlorobenzene.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
grinding montmorillonite, calcining, melting, precipitating, dissolving and precipitating for 5 times to form high-purity aluminum ammonium sulfate crystal, and calcining at 600W for 5min to form aluminum oxide. Oxidizing and carboxylating 0.5 g of carbon nano tube by using 40 mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid, ultrasonically dispersing the carboxylated carbon nano tube and 4.5g of alumina in ethanol solution to obtain alumina-carbon nano tube sol, calcining the dried mixed sol at 400 ℃ for 5 hours to obtain an alumina-carbon nano tube composite carrier, soaking the alumina-carbon nano tube composite carrier by using manganese nitrate and cerium nitrate solution with the molar ratio of 0.53 in equal volume for 36 hours, drying at 100 ℃ for 24 hours, calcining at 500 ℃ for 5 hours to obtain 0.53MnOx-CeO2/Al2O3The catalyst has a transition metal manganese cerium atom molar ratio of 0.53, a loading amount of active ingredients of 20 percent and carbon nano tubes accounting for 10 percent of the composite carrier by mass.
Example 2:
the kaolin is ground and then calcined and precipitated for 4 times to form high-purity aluminum ammonium sulfate crystals, and the aluminum ammonium sulfate crystals are calcined for 8min at 500W to form aluminum oxide. Oxidizing and carboxylating 0.5 g of carbon nano tube by using 50 mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid, ultrasonically dispersing the carboxylated carbon nano tube and 9.5g of alumina in ethanol solution to obtain alumina-carbon nano tube sol, calcining the dried mixed sol at 500 ℃ for 4h to obtain an alumina-carbon nano tube composite carrier, soaking the alumina-carbon nano tube composite carrier in equal volume of manganese nitrate and cerium nitrate solution with the molar ratio of 0.54 for 24 h, drying at 120 ℃ for 20 h, and cooling to 600 DEG CCalcining for 3h to obtain 0.54MnOx-CeO2/Al2O3O-CNTs, wherein the molar ratio of transition metal manganese to cerium atoms of the catalyst is 0.53, the loading amount of active ingredients is 10%, and the mass percent of carbon nanotubes in the composite carrier is 5%.
Example 3:
after being ground, the coal gangue is calcined and precipitated for 6 times to form high-purity aluminum ammonium sulfate crystals, and the high-purity aluminum ammonium sulfate crystals are calcined for 10min at 550W to form aluminum oxide. 0.5 g of carbon nano tube is oxidized and carboxylated by 60 mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid, the carboxylated carbon nano tube and 5.75 g of alumina are ultrasonically dispersed in ethanol solution to obtain alumina-carbon nano tube sol, the dried mixed sol is calcined for 3h at 600 ℃ to obtain an alumina-carbon nano tube composite carrier, the alumina-carbon nano tube composite carrier is soaked by the manganese nitrate and cerium nitrate solution with the molar ratio of 0.56 in equal volume for 12 h, dried at 110 ℃ for 12 h and calcined at 550 ℃ for 4h to obtain 0.56MnOx-CeO2/Al2O3O-CNTs, wherein the molar ratio of transition metal manganese to cerium atoms of the catalyst is 0.56, the loading amount of active ingredients is 15%, and the mass percent of carbon nano tubes in the composite carrier is 8%.
Application example 1:
air is used as an oxidant, a fixed bed oxidation reactor is used for carrying out catalytic oxidation degradation on chlorobenzene, the reaction temperature is 350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 11000 h-1The chlorobenzene concentration was 500 ppm. FIG. 1 shows the results of catalytic oxidative degradation of chlorobenzene catalyst activity. The chlorobenzene conversion rate at 350 ℃ is 100 percent, the chlorobenzene is not inactivated after being continuously used for 4 hours, and the chlorobenzene conversion rate is always 100 percent.
Application example 2:
air is used as an oxidant, a fixed bed oxidation reactor is used for carrying out catalytic oxidation degradation on chlorobenzene, the reaction temperature is 150-350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 22000 h-1The chlorobenzene concentration was 500 ppm. As can be seen from FIG. 2, when the airspeed increases to 22000 h-1When the temperature is 350 ℃, the catalytic oxidation degradation activity of the catalyst prepared by the method can reach 90 percent.
The embodiments are only preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A catalyst for catalytic oxidative degradation of chlorobenzene is characterized in that: manganese and cerium are used as active ingredients, coal gangue, coal-series bentonite and kaolin which are rich in alumina ingredients are used as raw materials, the raw materials are separated and enriched by alumina, and the raw materials and carbon nano tubes are prepared into a composite carrier, a catalyst which takes manganese and cerium oxides as the active ingredients is used, the atomic molar ratio of manganese to cerium is 0.53-0.56, the loading capacity of the active ingredients is 10-20%, and the carbon nano tubes account for 5-10% of the composite carrier by mass.
2. A method for preparing the catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, characterized by comprising the steps of:
(1) separating and enriching coal gangue, coal bentonite and kaolin coal solid waste to obtain an alumina carrier;
(2) carrying out mixed acid oxidation treatment on the carbon nano tube to obtain a carboxylated carbon nano tube;
(3) dropwise adding the ethanol dispersion liquid of the carboxylated carbon nano tube into the ethanol dispersion liquid of the alumina to obtain alumina-carbon nano tube sol, and then drying and calcining to obtain the alumina-carbon nano tube composite carrier;
(4) and (3) impregnating the alumina-carbon nanotube carrier with manganese nitrate and cerium nitrate solution, drying and roasting.
3. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 2, wherein: in the step (1), coal gangue, coal-series bentonite and kaolin coal-series solid waste are ground and then calcined and precipitated for 4-6 times to form high-purity aluminum ammonium sulfate crystals, and the high-purity aluminum ammonium sulfate crystals are calcined by microwave and calcined at 500-600W for 5-10 min to form alumina.
4. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 2, wherein: in the step (2), the mixed acid is a mixed solution of concentrated nitric acid and concentrated sulfuric acid, and the ratio of the mixed acid to the carbon nano tubes is 40-60 mL/g.
5. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 2, wherein: in the step (3), the content of the carboxylated carbon nanotubes in the carboxylated carbon nanotube ethanol dispersion liquid is 0.8-1 wt%, and the content of the alumina in the alumina ethanol dispersion liquid is 20-30 wt%.
6. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 2, wherein: in the step (3), the calcination temperature of the alumina-carbon nanotube sol is 400-600 ℃, and the calcination time is 3-5 h.
7. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 2, wherein: in the step (4), the solution is soaked for 12-36 hours, dried for 12-24 hours at 100-120 ℃, and roasted for 3-5 hours at 500-600 ℃.
8. The use method of the catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, characterized in that air is used as an oxidant, a fixed bed oxidation reactor is used for catalytic oxidative degradation of chlorobenzene, the reaction temperature is 150-350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 11000-22000 h-1The chlorobenzene concentration was 500 ppm.
9. Use according to claim 8, characterized in that: at the airspeed of up to 11000 h-1Under the condition, the catalytic oxidation degradation activity of chlorobenzene at 350 ℃ can reach 100%, the chlorobenzene is not inactivated after continuous reaction for 4 hours, and the chlorobenzene conversion rate is 100%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282971A (en) * | 2022-08-19 | 2022-11-04 | 太原理工大学 | High-performance denitrification non-noble metal catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734698A (en) * | 2009-09-08 | 2010-06-16 | 东北大学 | Method for preparing aluminum oxide from aluminiferous material |
| WO2010088902A2 (en) * | 2009-02-09 | 2010-08-12 | Nano-X Gmbh | Method for producing alkali and alkaline earth alloys and use of the alkali and alkaline earth alloys |
| CN105396578A (en) * | 2015-12-09 | 2016-03-16 | 哈尔滨工业大学 | A preparing method of a doped type nanometer MnO2-CeO2/Al2O3 catalyst and applications of the catalyst |
| WO2018023717A1 (en) * | 2016-08-03 | 2018-02-08 | 万华化学集团股份有限公司 | Catalyst for preparing chlorine by hydrogen chloride oxidation, and preparation method and application thereof |
| CN108704470A (en) * | 2018-05-15 | 2018-10-26 | 山西大学 | Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering and preparation method thereof |
| CN109225351A (en) * | 2018-09-18 | 2019-01-18 | 北京国能中林科技开发有限公司 | It is a kind of based on carbon nanotube/alumina composite carrier hydrogenation catalyst and its preparation method and application |
| CN111792650A (en) * | 2020-07-27 | 2020-10-20 | 青岛核盛智能环保设备有限公司 | Full-element recycling process of coal ash or coal gangue by hot-melt salt method |
-
2021
- 2021-06-30 CN CN202110737382.6A patent/CN113368848B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010088902A2 (en) * | 2009-02-09 | 2010-08-12 | Nano-X Gmbh | Method for producing alkali and alkaline earth alloys and use of the alkali and alkaline earth alloys |
| CN101734698A (en) * | 2009-09-08 | 2010-06-16 | 东北大学 | Method for preparing aluminum oxide from aluminiferous material |
| CN105396578A (en) * | 2015-12-09 | 2016-03-16 | 哈尔滨工业大学 | A preparing method of a doped type nanometer MnO2-CeO2/Al2O3 catalyst and applications of the catalyst |
| WO2018023717A1 (en) * | 2016-08-03 | 2018-02-08 | 万华化学集团股份有限公司 | Catalyst for preparing chlorine by hydrogen chloride oxidation, and preparation method and application thereof |
| CN108704470A (en) * | 2018-05-15 | 2018-10-26 | 山西大学 | Carbide slag composite calcium based desulphurizing agent based on biomass hardening, tempering and preparation method thereof |
| CN109225351A (en) * | 2018-09-18 | 2019-01-18 | 北京国能中林科技开发有限公司 | It is a kind of based on carbon nanotube/alumina composite carrier hydrogenation catalyst and its preparation method and application |
| CN111792650A (en) * | 2020-07-27 | 2020-10-20 | 青岛核盛智能环保设备有限公司 | Full-element recycling process of coal ash or coal gangue by hot-melt salt method |
Non-Patent Citations (2)
| Title |
|---|
| XIAOYU FAN: "Catalytic Oxidation of Chlorobenzene over MnOx/Al2O3-carbon Nanotubes Composites", 《CATAL LETT》 * |
| XINGYI WANG: "Low-temperature catalytic combustion of chlorobenzene over MnOx–CeO2 mixed oxide catalysts", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282971A (en) * | 2022-08-19 | 2022-11-04 | 太原理工大学 | High-performance denitrification non-noble metal catalyst and preparation method and application thereof |
| CN115282971B (en) * | 2022-08-19 | 2024-01-19 | 太原理工大学 | High-performance denitrification non-noble metal catalyst and preparation method and application thereof |
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