CN113368848B - 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
- Publication number
- CN113368848B CN113368848B CN202110737382.6A CN202110737382A CN113368848B CN 113368848 B CN113368848 B CN 113368848B CN 202110737382 A CN202110737382 A CN 202110737382A CN 113368848 B CN113368848 B CN 113368848B
- Authority
- CN
- China
- Prior art keywords
- chlorobenzene
- catalyst
- alumina
- coal
- nano tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000015556 catabolic process Effects 0.000 title claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 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 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 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
- 239000002910 solid waste Substances 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
- 239000000440 bentonite Substances 0.000 claims abstract description 9
- 229910000278 bentonite Inorganic materials 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
- 239000004480 active ingredient Substances 0.000 claims abstract description 8
- 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
- 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
- 239000002994 raw material Substances 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 22
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 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 7
- 239000013078 crystal Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 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
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 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 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 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
- 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
- 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
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- B01J35/394—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention 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 enriched by calcination, melting and separation, and the composite carrier is compounded with a carbon nano tube to form the composite carrier, so that the catalyst taking manganese and cerium oxides as the active ingredients is finally prepared, the molar ratio of transition metal manganese to cerium atoms is 0.53 to 0.56, the loading capacity of the active ingredients is 10 to 20 percent, and the carbon nano tube accounts for 5 to 10 percent 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 and kaolin which are rich in alumina components, and active components of manganese and cerium which are used as catalyst preparation raw materials, wherein the catalyst is prepared by separating and enriching alumina and preparing a composite carrier with a carbon nano tube to obtain the catalyst taking manganese-cerium oxide as the active component, the molar ratio of manganese to cerium atoms is 0.53-0.56, the loading capacity of the active components is 10-20%, and the carbon nano tube accounts 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 and precipitated for 4 to 6 times to form high-purity aluminum ammonium sulfate crystals, and the aluminum oxide is formed after calcination. Calcining at 500-600W for 3-10min.
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 tube 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 to 1wt%, the content of the alumina in the ethanol dispersion liquid of the alumina is 20 to 30wt%, the calcining temperature of the alumina-carbon nanotube sol is 400 to 600 ℃, and the calcining time is 3 to 5h.
The solution in the step (4) is soaked for 12 to 36 hours, dried for 12 to 24 hours at the temperature of 100 to 120 ℃, and roasted for 3 to 5 hours at the temperature of 500 to 600 ℃.
The present invention providesThe application method of the catalyst for catalytic oxidative degradation of chlorobenzene adopts air as an oxidant, adopts a fixed bed oxidation reactor to perform catalytic oxidative degradation on chlorobenzene, and has the reaction temperature of 150 to 350 ℃, the reaction pressure of 0.1MPa and the gas space velocity of 11000 to 22000 h -1 The 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 -1 Under the condition, the catalytic oxidation degradation activity of chlorobenzene at 350 ℃ can reach 100%, the chlorobenzene does not inactivate 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 catalytic 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 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. 0.5 g of carbon nano tube is oxidized and carboxylated by 40 mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid, the carboxylated carbon nano tube and 4.5g of alumina are ultrasonically dispersed in ethanol solution to obtain alumina-carbon nano tube sol, and the dried mixed sol is calcined at 400 DEG CBurning for 5h to obtain an alumina-carbon nanotube composite carrier, soaking the alumina-carbon nanotube composite carrier in a manganese nitrate and cerium nitrate solution with a molar ratio of 0.53 in equal volume for 36 h, drying at 100 ℃ for 24 h, and burning at 500 ℃ for 5h to obtain 0.53MnO x -CeO 2 /Al 2 O 3 The 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. 0.5 g of carbon nano tube is oxidized and carboxylated by 50 mL of mixed solution of concentrated nitric acid and concentrated sulfuric acid, the carboxylated carbon nano tube and 9.5g of alumina are ultrasonically dispersed in ethanol solution to obtain alumina-carbon nano tube sol, the dried mixed sol is calcined for 4 hours at 500 ℃ to obtain an alumina-carbon nano tube composite carrier, the alumina-carbon nano tube composite carrier is impregnated by the manganese nitrate and cerium nitrate solution with the molar ratio of 0.54 in the same volume for 24 hours, then dried for 20 hours at 120 ℃, calcined for 3 hours at 600 ℃ to obtain 0.54MnO x -CeO 2 /Al 2 O 3 O-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 3 hours at 600 ℃ to obtain an alumina-carbon nano tube composite carrier, the alumina-carbon nano tube composite carrier is soaked in equal volume of manganese nitrate and cerium nitrate solution with the molar ratio of 0.56 for 12 hours, then dried for 12 hours at 110 ℃, calcined for 4 hours at 550 ℃ to obtain 0.56MnO x -CeO 2 /Al 2 O 3 -O-CNTs, catalyst transition metal manganese cerium atom mole ratio of 0.56, activityThe loading amount of the components is 15%, and the carbon nano tube accounts for 8% of the composite carrier by mass.
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 -1 The 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 to 350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 22000 h -1 The chlorobenzene concentration was 500 ppm. As can be seen from FIG. 2, when the airspeed increases to 22000 h -1 When 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 also within 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 (8)
1. A preparation method of a catalyst for catalytic oxidation degradation of chlorobenzene is characterized by comprising the following steps: manganese and cerium are used as active ingredients, coal gangue, coal bentonite and kaolin which are rich in alumina ingredients are used as raw materials, the raw materials are separated and enriched by alumina, and are made into a composite carrier with a carbon nano tube, 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 to 0.56, the loading capacity of the active ingredients is 10 to 20 percent, and the carbon nano tube accounts for 5 to 10 percent of the mass of the composite carrier;
the preparation method of the catalyst for catalytic oxidative degradation of chlorobenzene comprises the following steps:
(1) Separating and enriching one of coal gangue, coal-series bentonite and kaolin coal-series solid waste to obtain an alumina carrier; the microwave calcination mode is adopted in the step;
(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.
2. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, wherein: in the step (1), one of coal gangue, coal-series bentonite and kaolin coal-series solid waste is ground, calcined and precipitated, dissolved and precipitated for 4 to 6 times to form high-purity aluminum ammonium sulfate crystals, and calcined for 5 to 10 minutes by microwave 500 to 600W to form alumina.
3. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, 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 tube is 40-60 mL/g.
4. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, wherein: in the step (3), the content of the carboxylated carbon nanotubes in the ethanol dispersion liquid of the carboxylated carbon nanotubes is 0.8 to 1wt%, and the content of the alumina in the ethanol dispersion liquid of the alumina is 20 to 30wt%.
5. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, wherein: in the step (3), the calcining temperature of the alumina-carbon nanotube sol is 400 to 600 ℃, and the calcining time is 3 to 5h.
6. The method for preparing a catalyst for catalytic oxidative degradation of chlorobenzene according to claim 1, wherein: in the step (4), the solution is soaked for 12 to 36 hours, dried for 12 to 24 hours at the temperature of 100 to 120 ℃, and baked for 3 to 5 hours at the temperature of 500 to 600 ℃.
7. A use method of the catalyst for catalytic oxidative degradation of chlorobenzene, which is prepared by the method of claim 1, is 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 to 350 ℃, the reaction pressure is 0.1MPa, and the gas space velocity is 11000 to 22000 h -1 The chlorobenzene concentration was 500 ppm.
8. Use according to claim 7, characterized in that: at the airspeed of 11000 h -1 Under the condition, the catalytic oxidation degradation activity of chlorobenzene at 350 ℃ can reach 100%, the continuous reaction is not inactivated for 4 hours, and the chlorobenzene conversion rate is 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110737382.6A CN113368848B (en) | 2021-06-30 | 2021-06-30 | Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110737382.6A CN113368848B (en) | 2021-06-30 | 2021-06-30 | Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113368848A CN113368848A (en) | 2021-09-10 |
| CN113368848B true CN113368848B (en) | 2023-03-24 |
Family
ID=77580248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110737382.6A Active CN113368848B (en) | 2021-06-30 | 2021-06-30 | Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113368848B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009008144A1 (en) * | 2009-02-09 | 2010-08-19 | Nano-X Gmbh | Process for the preparation of alkali and alkaline earth alloys and use of the alkali and alkaline earth alloys |
| CN101734698B (en) * | 2009-09-08 | 2013-01-09 | 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 |
| CN109225351B (en) * | 2018-09-18 | 2021-06-25 | 北京国能中林科技开发有限公司 | Hydrogenation catalyst based on carbon nano tube/alumina composite carrier and preparation method and application thereof |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113368848A (en) | 2021-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109126773B (en) | Catalyst for purifying waste incineration flue gas and preparation method thereof | |
| Skalska et al. | Trends in NOx abatement: A review | |
| CN101623631B (en) | Catalyst using TiO2-coated carbon nano tube composite material as carrier and preparation method thereof | |
| JP3772961B2 (en) | Method for treating exhaust gas containing dioxin and composite catalyst for dioxin suppression | |
| CN106975481B (en) | The preparation method of alkaline earth metal doping MnO2 catalyst with efficient photo-thermal concerted catalysis purifying VOCs | |
| CN110508274B (en) | Modified biochar low-temperature denitration catalyst and application thereof | |
| CN111229209B (en) | Lotus leaf source charcoal-loaded manganese oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof | |
| CN105797579A (en) | Technology for catalytically treating VOCs by means of synergy between plasma and mesoporous | |
| CN108786788B (en) | Method for removing dioxin and NO in flue gasxCatalyst, preparation method and application | |
| CN106622211A (en) | Catalytic ozonation material as well as preparation method and application thereof | |
| CN106944092A (en) | A kind of Fe MnO with efficient photo-thermal concerted catalysis purifying VOCs2The preparation method of catalyst | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN109433236B (en) | Porous carbon material loaded with zero-valent Fe-Fe3C denitration catalyst and preparation and use methods thereof | |
| CN102698578A (en) | Process for synchronously removing nitrogen oxide, dioxin and offensive odor in flue gas from waste incineration | |
| CN113786828A (en) | Catalyst for synergistic removal of NOx and CVOCs and preparation method and application thereof | |
| CN111939757A (en) | Method for removing nitrogen oxides in low-temperature flue gas | |
| CN113368848B (en) | Catalyst for catalytic oxidation and low-temperature degradation of chlorobenzene and preparation and use methods thereof | |
| CN103463972B (en) | Method for hydrolysis-oxidation coupled purification of HCN | |
| CN111229208A (en) | Lotus leaf-source biochar-loaded metal oxide low-temperature SCR (selective catalytic reduction) flue gas denitration catalyst and preparation method and application thereof | |
| CN107413350A (en) | Mischmetal denitrating catalyst and preparation method thereof | |
| Chen et al. | NO x attenuation in flue gas by• OH/SO 4•--based advanced oxidation processes | |
| CN110586073A (en) | Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof | |
| CN106732547B (en) | Demercuration catalyst for low-temperature oxidation of zero-valent mercury in coal-fired flue gas and preparation method thereof | |
| KR100402430B1 (en) | Catalyst for decomposition of toxic pollutants and producing process thereof | |
| Mengjie et al. | Application of and research on TiO2 photocatalysis technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |