Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation...Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.展开更多
For aromatic monomer compounds (AMCs), ozonation outcomes were usually predicted by the substituents of the benzene ring based on the electron inductive effect. However, the predicted results were occasionally unrelia...For aromatic monomer compounds (AMCs), ozonation outcomes were usually predicted by the substituents of the benzene ring based on the electron inductive effect. However, the predicted results were occasionally unreliable for complex substituents, and other factors caused concern. In this study, p-chloronitrobenzene (p-CNB) and ibuprofen (IBP) were selected for ozonation. According to the electron inductive theory, p-CNB should be less oxidizable, but the opposite was true. The higher rates of p-CNB were due to various sources of assistance. First, the hydroxyl radical (•OH) contributed 90 % to p-CNB removal at pH 7.0, while its contribution to IBP removal was 50 %. Other contributions came from molecular O3 oxidation. Second, p-CNB achieved 40 % of the total organic carbon (TOC) removal and fewer by-product types and quantities, when compared to the results for IBP. Third, the oxidation of p-CNB started with hydroxyl substitution reactions on the benzene ring;then, the ring opened. However, IBP was initially oxidized mainly on the butane branched chain, with a chain-shortening process occurring before the ring opened. Finally, the degradation pathway of p-CNB was single and consumed fewer oxidants. However, both branches of IBP were attacked simultaneously, and three degradation pathways that relied on more oxidants were proposed. All of these factors were determinants of the rapid removal of p-CNB.展开更多
基金supported by the National High Technology Research and Development Program of China(No.2012AA063101)the National Basic Research Program of China(No.2010CB732300)the"Strategic Priority Research Program"of the Chinese Academy of Sciences(No.XDB05050200)
文摘Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.
基金supported by the Education Commission Scientific Research Project of Tianjin(Natural Science)(No.2018KJ139).
文摘For aromatic monomer compounds (AMCs), ozonation outcomes were usually predicted by the substituents of the benzene ring based on the electron inductive effect. However, the predicted results were occasionally unreliable for complex substituents, and other factors caused concern. In this study, p-chloronitrobenzene (p-CNB) and ibuprofen (IBP) were selected for ozonation. According to the electron inductive theory, p-CNB should be less oxidizable, but the opposite was true. The higher rates of p-CNB were due to various sources of assistance. First, the hydroxyl radical (•OH) contributed 90 % to p-CNB removal at pH 7.0, while its contribution to IBP removal was 50 %. Other contributions came from molecular O3 oxidation. Second, p-CNB achieved 40 % of the total organic carbon (TOC) removal and fewer by-product types and quantities, when compared to the results for IBP. Third, the oxidation of p-CNB started with hydroxyl substitution reactions on the benzene ring;then, the ring opened. However, IBP was initially oxidized mainly on the butane branched chain, with a chain-shortening process occurring before the ring opened. Finally, the degradation pathway of p-CNB was single and consumed fewer oxidants. However, both branches of IBP were attacked simultaneously, and three degradation pathways that relied on more oxidants were proposed. All of these factors were determinants of the rapid removal of p-CNB.
