氨选择性催化氧化铜基催化剂的制备及其性能
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摘要
氨气(NH3)是一种恶臭污染物,它对人体健康和生态环境构成巨大的威胁。随着合成氨工业排放的氨尾气日益增加,氨气污染的控制和治理引起人们的广泛关注。氨的选择性催化氧化技术(SCO)是治理氨气污染的一种理想的技术,同时具有高效性、清洁性和经济性等优点。
本论文以氨选择性催化氧化技术的核心因素,即催化剂的选择为主要研究对象,旨在制备出一种同时具有高活性和高N2选择性的粉末催化剂。分别以Ti02粉末(P25)和活性氧化铝作为载体,Cu和Mn为活性组分,先采用浸渍法制备出Cu/Al2O3和Cu-Mn/TiO2以及不同负载量的Cu/TiO2催化剂,将它们用于氨的选择性催化氧化反应,并研究反应中影响催化剂性能的因素,NH3：02比例和空速大小。结果显示,Cu-Mn/TiO2的N2选择性较差,10%Cu/TiO2相比10%Cu/Al2O3催化剂具有更高的催化活性；NH3：02比例为1：250,空速为50000 h-1是采用10%Cu/TiO2催化剂催化氧化处理氨的最佳反应条件。
为了进一步提高Cu基催化剂的活性,在Cu/TiO2基础上,借助于向Ti02中添加助剂Ce作为载体,并采用均相沉淀法负载活性组分Cu,在不同条件下制备出系列Cu/Ce-TiO2催化剂。通过对它们对氨催化氧化的活性进行评价,筛选出催化效果最优的催化剂,并与Cu/TiO2催化剂进行对比,结果显示,对于Cu/Ce-TiO2系列催化剂,当铜的负载量为10 wt%,Ce的负载量为9 wt%,并且尿素浓度为15g L-1时,催化活性达到最高,在250℃能将NH3完全转化,N2选择性能达到95%,并且50% NH3被转化时的温度仅为190℃,相比Cu/TiO2催化剂,降低了20℃。
同时运用BET, XRD、XPS以及H2-TPR等表征手段对系列Cu/Ce-TiO2催化剂的性能进行了表征,以考察各因素对催化剂活性的影响。结果表明,表面高分散的Cu2+物种比体相大颗粒CuO和Cu+物种具有更高的氨选择性催化氧化活性。尿素浓度对Cu/Ce-TiO2催化剂活性的影响非常大,当尿素浓度为15 g L-1,部分Cu20物种转化成了Cu(OH)2物种,形成Cu2+→Cu+之间还原循环过程,同时Cu(OH)2物种也与NH3反应,并且由Cu(OH)2提供的Cu2+物种的还原能力更强,因而提高了该催化剂的氨选择性催化氧化活性。此外,当负载适量的Cu和Ce时,能使Cu组分呈高度分散态,抑制体相中大颗粒Cu组分的形成,而高分散的Cu物种更容易被还原,催化剂的活性随之提高。
Ammonia (NH3) is an inorganic odor-causing pollutant, and it not only endangers human health, but also threatens the ecological environment. With the increasing industrial ammonia waste stream, controling the NH3 pollution arouses great public concern. Selective catalytic oxidation of ammonia (SCO) is seen as an ideal technology to remove NH3 because of its high efficiency, cleanness and economic value.
This paper focuses on the catalyst which is the core of SCO technology, and aims to prepare a kind of catalyst which has both high activity and N2 selectivity. The selective catalytic oxidations of ammonia were investigated over Cu/Al2O3, Cu/TiO2 catalysts with different Cu loadings and Cu-Mn/TiO2 catalyst, which were all prepared by an impregnation method, and the effects of NH3:O2 ratio and space velocity on SCO were also evaluated. The results showed that the selectivity to N2 was lower on Cu-Mn/TiO2 catalyst and 10% Cu/TiO2 catalyst has a much higher activity than Cu/Al2O3. When NH3:O2 ratio was 1:250 and space velocity was 50000h-1, the condition was optimum for Cu/TiO2 catalyst in the SCO of NH3.
To further enhance the activity of copper-based catalyst, Cu/Ce-TiO2 catalysts under different conditions were prepared by a two-step method (added CeOx by the impregnation method and loaded Cu by homogeneous deposition precipitation) and their properties were tested in the selective catalytic oxidation of ammonia to nitrogen. The results showed that Cu/Ce-TiO2 (10 wt.%,9 wt.%,15 g L-1) catalyst exhibited the best performance for NH3 conversion and N2 selectivity, over which complete conversion of NH3 and the N2 selectivity of 95%were obtained at 250℃, moreover the temperature was only 190℃when 50% NH3 was converted, which descended 20℃compared to Cu/TiO2 catalyst.
BET, XRD, XPS and H2-TPR have been used to characterize the states and reactivities of Cu/Ce-TiO2 catalysts for the oxidation of ammonia to nitrogen. The results indicated that the highly dispersed Cu2+species on the surface was more active than the large sized CuO particles in the bulk phase and Cu+species for the selective catalytic oxidation of ammonia. The concentration of urea greatly influenced the activity of Cu/Ce-TiO2 catalyst. When the concentration of urea was 15g L-1, part of Cu2O species changed into Cu(OH)2 species to form a Cu2+→Cu+reduction cycle, while Cu(OH)2 species could also react with NH3 and the reducibility of Cu2+species provided by Cu(OH)2 was higher. Therefore, the catalytic activity for selective catalytic oxidation of ammonia was improved. In addition, when appropriate amounts of Cu and Ce were loaded, Cu component was highly dispersed on the surface and the growth of bulk phase Cu component was inhibited. Due to the former was easier reduced, the catalytic activity increased accordingly.
本论文以氨选择性催化氧化技术的核心因素,即催化剂的选择为主要研究对象,旨在制备出一种同时具有高活性和高N2选择性的粉末催化剂。分别以Ti02粉末(P25)和活性氧化铝作为载体,Cu和Mn为活性组分,先采用浸渍法制备出Cu/Al2O3和Cu-Mn/TiO2以及不同负载量的Cu/TiO2催化剂,将它们用于氨的选择性催化氧化反应,并研究反应中影响催化剂性能的因素,NH3：02比例和空速大小。结果显示,Cu-Mn/TiO2的N2选择性较差,10%Cu/TiO2相比10%Cu/Al2O3催化剂具有更高的催化活性；NH3：02比例为1：250,空速为50000 h-1是采用10%Cu/TiO2催化剂催化氧化处理氨的最佳反应条件。
为了进一步提高Cu基催化剂的活性,在Cu/TiO2基础上,借助于向Ti02中添加助剂Ce作为载体,并采用均相沉淀法负载活性组分Cu,在不同条件下制备出系列Cu/Ce-TiO2催化剂。通过对它们对氨催化氧化的活性进行评价,筛选出催化效果最优的催化剂,并与Cu/TiO2催化剂进行对比,结果显示,对于Cu/Ce-TiO2系列催化剂,当铜的负载量为10 wt%,Ce的负载量为9 wt%,并且尿素浓度为15g L-1时,催化活性达到最高,在250℃能将NH3完全转化,N2选择性能达到95%,并且50% NH3被转化时的温度仅为190℃,相比Cu/TiO2催化剂,降低了20℃。
同时运用BET, XRD、XPS以及H2-TPR等表征手段对系列Cu/Ce-TiO2催化剂的性能进行了表征,以考察各因素对催化剂活性的影响。结果表明,表面高分散的Cu2+物种比体相大颗粒CuO和Cu+物种具有更高的氨选择性催化氧化活性。尿素浓度对Cu/Ce-TiO2催化剂活性的影响非常大,当尿素浓度为15 g L-1,部分Cu20物种转化成了Cu(OH)2物种,形成Cu2+→Cu+之间还原循环过程,同时Cu(OH)2物种也与NH3反应,并且由Cu(OH)2提供的Cu2+物种的还原能力更强,因而提高了该催化剂的氨选择性催化氧化活性。此外,当负载适量的Cu和Ce时,能使Cu组分呈高度分散态,抑制体相中大颗粒Cu组分的形成,而高分散的Cu物种更容易被还原,催化剂的活性随之提高。
Ammonia (NH3) is an inorganic odor-causing pollutant, and it not only endangers human health, but also threatens the ecological environment. With the increasing industrial ammonia waste stream, controling the NH3 pollution arouses great public concern. Selective catalytic oxidation of ammonia (SCO) is seen as an ideal technology to remove NH3 because of its high efficiency, cleanness and economic value.
This paper focuses on the catalyst which is the core of SCO technology, and aims to prepare a kind of catalyst which has both high activity and N2 selectivity. The selective catalytic oxidations of ammonia were investigated over Cu/Al2O3, Cu/TiO2 catalysts with different Cu loadings and Cu-Mn/TiO2 catalyst, which were all prepared by an impregnation method, and the effects of NH3:O2 ratio and space velocity on SCO were also evaluated. The results showed that the selectivity to N2 was lower on Cu-Mn/TiO2 catalyst and 10% Cu/TiO2 catalyst has a much higher activity than Cu/Al2O3. When NH3:O2 ratio was 1:250 and space velocity was 50000h-1, the condition was optimum for Cu/TiO2 catalyst in the SCO of NH3.
To further enhance the activity of copper-based catalyst, Cu/Ce-TiO2 catalysts under different conditions were prepared by a two-step method (added CeOx by the impregnation method and loaded Cu by homogeneous deposition precipitation) and their properties were tested in the selective catalytic oxidation of ammonia to nitrogen. The results showed that Cu/Ce-TiO2 (10 wt.%,9 wt.%,15 g L-1) catalyst exhibited the best performance for NH3 conversion and N2 selectivity, over which complete conversion of NH3 and the N2 selectivity of 95%were obtained at 250℃, moreover the temperature was only 190℃when 50% NH3 was converted, which descended 20℃compared to Cu/TiO2 catalyst.
BET, XRD, XPS and H2-TPR have been used to characterize the states and reactivities of Cu/Ce-TiO2 catalysts for the oxidation of ammonia to nitrogen. The results indicated that the highly dispersed Cu2+species on the surface was more active than the large sized CuO particles in the bulk phase and Cu+species for the selective catalytic oxidation of ammonia. The concentration of urea greatly influenced the activity of Cu/Ce-TiO2 catalyst. When the concentration of urea was 15g L-1, part of Cu2O species changed into Cu(OH)2 species to form a Cu2+→Cu+reduction cycle, while Cu(OH)2 species could also react with NH3 and the reducibility of Cu2+species provided by Cu(OH)2 was higher. Therefore, the catalytic activity for selective catalytic oxidation of ammonia was improved. In addition, when appropriate amounts of Cu and Ce were loaded, Cu component was highly dispersed on the surface and the growth of bulk phase Cu component was inhibited. Due to the former was easier reduced, the catalytic activity increased accordingly.
引文
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[3]AMBLARD M, BURCH R, SOUTHWARD B W L. The selective conversion of ammonia to nitrogen on metal oxide catalysts under strongly oxidising conditions[J]. Applied Catalysis B: Environmental,1999,22(3):159-166.
[4]BUIJSMAN E, ASMAN W A H. Zure regen (Acid rain, in Dutch)[J]. Chemisch Magazine, 1983,12:654-658.
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