为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用...为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用于锅炉烟气脱硝。提出了氧浓度、[NH3]/[NO]以及空速对脱硝效率的影响,结合X射线衍射表征,获得了N掺杂催化剂的反应工艺参数和相应的晶型变化特性。研究结果表明,N掺杂后,催化剂脱硝活性明显,并对催化剂N掺杂量、Mn负载量及催化剂煅烧温度进行了优化,并对优化结果进行分析。在此基础上,考察了含氧量,得出在O2浓度5%、[NH3]/[NO]为1.2时,空速28 000 h 1,反应温度180℃的条件下,掺N量为1%以及Mn负载量为5%的N掺杂MnOx/TiO2催化剂的脱硝活性稳定在90%左右。展开更多
The effects of atmospheres and precursors on MnOx/TiO2 catalysts were studied, which were prepared by the impregnation method and tested for their NOx conversion activity in ammonia selective catalytic reduction （NH3...The effects of atmospheres and precursors on MnOx/TiO2 catalysts were studied, which were prepared by the impregnation method and tested for their NOx conversion activity in ammonia selective catalytic reduction （NH3-SCR） reactions. Results showed that the manganese carbonate （MC） precursor caused mainly Mn2O3, while the manganese nitrate （MN） precursor resulted primarily in MnO2 and the manganese sulfate （MS） precursor was unchanged. The manganese acetate （MA） precursor leaded obtaining a mixture of Mn2O3 and Mn304. NOn conversion decreased in the following order： MA/TiO2 〉 MC/TiO2 〉 MN/TiO2 〉 MS/TiO2 〉 P25, with a calcination temperature of 773 K in air. Catalysts that were prepared by MA and calcined in oxygen performed strong interaction between Ti and Mn, while MnTiO3 was observed. Compared to the catalysts calcined in nitrogen, those calcined in oxygen had larger diameter and smaller surface area and pore. Catalysts that were prepared by MA and calcined in nitrogen tended to gain higher denitration rates than those in air, since they could be prepared with significant specific surface areas. NO., conversion decreased with calcination atmospheres： Nitrogen〉 Air〉 Oxygen. Meanwhile, amorphous Mn2O3 turned into crystalline Mn2O3, when the temperatures increased from 673 to 873 K.展开更多
A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined ...A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.展开更多
文摘为研究具有良好活性的低温选择性催化还原催化剂,针对目前Mn基材料低温选择性催化还原脱硝催化剂研究的局限性,以超氧自由基促进光催化为理论基础,N掺杂改性非金属为研究思路,采用溶胶凝胶法及过量浸渍法制备了N掺杂MnOx/TiO2催化剂,用于锅炉烟气脱硝。提出了氧浓度、[NH3]/[NO]以及空速对脱硝效率的影响,结合X射线衍射表征,获得了N掺杂催化剂的反应工艺参数和相应的晶型变化特性。研究结果表明,N掺杂后,催化剂脱硝活性明显,并对催化剂N掺杂量、Mn负载量及催化剂煅烧温度进行了优化,并对优化结果进行分析。在此基础上,考察了含氧量,得出在O2浓度5%、[NH3]/[NO]为1.2时,空速28 000 h 1,反应温度180℃的条件下,掺N量为1%以及Mn负载量为5%的N掺杂MnOx/TiO2催化剂的脱硝活性稳定在90%左右。
基金supported by the National Natural Science Foundation of China(51306046,51166004,51376073)the Fundamental Research Funds for the Universities of Henan Province(NSFRF140204)~~
文摘研究了Mn-W/TiO2用于NH3选择性催化还原NOx体系的催化反应性能,探索了不同温度条件下该催化剂对抗不同SO2浓度的抗毒性能。结果显示WO3能够增加活性酸中心的数量和酸性,是MnOx/TiO2非常有效的助催化剂。在气体体积空速(gaseous hourly space velocity,GHSV)为18900h-1时100～350℃范围内,Mn-W/TiO2催化剂还原NOx的转化率高达80.3%～99.6%,N2选择性达100%～98.7%。当反应气中有0.01%SO2和6%H2O时,120℃NOx转化率可维持在98.5%,当SO2浓度超过0.01%时,则需将反应温度升高到250℃以上才可消除其干扰,而当SO2浓度高达0.07%时,300℃下转化率可长期维持在99%,达到了商用V-W/TiO2催化剂的水平。对于NH3选择性还原NOx体系Mn-W/TiO2显示了极好的催化性能,是目前抗SO2毒性最强的催化剂之一。试验发现,低温条件下,SO2对Mn-W/TiO2催化剂的影响是可逆的,随着反应温度的提高,活性将自然恢复。
基金Funded by the National "Twelfth Five-Year" Plan for Science&Technology Support of China(No.2011BAE29B02))
文摘The effects of atmospheres and precursors on MnOx/TiO2 catalysts were studied, which were prepared by the impregnation method and tested for their NOx conversion activity in ammonia selective catalytic reduction （NH3-SCR） reactions. Results showed that the manganese carbonate （MC） precursor caused mainly Mn2O3, while the manganese nitrate （MN） precursor resulted primarily in MnO2 and the manganese sulfate （MS） precursor was unchanged. The manganese acetate （MA） precursor leaded obtaining a mixture of Mn2O3 and Mn304. NOn conversion decreased in the following order： MA/TiO2 〉 MC/TiO2 〉 MN/TiO2 〉 MS/TiO2 〉 P25, with a calcination temperature of 773 K in air. Catalysts that were prepared by MA and calcined in oxygen performed strong interaction between Ti and Mn, while MnTiO3 was observed. Compared to the catalysts calcined in nitrogen, those calcined in oxygen had larger diameter and smaller surface area and pore. Catalysts that were prepared by MA and calcined in nitrogen tended to gain higher denitration rates than those in air, since they could be prepared with significant specific surface areas. NO., conversion decreased with calcination atmospheres： Nitrogen〉 Air〉 Oxygen. Meanwhile, amorphous Mn2O3 turned into crystalline Mn2O3, when the temperatures increased from 673 to 873 K.
基金supported by the National Natural Science Foundation of China (Grant No. 51078185)
文摘A series of Ce-doped MnOx/TiO2 catalysts were prepared by impregnation method and used for catalytic oxidation of NO in the presence of excess O2. The sample with the Ce doping concentration of Ce/Mn=l/3 and calcined at 300 ℃ shows a superior activity for NO oxidation to NO2. On Ce（1）Mn（3）Ti catalyst, 58% NO conversion was obtained at 200 ℃ and 85% NO conversion at 250 ℃ with a GHSV of 41000 h-1, which was much higher than that over MnOx/TiO2 catalyst （48% at 250 ℃）. Characterization results implied that the higher activity of Ce（1）Mn（3）Ti could be attributed to the enrichment of well-dispersed MnO2 on the surface and the abundance of Mn3＋ and Zi3＋ species. The addition of Ce into MnO2/TiO2 could improve oxygen storage capacity and facilitate oxygen mobility of the catalyst as shown by PL and ESR, so that its activity for NO oxidation could be enhanced. The effect of H2O and SO2 on the catalyst activity was also investigated.
