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采用溶胶-凝胶法制备TiO2-ZrO2载体,以硝酸锰为前驱体采用柠檬酸溶液浸渍法制备 Ce(n)-MnOx/TiO2-ZrO2复合催化剂.通过 XRD、SEM-EDS、XPS 等测试方法对催化剂的物化性能进行表征分析,并进行NH3选择性催化还原 NO 实验,考察其在低温下的活性及抗水抗硫性能.结果表明,Ce-Mn 氧化物和 TiO2-ZrO2载体间发生了相互作用,后者结晶度发生变化.与 MnOx/TiO2-ZrO2比较,Ce(n)-MnOx/TiO2-ZrO2中Mn4+的含量提高.Ce元素以Ce4+、Ce3+存在于Ce(n)-MnOx/TiO2-ZrO2中,在催化反应中能起到传递电子、离子和储氧的作用,提高催化剂的氧化还原能力,同时Ce元素的电离能和电负性要远小于Mn元素,优先于Mn发生化学反应,保护Mn元素的活性.Ce(0.2)-MnOx/TiO2-ZrO2的颗粒分散均匀、粒径达到20 nm 左右.制备的Ce(n)-MnOx/TiO2-ZrO2催化剂的低温活性和抗毒性都优于 MnOx/TiO2-ZrO2,其中 Ce(0.2)-MnOx/TiO2-ZrO2在80℃时脱硝效率为94%;100℃时脱硝效率达到100%,在同时通入5% H2 O 和100 mg/m3 SO2后,脱硝效率缓慢下降,反应210 min降到85%后趋于稳定.

Using the sol-gel prepared TiO2-ZrO2 carrier,Ce(n)-MnOx/TiO2-ZrO2 composite catalysts were syn-thesized with critic acid solution impregnation method with manganese nitrate as MnOx precursor.The physical and chemical properties of catalysts were characterized with XRD,SEM-EDS and XPS.Meanwhile,its low-temperature catalytic activities as well as sulfur and water resistance were evaluated with selective catalytic re-duction (SCR)of NO by NH3 .The results show that there is an interaction between Ce-Mn oxide and TiO2-ZrO2 carrier,which leads to a crystallinity change in carrier.Comparing to the MnOx/TiO2-ZrO2 ,there is a higher Mn4+ content in Ce(n)-MnOx/TiO2-ZrO2 .Furthermore,Ce in the Ce(n)-MnOx/TiO2-ZrO2 exists as Ce4+,Ce3+ state,which has the effect of transmission electron,ion and oxygen storage in the catalytic reac-tion,and then it improves the redox ability of catalysts.And ionization energy and electronegativity of Ce are much less than Mn.Therefore,Ce takes chemical reactions in preference to Mn.So the activity of Mn could be protected.The low temperature activity and antitoxic performance of Ce(n)-MnOx/TiO2-ZrO2 are superior to MnOx/TiO2-ZrO2 .Among the prepared five catalysts with different molar ratios of Ce/Mn,Ce(0.2)-MnOx/TiO2-ZrO2 demonstrates the best performance owing to the best particle dispersion and the small particle size about 20 nm,and a 94% denitrification efficiency can be achieved at 80 ℃ and 100% at 100 ℃.When 5% H2 O and 100 mg/m3 SO2 are simultaneously added,the denitrification efficiency decreases slowly and stabilizes at 8 5% after 2 1 0 min.

参考文献

[1] Fuyu Notoya;Caili Su;Eiji Sasaoka;Shigeru Nojima.Effect of SO_2 on the Low-Temperature Selective Catalytic Reduction of Nitric Oxide with Ammonia over TiO_2, ZrO_2, and Al_2O_3[J].Industrial & Engineering Chemistry Research,200117(17):3732-3739.
[2] 张恒建;张先龙;张连凤;杨保俊;解城华;程俊楠.前驱体对锰基SCR催化剂低温脱硝活性的影响[J].合肥工业大学学报(自然科学版),2014(7):860-864,870.
[3] Leonhard Schill;Siva Sankar Reddy Putluru;Rasmus Fehrmann.Low-Temperature NH3-SCR of NO on Mesoporous Mn_(0.6)Fe_(0.4)/ TiO2 Prepared by a Hydrothermal Method[J].Catalysis Letters,20143(3):395-402.
[4] Chen, Z.;Yang, Q.;Li, H.;Li, X.;Wang, L.;Chi Tsang, S..Cr-MnO_x mixed-oxide catalysts for selective catalytic reduction of NO_x with NH_3 at low temperature[J].Journal of Catalysis,20101(1):56-65.
[5] Yaping Wan;Wenru Zhao;Yu Tang.Ni-Mn bi-metal oxide catalysts for the low temperature SCR removal of NO with NH3[J].Applied Catalysis, B. Environmental: An International Journal Devoted to Catalytic Science and Its Applications,2014:114-122.
[6] 房晶瑞;吴彦霞;雷本喜;汪澜;考宏涛.负载型Mn-Co/TiO2催化剂的制备及其低温NH3选择催化还原NO[J].环境科学学报,2014(4):849-856.
[7] 房晶瑞;吴彦霞;雷本喜;汪澜.负载型Mn-Ce/TiO2催化剂的制备及其低温脱硝活性[J].环境工程学报,2014(2):636-640.
[8] 汪莉;郑芸芸;宋存义.锆掺杂钛负载锰氧化物用于低温选择性催化还原NO[J].北京科技大学学报,2013(7):922-928.
[9] 卢熙宁;宋存义;童震松;张东辉.锆掺杂 TiO2负载锰铈氧化物低温催化还原 NOx[J].北京科技大学学报,2014(9):1222-1232.
[10] Donovan A.Pena;Balu S.Uphade;Panagiotis G.Smirniotis.TiO_2-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH_3 I.Evaluation and characterization of first row transition metals[J].Journal of Catalysis,20042(2):421-431.
[11] Gongshin Qi;Ralph T.Yang.Characterization and FTIR Studies of MnO_x-CeO_2 Catalyst for Low-Temperature Selective Catalytic Reduction of NO with NH_3[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,200440(40):15738-15747.
[12] Huang ZG.;Zhu ZP.;Liu ZY..Combined effect of H2O and SO2 on V2O5/AC catalysts for NO reduction with ammonia at lower temperatures[J].Applied Catalysis, B. Environmental: An International Journal Devoted to Catalytic Science and Its Applications,20024(4):361-368.
[13] Zhong Yi Ding;Lixiong Li;Daniel Wade;Earnest F. Gloyna.Supercritical Water Oxidation of NH_3 over a MnO_2/CeO_2 Catalyst[J].Industrial & Engineering Chemistry Research,19985(5):1707-1716.
[14] Yang SX;Zhu WP;Jiang ZP;Chen ZX;Wang JB.The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts[J].Applied Surface Science: A Journal Devoted to the Properties of Interfaces in Relation to the Synthesis and Behaviour of Materials,200624(24):8499-8505.
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