自蔓延高温燃烧合成法制备CeWTiOx催化剂及其NH3-SCR性能

卢朋; 鲁卫哲; 李欢; 陈银飞; 张泽凯

自蔓延高温燃烧合成法制备CeWTiO_x催化剂及其NH₃-SCR性能

浙江工业大学化学工程学院能源化学工程系, 浙江杭州 310014

详细信息

通讯作者:
张泽凯, Tel:13968043221, E-mail:zzk@zjut.edu.cn

中图分类号: X511
计量
- 文章访问数: 64
- HTML全文浏览量: 21
- PDF下载量: 5
- 被引次数: 0
出版历程
- 收稿日期: 2017-02-20
- 修回日期: 2017-04-26
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-08-10

Preparation of CeWTiO_x catalysts via self-propagating high temperature synthesis and its NH₃-SCR performance

Department of Energy Reaction Engineerig, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

摘要

摘要: 采用自蔓延高温燃烧合成法制备了CeWTiO_x系列催化剂并考察了其氨选择性催化还原NO_x（NH₃-SCR）性能。利用X射线衍射、N₂吸附-脱附、H₂程序升温还原、X射线光电子能谱、NH₃程序升温脱附表征和分析了催化剂晶相、结构、氧化还原能力和酸性强度与其活性之间的关系。结果表明，Ce₄₀W₁₀TiO_x催化剂在150-430 ℃ NO转化率可达80%以上，含硫条件下200 ℃ NO转化率可保持在97%左右。结果表明，该催化剂的低温活性和抗硫性能主要与W的掺杂有关。钨的存在减弱了Ce-O键的强度，降低了CeO₂的结晶度和减小了晶粒粒径，增加了催化剂表面活性氧含量和酸量，提高了其性能。
- 自蔓延高温燃烧合成法 /
- CeWTiO_x /
- 钨 /
- 抗硫
Abstract: A series of CeWTiO_x catalysts were prepared by self-propagating high-temperature synthesis method, and their NH₃-SCR activities were evaluated. X-ray diffraction, N₂ adsorption-desorption, H₂-temperature-programmed reduction, X-ray photoelectron spectroscopy and NH₃-temperature-programmed desorption were performed to investigate the relationship between the catalyst activity and its physicochemical properties such as crystalline phase, specific surface area, redox ability and acidity. The results showed that 80% of NO conversion could be reached on the Ce₄₀W₁₀TiO_x catalyst sample in a range of 150-430 ℃. NO conversion of Ce₄₀W₁₀TiO_x could be kept above 97% in SO₂ atmosphere. The characterization indicated that the excellent low temperature activity and SO₂ resistance of Ce₄₀W₁₀TiO_x were mainly associated with the tungsten doping. The existence of tungsten weakened the strength of Ce-O bond, lowered the crystallinity and crystal size of CeO₂, increased the surface active oxygen content and the acid sites, thus improved the NH₃-SCR performance of the catalyst.
- self-propagating high-temperature synthesis /
- CeWTiO_x /
- tungsten /
- SO₂ resistance

HTML全文

图 1 Ce₄₀TiO_x、W₁₀TiO_x、CeWO_x及Ce₄₀W₁₀TiO_x的NH₃-SCR谱图

Figure 1 Activity of Ce₄₀TiO_x, W₁₀TiO_x, CeWO_x and Ce₄₀W₁₀TiO_x catalysts in NH₃-SCR reaction

(reaction conditions: 0.05% NO, 0.05% NH₃, 5% O₂, N₂ balance, GHSV =30 000 h^-1)
: Ce₄₀TiO_x; :W₁₀TiO_x; :CeWO_x; :Ce₄₀W₁₀TiO_x

下载: 全尺寸图片幻灯片

图 2 Ce₄₀TiO_x和Ce₄₀W₁₀TiO_x催化氧化单纯NO和NH₃性能

Figure 2 Catalytic oxidation ability of Ce₄₀TiO_x and Ce₄₀W₁₀TiO_x for single NO or NH₃

下载: 全尺寸图片幻灯片

图 3 Ce₄₀TiO_x、W₁₀TiO_x、CeWO_x及Ce₄₀W₁₀TiO_x催化剂的XRD谱图

Figure 3 XRD patterns of Ce₄₀TiO_x, W₁₀TiO_x, CeWO_x and Ce₄₀W₁₀TiO_x catalysts

下载: 全尺寸图片幻灯片

图 4 Ce₄₀TiO_x、W₁₀TiO_x、Ce₄₀W₁₀TiO_x和TiO₂的H₂-TPR谱图

Figure 4 H₂-TPR profiles of Ce₄₀TiO_x, W₁₀TiO_x, Ce₄₀W₁₀TiO_x and TiO₂ catalysts

下载: 全尺寸图片幻灯片

图 5 Ce₄₀TiO_x和Ce₄₀W₁₀TiO_x的O 1s (a)和Ce 3d(b)XPS谱图

Figure 5 XPS spectra of O 1s(a) and Ce 3d(b) of Ce₄₀TiO_x and Ce₄₀W₁₀TiO_x catalysts

下载: 全尺寸图片幻灯片

图 6 Ce₄₀TiO_x和Ce₄₀W₁₀TiO_x催化剂的NH₃-TPD谱图

Figure 6 NH₃-TPD profiles of Ce₄₀TiO_x and Ce₄₀W₁₀TiO_x catalysts

下载: 全尺寸图片幻灯片

图 7 200 ℃ H₂O和SO₂对Ce₄₀TiO_x、Ce₄₀W₁₀TiO_xNO转化率影响

Figure 7 Influence of SO₂ and H₂O on the performance of Ce₄₀TiO_x and Ce₄₀W₁₀TiO_x catalyst at 200 ℃

下载: 全尺寸图片幻灯片

表 1 不同催化剂的织构参数和晶粒粒径

Table 1 Textural properties and crystalline size of different catalysts

表 2 Ce₄₀TiO_x和Ce₄₀W₁₀TiO_x催化剂表面氧物种及铈物种含量

Table 2 Surface atomic concentration of Ce₄₀TiO_x and Ce₄₀W₁₀TiO_x catalysts

参考文献(30)

[1]	刘昕, 宁平, 李昊, 宋忠贤, 王燕彩, 张金辉, 唐小苏, 王明智, 张秋林.水相法制备Ce-W@TiO₂催化剂的氨选择性催化还原NO(NH₃-SCR)活性和抗SO₂性能研究[J].燃料化学学报, 2016, 44(2): 225-231. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18783.shtml LIU Xin, NING Ping, LI Hao, SONG Zhong-xian, WANG Yan-cai, ZHANG Jin-hui, TANG Xiao-su, WANG Ming-zhi, ZHANG Qiu-lin. Probing NH₃-SCR catalytic activity and SO₂ resistance over aqueous -phase synthesized Ce-W@TiO₂ catalyst[J]. J Fuel Chem Technol, 2016, 44 (2): 225-231) http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18783.shtml
[2]	HECK R M. Catalytic abatement of nitrogen oxides-stationary application[J]. Catal Today, 1999, 53(4): 519-523. doi: 10.1016/S0920-5861(99)00139-X
[3]	BUSCA G, LIETTE L, RAMIS G, BERTI F. Chemical and mechanistic aspects of the selective catalytic reduction of NO_x by ammonia over oxide catalysts: A review[J]. Appl Catal B: Environ, 1998, 18(1/2): 1-36. http://www.academia.edu/9406029/Chemical_and_mechanistic_aspects_of_the_selective_catalytic_reduction_of_NO_x_by_ammonia_over_oxide_catalysts_A_review
[4]	GRANGER P, PARVULESCU V I. Catalytic NO_x Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies[J]. Chem Rev, 2011, 111: 3155-3207. doi: 10.1021/cr100168g
[5]	ALEMANY L J, BERTI F, BUSCA G, RAMIS G, ROBBA D, TOLEDO G P, TROMBETTA M. Characterization and composition of commercial V₂O₅-WO₃-TiO₂ SCR catalysts[J]. Appl Catal B: Environ, 1996, 10(4): 299-311. doi: 10.1016/S0926-3373(96)00032-X
[6]	YATES M, MARTIN J A, LUENGO M A M, SUAREZ S, BLANCO J. N₂O formation in the ammonia oxidation and in the SCR process with V₂O₅-WO₃ catalysts[J]. Catal Today, 2005, 107/108: 120-125. doi: 10.1016/j.cattod.2005.07.015
[7]	CHEN L, LI J H, Ge M F. Promotional effect of Ce-doped V₂O₅-WO₃/TiO₂ with low vanadium loadings for selective catalytic reduction of NO_x by NH₃[J]. J Phys Chem C, 2009, 113(50): 21177-21184. doi: 10.1021/jp907109e
[8]	GAO X, JIANG Y, ZHONG Y, LUO Z Y, CEN K F. The activity and characterization of CeO₂-TiO₂ catalysts prepared by the sol-gel method for selective catalytic reduction of NO with NH₃[J]. J Hazard Mater, 2010, 174(1): 734-739. https://www.researchgate.net/publication/38018681_The_activity_and_characterization_of_CeO2-TiO2_catalysts_prepared_by_the_sol-gel_method_for_selective_catalytic_reduction_of_NO_with_NH3
[9]	PENG Y, LI K Z, LI J H. Identification of the active sites on CeO₂-WO₃ catalysts for SCR of NO_x with NH₃: An in situ IR and Raman spectroscopy study[J]. Appl Catal B: Environ, 2013, 140/141: 483-492. doi: 10.1016/j.apcatb.2013.04.043
[10]	REDDY B M, KHAN A, YAMADA Y, KOBAYASHI T, LORIDANT S, VOLTA J C. Structural characterization of CeO₂-TiO₂ and V₂O₅/CeO₂-TiO₂ catalysts by raman and XPS techniques[J]. J Phys Chem B, 2003, 107(22): 5162-5167. doi: 10.1021/jp0344601
[11]	QI G, YANG R T. A superior catalyst for low-temperature NO reduction with NH₃[J]. Chem Commun, 2003, 34(26): 848-849. http://pubs.rsc.org/en/Content/ArticleLanding/2003/CC/b212725c#!divAbstract
[12]	KWON D W, NAM K B, HONG S C. The role of ceria on the activity and SO₂ resistance of catalysts for the selective catalytic reduction of NO_x by NH₃[J]. Appl Catal B: Environ, 2014, 166/167(1): 37-44. http://www.sciencedirect.com/science/article/pii/S092633731400705X
[13]	ZHANG S L, ZHONG Q. Promotional effect of WO₃ on O^2- over V₂O₅/TiO₂ catalyst for selective catalytic reduction of NO with NH₃[J]. J Mole CatalA, 2013, 373(3): 108-113. http://www.sciencedirect.com/science/article/pii/S138111691300112X
[14]	LIU Z M, LIU Y X, LI Y, SU H, MA L L. WO₃ promoted Mn-Zr mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Chem Eng J, 2016, 283: 1044-1050. doi: 10.1016/j.cej.2015.08.040
[15]	CHEN L, WENG D, SI Z C, WU X D. Synergistic effect between ceria and tungsten oxide on WO₃-CeO₂-TiO₂ catalysts for NH₃-SCR reaction[J]. Prog Nat Sci-Mater, 2012, 22(4): 265-72. doi: 10.1016/j.pnsc.2012.07.004
[16]	KWON D W, HONG S C. Promotional effect of tungsten-doped CeO₂/TiO₂ for selective catalytic reduction of NO_x with ammonia[J]. Appl Surf Sci, 2015, 356: 181-190. doi: 10.1016/j.apsusc.2015.08.073
[17]	KONG Z J, WANG C, DING Z N, CHEN Y F, ZHANG Z K. Enhanced activity of MnxW_0.05Ti_0.95-xO_2-δ for selective catalytic reduction of NO_x with ammonia by self-propagating high-temperature synthesis[J]. Catal Commun, 2015, 64: 27-31. doi: 10.1016/j.catcom.2015.01.028
[18]	SHAN W P, LIU F D, HE H, SHI X Y, ZHANG C B. A superior Ce-W-Ti mixed oxide catalyst for the selective catalytic reduction of NO_x with NH₃[J]. Appl Catal B: Environ, 2012, 115/116(4): 100-106. https://www.researchgate.net/publication/257370848_A_superior_Ce-W-Ti_mixed_oxide_catalyst_for_the_selective_catalytic_reduction_of_NOx_with_NH3
[19]	LIU F D, SHAN W P, LIAN Z H, XIE L J, YANG W W, HE H. Novel MnWO catalyst with remarkable performance for low temperature NH₃-SCR of NO_x [J]. Catal Sci Technol, 2013, 3 (10): 2699-2707. doi: 10.1039/c3cy00326d
[20]	Z R MA, WENG D, WU X D, SI Z C. Effects of WO_x modification on the activity, adsorption and redox properties of CeO₂ catalyst for NO_x reduction with ammonia[J]. J Environ Sci-China, 2012, 24(7): 1305-1316. doi: 10.1016/S1001-0742(11)60925-X
[21]	SHAN W P, LIU F D, HE H, SHI X, ZHANG C. Novel cerium-tungsten mixed oxide catalyst for the selective catalyticreduction of NO_x with NH₃[J]. Chem Commun, 2011, 47 (28): 8046-8048. doi: 10.1039/c1cc12168e
[22]	WANG C Z, YANG S J, CHANG H Z, PENG Y, LI J H. Dispersion of tungsten oxide on SCR performance of V₂O₅-WO₃/TiO₂: Acidity, surface species and catalytic activity[J]. ChemEng J, 2013, 225 (6): 520-527. https://www.researchgate.net/publication/223919886_Vanadia-based_SCR_catalysts_supported_on_tungstated_and_sulfated_zirconia_Influence_of_doping_with_potassium
[23]	JIANG Y, XING Z M, WANG X C, HUANG S B, WANG X W, LIU Q Y. Activity and characterization of a Ce-W-Ti oxide catalyst prepared by a single step sol-gel method for selective catalytic reduction of NO with NH₃[J]. Fuel, 2015, 151: 124-129. doi: 10.1016/j.fuel.2015.01.061
[24]	GAO X, JIANG Y, FU Y C, ZHONG Y, LUO Z Y, CEN K F. Preparation and characterization of CeO₂/TiO₂ catalysts for selective catalytic reduction of NO with NH₃[J]. Catal Commun, 2010, 11(5): 465-469. doi: 10.1016/j.catcom.2009.11.024
[25]	ZHANG Q L, XU L S, NING P, GU J J, GUAN Q Q. Surface characterization of CuO-CeO₂-ZrO₂ catalysts for selective catalytic reduction of NO with NH₃[J]. Appl Surf Sci, 2014, 317: 955-961. doi: 10.1016/j.apsusc.2014.09.017
[26]	QI G, YANG R T, CHANG R. MnO_x-CeO₂ mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B: Environ, 2004, 51: 93-106. doi: 10.1016/j.apcatb.2004.01.023
[27]	XU W, HE H, YU Y. Deactivation of a Ce/TiO₂ catalyst by SO₂ in the selective catalytic reduction of NO by NH₃[J]. J Phys Chem C, 2009, 113(11):4426-4432. doi: 10.1021/jp8088148
[28]	YANG S J, GUO Y F, CHANG H Z, MA L, PENG Y, QU Z. YAN N Q, WANG C Z, LI J H. Novel effect of SO₂ on the SCR reaction over CeO₂: Mechanism and significance[J]. Appl Catal B: Environ, 2013, 136/137(12):19-28. http://www.sciencedirect.com/science/article/pii/S0926337313000489
[29]	CHEN L, LI J H, GE M F. DRIFT Study on Cerium-Tungsten/Titiania Catalyst for Selective Catalytic Reduction of NO_x with NH₃[J]. Environ Sci Technol, 2010, 44: 9590-9596. doi: 10.1021/es102692b
[30]	SANG M L, SUNG S K, SUNG C H. Systematic mechanism study of the high temperature SCR of NO_x by NH₃ over a W/TiO₂ catalyst[J]. Chem Eng Sci, 2012, 79: 177-185. doi: 10.1016/j.ces.2012.05.032