黄莎莎¹,苏亚欣¹,周夏¹,杨迪¹,王聪颖¹,温妮妮¹,邓文义¹,周皞²,田凤国¹

• 1:东华大学 环境科学与工程学院，上海 201620
• 2:常州工程技术学院 智能装备学院，江苏 常州 213164

摘要(Abstract)：

为了提高甲烷的选择性催化还原NO（CH₄-SCR）的效率及其抗烟气中的SO₂和H₂O的能力，以铝离子柱撑黏土为载体，制备铁-钴双金属催化剂（Fe-Co/Al-PILC）。采用X射线衍射（XRD）、N₂吸附-脱附、H₂程序升温还原（H₂-TPR）、吡啶吸附红外光谱（Py-FTIR）、X射线光电子能谱（XPS）等方法表征催化剂的物化性质，在固定床微型反应器上对其CH₄-SCR特性进行系统评估。结果表明，Fe-Co/Al-PILC具有较好的脱硝反应活性，其中0.27Fe-Co/Al-PILC（0.27为Fe与Co的质量分数比）在600℃时达到63.5%的脱硝效率和100%的N₂选择性，其抗水抗硫性能也大大提高。催化剂物化性质的表征结果表明，适量的Fe-Co负载量有利于催化剂中形成Co²⁺和游离态Fe³⁺，它们是影响催化剂活性的主要因素。H₂-TPR结果表明，Fe离子使催化剂的还原温度降低，还原性能增强。吡啶吸附-红外光谱结果表明，催化剂表面同时存在Lewis酸和Brønsted酸，Lewis酸是催化反应的活性酸性位，Fe离子增加了Lewis酸含量。

关键词(KeyWords)： 大气污染控制;选择性催化还原;CH₄-SCR;双金属催化剂;Fe-Co/Al-PILC

Abstract:

Keywords:

基金项目(Foundation): 上海市自然科学基金（19ZR1400700，19ZR1401800）；江苏省自然科学基金（BK20181161）；中央高校基本科研业务费（2232019D3-24）。

作者(Author): 黄莎莎¹,苏亚欣¹,周夏¹,杨迪¹,王聪颖¹,温妮妮¹,邓文义¹,周皞²,田凤国¹

DOI: 10.3969/j.issn.1003-9015.2021.06.016

参考文献(References)：

• [1] MRAD R, AISSAT A, COUSIN R, et al. Catalysts for NO_x selective catalytic reduction by hydrocarbons (HC-SCR)[J]. Applied Catalysis A:General, 2015, 504(S1):542-548.
  [2] 周皞, 苏亚欣, 邓文义, 等. 金属氧化物类催化剂上HC-SCR研究进展[J]. 环境科学与技术, 2016, 39(1):94-100. ZHOU H, SU Y X, DENG W Y, et al. A Review of HC-SCR over metal oxides-based catalysts[J]. Journal of Environmental Sciences, 2016, 39(1):94-100.
  [3] TIAN F G, LI K K, SU Y X. Catalytic performance and characterization of Ce-modified Fe catalysts supported on Al₂O₃ for SCR-C₃H₈[J]. Catalysis Surveys from Asia, 2020, 24(3):239-249.
  [4] STRöM L, CARLSSON P-A, SKOGLUNDH M, et al. Hydrogen-assisted SCR of NO over alumina-supported silver and indium catalysts using C₂-hydrocarbons and oxygenates[J]. Applied Catalysis B:Environmental, 2016, 181:403-412.
  [5] CHAIEB T, DELANNOY L, LOUIS C, et al. On the origin of the optimum loading of Ag on Al₂O₃ in the C₃H₆-SCR of NO_x[J]. Applied Catalysis B:Environmental, 2013, 142/143:780-784.
  [6] YUAN M H, DENG W Y, DONG S L, et al. Montmorillonite based porous clay heterostructures modified with Fe as catalysts for selective catalytic reduction of NO with propylene[J]. Chemical Engineering Journal, 2018, 353:839-848.
  [7] NEYLON M K, CASTAGNOLA M J, CASTAGNOLA N B, et al. Coated bifunctional catalysts for NO_x SCR with C₃H₆:Part I:Water-enhanced activity[J]. Catalysis Today, 2004, 96(1/2):53-60.
  [8] MARTíN J C, SUAREZ S, YATES M, et al. Pd/γ-Al₂O₃ monolithic catalysts for NO_x reduction with CH₄ in excess of O₂:Effect of precursor salt[J]. Chemical Engineering Journal, 2009, 150(1):8-14.
  [9] MENDIOROZ S, MARTíN-ROJO A B, RIVERA F, et al. Selective catalytic reduction of NO_x by methane in excess oxygen over Rh based aluminium pillared clays[J]. Applied Catalysis B:Environmental, 2006, 64(3/4):161-170.
  [10] MASUDA T, WATANABE T, MIYAHARA Y, et al. Synthesis of Ga₂O₃-Al₂O₃ Catalysts by a Coprecipitation method for CH₄-SCR of NO[J]. Topics in Catalysis, 2009, 52(6/7):699-706.
  [11] LóNYI F, SOLT H E, VAYON J, et al. The SCR of NO with methane over In, H- and Co, In, H-ZSM-5 catalysts:The promotional effect of cobalt[J]. Applied Catalysis B:Environmental, 2012, 117/118:212-223.
  [12] LóNYI F, SOLT H E, PáSZTI Z, et al. Mechanism of NO-SCR by methane over Co, H-ZSM-5 and Co, H-mordenite catalysts[J]. Applied Catalysis B:Environmental, 2014, 150/151:218-229.
  [13] LIM J B, SHIN J, AHN N H, et al. Selective catalytic reduction of NO with CH₄ over cobalt-exchanged cage-based, small-pore zeolites with different framework structures[J]. Applied Catalysis B:Environmental, 2020, 267:118710.
  [14] BELLMANN A, ATIA H, BENTRUP U, et al. Mechanism of the selective reduction of NO_x by methane over Co-ZSM-5[J]. Applied Catalysis B:Environmental, 2018, 230:184-193.
  [15] 林睿, 苏亚欣, 程江浩, 等. Fe/Ga₂O₃-Al₂O₃催化甲烷还原NO的性能[J]. 环境工程学报, 2020, 14(6):1592-1604. LIN R, SU Y X, CHENG J H, et al. The performance of Fe/Ga₂O₃-Al₂O₃ catalytic methane to reduce NO[J]. Chinese Journal of Environmental Engineering, 2020, 14(6):1592-1604.
  [16] 荆国华, 李俊华, 杨栋, 等. 分子筛类催化剂上甲烷选择性催化还原NO_x研究进展[J]. 化工进展, 2009, 28(3):504-510. JING G H, LI J H, YANG D, et al. Progress of selective catalytic reduction of NO_x with methane over zeolite-based catalysts[J]. Chemical Industry and Engineering Progress, 2009, 28(3):504-510.
  [17] 周皞, 苏亚欣, 邓文义, 等. 负载金属分子筛类催化剂上HC-SCR研究进展[J]. 环境科学与技术, 2015, 38(10):64-73. ZHOU H, SU Y X, DENG W Y, et al. A review of HC-SCR over metal-based zeolite catalysts[J]. Journal of Environmental Sciences, 2015, 38(10):64-73
  [18] 苏亚欣, 苏阿龙, 任立铭, 等. SO₂对甲烷在金属铁表面还原NO的反应影响[J]. 燃料化学学报, 2014, 42(3):377-384. SU Y X, SU A L, REN L M, et al. Effect of SO₂ on NO reduction by methane over iron[J]. Journal of Fuel Chemistry and Technology, 2014, 42(3):377-384.
  [19] 周皞, 苏亚欣, 戚越舟, 等. 水蒸气对甲烷在金属铁表面还原NO行为的影响[J]. 燃料化学学报, 2014, 42(11):1378-1386. ZHOU H, SU Y X, QI Y Z, et al. Effect of water vapor on NO reduction by methane over iron[J]. Journal of Fuel Chemistry and Technology, 2014, 42(11):1378-1386.
  [20] ZHOU H, SU Y X, LIAO W Y, et al. NO reduction by propane over monolithic cordierite-based Fe/Al₂O₃ catalyst:Reaction mechanism and effect of H₂O and SO₂[J]. Fuel, 2016, 182:352-360.
  [21] 杨溪, 苏亚欣, 钱文燕, 等. Fe-Ag/Al₂O₃催化丙烯还原NO的实验研究[J]. 燃料化学学报, 2017, 45(11):1365-1375. YANG X, SU Y X, QIAN W Y, et al. Experimental study on selective catalytic reduction of NO by C₃H₆ over Fe-Ag/Al₂O₃ catalysts[J]. Journal of Fuel Chemistry and Technology, 2017, 45(11):1365-1375.
  [22] 钱文燕, 苏亚欣, 杨溪, 等. Fe/Al-PILC催化C₃H₆选择性还原NO的实验研究[J]. 燃料化学学报, 2017, 45(12):1499-1507. QIAN W Y, SU Y X, YANG X, et al. Experimental study on selective catalytic reduction of NO with propene over iron based catalysts supported on aluminum pillared clays[J]. Journal of Fuel Chemistry and Technology, 2017, 45(12):1499-1507.
  [23] 李前程, 苏亚欣, 董士林, 等. Fe-PILC在贫燃条件下催化丙烯选择性还原NO_x[J]. 燃料化学学报, 2018, 46(10):1240-1248. LI Q C, SU Y X, DONG S L, et al. Fe-PILC for selective catalytic reduction of NO_x by propene under lean-burn conditions[J]. Journal of Fuel Chemistry and Technology, 2018, 46(10):1240-1248.
  [24] LONG R Q, YANG R T. Selective catalytic reduction of NO with NH₃ over Fe³⁺-exchanged mordenite (Fe-MOR):Catalytic performance, characterization, and mechanism study[J]. Journal of Catalysis, 2002, 207(2):274-285.
  [25] DEVADAS M, KRCER O, ELSNER M, et al. Characterization and catalytic investigation of Fe-ZSM5 for urea-SCR[J]. Catalysis Today, 2007, 119(1/2/3/4):137-144.
  [26] LONG R Q, YANG R T. Catalytic performance of Fe-ZSM-5 catalysts for selective catalytic reduction of nitric oxide by ammonia[J]. Journal of Catalysis, 1999, 188(2):332-339.
  [27] XUE T S, LI R, GAO Y S, et al. Iron mesh-supported vertically aligned Co-Fe layered double oxide as a novel monolithic catalyst for catalytic oxidation of toluene[J]. Chemical Engineering Journal, 2020, 384:123284.
  [28] SMEETS P J, MENG Q G, CORTHALS S, et al. Co-ZSM-5 catalysts in the decomposition of N₂O and the SCR of NO with CH₄:Influence of preparation method and cobalt loading[J]. Applied Catalysis B:Environmental, 2008, 84(3/4):505-513.
  [29] WANG X, CHEN H Y, SACHTLER W M H. Catalytic reduction of NO_x by hydrocarbons over Co/ZSM-5 catalysts prepared with different methods[J]. Applied Catalysis B:Environmental, 2000, 26(4):L227-L239.
  [30] QI G S, YANG R T. Selective catalytic oxidation (SCO) of ammonia to nitrogen over Fe/ZSM-5 catalysts[J]. Applied Catalysis A:General, 2005, 287(1):25-33.
  [31] FIERRO G, MORETTI G, FERRARIS G, et al. A Mössbauer and structural investigation of Fe-ZSM-5 catalysts:Influence of Fe oxide nanoparticles size on the catalytic behavior for the NO-SCR by C₃H₈[J]. Applied Catalysis B:Environmental, 2011, 102(1/2):215-223.
  [32] ZHANG H Y, LI N, LI L, et al. Selective catalytic reduction of NO with CH₄ Over In-Fe/sulfated zirconia catalysts[J]. Catalysis Letters, 2011, 141:1491-1497.
  [33] MOKAYA R, JONES W. Pillared clays and pillared acid-activated clays:A comparative-study of physical, acidic, and catalytic properties[J]. Journal of Catalysis, 1995, 153(1):76-85.
  [34] MHAMDI M, KHADDAR-ZINE S, GHORBEL A. Influence of the cobalt salt precursors on the cobalt speciation and catalytic properties of H-ZSM-5 modified with cobalt by solid-state ion exchange reaction[J]. Applied Catalysis A:General, 2009, 357(1):42-50.
  [35] PIETERSE J A Z, BRINK R W V D, BOONEXELD S, et al. Influence of zeolite structure on the activity and durability of Co-Pd-zeolite catalysts in the reduction of NO_x with methane[J]. Applied Catalysis B:Environmental, 2003, 46(2):239-250.
  [36] PIETROWSKI M, ZIELIŃSKI M, ALWIN E, et al. Cobalt-doped magnesium fluoride as a support for platinum catalysts:The correlation of surface acidity with hydrogenation activity[J]. Journal of Catalysis, 2019, 378:298-311.
  [37] DORADO F, LUCAS A D, GARCIA P B, et al. Preparation of Cu-ion-exchanged Fe-PILCs for the SCR of NO by propene[J]. Applied Catalysis B:Environmental, 2006, 65(3/4):175-184.