Abstract
Simultaneous oxidation of Hg0 and NH3-SCR of NO by catalyst is one of the key methods for co-purification of coal-fired flue gas. Till now, the interaction between the oxidation of Hg0 and NH3-SCR of NO and its mechanism have not clarified. In this study, a series of nanophase Ce x Zr y Mn z O2 was prepared for the simultaneous oxidation of Hg0 and NH3-SCR of NO at low temperature. The catalysts were characterized using surface area analysis, X-ray diffraction, temperature-programmed techniques, and several types of microscopy and spectroscopy. The experimental results indicated that the Ce0.47Zr0.22Mn0.31O2 exhibited superior Hg0 removal efficiency (> 99%) and NO conversion efficiency (> 90%) even at 150 °C, and it also exhibited a good durability in the presence of SO2 and H2O. The excellent performance of Ce0.47Zr0.22Mn0.31O2 on co-purifying Hg0 and NO was due to the stronger synergistic effects of Ce-Zr-Mn in Ce0.47Zr0.22Mn0.31O2 than that of the others, which was illustrated by the characterization results of XPS, XRD, and FT-IR. Moreover, it was found that the NO conversion of Ce0.47Zr0.22Mn0.31O2 could be slightly influenced by Hg0 and was decreased about 4% to the max, while that of Hg0 could rarely be affected by the selected catalytic reduction process of NO. It might be due to the co-purification mechanism of NO and Hg0. The mechanism of the simultaneous oxidation of Hg0 and NH3-SCR of NO was mainly due to the synergetic effect on the mobility of surface oxygen and the activation of lattice oxygen of Ce0.47Zr0.22Mn0.31O2. The effect of the oxidation of Hg0 on the NH3-SCR of NO was mainly due to the absorbed Hg0/Hg2+ on the surface of Ce0.47Zr0.22Mn0.31O2, which attenuated the formation of NH3(ad), −NH2(ad), and NH4+ on its acid sites. Similarly, the NH3-SCR of NO process could hardly influence the oxidation of Hg0 when NO and Hg0 were co-purified.
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Aghazadeha M, Maragheh MG, Ganjali MR, Norouzi P, Faridbod F (2016) Electrochemical preparation of MnO2 nanobelts through pulse base-electrogeneration and evaluation of their electrochemical performance. Appl Surf Sci 364:141–147
Bin F, Song C, Lv G, Song J, Wu S, Li X (2014) Selective catalytic reduction of nitric oxide with ammonia over zirconium-doped copper/ZSM-5 catalysts. Appl Catal B Environ 150:532–543
Boningari T, Smirniotis PG (2016) Impact of nitrogen oxides on the environment and human health: Mn-based materials for the NOx abatement. Cur Opin Chem Eng 13:133–141
Boningari T, Ettireddy PR, Somogyvari A, Liu Y, Vorontsov A, Mcdonald CA et al (2015) Influence of elevated surface texture hydrated titania on Ce-doped Mn/Tio2, catalysts for the low-temperature SCR of NOx, under oxygen-rich conditions. J Catal 325:145–155
Chi G, Shen B, Yu R, He C, Zhang X (2017) Simultaneous removal of NO and Hg0 over Ce-Cu modified V2O5/TiO2 based commercial SCR catalysts. J Hazard Mater 330:83–92
Ding S, Liu F, Shi X, Liu K, Lian Z, Xie L, He H (2015) Significant promotion effect of Mo additive on novel Ce-Zr mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. ACS Appl Mater Interfaces 7:9497
Ettireddy PR, Ettireddy N, Mamedov S, Boolchand P, Smirniotis PG (2007) Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl Catal B Environ 76:123–134
Ettireddy PR, Ettireddy N, Boningari T, Pardemann R, Smirniotis PG (2012) Investigation of the selective catalytic reduction of nitric oxide with ammonia over Mn/TiO2, catalysts through transient isotopic labeling and in situ, FT-IR studies. J Catal 292:53–63
Fan X, Li C, Zeng G, Zhang X, Tao S, Lu P, Tan Y, Luo D (2012) Hg0 removal from simulated flue gas over CeO2/HZSM-5. Energy Fuel 26:2082–2089
Fang J, Bi X, Si D, Jiang Z, Huang W (2007) Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides. Appl Surf Sci 253:8952–8961
Fang P, Cen CP, Wang XM, Tang ZJ, Tang ZX, Chen DS (2013) Simultaneous removal of SO2, NO and Hg0 by wet scrubbing using urea + KMnO4 solution. Fuel Process Technol 106:645–653
Gao X, Jiang Y, Zhong Y, Luo Z, Cen K (2010) The activity and characterization of CeO2-TiO2 catalysts prepared by the sol-gel method for selective catalytic reduction of NO with NH3. J Hazard Mater 174:734–739
He J, Reddy GK, Thiel SW, Smirniotis PG, Pinto NG (2011) Ceria-modified manganese oxide/titania materials for removal of elemental and oxidized mercury from flue gas. J Phys Chem C 115:24300–24309
He J, Reddy GK, Thiel SW, Smirniotis P, Pinto NG (2013) Simultaneous removal of elemental mercury and no from flue gas using CeO2 modified MnOx/TiO2 materials. Energy Fuel 27:4832–4839
He C, Shen B, Chen J, Cai J (2014) A novel Ce-Ta mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Environ Sci Technol 48:7891–7898
Lei J, Sreekanth PM, Smirniotis PG, Thiel SW, Pinto NG (2008) Manganese oxide/titania materials for removal of no, x, and elemental mercury from flue gas. Energy Fuel 22:2299–2306
Li J, Chang H, Ma L, Hao J, Yang RT (2011) Low-temperature selective catalytic reduction of NOx, with NH3, over metal oxide and zeolite catalysts—a review. Catal Today 175:147–156
Li H, Wu S, Li L, Wang J, Ma W, Shih K (2015) CuO-CeO2/TiO2 catalyst for simultaneous NO reduction and Hg0 oxidation at low temperatures. Catal Sci Technol 5:5129–5138
Lian Z, Liu F, He H (2014) Enhanced activity of Ti-modified V2O5/CeO2 catalyst for the selective catalytic reduction of NOx with NH3. Ind Eng Chem Res 53:19506–19511
Liu C, Chen L, Chang H, Ma L, Peng Y, Arandiyan H, Li J (2013) Characterization of CeO2-WO3 catalysts prepared by different methods for selective catalytic reduction of NOx with NH3. Catal Commun 40:145–148
Liu B, Huang C, Ke Y, Wang W, Kuo H, Lin D, Lin V, Lin S (2017) Enhanced selective catalytic reduction of NO over Mn-Ce catalysts with the acetic-acid-chelated titania support at low temperature. Appl Catal A Gen 538:74–80
Ma Y, Mu B, Yuan D, Zhang H, Xu H (2017) Design of MnO2/CeO2-MnO2 hierarchical binary oxides for elemental mercury removal from coal-fired flue gas. J Hazard Mater 333:186–193
Marzouk MA, ElBatal FH, Morsi RMM (2017) Optical and FTIR absorption spectra of CeO2-doped cadmium borate glasses and effects of gamma irradiation. SILICON 9:105–110
Mullins DR, Overbury SH, Huntley DR (1998) Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces. Surf Sci 409:307–319
Ozkan US, Cai Y, Kumthekar MW (1994) Investigation of the reaction pathways in selective catalytic reduction of no with NH3 over V2O5 catalysts: isotopic labeling studies using 18O2, 15NH3, 15NO, and 15N18O1. J Catal 149:375
Padmanathan N, Selladurai S (2014) Electrochemical capacitance of porous NiO-CeO2 binary oxide synthesized via sol–gel technique for supercapacitor. Ionics 20:409–420
Pappas DK, Boningari T, Boolchand P, Smirniotis PG (2016) Novel manganese oxide confined interweaved titania nanotubes for the low-temperature selective catalytic reduction (SCR) of NOX, by NH3. J Catal 334:1–13
Peng Y, Qu R, Zhang X, Li J (2013) The relationship between structure and activity of MoO3-CeO2 catalysts for NO removal: influences of acidity and reducibility. Chem Commun 49:6215–6217
Picasso G, Gutierrez M, Pina MP, Herguido J (2007) Preparation and characterization of Ce-Zr and Ce-Mn based oxides for n-hexane combustion: application to catalytic membrane reactors. Chem Eng J 126:119–130
Qu R, Gao X, Cen K, Li J (2013a) Relationship between structure and performance of a novel cerium-niobium binary oxide catalyst for selective catalytic reduction of NO with NH3. Appl Catal B Environ 142–143:290–297
Qu R, Gao X, Li KJ (2013b) Relationship between structure and performance of a novel cerium-niobium binary oxide catalyst for selective catalytic reduction of NO with NH3. Appl Catal B Environ 142–143:290–297
Reddy BM, Khan A, Lakshmanan P, Aouine M, Loridant S, Volta JC (2005) Structural characterization of nanosized CeO2-SiO2, CeO2-TiO2, and CeO2-ZrO2 catalysts by XRD, Raman, and HREM techniques. J Phys Chem B 109:3355–3363
Reddy GK, He J, Thiel SW, Pinto NG, Smirniotis PG (2015) Sulfur-tolerant Mn-Ce-Ti sorbents for elemental mercury removal from flue gas: mechanistic investigation by XPS. J Phys Chem C 119:8634–8644
Rivas B, López-Fonseca R, González-Velasco JR, Gutiérrez-Ortiz JI (2008) Adsorption and oxidation of trichloroethylene on Ce/Zr mixed oxides: in situ FTIR and flow studies. Catal Commun 9:2018–2021
Santos MLD, Lima RC, Riccardi CS, Tranquilin RL, Bueno PR, Varela JA, Longo E (2008) Preparation and characterization of ceria nanospheres by microwave-hydrothermal method. Mater Lett 62:4509–4511
Schmitt J, Flemming HC (1998) FTIR-spectroscopy in microbial and material analysis. Int Biodeterior Biodegrad 41:1–11
Sjostrom S, Durham M, Bustard CJ, Martin C (2010) Activated carbon injection for mercury control: overview. Fuel 89:1320–1322
Smirniotis PG, Peña DA, Uphade BS (2001) Low-temperature selective catalytic reduction (SCR) of NO with NH(3) by using Mn, Cr, and Cu oxides supported on hombikat Tio(2). Angew Chem Int Ed Engl 40:2479–2482
Song Z, Ning P, Zhang Q, Li H, Zhang J, Wang Y, Liu X, Huang Z (2016) Activity and hydrothermal stability of CeO2-ZrO2-WO3 for the selective catalytic reduction of NOx with NH3. J Environ Sci 42:168–177
Tompsett DA, Parker S,C, Islam MS (2014) Surface properties of α-MnO2: relevance to catalytic and supercapacitor behavior. J Mater Chem A 2: 15509–15518.
Wang Y, Shen B, He C, Yue S, Wang F (2015) Simultaneous removal of NO and Hg0 from flue gas over Mn–Ce/Ti-PILCs. Environ Sci Technol 49:9355–9363
Wang S, Guo R, Pan W, Chen Q, Sun P, Li M, Liu S (2017) The deactivation of Ce/TiO2 catalyst for NH3-SCR reaction by alkali metals: TPD and DRIFT studies. Catal Commun 89:143–147
Watanabe S, Ma X, Song C (2009) Characterization of structural and surface properties of nanocrystalline TiO2-CeO2 mixed oxides by XRD, XPS, TPR, and TPD. J Phys Chem C 113:14249–14257
Wen X, Li C, Fan X, Gao H, Zhang W, Chen L, Zeng G, Zhao Y (2011) Experimental study of gaseous elemental mercury removal with CeO2/γ-Al2O3. Energy Fuel 25:2939–2944
Xie J, Qu Z, Yan N, Yang S, Chen W, Hu L, Huang W, Liu P (2013) Novel regenerable sorbent based on Zr–Mn binary metal oxides for flue gas mercury retention and recovery. J Hazard Mater 261:206–213
Xu H, Qu Z, Zhao S, Mei J, Quan F, Yan N (2015) Different crystal-forms of one-dimensional MnO2 nanomaterials for the catalytic oxidation and adsorption of elemental mercury. J Hazard Mater 299:86–93
Yang S, Zhu W, Jiang Z, Chen Z, Wang J (2006) The surface properties and the activities in catalytic wet air oxidation over CeO2-TiO2 catalysts. Appl Surf Sci 252:8499–8505
Yang S, Wang C, Li J, Yan N, Ma L, Chang H (2011) Low temperature selective catalytic reduction of NO with NH3 over Mn-Fe spinel: performance, mechanism and kinetic study. Appl Catal B Environ 110:71–80
Yang J, Zhao Y, Chang L, Zhang J, Zheng C (2015) Mercury adsorption and oxidation over cobalt oxide loaded magnetospheres catalyst from fly ash in oxyfuel combustion flue gas. Environ Sci Technol 49:8210–8218
Younes MK, Ghorbel A, Rives A, Hubaut R (2003) Comparative study of the acidity of sulphated zirconia supported on alumina prepared by sol-gel and impregnation methods. J Sol-Gel Sci Technol 26:677–680
Yuan Y, Zhang JY, Li HL, Li Y, Zhao YC, Zheng CG (2012) Simultaneous removal of SO2, NO and mercury using TiO2-aluminum silicate fiber by photocatalysis. Chem Eng J 192:21–28
Zhang Q, Pan W, Guo R (2013) The research of SCR catalyst for elemental mercury conversion in coal-fired flue gas. Adv Mater Res 864–867:1470–1473
Zhang L, Li L, Cao Y, Yao X, Ge C, Gao F, Deng Y, Tang C, Dong L (2015a) Getting insight into the influence of SO2 on TiO2/CeO2 for the selective catalytic reduction of NO by NH3. Appl Catal B Environ 165:589–598
Zhang T, Qu R, Su W, Li J (2015b) A novel Ce-Ta mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Appl Catal B Environ 176–177:338–346
Zhang X, Li C, Zhao L, Zhang J, Zeng G, Xie Y, Yu M (2015c) Simultaneous removal of elemental mercury and NO from flue gas byV2O5-CeO2/TiO2 catalysts. Appl Surf Sci 347:392–400
Zhang J, Li C, Zhao L, Wang T, Li S, Zeng G (2017a) A sol-gel Ti-Al-Ce-nanoparticle catalyst for simultaneous removal of NO and Hg0 from simulated flue gas. Chem Eng J 313:1535–1547
Zhang X, Cui Y, Wang J, Tan B, Li C, Zhang H, He G (2017b) Simultaneous removal of Hg0 and NO from flue gas by Co0.3-Ce0.35-Zr0.35O2 impregnated with MnOx. Chem Eng J 326:1210–1222
Zhao Y, Hao R, Qi M (2015) Integrative process of peroxidation and absorption for simultaneous removal of SO2, NO and Hg0. Chem Eng J 269:159–167
Zhao L, Li C, Li S, Wang Y, Zhang J, Wang T, Zeng G (2016a) Simultaneous removal of elemental mercury and NO in simulated flue gas over V2O5/ZrO2-CeO2catalyst. Appl Catal B Environ 198:420–430
Zhao Y, Hao R, Yuan B, Jiang J (2016b) Simultaneous removal of SO2, NO and Hg0 through an integrative process utilizing a cost-effective complex oxidant. J Hazard Mater 301:74–83
Zheng L, Liu G, Chou C (2007) The distribution, occurrence and environmental effect of mercury in Chinese coals. Sci Total Environ 384:374–383
Zhu H, Qin Z, Shan W, Shen W, Wang J (2004) Pd/CeO2-TiO2 catalyst for CO oxidation at low temperature: a TPR study with H2 and CO as reducing agents. J Catal 225:267–277
Acknowledgements
This work was supported by the National Key R&D Program of China (No. 2017YFC0210303), Beijing Science and Technology Project (No. D161100004516001), Open Fund of National Engineering Laboratory for Mobile Source Emission Control Technology (NELMS2017A14), and Fundamental Research Funds for the Central Universities.
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Wu, W., Zeng, Z., Lu, P. et al. Simultaneous oxidation of Hg0 and NH3-SCR of NO by nanophase Ce x Zr y Mn z O2 at low temperature: the interaction and mechanism. Environ Sci Pollut Res 25, 14471–14485 (2018). https://doi.org/10.1007/s11356-018-1657-3
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DOI: https://doi.org/10.1007/s11356-018-1657-3