Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Low-temperature co-purification of NOx and Hg0 from simulated flue gas by CexZryMnzO2/r-Al2O3: the performance and its mechanism

  • 213 Accesses

  • 3 Citations


In this study, series of CexZryMnzO2/r-Al2O3 catalysts were prepared by impregnation method and explored to co-purification of NOx and Hg0 at low temperature. The physical and chemical properties of the catalysts were investigated by XRD, BET, FTIR, NH3-TPD, H2-TPR, and XPS. The experimental results showed that 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3 yielded higher conversion on co-purification of NOx and Hg0 than the other prepared catalysts at low temperature, especially at 200–300 °C. 91% and 97% convert rate of NOx and Hg0 were obtained, respectively, when 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3 catalyst was used at 250 °C. Moreover, the presence of H2O slightly decreased the removal of NOx and Hg0 owing to the competitive adsorption of H2O and Hg0. When SO2 was added, the removal of Hg0 first increased slightly and then presented a decrease due to the generation of SO3 and (NH4)2SO4. The results of NH3-TPD indicated that the strong acid of 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3 improved its high-temperature activity. XPS and H2-TPR results showed there were high-valence Mn and Ce species in 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3, which could effectively promote the removal of NOx and Hg0. Therefore, the mechanisms of Hg0 and NOx removal were proposed as Hg (ad) + [O] → HgO (ad), and 2NH3/NH4+ (ad) + NO2 (ad) + NO (g) → 2 N2 + 3H2O/2H+, respectively.

This is a preview of subscription content, log in to check access.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11


  1. Benson SA, Laumb JD, Crocker CR, Pavlish JH (2005) SCR catalyst performance in flue gases derived from subbituminous and lignite coals. Fuel Process Technol 86:577–613

  2. Buciuman F, Patcas F, Craciun R, Zahn D (1999) Chem inform abstract: vibrational spectroscopy of bulk and supported manganese oxides. Phys Chem Chem Phys 1:185–190

  3. Cao F, Xiang J, Su S, Wang PY, Sun LS, Hu S, Lei SY (2014) The activity and characterization of MnOx–CeO2–ZrO2/γ-Al2O3 catalysts for low temperature selective catalytic reduction of NO with NH3. Che Eng J 243:347–354

  4. Cao F, Xiang J, Su S, Wang PY, Hu S, Sun L (2015) Ag modified Mn-Ce/γ-Al2O3 catalyst for selective catalytic reduction of NO with NH3 at low-temperature. Fuel Process Technol 135:66–72

  5. Chang HZ, Li JH, Chen XY, Ma L, Yang SJ (2012) Effect of Sn on MnOx–CeO2 catalyst for SCR of NOX by ammonia: enhancement of activity and remarkable resistance to SO2. Catal Commun 27:54–57

  6. Chang HZ, Wu QR, Zhang T, Li MG, Sun XX, Li JH, Duan L, Hao JK (2015) Design strategies for CeO2-MoO3 catalysts for DeNOx and Hg0 oxidation in the presence of HCl: the significance of the surface acid-base properties. Environ Sci Technol 49:12388–12394

  7. Chen ZH, Wang FR, Li H, Yang Q, Wang LF, Li XH (2012) Low-temperature selective catalytic reduction of NOx with NH3 over Fe-Mn mixed-oxide catalysts containing Fe3Mn3O8 phase. Ind Eng Chem Res 51:202–212

  8. Deng H, Yu YB, Liu FD, Ma JZ, Zhang Y, He H (2014) Nature of Ag species on Ag/γ-Al2O3: a combined experimental and theoretical study. ACS Catal 4:2776–2784

  9. Du XS, Gao X, Cui LW, Fu YC, Luo ZY, Cen KF (2012) Investigation of the effect of Cu addition on the SO2-resistance of a Ce-Ti oxide catalyst for selective catalytic reduction of NO with NH3. Fuel 92:49–55

  10. Esteves P, Wu Y, Dujardin C, Dongare MK, Granger P (2011) Ceria–zirconia mixed oxides as thermal resistant catalysts for the decomposition of nitrous oxide at high temperature. Catal Today 176:453–457

  11. Ettireddy P, Ettireddy N, Mamedov S, Boolchand P, Smirniotis P (2007) Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl Catal B 76:123–134

  12. Fan XP, Li CT, Zeng GM, Gao Z, Chen L, Zhang W, Gao HL (2010) Removal of gas-phase element mercury by activated carbon fiber impregnated with CeO2. Energy Fuel 24:4250–4254

  13. Fernández-Miranda N, Lopez-Anton MA, Díaz-Somoano M, Martínez-Tarazona MR (2016) Mercury oxidation in catalysts used for selective reduction of NOx (SCR) in oxy-fuel combustion. Chem Eng J 285:77–82

  14. Gu TT, Liu Y, Weng XL, Wang HQ, Wu ZB (2010) The enhanced performance of ceria with surface sulfation for selective catalytic reduction of NO by NH3. Catal Commun 12:310–313

  15. Gunnarsson F, Granlund MZ, Englund M, Dawody J, Pettersson LJ, Härelind H (2015) Combining HC-SCR over Ag/Al2O3 and hydrogen generation over Rh/CeO2-ZrO2 using biofuels: an integrated system approach for real applications. Appl Catal B 162:583–592

  16. Guo RT, Zhen WL, Pan WG, Zhou Y, Hong JN, Xu HJ, Jin Q, Ding CG, Guo SY (2014) Effect of Cu doping on the SCR activity of CeO2 catalyst prepared by citric acid method. J Ind Eng Chem 20:1577–1580

  17. He C, Shen B, Chen J, Cai J (2014) Adsorption and oxidation of elemental mercury over Ce-MnOx/Ti-PILCs. Sci Technol 48:7891–7898

  18. He YY, Ford ME, Zhu MH, Liu QC, Tumuluri U, Wu ZL, Wachs IE (2016) Influence of catalyst synthesis method on selective catalytic reduction (SCR) of NO by NH3 with V2O5-WO3/TiO2 catalysts. Appl Catal B 193:141–150

  19. Hu JL, Ying Q, Wang YG, Zhang HL (2015) Characterizing multi-pollutant air pollution in China: comparison of three air quality indices. Environ Int 84:17–25

  20. Hutson ND, Attwood BC, Scheckel KG (2007) XAS and XPS characterization of mercury binding on brominated activated carbon. Environ Sci Technol 41:1747–1752

  21. Jampaiah D, Ippolito SJ, Sabri YM, Tardio J, Selvakannan P, Nafady A, Reddy BM, Bhargava S (2016) Ceria–zirconia modified MnOx catalysts for gaseous elemental mercury oxidation and adsorption. Catal Sci Technol 6:1792–1803

  22. Jin RB, Liu Y, Wang Y, Cen WL, Wu ZB, Wang HQ, Weng XL (2014) The role of cerium in the improved SO2 tolerance for NO reduction with NH3 over Mn-Ce/TiO2 catalyst at low temperature. Appl Catal B 148–149:582–588

  23. Karami A, Salehi V (2012) The influence of chromium substitution on an iron–titanium catalyst used in the selective catalytic reduction of NO. J Catal 292:32–43

  24. Kim J, Myeong W, Ihm S (2009) Characteristics of CeO2-ZrO2 mixed oxide prepared by continuous hydrothermal synthesis in supercritical water as support of Rh catalyst for catalytic reduction of NO by CO. J Catal 263:123–133

  25. Kim JR, Lee KY, Suh MJ, Ihm SK (2012) Ceria–zirconia mixed oxide prepared by continuous hydrothermal synthesis in supercritical water as catalyst support. Catal Today 185:25–34

  26. Kima YJ, Kwona HJ, Nama IS, Choung JW, Kil JK, Kimb HJ, Chac MS, Yeoc GK (2010) High deNOx performance of Mn/TiO2. Catal Today 151:244–250

  27. Lee W, Bae GN (2009) Removal of elemental mercury (Hg0) by nanosized V2O5/TiO2 catalysts. Environ Sci Technol 43:1522–1527

  28. Lee KJ, Kumar PA, Maqbool MS, Rao KN, Song KH, Ha HP (2013) Ceria added Sb-V2O5/TiO2 catalysts for low temperature NH3 SCR: physico-chemical properties and catalytic activity. Appl Catal B 142–143:705–717

  29. Leitenbur C, Trovarelli A, Llorca J, Cavani F, Bini G (1996) The effect of doping CeO2 with zirconium in the oxidation of isobutene. Appl Catal A 139:161–173

  30. Li J, Pan YB, Xiang CS, Ge QM, Guo JK (2006) Low temperature synthesis of ultrafine α-Al2O3 powder by a simple aqueous sol–gel process. Ceram Int 32:587–591

  31. Li Y, Murphy PD, Wu CY, Powers KW, Bonzongo JCJ (2008) Development of silica/vanadia/titania catalysts for removal of elemental mercury from coal-combustion flue gas. Environ Sci Technol 42:5304–5313

  32. Li JH, Chang HZ, Ma L, Hao JM, 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

  33. Li HL, Wu CY, Li Y, Zhang JY (2012) Superior activity of MnOx-CeO2/TiO2 catalyst for catalytic oxidation of elemental mercury at low flue gas temperatures. Appl Catal B 111:381–388

  34. Li HL, Wu SK, Li LQ, Wang J, Ma WW, Shih K (2015) CuO–CeO2/TiO2 catalyst for simultaneous NO reduction and Hg0 oxidation at low temperatures. Catal Sci Technol 5:5129–5138

  35. Li SJ, Wang XX, Tan S, Shi Y, Li W (2017) CrO3 supported on sargassum-based activated carbon as low temperature catalysts for the selective catalytic reduction of NO with NH3. Fuel 191:511–517

  36. Lian ZH, Liu FD, He H (2014) Enhanced activity of Ti-modified V2O5/CeO2 catalyst for the selective catalytic reduction of NOx with NH3. Ind Eng Chem Res 53:19503–19511

  37. Lietti L, Alemany JL, Forzatti P, Busca G, Ramis G, Giamello E, Bregani F (1996) Reactivity of V2O5-WO3/TiO2 catalysts in the selective catalytic reduction of nitric oxide by ammonia. Catal Today 29:143–148

  38. Liu SW, Zhou JC, Liu RX (2014) Preparation of nano t-ZrO2 particle by the integrated process of high-gravity field and hydrothermal crystallization. Adv Mater Res 881-883:933–939

  39. Liu YX, Wang Q, Pan JF (2016) Novel process on simultaneous removal of nitric oxide and sulfur dioxide using vacuum ultraviolet (VUV)-activated O2/H2O/H2O2 system in a wet VUV-spraying reactor. Environ Sci Technol 50:12966–12975

  40. Liu YX, Xu W, Pan JF, Wang Q (2017) Oxidative removal of NO from flue gas using ultrasound, Mn2+/Fe2+ and heat coactivation of Oxone in an ultrasonic bubble reactor. Chem Eng J 326:1166–1176

  41. Liu YX, Liu ZY, Wang Y, Yin YS, Pan JF, Zhang J, Wang Q (2018) Simultaneous absorption of SO2 and NO from flue gas using ultrasound/Fe2+/heat coactivated persulfate system. J Hazard Mater 342:326–334

  42. Ludvigsson M, Lindgren J, Tegenfeldt J (2001) Incorporation and characterisation of oxides of manganese, cobalt and lithium into Nafion 117 membranes. J Mater Chem 11:1269–1276

  43. Ma Z, Wu XD, Si ZC, Weng D, Ma J, Xu TF (2015) Impacts of niobia loading on active sites and surface acidity in NbOx/CeO2-ZrO2 NH3-SCR catalysts. Appl Catal B 179:380–394

  44. Madier Y, Descorme C, Le Govic AM, Duprez D (1999) Oxygen mobility in CeO2 and CexZr(1 - x)O2 compounds: study by CO transient oxidation and 18O/16O isotopic exchange. J Phys Chem B 103:10999–11006

  45. Mullins D, Overbury SH, Huntley DR (1998) Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces. Surf Sci 409:307–319

  46. Prabhakaran T, Mangalaraja RV, Denardin JC, Jimenez JA (2017) The effect of reaction temperature on the structural and magnetic properties of nano CoFe2O4. Ceram Int 43:5599–5606

  47. Presto AA, Granite EJ (2006) Survey of catalysts for oxidation of mercury in flue gas. Environ Sci Technol 40:5601–5609

  48. Qi GS, Yang RT (2003) Low-temperature selective catalytic reduction of NO with NH3 over iron and manganese oxides supported on titania. Appl Catal B 44:217–225

  49. Qi GS, Yang RT, Chang RS (2004) MnOX-CeO2 mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH3 at low temperatures. Appl Catal B 51:93–106

  50. Qu L, Li CT, Zeng GM, Zhang MY, Fu MF, Ma JF, Zhan FM, Luo DQ (2014) Support modification for improving the performance of MnOx–CeOy/r-Al2O3 in selective catalytic reduction of NO by NH3. Chem Eng J 242:76–85

  51. Rallo M, Lopez-Anton M, Contreras ML, Maroto-Valeret M (2012) Mercury policy and regulations for coal-fired power plants. Environ Sci Pollut Res Int 19:1084–1096

  52. Shen BX, Zhang XP, Ma HQ, Yao Y, Liu T (2013) A comparative study of Mn/CeO2, Mn/ZrO2 and Mn/Ce-ZrO2 for low temperature selective catalytic reduction of NO with NH3 in the presence of SO2 and H2O. J Environ Sci 25:791–800

  53. Shen BX, Wang YY, Wang FM, Liu T (2014) The effect of Ce–Zr on NH3-SCR activity over MnOx(0.6)/Ce0.5Zr0.5O2 at low temperature. Chem Eng J 236:171–180

  54. Shimizu T (1992) Partial oxidation of hydrocarbons and oxygenated compounds on perovskite oxides. Catal Rev 34:355–371

  55. Su YX, Fan BX, Wang LS, Liu YF, Huang BC, Fu ML, Chen LM, Ye DQ (2013) MnOx supported on carbon nanotubes by different methods for the SCR of NO with NH3. Catal Today 201:115–121

  56. Tang XF, Li YG, Huang XM, Xu YD, Zhu HQ, Wang JG, Shen WJ (2006) Manganese-cerium mixed oxide catalysts for complete oxidation of formaldehyde: effect of preparation method and calcination temperature. Appl Catal B 62:265–273

  57. Tang XF, Chen JL, Huang XM, Xu YD, Shen WJ (2008) Pt/MnOx–CeO2 catalysts for the complete oxidation of formaldehyde at ambient temperature. Appl Catal B 81:115–121

  58. Terribilea D, Trovarellia A, Llorcab J, Leitenburga C, Dolcetti G (1998) The preparation of high surface area CeO2-ZrO2 mixed oxides by a surfactant-assisted approach. Catal Today 43:79–88

  59. Trawczyński J, Bielak B, Miśta W (2005) Oxidation of ethanol over supported manganese catalysts—effect of the carrier. Appl Catal B 55:277–285

  60. Wan Q, Duan L, He KB, Li JH (2011) Removal of gaseous elemental mercury over a CeO2–WO3/TiO2 nanocomposite in simulated coal-fired flue gas. Chem Eng J 170:512–517

  61. Wang XH, Lu GZ, Guo Y, Xue YY, Jiang LZ, Guo YL, Zhang ZG (2007) Structure, thermal-stability and reducibility of Si-doped Ce-Zr-O solid solution. Catal Today 126:412–419

  62. Wang HQ, Cao S, Cen CP, Chen XB, Wu ZB (2013) Structure–activity relationship of titanate nanotube-confined ceria catalysts in selective catalytic reduction of NO with ammonia. Catal Lett 143:1312–1318

  63. Wang PY, Su S, Xiang J, You HW, Cao F, Sun LS, Hu S, Zhang Y (2014) Catalytic oxidation of Hg0 by MnOx–CeO2/r-Al2O3 catalyst at low temperatures. Chemosphere 101:49–54

  64. Wang YY, Shen BX, He C, Yue SJ, Wang FM (2015) Simultaneous removal of NO and Hg0 from flue gas over Mn–Ce/Ti-PILCs. Environ Sci Technol 49:9355–9363

  65. Wang B, Chi C, Xu M, Wang C, Meng D (2017) Plasma-catalytic removal of toluene over CeO2-MnOx catalysts in an atmosphere dielectric barrier discharge. Chem Eng J 322:679–692

  66. Wu ZB, Jiang BQ, Liu Y, Zhao WR, Guan BH (2007) Experimental study on a low-temperature SCR catalyst based on MnO(x)/TiO2 prepared by sol-gel method. J Hazard Mater 145:488–492

  67. Xie GY, Liu ZY, Zhu ZP, Liu QY, Ge J, Huang Z (2004) Simultaneous removal of SO2 and NOx from flue gas using a CuO/Al2O3 catalyst sorbent: I. Deactivation of SCR activity by SO2 at low temperatures. J Catal 224:36–41

  68. Xie JK, Yan NQ, Yang SJ, Qu Z, Chen WM, Zhang WQ, Li KH, Liu P, Jia JP (2012) Synthesis and characterization of nano-sized Mn–TiO2 catalysts and their application to removal of gaseous elemental mercury. Res Chem Intermed 38:2511–2522

  69. Xu WQ, Yu YB, Zhang CB, He H (2008) Selective catalytic reduction of NO by NH3 over a Ce/TiO2 catalyst. Catal Commun 9:1453–1457

  70. Xu WQ, He H, Yu YB (2009) Deactivation of a Ce/TiO2 catalyst by SO2 in the selective catalytic reduction of NO by NH3. J Phys Chem C 113:4426–4432

  71. Xu HD, Zhang QL, Qiu CT, Lin T, Gong MC, Chen YQ (2012) Tungsten modified MnOx-CeO2/ZrO2 monolith catalysts for selective catalytic reduction of NOx with ammonia. Chem Eng Sci 76:120–128

  72. Xu HD, Wang Y, Cao Y, Fang ZT, Lin T, Gong MC, Chen YQ (2014) Catalytic performance of acidic zirconium-based composite oxides monolithic catalyst on selective catalytic reduction of NOx with NH3. Chem Eng J 240:62–73

  73. Xu HM, Qu Z, Zong CX, Huang WJ, Quan FQ, Yan NQ (2015) MnOx/graphene for the catalytic oxidation and adsorption of elemental mercury. Environ Sci Technol 49:6823–6830

  74. Yang SJ, Guo YF, Yan NQ, Qu Z, Xie JK, Yang C, Jia JP (2011) Capture of gaseous elemental mercury from flue gas using a magnetic and sulfur poisoning resistant sorbent Mn/γ-Fe2O3 at lower temperatures. J Hazard Mater 186:508–515

  75. Yang J, Yang Q, Sun J, Liu QC, Zhao D, Gao W, Liu L (2015) Effects of mercury oxidation on V2O5–WO3/TiO2 catalyst properties in NH3-SCR process. Catal Commun 59:78–82

  76. Yang W, Liu YX, Wang Q, Pan JF (2017a) Removal of elemental mercury from flue gas using wheat straw chars modified by Mn-Ce mixed oxides with ultrasonic-assisted impregnation. Chem Eng J 326:169–181

  77. Yang YJ, Liu J, Zhang BK, Zhao YC, Chen XY, Shen FH (2017b) Experimental and theoretical studies of mercury oxidation over CeO2-WO3/TiO2 catalysts in coal-fired flue gas. Chem Eng J 317:758–765

  78. Yang ZQ, Li HL, Liu X, Li P, Yang JP, Lee PH, Shih K (2018) Promotional effect of CuO loading on the catalytic activity and SO2 resistance of MnOx/TiO2 catalyst for simultaneous NO reduction and Hg0 oxidation. Fuel 1:79–88

  79. Yu CL, Huang BC, Dong LF, Chen F, Liu XQ (2017) In situ FT-IR study of highly dispersed MnOx/SAPO-34 catalyst for low-temperature selective catalytic reduction of NOx by NH3. Catal Today 281:610–620

  80. Zhang YP, Zhu XQ, Shen K, Xu HT, Sun KQ, Zhou CC (2012) Influence of ceria modification on the properties of TiO2–ZrO2 supported V2O5 catalysts for selective catalytic reduction of NO by NH3. J Colloid Interface Sci 376:233–238

  81. Zhang YP, Guo WQ, Wang LF, Song M, Yang LJ, Shen K, Xu HT, Zhou CC (2015) Characterization and activity of V2O5-CeO2/TiO2-ZrO2 catalysts for NH3-selective catalytic reduction of NOx. Chin J Catal 36:1701–1710

  82. Zhang Y, Yang JP, Yu XH, Sun P, Zhao YC, Zhang JY, Chen G, Yao H, Zheng CG (2017) Migration and emission characteristics of Hg in coal-fired power plant of China with ultra low emission air pollution control devices. Fuel Process Technol 158:272–280

  83. Zhao Y, Hao RL, Qi M (2015) Integrative process of preoxidation and absorption for simultaneous removal of SO2, NO and Hg0. Chem Eng J 269:159–167

  84. Zhao LK, Li CT, Wang Y, Wu H, Gao L, Zhang J, Zeng GM (2016a) Simultaneous removal of elemental mercury and NO from simulated flue gas using a CeO2 modified V2O5-WO3/TiO2 catalyst. Catal Sci Technol 6:6076–6086

  85. Zhao LK, Li CT, Li SH, Wang Y, Zhang JY, Wang T, Zeng GM (2016b) Simultaneous removal of elemental mercury and NO in simulated flue gas over V2O5/ZrO2-CeO2 catalyst. Appl Catal B 198:420–430

  86. Zhou ZJ, Liu XW, Zhao B, Shao HZ, Xu YS, Xu MH (2016a) Elemental mercury oxidation over manganese-based perovskite-type catalyst at low temperature. Chem Eng J 288:701–710

  87. Zhou ZJ, Liu XW, Liao ZQ, Shao HZ, Lv C, Hu YC, Xu MH (2016b) Manganese doped CeO2-ZrO2 catalyst for elemental mercury oxidation at low temperature. Fuel Process Technol 152:285–293

Download references


This work was supported by the National Key R&D Program of China (No. 2017YFC0210303), Joint Funds of the National Natural Science Foundation of China (No. U1560110), Beijing Science and Technology Project (No. D161100004516001), and Fundamental Research Funds for the Central Universities.

Author information

Correspondence to Yi Xing or Jianjun Wei.

Additional information


• 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3 catalyst yielded over 90 and 97% conversion on co-catalytic NOx and Hg0 at 250 °C, respectively.

• 10% Ce0.2Zr0.3Mn0.5O2/r-Al2O3 was well behaved in the presence of SO2 and H2O.

• The shift among Mn4+ and Mn3+ was beneficial for the generation of oxygen species.

• Hg0 and NO2 were converted to HgO and N2, respectively by [O] and 2NH3/NH4+.

Responsible editor: Bingcai Pan

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Lu, P., Yue, H., Xing, Y. et al. Low-temperature co-purification of NOx and Hg0 from simulated flue gas by CexZryMnzO2/r-Al2O3: the performance and its mechanism. Environ Sci Pollut Res 25, 20575–20590 (2018). https://doi.org/10.1007/s11356-018-2199-4

Download citation


  • Low temperature
  • Co-purification
  • NOx and Hg0
  • Ce0.2Zr0.3Mn0.5O2
  • Performance and mechanism