Citation: ZHANG An-chao, ZHANG Zhi-hui, SHI Jin-ming, CHEN Guo-yan, ZHOU Chang-song, SUN Lu-shi. Effect of preparation methods on the performance of MnO_x-TiO₂ adsorbents for Hg⁰ removal and SO₂ resistance[J]. Journal of Fuel Chemistry and Technology, ;2015, 43(10): 1258-1266. shu

Effect of preparation methods on the performance of MnO_x-TiO₂ adsorbents for Hg⁰ removal and SO₂ resistance

1.
1. School of Mechanical and Power Engineering, Henan Polytechnic University, Jiaozuo 454003, China;

Corresponding author: ZHANG An-chao,
Received Date: 1 July 2015
Available Online: 23 August 2015
Fund Project: 国家自然科学基金(51306046,51166004,51376073) (51306046,51166004,51376073)河南省高校基本科研业务费(NSFRF140204) (NSFRF140204)

Aiming at the difficulty of elemental mercury (Hg⁰) removal from flue gas due to its indissolubility in water and the problem of lower SO₂ resistance performance of manganese-based adsorbent, the MnO_x-TiO₂ adsorbents prepared with impregnation (IM), sol-gel (SG) and deposition-precipitation method (DP) were employed to remove Hg⁰ in the absence and presence of SO₂. The adsorbents were characterized by N₂ adsorption-desorption, TG-DSC, XRD, TEM, H₂-TPR, and XPS techniques. The results showed that Hg⁰ removal performance over MnO_x-TiO₂ adsorbents was markedly influenced by the preparation methods. The adsorbent prepared by DP method exhibited a superior activity for Hg⁰ adsorption and the best SO₂ resistance performance. The characterization results indicated that the Hg⁰ removal activity did not correlate with the BET surface area. The preparation method of deposition-precipitation could not only lead to an increase of reducibility and high dispersion of MnO_x, but also significantly enhance a migration of well-dispersed active phase from bulk to surface, resulting in a higher Mn⁴⁺/Mn ratio and the presence of abundant chemisorbed oxygen, which would play an important role in promoting Hg⁰ removal.
- preparation method,
- MnO_x-TiO₂,
- Hg⁰ removal,
- SO₂ resistance
1. [1]
  [1] XU W Q, WANG H R, ZHU T Y, KUANG J Y, JING P F. Mercury removal from coal combustion flue gas by modified fly ash[J]. J Environ Sci, 2013, 25(2): 393-398.
2. [2]
  [2] UDDIN M A, YAMADA T, OCHIAI R. Role of SO₂ for elemental mercury removal from coal combustion flue gas by activated carbon[J]. Energy Fuels, 2008, 22(4): 2284-2289.
3. [3]
  [3] GRANITE E J, PENNLINE H W, HARGIS R A. Novel sorbents for mercury removal from flue gas[J]. Ind Eng Chem Res, 2000, 39(4): 1020-1029.
4. [4]
  [4] STREETS D G, HAO J M, WU Y, JIANG J K, CHAN M, TIAN H Z, FENG X B. Anthropogenic mercury emissions in china[J]. Atmos Environ, 2005, 39(40): 7789-7806.
5. [5]
  [5] YANG S J, GUO Y F, YAN N Q, WU D Q, HE, H P, XIE J K, QU Z, JIA J P. Remarkable effect of the incorporation of titanium on the catalytic activity and SO₂ poisoning resistance of magnetic Mn-Fe spinel for elemental mercury capture[J]. Appl Catal B: Environ, 2011, 101(3/4): 698-708.
6. [6]
  [6] PRESTO A A, GRANITE E J. Survey of catalysts for oxidation of mercury in flue gas[J]. Environ Sci Technol, 2006, 40(18): 5601-5609.
7. [7]
  [7] ZHANG H W, CHEN J T, LIANG P, WANG L. Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke[J]. J Environ Sci, 2012, 24(12): 2083-2090.
8. [8]
  [8] MA Y P, XU H M, ZAN Q, YAN N Q, WANG W H. Absorption characteristics of elemental mercury in mercury chloride solutions[J]. J Environ Sci, 2014, 26(11): 2257-2265.
9. [9]
  [9] WU Z B, JIN R B, WANG H Q, LIU Y. Effect of ceria doping on SO₂ resistance of Mn/TiO₂ for selective catalytic reduction of NO with NH₃ at low temperature[J]. Catal Commun, 2009, 10(6): 935-939.
10. [10]
  [10] LIU F D, HE H, DING Y, ZHANG C B. Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH₃[J]. Appl Catal B: Environ, 2009, 93(1/2): 194-204.
11. [11]
  [11] 王燕彩, 刘昕, 宁平, 张秋林, 张金辉, 徐利斯, 唐小苏, 王明智. 制备方法对氧化锰八面体分子筛的NH₃选择性催化还原NO_x性能的影响[J]. 燃料化学学报, 2014, 42(11): 1357-1364.
12. [12]
  (WANG Yan-cai, LIU Xin, NING Ping, ZHANG Qiu-lin, ZHANG Jin-hui, XU Li-si, TANG Xiao-su, WANG Ming-zhi. Effect of preparation methods on selective catalytic reduction of NO_x with NH₃ over manganese oxide octahedral molecular sieves[J]. J Fuel Chem Technol, 2014, 42(11): 1357-1364.)
13. [13]
  [12] SHEN B X, LIU T, ZHAO N, YANG X Y, DENG L D. Iron-doped Mn-Ce/TiO₂ catalyst for low temperature selective catalytic reduction of NO with NH₃[J]. J Environ Sci, 2010, 22(9): 1447-1454.
14. [14]
  [13] JIANG B Q, LIU Y, WU Z B. Low-temperature selective catalytic reduction of NO on MnO_x/TiO₂ prepared by different methods[J]. J Hazard Mater, 2009, 162(2/3): 1249-1254.
15. [15]
  [14] 张信莉, 王栋, 彭建升, 路春美, 徐丽婷. 煅烧温度对Mn改性γ-Fe₂O₃催化剂结构及低温SCR脱硝活性的影响[J]. 燃料化学学报, 2015, 43(2): 243-250.
16. [16]
  (ZHANG Xin-li, WANG Dong, PENG Jian-sheng, LU Chun-mei, XU Li-ting. Influence of calcination temperature on structural property of Mn doped γ-Fe₂O₃ catalysts and low-temperature SCR activity [J]. J Fuel Chem Technol, 2015, 43(2): 243-250.)
17. [17]
  [15] WU Z B, TANG N, XIAO L, LIU Y, WANG H Q. MnO_x/TiO₂ composite nanoxides synthesized by deposition-precipitation method as a superior catalyst for NO oxidation[J]. J Colloid Interf Sci, 2010, 352(1): 143-148.
18. [18]
  [16] QIAO S H, CHEN J, LI J F, QU Z, LIU P, YAN N Q, JIA J P. Adsorption and catalytic oxidation of gaseous elemental mercury in flue gas over MnO_x/alumina[J]. Ind Eng Chem Res, 2009, 48(7): 3317-3322.
19. [19]
  [17] JI L, SREEKANTH P M, SMIRNIOTIS P G, THIEL S W, PINTO N G. Manganese oxide/titania materials for removal of NO_x and elemental mercury from flue gas[J]. Energy Fuels, 2008, 22(4): 2299-2306.
20. [20]
  [18] XU Y L, ZHONG Q, LIU X Y. Elemental mercury oxidation and adsorption on magnesite powder modied by Mn at low temperature[J]. J Hazard Mater, 2015, 283: 252-259.
21. [21]
  [19] 游淑淋, 周劲松, 侯文慧, 孟帅琦, 高翔, 骆仲泱. 锰改性活性焦脱除合成气中单质汞的影响因素[J]. 燃料化学学报, 2014, 42(11): 1324-1331.
22. [22]
  (YOU Shu-lin, ZHOU Jin-song, HOU Wen-hui, MENG Shuai-qi, GAO Xiang, LUO Zhong-yang. Factors influencing the removal of elemental mercury by Mn-AC sorbent in syngas[J]. J Fuel Chem Technol, 2014, 42(11): 1324-1331.)
23. [23]
  [20] LI H L, WU C Y, LI Y, LI L, ZHAO Y C, ZHANG J Y. Role of flue gas components in mercury oxidation over TiO₂ supported MnO_x-CeO₂ mixed-oxide at low temperature[J]. J Hazard Mater, 2012, 243: 117-123.
24. [24]
  [21] ZHANG A C, ZHENG W W, SONG J, HU S, LIU Z C, XIANG J. Cobalt manganese oxides modified titania catalysts for oxidation of elemental mercury at low flue gas temperature[J]. Chem Eng J, 2014, 236: 29-38.
25. [25]
  [22] LI J W, ZHAO P, LIU S T. SnO_x-MnO_x-TiO₂ catalysts with high resistance to chlorine poisoning for low-temperature chlorobenzene oxidation[J]. Appl Catal A: Gen, 2014, 482: 363-369.
26. [26]
  [23] QI G, YANG R T. Performance and kinetics study for low-temperature SCR of NO with NH₃ over MnO_x-CeO₂ catalyst[J]. J Catal, 2003, 217(2): 434-441.
27. [27]
  [24] HUANG H Y, LONG R Q, YANG R T. A highly sulfur resistant Pt-Rh/TiO₂/Al₂O₃ storage catalyst for NO_x reduction under lean-rich cycles[J]. Appl Catal B: Environ, 2001, 33(2): 127-136.
28. [28]
  [25] KIJLSTRA W S, BIERVLIET M, POELS E K, BLIEK A. Deactivation by SO₂ of MnO_x/Al₂O₃ catalysts used for the selective catalytic reduction of NO with NH₃ at low temperatures[J]. Appl Catal B: Environ, 1998, 16(4): 327-337.
29. [29]
  [26] XU J J, AO Y H, FU D G, YUAN C W. Low-temperature preparation of F-doped TiO₂ film and its photocatalytic activity under solar light[J]. Appl Surf Sci, 2008, 254(10): 3033-3038.
30. [30]
  [27] ZHANG A C, ZHANG Z H, CHEN J J, SHENG W, SUN L S, XIANG J. Effect of calcination temperature on the activity and structure of MnO_x/TiO₂ adsorbent for Hg⁰ removal[J]. Fuel Process Technol, 2015, 135: 25-33.
31. [31]
  [28] KHAN A, SMIRNIOTIS P G. Relationship between temperature-programmed reduction profile and activity of modified ferrite-based catalysts for WGS reaction[J]. J Mol Catal A: Chem, 2008, 280(1/2): 43-51.
32. [32]
  [29] KAPTEIJN F, SINGOREDJO L, ANDREINI A, MOULIJN J A. Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J]. Appl Catal B: Environ, 1994, 3(2/3): 173-189.
33. [33]
  [30] 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.
34. [34]
  [31] WAN Q, DUAN L, HE K B, LI J H. Removal of gaseous elemental mercury over a CeO₂-WO₃/TiO₂ nanocomposite in simulated coal-fired flue gas[J]. Chem Eng J, 2011, 170(2/3): 512-517.
35. [35]
  [32] KARAMI A, SALEHI V. The influence of chromium substitution on an iron-titanium catalyst used in the selective catalytic reduction of NO[J]. J Catal, 2012, 292: 32-43.
36. [36]
  [33] CHEN Z H, WANG F R, LI H, YANG Q, WANG L F, LI X H. Low-temperature selective catalytic reduction of NO_x with NH₃ over Fe-Mn mixed-oxide catalysts containing Fe₃Mn₃O₈ phase[J]. Ind Eng Chem Res, 2012, 51(1): 202-212.
37. [37]
  [34] GAO R H, ZHANG D S, MAITARAD P, SHI L Y, RUNGROTMONGKOL T, LI H R, ZHANG J P, CAO W G. Morphology-dependent properties of MnO_x/ZrO₂-CeO₂ nanostructures for the selective catalytic reduction of NO with NH₃[J]. J Phys Chem C, 2013, 117(20): 10502-10511.
38. [38]
  [35] YU D Q, LIU Y, WU Z B. Low-temperature catalytic oxidation of toluene over mesoporous MnO_x-CeO₂/TiO₂ prepared by sol-gel method[J]. Catal Commun, 2010, 11(8): 788-791.
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沈阳化工大学材料科学与工程学院沈阳 110142

Effect of preparation methods on the performance of MnOx-TiO2 adsorbents for Hg0 removal and SO2 resistance

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通讯作者: 陈斌, bchen63@163.com

Effect of preparation methods on the performance of MnO_x-TiO₂ adsorbents for Hg⁰ removal and SO₂ resistance