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Frontiers of Environmental Science & Engineering

Front Envir Sci Eng    2013, Vol. 7 Issue (3) : 464-473     https://doi.org/10.1007/s11783-012-0430-y
RESEARCH ARTICLE |
Removal of elemental mercury with Mn/Mo/Ru/Al2O3 membrane catalytic system
Yongfu GUO1,2, Naiqiang YAN1(), Ping LIU1, Shijian YANG1, Juan WANG1, Zan QU1
1. School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China; 2. Department of Municipal Engineering, Suzhou University of Science and Technology, Suzhou 215011, China
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Abstract

In this work, a catalytic membrane using Mn/Mo/Ru/Al2O3 as the catalyst was employed to remove elemental mercury (Hg0) from flue gas at low temperature. Compared with traditional catalytic oxidation (TCO) mode, Mn/Al2O3 membrane catalytic system had much higher removal efficiency of Hg0. After the incorporation of Mo and Ru, the production of Cl2 from the Deacon reaction and the retainability for oxidants over Mn/Al2O3 membrane were greatly enhanced. As a result, the oxidization of Hg0 over Mn/Al2O3 membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HCl, the removal efficiency of Hg0 by Mn/Mo/Ru/Al2O3 membrane reached 95% at 423 K. The influence of NO and SO2 on Hg0 removal were insignificant even if 200 ppmv NO and 1000 ppmv SO2 were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/Al2O3 membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg0 removal. Therefore, the Mn/Mo/Ru/Al2O3 membrane catalytic system may be a promising technology for the control of Hg0 emission.

Keywords flue gas      elemental mercury      membrane      catalysis      transition metal     
Corresponding Authors: YAN Naiqiang,Email:nqyan@sjtu.edu.cn   
Issue Date: 01 June 2013
 Cite this article:   
Yongfu GUO,Naiqiang YAN,Ping LIU, et al. Removal of elemental mercury with Mn/Mo/Ru/Al2O3 membrane catalytic system[J]. Front Envir Sci Eng, 2013, 7(3): 464-473.
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http://journal.hep.com.cn/fese/EN/10.1007/s11783-012-0430-y
http://journal.hep.com.cn/fese/EN/Y2013/V7/I3/464
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Yongfu GUO
Naiqiang YAN
Ping LIU
Shijian YANG
Juan WANG
Zan QU
Fig.1  Experimental scheme of the MCs
Fig.2  X-ray diffraction patterns (a) Mn catalyst and (b) Mn-Mo-Ru catalyst
catalystsSBET/(m2·g-1)surface atom concentrations obtained by AAS or EDX/%pore diameter/μm
ClOMnMoRuO/Mn
virgin tube4.1-46.2----4.7
Mn1.4-40.88.1--5.01.9
Mn-Mo1.5-41.08.01.75-5.11.6
Mn-Ru2.1NA41.28.1-0.95.11.7
Mn-Mo-Ru1.3NA41.98.01.640.85.31.3
Tab.1  Composition and properties of different catalysts
Fig.3  Adsorption curves of Hg with catalysts doped with various transition metals, at 423 K, [HCl] = [SO] = 0, was about 24 ppbv, air was used as carrier gas except Mn/N with N as carrier gas
Fig.4  Removal efficiencies of Hg with the catalysts doped with various transition metals, at 423 K, [HCl] = 8 ppmv, [SO] = 0, was about 23.5 ppbv, and air was used as carrier gas
Fig.5  Influence of Cl on Hg removal with Mn-Mo-Ru catalyst, at 423 K, air as carrier gas, was about 23 ppbv, [Cl] = 0.5 ppmv, [SO] = [HCl] = 0
Fig.6  Influence on Hg removal with intermittent injection of HCl in the MCs and the TCO mode, [HCl] = 8 ppmv, was about 23 ppbv, air as carrier gas, [SO] = 0, Mn-Mo-Ru as catalyst, = 423 K
Fig.7  Influence of SO on the removal for Hg, was about 23 ppbv, air as carrier gas, = 423 K
Fig.8  Influence on Hg removal with various concentration of SO (a, [HCl] = [NO] = 0; b, [HCl] = 0, [NO] = 100 ppmv; c, [HCl] = 8 ppmv, [NO] = 0; d, [HCl] = 8 ppmv, [NO] = 100 ppmv; and e, [HCl] = 8 ppmv, [NO] = 200 ppmv. Air was used as carrier gas, Mn-Mo-Ru as catalyst, = 423 K, was about 23.2 ppbv)
concentration of SO2removal efficiencies of Hg0/%
[NO] = 0[NO] = 100 ppmv[NO] = 200 ppmv
50088.991.795.3
100080.583.386.8
150070.971.972.6
Tab.2  Influence of NO on sulfur-tolerance with Mn-Mo-Ru catalyst and 8 ppmv HCl
Fig.9  TPR profiles and the peak results (a) Mn catalyst, (b) Mn-Mo-Ru catalyst (dash is fitted results), symbol denotes the area of corresponding reduction peak
catalystsmaximum reduction temperature/Kratio of Mn4+/Mn3+ of TPR dataratio of Mn4+/Mn3+ of XPS data
MnO2→Mn2O3Mn2O3→Mn3O4MoO3→MoO2RuO2→Ru
Mn638739--1.771.63
Mn-Mo-Ru6607808405202.792.52
Tab.3  Results of H2-TPR profiles of Mn and Mn-Mo-Ru catalysts
Fig.10  XPS spectroscopes of Mn 2p, Mo 3d, Ru 3d, Hg 4f and S 2P (dash is fitted results) (a) Mn 2p, N as carrier gas; (b) Mn 2p, air as carrier gas; (c) S 2p, air as carrier gas; (d) Mo 3d, air as carrier gas; (e) Ru 3d, air as carrier gas; (f) Hg 4f, air as carrier gas. Mn-Mo-Ru catalyst was used, was about 15-20 ppbv, [HCl] = 8 ppmv, [SO] = 1000 ppmv
Fig.11  Mercury speciation results of three replicate tests, Mn-Mo-Ru was used as catalyst, was about 23 ppbv, [HCl] = 8 ppmv, [SO] = 0, = 423 K
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