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Aerosol and Air Quality Research, 15: 2094–2103, 2015 Copyright © Taiwan Association for Aerosol Research ISSN: 1680-8584 print / 2071-1409 online doi: 10.4209/aaqr.2015.03.0176 Simultaneous Control of Elemental Mercury/Sulfur Dioxide/Nitrogen Monoxide from Coal-Fired Flue Gases with Metal Oxide-Impregnated Activated Carbon Chun-Hsiang Chiu1, Hong-Ping Lin2, Tien-Ho Kuo3, Shiao-Shing Chen1, Tien-Chin Chang1, Kai-Han Su1, Hsing-Cheng Hsi4* 1 Institute of Environmental Engineering and Management, National Taipei University of Technology, No. 1, Sec. 3, Chung-Hsiao E. Rd., Taipei 106, Taiwan 2 Department of Chemistry, National Cheng-Kung University, No.1, University Rd., Tainan 701, Taiwan 3 Department of Environmental Engineering, Tungnan University, No. 152, Sec. 3, Peishen Rd., Shenkeng District, New Taipei City 222, Taiwan 4 Graduate Institute of Environmental Engineering, National Taiwan University, No. 71, Chou-Shan Rd., Taipei 106, Taiwan ABSTRACT This research investigated the effects of transition metal oxide impregnation on the physical/chemical properties and on 0 the multipollutant (i.e., Hg /SO2/NO) control of a commercial coconut shell-based activated carbon. V, Mn, and Cu oxides of 5 wt% as their precursor metal hydroxides were impregnated onto the activated carbon surface. After the transition metal oxide impregnation, the surface area and pore volume of activated carbon decreased. The surface morphology of activated carbons was similar prior to and after impregnation. Mn3+/Mn4+ and Cu+/Cu2+ were shown to be the major valence 0 states presenting in the MnOx and CuOx/CAC samples, respectively. CuOx/CAC possessed the greatest Hg removal efficiency of approximately 54.5% under N2 condition and 98.9% under flue gas condition, respectively at 150°C. When the gas temperature increased to 350°C, the metal oxide-impregnated activated carbon still possessed appreciable Hg0 removal, especially for CuOx/CAC. The VOx/CAC had the largest SO2 removal enhancement of approximately 28.3% at 350°C. The NO removal of raw and impregnated activated carbon was very small under flue gas condition, indicating that adsorption of NO using metal oxide-impregnated activated carbon may not be a suitable route for NO control. Keywords: Elemental mercury; Multipollutant control; Metal oxide; Activated carbon; Coal combustion. INTRODUCTION countries (UNEP, 2013). Consequently, several countries have implemented or is proposing more stringent regulations Mercury (Hg) is a global pollutant, highly harmful to on the abatement of Hg emissions. In October 2013, Taiwan human, animals, and plants. Coal combustion has been known Environmental Protection Administration has promulgated a as one of the major anthropogenic sources of atmospheric new regulation for limiting Hg emissions from coal-fired Hg, contributing 30% of the total anthropogenic Hg emission steam and cogeneration boilers; the Hg emission should be –3 (Pacyna et al., 2010). Hg emission from coal-fired power lowered than 2 and 5 µg Nm for new and existing plants (CFPPs) has aroused the greatest concern to the public facilities, respectively (Taiwan Environmental Protection due to its unique physicochemical properties, high toxicity, Administration, 2013). long retention time in the environment, and potentially The three stable forms of Hg in the coal-fired flue gas: 0 2+ adverse effects on the ecosystem. The Minamata Convention elemental (Hg ), oxidized (Hg ) and particulate-bound on Mercury delivered in March 19, 2013 addressed the (Hgp) govern the fate of this species (Yan et al., 2005; 2+ necessity of prevention and abatement of Hg emission and Granite et al., 2006; Li et al., 2012). The Hg and Hgp can release via global and legally-binding agreements between be successfully removed with the existing air pollution 2+ control devices (APCD) in CFPPs. Hg can be easily 2+ removed by wet flue gas desulfurization because Hg is highly soluble in water. HgP can be captured by fly ash by * Corresponding author. particulate control systems (e.g., electrostatic precipitators, Tel.: +886 2 33664374; Fax: +886 2 23928830 fabric filters, or baghouses) (Li et al., 2012). Nevertheless, 0 E-mail address: [email protected] low-level Hg in CFPP flue gases is very difficult to remove Chiu et al., Aerosol and Air Quality Research, 15: 2094–2103, 2015 2095 with conventional APCD because Hg0 is highly volatile MATERIALS AND METHODS and nearly insoluble in water. Activated carbon has been considered excellent adsorbent Preparation and Characterization of Metal Oxide- for Hg control (Granite et al., 2006; Hsi and Chen, 2012; Impregnated Activated Carbon Hsi et al., 2013). Some studies have reported the A commercial coconut shell-based activated carbon (G- individual and simultaneous removal of Hg, SO2, and NO 135; designated CAC in this paper) was obtained from under flue gas conditions by carbon-based materials (e.g., China Activated Carbon Industries Ltd., Taiwan. To prepare activated carbon, activated coke, and activated carbon the V, Mn, and Cu oxide-impregnated activated carbons, fibers) (Stencel and Rubel, 1995; Tsuji and Shiraishi, their corresponding metal hydroxides were precipitated to 1997; Mochida et al., 1999). Karatza et al. (2000) reported the activated carbon via a hydrothermal sol-gel method at a that S, Cl, I-impregnated activated carbon exhibited great weight percentage of 5 wt% (as the precursor) followed potential for Hg0 removal under flue gas condition. Hu et with calcination (Chiu et al., 2014a). Metal salts including al. (2014) showed that activated carbon (AC-CS, made V(OH)5, Mn(OH)2, and Cu(OH)2 were individually dissolved from coconut shell) can be used to remove Hg0 and the in water at a metal salt to water mass ratio of 0.04 wt%. The process was complete chemisorption in simulated flue gas. metal salt solution was then neutralized with 1.0 M NaOH One study also indicated that incorporation of sulfur aqueous solution to form precipitate at a proper pH value groups on the activated carbon can enhance the oxidation (i.e., V(OH)5 precipitates at pH ≈5.0; Mn(OH)2 precipitates at 0 2+ of Hg into Hg and subsequently bonded with oxidized pH ≈10.0; Cu(OH)2 precipitates at pH ≈11.0). After the Hg, resulting in higher Hg capacities (Yao et al., 2014). precipitation process, powdered activated carbon with a Besides sulfur and halogen surface functionality, metal precursor metal oxide to activated carbon mass ratio = 5.0 oxides have been shown to greatly increase the Hg0 wt% was added to the metal hydroxide gel solution and adsorption or oxidation performance of activated carbon. further stirred for 2–3 h. The mixture was then transferred Mei et al. (2008) indicated that high loading values and to an autoclave and statically heated at 100°C for 1 d. adsorption temperatures increased the Hg0 removal Filtration, washing, and drying gave the transition metal percentage by Co3O4-doped activated carbon; the CuCoO4- oxide-impregnated activated carbon products. The resulting doped activated carbon also showed the greatest SO2 metal oxide-impregnated activated carbons were ground removal efficiency. Tian et al. (2009) demonstrated that into powder, passed through 200-mesh sieve, and stored 0 the doped CeO2 in activated carbon significantly promoted for subsequent sample characterization and Hg /SO2/NO the adsorption ability for Hg0. Sumathi et al. (2010) indicated removal tests. that the raw and the palm shell-based activated carbons Detailed descriptions regarding physical characterization impregnated with Ni, V, Fe and Ce metal oxides can be of samples can be found elsewhere (Chiu et al., 2014a). used to simultaneous removal of SO2 and NOx. Liu and Briefly, the total surface area (SBET), total pore volume Liu (2013) suggested that activated coke doped with V (Vt), micropore (pore width < 2 nm) surface area (Smicro), metal oxide had high activities in adsorption and oxidation, and micropore volume (Vmicro) of raw and metal oxide- which are the key mechanisms for multipollutants removal impregnated activated carbon were determined based on N2 in coal-fired flue gas. Du et al. (2014) indicated that adsorption obtained at 77 K (Quantachrome NOVA 2000e). CuCl2-impregnated activated carbon had higher adsorption The surface morphology was characterized using a scanning 0 ability for Hg as compared to those for CuCl2-impregnated electron microscope (SEM; Hitachi S-4800). The crystal neutral Al2O3 and zeolite at 60–300°C. phase was examined with an X-ray diffractometer (XRD; The findings in the aforementioned literatures lead to a PANalytical X'Pert PRO). X-ray photoelectron spectroscopy conclusion that metal-oxide doped or impregnated activated (XPS; Physical Electronics ESCA PHI 1600) analysis was carbons could be highly feasible in control of Hg0 via used to understand the surface chemical compositions and adsorption or oxidation effectively. Nevertheless, better the valance state of metal oxides on the activated carbon comprehension on the effectiveness of multipollutant (i.e., surface. 0 Hg , SO2, and NO) control using activated carbon modified 0 with transition metal oxides is still limited and critical. The Multipollutant (Hg /SO2/NO) Control Tests present research investigated the effects of transition metal Hg0 removal tests were carried out at 150 and 350°C, oxide impregnation, including V, Mn, and Cu oxides, on respectively, in a fixed-bed testing apparatus using N2 or a 0 the physiochemical properties and simultaneous Hg /SO2/NO simulated coal-combustion flue gas as the carrier gas control using a coconut shell-based activated carbon. A containing 27 ± 5 µg Nm–3 Hg0 (Fig. 1; Chiu et al., 2014a, b). simulated coal-combustion flue gas generation platform The reason to conduct the tests at these two temperatures was associated a Hg0/flue gas component monitoring system was to evaluate the feasibility of applying the activated carbon 0 used for the simultaneous Hg , SO2, and NO removal directly at the outlet of a DeNOx catalyst or at the inlet of a experiments.

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