Removal of elemental mercury with Mn/Mo/Ru/Al<sub>2</sub>O<sub>3</sub> membrane catalytic system

doi:10.1007/s11783-012-0430-y

Front Envir Sci Eng

0, Vol.

Issue () : 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 GUO^1,2, 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

Download: PDF(404 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

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 Author(s): 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, 0, (): 464-473.

URL:

https://academic.hep.com.cn/fese/EN/10.1007/s11783-012-0430-y
https://academic.hep.com.cn/fese/EN/Y0/V/I/464

Fig.1 Experimental scheme of the MCs

Fig.2 X-ray diffraction patterns (a) Mn catalyst and (b) Mn-Mo-Ru catalyst

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)

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

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

1	Liu Y, Kelly D J A, Yang H Q, Lin C C H, Kuznicki S M, Xu Z G. Novel regenerable sorbent for mercury capture from flue gases of coal-fired power plant. Environmental Science & Technology , 2008, 42(16): 6205–6210 doi: 10.1021/es800532b pmid:18767688
2	Li Y, Murphy P D, Wu C Y, Powers K W, Bonzongo J C J. Development of silica/vanadia/titania catalysts for removal of elemental mercury from coal-combustion flue gas. Environmental Science & Technology , 2008, 42(14): 5304–5309 doi: 10.1021/es8000272 pmid:18754385
3	Guo Y F, Yan N Q, Yang S J, Qu Z, Wu Z B, Liu Y, Liu P, Jia J P. Conversion of elemental mercury with a novel membrane delivery catalytic oxidation system (MDCOs). Environmental Science & Technology , 2011, 45(2): 706–711 doi: 10.1021/es1020586 pmid:21158439
4	Niksa S, Fujiwara N. The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations. Journal of the Air & Waste Management Association , 2005, 55(7): 970–977 pmid:16111136
5	Kim M H, Ham S W, Lee J B. Oxidation of gaseous elemental mercury by hydrochloric acid over CuCl₂/TiO₂-based catalysts in SCR process. Applied Catalysis B: Environmental , 2010, 99(1-2): 272–278 doi: 10.1016/j.apcatb.2010.06.032
6	Lee W J, Bae G N. Removal of elemental mercury (Hg(O)) by nanosized V₂O₅/TiO₂ catalysts. Environmental Science & Technology , 2009, 43(5): 1522–1527 doi: 10.1021/es802456y PMID:19350929
7	He S, Zhou J, Zhu Y, Luo Z, Ni M, Cen K. Mercury oxidation over a vanadia-based selective catalytic reduction catalyst. Energy & Fuels , 2009, 23(1): 253–259 doi: 10.1021/ef800730f
8	Kamata H, Ueno S, Sato N, Naito T. Mercury oxidation by hydrochloric acid over TiO₂ supported metal oxide catalysts in coal combustion flue gas. Fuel Processing Technology , 2009, 90(7-8): 947–951 doi: 10.1016/j.fuproc.2009.04.010
9	Straube S, Hahn T, Koeser H. Adsorption and oxidation of mercury in tail-end SCR-DeNO_x plants—bench scale investigations and speciation experiments. Applied Catalysis B: Environmental , 2008, 79(3): 286–295 doi: 10.1016/j.apcatb.2007.10.031
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. Applied Catalysis B: Environmental , 2009, 93(1-2): 194–204 doi: 10.1016/j.apcatb.2009.09.029
11	Jing G H, Li J H, Yang D, Hao J M. Promotional mechanism of tungstation on selective catalytic reduction of NO_x by methane over In/WO₃/ZrO₂. Applied Catalysis B: Environmental , 2009, 91(1-2): 123–134 doi: 10.1016/j.apcatb.2009.05.015
12	Presto A A, Granite E J. Noble metal catalysts for mercury oxidation in utility flue gas gold, palladium and platinum formulations. Platinum Metals Review , 2008, 52(3): 144–154 doi: 10.1595/147106708X319256
13	Poulston S, Granite E J, Pennline H W, Myers C R, Stanko D P, Hamilton H, Rowsell L, Smith A W J, Ilkenhans T, Chu W. Metal sorbents for high temperature mercury capture from fuel gas. Fuel , 2007, 86(14): 2201–2203 doi: 10.1016/j.fuel.2007.05.015
14	Li J F, Yan N Q, Qu Z, Qiao S H, Yang S J, Guo Y F, Liu P, Jia J P. Catalytic oxidation of elemental mercury over the modified catalyst Mn/alpha-Al₂O₃ at lower temperatures. Environmental Science & Technology , 2010, 44(1): 426–431 doi: 10.1021/es9021206 pmid:19950921
15	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. Industrial & Engineering Chemistry Research , 2009, 48(7): 3317–3322 doi: 10.1021/ie801478w
16	Zhao Y C, Zhang J Y, Liu J, Diaz-Somoano M, Martinez-Tarazona M R, Zheng C G. Study on mechanism of mercury oxidation by fly ash from coal combustion. Chinese Science Bulletin , 2010, 55(2): 163–167 doi: 10.1007/s11434-009-0567-7
17	Li J H, Liang X, Xu S C, Hao J M. Catalytic performance of manganese cobalt oxides on methane combustion at low temperature. Applied Catalysis B: Environmental , 2009, 90(1-2): 307–312 doi: 10.1016/j.apcatb.2009.03.027
18	Galbreath K C, Zygarlicke C J. Mercury transformations in coal combustion flue gas. Fuel Processing Technology , 2000, 65-66: 289–310 doi: 10.1016/S0378-3820(99)00102-2
19	Pan H Y, Minet R G, Benson S W, Tsotsis T T. Process for converting hydrogen chloride to chlorine. Industrial & Engineering Chemistry Research , 1994, 33(12): 2996–3003 doi: 10.1021/ie00036a014
20	Li Y, Murphy P, Wu C Y. Removal of elemental mercury from simulated coal-combustion flue gas using a SiO₂-TiO₂ nanocomposite. Fuel Processing Technology , 2008, 89(6): 567–573 doi: 10.1016/j.fuproc.2007.10.009
21	Cao Y, Chen B, Wu J, Cui H, Smith J, Chen C K, Chu P, Pan W P. Study of mercury oxidation by a selective catalytic reduction catalyst in a pilot-scale slipstream reactor at a utility boiler burning bituminous coal. Energy & Fuels , 2007, 21(1): 145–156 doi: 10.1021/ef0602426
22	Lindbauer R L, Wurst F, Prey T. Combustion dioxin suppression in municipal solid-waste incineration with sulfur additives. Chemosphere , 1992, 25(7-10): 1409–1414 doi: 10.1016/0045-6535(92)90162-K
23	Norton G A, Yang H Q, Brown R C, Laudal D L, Dunham G E, Erjavec J. Heterogeneous oxidation of mercury in simulated post combustion conditions. Fuel , 2003, 82(2): 107–116 doi: 10.1016/S0016-2361(02)00254-5
24	Zhao Y X, Mann M D, Olson E S, Pavlish J H, Dunham G E. Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions. Journal of the Air & Waste Management Association (1995) , 2006, 56(5): 628–635 pmid:16739799
25	Krishnakumar B, Helble J J. Understanding mercury transformations in coal-fired power plants: evaluation of homogeneous Hg oxidation mechanisms. Environmental Science & Technology , 2007, 41(22): 7870–7875 doi: 10.1021/es071087s pmid:18075101
26	Niksa S, Helble J J, Fujiwara N. Kinetic modeling of homogeneous mercury oxidation: the importance of NO and H₂O in predicting oxidation in coal-derived systems. Environmental Science & Technology , 2001, 35(18): 3701–3706 doi: 10.1021/es010728v pmid:11783648
27	Agarwal H, Stenger H G, Wu S, Fan Z. Effects of H₂O, SO₂, and NO on homogeneous Hg oxidation by Cl2. Energy & Fuels , 2006, 20(3): 1068–1075 doi: 10.1021/ef050388p
28	Hall B, Schager P, Lindqvist O. Chemical reactions of mercury on combustion flue gases. Water, Air, and Soil Pollution , 1991, 56(1): 3–14 doi: 10.1007/BF00342256
29	Hrdlicka J A, Seames W S, Mann M D, Muggli D S, Horabik C A. Mercury oxidation in flue gas using gold and palladium catalysts on fabric filters. Environmental Science & Technology , 2008, 42(17): 6677–6682 doi: 10.1021/es8001844 pmid:18800548
30	álvarez-Galván M C, de la Pe?a O’Shea V A, Fierro J L G, Arias P L. Alumina-supported manganese- and manganese-palladium oxide catalysts for VOCs combustion. Catalysis Communications , 2003, 4(5): 223–228 doi: 10.1016/S1566-7367(03)00037-2
31	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. Energy & Fuels , 2008, 22(4): 2299–2306 doi: 10.1021/ef700533q
32	Liu H, Xu Y. H₂-TPR study on Mo/HZSM-₅ catalyst for CH4 dehydroaromatization. Chinese Journal of Catalysis , 2006, 27(4): 319–323 doi: 10.1016/S1872-2067(06)60020-X
33	Mazzieri V, Coloma-Pascual F, Arcoya A, L'Argentière P, Fígoli N S. XPS, FTIR and TPR characterization of Ru/Al₂O₃ catalysts. Applied Surface Science , 2003, 210(3-4): 222–230 doi: 10.1016/S0169-4332(03)00146-6
34	Bianchi C L. TPR and XPS investigations of Co/Al₂O₃ catalysts promoted with Ru, Ir and Pt. Catalysis Letters , 2001, 76(3-4): 155–159 doi: 10.1023/A:1012289211065
35	NIST XPS Database. http://srdata.nist.gov/xps/.accessed August, 2007
36	López N, Gómez-Segura J, Marín R P, Pérez-Ramírez J. Mechanism of HCl oxidation (Deacon process) over RuO₂. Journal of Catalysis , 2008, 255(1): 29–39 doi: 10.1016/j.jcat.2008.01.020

[1]	Yang Yu, Changchun Xin, Yuxiang Liu, Fei Gao, Lei Zhang, Hui Jia, Jie Wang. Portable fluorescence instrument for detecting membrane integrity in membrane bioreactor (MBR)[J]. Front. Environ. Sci. Eng., 2024, 18(2): 23-.
[2]	Huijuan Xie, Haiguang Zhang, Xu Wang, Gaoliang Wei, Shuo Chen, Xie Quan. Conductive and stable polyphenylene/CNT composite membrane for electrically enhanced membrane fouling mitigation[J]. Front. Environ. Sci. Eng., 2024, 18(1): 3-.
[3]	Manshu Zhao, Xinhua Wang, Shuguang Wang, Mingming Gao. Cr-containing wastewater treatment based on Cr self-catalysis: a critical review[J]. Front. Environ. Sci. Eng., 2024, 18(1): 1-.
[4]	Zhou Zhang, Kai Huo, Tingxuan Yan, Xuwen Liu, Maocong Hu, Zhenhua Yao, Xuguang Liu, Tao Ye. Mechanistic insights into the selective photocatalytic degradation of dyes over TiO₂/ZSM-11[J]. Front. Environ. Sci. Eng., 2023, 17(8): 101-.
[5]	Chenglin Cai, Juexiu Li, Yi He, Jinping Jia. Target the neglected VOCs emission from iron and steel industry in China for air quality improvement[J]. Front. Environ. Sci. Eng., 2023, 17(8): 95-.
[6]	Yuxin Lu, Xiang Li, Cagnetta Giovanni, Bo Wang. Construction of MOFs-based nanocomposite membranes for emerging organic contaminants abatement in water[J]. Front. Environ. Sci. Eng., 2023, 17(7): 89-.
[7]	Huan Xi, Fanlu Min, Zhanhu Yao, Jianfeng Zhang. Facile fabrication of dolomite-doped biochar/bentonite for effective removal of phosphate from complex wastewaters[J]. Front. Environ. Sci. Eng., 2023, 17(6): 71-.
[8]	Qian Li, Zhaoyang Hou, Xingyuan Huang, Shuming Yang, Jinfan Zhang, Jingwei Fu, Yu-You Li, Rong Chen. Methanation and chemolitrophic nitrogen removal by an anaerobic membrane bioreactor coupled partial nitrification and Anammox[J]. Front. Environ. Sci. Eng., 2023, 17(6): 68-.
[9]	Haiguang Zhang, Lei Du, Jiajian Xing, Gaoliang Wei, Xie Quan. Electro-conductive crosslinked polyaniline/carbon nanotube nanofiltration membrane for electro-enhanced removal of bisphenol A[J]. Front. Environ. Sci. Eng., 2023, 17(5): 59-.
[10]	Jie Liu, Junjun Ma, Weizhang Zhong, Jianrui Niu, Zaixing Li, Xiaoju Wang, Ge Shen, Chun Liu. Penicillin fermentation residue biochar as a high-performance electrode for membrane capacitive deionization[J]. Front. Environ. Sci. Eng., 2023, 17(4): 51-.
[11]	Zhijun Liu, Xi Luo, Senlin Shao, Xue Xia. Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes[J]. Front. Environ. Sci. Eng., 2023, 17(4): 40-.
[12]	Shuang Zhang, Shuai Liang, Yifan Gao, Yang Wu, Xia Huang. Nonpolar cross-stacked super-aligned carbon nanotube membrane for efficient wastewater treatment[J]. Front. Environ. Sci. Eng., 2023, 17(3): 30-.
[13]	Hanqing Fan, Yuxuan Huang, Ngai Yin Yip. Advancing ion-exchange membranes to ion-selective membranes: principles, status, and opportunities[J]. Front. Environ. Sci. Eng., 2023, 17(2): 25-.
[14]	Mourin Jarin, Zeou Dou, Haiping Gao, Yongsheng Chen, Xing Xie. Salinity exchange between seawater/brackish water and domestic wastewater through electrodialysis for potable water[J]. Front. Environ. Sci. Eng., 2023, 17(2): 16-.
[15]	Jiaheng Teng, Ying Deng, Xiaoni Zhou, Wenfa Yang, Zhengyi Huang, Hanmin Zhang, Meijia Zhang, Hongjun Lin. A critical review on thermodynamic mechanisms of membrane fouling in membrane-based water treatment process[J]. Front. Environ. Sci. Eng., 2023, 17(10): 129-.

Viewed

Full text

Abstract

Cited

Shared

Discussed