Mechanism for the enhancement of the resistance of the OMS-2 mercury oxidation catalyst to sulfur by modifying with cerium

HUANG Jin-jin; CAI Liang-feng; LIU Xi; YANG Jian-ping; QU Wen-qi; LI Hai-long

Volume 48 Issue 12

Dec. 2020

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2020 > 48(12): 1433-1441

HUANG Jin-jin, CAI Liang-feng, LIU Xi, YANG Jian-ping, QU Wen-qi, LI Hai-long. Mechanism for the enhancement of the resistance of the OMS-2 mercury oxidation catalyst to sulfur by modifying with cerium[J]. Journal of Fuel Chemistry and Technology, 2020, 48(12): 1433-1441.

Citation:

HUANG Jin-jin, CAI Liang-feng, LIU Xi, YANG Jian-ping, QU Wen-qi, LI Hai-long. Mechanism for the enhancement of the resistance of the OMS-2 mercury oxidation catalyst to sulfur by modifying with cerium[J]. Journal of Fuel Chemistry and Technology, 2020, 48(12): 1433-1441.

Citation:

HUANG Jin-jin, CAI Liang-feng, LIU Xi, YANG Jian-ping, QU Wen-qi, LI Hai-long. Mechanism for the enhancement of the resistance of the OMS-2 mercury oxidation catalyst to sulfur by modifying with cerium[J]. Journal of Fuel Chemistry and Technology, 2020, 48(12): 1433-1441.

PDF( 4744 KB)

Mechanism for the enhancement of the resistance of the OMS-2 mercury oxidation catalyst to sulfur by modifying with cerium

School of Energy Science and Engineering, Central South University, Changsha 410083, China

Funds:

the National Natural Science Foundation of China 51776227

the National Natural Science Foundation of China 51906260

More Information

Corresponding author: LI Hai-long, Tel:18670016725, E-mail:hailong_li@126.com
Received Date: 2020-09-11
Rev Recd Date: 2020-10-26

Available Online: 2021-01-23

Publish Date: 2020-12-10

Abstract

Abstract

In view of the poor resistance of manganese oxide octahedral molecular sieve (OMS-2) catalyst to sulfur in the oxidation of elemental mercury, CeO₂ was used to modify the OMS-2 catalyst. The mechanism for the enhancement of the resistance of the OMS-2 catalyst to sulfur by modifying with CeO₂ was investigated, with the help of thermodynamic analysis, fixed-bed reaction test and various characterization methods like nitrogen sorption, XRD ICP and XPS. The results indicate: The OMS-2 catalyst modified by Ce has a large surface area and void-rich structure, which can adsorb more Hg⁰ through chemical adsorption; More Mn defects are formed on the OMS-2 catalyst through modifying with Ce, leading to an increase in the electron mobility, the proportion of adsorbed oxygen (O_β) species, and the density of catalytically active sites; The Ce-modified OMS-2 catalyst can quickly re-oxidize the reduced Hg⁰ or HgSO₄ species (facilely formed on the pristine OMS-2 catalyst surface in the presence of SO₂) to HgO, which can then improve the apparent Hg⁰ oxidation efficiency. The results should be helpful for the development of high-performance anti-thio catalysts for mercury oxidation.
- mercury oxide,
- SO₂,
- reduction,
- thermodynamics,
- coal-fired flue gas

FullText(HTML)

References(36)

References

[1]	王立刚, 彭苏萍, 陈昌和.燃煤飞灰对锅炉烟道气中Hg⁰的吸附特性[J].环境科学, 2003, 24(6): 59-62. WANG Li-gang, PENG Su-ping, CHEN Chang-he. The experimental study to Hg⁰ adsorption of fly ash in flue gas[J]. Environ Sci, 2003, 24(6): 59-62.
[2]	任建莉, 周劲松, 骆仲泱, 徐璋, 张雪梅.钙基类吸附剂脱除烟气中气态汞的试验研究[J].燃料化学学报, 2006, 34(5): 557-561. REN Jian-li, ZHOU Jin-song, LUO Zhong-yang, XU Zhang, ZHANG Xue-mei. Ca-based sorbents for mercury vapor removal from flue gas[J]. J Fuel Chem Technol, 2006, 34(5): 557-561.
[3]	ZHAO Y X, MICHAEL D M, EDWIN S O, JOHN H P, GRANT E D. Effects of sulfur dioxide and nitric oxide on mercury oxidation and reduction under homogeneous conditions[J]. J Air Waste Manage Assoc, 2012, 56(5): 628-635.
[4]	WANG F, WANG H M, ZHANG F, ZHU J W, TIAN G, LIU Y, MAO J X. SO₂/Hg removal from flue gas by dry FGD[J]. Int J Min Sci Technol, 2012, 22(1): 107-110.
[5]	WANG Y Y, SHEN B X, HE C, YUE S J, WANG F M. Simultaneous removal of NO and Hg⁰ from flue gas over Mn-Ce/Ti-PILCs[J]. Environ Sci Technol, 2015, 49(15): 9355-9363.
[6]	YANG W, LIU Y X, WANG Q, PAN J F. Removal of elemental mercury from flue gas using wheat straw chars modified by Mn-Ce mixed oxides with ultrasonic-assisted impregnation[J]. Chem Eng J, 2017, 326(15): 169-181.
[7]	XU H M, QU Z, ZONG X, QUAN F Q, MEI J, YAN N Q. Catalytic oxidation and adsorption of Hg⁰ over low-temperature NH₃-SCR LaMnO₃ perovskite oxide from flue gas[J]. Appl Catal B: Environ, 2016, 186(5): 30-40.
[8]	ATRIBAK I, BUENO L A, GARCIA G A, NAVARO P, FRIAS D, MONTES M. Catalytic activity for soot combustion of birnessite and cryptomelane[J]. Appl Catal B: Environ, 2010, 93(3/4): 267-273.
[9]	DING Y S, SHEN X F, SITHAMBARAM S, GOMEZ S, KUMAR R, CRISOSTOMO V M B, SUIB S L, AINDOW M. Synthesis and catalytic activity of cryptomelane-type manganese dioxide nanomaterials produced by a novel solvent-free method[J]. Chem Mater, 2005, 17(21): 5382-5389.
[10]	HUANG W M, SHI J L. Water-promoted low-concentration NO removal at room temperature by Mg-doped manganese oxides OMS-2[J]. Appl Catal A: Gen, 2015, 507(25): 65-74.
[11]	GANDHE A R, JEANETTE S, REBELLO J, FIGUEIREDO L, FERNANDES J B. Manganese oxide OMS-2 as an effective catalyst for total oxidation of ethyl acetate[J]. Appl Catal B: Environ, 2007, 72(1/2): 129-135.
[12]	ADJIMI S, GARCIA V J, DIAZ J A, RETAILLEAU L, GIL S, PERA T M, GUO Y, GIROIR F A. Highly efficient and stable Ru/K-OMS-2 catalyst for NO oxidation[J]. Appl Catal B: Environ, 2017, 219(15): 459-466.
[13]	HERNANDEZ W Y, CENTENO M A, SVETLANA I, PIERRE E, GAIGNEAUXE M, ODRIOZOLA J A. Cu-modified cryptomelane oxide as active catalyst for CO oxidation reactions[J]. Appl Catal B: Environ, 2012, 123(23): 27-35.
[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[J]. Environ Sci Technol, 2010, 44(1): 426-431.
[15]	LIU X, JIANG S J, LI H L, YANG J P, YANG Z Q, ZHAO J X, PENG H Y, KAIMIN S. Elemental mercury oxidation over manganese oxide octahedral molecular sieve catalyst at low flue gas temperature[J]. Chem Eng J, 2019, 356(15): 142-150.
[16]	WU S J, KATAYAMA R, UDDIN M A, SASAOKA E, XIE Z M. Study on reactivity of HgO over activated carbon with HCl and SO₂ in the presence of moisture by temperature-programmed decomposition desorption mass spectrometry[J]. Energy Fuels, 2015, 29(10): 6598-6604.
[17]	李扬, 刘冰, 杨赫, 杨大伟, 胡浩权. MnO_x-TiO₂吸附剂对燃煤烟气中汞的脱除[J].燃料化学学报, 2020, 48(5): 513-524. LI Yang, LIU Bing, YANG He, YANG Da-wei, HU Hao-quan. Removal of elemental mercury(Hg⁰) from simulated flue gas over MnO_x-TiO₂ sorbents[J]. J Fuel Chem Technol, 2020, 48(5): 513-524.
[18]	WU S J, UDDIN M A, NAGANO S, MASAKI O, SASAOKA E. Fundamental study on decomposition characteristics of mercury compounds over solid powder by temperature-programmed decomposition desorption mass spectrometry[J]. Energy Fuels, 2011, 25(2): 144-153.
[19]	HE S, ZHOU J S, ZHU Y Q, LUO Z Y, NI M J, CEN K. Mercury oxidation over a vanadia-based selective catalytic reduction catalyst[J]. Energy Fuels, 2009, 23(1): 253-259.
[20]	赵莉, 何青松, 刘宇, 吴洋文, 陆强, 刘松涛, 董长青.湿法脱硫浆液中Hg²⁺的还原机制研究[J].燃料化学学报, 2017, 45(6): 755-760. ZHAO Li, HE Qing-song, LIU Yu, WU Yang-wen, LU Qiang, LIU Song-tao, DONG Chang-qing. Mechanism of Hg²⁺ reduction in wet flue gas desulfurization liquors[J]. J Fuel Chem Technol, 2017, 45(6): 755-760.
[21]	LI H L, WU C Y, LI Y, ZHANG J. CeO₂-TiO₂ catalysts for catalytic oxidation of elemental mercury in low-rank coal combustion flue gas[J]. Environ Sci Technol, 2011, 45(17): 7394-400.
[22]	WANG T, LIU J, YANG Y H, SUI Z F, ZHANG Y S, WANG J W, PAN W P. Catalytic conversion of mercury over Ce doped Mn/SAPO-34 catalyst: Sulphur tolerance and SO₂/SO₃ conversion[J]. J Hazard Mater, 2020, 381(5): 120986.
[23]	王艳坤. HSC Chemistry软件在高校化学科研中的应用[J].河南教育学院学报:自然科学版, 2013, 22(2): 32-34. WANG Yan-kun. Application of HSC chemistry software in university chemical scientific research[J]. J Henan Ins Edu Nat Sci Ed, 2013, 22(2): 32-34.
[24]	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.
[25]	WU Z B, JIANG B Q, YUE L, ZHAO W R, GUAN B H. Experimental study on a low-temperature SCR catalyst based on MnO_x/TiO₂ prepared by sol-gel method[J]. J Hazard Mater, 2007, 145(3): 488-494.
[26]	LI H L, ZHU L, WANG J, LI L Q, SHIH K. Development of nano-sulfide sorbent for efficient removal of elemental mercury from coal combustion fuel gas[J]. Environ Sci Technol, 2016, 50(17): 9551-9557.
[27]	HOU J T, LI Y Z, MAO M Y, ZHAO X J, YUE Y Z. The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation[J]. Nanoscale, 2014, 6(24): 15048-15058.
[28]	LIU C, CHEN L, LI J, MA L, ARANDIYAN H, DU Y, XU J, HAO J. Enhancement of activity and sulfur resistance of CeO₂ supported on TiO₂-SiO₂ for the selective catalytic reduction of NO by NH₃[J]. Environ Sci Technol, 2012, 46(11): 6182-6189.
[29]	WANG X Y, LAN Z X, ZHANG K, CHEN J J, JIANG L L, WANG R H. Structure activity relationships of AMn₂O₄ (A=Cu and Co) spinels in selective catalytic reduction of NO_x: Experimental and theoretical study[J]. J Chem Phys C, 2017, 121(6): 3339-3349.
[30]	KIVELSON, DANIEL. The determination of the potential constants of SO₂ from centrifugal distortion effects[J]. J Chem Phys, 1954, 22(5): 904-908.
[31]	王鹏鹰.铝基SCR催化剂催化氧化烟气中汞的实验与机理研究[D].武汉: 华中科技大学, 2014. WANG Peng-ying. A dissertation submitted in partial fulfllment of the requirements for the degree of doctor of philosophy in engineering[D]. Wuhan: Huazhong University of Science and Technology, 2014.
[32]	张旭楠. CeO₂改性SCR催化剂同时脱除烟气中Hg⁰和NO的实验研究[D].长沙: 湖南大学, 2015. ZHANG Xu-nan. The experimental study on the simultaneous removal of elemental mercury (Hg⁰) and NO from flue gas by CeO₂ modified SCR catalysts[D]. Changsha: Hunan University, 2015.
[33]	ZHUANG Y, JASON L, RICHARD L, MIKE H, JOHN P. Impacts of acid gases on mercury oxidation across SCR catalyst[J]. Fuel Process Technol, 2007, 88(10): 929-934.
[34]	LAUDAL D L, THOMPSON J S, PAVLISH J H, BRICKET L, CHU P, SRIVASTAVA R K, LEE C W, KILGROE J. Mercury speciation at power plants using SCR and SNCR control technologies[J]. Electron Manager, 2012, 53(1): 16-22.
[35]	SUI Z F, ZHANG Y S, LI W H, WILLIAM O, CAO Y, PAN W P. Partitioning effect of mercury content and speciation in gypsum slurry as a function of time[J]. J Therm Anal Calorim, 2015, 119(3): 1611-1618.
[36]	ZHANG Y S, ZHAO L L, GUO R T, WANG J W, CAO Y, WILLIAM O, PAN W P. Influences of NO on mercury adsorption characteristics for HBr modified fly ash[J]. Int J Coal Geol, 2017, 170(1): 77-83.