Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent

WANG Yong-xing; HUANG Ya-ji; DONG Lu; YUAN Qi; DING Shou-yi; CHENG Hao-qiang; WANG Sheng; DUAN Yu-feng

Volume 48 Issue 7

Jul. 2020

Turn off MathJax

Article Contents

Article Navigation > Journal of Fuel Chemistry and Technology > 2020 > 48(7): 785-794

WANG Yong-xing, HUANG Ya-ji, DONG Lu, YUAN Qi, DING Shou-yi, CHENG Hao-qiang, WANG Sheng, DUAN Yu-feng. Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent[J]. Journal of Fuel Chemistry and Technology, 2020, 48(7): 785-794.

Citation:

WANG Yong-xing, HUANG Ya-ji, DONG Lu, YUAN Qi, DING Shou-yi, CHENG Hao-qiang, WANG Sheng, DUAN Yu-feng. Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent[J]. Journal of Fuel Chemistry and Technology, 2020, 48(7): 785-794.

Citation:

WANG Yong-xing, HUANG Ya-ji, DONG Lu, YUAN Qi, DING Shou-yi, CHENG Hao-qiang, WANG Sheng, DUAN Yu-feng. Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent[J]. Journal of Fuel Chemistry and Technology, 2020, 48(7): 785-794.

PDF( 2632 KB)

Experimental study on mercury removal of coal-fired flue gas over Co-doped iron-based oxide sorbent

1.
Key Laboratory of Energy Thermal Conversion and Control of the Ministry of Education, Southeast University, Nanjing 210096, China
2.
Everbright Environmental Protection Technology Research Institute, Nanjing 210000, China
3.
China State Power Environmental Protection Research Institute, Nanjing 210031, China

Funds:

the National Key Research and Development Projec 2016YFC0201105

More Information

Corresponding author: HUANG Ya-ji, Tel:13851997665, E-mail:heyyj@seu.edu.cn
Received Date: 2020-04-20
Rev Recd Date: 2020-06-19

Available Online: 2021-01-23

Publish Date: 2020-07-10

Abstract

Abstract

In this paper, the citric acid method was used to prepare the Co-doped iron-based oxide sorbent. The mercury removal performance of the FeCo sorbent was investigated by a fixed-bed mercury removal experimental device system, and the characterization methods of the specific surface area (BET), X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR), Fourier infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) were performed to analyze the physical and chemical characteristics of the sorbent. The results of the study indicate that the specific surface area and pore structure characteristics are improved after the addition of Co into α -Fe₂O₃, and the redox performance of α -Fe₂O₃ is also improved. The maximum mercury removal efficiency of FeCo sorbent is obtained at 200-250 ℃ at the value of about 97%. The presence of O₂ and NO in the gas benefits the removal of Hg⁰ over FeCo sorbent, while SO₂ and H₂O inhibit the removal of Hg⁰ over FeCo sorbent. The presence of NO can weaken the inhibitory effect of SO₂ on mercury removal performance over FeCo. During the mercury removal process, the active components Fe³⁺, Co³⁺, and O^* on the surface of the FeCo sorbent are consumed, particitate in the Hg⁰ oxidation process, and HgO is formed on the surface of the sorbent. After the mercury removal reaction in the atmosphere containing SO₂, the sulfation of the sorbent surface is occurred, which weakens the mercury removal performance of the adsorbent.
- mercury,
- iron,
- cobalt,
- coal-fired flue gas

FullText(HTML)

References(40)

References

[1]	YANG Y J, LIU J, WANG Z. Reaction mechanisms and chemical kinetics of mercury transformation during coal combustion[J]. Prog Energy Combust, 2020, 79:100844. doi: 10.1016/j.pecs.2020.100844
[2]	周强, 段钰锋, 卢平.燃煤电厂吸附剂喷射脱汞技术的研究进展[J].化工进展, 2018, 37(11):4460-4467. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hgjz201811044 ZHOU Qiang, DUAN Yu-feng, LU Ping. Research progress on in-duct mercury removal by sorbent injection in power plant[J]. Chem Ind Eng Prog, 2018, 37(11):4460-4467. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=hgjz201811044
[3]	YANG J P, ZHANG M G, LI H L, QU W Q, ZHAO Y C, ZHANG J Y. Simultaneous NO reduction and Hg⁰ oxidation over La_0.8Ce_0.2MnO₃ perovskite catalysts at low temperature[J]. Ind Eng Chem Res, 2018, 57(29):9374-9385. doi: 10.1021/acs.iecr.8b01431
[4]	YANG Z Q, LI H L, YANG J P, FENG S H, LIU X, ZHAO J X, QU W Q, LI P, FENG Y, LEE P, SHIH K. Nanosized copper selenide functionalized zeolitic imidazolate framework-8(CuSe/ZIF-8) for efficient immobilization of gas-phase elemental mercury[J]. Adv Funct Mater, 2019, 29(17):1807191. doi: 10.1002/adfm.201807191
[5]	ZHOU Q, LEI Y, LIU Y B, TAO X, LU P, DUAN Y F, WANG Y J. Gaseous elemental mercury removal by magnetic Fe-Mn-Ce sorbent in simulated flue gas[J]. Energy Fuels, 2018, 32(12):12780-12786. doi: 10.1021/acs.energyfuels.8b03445
[6]	ZHANG S B, ZHAO Y C, YANG J P, ZHANG J Y, ZHENG C G. Fe-modified MnO_x/TiO₂ as the SCR catalyst for simultaneous removal of NO and mercury from coal combustion flue gas[J]. Chem Eng J, 2018, 348:618-629. doi: 10.1016/j.cej.2018.05.037
[7]	LIU Y, WANG Y J, WANG H Q, WU Z B. Catalytic oxidation of gas-phase mercury over Co/TiO₂ catalysts prepared by sol-gel method[J]. Catal Commun, 2011, 12(14):1291-1294. doi: 10.1016/j.catcom.2011.04.017
[8]	CHEN G Y, ZHANG D, ZHANG A C, ZHANG Z H, LIU Z C, HOU L. CrO_x-MnO_x-TiO₂ adsorbent with high resistance to SO₂ poisoning for Hg⁰ removal at low temperature[J]. J Ind Eng Chem, 2017, 55:119-127. doi: 10.1016/j.jiec.2017.06.035
[9]	ZHAO L K, LI C T, DU X Y, ZENG G M, GAO L, ZHAI Y B, WANG T, ZHANG J Y. Effect of Co addition on the performance and structure of V/ZrCe catalyst for simultaneous removal of NO and Hg⁰ in simulated flue gas[J]. Appl Surf Sci, 2018, 437:390-399. doi: 10.1016/j.apsusc.2017.08.165
[10]	HUANG W J, XU H M, QU Z, ZHAO S J, CHEN W M, YAN N Q. Significance of Fe₂O₃ modified SCR catalyst for gas-phase elemental mercury oxidation in coal-fired flue gas[J]. Fuel Process Technol, 2016, 149:23-28. doi: 10.1016/j.fuproc.2016.04.007
[11]	BAUER I, KNoLKER H-J. Iron catalysis in organic synthesis[J]. Chem Rev, 2015, 115(9):3170-3387. doi: 10.1021/cr500425u
[12]	CHEN C, ZUO W Q, YANG J C, CUI H J, FU M L. Yolk-shell structured CoFe₂O₄ microspheres as novel catalysts for peroxymonosulfate activation for efficient degradation of butyl paraben[J]. RSC Adv, 2016, 6(103):101361-101364. doi: 10.1039/C6RA24101H
[13]	LIU T, MAN C Y, GUO X, ZHENG C G. Experimental study on the mechanism of mercury removal with Fe₂O₃ in the presence of halogens:Role of HCl and HBr[J]. Fuel, 2016, 173:209-216. doi: 10.1016/j.fuel.2016.01.054
[14]	MENG B, ZHAO Z B, WANG X Z, LIANG J J, QIU J S. Selective catalytic reduction of nitrogen oxides by ammonia over Co₃O₄ nanocrystals with different shapes[J]. Appl Catal B:Environ, 2013, 129:491-500. doi: 10.1016/j.apcatb.2012.09.040
[15]	GAO L, LI C T, LI S H, ZHANG W, DU X Y, HUANG L, ZHU Y C, ZHAI Y B, ZENG G M. Superior performance and resistance to SO₂ and H₂O over CoO_x-modified MnO_x/biomass activated carbons for simultaneous Hg⁰ and NO removal[J]. Chem Eng J, 2019, 371:781-795. doi: 10.1016/j.cej.2019.04.104
[16]	ZHANG A C, ZHENG W W, SONG J, HU S, LIU ZX, 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. doi: 10.1016/j.cej.2013.09.060
[17]	ZHANG X P, CUI Y Z, WANG J X, TAN B J, LI C F, ZHANG H, HE G H. Simultaneous removal of Hg⁰ and NO from flue gas by Co_0.3-Ce_0.35-Zr_0.35O₂ impregnated with MnO_x[J]. Chem Eng J, 2017, 326:1210-1222. doi: 10.1016/j.cej.2017.06.014
[18]	SHI Y J, DENG S, WANG H M, HUANG J Y, LI Y K, ZHANG F, SHU X Q. Fe and Co modified vanadium-titanium steel slag as sorbents for elemental mercury adsorption[J]. RSC Adv, 2016, 6(19):15999-16009. doi: 10.1039/C5RA26712A
[19]	SHAO C Z, LIU X F, MENG D M, XU Q, GUO Y L, GUO Y, ZHAN W C, WANG L, LU G Z. Catalytic performance of Co-Fe mixed oxide for NH₃-SCR reaction and the promotional role of cobalt[J]. RSC Adv, 2016, 6(70):66169-66179. doi: 10.1039/C6RA12025C
[20]	LI H H, WANG S K, WANG X, HU J J. Activity of CuCl₂-modified cobalt catalyst supported on Ti-Ce composite for simultaneous catalytic oxidation of Hg⁰ and NO in a simulated pre-sco process[J]. Chem Eng J, 2017, 316:1103-1113. doi: 10.1016/j.cej.2017.02.052
[21]	ZHANG P, PAN W G, GUO R T, ZHU X B, LIU J, QIN L, SHE X L. The Mo modified Ce/TiO₂ catalyst for simultaneous Hg⁰ oxidation and NO reduction[J]. J Energy Inst, 2019, 92(5):1313-1328. doi: 10.1016/j.joei.2018.10.003
[22]	APOSTOLESCU N, GEIGER B, HIZBULLAH K, JAN M T, KURETI S, REICHERT D, SCHOTT F, WEISWEILER W. Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts[J]. Appl Catal B:Environ, 2006, 62(1):104-114. http://www.sciencedirect.com/science/article/pii/S0926337305002857
[23]	LIU C X, GONG L, DAI R Y, LU M J, SUN T T, LIU Q, HUANG X G, HUANG Z. Mesoporous Mn promoted Co₃O₄ oxides as an efficient and stable catalyst for low temperature oxidation of CO[J]. Solid State Sci, 2017, 71:69-74. doi: 10.1016/j.solidstatesciences.2017.07.006
[24]	LI H H, WANG S K, WANG X, TANG N, PAN S W, HU J J. Comparative study of Co/TiO₂, Co-Mn/TiO₂ and Co-Mn/Ti-Ce catalysts for oxidation of elemental mercury in flue gas[J]. Chem Pap, 2017, 71(9):1569-1578. doi: 10.1007/s11696-017-0152-5
[25]	CHEN W, ZHANG Z A, BAO W Z, LAI Y Q, LI J, GAN Y Q, WANG J J. Hierarchical mesoporous γ-Fe₂O₃/carbon nanocomposites derived from metal organic frameworks as a cathode electrocatalyst for rechargeable Li-O₂ batteries[J]. Electrochim Acta, 2014, 134:293-301. doi: 10.1016/j.electacta.2014.04.110
[26]	SMIRNIOTIS P G, SREEKANTH P M, PEND A, JENKINS R G. Manganese oxide catalysts supported on TiO₂, Al₂O₃, and SiO₂:A Comparison for Low-Temperature SCR of NO with NH3[J]. Ind Eng Chem Res, 2006, 45(19):6436-6443. doi: 10.1021/ie060484t
[27]	DONG L, HUANG Y J, CHEN H, LIU L Q, LIU C Q, XU L G, ZHA J R, WANG Y X, LIU H. Magnetic γ-Fe₂O₃-loaded attapulgite sorbent for Hg⁰ removal in coal-fired flue gas[J]. Energy Fuels, 2019, 33(8):7522-7533. doi: 10.1021/acs.energyfuels.9b01136
[28]	WU H Y, LI C T, ZHAO L K, ZHANG J, ZENG G M, XIE Y N, ZHANG X N, WANG Y. Removal of gaseous elemental mercury by cylindrical activated coke loaded with CoO_x-CeO₂ from simulated coal combustion flue gas[J]. Energy Fuels, 2015, 29(10):6747-6757. doi: 10.1021/acs.energyfuels.5b00871
[29]	LIU D J, ZHOU W G, WU J. Effect of Ce and La on the activity of CuO/ZSM-5 and MnO_x/ZSM-5 composites for elemental mercury removal at low temperature[J]. Fuel, 2017, 194:115-122. doi: 10.1016/j.fuel.2016.12.076
[30]	于贤群, 鲍静静, 姜小祥, 杨宏旻. Mn-TiO₂催化剂烟气脱汞性能及反应机理[J].中国电机工程学报, 2015, 35(13):3331-3337. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201513016 YU Xian-qun, BAO Jing-jing, JIANG Xiao-xiang, YANG Hong-min. Performance and mechanism of catalytic oxidation for mercury by Mn-doped TiO₂ catalysts in flue gas[J]. Proc CSEE, 2015, 35(13):3331-3337. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=zgdjgcxb201513016
[31]	ZHANG D, HOU L, CHEN G Y, ZHANG A C, WANG F H, WANG R R, LI C W. Cr Doping MnO_x adsorbent significantly improving Hg⁰ removal and SO₂ resistance from coal-fired flue gas and the mechanism investigation[J]. Ind Eng Chem Res, 2018, 57(50):17245-17258. doi: 10.1021/acs.iecr.8b04857
[32]	YANG W, LIU Y X, WANG, 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, 326:169-181. doi: 10.1016/j.cej.2017.05.106
[33]	SHAN Y, YANG W, LI Y, LIU Y X, PAN J F. Preparation of microwave-activated magnetic bio-char adsorbent and study on removal of elemental mercury from flue gas[J]. Sci Total Environ, 2019, 697:134049. doi: 10.1016/j.scitotenv.2019.134049
[34]	ZHANG X P, LI Z F, WANG J X, TAN B J, CUI Y Z, HE G H. Reaction mechanism for the influence of SO₂ on Hg⁰ adsorption and oxidation with Ce_0.1-Zr-MnO₂[J]. Fuel, 2017, 203:308-315. doi: 10.1016/j.fuel.2017.04.065
[35]	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):512-517. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=b15df7cc054faf86a82ac352c510127b
[36]	LI Y, MURPHY P D, WU C Y, POWERS K, BONZONGO J J. Development of silica/vanadia/titania catalysts for removal of elemental mercury from coal-combustion flue gas[J]. Environ Sci Technol, 2008, 42(14):5304-5309. doi: 10.1021/es8000272
[37]	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):698-708. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=495c63f00ef74aa3031a167b713ddd3e
[38]	GAO L, LI C T, ZHANG J, DU X Y, LI S H, ZENG J W, YI Y Y, ZENG G M. Simultaneous removal of NO and Hg⁰ from simulated flue gas over CoO_x-CeO₂ loaded biomass activated carbon derived from maize straw at low temperatures[J]. Chem Eng J, 2018, 342:339-349. doi: 10.1016/j.cej.2018.02.100
[39]	SHEN B X, ZHU S W, ZHANG X, CHI G L, PATEL D, SI M, WU C F. Simultaneous removal of NO and Hg⁰ using Fe and Co co-doped Mn-Ce/TiO₂ catalysts[J]. Fuel, 2018, 224:241-249. doi: 10.1016/j.fuel.2018.03.080
[40]	ZHANG A C, ZHANG Z H, LU H, LIU Z C, XIANG J, ZHOU C S, XING W B, SUN L S. Effect of promotion with Ru addition on the activity and SO₂ resistance of MnO_x-TiO₂ adsorbent for Hg⁰ removal[J]. Ind Eng Chem Res, 2015, 5(11):2930-2939. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=0147f4d8ac1da94d94c34490f8544b24