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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

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Front. Chem. Sci. Eng.    2024, Vol. 18 Issue (3) : 32    https://doi.org/10.1007/s11705-024-2396-2
Impact of H2S on Hg0 capture performance over nitrogen-doped carbon microsphere sorbent: experimental and theoretical insights
Guopei Zhang1, Xiaoyang Zhang2(), Xiangwen Xing1, Xiangru Kong1, Lin Cui1, Dong Yong1()
1. National Engineering Laboratory for Reducing Emissions from Coal Combustion, Shandong University, Jinan 250061, China
2. Bingtuan Energy Development Institute, Shihezi University, Shihezi 832000, China
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Abstract

A nitrogen-doped carbon microsphere sorbent with a hierarchical porous structure was synthesized via aggregation-hydrothermal carbonization. The Hg0 adsorption performance of the nitrogen-doped carbon microsphere sorbent was tested and compared with that of the coconut shell activated carbon prepared in the laboratory. The effect of H2S on Hg0 adsorption was also investigated. The nitrogen-doped carbon microsphere sorbent exhibited superior mercury removal performance compared with that of coconut shell activated carbon. In the absence of H2S at a low temperature (≤ 100 °C), the Hg0 removal efficiency of the nitrogen-doped carbon microsphere sorbent exceeded 90%. This value is significantly higher than that of coconut shell activated carbon, which is approximately 45%. H2S significantly enhanced the Hg0 removal performance of the nitrogen-doped carbon microsphere sorbent at higher temperatures (100–180 °C). The hierarchical porous structure facilitated the diffusion and adsorption of H2S and Hg0, while the nitrogen-containing active sites significantly improved the adsorption and dissociation capabilities of H2S, contributing to the generation of more active sulfur species on the surface of the nitrogen-doped carbon microsphere sorbent. The formation of active sulfur species and HgS on the sorbent surface was further confirmed using X-ray photoelectron spectroscopy and Hg0 temperature-programmed desorption tests. Density functional theory was employed to elucidate the adsorption and transformation of Hg0 on the sorbent surface. H2S adsorbed and dissociated on the sorbent surface, generating active sulfur species that reacted with gaseous Hg0 to form HgS.
Keywords nitrogen-doped carbon microsphere      H2S      Hg0 removal      adsorption mechanism     
Corresponding Author(s): Xiaoyang Zhang,Dong Yong   
Just Accepted Date: 21 December 2023   Issue Date: 07 February 2024
 Cite this article:   
Guopei Zhang,Xiaoyang Zhang,Xiangwen Xing, et al. Impact of H2S on Hg0 capture performance over nitrogen-doped carbon microsphere sorbent: experimental and theoretical insights[J]. Front. Chem. Sci. Eng., 2024, 18(3): 32.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-024-2396-2
https://academic.hep.com.cn/fcse/EN/Y2024/V18/I3/32
Fig.1  Scheme of the experimental system for elemental mercury removal.
Fig.2  (a) FT-IR spectra; (b) N2 adsorption-desorption isotherms and pore size distribution of NCM and AC; (c, d) SEM images of NCM.
SampleSBET/(m2·g?1)Smic/(m2·g?1)Micropore content/%Vtot/(cm3·g?1)Dave/nm
NCM68342462.10.2711.59
AC66060591.60.2741.61
Tab.1  Physical properties of NCM and AC
Fig.3  XPS spectra: (a) overall XPS spectra of NCM and AC; (b) C 1s spectra of NCM; (c) N 1s spectra of NCM; (d) O 1s spectra of NCM.
Fig.4  (a) Average Hg0 removal efficiency, (b) instantaneous Hg0 removal efficiency of NCM at different temperatures, and (c) the effect of H2S on instantaneous Hg0 removal efficiency at 60 and 140 °C.
Fig.5  Comparison of Hg0 removal efficiency of NCM with AC.
Fig.6  Hg0 removal efficiency over NCM and AC with and without adding H2S.
Fig.7  XPS patterns of (a) S 2p and (b) Hg 4f for fresh and spent NCM; (c) Hg0-TPD curves of spent NCM.
Fig.8  Hg0 chemisorption complexes for (a) AC surface and (b) NCM, where gray ball represnets carbon atom, red ball represents oxygen atom, blue ball represents nitrogen atom, small white ball represents hydrogen atom, and light blue ball represents mercury atom.
Fig.9  (a) Geometrical diagram and (b) energy profiles of H2S reaction with Hg0 over AC and NCM, where gray ball represents carbon atom, red ball represents oxygen atom, blue ball represents nitrogen atom, yellow ball represents sulfur atom, small white ball represents hydrogen atom, and light blue ball represents mercury atom.
1 F Wang , S Wang , L Zhang , H Yang , Q Wu , J Hao . Characteristics of mercury cycling in the cement production process. Journal of Hazardous Materials, 2016, 302: 27–35
https://doi.org/10.1016/j.jhazmat.2015.09.042
2 H Li , L Zhu , J Wang , L Li , K Shih . Development of nano-sulfide sorbent for efficient removal of elemental mercury from coal combustion fuel gas. Environmental Science & Technology, 2016, 50(17): 9551–9557
https://doi.org/10.1021/acs.est.6b02115
3 E Pacyna , J Pacyna , K Sundseth , J Munthe , K Kindbom , S Wilson , F Steenhuisen , P Maxson . Global emission of mercury to the atmosphere from anthropogenic sources in 2005 and projections to 2020. Atmospheric Environment, 2010, 44(20): 2487–2499
https://doi.org/10.1016/j.atmosenv.2009.06.009
4 N Pirrone , S Cinnirella , X Feng , R Finkelman , H Friedli , J Leaner , R Mason , A Mukherjee , G Stracher , D G Streets . et al.. Global mercury emissions to the atmosphere from anthropogenic and natural sources. Atmospheric Chemistry and Physics, 2010, 10(13): 5951–5964
https://doi.org/10.5194/acp-10-5951-2010
5 Y Guo , B Chen , J Li , Q Yang , Z Wu , X Tang . The evolution of China’s provincial shared producer and consumer responsibilities for energy-related mercury emissions. Journal of Cleaner Production, 2020, 245(1): 118678
https://doi.org/10.1016/j.jclepro.2019.118678
6 L Zhang , S Wang , L Wang , Y Wu , L Duan , Q Wu , F Wang , M Yang , H Yang , J Hao . et al.. Updated emission inventories for speciated atmospheric mercury from anthropogenic sources in China. Environmental Science & Technology, 2015, 49(5): 3185–3194
https://doi.org/10.1021/es504840m
7 Y Wang , Z Dou , X Tang , L Lian , Y Liu . Oxidative absorption of elemental mercury in combustion flue gas using biochar-activated peroxydisulfate system. Journal of the Energy Institute, 2023, 108: 101248
https://doi.org/10.1016/j.joei.2023.101248
8 S Wang , L Zhang , L Wang , Q Wu , F Wang , J Hao . A review of atmospheric mercury emissions, pollution and control in China. Frontiers of Environmental Science & Engineering, 2014, 8(5): 631–649
https://doi.org/10.1007/s11783-014-0673-x
9 A Minchener . Coal gasification for advanced power generation. Fuel, 2015, 84(17): 2222–2235
10 A Midilli , H Kucuk , M E Topal , U Akbulut , I Dincer . A comprehensive review on hydrogen production from coal gasification: challenges and opportunities. International Journal of Hydrogen Energy, 2021, 46(50): 25385–25412
https://doi.org/10.1016/j.ijhydene.2021.05.088
11 S Zhao , C Sun , Y Zhang , T Jiao , W Zhang , P Liang , H Zhang . Determination of mercury occurrence and thermal stability in high ash bituminous coal based on sink-float and sequential chemical extraction method. Fuel, 2019, 253: 571–579
https://doi.org/10.1016/j.fuel.2019.05.054
12 H Zhang , S Zhao , Q Niu , S Chen , X Meng , D Zhang , M Li , P Liang . Mercury distribution in Guizhou bituminous coal and its releasing behavior during mild pyrolysis process. Fuel Processing Technology, 2019, 185: 38–45
https://doi.org/10.1016/j.fuproc.2018.11.015
13 A Chalkidis , D Jampaiah , P G Hartley , Y M Sabri , S K Bhargava . Mercury in natural gas streams: a review of materials and processes for abatement and remediation. Journal of Hazardous Materials, 2020, 382: 121036
https://doi.org/10.1016/j.jhazmat.2019.121036
14 B Zhang , J Liu , J Zhang , C Zheng , M Chang . Mercury oxidation mechanism on Pd(100) surface from first-principles calculations. Chemical Engineering Journal, 2014, 237(1): 344–351
https://doi.org/10.1016/j.cej.2013.10.052
15 J Yang , Y Zhao , S Liang , S Zhang , S Ma , H Li , J Zhang , C Zheng . Magnetic iron-manganese binary oxide supported on carbon nanofiber (Fe3−xMnxO4/CNF) for efficient removal of Hg0 from coal combustion flue gas. Chemical Engineering Journal, 2018, 334: 216–224
https://doi.org/10.1016/j.cej.2017.10.004
16 F Shen , J Liu , Y Dong , D Wu . Mercury removal by biomass-derived porous carbon: experimental and theoretical insights into the effect of H2S. Chemical Engineering Journal, 2018, 348: 409–415
https://doi.org/10.1016/j.cej.2018.05.019
17 H Zhang , J Zhao , Y Fang , J Huang , Y Wang . Catalytic oxidation and stabilized adsorption of elemental mercury from coal-derived fuel gas. Energy & Fuels, 2012, 26(3): 1629–1637
https://doi.org/10.1021/ef201453d
18 Q Huo , Y Wang , H Chen , L Han , J Wang , W Bao , L Chang , K Xie . ZnS/AC sorbent derived from the high sulfur petroleum coke for mercury removal. Fuel Processing Technology, 2019, 191: 36–43
https://doi.org/10.1016/j.fuproc.2019.03.025
19 R Sun , G Luo , X Li , H Tian , H Yao . Theoretical research on role of sulfur allotropes on activated carbon surface in adsorbing elemental mercury. Chemical Engineering Journal, 2021, 404: 126639
https://doi.org/10.1016/j.cej.2020.126639
20 K S K Reddy , A A Shoaibi , C Srinivasakannan . Mercury removal using metal sulfide porous carbon complex. Process Safety and Environmental Protection, 2018, 114: 153–158
https://doi.org/10.1016/j.psep.2017.12.022
21 C Rungnim , V Promarak , S Hannongbua , N Kungwan , S Namuangruk . Complete reaction mechanisms of mercury oxidation on halogenated activated carbon. Journal of Hazardous Materials, 2016, 310: 253–260
https://doi.org/10.1016/j.jhazmat.2016.02.033
22 F Shen , J Liu , Y Dong , D Wu , C Gu , Z Zhang . Elemental mercury removal from syngas by porous carbon-supported CuCl2 sorbents. Fuel, 2019, 239: 138–144
https://doi.org/10.1016/j.fuel.2018.11.016
23 D Hong , J Zhou , C Hu , Q Zhou , J Mao , Q Qin . Mercury removal mechanism of AC prepared by one-step activation with ZnCl2. Fuel, 2019, 235: 326–335
https://doi.org/10.1016/j.fuel.2018.07.103
24 T K Das , S Banerjee , P Sharma , V Sudarsan , P U Sastry . Nitrogen doped porous carbon derived from EDTA: effect of pores on hydrogen storage properties. International Journal of Hydrogen Energy, 2018, 43(17): 8385–8394
https://doi.org/10.1016/j.ijhydene.2018.03.081
25 Z Yu , X Wang , Y Hou , Z Zhao , R Li , J Qiu . Facile preparation of nitrogen-doped porous carbons via salt melt synthesis with efficient catalytic desulfurization performance. Journal of Inorganic Materials, 2017, 32(7): 770–776
https://doi.org/10.15541/jim20160632
26 C Xu , J Chen , S Li , Q Gu , D Wang , C Jiang , Y Liu . N-doped honeycomb-like porous carbon derived from biomass as an efficient carbocatalyst for H2S selective oxidation. Journal of Hazardous Materials, 2021, 403: 123806
https://doi.org/10.1016/j.jhazmat.2020.123806
27 M Huang , H Teng . Nitrogen-containing carbons from phenol-formaldehyde resins and their catalytic activity in NO reduction with NH3. Carbon, 2003, 41(5): 951–957
https://doi.org/10.1016/S0008-6223(02)00436-0
28 X Li , F Sun , Z Qu , X Zhu , J Gao , G Zhao , L Zhang . Insight into synergistic effects of oxygen and nitrogen dual-dopants in carbon catalysts on selective catalytic reduction of NOx with NH3: a combined computational and experimental verification. Chemical Engineering Journal, 2023, 454: 140098
https://doi.org/10.1016/j.cej.2022.140098
29 Z Yu , X Wang , X Song , Y Liu , J Qiu . Molten salt synthesis of nitrogen-doped porous carbons for hydrogen sulfide adsorptive removal. Carbon, 2015, 95: 852–860
https://doi.org/10.1016/j.carbon.2015.08.105
30 Z Yu , X Wang , Y Hou , X Pan , Z Zhao , J Qiu . Nitrogen-doped mesoporous carbon nanosheets derived from metal-organic frameworks in a molten salt medium for efficient desulfurization. Carbon, 2017, 117: 376–382
https://doi.org/10.1016/j.carbon.2017.02.100
31 F Sun , J Liu , H Chen , Z Zhang , W Qiao , D Long , L Ling . Nitrogen-rich mesoporous carbons: highly efficient, regenerable metal-free catalysts for low-temperature oxidation of H2S. ACS Catalysis, 2013, 3(5): 862–870
https://doi.org/10.1021/cs300791j
32 M Shi , G Luo , Y Xu , R Zou , H Zhu , J Hu , X Li , H Yao . Using H2S plasma to modify activated carbon for elemental mercury removal. Fuel, 2019, 254: 115549
https://doi.org/10.1016/j.fuel.2019.05.132
33 H Zhang , D Zhang , J Wang , W Xu , D Yang , T Jiao , W Zhang , P Liang . Simultaneous removal of Hg0 and H2S at a high space velocity by water-resistant SnO2/carbon aerogel. Journal of Hazardous Materials, 2019, 371: 123–129
https://doi.org/10.1016/j.jhazmat.2019.02.112
34 S Clark , M Segall , C Pickard , P Hasnip , M Probert , K Refson , M Payne . First principles methods using CASTEP. Crystalline Materials, 2005, 220(5–6): 567–570
https://doi.org/10.1524/zkri.220.5.567.65075
35 J Perdew , K Burke , M Ernzerhof . Generalized gradient approximation made simple. Physical Review Letters, 1996, 77(18): 3865–3868
https://doi.org/10.1103/PhysRevLett.77.3865
36 N Govind , M Peterson , G Fitzgerald , D King-Smith , J Andzelm . A generalized synchronous transit method for transition state location. Computational Materials Science, 2003, 28(2): 250–258
https://doi.org/10.1016/S0927-0256(03)00111-3
37 Y Li , D Li , Y Rao , X Zhao , M Wu . Superior CO2, CH4, and H2 uptakes over ultrahigh-surface-area carbon spheres prepared from sustainable biomass-derived char by CO2 activation. Carbon, 2016, 105: 454–462
https://doi.org/10.1016/j.carbon.2016.04.036
38 C Long , D Qi , T Wei , J Yan , L Jiang , Z Fan . Nitrogen-doped carbon networks for high energy density supercapacitors derived from polyaniline coated bacterial cellulose. Advanced Functional Materials, 2014, 24(25): 3953–3961
https://doi.org/10.1002/adfm.201304269
39 P Veselá , V Slovák , T Zelenka , M Koštejn , M Mucha . The influence of pyrolytic temperature on sorption ability of carbon xerogel based on 3-aminophenol-formaldehyde polymer for Cu(II) ions and phenol. Journal of Analytical and Applied Pyrolysis, 2016, 121: 29–40
https://doi.org/10.1016/j.jaap.2016.06.016
40 G Zhang , S Sun , D Yang , J Dodelet , E Sacher . The surface analytical characterization of carbon fibers functionalized by H2SO4/HNO3 treatment. Carbon, 2008, 46(2): 196–205
https://doi.org/10.1016/j.carbon.2007.11.002
41 M T Izquierdo , B Rubio , C Mayoral , J M Andrés . Low cost coal-based carbons for combined SO2 and NO removal from exhaust gas. Fuel, 2003, 82(2): 147–151
https://doi.org/10.1016/S0016-2361(02)00249-1
42 H ZhangJ ChenK ZhaoQ NiuL Wang. Removal of vapor-phase elemental mercury from simulated syngas using semi-coke modified by Mn/Ce doping. Journal of Fuel Chemistry & Technology, 2016, 44(4): 394–400 (in Chinese)
43 Z Wang , J Liu , Y Yang , S Miao , F Shen . Effect of the mechanism of H2S on elemental mercury removal using the MnO2 sorbent during coal gasification. Energy & Fuels, 2018, 32(4): 4453–4460
https://doi.org/10.1021/acs.energyfuels.7b03092
44 R Sun , H Zhu , M Shi , G Luo , Y Xu , X Li , H Yao . Preparation of fly ash adsorbents utilizing non-thermal plasma to add S active sites for Hg0 removal from flue gas. Fuel, 2020, 266: 116936
https://doi.org/10.1016/j.fuel.2019.116936
45 S Zou , Y Liao , S Xiong , N Huang , Y Geng , S Yang . H2S-modified Fe–Ti spinel: a recyclable magnetic sorbent for recovering gaseous elemental mercury from flue gas as a co-benefit of wet electrostatic precipitators. Environmental Science & Technology, 2017, 51(6): 3426–3434
https://doi.org/10.1021/acs.est.6b05765
46 H Liu , X Xie , H Chen , S Yang , C Liu , Z Liu , Z Yang , Q Li , X Yan . SO2 promoted ultrafine nano-sulfur dispersion for efficient and stable removal of gaseous elemental mercury. Fuel, 2020, 261(1): 116367
https://doi.org/10.1016/j.fuel.2019.116367
47 Z Wang , J Liu , Y Yang , Y Yu , X Yan , Z Zhang . Regenerable CoxMn3−xO4 spinel sorbents for elemental mercury removal from syngas: experimental and DFT studies. Fuel, 2020, 266: 117105
https://doi.org/10.1016/j.fuel.2020.117105
48 S Yang , D Wang , H Liu , C Liu , X Xie , Z Xu , Z Liu . Highly stable activated carbon composite material to selectively capture gas-phase elemental mercury from smelting flue gas: copper polysulfide modification. Chemical Engineering Journal, 2019, 358: 1235–1242
https://doi.org/10.1016/j.cej.2018.10.134
49 P Sun , B Zhang , X Zeng , G Luo , X Li , H Yao , C Zheng . Deep study on effects of activated carbon’s oxygen functional groups for elemental mercury adsorption using temperature programmed desorption method. Fuel, 2017, 200: 100–106
https://doi.org/10.1016/j.fuel.2017.03.031
50 M Rumayor , M Diaz-Somoano , M Lopez-Anton , M Martinez-Tarazona . Application of thermal desorption for the identification of mercury species in solids derived from coal utilization. Chemosphere, 2015, 119: 459–465
https://doi.org/10.1016/j.chemosphere.2014.07.010
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