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Chemical Thermodynamics and Kinetics of Thiophenic Sulfur Removed from Coal by Microwave: A Density Functional Theory Study

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Abstract

The increasing use of high-sulfur coal contradicts with the stringent environmental pressure in metallurgical industry. Microwave has been confirmed to have efficient effect for coal desulfurization. However, the removal behavior of thiophenic sulfur, as the most difficult sulfur to remove from coal, is still unclear in microwave field. In this work, the feasibility of removing thiophenic sulfur from coal by microwave was evaluated by dielectric properties test, the chemical thermodynamics and kinetics of thiophenic sulfur migration with microwave irradiation were further analyzed by density functional theory (DFT) calculation. Dielectric properties test indicates that thiophenic sulfur is strong for converting electric field energy to heat energy than coal, which means the thiophenic sulfur will be selectively heated in the process of coal desulfurization by microwave. The magnetic loss powers of coal and thiophenic sulfur are very small and can be ignored. DFT calculation shows that under microwave irradiation, the energy barrier and activation energy of rate-limiting step for thiophenic sulfur removal decrease by 7.6 kJ/mol and 2.24 kcal/mol, and the logarithm of rate constant increases by 11.2 s−1. It suggests that the thiophenic sulfur removal is promoted by catalyzing the breaking of C–H and C–C bonds. In addition, the optimal removal path of thiophenic sulfur is also changed, accompanying the variation of sulfur-containing products from carbon monosulfide (CS) to thioketene (C2H2S). These findings reveal the catalytic mechanism of microwave on the thiophenic sulfur removal from coal, which are conducive to the sustainable utilization of high-sulfur coal in metallurgy process.

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References

  1. Li YJ (2021) A brief analysis of coke production and supply in China in 2020. China Steel Focus 2:19–23

    Google Scholar 

  2. National Bureau of Statistics China (2019) The 2019 National economic and social development statistics bulletin of the people’s republic of China (PRC). NBS, Beijing. https://doi.org/10.38309/n.cnki.nzgxx.2020.000341

    Book  Google Scholar 

  3. Tang Y, He X, Chen A, Li W, Deng X, Wei Q (2015) Occurrence and sedimentary control of sulfur in coals of China. J China Coal Soc 40:1977–1988

    CAS  Google Scholar 

  4. Liu J (2011) Reflection on low-carbon development of coal energy in China. J China Univ Min Technol 13:5–12

    Google Scholar 

  5. Lotfian S, Ahmed H, Samuelsson C (2017) Alternative reducing agents in metallurgical processes: devolatilization of shredder residue materials. J Sustain Metall 3(2):311–321. https://doi.org/10.1007/s40831-016-0094-0

    Article  Google Scholar 

  6. Nomura S (2015) Use of waste plastics in coke oven: a review. J Sustain Metall 1(1):85–93. https://doi.org/10.1007/s40831-014-0001-5

    Article  Google Scholar 

  7. Delley B (2000) From molecules to solids with the DMol(3) approach. J Chem Phys 113(18):7756–7764. https://doi.org/10.1063/1.1316015

    Article  CAS  Google Scholar 

  8. Yang N, Guo H, Liu F, Zhang H, Hu Y, Hu R (2018) Effects of atmospheres on sulfur release and its transformation behavior during coal thermolysis. Fuel 215:446–453. https://doi.org/10.1016/j.fuel.2017.11.099

    Article  CAS  Google Scholar 

  9. Kawashima H (2019) Changes in sulfur functionality during solvent extraction of coal in Hyper-coal production. Fuel Process Technol 188:105–109. https://doi.org/10.1016/j.fuproc.2019.02.011

    Article  CAS  Google Scholar 

  10. Chen H, Huo Q, Wang Y, Han L, Lei Z, Wang J et al (2020) Upcycling coal liquefaction residue into sulfur-rich activated carbon for efficient Hg0 removal from coal-fired flue gas. Fuel Process Technol. https://doi.org/10.1016/j.fuproc.2020.106467

    Article  Google Scholar 

  11. Meng X, Li L, Li K, Zhou P, Zhang H, Jia J et al (2018) Desulfurization of fuels with sodium borohydride under the catalysis of nickel salt in polyethylene glycol. J Clean Prod 176:391–398. https://doi.org/10.1016/j.jclepro.2017.12.152

    Article  CAS  Google Scholar 

  12. Tang L, Chen S, Wang S, Tao X, He H, Zheng L et al (2018) Heterocyclic sulfur removal of coal based on potassium tert-butoxide and hydrosilane system. Fuel Process Technol 177:194–199. https://doi.org/10.1016/j.fuproc.2018.04.031

    Article  CAS  Google Scholar 

  13. Zhang B, Zhu G, Lv B, Dong L, Yan G, Zhu X et al (2018) A novel high-sulfur fine coal clean desulfurization pretreatment: microwave magnetic separation, high-gradient effect and magnetic strengthen. J Clean Prod 202:697–709. https://doi.org/10.1016/j.jclepro.2018.08.088

    Article  CAS  Google Scholar 

  14. Tao X, Xu N, Xie M, Tang L (2014) Progress of the technique of coal microwave desulfurization. Int J Coal Sci Technol 1(1):113–128. https://doi.org/10.1007/s40789-014-0006-5

    Article  Google Scholar 

  15. Pecina ET, Camacho LF, Herrera CA, Martinez D (2012) Effect of complexing agents in the desulphurization of coal by H2SO4 and H2O2 leaching. Miner Eng 29:121–123. https://doi.org/10.1016/j.mineng.2011.10.011

    Article  CAS  Google Scholar 

  16. Blaesing M, Melchior T, Mueller M (2011) Influence of temperature on the release of inorganic species during high temperature gasification of Rhenish lignite. Fuel Process Technol 92(3):511–516. https://doi.org/10.1016/j.fuproc.2010.11.005

    Article  CAS  Google Scholar 

  17. Joriani E, Rezai B, Vossoughi M, Osanloo M, Abdollahi M (2004) Oxidation pretreatment for enhancing desulfurization of coal with sodium butoxide. Miner Eng 17(4):545–552. https://doi.org/10.1016/j.mineng.2003.12.007

    Article  CAS  Google Scholar 

  18. Jorjani E, Chelgani SC, Mesroghli S (2008) Application of artificial neural networks to predict chemical desulfurization of Tabas coal. Fuel 87(12):2727–2734. https://doi.org/10.1016/j.fuel.2008.01.029

    Article  CAS  Google Scholar 

  19. Wijaya N, Choo TK, Zhang L (2011) Generation of ultra-clean coal from Victorian brown coal—sequential and single leaching at room temperature to elucidate the elution of individual inorganic elements. Fuel Process Technol 92(11):2127–2137. https://doi.org/10.1016/j.fuproc.2011.05.022

    Article  CAS  Google Scholar 

  20. Zhang B, Ma Z, Zhu G, Yan G, Zhou C (2018) Clean coal desulfurization pretreatment: microwave magnetic separation, response surface, and pyrite magnetic strengthen. Energy Fuels 32(2):1498–1505. https://doi.org/10.1021/acs.energyfuels.7b03561

    Article  CAS  Google Scholar 

  21. Wiser WH (1984) Conversion of bituminous coal to liquids and gases: chemistry and representative processes. In: Petrakis L, Fraissard JP (eds) Magnetic resonance. Springer, Dordrecht, pp 325–350. https://doi.org/10.1007/978-94-009-6378-8_12

    Chapter  Google Scholar 

  22. Zhang L, Wang Y, Li X, Wang S (2016) Region-of-interest extraction based on spectrum saliency analysis and coherence-enhancing diffusion model in remote sensing images. Neurocomputing 207:630–644. https://doi.org/10.1016/j.neucom.2016.05.045

    Article  Google Scholar 

  23. Jorjani E, Chelgani SC, Mesroghli S (2007) Prediction of microbial desulfurization of coal using artificial neural networks. Miner Eng 20(14):1285–1292. https://doi.org/10.1016/j.mineng.2007.07.003

    Article  CAS  Google Scholar 

  24. Qin ZH, Zhang HF, Dai DJ, Zhao CC, Zhang LF (2014) Study on occurrence of sulfur in different group components of Xinyu clean coking coal. J Fuel Chem Technol 42(11):1286–1294

    Article  CAS  Google Scholar 

  25. Tang L, Chen S, Wang S, Tao X, He H, Fan H (2017) Exploration of the combined action mechanism of desulfurization and ash removal in the process of coal desulfurization by microwave with peroxyacetic acid. Energy Fuels 31(12):13248–13258. https://doi.org/10.1021/acs.energyfuels.7b02112

    Article  CAS  Google Scholar 

  26. Yao Q, Sun M, Gao J, Wang R, Zhang Y, Xu L et al (2019) Organic sulfur compositions and distributions of tars from the pyrolysis of solvent pretreatment vitrinite of high sulfur coal. J Anal Appl Pyrolysis 139:291–300. https://doi.org/10.1016/j.jaap.2019.03.002

    Article  CAS  Google Scholar 

  27. Saikia BK, Khound K, Baruah BP (2014) Extractive desulfurization and deashing of high sulfur coals by oxidation with ionic liquids. Energy Convers Manag 81:298–305. https://doi.org/10.1016/j.enconman.2014.02.043

    Article  CAS  Google Scholar 

  28. Mursito AT, Hirajima T, Sasaki K (2011) Alkaline hydrothermal de-ashing and desulfurization of low quality coal and its application to hydrogen-rich gas generation. Energy Convers Manag 52(1):762–769. https://doi.org/10.1016/j.enconman.2010.08.001

    Article  CAS  Google Scholar 

  29. Tang L, Long K, Chen S, Gui D, He C, Li J et al (2020) Removal of thiophene sulfur model compound for coal by microwave with peroxyacetic acid. Fuel 272:1137–1148. https://doi.org/10.1016/j.fuel.2020.117748

    Article  CAS  Google Scholar 

  30. Bichot A, Lerosty M, Radoiu M, Méchin V, Bernet N, Delgenès J-P et al (2020) Decoupling thermal and non-thermal effects of the microwaves for lignocellulosic biomass pretreatment. Energy Convers Manag. https://doi.org/10.1016/j.enconman.2019.112220

    Article  Google Scholar 

  31. Mong GR, Chong CT, Ng JH, Chong WWF, Lam SS, Ong HC et al (2020) Microwave pyrolysis for valorization of horse manure biowaste. Energy Convers Manag. https://doi.org/10.1016/j.enconman.2020.113074

    Article  Google Scholar 

  32. Wu Q, Wang Y, Peng Y, Ke L, Yang Q, Jiang L et al (2020) Microwave-assisted pyrolysis of waste cooking oil for hydrocarbon bio-oil over metal oxides and HZSM-5 catalysts. Energy Convers Manag. https://doi.org/10.1016/j.enconman.2020.113124

    Article  Google Scholar 

  33. Cai SS, Zhang SF, Wei Y, Sher F, Wen LY, Xu J et al (2021) A novel method for removing organic sulfur from high-sulfur coal: Migration of organic sulfur during microwave treatment with NaOH-H2O2. Fuel 289:119800. https://doi.org/10.1016/j.fuel.2020.119800

    Article  CAS  Google Scholar 

  34. Liu J, Wang Z, Qiao Z, Chen W, Zheng L, Zhou J (2020) Evaluation on the microwave-assisted chemical desulfurization for organic sulfur removal. J Clean Prod 267:121878. https://doi.org/10.1016/j.jclepro.2020.121878

    Article  CAS  Google Scholar 

  35. Wu Y, Zhang SF, Cai SS, Xiao X, Yin C, Xu J et al (2019) Transformation of organic sulfur and its functional groups in nantong and laigang coal under microwave irradiation. J Comput Chem 40(31):2749–2760. https://doi.org/10.1002/jcc.26051

    Article  CAS  Google Scholar 

  36. Tao X, Tang L, Xie M, He H, Xu N, Feng L et al (2016) Dielectric properties analysis of sulfur-containing models in coal and energy evaluation of their sulfur-containing bond dissociation in microwave field. Fuel 181:1027–1033. https://doi.org/10.1016/j.fuel.2016.05.005

    Article  CAS  Google Scholar 

  37. Nicolson AM, Ross GF (1970) Measurement of the intrinsic properties of materials by time-domain techniques. IEEE Trans Instrum Meas IM–19(4):377–382. https://doi.org/10.1109/TIM.1970.4313932

    Article  Google Scholar 

  38. Song X, Parish CA (2011) Pyrolysis mechanisms of thiophene and methylthiophene in asphaltenes. J Phys Chem A 115(13):2882–2891. https://doi.org/10.1021/jp1118458

    Article  CAS  Google Scholar 

  39. Ling LX, Zhang RG, Wang BJ, Xie KC (2010) DFT study on the sulfur migration during benzenethiol pyrolysis in coal. J Mol Struct Theochem 952(1–3):31–35. https://doi.org/10.1016/j.theochem.2010.04.001

    Article  CAS  Google Scholar 

  40. Ling LX, Zhang RG, Wang BJ, Xie KC (2009) Density functional theory study on the pyrolysis mechanism of thiophene in coal. J Mol Struct Theochem 905(1–3):8–12. https://doi.org/10.1016/j.theochem.2009.02.040

    Article  CAS  Google Scholar 

  41. Zhang F, Guo H, Liu Y, Liu F, Hu R (2019) Theoretical study on desulfurization mechanisms of a coal-based model compound 2-methylthiophene during pyrolysis under inert and oxidative atmospheres. Fuel 257:116028. https://doi.org/10.1016/j.fuel.2019.116028

    Article  CAS  Google Scholar 

  42. Fan W, Jia C, Hu W, Yang C, Liu L, Zhang X et al (2015) Dielectric properties of coals in the low-terahertz frequency region. Fuel 162:294–304. https://doi.org/10.1016/j.fuel.2015.09.027

    Article  CAS  Google Scholar 

  43. Ge T, Cai C, Chen P, Min F, Zhang M-X (2020) The characterization on organic sulfur occurrence in coking coal and mechanism of microwave action on thiophene. Spectrosc Spectral Anal 40(4):1321–1327. https://doi.org/10.3964/j.issn.1000-0593(2020)04-1321-07

    Article  Google Scholar 

  44. Ge T, Deng N, Min F (2020) The dielectric properties of thiophene model compounds: insights for microwave desulfurization of coking coal. Energy Fuels 34(11):14101–14108. https://doi.org/10.1021/acs.energyfuels.0c03001

    Article  CAS  Google Scholar 

  45. Quan B, Liang XH, Ji GB, Cheng Y, Liu W, Ma JN et al (2017) Dielectric polarization in electromagnetic wave absorption: review and perspective. J Alloys Compd 728:1065–1075. https://doi.org/10.1016/j.jallcom.2017.09.082

    Article  CAS  Google Scholar 

  46. Ge T, Li F, Li Y (2020) Influence of dielectric property of organic sulfur compounds on coal microwave desulfurization. Asia-Pac J Chem Eng. https://doi.org/10.1002/apj.2581

    Article  Google Scholar 

  47. Chen J, Li N, Cui HJ, Liu JY (2007) Study on electromagnetic properties of anthracite and soft coal in microwave field. J Taiyuan Univ Technol 05:405–411. https://doi.org/10.16355/j.cnki.issn1007-9432tyut.2007.05.001

    Article  Google Scholar 

  48. Sutton WH (1989) Microwave processing of ceramic materials. Am Ceram Soc Bull 68(2):376–386

    CAS  Google Scholar 

  49. Ge T, Zhang M (2016) Dielectric properties of the model compounds of thiophene sulfur in coals and its relation to molecular polarity. J China Univ Min Technol 45(6):1245–1250

    Google Scholar 

  50. Peng ZW, Hwang JY, Mouris J, Hutcheon R, Huang XD (2010) Microwave penetration depth in materials with non-zero magnetic susceptibility. ISIJ Int 50(11):1590–1596. https://doi.org/10.2355/isijinternational.50.1590

    Article  CAS  Google Scholar 

  51. Peng ZW, Lin XL, Li ZZ, Hwang JY, Kim BG, Zhang YB et al (2017) Dielectric characterization of Indonesian low-rank coal for microwave processing. Fuel Process Technol 156:171–177. https://doi.org/10.1016/j.fuproc.2016.11.001

    Article  CAS  Google Scholar 

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Acknowledgements

The work is supported by the National Natural Science Foundation of China (Project Nos. 51774061 & 52074055) and Chongqing Talent program (Project No. CQYC201905039). The authors also thank Mr. Yang Zhang (Ingle Testing Technology Services (Shanghai) Co., Ltd) for the support of dielectric measurement.

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Authors and Affiliations

  1. College of Materials Science & Engineering, Chongqing University, Chongqing, 400044, People’s Republic of China

    Chen Yin, Shengfu Zhang, Jincheng Wang, Shuangshuang Cai, Jian Xu, Meilong Hu & Liangying Wen

  2. Chongqing Key Laboratory of Vanadium-Titanium Metallurgy & Advanced Materials, Chongqing University, Chongqing, 400044, People’s Republic of China

    Shengfu Zhang

  3. Department of Engineering, School of Science and Technology, Nottingham Trent University, Nottingham, NG11 8NS, UK

    Farooq Sher

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  1. Chen Yin
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Yin, C., Zhang, S., Wang, J. et al. Chemical Thermodynamics and Kinetics of Thiophenic Sulfur Removed from Coal by Microwave: A Density Functional Theory Study. J. Sustain. Metall. 7, 1379–1392 (2021). https://doi.org/10.1007/s40831-021-00425-4

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