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Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale

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Abstract

A mixture of Pingdingshan lean coal and acid-treated Huadian oil shale was co-pyrolyzed in a drop-tube fixed-bed reactor in the temperature range of 300 °C–450 °C. To reveal the formation mechanism of the solid co-pyrolysis product, changes in some physico-chemical properties were investigated, using analysis by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, pore analysis, thermogravimetry, and electron spin resonance. X-ray diffraction showed that the lattice plane spacing for the co-pyrolyzed mixture decreased from 0.357 nm to 0.346 nm and the average stacking height increased from 1.509 nm to 1.980 nm in the temperature range of 300 °C–450 °C, suggesting that pyrolysis treatment increased its degree of metamorphism. The amount of oxygen-containing functional groups and pore volume decreased with increasing temperature. Thermogravimetry and electron spin resonance results showed that synergistic effects occurred during the copyrolysis process. A formation mechanism for the solid product was proposed. Hydrogen-rich radicals generated from the pyrolysis of the oil shale were trapped by hydrogen-poor macromolecular radicals of the intermediate metaplast produced from coal pyrolysis, thereby increasing the yield of solid product.

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References

  1. Solomon P R, Fletcher T H, Pugmire R J. Progress in coal pyrolysis. Fuel, 1993, 72(5): 587–597

    Article  CAS  Google Scholar 

  2. Zhao X, Liu Z, Liu Q. The bond cleavage and radical coupling during pyrolysis of Huadian oil shale. Fuel, 2017, 199: 169–175

    Article  CAS  Google Scholar 

  3. Gavalas G. Coal Pyrolysis. Amsterdam: Elsevier, 1982, 39–72

    Google Scholar 

  4. Chen Z, Li Y, Lai D, Geng S, Zhou Q, Gao S, Xu G. Coupling coal pyrolysis with char gasification in a multi-stage fluidized bed to co-produce high-quality tar and syngas. Applied Energy, 2018, 215: 348–355

    Article  CAS  Google Scholar 

  5. Jiang Y, Zong P, Tian B, Xu F, Tian Y, Qiao Y, Zhang J. Pyrolysis behaviors and product distribution of Shenmu coal at high heating rate: a study using TG-FTIR and Py-GC/MS. Energy Conversion and Management, 2019, 179: 72–80

    Article  CAS  Google Scholar 

  6. Chen G, Ma X, Lin M, Lin Y, Yu Z. Study on thermochemical kinetic characteristics and interaction during low temperature oxidation of blended coals. Journal of the Energy Institute, 2015, 88(3): 221–228

    Article  CAS  Google Scholar 

  7. National Bureau of Statistics of China. China Statistical Yearbook. Beijing: China Statisticals Press, 2018, 129–145

    Google Scholar 

  8. Ministry of Natural Resources of China. 2018 China Mineral Resources. Beijing: Geological Publishing House, 2018, 1–4

    Google Scholar 

  9. Han X, Kulaots I, Jiang X, Suuberg E M. Review of oil shale semicoke and its combustion utilization. Fuel, 2014, 126: 143–161

    Article  CAS  Google Scholar 

  10. Bai F, Sun Y, Liu Y, Li Q, Guo M. Thermal and kinetic characteristics of pyrolysis and combustion of three oil shales. Energy Conversion and Management, 2015, 97: 374–381

    Article  Google Scholar 

  11. Speight J G. Shale Oil Production Processes. Boston: Gulf Professional Publishing, 2012, 19–24

    Google Scholar 

  12. Zhang S. Coal Chemistry. Xuzhou: China University of Mining and Technology Press, 2009, 157–158 (in Chinese)

    Google Scholar 

  13. Lin Y, Liao Y, Yu Z, Fang S, Lin Y, Fan Y, Peng X, Ma X. Co-pyrolysis kinetics of sewage sludge and oil shale thermal decomposition using TGA-FTIR analysis. Energy Conversion and Management, 2016, 118: 345–352

    Article  CAS  Google Scholar 

  14. Abnisa F, Daud W M A. A review on co-pyrolysis of biomass: an optional technique to obtain a high-grade pyrolysis oil. Energy Conversion and Management, 2014, 87: 71–85

    Article  CAS  Google Scholar 

  15. GB/T1996-2003, Coke for Metallurgy. Chinese Standard, 2003

  16. Saxby J D. Isolation of kerogen in sediments by chemical methods. Chemical Geology, 1970, 6: 173–184

    Article  CAS  Google Scholar 

  17. Alnawafleh H M, Fraige F Y. Shale oil solvent extraction of central Jordan El-Lajjun oil shale. Journal of Analytical Sciences. Methods and Instrumentation, 2015, 5: 35–43

    Article  CAS  Google Scholar 

  18. Nassef E, Soliman A, Al-Alla R A, Eltaweel Y. Experimental study on solvent extraction of Quseir oil shale in Egypt. Journal of Surface Engineered Materials and Advanced Technology, 2015, 5(03): 147–153

    Article  Google Scholar 

  19. Hu H, Zhang J, Guo S, Chen G. Extraction of Huadian oil shale with water in sub- and supercritical states. Fuel, 1999, 78(6): 645–651

    Article  CAS  Google Scholar 

  20. Fedyaeva O N, Antipenko V R, Dubov D Y, Kruglyakova T V, Vostrikov A A. Non-isothermal conversion of the Kashpir sulfur-rich oil shale in a supercritical water flow. Journal of Supercritical Fluids, 2016, 109: 157–165

    Article  CAS  Google Scholar 

  21. Wang Z, Deng S, Gu Q, Cui X, Zhang Y, Wang H. Subcritical water extraction of Huadian oil shale under isothermal condition and pyrolysate analysis. Energy & Fuels, 2014, 28(4): 2305–2313

    Article  CAS  Google Scholar 

  22. Yürüm Y, Dror Y, Levy M. Effect of acid dissolution on the mineral matrix and organic matter of Zefa EFE oil shale. Fuel Processing Technology, 1985, 11(1): 71–86

    Article  Google Scholar 

  23. Yan J, Jiang X, Han X, Liu J. A TG-FTIR investigation to the catalytic effect of mineral matrix in oil shale on the pyrolysis and combustion of kerogen. Fuel, 2013, 104: 307–317

    Article  CAS  Google Scholar 

  24. Li S, Ma X, Liu G, Guo M. A TG-FTIR investigation to the co-pyrolysis of oil shale with coal. Journal of Analytical and Applied Pyrolysis, 2016, 120: 540–548

    Article  CAS  Google Scholar 

  25. Miao Z, Wu G, Li P, Meng X, Zheng Z. Investigation into co-pyrolysis characteristics of oil shale and coal. International Journal of Mining Science and Technology, 2012, 22(2): 245–249

    Article  CAS  Google Scholar 

  26. He D, Guan J, Hu H Q, Zhang Q M. Pyrolysis and co-pyrolysis of Chinese Longkou oil shale and Mongolian Huolinhe lignite. Oil Shale, 2015, 32(2): 151–159

    Article  CAS  Google Scholar 

  27. Vassilev S V, Baxter D, Andersen L K, Vassileva C G. An overview of the composition and application of biomass ash. Part 1. Phasemineral and chemical composition and classification. Fuel, 2013, 105: 40–76

    Article  CAS  Google Scholar 

  28. Zhang L, Xu S, Zhao W, Liu S. Co-pyrolysis of biomass and coal in a free fall reactor. Fuel, 2007, 86(3): 353–359

    Article  CAS  Google Scholar 

  29. Sonobe T, Worasuwannarak N, Pipatmanomai S. Synergies in co-pyrolysis of Thai lignite and corncob. Fuel Processing Technology, 2008, 89(12): 1371–1378

    Article  CAS  Google Scholar 

  30. Sahu S G, Chakraborty N, Sarkar P. Coal-biomass co-combustion: an overview. Renewable & Sustainable Energy Reviews, 2014, 39: 575–586

    Article  CAS  Google Scholar 

  31. Yu J, Lucas J A, Wall T F. Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: a review. Progress in Energy and Combustion Science, 2007, 33(2): 135–170

    Article  CAS  Google Scholar 

  32. Liu Z, Guo X, Shi L, He W, Wu J, Liu Q, Liu J. Reaction of volatiles—A crucial step in pyrolysis of coals. Fuel, 2015, 154: 361–369

    Article  CAS  Google Scholar 

  33. Miura K. Mild conversion of coal for producing valuable chemicals. Fuel Processing Technology, 2000, 62(2): 119–135

    Article  CAS  Google Scholar 

  34. Srinivasan G, Seehra M S. Effect of pyrite and pyrrhotite on free radical formation in coal. Fuel, 1983, 62(7): 792–794

    Article  CAS  Google Scholar 

  35. Zhao X, Liu Z, Lu Z, Shi L, Liu Q. A study on average molecular structure of eight oil shale organic matters and radical information during pyrolysis. Fuel, 2018, 219: 399–405

    Article  CAS  Google Scholar 

  36. Zhang X, Liu Z, Chen Z, Xu T, Liu Q. Bond cleavage and reactive radical intermediates in heavy tar thermal cracking. Fuel, 2018, 233: 420–426

    Article  CAS  Google Scholar 

  37. Liu M, Yang J, Yang Y, Liu Z, Shi L, He W, Liu Q. The radical and bond cleavage behaviors of 14 coals during pyrolysis with 9,10-dihydrophenanthrene. Fuel, 2016, 182: 480–486

    Article  CAS  Google Scholar 

  38. Wang W, Ma Y, Li S, Shi J, Teng J. Effect of Temperature on the EPR properties of oil shale pyrolysates. Energy & Fuels, 2016, 30 (2): 830–834

    CAS  Google Scholar 

  39. Bai F, Sun Y, Liu Y, Guo M. Evaluation of the porous structure of Huadian oil shale during pyrolysis using multiple approaches. Fuel, 2017, 187: 1–8

    Article  CAS  Google Scholar 

  40. Chen B, Han X, Li Q, Jiang X. Study of the thermal conversions of organic carbon of Huadian oil shale during pyrolysis. Energy Conversion and Management, 2016, 127: 284–292

    Article  CAS  Google Scholar 

  41. Lai D, Zhang G, Xu G. Characterization of oil shale pyrolysis by solid heat carrier in moving bed with internals. Fuel Processing Technology, 2017, 158: 191–198

    Article  CAS  Google Scholar 

  42. Liu X, Ling Q, Zhao Z, Xie R, Yu D, Ke Q, Lei Z, Cui P. Effects of low-temperature rapid pyrolysis treatment on the improvement in caking property of a Chinese sub-bituminous coal. Journal of Analytical and Applied Pyrolysis, 2018, 135: 319–326

    Article  CAS  Google Scholar 

  43. Liu X C, Fang B, Zhao Z G, Xie R L, Lei Z, Ling Q, Cui P. Modification mechanism of caking and coking properties of Shenmu subbituminous coal by low-temperature rapid pyrolysis treatment. Journal of Iron and Steel Research International, 2019, 10 (10): 1052–1060

    Article  CAS  Google Scholar 

  44. Liu X, Cheng F, Hirajima T, Cui P. Effects of activated carbon on optimization of microwave irradiation upgrading of Loy Yang lignite. Asia-Pacific Journal of Chemical Engineering, 2019, 14(1): 1–9

    Google Scholar 

  45. Liu X, Yu D, Zhao Z, Xie R, Cui P. Dewatering of Loy Yang lignite using microwave irradiation treatment and the microscopic description of the process. Drying Technology, 2019, 37(12): 1481–1489

    Article  CAS  Google Scholar 

  46. Zhong M, Gao S, Zhou Q, Yue J, Ma F, Xu G. Characterization of char from high temperature fluidized bed coal pyrolysis in complex atmospheres. Particuology, 2016, 25: 59–67

    Article  CAS  Google Scholar 

  47. Sonibare O O, Haeger T, Foley S F. Structural characterization of Nigerian coals by X-ray diffraction, Raman and FTIR spectroscopy. Energy, 2010, 35(12): 5347–5353

    Article  CAS  Google Scholar 

  48. Baysal M, Yürüm A, Yıldız B, Yürüm Y. Structure of some western Anatolia coals investigated by FTIR, Raman, 13C solid state NMR spectroscopy and X-ray diffraction. International Journal of Coal Geology, 2016, 163: 166–176

    Article  CAS  Google Scholar 

  49. Tian B, Qiao Y, Tian Y, Xie K, Li D. Effect of heat reflux extraction on the structure and composition of a high-volatile bituminous coal. Applied Thermal Engineering, 2016, 109: 560–568

    Article  CAS  Google Scholar 

  50. Shui H, Wu Y, Wang Z, Lei Z, Lin C, Ren S, Pan C, Kang S. Hydrothermal treatment of a sub-bituminous coal and its use in coking blends. Energy & Fuels, 2013, 27(1): 138–144

    Article  CAS  Google Scholar 

  51. Wang H, Liu S, Li X, Yang D, Wang X, Song C. Morphological and structural evolution of bituminous coal slime particles during the process of combustion. Fuel, 2018, 218: 49–58

    Article  CAS  Google Scholar 

  52. Zhang Y, Wu J, Wang Y, Miao Z, Si C, Shang X, Zhang N. Effect of hydrothermal dewatering on the physico-chemical structure and surface properties of Shengli lignite. Fuel, 2016, 164: 128–133

    Article  CAS  Google Scholar 

  53. Liu X C, Cui P, Ling Q, Zhao Z G, Xie R L. A review on co-pyrolysis of coal and oil shale to produce coke. Frontiers of Chemical Science and Engineering, 2020, 14(4): 504–512

    Article  CAS  Google Scholar 

  54. He W, Liu Z, Liu Q, Ci D, Lievens C, Guo X. Behaviors of radical fragments in tar generated from pyrolysis of 4 coals. Fuel, 2014, 134: 375–380

    Article  CAS  Google Scholar 

  55. Lewis I C, Singer L S. Electron spin resonance of stable aromatic radical intermediates in pyrolysis. Carbon, 1969, 7(1): 93–99

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 21776002), the Natural Science Foundation of Anhui Provincial Education Department (Grant Nos. KJ2016A097, KJ2017A056, and KJ2019A0076), the Innovation Project of Overseas People of Anhui Province, the Science and Technology Major Projects of Anhui Province (Grant Nos. 17030901086), and the Natural Science Foundation of Anhui Province (Grant Nos. 1708085QB33 and 2008085QB87).

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Correspondence to Ping Cui.

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Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale

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Liu, X., Hu, J., Xie, R. et al. Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale. Front. Chem. Sci. Eng. 15, 363–372 (2021). https://doi.org/10.1007/s11705-020-1944-7

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