Citation: Dian-Kai ZHANG, Yan-Hong LI, Li-Ping CHANG, Chang-Yu ZI, Yuan-Qin ZHANG, Guo-Cai TIAN, Wen-Bo ZHAO. Construction of the Molecular Structure Model of the Zhaotong Lignite Using Simulation and Experiment Data[J]. Chinese Journal of Structural Chemistry, ;2022, 41(3): 220313. doi: 10.14102/j.cnki.0254-5861.2011-3293 shu

Construction of the Molecular Structure Model of the Zhaotong Lignite Using Simulation and Experiment Data

a.
Faculty of Chemical Engineering, Kunming University of Science and Technology, Kunming 650500, China
b.
Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province 030024, China
c.
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, China

Corresponding author: Yan-Hong LI, liyh_2004@163.com
Received Date: 23 June 2021
Accepted Date: 20 August 2021

Fund Project: the National Natural Science Foundation of China 21766013Analysis and Testing Foundation of Kunming University of Science and Technology 2020M20192208021

Figures(6)

Aiming to better understand the physiochemical properties of lignite, we select Zhaotong lignite as object and adopt simulation and experiment data to construct its molecular structure. Firstly, the important parameters including carbon skeleton, valence state and functional group of the sample are obtained by ultimate analysis, ¹³C NMR, XPS and Py-GC/MS. Results indicate that the ratio of aromatic carbon and aromatic bridge carbon to surrounding carbon of the sample are 40.32% and 0.14, respectively. Such results imply that the aromatic structure of the sample is dominated by benzene and naphthalene. Moreover, the ratio of aliphatic carbon is 51.55%, and the aliphatic structure is mainly comprised by methyl, methylene, quaternary carbon and oxygen-aliphatic carbon. Oxygen atoms principally exist in ether, carbonyl and carboxyl groups, of which ether accounts for 70.2%. Additionally, the contents of pyridine, pyrrole and quaternary nitrogen are 25.2%, 46.3% and 13.0%, respectively. Based on the aforementioned results, the molecular structure model of Zhaotong lignite is constructed by the method of computer-aided molecular design. Subsequently, the molecular formula of Zhaotong lignite is calculated as C₁₈₃H₂₁₁O₅₅N₄. Finally, in order to verify the reasonability of the constructed model, the ¹³C NMR of the molecular structure model is simulated by employing the basis set of GIAO/6-31G at the Gaussian 09 computing platform. These simulated results agree well with the experimental ones, which suggests that the molecular structure model of Zhaotong lignite is accurate and reasonable.
- molecular structure model,
- Zhaotong lignite,
- simulated ¹³C NMR,
- molecular simulation
1. [1]
  Zhang, Y. Q.; Li, Y. H.; Chang, L. P.; Zi, C. Y.; Liang, G. B.; Zhang, D. F.; Su, Y. A comparative study on the structural features of humic acids extracted from lignites using comprehensive spectral analyses. RSC Adv. 2020, 10, 22002–22009. doi: 10.1039/D0RA03166F
2. [2]
  Li, Y. H.; Zhang, Y. Q.; Chang, L. P.; Zi, C. Y.; Liang, G. B.; Zhang, D. F.; Xie, W. Analyses on thermal stability of lignites and its derived humic acids. Energ. Source 2020, 4, 1–12.
3. [3]
  Mochidai, O.; Okuma, O.; Yoon, S. H. Chemicals from direct coal liquefaction. Chem. Rev. 2014, 114, 481–488.
4. [4]
  Cong, X. S.; Zong, Z. M.; Zhou, Y.; Li, M.; Wang, W. L.; Li, F. G.; Zhou, J.; Fan, X.; Zhao, Y. P.; Wei, X. Y. Isolation and identification of 3-ethyl-8-methyl-2, 3-dihydro-1H-cyclopenta[a]chrysene from Shengli lignite. Energ. Fuels 2014, 28, 6694–6697. doi: 10.1021/ef402403y
5. [5]
  Yang, Z.; Cao, J. P.; Zhao, X. Y.; Ren, X. Y.; Zhu, C.; Feng, X. B.; Wei, X. Y. Enhanced light aromatic yield from lignite pyrolysis by remedying the acid sites of different hierarchical hzsm-5. Energ. Fuels 2019, 12, 12346–12352.
6. [6]
  Zhang, Z. Q.; Kang, Q. N.; Wei, S.; Yun, T.; Yan, G. C.; Yan, K. F. Large scale molecular model construction of Xishan bituminous coal. Energ. Fuels 2017, 2, 1310–1317.
7. [7]
  Zhang, Y.; Zhang, X. Q.; Zhong, Q. F.; Hu, S. R.; Mathews, J. P. Structural differences of spontaneous combustion prone inertinite-rich Chinese lignite coals: insights from XRD, solid state ¹³C NMR, LDIMS, and HRTEM. Energ. Fuels 2019, 5, 4575–4584.
8. [8]
  Yan, J. C.; Lei, Z. P.; Li, Z. K.; Wang, Z. C.; Ren, S. B.; Kang, S. G.; Wang, X. L.; Shui, H. Molecular structure characterization of low-medium rank coals via XRD, solid state ¹³C NMR and FTIR spectroscopy. Fuel 2020, 268, 117038. doi: 10.1016/j.fuel.2020.117038
9. [9]
  Zhang, D. K.; Li, Y. H.; Zi, C. Y.; Zhang, Y. Q.; Hu, X.; Tian, G. C.; Zhao, W. B. Structural characterization and molecular simulation of Baoqing lignite. ACS Omega 2021, 6, 102881–102887.
10. [10]
  Kaushik, S.; Pratik, S. D. Quantum chemical perspective of coal molecular modeling: a review. Fuel 2020, 279, 118539. doi: 10.1016/j.fuel.2020.118539
11. [11]
  Mathews, J. P.; Chaffee, A. L. The molecular representations of coal – a review. Fuel 2012, 96, 1–14. doi: 10.1016/j.fuel.2011.11.025
12. [12]
  Guo, J. J.; Zhu, C.; He, Q. Q.; Wang, X. H.; Feng, L.; Wu, J. J.; Liu, J. T.; Cao, Z. X. Infrared spectra and pyrolysis of selected molecular models of coal: insight from density functional calculations. Chin. J. Struct. Chem. 2013, 6, 863–870.
13. [13]
  Feng, W.; Gao, H. F.; Wang, G.; Wu, L. L.; Xu, J. Q.; Li, Z. M.; Li, P.; Bai, H. C.; Guo, Q. J. Molecular model and pyrolysis simulation of Zaoquan coal. J. Chem. Ind. Eng. 2019, 70, 1522–1531.
14. [14]
  Shi, K. Y.; Gui, X. H.; Tao, X. X.; Long, J.; Ji, Y. H. Macromolecular structural unit construction of Fushun nitric-acid-oxidized coal. Energ. Fuels 2015, 29, 3566–3572. doi: 10.1021/ef502859r
15. [15]
  Liu, J. X.; Jiang, Y. Z.; Yao, W.; Jiang, X.; Jiang, X. M. Molecular characterization of Henan anthracite coal. Energ. Fuels 2019, 33, 6215–6225. doi: 10.1021/acs.energyfuels.9b01061
16. [16]
  Li, Z. K.; Yan, H. L.; Yan, J. C.; Wang, Z. C.; Lei, Z. P.; Ren, S. B.; Shui, H. F. Drying and depolymerization technologies of Zhaotong lignite: a review. Fuel Process. Technol. 2019, 186, 88–98. doi: 10.1016/j.fuproc.2019.01.002
17. [17]
  Zhao, Y.; Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 2008, 120, 215–241. doi: 10.1007/s00214-007-0310-x
18. [18]
  Wolinski, K. H. R.; Hinton, J. F.; Pulay, P. Methods for parallel computation of SCF NMR chemical shifts by GIAO method: efficient integral calculation, multi-Fock algorithm, and pseudodiagonalization. J. Comput. Chem. 2015, 18, 816–825.
19. [19]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B. Gaussian 09[CP]. Wallingford CT: Gaussian Inc. 2009.
20. [20]
  Mo, Z.; Li, X. X.; Liu, J.; Wang, Z.; Gong, X. M.; Guo, L.; Song, W. L. Pyrolysis of Liulin coal simulated by gpu-based reaxff MD with cheminformatics analysis. Energ. Fuels 2014, 28, 522–534. doi: 10.1021/ef402140n
21. [21]
  Wu, L.; Zhu, Y. M.; Wang, G.; Wang, Y.; Liu, Y. Molecular model and reaxff molecular dynamics simulation of coal vitrinite pyrolysis. J. Mol. Model. 2015, 21, 188. doi: 10.1007/s00894-015-2738-6
22. [22]
  Li, Z. M.; Wang, Y. M.; Li, P.; Li, H. P.; Bai, H. C.; Guo, Q. J. Macromolecular model construction and quantum chemical calculation of Ningdong Hongshiwan coal. J. Chem. Ind. Eng. 2018. 69, 2208–2146.
23. [23]
  Xiang, J. H.; Zeng, F. G.; Li, B.; Zhang, L.; Li, M. F.; Liang, H. Z. Construction of macromolecular structural model of anthracite from Chengzhuang coal mine and its molecular simulation. J. Fuel Chem. Technol. 2013, 41, 391–399. doi: 10.1016/S1872-5813(13)60022-5
24. [24]
  Fan, Y.; Hou, Y. C.; Wu, W. Z.; Liu, Z. Y. The generation of benzene carboxylic acids from lignite and the change in structural characteristics of the lignite during oxidation. Fuel 2017, 203, 214–221. doi: 10.1016/j.fuel.2017.04.096
25. [25]
  Zhou, X. Y.; Zeng, F. G.; Xiang, J. H.; Deng, X. P.; Xiang, X. H. Macromolecular model construction and molecular simulation of organic matter in Majiliang vitrain. J. Chem. Ind. Eng. 2020, 71, 1802–1811.
26. [26]
  Liu, F. J.; Wei, X. Y.; Xie, R. L.; Wang, Y. G.; Li, W. T.; Li, Z. K.; Li, P.; Zong, Z. M. Characterization of oxygen-containing species in methanolysis products of the extraction residue from Xianfeng lignite with negative-ion electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Energ. Fuels 2014, 28, 5596–5605. doi: 10.1021/ef501414g
27. [27]
  Yang, Z.; Wei, X. Y.; Li, Z. M.; Zhang, M.; Teng, D. G.; Zong, Z. M. Comparative studies on the structural features of soluble portions from thermal dissolution/methanolysis and catalytic hydroconversion of an extraction residue from Heishan lignite. Fuel 2019, 241, 1138–1144. doi: 10.1016/j.fuel.2018.11.012
28. [28]
  Phiri, Z.; Everson, R. C.; Neomagus, H. W. J. P.; Wood, B. J. Transformation of nitrogen functional forms and the accompanying chemical-structural properties emanating from pyrolysis of bituminous coals. Appl. Energ. 2018, 146, 414–427.
29. [29]
  Feng, W.; Li, Z. M.; Gao, H. F.; Wang, Q.; Bai, H. C.; Li, P. Understanding the molecular structure of HSW coal at atomic level: a comprehensive characterization from combined experimental and computational study. Green Energy. Environ. 2021, 6, 150–159. doi: 10.1016/j.gee.2020.03.013
30. [30]
  Ma, Y. P.; Xiang, J. H.; Li, M. F.; Zeng, F. G. Macromolecular structural model of the pyridine extracted residue of vitrain from No. 3 coalbed, Liulin and molecular simulation. J. Fuel Chem. Technol. 2012, 40, 1300–1308.
31. [31]
  Chang, H. Z.; Wang, C. G.; Zeng, F. G.; Li, J.; Li, W. Y.; Xie, K. C. XPS comparative analysis of coal macerals with different reducibility. J. Fuel Chem. Technol. 2006, 34, 389–394.
32. [32]
  Zhang, A. H.; Tao, M. X.; Liu, P. Y.; Chen, X. R.; Li, D. D. Advance of research on the occurrence state and content of nitrogen in coal. Coal Goel. Explore. 2016, 44, 9–16.
33. [33]
  Wang, Y. G.; Wei, X. Y.; Wang, S. K.; Li, Z. K.; Li, P.; Liu, F. J.; Zong, Z. M. Structural evaluation of Xiaolongtan lignite by direct characterization and pyrolytic analysis. Fuel Process. Technol. 2016, 144, 248–254. doi: 10.1016/j.fuproc.2015.12.034
34. [34]
  Jiang, Y.; Zong, P. J.; Tian, B.; Xu, F. F.; Tian, Y. Y.; Qiao, Y. Y.; Zhang, J. H. Pyrolysis behaviors and product distribution of Shenmu coal at high heating rate: a study using TG-FTIR and Py-GC/MS. Energ. Convers. Manage. 2019, 179, 72–80. doi: 10.1016/j.enconman.2018.10.049
35. [35]
  Yan, L. J.; Bai, Y. H.; Kong, X. J.; Li, F. Effects of alkali and alkaline earth metals on the formation of light aromatic hydrocarbons during coal pyrolysis. J. Anal. Appl. Pyrol. 2016, 122, 169–174. doi: 10.1016/j.jaap.2016.10.001
36. [36]
  Kong, J.; Zhao, R.; Bai, Y.; Li, G.; Zhang, C.; Li, F. Study on the formation of phenols during coal flash pyrolysis using pyrolysis-GC/MS. Fuel Process. Technol. 2014, 127, 41–46. doi: 10.1016/j.fuproc.2014.06.004
37. [37]
  Lin, H. L; Lian, J.; Liu, Y. P.; Xue, Y.; Yan, S.; Han, S.; Wei, W. Comprehensive study of structure model, pyrolysis and liquefaction behavior of Heidaigou lignite and its liquefied oil. Fuel 2019, 240, 84–91. doi: 10.1016/j.fuel.2018.11.067
38. [38]
  Lin, H. L.; Li, K. J.; Zhang, X. W.; Wang, H. X. Structure characterization and model construction of indonesian brown coal. Energ. Fuels 2016, 30, 3809–3814. doi: 10.1021/acs.energyfuels.5b02696
39. [39]
  Fu, X. H.; Lu, L.; Ge, Y. Y.; Tian, J. J.; Luo, P. P. China lignite resources and physical features. Coal Sci. Technol. 2012, 40, 104–107.
40. [40]
  Zhang, S.; Ma, R. J.; Liu, L.; Zhang, H.; Liu, Q. F. Molecular structure characteristics and model construction of anthracite in Jarud. Coal Goel. Explore. 2020, 48, 62–69.
41. [41]
  Feng, L.; Zhao, G. Y.; Zhao, Y. Y.; Zhao, M. S.; Tang, J. W. Construction of the molecular structure model of the Shengli lignite using TG-GC/MS and FTIR spectrometry data. Fuel 2017, 203, 924–931.
42. [42]
  Jia, J. B.; Wang, Y.; Li, F. H.; Yi, G. Y.; Zeng, F. G.; Guo, H. Y. IR spectrum simulation of molecular structure model of Shendong coal vitrinite by quantum chemistry method. Spectrosc. Spect. Anal. 2014, 34, 47–51.
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