In view of the frequent occurrence of gas accidents in coal mines, the mechanism of oxygen-containing functional groups (OCFGs) in Danhou lignite adsorbing gas was studied by experiment and simulation. Elemental analysis, X-ray photoelectron spectroscopy (XPS), solid-state 13C nuclear magnetic resonance spectroscopy (13C-NMR), and adsorption experiment of CH4 were applied to establish the macromolecular model of Danhou lignite. Then, molecular mechanics (MM) and molecular dynamics (MD) were utilized to optimize the coal macromolecular model, and the density of coal was determined via adding periodic boundary conditions. The mechanism of gas adsorption by OCFGs was studied by grand canonical Monte Carlo (GCMC) and density functional theory (DFT). The results showed that the aromatic structures mostly exist in the form of pyrenes; the structure of aliphatic carbons are mostly methylene and methine groups; the alkanes are mostly long chains; oxygen atoms are mainly in the form of hydroxyl groups and ether groups; nitrogen atoms are mainly in the form of pyridines; and the density of Danhou lignite is 1.25 g/cm3. The isotherm adsorption curve and Langmuir adsorption curve have a good fit, a single coal molecule reaches saturation after absorbing four CH4 molecules, and the error between experiment and simulation is small. The results of DFT calculation showed that the adsorption of CH4 by OCFGs is affected by the adsorption positions and adsorption directions. Due to CH4 molecules are affected by different electrostatic forces, the adsorption capacities of OCFGs are different, and the order is carbonyl groups > ether bonds > hydroxyl groups > carboxyl groups. The results can be used for reference in the prevention and control of coal and gas outburst.
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Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimo-lecular layers. J Am Chem Soc 60:309–319
Carlson GA (1992) Computer simulation of the molecular structure of bituminous coal. Energy Fuel 6:771–778
Chen G, Lu S, Liu K, Xue Q, Han T, Xu C, Tong M, Pang X, Ni B, Lu S (2019) Critical factors controlling shale gas adsorption mechanisms on different minerals investigated using GCMC simulations. Mar Pet Geol 100:31–42
Chermin HAG, Van Krevelen DW (1957) Chemical structure and properties of coal. XVII-A mathematical model of coal pyrolysis. Fuel 36:85–104
Fisne A, Esen O (2014) Coal and gas outburst hazard in Zonguldak Coal Basin of Turkey, and association with geological parameters. Nat Hazards 74:1363–1390
Freundlich H (1930) Second liversidge lecture. Surface forces and chemical equilibrium. J Chem Soc 4:164–179
Fu Y, Song Y (2018) CO2-adsorption promoted CH4-desorption onto low-rank coal vitrinite by density functional theory including dispersion correction (DFT-D3). Fuel 219:259–269
Gao Z, Yang W (2017) Adsorption mechanism of water molecule on different rank coals molecular surface. J China Coal Soc 42:753–759 (in Chinese)
Given PH (1960) The distribution of hydrogen in coals and its relation to coal structure. Fuel 39:147
Grimme S (2011) Density functional theory with London dispersion corrections. Wiley Interdiscip Rev: Comput Mol Sci 1:211–228
Grimme S, Antony J, Ehrlich S, Krieg H (2010) A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 132:154104
Hao S, Wen J, Xu X (2013) Effect of the surface oxygen groups on methane adsorption on coals. Appl Surf Sci 264:433–442
Jin D, Lu X, Zhang M, Wei S, Zhu Q, Shi X, Yang S, Wang W, Guo W (2014) The adsorption behaviour of CH4 on microporous carbons: effects of surface heterogeneity. Phys Chem Chem Phys 16:11037–11046
Kang Y, Huang F, You L, Li X, Gao B (2016) Impact of fracturing fluid on multi-scale mass transport in coalbed methane reservoirs. Int J Coal Geol 154:123–135
Khaddour F, Knorst-Fouran A, Plantier F, Pineiro MM, Mendiboure B, Miqueu C (2014) A fully consistent experimental and molecular simulation study of methane adsorption on activated carbon. Adsorption 20:649–656
Kong X, Wang J (2016) Copper (II) adsorption on the kaolinite (001) surface: Insights from first-principles calculations and molecular dynamics simulations. Appl Surf Sci 389:316–323
Langmuir I (1917) The constitution and fundamental properties of solids and liquids. Pergamon 183:1
Liu Y (2019) Effect of coal vitrinite macromolecular structure evolution on methane adsorption capacity at molecular level. China University of Mining and Technology (in Chinese)
Liu Y, Wang D, Hao F, Liu M, Mitri HS (2017) Constitutive model for methane desorption and diffusion based on pore structure differences between soft and hard coal. Int J Min Sci Technol 27:937–944
Ma R, Zhang S, Hou D, Liu W, Yuan L, Liu Q (2019) Model construction and optimization of molecule structure of high-rank coal in Feng County, Shaanxi Province. J China Coal Soc 44:1827–1835 (in Chinese)
Ma Y, Nie B, He X, Li X, Meng J, Song D (2020) Mechanism investigation on coal and gas outburst: an overview. Int J Miner Metall Mater 27:872–887
Mathews JP, Chaffee AL (2012) The molecular representations of coal-A review. Fuel 96:1–14
Meng J, Zhong R, Li S, Yin F, Nie B (2018) Molecular model construction and study of gas adsorption of Zhaozhuang coal. Energy Fuel 32:9727–9737
Meng J, Yin F, Li S, Zhong R, Sheng Z, Nie B (2019) Effect of different concentrations of surfactant on the wettability of coal by molecular dynamics simulation. Int J Min Sci Techono 29:577–584
Perdew JP, Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:13244–13249
Shinn JH (1984) From coal to single-stage and two-stage products: a reactive model of coal structure. Fuel 63:1187–1196
Shinn JH (1996) Visualization of complex hydrocarbon reaction systems. Prepr Pap Am Chem Soci Div Fuel Chem 37:418
Song Y (2019) Evolution mechanism of nano-pore and macromolecule in low and middle-rank tectonically deformed coals (TDCs). China Univ Min Technol (in Chinese)
Song Y, Jiang B, Li J (2017a) Simulations and experimental investigations of the competitive adsorption of CH4 and CO2 on low-rank coal vitrinite. J Mol Model 23:280
Song Y, Jiang B, Li W (2017b) Molecular simulation of CH4/CO2/H2O competitive adsorption on low rank coal vitrinite. Phys Chem Chem Phys 19:17773–17788
Song Y, Jiang B, Qu M (2018) Molecular dynamic simulation of self- and transport diffusion for CO2/CH4/N2 in low-rank coal vitrinite. Energy Fuel 32:3085–3096
Song Y, Jiang B, Lan F (2019) Competitive adsorption of CO2/N2/CH4 onto coal vitrinite macromolecular: effects of electrostatic interactions and oxygen functionalities. Fuel 235:23–38
Song Z, Huang X, Kuenzer C, Zhu H, Jiang J, Pan X, Zhong X (2020) Chimney effect induced by smoldering fire in a U-shaped porous channel: a governing mechanism of the persistent underground coal fires. Process Saf Environ 136:136–147
Sun Q, Li W, Chen H, Li B (2004) Molecular modeling of coal macerals by using quantum chemistry. J Fuel Chem Technol 3:282–286 (in Chinese)
Takanohashi T, Nakamura K, Terao Y, Iino M (2000) Computer simulation of solvent swelling of coal molecules: effect of different solvents. Energy Fuel 14:393–399
Tan B, Zhang F, Zhang Q, Wei H, Shao Z (2019) Firefighting of subsurface coal fires with comprehensive techniques for detection and control: a case study of the Fukang coal fire in the Xinjiang region of China. Environ Sci Pollut Res 29:29570–29584
Tian H, Li T, Zhang T, Xiao X (2016) Characterization of methane adsorption on overmature Lower Silurian-Upper Ordovician shales in Sichuan Basin, southwest China: experimental results and geological implications. Int J Coal Geol 156:36–49
Trewhella MJ, Poplett LJF, Grint A (1986) Structure of Green River oil shale kerogen determination using solid state13C NMR spectroscopy. Fuel 65:541–546
Van ND, Mathews JP (2010) Molecular representations of Permian-aged vitrinite-rich and inertinite-rich South African coals. Fuel 89:73–82
Wang X, Wang J, Deng H, Ye B (2008) Physical adsorption mechanism of coal surface containing sulfur group adsorption to more oxygen molecule. J China Coal Soc 5:556–560 (in Chinese)
Wang Y, Lian J, Xue Y, Liu P, Dai B, Lin H, Han S (2020) The pyrolysis of vitrinite and inertinite by a combination of quantum chemistry calculation and thermogravimetry-mass spectrometry. Fuel 264:116794
Wiser WH (1975) Reported in division of fuel chemistry. Preprints 20:122
Wu S, Deng C, Wang X (2019) Molecular simulation of flue gas and CH4 competitive adsorption in dry and wet coal. J Nat Gas Sci Eng 71:102980
Wu S, Zheng X, Khanna N, Feng W (2020) Fighting coal - effectiveness of coal-replacement programs for residential heating in China: empirical findings from a household survey. Energy Sustain Dev 55:170–180
Xiang J, Zeng F, Liang H, Li B, Song X (2014) Molecular simulation of the CH4/CO2/H2O adsorption onto the molecular structure of coal. Sci China Earth Sci 57:1749–1759
Xin H, Wang D, Qi X, Xu T, Dou G, Zhong X (2013) Distribution and quantum chemical analysis of lignite surface functional groups. China J Eng 3502:135–139 (in Chinese)
Xu S, Ge J (2020) Sustainable shifting from coal to gas in North China: an analysis of resident satisfaction. Energy Policy 138:111296
Zeng F, Xie K (2004) Theoretical system and methodology of coal structural chemistry. J China Coal Soc 4:443 (in Chinese)
Zhang J, Zhang D, Huo P, Jiang W, Yang Z, Yang R, Li W, Jia S (2017) Functional groups on coal matrix surface dependences of carbon dioxide and methane adsorption: a perspective. Chem Ind Eng Prog 36:1977–1988 (in Chinese)
Zhao J, Wang T, Deng J, Shu CM, Zeng Q, Guo T, Zhang Y (2020) Microcharacteristic analysis of CH4 emissions under different conditions during coal spontaneous combustion with high-temperature oxidation and in situ FTIR. Energy 2020:209
This study was funded by the National Key R&D Program of China (Grant No. 2016YFC0801800), the National Natural Science Foundation of China (Grant No. 51704299 and Grant No. 51804311), and the Open Research Fund of State Key Laboratory of Coal Mine Safety Technology (Project No. sklcmst102).
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Zhu, H., Huo, Y., He, X. et al. Molecular model construction of Danhou lignite and study on adsorption of CH4 by oxygen functional groups. Environ Sci Pollut Res (2021). https://doi.org/10.1007/s11356-021-12399-7
- Construction of coal molecular model
- Isotherm adsorption curve
- Oxygen functional groups
- Methane adsorption mechanism