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

doi:10.1007/s11705-020-1944-7

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (2) : 363-372 https://doi.org/10.1007/s11705-020-1944-7

RESEARCH ARTICLE

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

Xiangchun Liu, Jun Hu, Ruilun Xie, Bin Fang, Ping Cui(

)

Anhui Key Laboratory of Coal Clean Conversion & Utilization, Anhui Province Key Laboratory of Coal Clean Conversion and High Valued Utilization, School of Chemistry and Chemical Engineering, Anhui University of Technology, Ma’anshan 243032, China

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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 physicochemical 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 co-pyrolysis 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.

Keywords co-pyrolysis coal oil shale electron spin resonance mechanism

Corresponding Author(s): Ping Cui

Online First Date: 31 July 2020 Issue Date: 10 March 2021

Cite this article:

Xiangchun Liu,Jun Hu,Ruilun Xie, et al. Formation mechanism of solid product produced from co-pyrolysis of Pingdingshan lean coal with organic matter in Huadian oil shale[J]. Front. Chem. Sci. Eng., 2021, 15(2): 363-372.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-020-1944-7
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I2/363

Tab.1 Proximate and ultimate analyses of LC, OS, and OSA

Fig.1 Schematic of experimental setup.

Tab.2 Yields of all solid products obtained from pyrolysis in the fixed-bed reactor

Fig.2 XRD patterns of (a–c) all samples and (d) curve-fitted XRD pattern in the 2q range 10°?50° for LC.

Tab.3 Crystalline structural parameters of all samples from XRD patterns

Fig.3 C1s fitting spectrum of XPS for MS.

Fig.4 Relative contents of different types of carbon functionalities from XPS analysis.

Fig.5 SEM images of representative samples.

Tab.4 Pore volumes for eight representative samples

Fig.6 TG-DTG curves for MS-experimental, LC, OSA, and MS-calculated.

Fig.7 Changes in radical concentration (N_g) during the co-pyrolysis process (N_g of MS-calculated= 0.7 (N_g of LC) + 0.3 (N_g of OSA)).

Fig.8 A proposed mechanism for the solid product produced from the co-pyrolysis of coal with OSA.

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