Extractive distillation of cycloalkane monomers from the direct coal liquefaction fraction

Abstract

Separating monomeric cycloalkanes from naphtha obtained from direct coal liquefaction not only facilitates the valuable utilization of naphtha but also holds potential for addressing China’s domestic chemical feedstock market demand for these compounds. In extractive distillation processes of naphtha, relative volatility serves as a crucial parameter for extractant selection. However, determining relative volatility through conventional vapor-liquid equilibrium experiments for extractant selection proves challenging due to the complexity of naphtha’s compound composition. To address this challenge, a prediction model for the relative volatility of n-heptane/methylcyclohexane in various extractants has been developed using machine-learning quantitative structure-property relationship methods. The model enables rapid and cost-effective extractant selection. The statistical analysis of the model revealed favorable performance indicators, including a coefficient of determination of 0.88, cross-validation coefficient of 0.94, and root mean square error of 0.02. Factors such as α, E_HOMO, ρ, and logP_oct/water collectively influence relative volatility. Analysis of standardized coefficients in the multivariate linear regression equation identified density as the primary factor affecting the relative volatility of n-heptane/methylcyclohexane in the different extractants. Extractants with higher densities, devoid of branched chains, exhibited increased relative volatility compared to their counterparts with branched chains. Subsequently, the process of separating cycloalkane monomers from direct coal liquefaction products via extractive distillation was optimized using Aspen Plus software, achieving purities exceeding 0.99 and yields exceeding 0.90 for cyclohexane and methylcyclohexane monomers. Economic, energy consumption, and environmental assessments were conducted. Salicylic acid emerged as the most suitable extractant for purifying cycloalkanes in direct coal liquefaction naphtha due to its superior separation effectiveness, cost efficiency, and environmental benefits. The tower parameters of the simulated separation unit provide valuable insights for the design of actual industrial equipment.

Graphical abstract

Keywords

naphtha / relative volatility / molecular descriptor / quantitative structure-property relationship model

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Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (Grant No. 22178243).

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11705-024-2482-5 and is accessible for authorized users.

Nomenclature

AF	The surface area corresponding to an equivalent surface with an electron density of 0.001 a.u. when the molecule is in the gas phase, Å2
EHOMO	Energy of the highest occupied molecular orbital, eV
ELUMO	Energy of the lowest unoccupied molecular orbital, eV
logPoct/water	Partition coefficient of molecules in n-octanol-water, kg·mol−1
SASA	Solvent accessible biomolecular surface area, Å2
V	The volume corresponding to an equivalent surface with an electron density of 0.001 a.u. when the molecule is in the gas phase, Å3
α	Molecular polarizability, a.u.
ρ	The density corresponding to an equivalent surface with an electron density of 0.001 a.u. when the molecule is in the gas phase, g·cm−3

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