1. State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China 2. College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
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, EHOMO, ρ, and logPoct/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.
Corresponding Author(s):
Xing-Bao Wang,Wen-Ying Li
引用本文:
. [J]. Frontiers of Chemical Science and Engineering, 2024, 18(11): 130.
Shuo-Shuo Zhang, Xing-Bao Wang, Wen-Ying Li. Extractive distillation of cycloalkane monomers from the direct coal liquefaction fraction. Front. Chem. Sci. Eng., 2024, 18(11): 130.
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, ?2
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, ?2
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, ?3
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
1
S Vasireddy , B Morreale , A Cugini , C Song , J J Spivey . Clean liquid fuels from direct coal liquefaction: chemistry, catalysis, technological status and challenges. Energy & Environmental Science, 2011, 4(2): 311–345 https://doi.org/10.1039/C0EE00097C
2
M N Akhtar , A M Aitani , A C Ummer , H S Alasiri . Review on the catalytic conversion of naphtha to aromatics: advances and outlook. Energy & Fuels, 2023, 37(4): 2586–2607 https://doi.org/10.1021/acs.energyfuels.2c03716
3
Z D Qi . Study on product property, application and new product development of direct coal liquefaction. Coal and Chemical Industry, 2021, 49(5): 19–23
4
Z Liu , S Shi , Y Li . Coal liquefaction technologies-development in China and challenges in chemical reaction engineering. Chemical Engineering Science, 2010, 65(1): 12–17 https://doi.org/10.1016/j.ces.2009.05.014
5
F Mirshafiee , S Movahedirad , M A Sobati , R Alaee , S Zarei , H Sargazi . Current status and future prospects of oxidative desulfurization of naphtha: a review. Process Safety and Environmental Protection, 2023, 170: 54–75 https://doi.org/10.1016/j.psep.2022.11.080
6
Y Zhang , L Zhao , F Chen , Y Wang , J Gao , L Cao , H Wang , C Xu . High efficient separation of olefin from fluid catalytic cracking naphtha: separation mechanism and universal simulation method. AIChE Journal. American Institute of Chemical Engineers, 2021, 67(5): e17153 https://doi.org/10.1002/aic.17153
7
A Landera , R P Bambha , N Hao , S P Desai , C M Moore , A D Sutton , A George . Building structure-property relationships of cycloalkanes in support of their use in sustainable aviation fuels. Frontiers in Energy Research, 2022, 9: 771697 https://doi.org/10.3389/fenrg.2021.771697
8
W Wang , N Li , G Li , S Li , W Wang , A Wang , Y Cong , X Wang , T Zhang . Synthesis of renewable high-density fuel with cyclopentanone derived from hemicellulose. ACS Sustainable Chemistry & Engineering, 2017, 5(2): 1812–1817 https://doi.org/10.1021/acssuschemeng.6b02554
9
S Dutta , A Bohre , W Zheng , G R Jenness , M Núñez , B Saha , D G Vlachos . Solventless C–C coupling of low carbon furanics to high carbon fuel precursors using an improved graphene oxide carbocatalyst. ACS Catalysis, 2017, 7(6): 3905–3915 https://doi.org/10.1021/acscatal.6b03113
10
Q Liu , X Zhang , Q Zhang , Q Liu , C Wang , L Ma . Synthesis of jet fuel range cycloalkanes with cyclopentanone and furfural. Energy & Fuels, 2020, 34(6): 7149–7159 https://doi.org/10.1021/acs.energyfuels.0c00919
11
J Qi , Y Li , J Xue , R Qiao , Z Zhang , Q Li . Comparison of heterogeneous azeotropic distillation and energy-saving extractive distillation for separating the acetonitrile-water mixtures. Separation and Purification Technology, 2020, 238: 116487 https://doi.org/10.1016/j.seppur.2019.116487
12
X Li , H Li , C Li , Y Wang , W Wang , P Cui , Z Zhu , Y Wang . Process design and 4E analysis of different distillations of ethyl acetate/ethanol/cyclohexane separation based on extractive and pressure-swing properties. Separation and Purification Technology, 2023, 323: 124454 https://doi.org/10.1016/j.seppur.2023.124454
13
Y Li , T Sun , Q Ye , Y Xu , X Jian , J Li . Investigation on energy-efficient extractive distillation for the recovery of ethyl acetate and 1,4-dioxane from industrial effluent. Journal of Cleaner Production, 2021, 329: 129759 https://doi.org/10.1016/j.jclepro.2021.129759
14
M Salman , N Javed , X Liu , M He . Azeotrope separation of ethyl propionate and ethanol by extractive distillation and pressure swing distillation method. Separation and Purification Technology, 2023, 311: 123361 https://doi.org/10.1016/j.seppur.2023.123361
15
Z Zhu , G Li , Y Dai , P Cui , D Xu , Y Wang . Determination of a suitable index for a solvent via two-column extractive distillation using a heuristic method. Frontiers of Chemical Science and Engineering, 2020, 14(5): 824–833 https://doi.org/10.1007/s11705-019-1867-3
16
A Yang , Y Su , T Shi , J Ren , W Shen , T Zhou . Energy-efficient recovery of tetrahydrofuran and ethyl acetate by triple-column extractive distillation: entrainer design and process optimization. Frontiers of Chemical Science and Engineering, 2022, 16(2): 303–315 https://doi.org/10.1007/s11705-021-2044-z
17
Y Jiao , K Yin , T Liu , F Meng , X Li , L Zhong , Z Zhu , P Cui , Y Wang . Process design and mechanism analysis of reactive distillation coupled with extractive distillation to produce an environmentally friendly gasoline additive. Journal of Cleaner Production, 2022, 369: 133290 https://doi.org/10.1016/j.jclepro.2022.133290
18
F Niu , Y Liu , X Wang , X Wang . Separation of methylcyclopentane, cyclohexane and methylcyclohexane mixture by atmospheric distillation. Journal of Chemical Thermodynamics, 2021, 161: 106535 https://doi.org/10.1016/j.jct.2021.106535
19
Y M Kang , Y Jeon , G Lee , H Son , S W Row , S Choi , Y J Seo , Y H Chu , J M Shin , Y G Shul . et al.. Quantitative structure relative volatility relationship model for extractive dstillation of ethylbenzene/p-xylene mixtures. Industrial & Engineering Chemistry Research, 2014, 53(27): 11159–11166 https://doi.org/10.1021/ie403235r
20
Y Wu , D Meng , F Zhao , Y Wang , J Gao . Quantitative structure property relationship for relative volatility of isopropanol and water mixture. Separation Science and Technology, 2020, 55(17): 3252–3259 https://doi.org/10.1080/01496395.2019.1675697
21
S Sun , L Lü , A Yang , S Wei , W Shen . Extractive distillation: Advances in conceptual design, solvent selection, and separation strategies. Chinese Journal of Chemical Engineering, 2019, 27(6): 1247–1256 https://doi.org/10.1016/j.cjche.2018.08.018
22
W L Luyben . Pressure-swing distillation for minimum- and maximum-boiling homogeneous azeotropes. Industrial & Engineering Chemistry Research, 2012, 51(33): 10881–10886 https://doi.org/10.1021/ie3002414
23
V Gerbaud , I Rodriguez-donis , L Hegely , P Lang , F Denes , X You . Review of extractive distillation: process design, operation, optimization and control. Chemical Engineering Research & Design, 2019, 141: 229–271 https://doi.org/10.1016/j.cherd.2018.09.020
24
Y Zhao , X Dong , M Gong , H Li , Q Zhong , J Shen . Evaluation of PR, NRTL, UNIFAC, and PCSAFT on the VLE of binary systems containing ammonia. Industrial & Engineering Chemistry Research, 2017, 56(8): 2287–2297 https://doi.org/10.1021/acs.iecr.6b04525
25
Y Wang , H Zhang , X Yang , Y Shen , Z Chen , P Cui , L Wang , F Meng , Y Ma , J Gao . Insight into separation of azeotrope in wastewater to achieve cleaner production by extractive distillation and pressure-swing distillation based on phase equilibrium. Journal of Cleaner Production, 2020, 276: 124213 https://doi.org/10.1016/j.jclepro.2020.124213
26
T Brouwer , B Schuur . Biobased entrainer screening for extractive distillation of acetone and diisopropyl ether. Separation and Purification Technology, 2021, 270: 118749 https://doi.org/10.1016/j.seppur.2021.118749
27
A Kaufmann , L Maier , M Kienberger . Solvent screening for the extraction of aromatic aldehydes. Separation and Purification Technology, 2024, 340: 126780 https://doi.org/10.1016/j.seppur.2024.126780
28
S Zaman , A Ullah , A Shafaqat . Structural modeling and topological characterization of three kinds of dendrimer networks. European Physical Journal E, 2023, 46(5): 36 https://doi.org/10.1140/epje/s10189-023-00297-4
29
F Luan , H Liu , Y Gao , Q Li , X Zhang , Y Guo . Prediction of hydrophile-lipophile balance values of anionic surfactants using a quantitative structure–property relationship. Journal of Colloid and Interface Science, 2009, 336(2): 773–779 https://doi.org/10.1016/j.jcis.2009.04.002
30
Z Zhu , Y Wang , X Xu , L Liu , D Du , Y Wang . Determination of relative volatility from molecular descriptor and its application to extractive distillation process. Chemical Engineering Transactions, 2017, 61: 679–684
H Allal , H Nemdili , M A Zerizer , B Zouchoune . Molecular structures, chemical descriptors, and pancreatic lipase (1LPB) inhibition by natural products: a DFT investigation and molecular docking prediction. Structural Chemistry, 2024, 35: 223–239
33
T Lu , F Chen . Multiwfn: a multifunctional wavefunction analyzer. Journal of Computational Chemistry, 2012, 33(5): 580–592 https://doi.org/10.1002/jcc.22885
34
Y Mu , X Liu , L Wang . A Pearson’s correlation coefficient based decision tree and its parallel implementation. Information Sciences, 2018, 435: 40–58 https://doi.org/10.1016/j.ins.2017.12.059
35
H Benimam , C Si Moussa , M Laidi , S Hanini . Modeling the activity coefficient at infinite dilution of water in ionic liquids using artificial neural networks and support vector machines. Neural Computing & Applications, 2020, 32(12): 8635–8653 https://doi.org/10.1007/s00521-019-04356-w
36
K Klimenko , G V S M Carrera . QSPR modeling of selectivity at infinite dilution of ionic liquids. Journal of Cheminformatics, 2021, 13: 83 https://doi.org/10.1186/s13321-021-00562-8
37
T Zhu , L Gu , M Chen , F Sun . Exploring QSPR models for predicting PUF-air partition coefficients of organic compounds with linear and nonlinear approaches. Chemosphere, 2021, 266: 128962 https://doi.org/10.1016/j.chemosphere.2020.128962
38
G B Luilo , S E Cabaniss . Quantitative structure-property relationship for predicting chlorine demand by organic molecules. Environmental Science & Technology, 2010, 44(7): 2503–2508 https://doi.org/10.1021/es903164d
T M Martin , P Harten , D M Young , E N Muratov , A Golbraikh , H Zhu , A Tropsha . Does rational selection of training and test sets improve the outcome of QSAR modeling. Journal of Chemical Information and Modeling, 2012, 52(10): 2570–2578 https://doi.org/10.1021/ci300338w
41
Y Ni , Y Pan , J Jiang , Y Liu , C Shu . Predicting both lower and upper flammability limits for fuel mixtures from molecular structures with same descriptors. Process Safety and Environmental Protection, 2021, 155: 177–183 https://doi.org/10.1016/j.psep.2021.09.023
42
X B Zhang , A Rajendran , X B Wang , W Y Li . Solubility study of hydrogen in direct coal liquefaction solvent based on quantitative structure-property relationships model. Chinese Journal of Chemical Engineering, 2023, 64: 250–258 https://doi.org/10.1016/j.cjche.2023.05.014
43
Z R Chen , Y L Zhang , M J Zhou , K X Yin , Y Zhou , P Z Cui , Z Y Zhu , L M Zhong , Y L Wang . Mechanism analysis and process optimization of acetone-methanol azeotrope separation using 1-ethyl-3-methylimidazolium acetate based mixed extractants. Journal of Cleaner Production, 2022, 379: 134687 https://doi.org/10.1016/j.jclepro.2022.134687
44
H Zhang , F Zhao , Z Ma , X Liu , P Cui , J Gao , Y Wang , S Zheng . Design and optimization for the separation of cyclohexane-isopropanol-water using mixed extractants with thermal integration based on molecular mechanism. Separation and Purification Technology, 2021, 266: 118541 https://doi.org/10.1016/j.seppur.2021.118541
45
J M Douglas. Conceptual Design of Chemical Processes. New York: University of Massachusetts, 1988, 23–37
46
H W Kang , F Zhao , R S Zhu , Z G Lei . Extractive distillation for separation of isopropanol-n-propanol-water ternary system: mechanism analysis and process design. Chemical Engineering Research & Design, 2023, 200: 793–802 https://doi.org/10.1016/j.cherd.2023.11.036
47
Z Chen , Y Dai , S Chi , Z Su , J Xing , Y Wang , Y Lu . Analysis and intensification of energy saving process for separation of azeotrope by ionic liquid extractive distillation based on molecular dynamics simulation. Separation and Purification Technology, 2021, 276: 119254 https://doi.org/10.1016/j.seppur.2021.119254
48
Z B YangS K Wang. A method for preparing monomer cycloalkanes and solvent oils from coal-based naphtha. China Patent, 201610788346.1, 2017-02-22 (in Chinese)
49
Z G Gu. A method for extracting n-heptane and methylcyclohexane by combining distillation and composite extraction distillation. China Patent, 200610039269.6, 2008-05-28 (in Chinese)
