Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data

doi:10.1016/j.cjche.2025.02.031

中国化学工程学报 ›› 2025, Vol. 83 ›› Issue (7): 160-170.DOI: 10.1016/j.cjche.2025.02.031

Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data

Xuehui Wang¹, Dan Dan², Xinyue Hao³, Wei Lin⁴, Edward Wright⁵

1 School of Mechanical & Materials Engineering, University College Dublin, D04 V1W8, Dublin, Ireland;
2 School of Mechanical Engineering, Beijing Institute of Technology, Beijing, 100081, China;
3 Department of Building Environment and Energy Application Engineering, Ningbo University of Technology, Ningbo, 315211, China;
4 Zhejiang Fangyuan Test Group Co., Ltd., Hangzhou, 310018, China;
5 Faculty of Engineering, University of Nottingham, NG7 2RD, Nottingham, United Kingdom

收稿日期:2024-08-03 修回日期:2025-01-15 接受日期:2025-02-19 出版日期:2025-07-28 发布日期:2025-07-28
通讯作者: Dan Dan,E-mail:dandan@bit.edu.cn
基金资助:
This work is supported financially by the National Natural Science Foundation of China (52202434) and the National Natural Science Foundation of Ningbo (2023J275).

Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data

Xuehui Wang¹, Dan Dan², Xinyue Hao³, Wei Lin⁴, Edward Wright⁵

1 School of Mechanical & Materials Engineering, University College Dublin, D04 V1W8, Dublin, Ireland;
2 School of Mechanical Engineering, Beijing Institute of Technology, Beijing, 100081, China;
3 Department of Building Environment and Energy Application Engineering, Ningbo University of Technology, Ningbo, 315211, China;
4 Zhejiang Fangyuan Test Group Co., Ltd., Hangzhou, 310018, China;
5 Faculty of Engineering, University of Nottingham, NG7 2RD, Nottingham, United Kingdom

Received:2024-08-03 Revised:2025-01-15 Accepted:2025-02-19 Online:2025-07-28 Published:2025-07-28
Contact: Dan Dan,E-mail:dandan@bit.edu.cn
Supported by:
This work is supported financially by the National Natural Science Foundation of China (52202434) and the National Natural Science Foundation of Ningbo (2023J275).

摘要/Abstract

摘要： Natural gas is widely regarded as an efficient, relatively clean, and economically viable energy source. Its safe operation and continuous supply through pipeline infrastructure has led to its prominence in the energy sector. Methanol plays an important role in the natural gas industry, typically serving as a solvent or hydrate inhibitor. Therefore, the accurate estimation of thermodynamic properties for methane/ methanol binary is extremely important to optimise the operating parameter, maximise the dehydration effect, and reduce the cost. As the Helmholtz energy equation of state is expected to offer high accuracy in predicting the vapour liquid equilibrium of methane/methanol binary, four reducing parameters were derived based on collected experimental data. Additionally, the sensitivities of various reducing parameter combinations were simultaneously investigated. The results demonstrated a strong agreement between predicted fractions and experimental data, with the UMADs (uncertainty-weighted mean absolute deviation) of 3.484 and 0.665 for liquid and vapour phases, respectively. Meanwhile, it is deemed “very likely”, “likely”, and “unlikely” to achieve acceptable prediction for 3-parameter optimisation, 2-parameter optimisation and, 1-parameter optimisation, respectively.

关键词: Solubility, Methane, Vapour liquid equilibrium (VLE), Equation of state, Reducing parameters

Abstract: Natural gas is widely regarded as an efficient, relatively clean, and economically viable energy source. Its safe operation and continuous supply through pipeline infrastructure has led to its prominence in the energy sector. Methanol plays an important role in the natural gas industry, typically serving as a solvent or hydrate inhibitor. Therefore, the accurate estimation of thermodynamic properties for methane/ methanol binary is extremely important to optimise the operating parameter, maximise the dehydration effect, and reduce the cost. As the Helmholtz energy equation of state is expected to offer high accuracy in predicting the vapour liquid equilibrium of methane/methanol binary, four reducing parameters were derived based on collected experimental data. Additionally, the sensitivities of various reducing parameter combinations were simultaneously investigated. The results demonstrated a strong agreement between predicted fractions and experimental data, with the UMADs (uncertainty-weighted mean absolute deviation) of 3.484 and 0.665 for liquid and vapour phases, respectively. Meanwhile, it is deemed “very likely”, “likely”, and “unlikely” to achieve acceptable prediction for 3-parameter optimisation, 2-parameter optimisation and, 1-parameter optimisation, respectively.

Key words: Solubility, Methane, Vapour liquid equilibrium (VLE), Equation of state, Reducing parameters

Xuehui Wang, Dan Dan, Xinyue Hao, Wei Lin, Edward Wright. Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data[J]. 中国化学工程学报, 2025, 83(7): 160-170.

参考文献

[1] M. Büchs, N. Cass, C. Mullen, K. Lucas, D. Ivanova, Emissions savings from equitable energy demand reduction, Nat. Energy 8(7) (2023) 758-769.
[2] A.T.D. Perera, K. Javanroodi, D. Mauree, V.M. Nik, P. Florio, T.Z. Hong, D.L. Chen, Challenges resulting from urban density and climate change for the E energy transition, Nat. Energy 8(2023) 397-412.
[3] J.E. Carruthers, L.H. Solomon, G.I. Atwater, J.P. Riva, A.L. Waddams, natural gas, Encycl. Britannica, London, (2025), https://www.britannica.com/science/ natural-gas.
[4] M. Sesini, S. Giarola, A.D. Hawkes, The impact of liquefied natural gas and storage on the EU natural gas infrastructure resilience, Energy 209(2020) 118367.
[5] Y.H. Wang, S.S. Fan, X.M. Lang, Reviews of gas hydrate inhibitors in gasdominant pipelines and application of kinetic hydrate inhibitors in China, Chin. J. Chem. Eng. 27(9) (2019) 2118-2132.
[6] S. Elhenawy, M. Khraisheh, F. Almomani, M.A. Al-Ghouti, M.K. Hassan, A. AlMuhtaseb, Towards gas hydrate-free pipelines: a comprehensive review of gas hydrate inhibition techniques, Energies 15(22) (2022) 8551.
[7] H.R. Sun, B.B. Chen, K.H. Li, Y.C. Song, M.J. Yang, L.L. Jiang, J.Y. Yan, Methane hydrate re-formation and blockage mechanism in a pore-level water-gas flow process, Energy 263(2023) 125851.
[8] J. Zhang, L. Shi, C.X. Li, F. Yang, B. Yao, G.Y. Sun, Research methods and devices for hydrate characteristics during oil and gas transportation: A review, Chin. Chem. Eng. 73(2024) 130-145.
[9] A.P. Semenov, Y.H. Gong, V.I. Medvedev, A.S. Stoporev, V.A. Istomin, V.A. Vinokurov, T.D. Li, New insights into methane hydrate inhibition with blends of vinyl lactam polymer and methanol, monoethylene glycol, or diethylene glycol as hybrid inhibitors, Chem. Eng. Sci. 268(2023) 118387.
[10] A. Qasim, M.S. Khan, B. Lal, A.M. Shariff, A perspective on dual purpose gas hydrate and corrosion inhibitors for flow assurance, J. Petrol. Sci. Eng. 183(2019) 106418.
[11] R.K. Srivastava, P.K. Sarangi, L. Bhatia, A.K. Singh, K.P. Shadangi, Conversion of methane to methanol: technologies and future challenges, Biomass Convers. Biorefin. 12(5) (2022) 1851-1875.
[12] H. Soucie, M. Elam, W.E. Mustain, Practical assessment for at-scale electrochemical conversion of methane to methanol, ACS Energy Lett. 8(2) (2023) 1218-1229.
[13] X.H. Wang, E. Wright, N. Gao, Y. Li, Evaluation on excess entropy scaling method predicting thermal transport properties of liquid HFC/HFO refrigerants, J. Therm. Sci. 31(5) (2022) 1465-1475.
[14] N. Li, X.H. Wang, G.M. Chen, N. Gao, Linking thermal conductivity and selfdiffusion coefficient with a simple dimensionless calorimetric parameter for saturated liquids, Ind. Eng. Chem. Res. 61(41) (2022) 15414-15422.
[15] J.P. Hern andez, L.A. Forero, J.A. Velasquez, Modelling low pressure LLE and VLE of methanol/alkane mixtures with a modified Peng-Robinson EoS and the Huron-Vidal mixing rules, Fluid Phase Equilib. 546(2021) 113123.
[16] S. Avaji, M.J. Amani, M. Ghaedi, Modeling the equilibrium of two and threephase systems including water, alcohol, and hydrocarbons with CPA EOS and its improvement for electrolytic systems by Debye-Huckel equation, J. Nat. Gas Sci. Eng. 90(2021) 103905.
[17] Y.B. Wang, Z.Y. Li, S.J. Zhi, Q. Yang, C.J. Li, W.L. Jia, A predictive model for hydrate formation conditions in alcohol-containing systems based on the cubic-plus-association state equation, Energies 16(23) (2023) 7728.
[18] A. Kumar, R. Upadhyay, A new two-parameters cubic equation of state with benefits of three-parameters, Chem. Eng. Sci. 229(2021) 116045.
[19] E.W. Lemmon, I.H. Bell, M.L. Huber, M.O. McLinden, Refprop, 2018.
[20] Ma Xia, Hua Guo, Determination and study on the solubility of methane in heptane + cyclohexane and heptane + ethanol at high pressures, J. Chem. Eng. Data 49(3) (2004) 479-482.
[21] M.H. Kapateh, A. Chapoy, R. Burgass, B. Tohidi, Experimental measurement and modeling of the solubility of methane in methanol and ethanol, J. Chem. Eng. Data 61(1) (2016) 666-673.
[22] L.K. Wang, G.J. Chen, G.H. Han, X.Q. Guo, T.M. Guo, Experimental study on the solubility of natural gas components in water with or without hydrate inhibitor, Fluid Phase Equilib. 207(1-2) (2003) 143-154.
[23] K. Takeuchi, K. Matsumura, K. Yaginuma, Vapor-liquid equilibria for multicomponent systems containing methanol-acid gases 1. The solubility of inert gases in methanol, Fluid Phase Equilib. 14(1983) 255-263.
[24] L.M.C. Oliveira, F.R.G. Ribeiro, M.L. Alcantara, G.O. Pisoni, V.F. Cabral, L. Cardozo-Filho, S. Mattedi, High pressure vapor-liquid equilibria for binary methane and protic ionic liquid based on propionate anions, Fluid Phase Equilib. 426(2016) 65-74.
[25] Z.X. Lyu, H.F. Ma, W.X. Qian, H.T. Zhang, W.Y. Ying, Measurement and modelling of isothermal solubility of methane in methanol from 213.15 K to 273.15 K, J. Chem. Thermodyn. 141(2020) 105917.
[26] M. Frost, N. von Solms, D. Richon, G.M. Kontogeorgis, Measurement of vaporeliquideliquid phase equilibrium: equipment and results, Fluid Phase Equilib. 405(2015) 88-95.
[27] A.Z. Francesconi, H. Lentz, E.U. Franck, Phase equilibriums and PVT data for the methane-methanol system to 300 MPa and 240.degree.C, J. Phys. Chem. 85(22) (1981) 3303-3307.
[28] H. Nourozieh, M. Kariznovi, J. Abedi, Phase equilibrium measurements and thermodynamic modeling of methane alcohol systems at ambient temperature, J. Chem. Thermodyn. 54(2012) 165-170.
[29] T.J. Hughes, M.E. Kandil, B.F. Graham, E.F. May, Simulating the capture of CO₂ from natural gas: new data and improved models for methane+carbon dioxide+methanol, Int. J. Greenh. Gas Control 31(2014) 121-127.
[30] T. Ukai, D. Kodama, J. Miyazaki, M. Kato, Solubility of methane in alcohols and saturated density at 280.15 K, J. Chem. Eng. Data 47(5) (2002) 1320-1323.
[31] H. Lazalde-Crabtree, G.J.F. Breedveld, J.M. Prausnitz, Solvent losses in gas absorption. Solubility of methanol in compressed natural and synthetic gases, AIChE J. 26(3) (1980) 462-470.
[32] J.H.Hong,P.V.Malone,M.D. Jett,R.Kobayashi, Themeasurement and interpretation of the fluid-phase equilibria of a normal fluid in a hydrogen bonding solvent: the methaneemethanol system, Fluid Phase Equilib. 38(1-2) (1987) 83-96.
[33] A. Vetere, Vapor-liquid equilibria with supercritical gases calculated by the excess Gibbs energy method, Fluid Phase Equilib. 28(3) (1986) 265-281.
[34] I.H. Bell, E.W. Lemmon, Automatic fitting of binary interaction parameters for multi-fluid Helmholtz-energy-explicit mixture models, J. Chem. Eng. Data 61(11) (2016) 3752-3760.

Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data

Investigation on the reducing parameters of the Helmholtz energy equation of state for methane/methanol binary with VLE data

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