A Simulation Study of CO2 Hydrate Inhibition in CO2+CH4 Seawater Mixture

Authors

  • Dileep Kumar Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia | Centre of Carbon Capture, Utilization and Storage (CCCUS), Institute of Sustainable Energy & Resources (ISER), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia
  • Bhajan Lal Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia | Centre of Carbon Capture, Utilization and Storage (CCCUS), Institute of Sustainable Energy & Resources (ISER), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia
  • Ismail Mohd Saaid Petroleum Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia
  • Khor Siak Foo PTTEP Sarawak, Sabah Oil Limited, Levels 22, 33-35, Menara Prestige, No.1 Jalan Pinang, Kuala Lumpur, Malaysia
  • Syahrir Ridha Petroleum Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia
  • Nurul Athirah Basnih PTTEP Sarawak, Sabah Oil Limited, Levels 22, 33-35, Menara Prestige, No.1 Jalan Pinang, Kuala Lumpur, Malaysia
Volume: 16 | Issue: 1 | Pages: 31923-31929 | February 2026 | https://doi.org/10.48084/etasr.12311

Abstract

In the oil and gas industry, wax deposition, scaling, corrosion, and hydrates are the main challenges in pipeline flow. Among these, gas hydrate formation is one of the most critical issues, costing the industry millions of dollars annually in mitigation efforts. Various techniques have been employed to prevent hydrate formation, with chemical inhibition being one of the most widely used methods. Several chemical inhibitors have been utilized, but methanol, ethanol, and Mono-Ethylene Glycol (MEG) hold significant commercial importance. These chemical inhibitors were used to inhibit CO2 hydrate formation in 70 mol% CO2 and 30 mol% CH4 synthetic seawater with a salinity of 3.5 mol% NaCl using PVTSim software. The PVTSim software, coupled with the Peng-Robinson (PR) Peneloux equation of state, provided accurate results for flow assurance analysis in the oil and gas industry. The software predictions for pure CO2 and CH4 hydrates were validated against experimental data available in the literature. Furthermore, the PVTSim software with the PR Peneloux fluid package was applied to salty water systems containing 5, 7, and 10 mol% concentrations of methanol, ethanol, and MEG inhibitors. Hydrate-Liquid-Vapor Equilibrium (HLVE) curves, average temperature depression, and enthalpy of dissociation were estimated. It was concluded that methanol at a concentration of 7 mol% is the most effective commercial inhibitor.

Keywords:

hydrate inhibition, HLVE, average depression temperature, enthalpy of dissociation

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References

E. D. Sloan, "A changing hydrate paradigm—from apprehension to avoidance to risk management," Fluid Phase Equilibria, vol. 228–229, pp. 67–74, Feb. 2005. DOI: https://doi.org/10.1016/j.fluid.2004.08.009

I. M. Onyejekwe, N. Uwaezuoke, G. O. Gborienemi, U. J. Obibuike, and N. O. Okoli, "Hydrate formation and its influence on natural gas pipeline: Simulation study," Zastita Materijala, vol. 66, no. 1, pp. 102–108, Mar. 2025. DOI: https://doi.org/10.62638/ZasMat1088

M. A. Kelland, "History of the Development of Low Dosage Hydrate Inhibitors," Energy & Fuels, vol. 20, no. 3, pp. 825–847, May 2006. DOI: https://doi.org/10.1021/ef050427x

C.-K. Chu, P.-C. Chen, Y.-P. Chen, S.-T. Lin, and L.-J. Chen, "Inhibition effect of 1-ethyl-3-methylimidazolium chloride on methane hydrate equilibrium," The Journal of Chemical Thermodynamics, vol. 91, pp. 141–145, Dec. 2015. DOI: https://doi.org/10.1016/j.jct.2015.07.040

S.-C. Sun, C.-L. Liu, and Q.-G. Meng, "Hydrate phase equilibrium of binary guest-mixtures containing CO2 and N2 in various systems," The Journal of Chemical Thermodynamics, vol. 84, pp. 1–6, May 2015. DOI: https://doi.org/10.1016/j.jct.2014.12.018

B. Partoon, N. M. S. Wong, K. M. Sabil, K. Nasrifar, and M. R. Ahmad, "A study on thermodynamics effect of [EMIM]-Cl and [OH-C2MIM]-Cl on methane hydrate equilibrium line," Fluid Phase Equilibria, vol. 337, pp. 26–31, Jan. 2013. DOI: https://doi.org/10.1016/j.fluid.2012.09.025

H. Liu, J. Qu, M. Pan, B. Zhang, Q. Chen, and C. He, "Design and optimization of small-scale methanol production from sour natural gas by integrating reforming with hydrogenation," International Journal of Hydrogen Energy, vol. 45, no. 59, pp. 34483–34493, Dec. 2020. DOI: https://doi.org/10.1016/j.ijhydene.2019.11.229

A. Abbasi and F. M. Hashim, "Evaluating Pressure in Deepwater Gas Pipeline for the Prediction of Natural Gas Hydrate Formation," Engineering, Technology & Applied Science Research, vol. 9, no. 6, pp. 5033–5036, Dec. 2019. DOI: https://doi.org/10.48084/etasr.3174

Y. Meng et al., "Hydrate Blockage in Subsea Oil/Gas Pipelines: Characterization, Detection, and Engineering Solutions," Engineering, vol. 46, pp. 363–382, Mar. 2025. DOI: https://doi.org/10.1016/j.eng.2024.10.020

A. Farhadian et al., "Challenges and advantages of using environmentally friendly kinetic gas hydrate inhibitors for flow assurance application: A comprehensive review," Fuel, vol. 336, Mar. 2023, Art. no. 127055. DOI: https://doi.org/10.1016/j.fuel.2022.127055

S. Elhenawy, M. Khraisheh, F. Almomani, M. A. Al-Ghouti, M. K. Hassan, and A. Al-Muhtaseb, "Towards Gas Hydrate-Free Pipelines: A Comprehensive Review of Gas Hydrate Inhibition Techniques," Energies, vol. 15, no. 22, Jan. 2022, Art. no. 8551. DOI: https://doi.org/10.3390/en15228551

D. Lee, W. Go, G. Ko, and Y. Seo, "Inhibition synergism of glycine (an amino acid) and [BMIM][BF4] (an ionic liquid) on the growth of CH4 hydrate," Chemical Engineering Journal, vol. 393, Aug. 2020, Art. no. 124466. DOI: https://doi.org/10.1016/j.cej.2020.124466

O. T. Olabisi and U. C. Emmanuel, "Simulation of Laboratory Hydrate Loop Using Aspen Hysys," Engineering and Applied Sciences, vol. 4, no. 3, pp. 52–58, Jul. 2019. DOI: https://doi.org/10.11648/j.eas.20190403.11

I. Ismail, V. Gaganis, D. Marinakis, R. Mousavi, and B. Tohidi, "Accuracy of different thermodynamic software packages in predicting hydrate dissociation conditions," Chemical Thermodynamics and Thermal Analysis, vol. 9, Mar. 2023, Art. no. 100103. DOI: https://doi.org/10.1016/j.ctta.2022.100103

Z. T. Ward, C. E. Deering, R. A. Marriott, A. K. Sum, E. D. Sloan, and C. A. Koh, "Phase Equilibrium Data and Model Comparisons for H2S Hydrates," Journal of Chemical & Engineering Data, vol. 60, no. 2, pp. 403–408, Feb. 2015. DOI: https://doi.org/10.1021/je500657f

A. Saberi, A. Alamdari, A. Shariati, and A. H. Mohammadi, "Experimental measurement and thermodynamic modeling of equilibrium condition for natural gas hydrate in MEG aqueous solution," Fluid Phase Equilibria, vol. 459, pp. 110–118, Mar. 2018. DOI: https://doi.org/10.1016/j.fluid.2017.11.034

B. Kvamme et al., "Alcohols for hydrate inhibition – Different alcohols and different mechanisms," Petroleum, vol. 8, no. 1, pp. 1–16, Mar. 2022. DOI: https://doi.org/10.1016/j.petlm.2021.10.007

P. F. Ferrari, A. Z. Guembaroski, M. A. Marcelino Neto, R. E. M. Morales, and A. K. Sum, "Experimental measurements and modelling of carbon dioxide hydrate phase equilibrium with and without ethanol," Fluid Phase Equilibria, vol. 413, pp. 176–183, Apr. 2016. DOI: https://doi.org/10.1016/j.fluid.2015.10.008

I. A. de Oliveira, A. G. Jr. Barreto, F. W. Tavares, and A. K. Sum, "Phase Equilibria Data and Thermodynamic Analysis for Liquid–Hydrate–Vapor (LHV) with High Ethanol Concentrations," Journal of Chemical & Engineering Data, vol. 65, no. 2, pp. 349–359, Feb. 2020. DOI: https://doi.org/10.1021/acs.jced.9b00691

V. W. S. Lim, P. J. Metaxas, M. L. Johns, Z. M. Aman, and E. F. May, "The impact of mono-ethylene glycol and kinetic inhibitors on methane hydrate formation," Chemical Engineering Journal, vol. 427, Jan. 2022, Art. no. 131531. DOI: https://doi.org/10.1016/j.cej.2021.131531

B. Kvamme, J. Selvåg, N. Saeidi, and T. Kuznetsova, "Methanol as a hydrate inhibitor and hydrate activator," Physical Chemistry Chemical Physics, vol. 20, no. 34, pp. 21968–21987, Aug. 2018. DOI: https://doi.org/10.1039/C8CP02447B

P. G. Lafond, K. A. Olcott, E. Dendy Sloan, C. A. Koh, and A. K. Sum, "Measurements of methane hydrate equilibrium in systems inhibited with NaCl and methanol," The Journal of Chemical Thermodynamics, vol. 48, pp. 1–6, May 2012. DOI: https://doi.org/10.1016/j.jct.2011.12.023

H. Ghaedi, J. Javanmardi, A. Rasoolzadeh, and A. H. Mohammadi, "Experimental Study and Thermodynamic Modeling of Methane Hydrate Dissociation Conditions in the Simultaneous Presence of BMIM-BF4 and Ethanol in Aqueous Solution," Journal of Chemical & Engineering Data, vol. 63, no. 5, pp. 1724–1732, May 2018. DOI: https://doi.org/10.1021/acs.jced.8b00046

J. S. Pandey, C. Karantonidis, A. P. Karcz, and N. von Solms, "Enhanced CH4-CO2 Hydrate Swapping in the Presence of Low Dosage Methanol," Energies, vol. 13, no. 20, Jan. 2020, Art. no. 5238. DOI: https://doi.org/10.3390/en13205238

F. A. Idrus, M. D. Chong, N. S. Abd Rahim, M. Mohd Basri, and J. Musel, "Physicochemical Parameters of Surface Seawater in Malaysia Exclusive Economic Zones Off the Coast of Sarawak," Borneo Journal of Resource Science and Technology, vol. 7, no. 1, pp. 1–10, Jul. 2017. DOI: https://doi.org/10.33736/bjrst.388.2017

C. Xiao, N. Wibisono, and H. Adidharma, "Dialkylimidazolium halide ionic liquids as dual function inhibitors for methane hydrate," Chemical Engineering Science, vol. 65, no. 10, pp. 3080–3087, May 2010. DOI: https://doi.org/10.1016/j.ces.2010.01.033

M. B. Rydzy, J. M. Schicks, R. Naumann, and J. Erzinger, "Dissociation Enthalpies of Synthesized Multicomponent Gas Hydrates with Respect to the Guest Composition and Cage Occupancy," The Journal of Physical Chemistry B, vol. 111, no. 32, pp. 9539–9545, Aug. 2007. DOI: https://doi.org/10.1021/jp0712755

J. Ren et al., "Effect of marine clay minerals on the thermodynamics of CH4 hydrate: Evidence for the inhibition effect with implications," Chemical Engineering Journal, vol. 488, May 2024, Art. no. 151148. DOI: https://doi.org/10.1016/j.cej.2024.151148

A. P. Semenov et al., "Dimethyl sulfoxide as a novel thermodynamic inhibitor of carbon dioxide hydrate formation," Chemical Engineering Science, vol. 255, Jun. 2022, Art. no. 117670. DOI: https://doi.org/10.1016/j.ces.2022.117670

K. Tumba et al., "Phase Equilibria of Methane and Carbon Dioxide Clathrate Hydrates in the Presence of Aqueous Solutions of Tributylmethylphosphonium Methylsulfate Ionic Liquid," Journal of Chemical & Engineering Data, vol. 56, no. 9, pp. 3620–3629, Sep. 2011. DOI: https://doi.org/10.1021/je200462q

A. Qasim, M. S. Khan, B. Lal, Mohd. Z. Abdullah, and A. S. Maulud, "Simulation of Hydrate Phase Boundary for Natural Gas Mixture with High CO2 Content through Simulation," International Journal of Engineering and Advanced Technology, vol. 9, no. 2, pp. 4030–4034, Dec. 2019. DOI: https://doi.org/10.35940/ijeat.B4940.129219

F. E. Anderson and J. M. Prausnitz, "Inhibition of gas hydrates by methanol," AIChE Journal, vol. 32, no. 8, pp. 1321–1333, 1986. DOI: https://doi.org/10.1002/aic.690320810

J. N. Israelachvili, Intermolecular and surface forces, 3rd ed. Burlington, MA: Academic Press, 2011. DOI: https://doi.org/10.1016/B978-0-12-391927-4.10001-5

A. P. Semenov et al., "Synergistic effect of salts and methanol in thermodynamic inhibition of sII gas hydrates," The Journal of Chemical Thermodynamics, vol. 137, pp. 119–130, Oct. 2019. DOI: https://doi.org/10.1016/j.jct.2019.05.013

C. B. Bavoh, B. Partoon, B. Lal, G. Gonfa, S. Foo Khor, and A. M. Sharif, "Inhibition effect of amino acids on carbon dioxide hydrate," Chemical Engineering Science, vol. 171, pp. 331–339, Nov. 2017. DOI: https://doi.org/10.1016/j.ces.2017.05.046

I. Ul Haq, B. Lal, and D. B. Zaini, "Experimental and modelling study of ammonium based ionic liquids in the absence and presence of methanol for CO2 hydrates," Journal of Molecular Liquids, vol. 349, Mar. 2022, Art. no. 118214. DOI: https://doi.org/10.1016/j.molliq.2021.118214

A. Bharathi, O. Nashed, B. Lal, and K. S. Foo, "Experimental and modeling studies on enhancing the thermodynamic hydrate inhibition performance of monoethylene glycol via synergistic green material," Scientific Reports, vol. 11, Jan. 2021, Art. no. 2396. DOI: https://doi.org/10.1038/s41598-021-82056-z

B. Ruscic, "Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol and the Related Thermochemistry," The Journal of Physical Chemistry A, vol. 119, no. 28, pp. 7810–7837, Jul. 2015. DOI: https://doi.org/10.1021/acs.jpca.5b01346

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[1]
D. Kumar, B. Lal, I. M. Saaid, K. S. Foo, S. Ridha, and N. A. Basnih, “A Simulation Study of CO2 Hydrate Inhibition in CO2+CH4 Seawater Mixture”, Eng. Technol. Appl. Sci. Res., vol. 16, no. 1, pp. 31923–31929, Feb. 2026.

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