Document Type : ACEC-2023


1 Department of Chemical Engineering, University of Bojnourd, Bojnord, Iran

2 Department of Chemical Engineering, Babol Noshirvani University of Technology, Babol, Iran


Gas hydrate formation is a new technology to uptake carbon dioxide. In the present work, the kinetics of changes in the volume of unreacted water, the formed carbon dioxide hydrate, and also the unreacted gas inside the reactor were investigated with the passage of time. Experiments were performed in a stagnant 169 cm3 double-walled reactor at a temperature of 275.15 K and a pressure of 3 MPa. The tests were done by using the isochoric-isothermal method. The results of the experiments showed that the volume of unreacted water decreased with respect to time and the volume of hydrate formed increased. Taking into account the different molar volumes of hydrate formed and the molar volume of reacted water in the test conditions, the changes in gas volume inside the reactor were calculated with the passage of time. The gas volume inside the reactor decreased from 144 cm3 at the beginning of the process to 141.62 cm3 at the end of the reaction. By decreasing the pressure during carbon dioxide hydrate formation process, the amount of hydration number increased from 6.047 mol/mol to 6.109 mol/mol.


Main Subjects

  1. Nicholls, R.J., and Leatherman, S.P., 1996. Adapting to sea‐level rise: Relative sea‐level trends to 2100 for the United States. Coastal Management, 24(4), pp.301–324. Doi: 10.1080/08920759609362298
  2. Pahlavanzadeh, H., Nouri, S., Mohammadi, A.H., and Manteghian, M., 2020. Experimental measurements and thermodynamic modeling of hydrate dissociation conditions in CO2 + THF + NaCl + water systems. The Journal of Chemical Thermodynamics, 141, pp.105956. Doi: 10.1016/j.jct.2019.105956
  3. Carroll, J., 2020. Natural Gas Hydrates: A Guide for Engineers. Gulf Professional Publishing.
  4. Kim, E., Lee, S., Lee, J.D., and Seo, Y., 2015. Influences of large molecular alcohols on gas hydrates and their potential role in gas storage and CO2 sequestration. Chemical Engineering Journal, 267, pp.117–123. Doi: 10.1016/j.cej.2015.01.023
  5. Lee, Y., Lee, S., Lee, J., and Seo, Y., 2014. Structure identification and dissociation enthalpy measurements of the CO2+ N2 hydrates for their application to CO2 capture and storage. Chemical Engineering Journal, 246, pp.20–26. Doi: 10.1016/j.cej.2014.02.045
  6. Sloan, E.D., 2011. Natural Gas Hydrates in Flow Assurance. Gulf Professional Publishing.
  7. Sloan, E.D., and Koh, C.A., 2007. Clathrate Hydrates of Natural Gases. CRC press.
  8. Nguyen, N.N., Galib, M., and Nguyen, A. V., 2020. Critical Review on Gas Hydrate Formation at Solid Surfaces and in Confined Spaces—Why and How Does Interfacial Regime Matter? Energy & Fuels, 34(6), pp.6751–6760. Doi: 10.1021/acs.energyfuels.0c01291
  9. Mohammadi, A., 2020. The roles TBAF and SDS on the kinetics of methane hydrate formation as a cold storage material. Journal of Molecular Liquids, 309, pp.113175. Doi: 10.1016/j.molliq.2020.113175
  10. Mohammadi, A., Babakhanpour, N., Mohammad Javidani, A., and Ahmadi, G., 2021. Corn’s dextrin, a novel environmentally friendly promoter of methane hydrate formation. Journal of Molecular Liquids, 336, pp.116855. Doi: 10.1016/j.molliq.2021.116855
  11. Mohammadi, A., Fazli, R.H., and Asil, A.G., 2021. Influence of Tetra n-Butylammonium Chloride and Polysorbate 80 on the Kinetics of Methane Hydrate Formation. Journal of the Japan Petroleum Institute, 64(1), pp.22–28. Doi: 10.1627/jpi.64.22
  12. Mohammadi, A., Kamran-Pirzaman, A., and Rahmati, N., 2021. The effect tetra butyl ammonium hydroxide and tween on the kinetics of carbon dioxide hydrate formation. Petroleum Science and Technology, pp.1–19. Doi: 10.1080/10916466.2021.1947321
  13. Dong, H., Wang, J., Xie, Z., Wang, B., Zhang, L., and Shi, Q., 2021. Potential applications based on the formation and dissociation of gas hydrates. Renewable and Sustainable Energy Reviews, 143, pp.110928. Doi: 10.1016/j.rser.2021.110928
  14. Wu, Q., Yu, Y., Zhang, B., Gao, X., and Zhang, Q., 2019. Effect of temperature on safety and stability of gas hydrate during coal mine gas storage and transportation. Safety Science, 118, pp.264–272. Doi: 10.1016/j.ssci.2019.04.034
  15. Gambelli, A.M., Castellani, B., Nicolini, A., and Rossi, F., 2019. Gas hydrate formation as a strategy for CH4/CO2 separation: Experimental study on gaseous mixtures produced via Sabatier reaction. Journal of Natural Gas Science and Engineering, 71, pp.102985. Doi: 10.1016/j.jngse.2019.102985
  16. Sergeeva, M.S., Mokhnachev, N.A., Shablykin, D.N., Vorotyntsev, A. V., Zarubin, D.M., Atlaskin, A.A., Trubyanov, M.M., Vorotyntsev, I. V., Vorotyntsev, V.M., and Petukhov, A.N., 2021. Xenon recovery from natural gas by hybrid method based on gas hydrate crystallisation and membrane gas separation. Journal of Natural Gas Science and Engineering, 86, pp.103740. Doi: 10.1016/j.jngse.2020.103740
  17. Zheng, J., and Yang, M., 2020. Experimental investigation on novel desalination system via gas hydrate. Desalination, 478, pp.114284. Doi: 10.1016/j.desal.2019.114284
  18. Khan, M.N., Peters, C.J., and Koh, C.A., 2019. Desalination using gas hydrates: The role of crystal nucleation, growth and separation. Desalination, 468, pp.114049. Doi: 10.1016/j.desal.2019.06.015
  19. Khan, M.S., Lal, B., Sabil, K.M., and Ahmed, I., 2019. Desalination of seawater through gas hydrate process: an overview. Journal of Advanced Research in Fluid Mechanics and Thermal Sciences, 55(1), pp.65–73
  20. Mohammadi, A., 2022. The Effect of Various Concentrations of Tetra-n-butylammonium Fluoride on the Dissociation Enthalpy of Gas Hydrates. Iranian Journal of Energy and Environment, 13(2), pp.151–157. Doi: 10.5829/IJEE.2022.13.02.06
  21. Montazeri, V., ZareNezhad, B., and Ghazi, A., 2022. Sequestration and Storage of Carbon Dioxide Using Hydrate Formation Method in the Presence of Copper Oxide Nanoparticles. Iranian Journal of Energy and Environment, 13(1), pp.46–54. Doi: 10.5829/IJEE.2022.13.01.06
  22. Zhong, D.-L., Wang, Y.-R., Lu, Y.-Y., Wang, W.-C., and Wang, J.-L., 2016. Phase equilibrium and kinetics of gas hydrates formed from CO2/H2 in the presence of tetrahydrofuran and cyclohexane. Journal of Natural Gas Science and Engineering, 35, pp.1566–1572. Doi: 10.1016/j.jngse.2016.03.036
  23. Chaturvedi, E., Laik, S., and Mandal, A., 2021. A comprehensive review of the effect of different kinetic promoters on methane hydrate formation. Chinese Journal of Chemical Engineering, 32, pp.1–16. Doi: 10.1016/j.cjche.2020.09.027
  24. Yang, L., Wang, X., Liu, D., Cui, G., Dou, B., Wang, J., and Hao, S., 2020. Accelerated methane storage in clathrate hydrates using surfactant-stabilized suspension with graphite nanoparticles. Chinese Journal of Chemical Engineering, 28(4), pp.1112–1119. Doi: 10.1016/j.cjche.2019.12.009
  25. Veluswamy, H.P., Bhattacharjee, G., Liao, J., and Linga, P., 2020. Macroscopic Kinetic Investigations on Mixed Natural Gas Hydrate Formation for Gas Storage Application. Energy & Fuels, 34(12), pp.15257–15269. Doi: 10.1021/acs.energyfuels.0c01862
  26. Song, R., Yan, Y., Shang, L., Li, P., and Xu, J., 2020. A comparison of kinetics and thermodynamics of methane hydrate formation; dissociation in surfactant and solid dispersed emulsion. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 599, pp.124935. Doi: 10.1016/j.colsurfa.2020.124935
  27. Mahmood, M.E., and Al-Koofee, D.A.F., 2013. Effect of temperature changes  on critical  micelle  concentration  for  tween series surfactant. Global Journal of Science Frontier Research Chemistry, 13(1), pp.1–8
  28. Sun, Q., and Kang, Y.T., 2016. Review on CO2 hydrate formation/dissociation and its cold energy application. Renewable and Sustainable Energy Reviews, 62, pp.478–494. Doi: 10.1016/j.rser.2016.04.062
  29. Mohammadi, A., Manteghian, M., and Mohammadi, A.H., 2013. Dissociation Data of Semiclathrate Hydrates for the Systems of Tetra- n -butylammonium Fluoride (TBAF) + Methane + Water, TBAF + Carbon Dioxide + Water, and TBAF + Nitrogen + Water. Journal of Chemical & Engineering Data, 58(12), pp.3545–3550. Doi: 10.1021/je4008519
  30. Bardool, R., Javanmardi, J., Roosta, A., and Mohammadi, A.H., 2016. Phase stability conditions of clathrate hydrates for methane+aqueous solution of water soluble organic promoter system: Modeling using a thermodynamic framework. Journal of Molecular Liquids, 224, pp.1117–1123. Doi: 10.1016/j.molliq.2016.09.084
  31. Belandria, V., Mohammadi, A.H., Eslamimanesh, A., Richon, D., Sánchez-Mora, M.F., and Galicia-Luna, L.A., 2012. Phase equilibrium measurements for semi-clathrate hydrates of the (CO2+N2+tetra-n-butylammonium bromide) aqueous solution systems: Part 2. Fluid Phase Equilibria, 322–323, pp.105–112. Doi: 10.1016/j.fluid.2012.02.020
  32. Lee, S., Lee, Y., Park, S., and Seo, Y., 2010. Phase Equilibria of Semiclathrate Hydrate for Nitrogen in the Presence of Tetra- n -butylammonium Bromide and Fluoride. Journal of Chemical & Engineering Data, 55(12), pp.5883–5886. Doi: 10.1021/je100886b
  33. Lin, W., Delahaye, A., and Fournaison, L., 2008. Phase equilibrium and dissociation enthalpy for semi-clathrate hydrate of CO2+TBAB. Fluid Phase Equilibria, 264(1–2), pp.220–227. Doi: 10.1016/j.fluid.2007.11.020
  34. Vlahakis, J.J., 1972. The Growth Rate of Ice Crystals: The Properties of carbon dioxide hydrate a review of properties of 51 gas hydrates. Office of Water, 830, pp.56–86
  35. Peng, D.-Y., and Robinson, D.B., 1976. A New Two-Constant Equation of State. Industrial & Engineering Chemistry Fundamentals, 15(1), pp.59–64. Doi: 10.1021/i160057a011
  36. Mohammadi, A., Manteghian, M., Haghtalab, A., Mohammadi, A.H., and Rahmati-Abkenar, M., 2014. Kinetic study of carbon dioxide hydrate formation in presence of silver nanoparticles and SDS. Chemical Engineering Journal, 237, pp.387–395. Doi: 10.1016/j.cej.2013.09.026