Pyrrolidine as a Promoter for Methane Hydrate Formation: Comparative Study on the Thermodynamics, Kinetics, and Morphology with Tetrahydrofuran

• Main Author: Junthong, Siravich
• Format: Text
• Language: English
• Published: Chula Digital Collections 2020
• Subjects: Polymer Chemistry; Methane hydrate
• Online Access: https://digital.car.chula.ac.th/chulaetd/272; https://doi.org/10.58837/CHULA.THE.2020.360; https://digital.car.chula.ac.th/context/chulaetd/article/1271/viewcontent/Pet_Siravich_Jun_6271006063_2020.pdf

Solidified natural gas (SNG) via clathrate hydrates has been proposed as an alternative approach for natural gas storage and transportation due to its numerous advantages. However, a slow hydrate formation rate and a requirement of operating conditions are the major limitations, which need to be improved to make SNG competitive in a large scale deployment. In this work, the roles of 5.56 mol% pyrrolidine were investigated for the methane hydrate formation in terms of thermodynamics and kinetics along with morphology. The results showed that pyrrolidine generally improved the thermodynamic stability of mixed methane hydrates, enhancing the formation at milder conditions than those of pure methane hydrates. To demonstrate the kinetic performance of pyrrolidine, the experiments were performed at 8 MPa and 285.2 K in a quiescent configuration. The results showed that a very short induction time and a rapid rate of hydrate formation with desirable methane uptake were achieved. In addition, a distinct methane bubble with breathing effect, assisting methane gas to interact with the bulk solution, was observed during the hydrate formation morphology. The comparative kinetic study with 5.56 mol% THF was also carried out under the same driving force and the same experimental condition. Surprisingly, although THF gave a high methane uptake, pyrrolidine could give more than 10 times higher rate of hydrate formation at the same driving force; moreover, it provided a competitive rate with THF at the similar formation condition. These findings may provide the fundamental backgrounds and give a useful insight to select the appropriate hydrate promoter for the clathrate hydrates and the commercialized SNG technology.