화학공학소재연구정보센터
Energy & Fuels, Vol.27, No.8, 4534-4544, 2013
Stoichiometric Approach toward Modeling the Decomposition Kinetics of Gas Hydrates Formed from Mixed Gases
Following a recent study by Giraldo et al. (Giraldo, C.; Maini, B.; Bishnoi, P. R A simplified approach to modeling the rate of formation of gas hydrates formed from mixtures of gases. Energy Fuels 2013, 27, 1204-1211), in which a new stoichiometry-based approach was taken to model the rate of gas hydrate formation for mixed gases, a new stoichiometric approach has been proposed to describe the kinetics of gas hydrate decomposition from mixed gases. Similar to the model of gas hydrate formation by Giraldo et al., the newly proposed model of gas hydrate decomposition has the advantage that the intrinsic rate constant of gas hydrate decomposition is only required for a single component. To test the model, gas hydrate decomposition experiments were conducted in a semi-batch stirred-tank reactor, equipped with an in situ particle size analyzer, to study the rate of decomposition of gas hydrates formed from mixtures of carbon dioxide and methane. Two gas mixtures of CO2 (1) + CH4 (2), one with x(1) = 0.4 and the other with x(1) = 0.6, were used for the current study. The experimental temperatures ranged from 274 to 276 K, and the experimental pressures ranged from 16 to 22 bar. The new approach was used to model the kinetics of gas hydrate decomposition, and the results from these predictions were compared to the results obtained using the model by Clarke and Bishnoi (Clarke, M. A.; Bishnoi, P. R. Measuring and modelling the rate of decomposition of gas hydrates formed from mixtures of methane and ethane. Chem. Eng. Sri. 2001, 56, 4715-4724 and Clarke, M. A.; Bishnoi, P. It Determination of the intrinsic rate constant and activation energy of CO2 gas hydrate decomposition using in-situ particle size analysis. Chem. Eng. Sci. 2004, 59, 2983-2993). The root-mean-square of the relative errors between the predictions of the new model and the model by Clarke and Bishnoi are 4.15 and 6.21%, respectively. Further validation of the new model was performed using it to fit the data by Clarke and Bishnoi on the decomposition of both sI and sII gas hydrates formed from mixtures of CH4 (1) + C2H6 (2). When applied to these data sets, the root-mean-square of the relative errors between the predictions of the new model and the model by Clarke and Bishnoi are 2.58 and 1.60%, respectively.