“…Unlike ordinary hydrates having well defined structures (Structure I, Structure II, and Structure H), SCHs have diverse structures and have hydrogen-bonding interaction between guests and hosts molecules, which is much stronger than the van der Waals force in ordinary hydrates 5 SCHs have drawn increasingly more interest from researchers for their potential applications in hydrogen storage 8 , carbon dioxide storage 9 , and gas separation [10][11][12][13][14] . The thermodynamic data of SCHs are limited, and the majority of them are for TBAB 8,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] . More phase equilibrium data on SCHs are needed for acquiring in-depth knowledge of gas hydrate formation, optimizing the thermodynamic models, and developing effective gas processing technologies.…”
We measured the thermodynamic stability conditions for the N 2 , CO 2 , or CH 4 semi-clathrate hydrate formed from the aqueous solution of Tri-n-butylphosphine Oxide (TBPO) at 26 wt%, corresponding to the stoichiometric composition for TBPO·34.5H 2 O. The measurements were performed at the temperature range of (283.71 to 300.34) K and pressure range of (0.35 to 19.43) MPa with using an isochoric equilibrium step-heating pressure search method. The results showed that the presence of TBPO made these semi-clathrate hydrates much more stable than the corresponding pure N 2 , CO 2 , and CH 4 hydrates. At a given temperature, the semi-clathrate hydrate of 26 wt% TBPO solution + CH 4 was more stable than that of 26 wt% TBPO solution + CO 2 , which in turn was more stable than 26 wt% TBPO solution + N 2. We analyzed the phase equilibrium data using the Clausius-Clapeyron equation and found that at the pressure range of (0 to 20) MPa, the mean dissociation enthalpies for the semi-clathrate hydrates systems of 26 wt% TBPO solution + N 2 , 26 wt% TBPO solution + CO 2 , and 26 wt% TBPO solution + CH 4 were 177.75 kJ·mol -1 , 206.23 kJ·mol -1 and 159.00 kJ·mol -1 , respectively.
“…Unlike ordinary hydrates having well defined structures (Structure I, Structure II, and Structure H), SCHs have diverse structures and have hydrogen-bonding interaction between guests and hosts molecules, which is much stronger than the van der Waals force in ordinary hydrates 5 SCHs have drawn increasingly more interest from researchers for their potential applications in hydrogen storage 8 , carbon dioxide storage 9 , and gas separation [10][11][12][13][14] . The thermodynamic data of SCHs are limited, and the majority of them are for TBAB 8,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] . More phase equilibrium data on SCHs are needed for acquiring in-depth knowledge of gas hydrate formation, optimizing the thermodynamic models, and developing effective gas processing technologies.…”
We measured the thermodynamic stability conditions for the N 2 , CO 2 , or CH 4 semi-clathrate hydrate formed from the aqueous solution of Tri-n-butylphosphine Oxide (TBPO) at 26 wt%, corresponding to the stoichiometric composition for TBPO·34.5H 2 O. The measurements were performed at the temperature range of (283.71 to 300.34) K and pressure range of (0.35 to 19.43) MPa with using an isochoric equilibrium step-heating pressure search method. The results showed that the presence of TBPO made these semi-clathrate hydrates much more stable than the corresponding pure N 2 , CO 2 , and CH 4 hydrates. At a given temperature, the semi-clathrate hydrate of 26 wt% TBPO solution + CH 4 was more stable than that of 26 wt% TBPO solution + CO 2 , which in turn was more stable than 26 wt% TBPO solution + N 2. We analyzed the phase equilibrium data using the Clausius-Clapeyron equation and found that at the pressure range of (0 to 20) MPa, the mean dissociation enthalpies for the semi-clathrate hydrates systems of 26 wt% TBPO solution + N 2 , 26 wt% TBPO solution + CO 2 , and 26 wt% TBPO solution + CH 4 were 177.75 kJ·mol -1 , 206.23 kJ·mol -1 and 159.00 kJ·mol -1 , respectively.
“…5 K) [49] whereas the difference between 30.2 wt% TBPO (TBPO·28H 2 O) and 26.0 wt% TBPO (TBPO·34.5H 2 O) was rather small (less than 1 K) [45,46]. Moreover, the measured dissociation temperature of 5 wt% TBPO at ambient pressure was 276.2 K (with uncertainty of 0.5 K), whereas the corresponding temperature of 5 wt% TBAB was estimated by extrapolation to be 274.8 K or lower, depending on the hydrate type [40]. Figure 5 compares the effects of TBPO and TBAB on lowering the pressure requirement for flue gas hydrate formation.…”
Please cite this article as: J. Du, L. Wang, Phase equilibrium measurements for clathrate hydrates of flue gas (CO 2 + N 2 + O 2 ) in the presence of tetra-n-butyl ammonium bromide or tri-n-butylphosphine oxide, J. Chem. Thermodynamics (2015), doi: http://dx.doi.org/10. 1016/j.jct.2015.04.023 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. Abstract This paper reports the measured hydrate phase equilibria of simulated flue gas (12.6 vol% CO 2 , 80.5 vol% N 2 , 6.9 vol% O 2 ) in the presence of tetra-n-butyl ammonium bromide (TBAB) or tri-n-butylphosphine oxide (TBPO), at 0 wt%, 5 wt%, and 26 wt%, respectively. The measurements of the phase boundary between hydrate-liquid-vapor (H-L-V) phases and liquid-vapor (L-V) phases were performed within the temperature range (275.97 -293.99) K and pressure range (1.56 -18.78) MPa with using the isochoric step-heating pressure search method. It was found that addition of TBAB or TBPO allowed the incipient equilibrium hydrate formation conditions for the flue gas to become milder. Compared to TBAB, TBPO was largely more effective in reducing the phase equilibrium pressure.
“…Equilibrium pressures of mixed-gas hydrates are also moderated by these hydrate formation promoters ( Figure 2). Formation conditions of gas-containing semi-clathrate hydrates and gas hydrates [28,30,31,39,[42][43][44][45][46][47][48]. Double circle represents formation condition in the present study.…”
This paper proposes an innovative CO 2 enrichment system for crop production under a controlled greenhouse environment by means of tetra-n-butylammonium bromide (TBAB) + CO 2 semi-clathrate hydrate (SC). In this system, CO 2 is captured directly from exhaust gas from a combustion heater at night, which can be used for stimulating photosynthesis of crops in greenhouses during daytime. Although the gas capacity of TBAB + CO 2 SC is less than that of CO 2 gas hydrate, it is shown that TBAB + CO 2 SC can store CO 2 for CO 2 enrichment in crop production even under moderate pressure conditions (<1.0 MPa) at 283 K.
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