Mechanisms, Growth Rates, and Morphologies of Gas Hydrates of Carbon Dioxide, Methane, and Their Mixtures
Abstract
:1. Introduction
- It is not clear whether morphology is dependent on the guest molecule, the driving force, or other variables. Some authors report morphological differences between CO and CH hydrates and their mixtures, but for other groups, those differences are less evident or even negligible.
- Although there is a clear correlation between and morphology, CO and CH hydrates have not been formed at the exact same temperatures, subcoolings, and precursor phases, which makes it difficult to compare morphology and growth mechanisms between methane, carbon dioxide, and their mixtures.
- It has not been established whether the formation of these hydrates is a mass transfer or heat transfer limited process. Solubilities, heat of formation, and intrinsic rates of formation for CO and CH differ considerably between each other and may have a role on the hydrate growth velocities and morphologies.
2. Materials and Methods
2.1. Apparatus
2.2. Methods
2.2.1. Mass Transfer-Based Driving Force
2.2.2. Extension for Mixtures
2.3. Experimental Conditions
3. Results and Discussion
3.1. Hydrate Morphology
3.1.1. Subcooling
3.1.2. Mass Transfer-Based Driving Force
3.1.3. Gradient
3.1.4. Growth Velocity
3.2. Growth and Dissociation
3.2.1. Growth Mechanism
3.2.2. Partial Dissociation during Growth
3.2.3. Dissociation Mechanism
3.3. Growth Rates
Morphology and Growth Velocity
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Nomenclature
difference | |
stoichiometric coefficient | |
Greek Letters | |
f | fugacity |
H | Henry’s law constant |
v | hydrate film growth velocity |
n | hydration number |
x | mole fraction |
P | pressure |
g | temperature gradient |
T | temperature |
volumetric growth rate | |
Subscripts and Abbreviations | |
L | coldest side of the stage |
j | dissociation step |
experimental value | |
gradient experiments | |
h | halo |
H | hottest side of the stage |
hydrate front | |
hydrate–Liquid water–vapor | |
interface | |
subcooling | |
uniform experiments |
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Composition | 10y | 10y | Source |
---|---|---|---|
CH | 99.999 | 0 | Air Liquide, QC, CA |
80:20 | 80.02 | 19.98 | |
30:70 | 29.94 | 70.06 | |
CO | 0 | 100 |
Vapor Phase | P/MPa | /K | /K | /K |
---|---|---|---|---|
4.00 | 277.4 | 279.2 | 275.2 | |
4.00 | 277.4 | 279.0 | 275.0 | |
4.01 | 277.5 | 279.0 | 275.0 | |
4.00 | 277.4 | 276.9 | 276.9 | |
4.00 | 277.4 | 277.1 | 277.1 | |
6.60 | 282.3 | 274.4 | 274.4 | |
8.60 | 284.7 | 275.5 | 275.5 | |
8.60 | 284.7 | 276.7 | 276.7 | |
2.10 | 277.5 | 277.5 | 277.5 | |
2.09 | 277.5 | 277.5 | 277.5 | |
2.09 | 277.5 | 277.5 | 277.5 | |
2.10 | 277.5 | 279.5 | 275.5 | |
2.10 | 277.5 | 279.0 | 275.0 | |
2.10 | 277.5 | 275.7 | 279.7 | |
80:20 | 3.25 | 277.4 | 279.2 | 275.2 |
80:20 | 3.25 | 277.4 | 275.0 | 279.0 |
80:20 | 3.25 | 277.4 | 273.5 | 277.5 |
80:20 | 3.25 | 277.4 | 271.8 | 275.8 |
80:20 | 3.25 | 277.4 | 277.1 | 277.1 |
80:20 | 3.25 | 277.4 | 277.2 | 277.2 |
80:20 | 3.25 | 277.4 | 277.1 | 277.1 |
80:20 | 4.40 | 280.2 | 274.2 | 274.2 |
80:20 | 4.40 | 280.2 | 273.4 | 273.4 |
30:70 | 2.35 | 277.4 | 277.3 | 277.3 |
30:70 | 2.35 | 277.4 | 277.2 | 277.2 |
30:70 | 2.35 | 277.4 | 277.3 | 277.3 |
30:70 | 2.35 | 277.4 | 279.5 | 275.5 |
30:70 | 2.35 | 277.4 | 279.2 | 275.2 |
30:70 | 2.35 | 277.4 | 277.2 | 277.2 |
30:70 | 2.35 | 277.4 | 277.1 | 277.1 |
30:70 | 2.35 | 277.4 | 274.2 | 274.2 |
30:70 | 2.35 | 277.4 | 276.4 | 276.4 |
30:70 | 2.35 | 277.4 | 275.4 | 275.4 |
30:70 | 2.35 | 277.4 | 273.4 | 273.4 |
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Martinez, C.; Sandoval, J.F.; Ortiz, N.; Ovalle, S.; Beltran, J.G. Mechanisms, Growth Rates, and Morphologies of Gas Hydrates of Carbon Dioxide, Methane, and Their Mixtures. Methane 2022, 1, 2-23. https://doi.org/10.3390/methane1010002
Martinez C, Sandoval JF, Ortiz N, Ovalle S, Beltran JG. Mechanisms, Growth Rates, and Morphologies of Gas Hydrates of Carbon Dioxide, Methane, and Their Mixtures. Methane. 2022; 1(1):2-23. https://doi.org/10.3390/methane1010002
Chicago/Turabian StyleMartinez, Camilo, Juan F. Sandoval, Nathalia Ortiz, Sebastian Ovalle, and Juan G. Beltran. 2022. "Mechanisms, Growth Rates, and Morphologies of Gas Hydrates of Carbon Dioxide, Methane, and Their Mixtures" Methane 1, no. 1: 2-23. https://doi.org/10.3390/methane1010002