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Shorter Communication
Abstract
An elementary model for the dissolution of pure hydrate in undersaturated water is proposed that combines intrinsic decomposition within a
desorption lm and the subsequent diffusion of the released hydrate guest species into bulk water. Applying the proposed approach to recently
published measurements of the decomposition rates of methane (CH4 ) and carbon dioxide (CO2 ) hydrates in deep seawater suggests that the
concentration of the hydrate guest species at the interface between desorption lm and diffusive boundary layer may be much lower than
ambient solubility. Calculations, however, fail to account for the observed proportionality of decomposition rate with solubility for both CH4
and CO2 hydrates. This may indicate a limitation in the range of applicability of published formulas for intrinsic hydrate decomposition rates.
2005 Elsevier Ltd. All rights reserved.
Keywords: Gas hydrate; Dissolution; Decomposition; Kinetics; Phase equilibria; Phase change
1. Background
Vast deposits of methane hydrates below the seaoor of most
continental margins represent an energy resource that could be
exploited in the future (Max, 2000). In some cases, hydrates
have been found lying exposed on the seaoor, in contact with
the water column (MacDonald et al., 1994). Warmer ocean waters in a changing climate may destabilize some marine hydrate
deposits and potentially generate an adverse climatic feedback
in the process (Harvey and Huang, 1995). Furthermore, sequestration of anthropogenic CO2 in the deep ocean has been proposed at conditions that foster hydrate formation. The stability
of the CO2 hydrate phase will affect the term of sequestration and extent of local environmental impact (Fer and Haugan,
2003). It is important, therefore, to understand well the phenomena governing the evolution of hydrates immersed in water
greatly undersaturated with the hydrate-forming species.
While the kinetics of hydrate dissociation have been investigated experimentally in the laboratory, the liquid phase in
contact with the hydrate was typically saturated with the guest
species, or, in the case of CO2 , the hydrate formed as a thin
Corresponding author. Tel.: +1 808 956 2338; fax: +1 808 956 2336.
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G.C. Nihous, S.M. Masutani / Chemical Engineering Science 61 (2006) 7827 7830
Fig. 1. Equilibrium phase diagram for methane hydrate, gas (CH4 -rich solution) and seawater solution (equation of Handa, 1990, for pure water with
an offset of 1.15 K following Peltzer and Brewer, 2000).
falls to the left of the solubility curve; i.e., when the reactiondesorption layer is not saturated. For example, hydrate will decompose when the liquid desorption layer corresponds to Point
B, but not to Point A. A fugacity difference between the hydrate
solid surface at equilibrium (Point C) and the desorption layer
(Point B) then arises, as shown in Fig. 3. This decomposition
mechanism does not allow a gas cloud to exist around the hydrate particle and its desorption layer. Instead, two liquid lms
separate the solid surface and bulk water: the desorption layer
and a diffusive boundary layer. As discussed above, however,
the concentration at the interface between these two lms theoretically should be lower than ambient solubility (xB < xA ).
This is a point of departure from the standard assumption that
diffusion is driven from xA .
3. Interpreting methane hydrate dissolution data
A decomposition rate per unit area of 3.7 104 mol/m2 s
was measured by Rehder et al. (2004) for methane hydrate
samples in deep seawater (ambient conditions: T = 3.6 C,
G.C. Nihous, S.M. Masutani / Chemical Engineering Science 61 (2006) 7827 7830
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mole fraction 1/(1+nH ), where nH is the hydrate number typically close to 6. If we assume that only one hydrate layer at a
time is decomposing, we should have:
L
xB (1 + nH )
(5)
dt
Z
(6)
(1/A)(dn/dt)(CO2 )
CA (CO2 )
(7)
Since the parameters D and Z are similar for CH4 and CO2 , they
explained this result by considering diffusive boundary layers
where diffusion takes place from saturated concentrations (with
near zero ambient concentrations), i.e., Eq. (6) for either species
but with a concentration equal to the solubility CA . If instead
the hydrate desorption lm is undersaturated, then the ratio of
the dissolution rates should match the ratio of the interfacial
concentrations CB by the same argument:
(1/A)(dn/dt)(CH4 )
CB (CH4 )
.
(1/A)(dn/dt)(CO2 )
CB (CO2 )
(8)
Eqs. (7) and (8) together suggest that the degree of undersaturation is about the same for the two types of decomposing
hydrates.
Clarke and Bishnoi (2004) measured the intrinsic decomposition parameters for CO2 hydrates, K0 = 1.83
108 mol/(s m2 Pa) and E = 102.88 kJ/mol, respectively. The
analysis done in the previous section was repeated using those
values. To relate fugacity to mole fraction as in Eq. (2), the
model of Edwards et al. (1978) for the equilibrium of volatile
weak electrolytes in non-ideal solutions was used in combination with the seawater solubility data of Weiss (1974). Here,
vliq = 32.8 cm3 (Akinev and Diamond, 2003). We found a
very high equilibrium pressure PC and a desorption layer
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G.C. Nihous, S.M. Masutani / Chemical Engineering Science 61 (2006) 7827 7830
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