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Kinetics of methane hydrate dissociation

Article in Doklady Physical Chemistry · October 2015

DOI: 10.1134/S0012501615100061

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ISSN 00125016, Doklady Physical Chemistry, 2015, Vol. 464, Part 2, pp. 244–246. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © V.E. Nakoryakov, S.Ya. Misyura, 2015, published in Doklady Akademii Nauk, 2015, Vol. 464, No. 6, pp. 693–695.

PHYSICAL
CHEMISTRY

Kinetics of Methane Hydrate Dissociation

Academician V. E. Nakoryakov and S. Ya. Misyura
Received July 2, 2015

Abstract—The methane hydrate dissociation at an external pressure of 1 bar has been experimentally studied.
The methane dissociation rate depends on the heat transfer intensity in the course of dissociation. Quasiiso
thermal and nonisothermal conditions of clathrate dissociation have been compared. Under nonisothermal
conditions, the dissociation rate depends on the heat flux density. The lowest heat flux was achieved in a
quasistationary mode, and the highest heat flux was achieved through combustion of methane released from
the clathrate powder. The 54fold increase in heat flux leads to the ninefold increase in the methane dissoci
ation rate. Depending on the heat flux density, the following variants of clathrate dissociation were observed:
without selfpreservation, partial selfpreservation with one dissociation rate minimum, and partial selfpres
ervation with two minima.
DOI: 10.1134/S0012501615100061

Formation and dissociation of gas hydrate [1]
depend on a large number of factors: pressure, tem
perature, subcooling degree, and structural character
istics of a sample. The dissociation kinetics has been
studied in [2] where the clathrate decomposition rate
as a function of gas volatility has been determined. The
kinetics of dissociation at various heating rates has
been studied in [3]. To date, available experimental
data mainly pertain to clathrate decomposition in low
heat fluxes. In studies dealing with methane combus
tion [4–7], heat fluxes have not been measured and
local rates of methane hydrate decomposition have not
been determined. Therefore, quantitative data on the
decomposition kinetics in combustion are of interest.
Special attention focuses on the phenomenon of “self
preservation” [8, 9] where extremely low clathrate
decomposition rates are observed. Currently, we are
still far from a deep understanding of the selfpreserva
tion mechanism. Anomalous stability is attributed to
the formation of the solid ice crust and to the appear
ance of characteristic texture in the course of anneal
ing. Quantitative data on the growth of ice crust as a
function of time have been reported [10]. The present
paper deals with methane hydrate dissociation mech
anisms and selfpreservation.
The scheme of the experimental setup was
described in [6]. The initial weight concentration of
methane in a gas hydrate was 12.1 wt %, and the initial
average diameter of powder grains was d = 2.1–2.6 mm.
The gas hydrate dissociation occurred under noniso
thermal conditions: the sample temperature continu
Kutateladze Institute of Thermophysics, Siberian Branch,
Russian Academy of Sciences, pr. Akademika Lavrent’eva 1,
Novosibirsk, 630090 Russia
email: misura@itp.nsc.ru
ously increased from the initial liquid nitrogen tem
perature to the melting point of ice at ambient pres
sure. Methane hydrate had an sI structure.
Characteristics of the methane hydrate powder were
determined by gravimetric and volumetric methods.
Methane hydrate decomposition leads to the
appearance of a multilayer structure (Fig. 1a). With a
lapse of time, the ice crust thickness δ increases, and
the ice crust radius Ri decreases. Measurements with a
scanning electron microscope [11] have shown that
clathrate decomposition leads to the formation of
pores in ice. Gas diffusion through the pores exceeds
by many orders of magnitude the diffusion through the
solid crust (Fig. 1b). In the course of dissociation, a gas
hydrate can exhibit anomalously slow decomposition
at annealing temperatures, i.e., selfpreservation. In
this case, the pores are closed with ice, and the crust
becomes continuous, as shown in Fig. 1a. Crank [12]
has derived the equation that relates the change in ice
layer thickness (without pores) in time with diffusion
and pressure.
A = 3(1 – R2) + 2(R3 – 1) = c1D(Pd(T) – Pa)τ, (1)
where с1 is a constant; Pd(T) is the methane dissocia
tion pressure at temperature T; Pa is the ambient
methane dissociation pressure; D is the methane diffu
sion coefficient through the surface ice layer; R =
Ri/R0, where R0 is the initial radius of the forming ice
crust, which corresponds to the grain (sphere) radius,
and Ri is the current ice crust radius; τ is time. Analysis
of experimental data has shown that the ice layer
thickness δ actually becomes equal to the sphere
radius R0 at the moment of time τ = τ1 = (0.3–0.5)τmax
(Fig. 1c), where τ1 corresponds to the complete tran
sition of the gas hydrate to ice. The powder surface
temperature for a given segment is 270–273 K, and the
temperature curve is linear. The grain surface temper
ature was measured by means of a heat imager. Such a

244
 KINETICS OF METHANE HYDRATE DISSOCIATION 245

(a) (b) T, °C (c)

2 0

Ri 1
τ1 τmax

Fig. 1. (a) A multilayer structure formed during the gas hydrate dissociation: 1 is the outer ice shell, 2 is the gas layer under ice,
and 3 is the inner gas hydrate core. (b) Methane release from pores formed in the ice shell. (c) Temperature of the grain surface
as a function of time.

long time interval from τ1 to τmax is caused by a low
temperature gradient and insignificant heat flux rather
than by the phase transition. All gas hydrate converts
into ice long before all methane is released, which is
caused by small pore diameters (on the order of 0.1–
1.0 µm) and the high resistance to gas passage through
the pores. The crystallization front velocity exceeds
the average gas outflow rate through the pores. Gas
outflow is accompanied by a decrease in the gas pres
sure in the pores, so that the gas flow rate decreases.
Experimental methane hydrate dissociation curves
when a solid ice crust is formed, i.e., under selfpres
ervation conditions, have been obtained [10]. It has
been established that even at very low decomposition
rates (ΔV/V) on the order of 0.1% per hour, the diffu
sion coefficients are many orders of magnitude higher
than the vacancy diffusion coefficients. Evaluation
also indicates a substantial decrease in activation
energy. Thus, it is more correct to speak about partial
(rather than complete) selfpreservation in which even
a very low pore density plays a decisive role in the
mechanism of gas hydrate dissociation. The diffusion
coefficient in Eq. (1) shall be a function of defect con
tent even at an extremely low pore density, and Eq. (1)
shall be nonlinear (D = var). Figure 2 shows the meth
ane hydrate dissociation curves at the atmospheric
pressure 1 bar. The high heat flux (curve 3) was
achieved through combustion of methane released
from the powder. The heat flux was determined from
the gas temperature profile near the powder surface
and was linear (low Rayleigh numbers). The low heat
flux (curve 4) was achieved by regulating the ambient
temperature, which was 10–13°C higher than the
powder temperature during the entire decomposition
period. Curve 2 was obtained at constant ambient tem
perature 23°C, while the sample temperature was
changed from liquid nitrogen temperature to 0°C. The
54fold increase in the heat flux density (from 255 to
13 700 W/m2) led to the ninefold increase in the max
imum dissociation rate. The second minimum in the
decomposition rate curve begins to appear at q =
65 W/m2 or at lower values. The lowest heat flux is
realized for curve 1. Usually, upon the phase transi
tion, the powder temperature decreases by several
kelvins. At higher heat fluxes, only one dissociation
minimum is observed. It should be emphasized that,
when the second minimum is observed under noniso
thermal conditions, the ice crust is rather thick, and 10
to 40% of methane is retained in the sample [14].
Under quasiisothermal conditions (curve 1), decom
position begins just at annealing temperature (the
external pressure rapidly decreases to 1 bar), and self
preservation occurs for a very thin ice film. Before the
onset of selfpreservation, the sample can lose only a
few percent of the methane weight.
Thus, under nonisothermal conditions, the meth
ane hydrate dissociation rate depends on the heat flux
density. The 54fold increase in the heat flux density
led to the ninefold increase in the dissociation rate.
Depending on the heat flux density, different variants
of gas hydrate decomposition can be observed with
ν, %/s
1
0.1
0.01
0.001
0.0001
1
1E05 2
3
1E06 4
1E07
180 200 220 240 260 280 300
T, K
Fig. 2. Methane hydrate dissociation: (1) quasiisothermal
conditions [13], (2) nonisothermal conditions at the average
heat flux density q = 255 W/m2, (3) for q = 13 700 W/m2
(methane combustion), and (4) for q = 65 W/m2.

DOKLADY PHYSICAL CHEMISTRY Vol. 464 Part 2 2015

246 NAKORYAKOV, MISYURA
one or two minima of anomalously low decomposition
rate.
ACKNOWLEDGMENTS
This work was supported by the Russian Science
Foundation (project no. 15–19–10025).
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Translated by G. Kirakosyan
Vol. 464 Part 2 2015