Chemical En@wering Science, Vol. 39, No.

Printed in Great Britain.

10, pp. k435-1442,

1984.

cuKw-2509/w
53.M + 0.00
Pergamon Press Ltd.

THREE PHASE INTERFACIAL HEAT TRANSFER

DURING THE DISSOCIATION OF PROPANE
HYDRATES
V. A. KAMATH,

G. D. HOLDER

and P. F. ANGERT

Department of Chemical Engineering, University of Pittsburgh, Pittsburgh, PA 15261, U.S.A.

(Received 25 April 1983)

Abstract-An
experimental technique was developed to obtain measurements on the rate of heat transfer to
a solid hydrate phase which decomposes into gas and liquid phases simultaneously. Since all the three phases
are present, this phenomenon is termed three phase heat transfer.
The results indicate that the rate of heat transfer is a power function of AK which is the difference in
temperature between the (warm) bulk heating fluid and the (coId) hydrate surface which is undergoing the
phase change (dissociation). A correlation for heat transfer was developed and is analogous to that used for

describing heat transfer during nucleate boiling of liquids.

INTRODUCFION

are clathrate ices in which each water

molecule forms hydrogen bonds with four nearest
neighbours
to build a solid lattice which encages gas
molecules such as methane, ethane or propane, in its
interstitial
cavities. These solid, ice-like mixtures of
natural gas and water have been found in rocks
beneath the permafrost, in Arctic basins, and in muds
under deep water along the continental margins of
America. Although they have been known to exist for
over a century and half, it was the discovery of natural
gas in the frozen state in Siberia in the early sixties
[l] that stimulated widespread interest in naturally
occurring gas hydrates.
Estimates of the amount of hydrated natural gas
in the world cover wide ranges (1.4 x lOi m3 to
7.6 x 10 m) but in all cases are enormous [24]_
Because of this potential resource, the problems asso&ted with the production of natural gas from these
hydrate zones have become of greater interest to the
hydrocarbon industries.
Aspects of gas hydrates which have been studied
extensively in the past include: (a) structures [5-71,
(b)conditions under which hydrates form or dissociate
[S-lo],
(c) compositions
[ll],
(d) thermodynamic
properties [12], (e) hydrate inhibition [13] and (f) the
natural occurrence of gas hydrates [14]. In addition,
preliminary work on modeling production of gas in
hydrate form has been done by Makogen et al. [IS],
Holder er al. [16] and McGuire [17]. However, one
area which is important but which has not been studied
is the rates of heat and mass transfer during hydrate
growth and dissociation.
In the present study, an improved understanding of
the interfacial heat transfer phenomena during dissociation of propane hydrates has been obtained.
Because hydrates are solids which form gas and liquid
(water) phases upon decomposition,
heat transfer to
dissociating hydrate is a three phase heat transfer
process. Processes such as these have not been studied
for dissociation of hydrates or for other systems prior to

Gas

hydrates

CES34:10-A

this work and modeling of such heat transfer has been

speculative at best.
THREE PHASE HEAT TRANSFER TO
DISSOCIATING

HYDRATES

The process by which the hydrates breakdown is a

solid to gas+ water phase transition and requires
120-140 kJ of energy per mole of propane gas
liberated from the hydrate phase. At a given temperature, T, the heat of dissociation can be calculated from a
modification of the Clapeyron equation.

where R is the universal gas constant, Z is the

compressibility factor of the gas, P is the dissociation
pressure and d(ln F)/dTis the slope of the three phase,
vapor-water-hydrate,
vapor (dissociation)
pressure
curve.
As hydrates (solid) dissociate, they form liquid
(water) and gaseous phases. Hence, at the dissociating
interface three phases will be present. The presence of
three phases at an interface during a heat transfer
process also occurs in nucleate boiling where the
heating element (solid) converts a liquid to a gas. It is
not unreasonable to draw an analogy between nucleate
boiling phenomena and heat transfer during hydrate
dissociation. However, in hydrate dissociation, unlike
nucleate boiling, the solid is involved in the phase
transition and the direction of heat transfer is reversed.
Because of the potential analogy, correlations for
nucleate
boiling heat transfer
are summarized.
Rohsenow (19) proposed a dimensionless correlation
for nucleate boiling data using a bubble Reynolds
number based on the bubble diameter and departure
velocity. The following dimensionless
groups were
used:
Nusselt number,

Nu, = w

I
1435

(2)

1436

V. A. KA~M.4TI-let
Reynolds

number,

Re, = PI

(3)

where D, is the maximum bubble diameter after

departure and Gb is the average mass velocity of vapor
receding from the surface. The exact form of the final
correlation was:

(pr),

(4)

where, h, is the heat of boiling and c,, is a constant

depending upon the nature of the heating surfac+fluid
combination.
The effect of forced convection was
incorporated additively as:

: =

(4),+(z),

where (Q/A), is the heat transfer associated with either

forced or natural convection in the absence of boiling
and (Q/A)) is the heat flux due to boiling and can be
obtained from eq. (4).
For dissociation of hydrates, eqs (4) and (5) were
used to develop a new correlation and the constants
cS,. r and s were obtained to fit the data for dissociation
of propane hydrates.
EXPERIMENTAL

APPARATUS

Figure 1 is a schematic diagram of the apparatus

used to form and dissociate hydrate cores under
controlled
pressures
and temperatures.
Pressure
vessels A and B have a removable llange at the top end
and a permanent flangeat the bottom end. Both vessels
are 9ScmID,
30cm high and designed for pressures
up to 13.8 MPa.

al.

Vessel B is used to form and dissociate hydrate cores.

A Heise pressure gauge (2) with a range of 6500 psia
(O-3.45 MPa) is connected to vessel B. For cooling
purposes, vessel B is equipped with a coiled tube jacket
(34 A) around the vessel and an independent cooling
manifold (7) at the bottom. By keeping the coolant in
the manifold colder than that in the coils, a temperature gradient can be maintained in the hydrate vessel.
Vessel A is used for separation of the gas and water
overflow (through valve 13) from vessel B during the
dissociation
of gas hydrates. It is connected to a
Jerguson gauge (3) which acts as a liquid level indicator
and also to a pressure gauge (32) having a range of O-60
psia (O-O.4 MPa) pressure. A 1000 W control heater (5)
is used to keep the temperature of the bulk water phase
higher than the hydrate temperature.
The warmer
water in vessel A is circulated to vessel B using a liquid
circulating pump (6) having an adjustable flow rate of0
to 27.3 x 10e6 m3 s-l. This warm water provides the
heat needed to dissociate the hydrate. The gas liberated
during hydrate dissociation in vessel B, flows through
vessel A, where it is separated from the water and into a
wet test meter which is accurate to 0.5 %.
The refrigerated methanol bath is partitioned into
two parts, which are maintained at different temperatures. This allows slight temperature gradients to be
maintained
in the hydrate vessel (B) as discussed
below.
Experimental

procedure

The objective of these experiments was to form solid

cylinders of hydrate in vessel B and to use warm water
to dissociate these hydrates at steady state rates. The
top of the hydrate cylinder (core) is indicated by the

Disaoeiation of propane hydrates

dashed line in Fig. I. The rate of heat transfer to the

hydrate phase is measured by measuring the rate at
which hydrates dissociate (melt) which is calculated
from the flow rate of gas. The data obtained in these
experiments was used to calculate rates of heat transfer
during the three phase transition which occurs as
hydrates dissociate.
The method used to form the hydrate cores is similar
to that used by De&on and Frost Cl83 and was highly
successful for forming about 0.3-0.35 kg of propane
hydrates. The procedure used in this method is as
follows: initially, a known quantity of frost (finely
divided ice crystals) is charged to vessel B which is kept
at very low temperatures to prevent melting. The frost
is added to vessel B in four portions with each portion
being compactedby the piston prior to adding the next
portion. This ensured a uniform void fraction of
0.40.5. Vessel B is then closed, evacuated and saturated with a known quantity of liquid propane. While
condensing propane into the frost, the bottom of the
frost is kept at about 250K and the top of the frost
zone is kept at about 268 K, to insure that the liquid
propane starts saturating the frost from the bottom
upwards. Thus, the temperature gradient in the frost
zone helps to Saturate the frost completely. The
temperature of the frost zone is monitored during the
process in order to keep it lower than 273.15 K,
thereby preventing any premature melting of the frost.
After the frost zone is saturated completely, the
temperature of vessel B is raised to 274 K and maintained at this temperature for a period generally longer
than 24 h. During this time, nucleation and formation
of hydrates takes place. After the formation of the
hydrates, excess liquid hydrocarbon is distilled off into
vessel 37 leaving a core composed of hydrates, ice and
free hydrocarbon gas. Distillation of excess propane is
accomplished simply by reducing the pressure of vessel
B to a point lower than the vapor pressure of propane,
yet higher than the dissociation
pressure of the
hydrates.
Once a hydrate core has been prepared in vessel B
and the excess propane within the core is distilled, the
free gas space above the hydrate core is flooded with
cold distilled (Z 275 K) water from vessel A by use of
circulating pump 6. Vessel A and all other pertinent
lines are then evacuated. Additional hot water is then
added to vessel A from a water storage tank through
valve 11. This water is continuously
circulated by
pumping it into vessel B, which has its overflow (gas
f water) piped back into vessel A, where the gas and
water are separated. The temperature of this water
(TB) is controlled in such a way that the desired
AL\f= (TB - T,) is obtained for a given run. The interfacial temperature TI is assumed to be the equilibrium
temperature of dissociating propane hydrate at the
system pressure. The pressure, and thus T,, are controlled using the back pressure regulator (27). Each
minute, the volume of gas flowing out, the temperature, the pressure and the height of the water in vessel A
are measured. During a dissociation run, the space
above the hydrate core is completely filled with water

1437

except for the gas bubbles

hydrate&e-water
interface.

which depart

from the

HEAT FLUX CALCULATIONS

Figure 2 shows a plot of heat flux vs time for a typical

dissociation run. From this figure, it is clear that the
heat flux is very high at the start of the run, subsequently leveling off to a steady state value. Similar
plots of heat flux vs time, and rate of dissociation vs
time were obtained to select the steady state zones for
each run. In order to calculate the rate of dissociation,
the heat flux and the heat transfer coefficient, the
following assumptions are made.
(1) The hydrattwater
interface remains flat with
an area equal to the inside cross-sectional area, A, of
vessel B. Visual observation of the interface during
the dissociation of the hydrate core in an open vessel
supported this assumption. In addition, the section
of hydrate which might protrude into the water
would tend to melt more rapidly since such sections
would have a larger surface area protruding into the
water. The rapid melting would smooth the surface.
(2) The hydrate core is a uniform dispersion of
ice, hydrate and gas. Since the hydrates were formed
under volumetrically uniform conditions, the assumption that ice is converted uniformly to hydrate
is reasonable.
The heat transferred through the interface, Q/A,
melts the hydrate and the ice and is conducted away.
An energy balance gives
Q
-=
A

nf,@f,

+ WH,
A

- Qc,,,,d

(6)

where ni, is the experimentally measured molar flow

rate of gas which comes from dissociated hydrates, nir
is the molar rate of ice melting, AH, is the latent heat of
hydrate dissociation per mole of dissociated gas [eq.
(l)], AH, is the latent heat of ice melting and Qmti is
the heat transferred
away from interface due to
conduction in the core to the cooling manifold. The
7

IO

I5
Time

Fig

20

25

50

(min)

2. Hsat flux vs time for a typical dissociation run.

1438

V.

A. ~IUATH

largest term is ni,AH,

which is the energy used to
dissociate the hydrate. The energy used to melt the ice,
nim,,is
small,but important and the conduction term
is negligible. We assume that the dissociated gas and
water leave the interface
at T, the interfacial
temperature.
The rate of ice melting, ni, is a fixed percentage of the
hydrate dissociation rate since the solid phase, which is
decreasing in height, is a uniform mixture of ice and
hydrate. A mass balance gives:

et al.

measured

volumetrically as all the hydrates are dissociated. The following equation is used to calculate
the fractional conversion:

where H is the initial height of the hydrate zone and m

is the amount of frost charged.
The interfacial temperature
can be obtained by
knowing the P-Trelationship
for hydrate equilibrium.
T = (In(P)+ B)
(dln P/d T)

(7)
where nH is the ratio of moles of water to moles of gas
in the hydrate phase (about 17 for propane hydrate), p,
is the density of pure ice, M, is the molecular weight of
water, pHzO,.,is the molar density of water in hydrate
phase, 4, is the ice volume fraction of the hydrate zone
and &, is the hydrate volume fraction.
The fractional conversion of frost to hydrates,fcan
be calculated by knowing the amount of gas in the
hydrate phase. The amount of water in the hydrate
phase is 17 moles per mole of gas and the fractional
conversion is the amount of water in the hydrate phase
divided by the amount of water (frost) charged to the
hydrate cell. The amount of gas in the hydrate phase is

where

dlnP
B (= 54.73) and dT

(9)

(= 0.2192 K-)

respectively the intercept and slope of the propane

hydrate dissociation curve.
RESULTS

AND

DISCUSSION

Correlation for heat transfer

Fourteen experimental
runs were carried out to
investigate the effect of AT on heat flux Q/A. In these
runs, the rate of circulation of water was held constant
so that forced convection effects would he similar.
Tables 1 and 2 summarize the information obtained
from these dissociation runs. It should be noted that
the heat flux increased from 0.52 x 104 to 2.71

Table 1. Properties of hydrate cores of propane (etlkct of AT)

Run
NO.

% conversion
or frost

Height of
hyd. zone (m)

T-l
T-2
T-3
T-4
T-5
T-6
T-7
T-8
T-9
T-10
T-11
T-12
T-13
T-14

52.0
52.5
67.7
51.2
65.2
50.3
63.1
45.3
33.6
22.6
43.3
30.4
76.4
72.2

0.191
0.100
0.114
0.110
0.120
0.138
0.113
0.140
0.120
0.152
0.173
0.141
0.098
0.100

16
101
57
87
48
24
24
zt
24
24
3.5
48

% hydrate

% ice

%pas

29.2
30.4
38.7
33.7
36.4
26.0
26.0
22.0
17.8
13.9
28.5
19.1
51.4
48.1

23.3
23.9
16.0
27.8
16.8
22.2
13.1
22.9
30.4
41.1
32.3
37.7
13.7
16.2

47.5
45.7
45.3
38.5
46.8
51.8
60.9
55.1
5 1.8
45.0
39.2
43.2
34.9
35.1

Table 2. Summary of dissociation runs for AT

RUII
No.
T-l
T-2
T-3
T-4
T-5
T-6
T-7
T-8
T-9
T-10
T-11
T-12
T-13
T-14

14.7
13.0
t3.6

15.9
11.9
7.6
6.5
10.2
17.2
20.9
16.8
10.7
12.5
12.2

290.4
287.0
287.9
290.3
288.5
283.7
282.9
286.3
293.4
296.8
292.9
286.9
288.7
288.5

are

(La)

Q/A
(W m -2) x 10-d

UI,
(W m- K)

293.0
202.7
220.6
224.1
340.6
326.1
346.8
324.7
324.7
312.3
321.3
331.6
336.5
338.5

2.6071
2.2619
1.5376
2.9761
2.2701
0.7206
0.5204
1.2010
2.8963
2.7105
2.7934
1.0836
1.5228
2.5275

1773.6
1739.8
1130.4
1871.3
1907.3
947.8
800.1
1177.0
1684.0
1296.7
1663.1
1013.0
1218.8
2071.3

of

Dissociation

x IO4 W rnm2, when AT was increased from 6.5 to

20.9 K. The experimental
results did not indicate a
peak in the heat flux. If the phenomenon of critical heat
flux occurs (as in nucleate boiling) it would be at higher
AT values.
The effects of forced convection will be different for
different experimental
systems. To obtain results
which would be general in nature we carried out runs at
different water circulation rates. When extrapolated
to
zero flow rate, the heat transfer consists only of that
due to natural convection and can be generalized to
any propane hydrate dissociation heat transfer across a
flat surface. Consequently, 11 experimental runs were
carried out to quantify the effect of forced convection
on the heat flux for constant AT. It was found that
when the rate of water circulation was increased from
5.33 x low6 to 27.33 x low6 m3 s-t; the heat flux
increased from 0.96 x lo4 to 1.41 x IO4 W mm2 at AT
of 10 K. Tables 3 and 4 summarize these dissociation
runs. Using eq. (5) as a model, the effect of forced
convection was determined and subtracted from the
total heat transfer. The correlation for heat transfer
during dissociation in the absence of forced convection
is
Ja, = 0.0405 Ret.64 Pr .O
w
The heat flux due to forced convection

is obtained

0=
Q

2,

kAT
0.0019N~gPr0~4~
Re
D *

as

(11)

The correlation
for describing all of the data is
obtained by combining eqs (S), (10) and (11) and is

propane hydrates

Q
-=
A

% conversion

Height of

of frost

hyd. zone (m)

W-l
w-2
w-3
W-4
W-5
W-6
w-7
W-8
w-9
w-10
W-11

34.4
34.5
35.8
54.0
48.6
36.9
40.8
40.7
44.1
62.0
69.7

0.164
0.136
0.140
0.143
0.153
0.140
0.132
0.128
0.128
0.153
0.141

kAT
+00019N~*Rt- Pr0,4p
D

148.48 Jai.56
Pr1.56 Re,/(Q/A,)

u-a
The dimensionless
numbers Ju,, the bubble Jakob
number; Ret,, the bubble Reynolds number; NRe. the
fluid Reynolds number and Pr, the Prandtl number are
given by:
(13)

0 Q

b ~/90a
Re,=-----P,AH, a@, P,)

(14)

(1%

p,=5!!5,

(16)

k,

The correlation has an accuracy of f 15% of the

measured heat flux. Figures 3-5 show the comparison
between the heat fluxes predicted by the correlation
and the heat fluxes obtained experimentally. Figure 4
shows predicted and experimental
heat flux versus
temperature driving force AT. Figure 5 shows experimental and predicted heat flux versus Reynolds
number. Overall, the correlations,
which are of the
same form as the nucleate boiling correlations given
above, describe the experimental
results quite well.

Table 3. Properties of hydrate cores of propane (effect

Run
No.

1439

given by

37
36
30
25
24
24
;t
24
48
48

of rate of circulation of water)

% hydrate

% ice

% gas

16.9
19.5
16.6
28.1
23.2
22.2
24.1
26.0
23.6
39.3
39.5

33.4
37.8
31.4
29.2
30.1
35.8
37.3
37.4
26.3
16.4
14.9

49.1
42.7
52.0
42.1
46.7
42.0
38.6
36.6
50.1
44.3
45.6

Table 4. Summary of dissociation runs for rate of circulation of water

Run
No.

W-l
w-2
w-3
W-4
W-5
W-6
w-7
W-8
w-9
w-10
W-11

9.6
11.8
10.9
7.6
11.1
12.0
11.2
12.1
10.9
9.2
9.1

285.9
287.7
286.8
283.6
286.8
287.2
266.8
286.8
286.7
285.4
286.2

345.6
307.4
310.3
317.2
296.5
262.0
290.5
298.2
303.4
326.3
401.8

Pump flow rate

(m3CL) x lo6

QIA
(W me2) x lO-4

27.33
22.83
11.33
27.33
17.33
5.33
26.33
14.33
17.33
5.33
8.33

1.3509
1.5805
1.1726
1.0081
1.1736
1.1488
1.4658
1.93 56
1.5237
1.1801
0.9549

1410.1
1338.3
1077.7
1328.2
1053.5
956.5
1313.5
1601.0
1403.0
1278.5
1045.9

V. A. KAMATHet al.

1440

.I

0.5

I .o

Expertmental

1.5
heat

flux

25

3.0

fW/SQ.M)

Fig. 3. Comparison of experimental and

1,

20

x IO4

Fig. 6. Predicted heat flux vs AT at different NRI.

predicted heat flux.

100

Tb-Ti. (K)

35

IO

Temperature difference,

I02

TD -T,

(Kl

Fig. 4. Predicted (-) and experimental (A) heat flux vs

temperature driving force AT.
0.2

Fractional

0.4

conversion

0.6

0.8

to hydrates.

Fig. 7. Experimental heat flux vs fractional conversion

hydrates.

9,03

45

Reynolds number

Fig 5. Experimental (A) aad predicted (-)

Reynolds number Nae.

heat flux YS fluid

to

Figure 6 shows the predicted (correlated) heat flux

versus AT at different N,, values. These curves show
that the heat transfer is expected to be very sensitive to
AT, but considerably less sensitive to forced convection
effects as represented
by N,. Note that the dissociation heat flux is shown by the curve N, = 0 in
Fig. 6 is the heat flux which applies to the general
system.
Eflect of hydrate conversion
Figure 7 shows that the relative amounts of ice and
hydrate present do not significantly affect the heat flux.
The hydrate dissociation results in the rapid liberation
of gas and the turbulence generated by these bubbles
appears to dominate the heat transfer process.

Dissociation of propane hydrates

SUMMARY

This work has two major accomplishments.

First, an
experimental technique for forming hydrate cores and
for conducting three phase heat transfer measurements
for systems undergoing phase transitions
has been
developed. Second, a general correlation for describing
three phase heat transfer to dissociating
propane
hydrates has been obtained. This may be the first
instance of measurements
and correlations
of heat
transfer at gas--solid-liquid
equilibrium conditions
and therefore is of fundamental value in the general
field of heat transfer with phase change. The correlated
results follow the same form as those for nucleate
boiling heat transfer in that dependence of the heat
transfer rate on the temperature difference is similar in
both the cases. The fact that this heat transfer follows
the same form despite the direction of heat flowfrom
the solid in nucleate boiling and to the solid in hydrate
dissociation indicates thacthe bubble formation plays
an important role in both instances.
These results will be of use in modelling hydrate
dissociation processes such as might occur if hydrates
are used for temporary gas storage or for desalination
of sea water. If hydrates in the earth are to be
dissociated through thermal injection of warm water, a
process which has been suggested[17]
the rates at
which they dissociate will be limited, in part, by the rate
of heat transfer to the hydrate phase. The results
presented here can be used to estimate such rates, at
least for propane hydrate. Methane hydrates, which
form structure I hydrate as opposed to the structure II
which is formed by propane, will be studied in future
experiments to verify that the correlation development
here is of a general nature. Of course, in a practical
location, the dissociation of hydrates will be limited
not only by the interfacial resistance, but also by the
resistance of the surrounding media. These resistances
must be coupled.
Acknowledgement-This material is based upon work supported by the Gas Re-h
Institute under Grant No. 5080X3-0431.
NOTATION

A
B
C,

C sf
D
?
9
go
Gb
h
h
LL;;,
AH,

Jab

interfacial heat transfer area, m2

intercept of P-T curve for propane
speciiic heat of saturated liquid, kJ/kg K
constant depending upon the nature of heating surface-fluid combination
diameter of inlet water port, m
maximum bubble diameter, m
fractional conversion of frost to hydrates
acceleration due to gravity, m/h*
gravitational constant, kg m/N hz
average mass velocity of vapor, kg/mh
height of hydrate zone, m
latent heat of boiling, kJ Kmol-
latent
heat
of
hydrate
dissociation,
kJ Kmol-
latent heat of fusion of water, kJ Kmol-
Jakob number

1441

thermal conductivity
of saturated liquid,
kJh-rn-K-l
mass of the frost charged, kg
molecular weight of water, kg kmol _
rate of hydrate dissociation, kmol h -
rate of ice melting, kmol h 1
rate of dissociation
for pure hydrates,
kmol h-l
hydrate number or the ratio of number of
moles of water to moles of gas in structure II
hydrates
Fluid Reynolds number
dissociation pressure, kPa
Prandtl number

k,
m

MW
mH

h/
*H,
nH

Nil,
P

Pr

heat flux due to boiling, kJ/h m2

0 Ab

Q
heat flux due to forced convection, kJ/h m2
0 2,
QCond heat transferred due to conduction, kJ/h
universal gas constant
exponents in eq. (4)
bubble Reynolds number
temperature, K
temperature driving force (TB - T,), K
temperature of bulk water phase, K
temperature at the interface, K
velocity of bulk water phase, m h-
compressibility factor

R
r, s
Reb
T

AT
TB
TI
vb
2.

Greek symbols
viscosity of saturated liquid, kg/m h
surface tension, N mm
density of ice, kg mm3
PI
density of saturated liquid, kg mm3
PI
density of vapor, kg m-3
P
pHaO,u
molar density of water in structure II hydrates, kmol m - 3
volume of fraction of hydrate in the core
the hydrate formation period, h

I4
-3

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