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343
He
II
TO
A NA L Y S
UNl T
SAMPLE
F OM A U T O C L A V E
FIGURE
2. Hydrocarbon withdrawal.
lower column in the figure, and separated by differential glycerol loadings in each analysis column.
The advantages of the hydrocarbon withdrawal
system is that the withdrawn hydrocarbon phase may
be measured very accurately. Although the accuracy
has never been explicitly cited, it is almost certainly
within 10 ppm (mole basis). There are only a few disadvantages, the chief of which is that the method is
very time consuming and relatively expensive. As
with any rotating equilibrium cell, connecting line
fatigue and rupture is a small problem. There may
also be water drops on the ends of the cell cylinder,
which are not ground by the balls to prevent occlusion. In spite of these small problems, the method is
excellent, and remains the only apparatus available
for the vapour-hydrate measurement. As an indication of accuracy of measurement, a neoprene diaphragm on the elution helium regulator (see Figure-2)
345
In Situ Water'Measurement
Recently a new apparatus has been constructed in
this laboratory for the measurement of the water content of hydrocarbon liquid in equilibrium with
hydrate. While only preliminary measurements have
been made to date, the initial indications are that the
method is viable and rapid. The oscilliometric apparatus is shown to be a capacitance measurement of
liquid above the hydrate phase (Figure 3). In fact, the
apparatus is identical to the one described by Pan et
al. (1975), but the application of the apparatus is
new. The hydrates are formed in a free-water phase
below the capacitance plates, where they remain, and
the capacitance of the hydrocarbon liquid is meas-
Capacitance
Bridge
Proportional
Controller
Propane
Cylinder
Refrigeration
Unit
FIGURE
3. I n situ hydrocarbon-hydrate apparatus.
Prediction Techniques
The determination of the molecular structure of
hydrates during the early 1950's enabled van der
Waals and Platteeuw (1959) to derive a statistical
mechanics model for the chemical potential of water
in hydrate as:
pwH= pwMT + R E q l n ( 1 - 1Oij)
[l]
I
366
I
376
3.S
398
UX
IO~IT,
T in
1
416
1
4 26
FIGURE
4. Structure I empty hydrate vapour pressure as a function of reciprocal temperature.
PI
f w H = f w M T exp(-&w/RT)
where fwMT is an experimentally determined parameter related to the hypothetical vapour pressure of
the empty hydrate.
Ng and Robinson (1980) give expressions for fwMT
in both structures, obtained by fitting the data of
R. Kobayashi and co-workers (Aoyagi et al. 1978,
1979). Therefore their method may be considered a
correlation of existing two-phase (vapour-hydrate)
data.
= z+p
347
TABLE1. The prediction of the water content inthe methane vapour phase in equilibriumwith the hydrate phase
Temp.
"F
26.33
26.33
26.33
8.33
8.33
8.33
-9.67
-9.67
-9.67
-27.67
-27.67
-27.67
Pressure
psi
500.
1000.
1500.
500.
1000.
1500.
500.
1000.
1500.
500.
1000.
1500.
Kobayashi
and co-workers
(Aoyagi et al. 1979)
Exp. data
P P (mole)
~
178.09
94.43
64.22
78.24
39.56
24.23
32.17
15.45
8.46
12.30
5.60
2.72
P P ~
P P ~
176.89
95.28
65.48
79.23
38.51
23.95
33.67
14.83
8.40
13.45
5.42
2.82
144.99
77.11
57.44
57.09
3 1.09
23.80
20.88
11.71
9.29
7.04
4.10
3.41
150.38
82.42
63.28
60.54
34.01
26.87
22.68
13.14
10.77
7.84
4.72
4.06
System: Methane-water
Phase identification: Hydrate phase (methane hydrate) and vapour phase (methane and water)
[Ed. note: Data have not been converted to SI units]
Conclusions
Two-phase, hydrate equilibria data are necessary
for the processing and transportation of natural gas.
However, there is a paucity of data available. Such
data are vital to enable the verification of several prediction and correlation schemes.
References
AOYAGI,
K. AND KOBAYASHI,
R. 1978. Report of water content
measurement of high carbon dioxide content simulated Prudoe
Bay gas in equilibrium with hydrates. Proc. 57th Ann. Conv.
Gas Process. Assoc., New Orleans, LA., p. 3.
AOYAGI,
K., SONG,K.Y., SLOAN,E.D., DHARMAWARDHANA,
P.B.,
AND KOBAYASHI,
R. 1979. Improved measurements and correlation of the water content of methane gas in equilibrium with
hydrate. Proc. 58th Ann. Conv. Gas Process. Assoc., Denver,
CO., p. 25.
DAVIDSON.
D.W. 1973. Clathrate hydrates. In: Water: A ComprehensiveTreatise. F. Franks, ed., vol. 2, pp. 115-234.
DHARMAWARDHANA,
P.B. 1980. The measurement of the thermodynamic parameters of the hydrate structure and the application
of them in the prediction of the properties of natural gas hydrates. Ph.D. Thesis, Colorado School of Mines, Golden, CO.
ERTL,H., KHOURY,
F., SLOAN,D., A N D KOBAYASHI,
R. 1976.
Improved chromatographic method for absolute moisture determination in gases at very low concentrations. Chern. Ing. Tech.,
vol. 48, p. 811.
FIGURE
5. Water concentration of liquid propane in equilibrium
with hydrates.