PETROLEUM SOCIETY OF CIM PAPER NO.

99-94

THIS IS A PREPRINT - SUBJECT TO CORRECTION

PRODUCTION AND TRANSPORTATION

OF NATURAL GAS HYDRATE

R. Amin
M. Pogson
Chin University of Technology
A. Jackson
Woodside Energy

PUBLICATION RIGHTS RESERVED

THIS PAPER IS TO BE PRESENTED AT THE EIGHTH PETROLEUM CONFERENCE OF THE SOUTH SASKATCHEWAN SECTION, THE
PETROLEUM SOCIETY OF CIM. HELD IN REGINA OCTOBER 18-21. 1999. DISCUSSION OF THIS PAPER IS INVITED. SUCH
DISCUSSION MAY BE PRESENTEDATTHE TECHNICAL MEETING AND-WILL BE CONSIDERED FOR PUBLICATION IN CIM JOURNALS
IF FILED IN WRITING WlTH THE TECHNICAL PROGRAM CHAIRMAN PRIOR TO THE CONCLUSION OF THE MEETING.

Abstract sm3/sm3 compared with 150-180 sm3/sm3 for pure water

The storage of natural gas in hydrates has been
investigated since it was discovered that they store large
quantities of gas. Dtflerent storage methods have been
suggested: either keeping hydrate under low temperature
or under pressure.
This work presents the results of experiments aimed at
improving the quality of the produced hydrate in term of
gas content per unit volume of water. We have tested and
developed a new water-soluble chemical that promotes
methane hydrate formation by reducing the interfacial
tension properties of the water. A series of investigations
identijied that, depending on the concentration, the effect
of hydrate inhibiting agents such as sodium chloride,
alcohols and Carbonyl Compounds on gas hydrate
formation, can either promote or suppress formation of gas
hydrates in systems of water and natural gas.
It was also proven that growth rates of a crystal face
depend on how fast the heat is removed from the surface
and this depends on the rate of heat transfer at the
interface.
The quality and quantity of hydrates were examined for
their gas contents in a low temperature PVT apparatus.
The total water conversion to hydrate in case of sH and sII
hydrates was improved using hydrate promoters
discovered during this work The rate of gas content per
volume of hydrate was significantly improvedfiom to 196
hydrate.
Introduction
The manufacture of natural gas hydrates (NGH), a stable
solid comprising natural gas and water, is proposed as an
alternative storage and transportation technology for
natural gas instead of LNG and pipeline transportation. It
is also valid to view this technology as a potential
competitor to other energy forms such as LPG, fuel oil and
coal. The manufacture of NGH requires only moderate
cooling (typically -15 “C) and provides a stable solid when
stored in an insulated environment. NHG’s are readily
decomposed into their hydrocarbon constituents and water
at the point of delivery.
Commercialisation of this technology in Western Australia
could be undertaken via two principal routes. The first is to
directly compete in the small to medium-scale domestic
energy market. This market is currently serviced by road
and rail transported LPG, fuel oil and increasingly LNG.
This market may provide a low cost opportunity to test and
commercialise the various NGH technologies. The
economics screening study for a road based domestic
energy market indicates that the cost of energy from NGH
may compete with LPG and diesel delivering energy for a
base case scenario at approximately A$6/GJ.
The second route would be via large scale NGH
production, competing directly in the global LNG market.
This will be reviewed at a later date; some studies
supporting this commercialisation route have already been
carried out in Scandinavia but are not reviewed in this
paper.
Experimental Procedures
The experimental apparatus consists of two equilibrium
cells, the main cell is a synthetic sapphire providing 3-
dimensional visibility, and it has a total volume of 700 ml
and is designed to handle pressures up 1500 bar. The
bottom of this cell is equipped with an optical fibre link
that provides for automatic detection of phase transition
and also for determination of the volume of the deposition
by measurement of the location of the interface formed
between the phases.
The secondary cell is made from stainless steel and has a
total volume of two litres. This cell is linked directly the
main cell and is used for sample storage and gas
circulation.
Procedures
After the sapphire cell had been evacuated, it was
pressurised with a fixed volume of methane gas below the
equilibrium of sl hydrate. The temperature of the system
was then reduced at a controlled rate of 0.1 °e I minute
using the thermostat air bath. The heat transfer rate was
improved by continuously circulating the gas in between
the two cells; this was achieved by synchronizing the
movements between the main and secondary cell.
The hydrate formation temperature was established when
crystals of hydrates started to form on the sapphire window
and gas hydrate formation was assumed to be complete
when there was no further pressure drop observed in the
cell and no further crystal formation. The hydrate appeared
on the sight glass of test cell in less than two minutes. The
pressure and temperature of two cells were monitored for
hydrate formation.
The methane gas storage experiments with and without
hydrate promoters were also conducted in the same cell.
Two different experimental procedures were used to study
the hydrate formation: first by reducing the temperature at
constant pressure, and second by maintaining a constant
temperature and varying the pressure.
Gas-Water Interfacial Tension
Methane gas-formation, water interfacial tension at
atmospheric temperature and pressure is approximately 70
dynes/cm. Gas-water interfacial tension varies with the
amount of surface-active agents in the water, the amount of
heavy hydrocarbons in solution in the gas, the temperature,
and the pressure. Gas-water interfacial tension decreases 5
to 10 dynes/cm/l,OOO-psi pressure increase, depending on
the temperature (Hocutt, 1938; Hough et aI, 1951). Gas-
water interfacial tension decreases with increasing
temperature from 0.1 to 1.0 dynes/crn/°F, depending on the
pressure (Hough et ai, 1951). Excessive amounts of ethane,
propane, and other heavy gases in the gas phase will
decrease interfacial tension from that of the pure methane-
water systems.
Interfacial Tension Effect on Hydrate Formation,
Experimental Procedures
The interfacial tension of the water was decreased by the
addition of isopropyl alcohol to the water phase. The 1FT
value of the methane-water system was reduced to
approximately 35 dynes/cm after adding only 0.1 volume
% of the alcohol to the water.
The cell was pressurised with methane gas above the
hydrate equilibrium pressure for a normal water methane
system, bubbling the methane through the water phase to
achieve rapid equilibrium did this. The system was
stabilised at a pressure of 206 bars (3000psia) and a room
temperature of23 °e.
The temperature of the system was then reduced down to
17.73°e at a rate of 0.1 °e I minute using the thermostat
air bath, Hydrate crystals began to appear on the sapphire
window at this point. Gas hydrate formation was assumed
to be complete when there was no further pressure drop
observed in the cell.
The procedure was repeated at three pressures, firstly at
138 bars (2000 psia) where hydrate appeared at 15.5°e. At
a pressure of 102 bars (1500 psia) the hydrate formed at
13.1°e and fmally at 54.5 bars (800 psia) the hydrate
crystals formed at 8.1 °e. The pressure temperature relation
from the above experiment is plotted in Figure 1.0.
Hydrate Re-gasification Temperature and Quality
The temperature of the system was reduced to -15 °e at
the same rate as before and the pressure of the system
reduced to zero.
The hydrate produced appeared to remain stable for more
than 12 hours at -15°e and showed no change in it is
appearance or pressure.
After this period of stability, the temperature of the system
was increased at the rate of 0.2 °e/minute to reverse the
hydrate formation process. The pressure of the system was
monitored and recorded carefully via high precision,
digital pressure gauges. The pressure of the system
remained stable until the temperature reached -11.5 °e
when some increase in the pressure was observed. The
pressure was stabilised at 206.3 bars at the initial room
temperature 23°e.
The Effect of Water Salinity on Hydrate Formation
The above experiment was repeated using 0.11% Wt of
salt dissolved in the water, it was carried out at exactly the
same temperature and pressure conditions as above. The