Natural Gas Hydrates
E. Dendy Sloan Jr., SPE, Colorado School of Mines
Introduction
Gas clathrates (commonly called hydrates)
are crystalline compounds that occur when
water forms a cage-like structure around
smaller guest molecules. Gas hydrates of
interest to the natural gas hydrocarbon in-
dustry are composed of water and eight·
molecules: methane, ethane, propane, isobu-
tane, normal butane, nitrogen, carbon diox-
ide, and hydrogen sulfide. Hydrate forma-
tion is possible in any place where water
exists with such molecules-in natural or ar-
tificial environments and at temperatures
above and below 32°F when the pressure
is elevated.
Hydrates are considered a nuisance be-
cause they block transmission lines, plug
blowout preventers, jeopardize the founda-
tions of deepwater platforms and pipelines,
cause tubing and casing collapse, and foul
process heat exchangers, valves, and ex-
panders. Common examples of preventive
measures are the regulation of pipeline water
content, unusual drilling-mud compositions,
and large quantities of methanol injection
into pipelines. We encounter conditions that
encourage hydrate formation as we explore
more unusual environments for gas and oil,
including deepwater frontiers and perma-
frost regions.
Hydrates act to concentrate hydrocarbons;
1 ft3 of hydrates may contain as much as
180 scf of gas. Large natural reserves of
hydrocarbons exist in hydrated form, both
in deep oceans and in the permafrost. Eval-
uation of these reserves is highly uncertain,
yet even conservative estimates indicate that
there is perhaps twice as much energy in
hydrated form as in all other hydrocarbon
sources combined. While there is one com-
mercial example of gas recovery from hy-
drates, the problems of in-situ hydrate
dissemination in deepwater/permafrost en-
vironments will prevent their cost-effective
recovery until the next century.
Basic Structures
Hydrates normally form in one of two small,
repeating crystal structures, shown in Fig.
1. The two hydrate structures are formed
from a basic' 'building block" water cavity
that has 12 faces with 5 sides per face
(5 12 ). Linking the vertices of the 5 12 cavi-
1414
ties results in Structure 1, with interstices
oflarge cavities composed of 12 pentagons
and 2 hexagons (5 12 6 2 ). Linking the faces
of the 5 12 cavities results in Structure 2,
with interstices of large cavities composed
of 12 pentagons and 4 hexagons (5 12 6 4 ).
Details of structure are given in a recent
monograph. 1
Structure 1, a body-centered cubic struc-
ture, forms with natural gases containing
molecules smaller than propane; conse-
quently Structure 1 hydrates are found in situ
in deep oceans with biogenic gases contain-
ing mostly methane, carbon dioxide, and
hydrogen sulfide. Structure 2, a diamond lat-
tice within a cubic framework forms when
natural gases or oils contain molecules larger
than ethane but smaller than pentane; Struc-
ture 2 represents hydrates that commonly
occur in production and processing condi-
tions, as well as in the cases of gas seeps
in shallow ocean environments. The newest
hydrate, Structure H, is neglected in this
overview; it is yet to be found outside the
laboratory .
Inside each structure cavity resides a max-
imum of one of the eight guest molecules.
The cavity occupied is a function of the size
ratio of the guest molecule within the host
cavity. To a first approximation, the con-
cept of "a ball fitting within a ball" is the
key to understanding many hydrate proper-
ties. Much more certainty exists with respect
to the molecular structure of hydrates than
to the kinetic mechanism of hydrate forma-
tion; hydrate kinetics are currently at the
forefront of research.
On a macroscopic level, hydrate forma-
tion and dissociation may be considered
using a phase diagram, such as Fig. 2. In
this figure, pressure is plotted vs. tempera-
ture, with gas composition as a parameter,
for methane/propane mixtures. Consider a
gas of any composition given on a line in
Fig. 2. At conditions to the right of the line,
a gas of that composition will exist in equi-
librium with liquid water. As the tempera-
ture is reduced (or as the pressure is
increased), hydrates will form from the gas
and liquid at the line, so that three phases
(hydrates/gas/liquid water) will be in equi-
Copyright 1991 Society of Petroleum Engineers
librium. With further reduction of temper-
ature (or increase in pressure), the fluid
phase that is not in excess (normally water)
will be exhausted, so that to the left of the
line the hydrate will exist with the excess
phase (normally gas).
Note that all the conditions given in Fig.
2 are for temperatures above 32 OF, and that
pressures along the lines vary exponentially
with temperature. This figure also illustrates
the dramatic effect of gas composition on
hydrate stability; as any amount of propane
is added to methane, the structure changes
(Structure I-Structure 2) to a hydrate with
much wider stability conditions. Note the
marked decrease in pressure (or increase in
temperature) needed to form hydrates, when
as little as 1 % propane is in the gas.
Hydrates can result from either saturated
gas or liquid hydrocarbon, without a free-
water phase; these two-phase conditions are
relatively rare and, thus, not addressed in
this overview. Three common methods are
used to predict the three-phase conditions
like those of Fig. 2. They are, in order of
increasing accuracy, the gas-gravity chart, 2
the Katz K j charts, 3 and a statistical ther-
modynamics method. 4 The first two calcu-
lation methods may be done by hand; a
computer is required for the third method,
which may be used to predict most three-
phase conditions with acceptable accuracy.
Applications in
the Petroleum Industry
InhibitionlDissociation. The four common
means of inhibiting/dissociating hydrates are
(1) removing one ofthe components, either
the hydrocarbon or water; (2) heating the
system beyond the hydrate formation tem-
perature at a pressure; (3) decreasing the
system pressure below hydrate stability at
a temperature; and (4) injecting an inhibitor,
such as methanol or glycol, to decrease hy-
drate stability conditions, so that higher
pressures and lower temperatures will be re-
quired for hydrate stability.
These techniques are called thermody-
namic inhibition because they remove the
system from thermodynamic stability by
changes in composition, temperature, or
pressure. As long as the system is kept out-
side thermodynamic stability conditions,
December 1991 • JPT

hydrates can never form. A newer method,
called Idnetic inhibition, allows the system
to exist in the hydrate thermodynamic sta-
bility region. Small hydrate nuclei are hin-
dered from agglomerating to larger masses
by means of new inhibitors. Kinetic inhibi-
tion is the focus of a substantial amount of
current research, in both Europe and North
America.
Pipeline and Platform Applications. When
hydrate problems occur, consequences can
be formidable. Depressurization of deep-
water pipelines to remove plugs frequently
requires days of flow interruption. When
flow is halted because of a plug in a pipeline,
it is difficult to place heat at the precise plug
site. The line is usually depressurized at each
end of the plug. Depressurization decreases
the hydrate formation temperature to below
that of the environment, which enables the
plug to be dissociated by ambient heat. After
the plug is dissociated, a pig is used to clean
the line.
For long gas and multi phase pipelines in
cold, high-pressure conditions, insulation
alone will not suffice to maintain a hydrate-
free channel. Methanol is injected into the
gas phase, which carries it to the site of free
liquid water where methanol dissolves and
provides hydrate inhibition. Because metha-
nol is easily vaporized, but concentrates in
free water, it is preferred over such other
inhibitors as salts or glycols, which have
lower vapor pressures. However, much of
the methanol does not dissolve in free water
and is lost in the gas or hydrocarbon liquid
phase.
As E&P operations move to regions of
deeper water or lower temperature, much
more methanol will be required and the is-
sue of economics will receive more atten-
tion. One company estimated the 1988 cost
of methanol inhibition in a North Sea pipe-
line to approach 1 % of the gross revenue.
On another North Sea platform, the 1990
methanol injection costs exceeded $2.5 mil-
lion. Typical capital costs to prevent hy-
drates in a processing plant are 5 % to 8 %
of the total plant cost. As a result of such
economics, work is under way to find al-
ternative and more economical means of in-
hibition.
JPT • December 1991
On most platforms, two of the three pri-
mary functions (compression, separation,
and dehydration/inhibition) are associated
with hydrate prevention. Floating, deep-
water tension-leg platforms (TLP's) usually
do a minimum of processing before feeding
gas to a central processing platform (CPP)
with fixed legs in shallow water on the con-
tinental shelf. Because weight is at an ex-
treme premium on TLP's, there is an
incentive for partial inhibition alternatives
until the gas can reach a CPP where a more
thorough inhibition/dehydration can be
applied.
A second problem associated with pipe-
lines concerns routing in deep water around
large in-situ hydrate mounds associated with
gas seeps along salt diapirs. If warm fluids
flowing through a pipeline were to degrade
underlying hydrates, a reduced shear
strength would result and damage to the
pipeline foundation could occur. This was
a recent concern for both the pipeline 5 and
platform 6 foundations associated with the
Jolliet TLP in the Gulf of Mexico.
Because of anticipated deepwater hydrate
problems, large-scale, multiphase flow-loop
studies have been begun to allow scaling of
laboratory results to deepwater pipeline con-
ditions. Such flow loops require temperature
and pressure control with a minimum of 300
ft of 3-in.-ID pipe. Investments in multi-
phase hydrate flow loops typically are at
least $1.5 million and 2 years of construc-
tion/startup time. Such flow loops are being
constructed in Europe and independently by
two major U.S. oil firms.
Drilling Applications. The depth of hydrate
stability in the earth can be obtained through
a plot of the geothermal gradient and the hy-
drate thermodynamic stability envelope.
Fig. 3 shows a hydrate envelope 7 for meth-
ane above and below the permafrost and in
ocean sediments. As discussed previously,
when any amount of propane is added to the
gas, the stability field will be appreciably
broader. Verma et al., 8 have shown that
hydrates can denude lighter hydrocarbons
from oil, thereby explaining instances of
highly viscous "dead oil reservoirs" near
the surface in permafrost regions.
sPETechnology
Today SERIES
The first instances of drilling through hy-
drates in permafrost regions of the earth
were published 2 decades ago. If hydrates
are dissociated upon drilling, large amounts
of gas within the hydrate will be released and
may cause problems associated with high
pressure or melting. Techniques of cooling
the drilling fluid have been used to prevent
hydrate dissociation during drilling, and in-
sulation has occasionally been considered to
prevent hydrate dissociation by warmer
flowing fluid. Collapsed tubing 9 in the
USSR has been attributed to hydrate dis-
sociation.
Because water-based drilling fluids con-
tain so many sites for crystal nucleation, an
order of magnitude more hydrates can form
in drilling fluid than in an equal volume of
pure water. Laboratory experiments 10 have
also shown that oil-based drilling fluids con-
tain enough water to form hydrates, but un-
der more stringent conditions than water-
based fluids. Hydrate formation in water-
based fluids was first recognized II offshore
California and in the Gulf of Mexico. A
number of water-based mud formulations
have been suggested as inhibitors. 12,13 It
has been shown 14 that the aqueous concen-
tration of salt/glycol/glycerol largely deter-
mines the hydrate formation conditions in
the drilling fluid, regardless of the other con-
stituents.
Gas From In-Situ Hydrates. While esti-
mates of hydrates as an energy resource are
very uncertain, studies in both the USSR and
the U.S. have estimated the amount of gas in
in-situ hydrates at 1 x 10 17 scf. The amount
of energy in ocean hydrates is estimated to
surpass that in permafrost hydrate reservoirs
by two orders of magnitude. Proposed meth-
ods of gas recovery (thermal stimulation,
depressurization, and inhibitor injection) de-
rive from the four inhibition/dissociation
phenomena described earlier. Economics
has been evaluated and suggests that recov-
ery is hindered because the gas is in solid
form and the solids are dispersed in hostile
environments of permafrost and deep
oceans. Kvenvolden 15 recently determined
that in-situ hydrates probably do not con-
tribute to the greenhouse effect through the
1415
"We encounter
conditions that
encourage hydrate
formation as we
explore more unusual
environments for gas
and oil, including
deepwater frontiers
and permafrost
regions." a b

Fig. i-Two hydrate unit structures: (a) Structure 1 with 12 Ato a side and (b) Struc-
ture 2 with 17.3 A to a side.

release of substantial methane on hydrate
dissociation.
There is one instance 9 of the recovery of
gas from hydrates. In the Messoyakha field
in Siberia, in-situ gas hydrates acted as a cap
to a gas reservoir so that as the reservoir gas
was depleted, the pressure decreased below
the hydrate dissociation pressure at the hy-
drate/gas interface. Because oflarge surface
exposure, the hydrates dissociated at an ef-
fective rate to replenish the gas reservoir.
In this case, hydrates acted as a separate gas
reserve that could be recovered at essentially
no cost to the producer. Other such reserves
probably exist in permafrost or deep-ocean
environments.
Other Applications. Because hydrates
separate guest molecules on the basis of size
and exclude salt ions from the water frame-
work, work has been done to investigate the
use of hydrates as means for separations,
both for hydrocarbons 16 and desaJi'na-
tion. 17 Hydrates have also been used 18 as
a means of "thermal cold storage" because
they can freeze above 32 of, yet have a heat
of dissociation almost equal to the heat of
ice fusion. Hydrates are periodically sug-
gested as a gas storage medium in peak shav-
ing applications and in salt caverns. While
all these applications are interesting, none
has proved commercially viable to date.
Conclusions
Most of the hydrocarbon industry views hy-
drates as a drilling/production/processing
nuisance that can be handled through the use
of copious amounts of inhibitors, such as
methanol or salt/glycerol. However, with
the projections oflarge deepwater reserves,
we will reach the point of economic invia-
bility for such inhibitor injection. Lessons
can be learned from industry in the USSR,
which has had a long history of combating
hydrates in severe environments, albeit in
permafrost rather than deep waters.
In the future we must investigate alterna-
tive hydrate inhibition schemes. Deepwater
challenges will require the construction of
costly multiphase flow loops to anticipate
and mitigate hydrate problems offshore. The
long-range challenge to the hydrate research
community is to use the problem aspects of
hydrates to provide a vehicle for basic
science and engineering that will enable the
future recovery of this energy resource.

.~ ....................................................................................................- - , Acknowledgments
A portion of the time for writing this review
was sponsored by the Gas Research Inst. and
mol II Propane in the Gas Processors Assn. under joint grant
10 • of Methane+Propane
• No. 5091-260-2124.

• References
1. Sloan, E.D. Jr.: Clathrate Hydrates of Na-
tural Gases, Marcel Dekker Inc., New York
City (1990).
2. Katz, D.K.: "Prediction of Conditions for
Hydrate Formation in Natural Gas," Trans.,
Q) • AIME (1945) 160, 140-49.
~ 3. Katz, D.L. and Carson, D.B.: "Natural Gas
Hydrates," Trans., AIME (1942) 146,
~ ISO-58.
0010 • 4. Parrish, W.R. and Prausnitz, J.M.: "Dissoci-
00 • ation Pressures of Gas Hydrates by Gas Mix-
Q) ture," Ind. Eng. Chern. Proc. Des. & Dev.
~ • (1972) 11, 26.
~ 5. Franco, A.: "Jolliet's TLWP Brings Inno-
4 vation to the Gulf," Drilling Contractor
(June-July 1989) 9.
6. Campbell, K.J. et al.: "Geohazards Survey-
ing and Complex Seafloor Conditions Along
• 00000Data of Deaton + Frost (1946)
Deepwater Jolliet Pipeline Routes," paper
OTC 6370 presented at the 1990 Offshore
_ _ Calculated from CSUHYD Technology Conference, Houston, May
7-10.
10· ~. .rrrrTTTTTT~,,~~~. .rrrrrrTTTTTT~~ 7. Kvenvolden, K.A.: "Methane Hydrate-A
270 275 280 285 290 Major Reservoir of Carbon in the Shallow
Geosphere," Chemical Geology (1988) 71,
Temperature, K 41.
8. Verma, V.K. et al.: "Denuding Hydrocarbon
Liquids of Natural Gas Constituents by Hy-
Fig. 2-A phase diagram for hydrates from methane and propane. drate Formations," JPT (Feb. 1975) 223-26.

1416 December 1991 • JPT

 0 , 0
i Author
A \ B
\
200
Geothermal
Gradient
-J.:
\
SEOIMENT 200
,
'...- Hydrothermal
I Gradient E;~. Sloan
dr. IS II professor in
400
in Permafrost \ 1 400
WATER the Chemical Engl-
\1 heering & Petrole-
'"a:w Deeth of PermOfrost\J um .Refining Dept.
600 '"a:w 600
at the Colorado
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I-

"<: 800 I \
,, _PhOBe
Boundary
800
School of Mines in
:t:
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0-
w 1000
I
I
,, <:
:t:
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Golden, where he
has taught since
0 80se of I OJ
0
1000 1975. Sloan has
Gos Hydrate I \ written more than
Water
1200 I \\ 1200 40 publicaHons on hydrates. and heads
I G'\~
"Q,.... a. group of 20 researchers In the area.
1400
I ~~~~/ 1400 His book Clathrate Hydtates 01 Natural
I \
~ and accompanying software were
1600
253 263
I
273 283 293
\

303
1600
253 263 273 283 293 303
published In 1990. He holds BS, MS,
PhD degrees from Clemson U., all in
.nd
a TEMPERATURE K
b TEMPERATURE K chemical engineering.

Fig. 3-Hydrate stability depths in (a) permafrost and (b) ocean environments.

9. Makogon, Y.F.: "Natural Gas Hydrates: The SPEDE(June 1990) 109-15; Trans., AIME, SI Metric Conversion Factors
State of Study in the USSR and Perspectives 289. A x l.0" E-OJ = run
for Its Use," 1988 Third Chemical Congress 14. Kotkoskie, T. et al.: "Inhibition of Gas Hy- ft x 3.048" E-OJ =m
of North America, Toronto, June 5-10. drates in Water-Based Drilling Muds, " paper ft3 X 2.83J 685 E-02 = m3
10. Grigg, R.B. and Lynes, G.L.: "Oil-Based SPE 20437 presented at the 1990 SPE An- 'F ('F-32)/1.8 °C
nual Technical Conference and Exhibition, OF (OF+459.67)/1.8 K
Drilling Mud as a Gas Hydrate Inhibitor,"
New Orleans, Sept. 23-26. in. x 2.54" E+OO em
paper SPE 19560 presented at the 1989 SPE psi x 6.894757
15. Kvenvolden, K.A.: "Methane Hydrates and E+OO kPa
Annual Technical Conference and Exhibition,
San Antonio, Oct. 8-11. Global Climate, " Global Biochemical Cycles 'Conversion factor is exact.
(1988) 2, No.3, 221.
II. Barker, J.W. and Gomez, R.K.: "Formation
16. Glew, D.N.: "Liquid Fractionation Process
of Hydrates During Deepwater Drilling Op-
Using Gas Hydrates," U.S. Patent No. Provenance
erations," JPT (March 1989) 297-301. 3,231,630 (1966) 193,355, 1437.
12. Lai, D. and Dzialowski, A.K.: "Investiga- 17. Barduhn, A.J.: "'Desalination by Crystalline This paper is SPE 23562. Technology Today Series arti-
tion of Natural Gas Hydrates in Various Drill- cles provide useful summary information on both classic and
Process," Chemical Engineering Progress emerging concepts in petroleum engineering. Purpose: To
ing Fluids," paper SPE 18637 presented at (1967) 63, No. I, 98. provide the general reader with a basic understanding of
the 1989 SPE/IADC Drilling Conference, 18. Mori, T. and Mori, Y.H.: "Characterization a significant concept, technique, or development within a
specific area of technology.
New Orleans, Feb. 28-March 3. of Gas Hydrate Formation in Direct Contact
13. Hale, A.H. and Dewan, A.K.R.: "Inhibition Cool Storage Process," Inti. J. Refrig. (1989)
of Gas Hydrates in Deepwater Drilling," 12, No.5, 259. JPT

JPT • December 1991 1417