Natural Gas Hydrates

E. Dendy Sloan Jr., SPE, Colorado School of Mines

Introduction ties results in Structure 1, with interstices librium. With further reduction of temper-
Gas clathrates (commonly called hydrates) oflarge cavities composed of 12 pentagons ature (or increase in pressure), the fluid
are crystalline compounds that occur when and 2 hexagons (5 12 6 2 ). Linking the faces phase that is not in excess (normally water)
water forms a cage-like structure around of the 5 12 cavities results in Structure 2, will be exhausted, so that to the left of the
smaller guest molecules. Gas hydrates of with interstices of large cavities composed line the hydrate will exist with the excess
interest to the natural gas hydrocarbon in- of 12 pentagons and 4 hexagons (5 12 6 4 ). phase (normally gas).
dustry are composed of water and eight· Details of structure are given in a recent Note that all the conditions given in Fig.
molecules: methane, ethane, propane, isobu- monograph. 1 2 are for temperatures above 32 OF, and that
tane, normal butane, nitrogen, carbon diox- Structure 1, a body-centered cubic struc- pressures along the lines vary exponentially
ide, and hydrogen sulfide. Hydrate forma- ture, forms with natural gases containing with temperature. This figure also illustrates
tion is possible in any place where water molecules smaller than propane; conse- the dramatic effect of gas composition on
exists with such molecules-in natural or ar- quently Structure 1 hydrates are found in situ hydrate stability; as any amount of propane
tificial environments and at temperatures in deep oceans with biogenic gases contain- is added to methane, the structure changes
above and below 32°F when the pressure ing mostly methane, carbon dioxide, and (Structure I-Structure 2) to a hydrate with
is elevated. hydrogen sulfide. Structure 2, a diamond lat- much wider stability conditions. Note the
Hydrates are considered a nuisance be- tice within a cubic framework forms when marked decrease in pressure (or increase in
cause they block transmission lines, plug natural gases or oils contain molecules larger temperature) needed to form hydrates, when
blowout preventers, jeopardize the founda- than ethane but smaller than pentane; Struc- as little as 1 % propane is in the gas.
tions of deepwater platforms and pipelines, ture 2 represents hydrates that commonly Hydrates can result from either saturated
cause tubing and casing collapse, and foul occur in production and processing condi- gas or liquid hydrocarbon, without a free-
process heat exchangers, valves, and ex- tions, as well as in the cases of gas seeps water phase; these two-phase conditions are
panders. Common examples of preventive in shallow ocean environments. The newest relatively rare and, thus, not addressed in
measures are the regulation of pipeline water hydrate, Structure H, is neglected in this this overview. Three common methods are
content, unusual drilling-mud compositions, overview; it is yet to be found outside the used to predict the three-phase conditions
and large quantities of methanol injection laboratory . like those of Fig. 2. They are, in order of
into pipelines. We encounter conditions that Inside each structure cavity resides a max- increasing accuracy, the gas-gravity chart, 2
encourage hydrate formation as we explore imum of one of the eight guest molecules. the Katz K j charts, 3 and a statistical ther-
more unusual environments for gas and oil, The cavity occupied is a function of the size modynamics method. 4 The first two calcu-
including deepwater frontiers and perma- ratio of the guest molecule within the host lation methods may be done by hand; a
frost regions. cavity. To a first approximation, the con- computer is required for the third method,
Hydrates act to concentrate hydrocarbons; cept of "a ball fitting within a ball" is the which may be used to predict most three-
1 ft3 of hydrates may contain as much as key to understanding many hydrate proper- phase conditions with acceptable accuracy.
180 scf of gas. Large natural reserves of ties. Much more certainty exists with respect
hydrocarbons exist in hydrated form, both to the molecular structure of hydrates than Applications in
in deep oceans and in the permafrost. Eval- to the kinetic mechanism of hydrate forma- the Petroleum Industry
uation of these reserves is highly uncertain, tion; hydrate kinetics are currently at the InhibitionlDissociation. The four common
yet even conservative estimates indicate that forefront of research. means of inhibiting/dissociating hydrates are
there is perhaps twice as much energy in On a macroscopic level, hydrate forma- (1) removing one ofthe components, either
hydrated form as in all other hydrocarbon tion and dissociation may be considered the hydrocarbon or water; (2) heating the
sources combined. While there is one com- using a phase diagram, such as Fig. 2. In system beyond the hydrate formation tem-
mercial example of gas recovery from hy- this figure, pressure is plotted vs. tempera- perature at a pressure; (3) decreasing the
drates, the problems of in-situ hydrate ture, with gas composition as a parameter, system pressure below hydrate stability at
dissemination in deepwater/permafrost en- for methane/propane mixtures. Consider a a temperature; and (4) injecting an inhibitor,
vironments will prevent their cost-effective gas of any composition given on a line in such as methanol or glycol, to decrease hy-
recovery until the next century. Fig. 2. At conditions to the right of the line, drate stability conditions, so that higher
a gas of that composition will exist in equi- pressures and lower temperatures will be re-
Basic Structures librium with liquid water. As the tempera- quired for hydrate stability.
Hydrates normally form in one of two small, ture is reduced (or as the pressure is These techniques are called thermody-
repeating crystal structures, shown in Fig. increased), hydrates will form from the gas namic inhibition because they remove the
1. The two hydrate structures are formed and liquid at the line, so that three phases system from thermodynamic stability by
from a basic' 'building block" water cavity (hydrates/gas/liquid water) will be in equi- changes in composition, temperature, or
that has 12 faces with 5 sides per face pressure. As long as the system is kept out-
(5 12 ). Linking the vertices of the 5 12 cavi- Copyright 1991 Society of Petroleum Engineers side thermodynamic stability conditions,

1414 December 1991 • JPT

 sPETechnology
Today SERIES

hydrates can never form. A newer method, On most platforms, two of the three pri- The first instances of drilling through hy-
called Idnetic inhibition, allows the system mary functions (compression, separation, drates in permafrost regions of the earth
to exist in the hydrate thermodynamic sta- and dehydration/inhibition) are associated were published 2 decades ago. If hydrates
bility region. Small hydrate nuclei are hin- with hydrate prevention. Floating, deep- are dissociated upon drilling, large amounts
dered from agglomerating to larger masses water tension-leg platforms (TLP's) usually of gas within the hydrate will be released and
by means of new inhibitors. Kinetic inhibi- do a minimum of processing before feeding may cause problems associated with high
tion is the focus of a substantial amount of gas to a central processing platform (CPP) pressure or melting. Techniques of cooling
current research, in both Europe and North with fixed legs in shallow water on the con- the drilling fluid have been used to prevent
America. tinental shelf. Because weight is at an ex- hydrate dissociation during drilling, and in-
treme premium on TLP's, there is an sulation has occasionally been considered to
Pipeline and Platform Applications. When incentive for partial inhibition alternatives prevent hydrate dissociation by warmer
hydrate problems occur, consequences can until the gas can reach a CPP where a more flowing fluid. Collapsed tubing 9 in the
be formidable. Depressurization of deep- thorough inhibition/dehydration can be USSR has been attributed to hydrate dis-
water pipelines to remove plugs frequently applied. sociation.
requires days of flow interruption. When A second problem associated with pipe- Because water-based drilling fluids con-
flow is halted because of a plug in a pipeline, lines concerns routing in deep water around tain so many sites for crystal nucleation, an
it is difficult to place heat at the precise plug large in-situ hydrate mounds associated with order of magnitude more hydrates can form
site. The line is usually depressurized at each gas seeps along salt diapirs. If warm fluids in drilling fluid than in an equal volume of
end of the plug. Depressurization decreases flowing through a pipeline were to degrade pure water. Laboratory experiments 10 have
the hydrate formation temperature to below underlying hydrates, a reduced shear also shown that oil-based drilling fluids con-
that of the environment, which enables the
strength would result and damage to the tain enough water to form hydrates, but un-
plug to be dissociated by ambient heat. After
pipeline foundation could occur. This was der more stringent conditions than water-
the plug is dissociated, a pig is used to clean
a recent concern for both the pipeline 5 and based fluids. Hydrate formation in water-
the line.
platform 6 foundations associated with the based fluids was first recognized II offshore
For long gas and multi phase pipelines in
Jolliet TLP in the Gulf of Mexico. California and in the Gulf of Mexico. A
cold, high-pressure conditions, insulation
Because of anticipated deepwater hydrate number of water-based mud formulations
alone will not suffice to maintain a hydrate-
problems, large-scale, multiphase flow-loop have been suggested as inhibitors. 12,13 It
free channel. Methanol is injected into the
studies have been begun to allow scaling of has been shown 14 that the aqueous concen-
gas phase, which carries it to the site of free
laboratory results to deepwater pipeline con- tration of salt/glycol/glycerol largely deter-
liquid water where methanol dissolves and
ditions. Such flow loops require temperature mines the hydrate formation conditions in
provides hydrate inhibition. Because metha-
nol is easily vaporized, but concentrates in and pressure control with a minimum of 300 the drilling fluid, regardless of the other con-
free water, it is preferred over such other ft of 3-in.-ID pipe. Investments in multi- stituents.
inhibitors as salts or glycols, which have phase hydrate flow loops typically are at
lower vapor pressures. However, much of least $1.5 million and 2 years of construc- Gas From In-Situ Hydrates. While esti-
the methanol does not dissolve in free water tion/startup time. Such flow loops are being mates of hydrates as an energy resource are
and is lost in the gas or hydrocarbon liquid constructed in Europe and independently by very uncertain, studies in both the USSR and
phase. two major U.S. oil firms. the U.S. have estimated the amount of gas in
As E&P operations move to regions of in-situ hydrates at 1 x 10 17 scf. The amount
deeper water or lower temperature, much Drilling Applications. The depth of hydrate of energy in ocean hydrates is estimated to
more methanol will be required and the is- stability in the earth can be obtained through surpass that in permafrost hydrate reservoirs
sue of economics will receive more atten- a plot of the geothermal gradient and the hy- by two orders of magnitude. Proposed meth-
tion. One company estimated the 1988 cost drate thermodynamic stability envelope. ods of gas recovery (thermal stimulation,
of methanol inhibition in a North Sea pipe- Fig. 3 shows a hydrate envelope 7 for meth- depressurization, and inhibitor injection) de-
line to approach 1 % of the gross revenue. ane above and below the permafrost and in rive from the four inhibition/dissociation
On another North Sea platform, the 1990 ocean sediments. As discussed previously, phenomena described earlier. Economics
methanol injection costs exceeded $2.5 mil- when any amount of propane is added to the has been evaluated and suggests that recov-
lion. Typical capital costs to prevent hy- gas, the stability field will be appreciably ery is hindered because the gas is in solid
drates in a processing plant are 5 % to 8 % broader. Verma et al., 8 have shown that form and the solids are dispersed in hostile
of the total plant cost. As a result of such hydrates can denude lighter hydrocarbons environments of permafrost and deep
economics, work is under way to find al- from oil, thereby explaining instances of oceans. Kvenvolden 15 recently determined
ternative and more economical means of in- highly viscous "dead oil reservoirs" near that in-situ hydrates probably do not con-
hibition. the surface in permafrost regions. tribute to the greenhouse effect through the

JPT • December 1991 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 and exclude salt ions from the water frame- of copious amounts of inhibitors, such as
dissociation. work, work has been done to investigate the methanol or salt/glycerol. However, with
There is one instance 9 of the recovery of use of hydrates as means for separations, the projections oflarge deepwater reserves,
gas from hydrates. In the Messoyakha field both for hydrocarbons 16 and desaJi'na- we will reach the point of economic invia-
in Siberia, in-situ gas hydrates acted as a cap tion. 17 Hydrates have also been used 18 as bility for such inhibitor injection. Lessons
to a gas reservoir so that as the reservoir gas a means of "thermal cold storage" because can be learned from industry in the USSR,
was depleted, the pressure decreased below they can freeze above 32 of, yet have a heat which has had a long history of combating
the hydrate dissociation pressure at the hy- of dissociation almost equal to the heat of hydrates in severe environments, albeit in
drate/gas interface. Because oflarge surface ice fusion. Hydrates are periodically sug- permafrost rather than deep waters.
exposure, the hydrates dissociated at an ef- gested as a gas storage medium in peak shav- In the future we must investigate alterna-
fective rate to replenish the gas reservoir. ing applications and in salt caverns. While tive hydrate inhibition schemes. Deepwater
In this case, hydrates acted as a separate gas all these applications are interesting, none challenges will require the construction of
reserve that could be recovered at essentially costly multiphase flow loops to anticipate
has proved commercially viable to date.
no cost to the producer. Other such reserves
and mitigate hydrate problems offshore. The
probably exist in permafrost or deep-ocean
environments.
Conclusions long-range challenge to the hydrate research
Most of the hydrocarbon industry views hy- community is to use the problem aspects of
drates as a drilling/production/processing hydrates to provide a vehicle for basic
Other Applications. Because hydrates
separate guest molecules on the basis of size science and engineering that will enable the
nuisance that can be handled through the use
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
l-
w ~\ ,.w
I-

"<: 800 I \
,, _PhOBe
Boundary
800
School of Mines in
:t:
l-
0-
w 1000
I
I
,, <:
:t:
I-
0-
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