EUROPEAn
SPE 8137
PREDICTION AND CONTROL
OF NATURAL GAS HYDRATES
by Wilfred R. McLeod,
Marathon Oil Company
© Copyright 1978, European Offshore Petroleum Conference and Exhibition on behalf of the Society of Petroleum Engineers (U.K.) Limited
This paper was presented at the European Offshore Petroleum Conference and Exhibition in London 24-27, October, 1978. The material is subject to correction by the author. Permission to
copy is restricted to an abstract of not more than 300 words.
ABSTRACT
This paper discusses the more significant
advances in hydrate control technology in the past
twenty years. It al so presents a compari son of
four of the more widely used methods for predicting
the water content of natural gas hydrates and
comments on their limitations.
Some deve 1opment is reported on the problem
of controlling and preventing hydrate formation in
offshore wells and onshore Arctic completions.
Control techniques commonly used in these areas
comprise variations on long-established practices
such as application of heat, lowering system pres-
sure, at least a partial dehydration of gas and/or
liquid phases, addition of inhibitors, and purpose-
ful formation of gas hydrates followed by thei r
entrapment, decomposition and discharge of the
water phase (known to wany as the LTX system).
HISTORICAL BACKGROUND:
Although Sir Humphrey Davy first reported on
hydrates of organi c compounds in 1810, 1it was not
until 1934 that Elmer G. Hammerschmi dt described
natural gas hydrates and their formation in natural
gas transmission systems. A growing awareness of
this problem led to extensive research or. several
facets of gas hydrate formation by W. M. Deaton and
E. M. Frost, Jr. of the USBM prior to World War II.
These studies, though nearly complete, were inter-
rupted by wartime activi ties and the results wer
not published until 1946 as USBM MONOGRAPH 8. Z
These and other investigations established
the nature of hydrate formation in multicomponent
mixtures of hydrocarbons and water and the effect
of other gases such as H , CO ,N and H S on
hydrate formation by hydrO~arbo~ ga;ks. M;r,:hods
were developed to cal cul ate the equi 1i bri um con-
ditions of hydrate formation, or in essence to
predict the conditions under which hydrate forma-
tion is likely to occur in any of several pure and
mul ticomponent hydrocarbon gas systems.
References and illustrations at end of paper.
OFFSHORE
PETROLEum
conFEREnCE
I EXHIBITion
formi ng conditi ons for a number of bi nary systems
containing water and hydrocarbons or CO?_ and H2S
are shown by the equilibrium curves of1-igure T.
Generally, each component has a criti cal tempera-
ture above which no hydrate of this compound is
formed. This temperature corresponds to the point
of intersection of the equilibrium hydrate-forma-
ti on curve of the hydrate formi ng compound. The
figure shows :, S with the highest critical tem-
perature. jlll:;r~fore, natural gas systems contain-
i ng H2S fonn lIyurates more readi ly than do gases
of the- same den s ity wi thou t H S.
2
By 191::1::, present-day technology had been de-
veloped and was in use by the petroleum industry.
Several tenets were well-established, such as:
A. Essential Conditions for Gas Hydrate Formation
1. Favorable conditions of pressure and
temperature of the gas.
2. Presence of a liquid water phase.
3. Thorough agitation between the phases.
B. Methods for Preventing Gas Hydrate Formation
1. Heating gas above hydrate formation
temperature.
2. Loweri ng gas pressure on the system.
3. Dehydrate the gas to a level where
no condensation occurs.
4. Use of inhibitors to depress hydrate
formation temperature.
5. Use of the low-temperature separati on
process (LTX) which purposely forms hy-
drates by Joule-Thomson (J-Tl expansion,
separates them from the cold gas, moves
them to a wann zone, and there hydrates are
decomposed into hydrocarbons and water.
The latter is discharged from the system.
C. Inhibitor Choices
1. Methanol
2. Ethylene Glycol
3. Diethylene Glycol
4. Others, including triethylene glycol,
Hydrate amonia, calCium, chloride brine, oil field
brines, heavier alcohols, and aqueous sugar
solutions.
449
WATER CONTENT PREDICTION TECHNIQUES
Many investigators have developed procedures
for predicting the water content of natural gases.
These have ranged in complexity from plots of wa~er
content versus saturation temperature as a functlon
of pressures to a more recent approach whi ch
utilizes the total gas composition, the Eykman
Molecular Refraction (EMRl, and basic fugacity con-
cepts. Needless to say, there have been claims and
counter c 1ai ms concerni ng the accuracy of each of
these methods in dealing with complex hydrocarbon
gases containing CO and H S. It is for this
reason the author co~ares fofir of ~e more widely
acce~ted methods: ~cCarthy et al., McKetta a?d
We he • Hammerschmi dt , and Sharma and Campbell 6 ' •
Nomogram solutions were used for the first two
methods while computer solutions were employed for
the others.
It must be noted that the groups of the gas
components as shown in Figures 2 through 7 and
Table I of the ~ppendix di~fer some1r~ from t~o~e
previously publlshed by thlS author'. Speclfl-
cally, gases formerly assigned to Group 1 have been
split into Groups la and lb primarily to reflect
more reliable refractive indices of gas components.
Plots of T Iff versus EMR for Groups la, lb,
and 2 whichc wer~ originally included in a single
correlation curve, have been separated into three
curves for greater accuracy. Finally, the method
has been extended to cover most of the components
normally found in refinery gas streams.
Experimental data on the water content of one
hundred twenty (120 1 di fferent mi xture - tempera-
ture - pressure combinations were used in the
preparation of this paper. The mixtures and the
resul ts of the compari sons at pressures of 1000
psig and above are shown in Tables II and III.
For all 120 data cases, the Sharma method best
approximates the experimental values, followed by
the McKetta, McCarthy, and finally Hammerschmidt,
as shown in Table IV. For pressures less than 1000
psi g, the di fferences between the vari ous methods
diminish to less than two percent. Thus, for lower
pressures all methods approximate the experimental
values fairly well. However, at pressures in
excess of 1000 psig, the discrepancy between the
most accurate and least accurate methods again
widened appreciably. Similar results were observed
for the 36 CO 2 mi xture - pressure - temperature
combinations. In cases involving H S, the Sharma
method di sp 1 ayed a trend towa rds gr~ater accuracy
as the H?S concentrati on and pressure increased,
a lthough '""the McKetta method gave sl i ghtly better
results overall. Clearly, Sharma's method showed
the greatest versatility of the methods compared.
It is doubtful that anyone method will ever
be capable of predicting accurately the water
content of all types of compl ex gas mi xtures,
particularly those containing H~S, CO , H2 and
2
other non-bycarbons, over an unllmited range of
temperatures and pressures. Certainly, more exper-
imental data is needed to better establish the
limitations of each of the methods discussed above.
Control of gas hydrates in gas-condensate
450
production systems located in hostile environments
poses new and seri ous chall enges. No longer
does the old adage, "Move closer to the wellhead,"
apply when that haven is submerged ina thousand
feet of cold water or located in the high Arctic
regions and hydrates are to be. found in the flow
string beneath the wellhead.
Injection of methanol is thought to be the
most uni versally used tool of preventi ng gas
hydrate formation, whether it be temporary to
decompose blockages as they form, or for continuous
use. Methanol is lost with liquids removed from
the system and the vapors rema i ni ng with the gas
phase are absorbed in any glycol absorption or
glycol injection process, or in any amine treating
process used to condition the gas en route to
market.
There appear to be no lower operating temper-
ature - or pressure - limits for methanol when
used to inhibit gas hydrates. Methanol has been
injected into flow systems at pressures at least as
high as 4000 pSig to inhibit hydrate formation when
the gas is expanded to lower pressures. It has
been used at temperatures as low as minus 150°F in
hydrocarbon 1 iqui d recovery processes and at
temperatures lower than mi nus 300°F in the Lurgi
RECTI SOL process for removal of CO and water
vapor by physical absorption. 2
Economic use of methanol in cold water, subsea
production systems is dependent upon early separ-
ation and discharge of free water from the well
effluent. This conjures up visions of complicating
features such as bottom-hole water separators, a
water decanter addi ti on to a sub-sea modul e,
separate water flow lines to a central station or
platform, etc. The alternative is to continue to
endure methanol losses in the water phase.
Use of glycol inhibitors was conceived in 1943
as a production process for high-pressure gas-con-
densate fields as an improvement over the use of
calCium chloride brine to prevent gas hydrate
formation in some East Texas gas cycling plants.
As processing technology developed, system temper-
atures dropped to the range of minus 20° to minus
50°F in col d oi 1 absorpti on pl ants where the
glycol injection process has found its prinCipal
use. Under these conditions, ethylene glycol has
been used because of vastly improved fluid pro-
perties and because vapor losses are insignificant
even though the other glycols have lower vapor
pressures.
Unlike methanol, which is dispersed into the
vapor phase of a gas flow system to condense and
form an equi 1 i bri um system wi th water wherever it
is found in a sag, essentially all glycol remains
in the liquid phase when injected into a pipeline.
To be truly effecive, it must travel far enough
from the injection point to establish a thin glycol
film which uniformly coats the entire inner surface
of the fl ow condu i t whether that be pi pe, or the
channel cover and tube bundle of a heat exchanger
or chi 11 er. Any bare, uncoated surface wi 11
collect gas hydrate crystals when they condense
from the vapor phase, and enough crystals form
quickly to shut off flow. To cope with the vexing
problem of coating the conduit surfaces where pipe
lengths are short, as in most plants and platforms,
 some exotic spray heads are installed which atomize
the glycol and spray it unifor;nly on peri pheral
surfaces. Success in this area requires little
engineering and much witchcraft. A corollary to
this problem is that of removing the glycol film
frofTl the sy stem once its mi 5S i on has been accom-
pl ished so that the glycol can De recovered,
regenerated and used again.
The quantity of glycol which must be added to
d water-saturated gas in order to depress its
hydrate for~ing temperature to a predetermined
level can be calculated /rom the relationship
proposed by Haillmerschmi dt. However, the temper-
ature at which hydrates form in the presence of
glycol is very difficultz. to determine with a~y
~recision. Polderman best expresses thlS
condition as "hard to handle" in which the fluid
na ss approaches a p 13s tic s ta te wh i ch fl ows very
slowly but is not truly solid. It is restrictive to
flow but does not plug.
Properly applied, the glycol injection process
works very well. The quantity of ethylene glycol,
for exampl e, that is requi red to protect a system
flowing at 1000 psig with gas saturated at lOO°F
which is chilled to minus 40°F is surprisingly
small -- 35 gallons per ~l~lSCF to be injected at a
7~ weight percent concentration and withdrawn at 60
weight percent concentration. Injection of too
much glycol will affect only the heat load on
the refrigeration system. Too little solution will
result in a freeze-up of an excessively diluted
glycol.
If glycol injection follows methanol. injec-
t ion, the methanol wi 11 be absorbed a nd removed
by the glycol. It can be recovered by fraction-
ating the alcohol-water vapors that comprise the
overhead stream from the glycol-water still of the
glycol regenerator unit.
Glycol injection has never been popular as
production tool for two reasons. First is cost of
a well-head facility. The LTX (low temperature
separation) system, which employs J-T expansion, is
less costly, has fewer illoving parts and requires
less attendance. Second is the inevitable con-
tamination of glycol with salt. Here, the water
phase of the brine is distilled off, leaving the
chlorides of sodium, potassium and calcium in the
glycol where it plates out on firetube surfaces,
vastly increasing heat transfer so that firetubes
burn out and fail in service. Salt can be removed
from glycol only by steam distillation or vacuum
distillation at considerable expense in fuel and
1 abor.
A third disadvantage should be mentioned. The
glycols are ,;]utually soluble in aromatic hydro-
carbon 1 i qui ds. Where these, and to some extent
saturated cyclic hydrocarbon liquids, are present
in condensates, the expensive glycol will be lost
in the oil phase making the appl ication economi-
cally unsound. If use of glycol injection is
antiCipated, a PONA analysis of the liquids should
be obtained to indicate the absence or presence of
aromatics and/or naphthenes. separate runs of resistive heating tape (trade-
named I Thermon I) \~hi ch are c1arnped to the fl owl i ne
OFFSHORE AND ARCTIC HYDRATE CONTROL PRACTICES at intervals. Two tapes are used at anyone tiqle
---------------------
with the third available as a back up. The flow-
In the t~olino gas field looted approximately 1 i ne is then jacketed i 11 a po lyethy1 ene tube and
~. ___________________________________________L-____________________________________________
three miles offshore Southern California, glycol is
pumped from shore through a 2-inch line and in-
jected i nto ;~ f10w1 ine at a point downstream of
the wellhead. The glycol is later reclaimed from
the gas stream by a regenerator at the onshore
processing plant.
Shell Oil Company13 operates a subsea gas well
in 200 feet of water at Vermilion Block 302 uti1iz-
i ng a Lockheed Petrol eum Servi ces one-atmosphere
we 11 head chamber and produc i ng through a subsea
flowline to existing platform production facilities.
Due to hydrate freeze-ups occurring in the flowline
and at the choke, methanol is injected at two
points: the platform choke and the flowline cross-
over valve. The latter is accomplished utilizing
one of the two flowlines. An injection line to the
WHC was provided in the original pipe bundle but it
subsequently developed a leak. There is no provi-
sion for recovering the methanol, Figure 8.
Methanol injection rates are 1 to 1-1/2 bpd at
the choke and 2-1/2 to 3 bpd at the crossover valve.
The well produces approximately 8 MMCFPO through a
13,000 foot flow1 ine at a wellhead temperature of
130°F and a pressure of 3400 psi. Temperatures
upstream and dovmstream of the choke are estirnated
at 60°F and 20°F respectively. Since the initia-
tion of this injection program, no further hydrate
problems have occurred.
Shell's LPS completion #S at Eugene Island
14
331 was subjected to a batch treatment of meth-
anol down the tubing and continuous methanol injec-
tion upstream of the choke while the well was being
tes ted over a two week peri od in trle fa 11 of 1977.
The well is presently flowing again and producing
enough liquids to preclude a lowering of tempera-
ture sufficient to allow hydrate formation. Metha-
nol is still injected occasionally at the Choke as
dictated by the actual gas stream being produced.
Panarctic Oils, Ltd. recently comv1eted an
Arctic Ocean offshore gas well in 200 foot water
deptl1 uti11fing a wet subsea tree and submarine
flowlines. A series of preventive measures have
been taken to preclude the formation of and to aid
in the removal of hydrate plugs in the tubing and
flowlines. Two separate 6" diameter flowlines are
used, each provided vlith a different heating system
for evaluation and comparison, Figure 9. All hy-
draulic control lines, the annulus line, flowlines
and injection lines are housed within an 18"
diameter pipe bundle. One of the two 6" diameter
fl owl i nes is i nsul ated with polyurethane and pro-
vided with a 'Thermon' resistive heating system
to allow melting of any hydrates which form. The
other flowline is not insulated and is provided
with a 'Skin Effect Current Tracing' (SECT) heating
system, a procesfr ~o/eloped by Chisso Engineering
of Tokyo, Japan. 0, The 4000' well produces 7'13
MMCFPD through 5-1/2" diameter tubing with a flow-
line temperature of 55°F. Hydrates are expected to
form at 50°F and the ar:Jhient sea water temperature
is 2yOF.
The 'Thermon' system
18 is made up of three
~
451
the annular space filled with polyurethane. This
system is suppl ied by a 25 KVA power source for
each tape and heat output is estimated at 12 watts/
foot per tape. Flowline insulation was provided to
keep the electrical power requirements for heating
within the system's capabilities.
The SEC, system is based on the electrical
phenomenon by which alternating current is carried
on the surface of a magneti ca lly permeable con-
ductor wi thout penetrati ng deeply into or through
the conductor. In the Panarctic appl ication two
3/4" diameter 'heat tubes' are seam welded t~ one
of the 6" diameter flowlines. These represent
redundant systems with only one required to provide
sufficient heating. An insul ated copper conductor
is run inside each tube and electrically connected
to the tube at the far end. Both heat tube and
copper wi re are connected to a 20" KVA power
source. 60 Hz alternating current is applied to
the conductor and is returned along the inner sur-
face of the heat tube, which becomes heated due to
metallic resistance. This heat is then uniformly
conducted to the flowline via the weldments. Heat
output of this system is estimated at 34 .vatts/
meter. The system is controlled by remote tem-
perature sensors spaced along the pi pe 1 i ne whi ch
energi ze the system any time the temperature fall s
below a preset minimum. The system is electrically
isolated due to the confinement of the current to
the ID of the heat tube. In a test performed at the
site, hydrate formation was induced in the flowline
and successfully melted util izing the SECT system.
Glycol/alcohol is injected into the gas stream
at two points: downstream of the wing valves on the
tree and immediately above the production packer.
The latter location is serviced by a 1/4" diameter
injection line run through the tubing hangar and
strapped to the 5-1/2" tubing.
NEW IDEAS
There are many who contend that gas hydrates
pose no significant production problem and that
hydrate control technology was fully developed 25
years ago. While it is true that the basic tech-
niques for gas hydrate control - application of
heat, injection of ethylene glycol, and injection
of methanol - remain essentially unchanged, some
substantial improvements have been made during the
last two decades.
Glycol injection is not as well suited as
methanol for controlling gas hydrates in a high-
pressure flow string or flow line because it is
very eas ily CQntami na ted with sa lt, and the wa ter
it picks up must be evaporated in order to regen-
~r~te ~nd recover the glycol. Nevertheless, glycol
1nJect10n has numerous applications and its tech-
nology is very well-defi ned. Glycol i njecti on
would be enhanced by any process which will remove
salt from the glycol and maintain its concentration
at an acceptable level, say 0.5 percent. Contempo-
rary glycol recl a i mers vacuum di s ti 11 the glycol
from the salt residue, a thermally-inefficient and
labor intensive process that needs to be replaced.
Some promise is shown for new methods involving
electro-dialysis.
Where large quantities of methanol may be
required to produce large wells flowing at high
452
pressures and low temperatures, both the cost and
avail abil ity are matters of concern. Although
essenti ally a 11 methanol is was ted in present day
operations, it is bel ieved that attention wi 11 De
direc~ed to recovering methanol from the gas phase,
the 011 phase and the water phase when the flow
reaches the platform (or shore station) where it
can be separated and treated.
Concerning the application of heat, there have
been some significant improvements in electrical
resistance heaters, both as Cal-rod units and
so-called "heat tape". The reliability of these
heaters and heat tapes has improved immeasurably in
recent years as demonstrated by the Thermon system
mentioned above. Among the heating systems however,
the SECT system appears to offer the most attrac-
tive al ternative at the present time. It requi res
only small amounts of electrical current for opera-
tion and does not need constant attention and
maintenance. It can also be used on long lengths
of flowline in remote locations. The Panarctic
tests shoul d serve to answer many questi ons per-
taining to the SECT system's practical and economic
viability in remote offshore and Arctic production
fields.
Heat can be applied in other ways that may
seem unconventional at first glance. For example,
heat capacity of the hydrocarbon stream can be
increased by recycl ing a compatible 1 iqui d, pre-
ferably one with large heat capacity, and certainly
in sufficient quantity to build the heat supply to
the desired level. Fresh water, sea water or
oilfield brine have greater density and almost
twi ce the heat capaci ty that gas, condensate
or crude oil exhibit. One of these waters might be
used, taking care not to heat it to a temperature
where scale would form; or a portion of the liquid
condensate or crude oil could be warmed and recir-
cul ated. Some speci ally compounded heat transfer
fluid might be developed with large heat capacity,
unique fluid properties and salt contamination
resistance which would make it well-suited to such
applications.
The recycle principle might be applied by
using concentric flow 1 ines to pump the warm heat
transfer fluid - water, oil, or special fluid -
through the annulus to a point downstream from the
submerged wellhead where the concentric pipe would
end. There the heat transfer fluid would commingle
with the gas, condensate, and any free water, then
return to the producti on platform vi a the concen-
tric, or inside line. In any of these recycle
arrangements, the key to mi nimum heat transfer is
to lower the temperature di fference between the
fl u i d contents of the 1 i ne and its envi ronment.
Extra heat is suppl ied only to be wasted through
the pipe walls but in quantity sufficient to
maintain the temperature of the fluid mixture (well
production and recycle fluid) safely above its
hydrate poi nt.
Perhaps these are some of the more important -
and more urgent - of the new developments needed
to refine and improve the techniques of gas hydrate
control. As the industry moves into deeper waters
farther from shore and into the remote areas of the
offshore Arctic with the attendant use of subsea
completions and floating production systems de-
manded by these 1 ocat ions, costs associ ated with
 c~rrently accepted hydrate control techniques are
llkely to become prohibitive. Economics, then,
will eventually dictate the development of new
methods or improvements on older methods which can
be adapted to meet the requirements of these new
envi ronments.
ACKNOWLEDGEMENTS:
The author wi shes to acknowl edge the i n-
valuable assistance of r~essrs. Laurance Reid of
Laurance Reid Associates, Inc., and Norman Giese
of Marathon Oil Company in the preparation of
thlS paper.
REFERENCES AND BIBLIOGRAPHY:
1. ~amilerschmid~, E.G., "Formation of Gas Hydrates
ln N3tural Gas Transmission Lines", Ind. Eng.
~em., vol. 26, pp. 851-855 (Aug. 1934).
2. Deaton, W.lvi. and Frost, E.M., "Gas Hydrates and
Their Relation to the Operation of Natural Gas
Pi~e Lines·, U.S. Bureau of Mines Mono. 8, 1948.
3. Mc"arthy, E.L., Boyd, W.L. and Reid, L.S. "The
Water Vapor Content of Essentially Nitrogen-
Free Natural Gas Saturated at Various Condi-
tions of Temperature and Pressure," Trans.
A.I.M.E. (1950), 189,241. --
4. McKetta, J.J. J-r:- and Wehe, A.H. "Use thi s
Cha~t for Water Content of Natural Gases," Pet.
Reflner (1958),37, No.8, 153. --
5. Hammerschmi dt, E.G. "Calcul ation and Determi n-
ation of the Moisture Content of Compressed
Natural Gas," Western Gas (1933),2.,9-11,29.
6. Sharma, S.C. Equilibrium Water Content of
Gaseous Mixtures, Ph.D. Dissertation Univer-
sity of Oklahoma (1969). ' mated Offshore Gas Production and Dehydration
7. Sharma, S.C. and Campbell, J.M., "Predict
Natural Gas Content ',vi th Total Gas Usage",
paper presented at the 48th NGPA Annual Con-
vention, March 11-13, 1969, Dallas, Texas.
8. McLeod, W.R. Applications of Molecular Refrac-
tion to the Principle of Corresponding States.
Ph.D. Thesis, University of Oklahoma (1968).
9. McLeod, W.R. and Campbell, J .M., "Predi cti on
of the Critical Temperature and Pressure, and
Density of Natural Gas", paper presented at
the 48th NGPA Annual Convention March 11-16
'-___19~_9"'_QtllJCls, l~)(as. ' _ _ _....J..._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
,
10. Hammersch~i dt, E.G., "Preventi ng and Removi ng
Hydrates 1 n Natural Gas Pipe Lines", Gas Age,
vol. 83, no. 9, pp. 45-49, 63 (Apr. 27, 1939);
Gas, vol. 15, no. 5, pp. 30-34, 94 (1939); Oil
and Gas Journal, vol. 37, no. 52 pp. 66 69
71,72 (1939). " ,
11. Pol derman, L.D., "The Glycol s as Hydrate Point
Depressants in Natural Gas Systems", Proc. Gas
Condo Conf., Univ. of Okla. Norman Okla.
(1958). "
12. Bleakley, W.B., "Shell Reviews Underwater Well-
head Experience - and Likes What It Sees", Oil
and Gas Journal, vol. 69, no. 34, pp. 106, 108,
(Aug. 23, 1971).
13. Personal Communication, 1978.
14. Personal Communication, 1978.
15. Anon, "Offshore Arctic Gas: Can It Be Produced
Economically?", World Oil, vol. 185, no. 5,
pp. 106I-106M (October 1977).
16. C~rso.n, ~,.B., "A New Method for Heat Tracing
Plpellnes , ASME Technical Paper No. 74-Pet.-35
(1974).
17. Personal communication, Aug. 22, 1978.
18. Burpee, W.E. and Carson, N.B., "Skin Effect
Current Tracing", Technical Paper presented at
IEEE, 1975, Paper No. PCI 75-45.
19. Makogan, Yu 1. and Sarkis' yants G.A. "Pre-
vention of Hydrate Formation in the Ext~action
and Transport of Gas", Moscow, 1966, National
Resea rch Council of Canada Techni ca 1 Trans 1 a-
tion No. NRCC-15476 (1976).
20. Bleakley, W.B., "Mobil's r-1ethanol Injection
System Prevents Gul f Hydrate Formati on", Oi 1
and Gas Journal, vol. 68, no. 49, pp. 65,"
(Dec. 1970).
21. Hicks, R.H. et al, "A Prefabricated and Auto-
Faci 1ity", Paper presented at 3rd Ann. Offshore
Tech. Conf. Houston, TX, 1971, OTD Paper #1387.
22. Thomas, S.J., "Design of Offshore Gas Platform
Facilities", 9th Ann. Heart of Amer. Pipeline
Oper. &Maint. Inst. Mtg., Liberal, Kan., 1973,
Select Paper.
23. Katz, D.L., et al. Handbook of Natural Gas
Engineering. McGraw-Hill Book Co. ,Inc. (1959).
24. London, F. "The General Theory of Molecular
Forces," Trans. Faraday Soc. (1937), 38, 8.
453
 Tab1 e 1
GROUP PARN1ETERS

Grou~ Com~osition Mol. Wt. EMR Tc(oR) Pc(~sia) Tc/JPc

CH 16.042 14.193 343.30 673.10 13.2322

N
4 28.020 9.708 227.70 492.00 10.2655
2 28.010 10.809 241.20 514.40 10.6347
CO
CO2 44.010 14.440 548.00 1073.00 16.7294

Ia 32.000 8.692 278.00 730.00 10.2892

HQ2 34.076 20.279 672.70 1306.00 18.6144
2S 2.016 4.228 60.20 188.10 4.3894
H2
II C 30.068 24.365 549.77 617.40 22.1258
C2 44.094 34.628 765.31 550.70 32.6122
nC 43 58.120 44.243 734.65 529.10 31.9384
1·C 4 58.120 44.741 845.60 489.50 38.2199
nC 5 72.146 55.267 829.80 483.00 37.7571
iC5 72.146 55.302 914.80 439.70 43.6263
C6 86.172 65.575 896.60 440.14 42.7370
C 100.198 75.875 972.31 396.90 48.8051
C7 114.224 86.193 1024.31 362.10 53.8292
C8 128.250 96.529 1073.06 345.00 57.7715
C9lO 142.276 106.859 1114.70 306.00 63.7230
156.302 117.173 1153.70 282.00 68.7017
C" 1187.70 263.00 73.2366
C12 170.328 127.499
III C5Hl0 70.130 54.456 830.00 485.7 37.6612
C6H12 84.156 64.763 902.00 438.4 43.0796
C7H14 98.182 74.696 963.20 402.6 48.0042
C8 H16 112.208 85.418 1017.20 371.3 52.7892
C9 H]8 126.234 95.739 1069.40 348.2 57.3094
ClOR 20 140.260 106.084 1109.00 313.5 62.6345
C H 154.286 116.406 1114.80 289.1 65.5653
C11 H22 168.312 126.725 1182.80 269.1 72.1030
12 24
IV Cyc10pentane 70.130 50.946 921. 17 654.7 36.0013
Methy1cy1copentane 84.156 61.328 958.99 549.0 40.9288
Cy10hexane 84.156 61.210 995.20 591.5 40.9197
Methy1cyc1ohexane 98.182 71 .762 1029.80 504.4 45.8526
Ethy1cyc10hexane 112.208 81.862 1025.03 492.8 46.1744
V Benzene 78.108 58.586 1012.70 714.0 37.8993
Toluene 92.134 59.522 1069.20 590.0 44.0183
Ethyl benzene 106.160 79.931 1115.50 540.0 48.0035
0-Xy1ene 106.160 80.173 1138.00 530.0 49.4316
M-Xy1ene 106.160 80.405 1114.60 510.0 49.3553
P-Xy1ene 106.160 80.494 1112.80 500.0 49.7659
N-Propylbenzene 120.186 90.364 1148.00 460.0 53.5258
IsoPropylbenzene 120.186 90.289 1145.00 460.0 53.3859
O-Cymene 134.212 100.848 1177.76 405.5 58.4874
M-Cymene 134.212 101.210 1166.40 396.6 58.5695
P-Cymene 134.212 101.245 1170.40 390.0 59.2656
N-Pentylbenzene 148.348 111.013 1222.20 384.8 62.3053

Table 2
EXPERIMENTAL HIX'l'URES 6 - Hole %
(1) (2) (3) (4) (5) (6)
C = 0.9173 C1 = 0.8404 N2 = 0.0855 N2 = 0.1886 CO2 = 0.1132 CO 2 = 0.2022
C12 = 0.0827 C2 = 0.1596 C1 = 0.9145 C1 = 0.8114 C1 = 0.8868 C1 = 0.7978

(7) (8) (9) (10) (11) (12)

H2S = 0.0830 H2S = 0.1783 H2S = 0.1600 H2S = 0.1700 H2S = 0.1900 H2S = 0.2100
C = 0.9170 C1 = 0.8217 C1 = 0.8400 C1 = 0.8300 C = 0.8100 C1 = 0.7900
1 1

(13) (14) (15) (16) (17)

H2S = 0.2750 H2S = 0.2900 Cl = 0.8851 N2 = 0.0100 C02 = 0.0060
C1 = 0.7250 C1 = 0.7100 C2 = 0.0602 CO 2 = 0.0060 O
2 = 0.0020
C3 = 0.0318 C1 = 0.9436 C1 = 0.8530
IC4 = 0.0046 C2 = 0.0264 C2 = 0.1350
NC 5 = 0.0085 C3 = 0.0096
IC 5 = 0.0098 NC 4 = 0.0044
 Table 3
COMPARISON OF METHODS

Mole Fraction H 0
Press. 2
Mixture (psia) Exp. McKetta McCarthy Sharma Hammerschmidt

1-3 100 1014 0.001320 0.001539 0.001226 0.001270 0.00112

1-4 100 1514 0.000924 0.000949 0.000967 0.000950 0.00081
1-5 100 2014 0.000753 0.000801 0.000797 0.000805 0.00064
1-8 130 1014 0.002805 0.002762 0.002882 0.002790 0.00256
1-9 130 1514 0.002225 0.002084 0.002164 0.002090 0.00182
1-10 130 2014 0.001720 0.001729 0.001765 0.001720 0.00143
1-13 160 1014 0.005660 0.005800 0.005894 0.005750 0.00535
1-14 160 1514 0.004150 0.004302 0.004378 0.004250 0.00377
1-15 160 2054 0.003380 0.003396 0.003470 0.003490 0.00290

2-3 100 1014 0.001330 0.001537 0.001226 0.001300 0.00116

2-4 100 1514 0.000912 0.000948 0.000967 0.000995 0.00084
2-5 100 2014 0.000740 0.000800 0.000797 0.000850 0.00067
2-8 130 1014 0.002795 0.002760 0.002882 0.002790 0.00262
2-9 130 1514 0.002230 0.002001 0.002164 0.002110 0.00188
2-10 130 2014 0.001711 0.001731 0.001765 0.001780 0.00148
2-13 160 1014 0.005690 0.005794 0.005894 0.005750 0.00544
2-14 160 1514 0.004170 0.004298 0.004378 0.004330 0.00386
2-15 160 2014 0.003580 0.003393 0.003540 0.003600 0.00303

3-3 100 1014 0.001310 0.001554 0.001226 0.001220 0.00108

3-4 100 1514 0.000915 0.000958 0.000967 0.000900 0.00077
3-5 100 1924 0.000717 0.000851 0.000827 0.000750 0.00063
3-8 130 1014 0.002495 0.002790 0.002882 0.002690 0.00249
3-9 130 1514 0.001970 0.002023 0.002164 0.001950 0.00175
3-10 130 2034 0.001480 0.001747 0.001745 0.001550 0.00135
3-13 160 1014 0.005410 0.005858 0.005894 0.005600 0.00523
3-14 160 1514 0.003970 0.004345 0.004378 0.004080 0.00365
3-15 160 2064 0.003260 0.003430 0.003450 0.003260 0.00277
4-3 100 1014 0.001230 0.001537 0.001226 0.001220 0.00107
4-4 100 1514 0.000848 0.000948 0.000967 0.000895 0.00075
4-5 100 2014 0.000710 0.000800 0.000797 0.000722 0.00059
4-8 130 1014 0.002520 0.002760 0.002882 0.002670 0.00247
4-9 130 1514 0.001840 0.002001 0.002164 0.001920 0.00172
4-10 130 2014 0.001610 0.001731 0.001765 0.001550 0.00134
4-13 160 1014 0.005450 0.005794 0.005894 0.005600 0.00519
4-14 160 1514 0.003630 0.004298 0.004378 0.004000 0.00360
4-15 160 1994 0.003050 0.003435 0.003580 0.003200 0.00281

5-3 100 1014 0.001361 0.001526 0.001226 0.001264 0.00113

5-4 100 1414 0.000973 0.000940 0.001027 0.001011 0.00086
5-5 100 2014 0.000855 0.000793 0.000797 0.000804 0.00065
5-8 130 1014 0.002820 0.002738 0.002882 0.002730 0.00256
5-9 130 1514 0.001900 0.001985 0.002164 0.002050 0.00183
5-10 130 2014 0.001820 0.001714 0.001765 0.001720 0.00144
5-13 160 1014 0.006020 0.005748 0.005894 0.005720 0.00535
5-14 160 1514 0.004330 0.004263 0.004376 0.004230 0.00379
5-15 160 2014 0.003740 0.003365 0.003540 0.003510 0.00297

6-3 100 1014 0.001270 0.001526 0.001226 0.001260 0.00116

6-4 100 1514 0.000926 0.000940 0.000967 0.000960 0.00085
6-5 100 2014 0.000856 0.000793 0.000797 0.000820 0.00068
6-8 130 1014 0.002880 0.002727 0.002882 0.002790 0.00262
6-9 130 1514 0.002050 0.001977 0.002164 0.002090 0.00189
6-10 130 2014 0.001852 0.001707 0.001765 0.001730 0.00150
6-13 160 1014 0.005950 0.005690 0.005894 0.005720 0.00544
6-14 160 1514 0.004400 0.004220 0.004378 0.004220 0.00388
6-15 160 2014 0.003635 0.003331 0.003540 0.003510 0.00306
 Table 3, cont'd.
COMPARISON OF METHODS

Mole Fraction H O
Temp. Press. 2
Mixture (OF) (;esia) Ex;e. McKetta McCarthy Sharma Hammerschmidt

7-3 130 1014 0.003030 0.002762 0.002882 0.002770 0.00258

7-4 130 1514 0.002350 0.002003 0.002164 0.002080 0.00185
7-5 130 2014 0.001870 0.001729 0.001765 0.001730 0.00146

8-3 130 1014 0.003270 0.002738 0.002882 0.002820 0.00270

8-4 130 1514 0.002110 0.001985 0.002164 0.002150 0.00197
8-5 130 2014 0.001890 0.001705 0.001765 0.001820 0.00157

9 160 1395 0.004750 0.004612 0.004657 0.004570 0.00424

J.O 160 1010 0.006160 0.005649 0.005894 0.005870 0.00557
13 160 1392 0.005200 0.004658 0.004677 0.004920 0.00456
14 160 925 0.006900 0.006081 0.006383 0.006410 0.00632

15-2 100 1000 0.001251 0.001295 0.001306 0.001299 0.001l7

15-3 100 1500 0.000957 0.000951 0.000967 0.000992 0.00085
15-4 100 2000 0.000810 0.000793 0.000797 0.000812 0.00067
15-6 150 1000 0.004710 0.004494 0.004737 0.004640 0.00436
15-7 150 1500 0.003386 0.003386 0.003470 0.003435 0.00309
15-8 150 2000 0.002800 0.002758 0.002822 0.002B25 0.00243

16-2 100 1000 0.001241 0.001307 0.001306 0.001271 0.001l3

16-3 100 1500 0.000946 0.000959 0.000967 0.000971 0.00080
16-4 100 2000 0.000758 O.OOOBOI 0.000797 0.000B06 0:00063

Table 4

ABSOLUTE PERCENT ERROR BETWEEN EXPERIMENTAL

AND CALCULATED VALUES

Data Case McKetta McCarthy Sharma Hammerschmidt

All Data Cases 5.B33 6.980 4.443 9.B06

Greater than 1000 psig 6.150 7.223 4.246 11.994

Less than 1000 psig 5.224 6.474 4.619 6.4B1

CO Mixtures 4.358 5.313 3.913 10.037

2

H S Mixtures 5.702 8.505 6.441 10.745

2
 12,000
10,000
8000
6000 --

4000 -

GROUP la
2000 - - --- -- 0,6

0.5

..... "
.......
::;)
IL

.
"- 0.4
"
...
0.3

0.2

40 50 60 70 80 90
TEMPERATURE, F EMR
Fig, 1 - Conditions of hydrate formation. Fig. 2 - EMR versus Tc/Pc for group I and la,

STRAIGHT AND IRANCHED CHAIN /

SATU RAT ED H YD' OCA RI 0 N S / '
2.5
(EXCEPT METHANE)

2.0

... "
~ 1.5
..
"- 1.5
" ."
1.0 1.0

0.5

/
0.5
/
oL-L-L-L-L-L-L-L-L-L-L-L-L-L-L-L-L-L-~~

o 20 40 60 10 100
EMR EMR
Fig. 3 - EMR versus Tc/Pc for group II. Fig. 4 - EMR versus Tc/Pc for group III.
 3.0
7or----,-----,----,-----,----,-----r-----,----.-----r----,

'.5 60

50
'.0

l;
.
.... 1.5
40

GROUP 10
;:
30 '0 Y
1.0
k·
/" \ GROUP 1b
.0 , 0
/1
0.5 '0 00':----''-0---''-0--3'''0

°0~-~,~0--.~0~--3~0~--4~0~--5~0~--6~0---7LO---.LO---.LO--'~OO
0
0 40 60 '00 EM.
EM. Fig. 6 - EMR versus Tel IP e.
Fig. 5 - EMR versus TclPc for groups IV and V.

160

'40

120
~

%
~

..
:J

:>
'00

.0
GROUP 3

...
0 GROUP 2
:Ii 60 o GROUP 3
GROUP 4
I:J. GROUP 5
40

.~LO--~3-0--4~0---5~0---.~0---7~0---.~0---.~0---,OL-0--"LO--'~'O
IYKMAN MOLECULAR REfRACTION
Fig. 7 - Molecular weight vs Eykman molecular refraction.

ONE
OUTLETS
WElLHEAD
CHAMIER c'=~~~~~;1PROD.
MANIFOLD

PI P E
fACILITIES

" .. ---hf-*","'I

G) METHANOL INJECTION POINT

o METHANOL TRANSPORT

"THIRMON"
HIATING
C .... LI & .... CEW ... y

I
Fig. 8 _. Typical flow schematic using LPS one-atmosphere subsea system. Fig. 9 - Flowline bundle and carrier used in Arctic subsea well.