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EUROPEAn

SPE 8137 OFFSHORE


PETROLEum
PREDICTION AND CONTROL conFEREnCE
OF NATURAL GAS HYDRATES I EXHIBITion
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 formi ng conditi ons for a number of bi nary systems


containing water and hydrocarbons or CO?_ and H2S
This paper discusses the more significant are shown by the equilibrium curves of1-igure T.
advances in hydrate control technology in the past Generally, each component has a criti cal tempera-
twenty years. It al so presents a compari son of ture above which no hydrate of this compound is
four of the more widely used methods for predicting formed. This temperature corresponds to the point
the water content of natural gas hydrates and of intersection of the equilibrium hydrate-forma-
comments on their limitations. ti on curve of the hydrate formi ng compound. The
figure shows :, S with the highest critical tem-
Some deve 1opment is reported on the problem perature. jlll:;r~fore, natural gas systems contain-
of controlling and preventing hydrate formation in i ng H2S fonn lIyurates more readi ly than do gases
offshore wells and onshore Arctic completions. of the- same den s ity wi thou t H S.
Control techniques commonly used in these areas 2
comprise variations on long-established practices By 191::1::, present-day technology had been de-
such as application of heat, lowering system pres- veloped and was in use by the petroleum industry.
sure, at least a partial dehydration of gas and/or Several tenets were well-established, such as:
liquid phases, addition of inhibitors, and purpose-
ful formation of gas hydrates followed by thei r A. Essential Conditions for Gas Hydrate Formation
entrapment, decomposition and discharge of the 1. Favorable conditions of pressure and
water phase (known to wany as the LTX system). temperature of the gas.
2. Presence of a liquid water phase.
HISTORICAL BACKGROUND: 3. Thorough agitation between the phases.
Although Sir Humphrey Davy first reported on B. Methods for Preventing Gas Hydrate Formation
hydrates of organi c compounds in 1810, 1it was not 1. Heating gas above hydrate formation
until 1934 that Elmer G. Hammerschmi dt described temperature.
natural gas hydrates and their formation in natural 2. Loweri ng gas pressure on the system.
gas transmission systems. A growing awareness of 3. Dehydrate the gas to a level where
this problem led to extensive research or. several no condensation occurs.
facets of gas hydrate formation by W. M. Deaton and 4. Use of inhibitors to depress hydrate
E. M. Frost, Jr. of the USBM prior to World War II. formation temperature.
These studies, though nearly complete, were inter- 5. Use of the low-temperature separati on
rupted by wartime activi ties and the results wer process (LTX) which purposely forms hy-
not published until 1946 as USBM MONOGRAPH 8. Z drates by Joule-Thomson (J-Tl expansion,
separates them from the cold gas, moves
These and other investigations established them to a wann zone, and there hydrates are
the nature of hydrate formation in multicomponent decomposed into hydrocarbons and water.
mixtures of hydrocarbons and water and the effect The latter is discharged from the system.
of other gases such as H , CO ,N and H S on
hydrate formation by hydrO~arbo~ ga;ks. M;r,:hods C. Inhibitor Choices
were developed to cal cul ate the equi 1i bri um con- 1. Methanol
ditions of hydrate formation, or in essence to 2. Ethylene Glycol
predict the conditions under which hydrate forma- 3. Diethylene Glycol
tion is likely to occur in any of several pure and 4. Others, including triethylene glycol,
mul ticomponent hydrocarbon gas systems. Hydrate amonia, calCium, chloride brine, oil field
brines, heavier alcohols, and aqueous sugar
solutions.
References and illustrations at end of paper.

449
WATER CONTENT PREDICTION TECHNIQUES production systems located in hostile environments
poses new and seri ous chall enges. No longer
Many investigators have developed procedures does the old adage, "Move closer to the wellhead,"
for predicting the water content of natural gases. apply when that haven is submerged ina thousand
These have ranged in complexity from plots of wa~er feet of cold water or located in the high Arctic
content versus saturation temperature as a functlon regions and hydrates are to be. found in the flow
of pressures to a more recent approach whi ch string beneath the wellhead.
utilizes the total gas composition, the Eykman
Molecular Refraction (EMRl, and basic fugacity con- Injection of methanol is thought to be the
cepts. Needless to say, there have been claims and most uni versally used tool of preventi ng gas
counter c 1ai ms concerni ng the accuracy of each of hydrate formation, whether it be temporary to
these methods in dealing with complex hydrocarbon decompose blockages as they form, or for continuous
gases containing CO and H S. It is for this use. Methanol is lost with liquids removed from
reason the author co~ares fofir of ~e more widely the system and the vapors rema i ni ng with the gas
acce~ted methods: ~cCarthy et al., McKetta a?d phase are absorbed in any glycol absorption or
We he • Hammerschmi dt , and Sharma and Campbell 6 ' • glycol injection process, or in any amine treating
Nomogram solutions were used for the first two process used to condition the gas en route to
methods while computer solutions were employed for market.
the others.
There appear to be no lower operating temper-
It must be noted that the groups of the gas ature - or pressure - limits for methanol when
components as shown in Figures 2 through 7 and used to inhibit gas hydrates. Methanol has been
Table I of the ~ppendix di~fer some1r~ from t~o~e injected into flow systems at pressures at least as
previously publlshed by thlS author'. Speclfl- high as 4000 pSig to inhibit hydrate formation when
cally, gases formerly assigned to Group 1 have been the gas is expanded to lower pressures. It has
split into Groups la and lb primarily to reflect been used at temperatures as low as minus 150°F in
more reliable refractive indices of gas components. hydrocarbon 1 iqui d recovery processes and at
Plots of T Iff versus EMR for Groups la, lb, temperatures lower than mi nus 300°F in the Lurgi
and 2 whichc wer~ originally included in a single RECTI SOL process for removal of CO and water
correlation curve, have been separated into three vapor by physical absorption. 2
curves for greater accuracy. Finally, the method
has been extended to cover most of the components Economic use of methanol in cold water, subsea
normally found in refinery gas streams. production systems is dependent upon early separ-
ation and discharge of free water from the well
Experimental data on the water content of one effluent. This conjures up visions of complicating
hundred twenty (120 1 di fferent mi xture - tempera- features such as bottom-hole water separators, a
ture - pressure combinations were used in the water decanter addi ti on to a sub-sea modul e,
preparation of this paper. The mixtures and the separate water flow lines to a central station or
resul ts of the compari sons at pressures of 1000 platform, etc. The alternative is to continue to
psig and above are shown in Tables II and III. endure methanol losses in the water phase.
For all 120 data cases, the Sharma method best Use of glycol inhibitors was conceived in 1943
approximates the experimental values, followed by as a production process for high-pressure gas-con-
the McKetta, McCarthy, and finally Hammerschmidt, densate fields as an improvement over the use of
as shown in Table IV. For pressures less than 1000 calCium chloride brine to prevent gas hydrate
psi g, the di fferences between the vari ous methods formation in some East Texas gas cycling plants.
diminish to less than two percent. Thus, for lower As processing technology developed, system temper-
pressures all methods approximate the experimental atures dropped to the range of minus 20° to minus
values fairly well. However, at pressures in 50°F in col d oi 1 absorpti on pl ants where the
excess of 1000 psig, the discrepancy between the glycol injection process has found its prinCipal
most accurate and least accurate methods again use. Under these conditions, ethylene glycol has
widened appreciably. Similar results were observed been used because of vastly improved fluid pro-
for the 36 CO 2 mi xture - pressure - temperature perties and because vapor losses are insignificant
combinations. In cases involving H S, the Sharma even though the other glycols have lower vapor
method di sp 1 ayed a trend towa rds gr~ater accuracy pressures.
as the H?S concentrati on and pressure increased,
a lthough '""the McKetta method gave sl i ghtly better Unlike methanol, which is dispersed into the
results overall. Clearly, Sharma's method showed vapor phase of a gas flow system to condense and
the greatest versatility of the methods compared. form an equi 1 i bri um system wi th water wherever it
is found in a sag, essentially all glycol remains
It is doubtful that anyone method will ever in the liquid phase when injected into a pipeline.
be capable of predicting accurately the water To be truly effecive, it must travel far enough
content of all types of compl ex gas mi xtures, from the injection point to establish a thin glycol
particularly those containing H~S, CO , H2 and film which uniformly coats the entire inner surface
2
other non-bycarbons, over an unllmited range of of the fl ow condu i t whether that be pi pe, or the
temperatures and pressures. Certainly, more exper- channel cover and tube bundle of a heat exchanger
imental data is needed to better establish the or chi 11 er. Any bare, uncoated surface wi 11
limitations of each of the methods discussed above. 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
Control of gas hydrates in gas-condensate lengths are short, as in most plants and platforms,

450
some exotic spray heads are installed which atomize three miles offshore Southern California, glycol is
the glycol and spray it unifor;nly on peri pheral pumped from shore through a 2-inch line and in-
surfaces. Success in this area requires little jected i nto ;~ f10w1 ine at a point downstream of
engineering and much witchcraft. A corollary to the wellhead. The glycol is later reclaimed from
this problem is that of removing the glycol film the gas stream by a regenerator at the onshore
frofTl the sy stem once its mi 5S i on has been accom- processing plant.
pl ished so that the glycol can De recovered,
regenerated and used again. Shell Oil Company13 operates a subsea gas well
in 200 feet of water at Vermilion Block 302 uti1iz-
The quantity of glycol which must be added to i ng a Lockheed Petrol eum Servi ces one-atmosphere
d water-saturated gas in order to depress its we 11 head chamber and produc i ng through a subsea
hydrate for~ing temperature to a predetermined flowline to existing platform production facilities.
level can be calculated /rom the relationship Due to hydrate freeze-ups occurring in the flowline
proposed by Haillmerschmi dt. However, the temper- and at the choke, methanol is injected at two
ature at which hydrates form in the presence of points: the platform choke and the flowline cross-
glycol is very difficultz. to determine with a~y over valve. The latter is accomplished utilizing
~recision. Polderman best expresses thlS one of the two flowlines. An injection line to the
condition as "hard to handle" in which the fluid WHC was provided in the original pipe bundle but it
na ss approaches a p 13s tic s ta te wh i ch fl ows very subsequently developed a leak. There is no provi-
slowly but is not truly solid. It is restrictive to sion for recovering the methanol, Figure 8.
flow but does not plug.
Methanol injection rates are 1 to 1-1/2 bpd at
Properly applied, the glycol injection process the choke and 2-1/2 to 3 bpd at the crossover valve.
works very well. The quantity of ethylene glycol, The well produces approximately 8 MMCFPO through a
for exampl e, that is requi red to protect a system 13,000 foot flow1 ine at a wellhead temperature of
flowing at 1000 psig with gas saturated at lOO°F 130°F and a pressure of 3400 psi. Temperatures
which is chilled to minus 40°F is surprisingly upstream and dovmstream of the choke are estirnated
small -- 35 gallons per ~l~lSCF to be injected at a at 60°F and 20°F respectively. Since the initia-
7~ weight percent concentration and withdrawn at 60 tion of this injection program, no further hydrate
weight percent concentration. Injection of too problems have occurred.
much glycol will affect only the heat load on
the refrigeration system. Too little solution will Shell's LPS completion #S at Eugene Island
result in a freeze-up of an excessively diluted 14
331 was subjected to a batch treatment of meth-
glycol. anol down the tubing and continuous methanol injec-
tion upstream of the choke while the well was being
If glycol injection follows methanol. injec- tes ted over a two week peri od in trle fa 11 of 1977.
t ion, the methanol wi 11 be absorbed a nd removed The well is presently flowing again and producing
by the glycol. It can be recovered by fraction- enough liquids to preclude a lowering of tempera-
ating the alcohol-water vapors that comprise the ture sufficient to allow hydrate formation. Metha-
overhead stream from the glycol-water still of the nol is still injected occasionally at the Choke as
glycol regenerator unit. dictated by the actual gas stream being produced.
Glycol injection has never been popular as Panarctic Oils, Ltd. recently comv1eted an
production tool for two reasons. First is cost of Arctic Ocean offshore gas well in 200 foot water
a well-head facility. The LTX (low temperature deptl1 uti11fing a wet subsea tree and submarine
separation) system, which employs J-T expansion, is flowlines. A series of preventive measures have
less costly, has fewer illoving parts and requires been taken to preclude the formation of and to aid
less attendance. Second is the inevitable con- in the removal of hydrate plugs in the tubing and
tamination of glycol with salt. Here, the water flowlines. Two separate 6" diameter flowlines are
phase of the brine is distilled off, leaving the used, each provided vlith a different heating system
chlorides of sodium, potassium and calcium in the for evaluation and comparison, Figure 9. All hy-
glycol where it plates out on firetube surfaces, draulic control lines, the annulus line, flowlines
vastly increasing heat transfer so that firetubes and injection lines are housed within an 18"
burn out and fail in service. Salt can be removed diameter pipe bundle. One of the two 6" diameter
from glycol only by steam distillation or vacuum fl owl i nes is i nsul ated with polyurethane and pro-
distillation at considerable expense in fuel and vided with a 'Thermon' resistive heating system
1 abor. to allow melting of any hydrates which form. The
other flowline is not insulated and is provided
A third disadvantage should be mentioned. The with a 'Skin Effect Current Tracing' (SECT) heating
glycols are ,;]utually soluble in aromatic hydro- system, a procesfr ~o/eloped by Chisso Engineering
carbon 1 i qui ds. Where these, and to some extent of Tokyo, Japan. 0, The 4000' well produces 7'13
saturated cyclic hydrocarbon liquids, are present MMCFPD through 5-1/2" diameter tubing with a flow-
in condensates, the expensive glycol will be lost line temperature of 55°F. Hydrates are expected to
in the oil phase making the appl ication economi- form at 50°F and the ar:Jhient sea water temperature
cally unsound. If use of glycol injection is is 2yOF.
antiCipated, a PONA analysis of the liquids should
be obtained to indicate the absence or presence of The 'Thermon' system
18 is made up of three
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-____________________________________________ ~

451
the annular space filled with polyurethane. This pressures and low temperatures, both the cost and
system is suppl ied by a 25 KVA power source for avail abil ity are matters of concern. Although
each tape and heat output is estimated at 12 watts/ essenti ally a 11 methanol is was ted in present day
foot per tape. Flowline insulation was provided to operations, it is bel ieved that attention wi 11 De
keep the electrical power requirements for heating direc~ed to recovering methanol from the gas phase,
within the system's capabilities. the 011 phase and the water phase when the flow
reaches the platform (or shore station) where it
The SEC, system is based on the electrical can be separated and treated.
phenomenon by which alternating current is carried
on the surface of a magneti ca lly permeable con- Concerning the application of heat, there have
ductor wi thout penetrati ng deeply into or through been some significant improvements in electrical
the conductor. In the Panarctic appl ication two resistance heaters, both as Cal-rod units and
3/4" diameter 'heat tubes' are seam welded t~ one so-called "heat tape". The reliability of these
of the 6" diameter flowlines. These represent heaters and heat tapes has improved immeasurably in
redundant systems with only one required to provide recent years as demonstrated by the Thermon system
sufficient heating. An insul ated copper conductor mentioned above. Among the heating systems however,
is run inside each tube and electrically connected the SECT system appears to offer the most attrac-
to the tube at the far end. Both heat tube and tive al ternative at the present time. It requi res
copper wi re are connected to a 20" KVA power only small amounts of electrical current for opera-
source. 60 Hz alternating current is applied to tion and does not need constant attention and
the conductor and is returned along the inner sur- maintenance. It can also be used on long lengths
face of the heat tube, which becomes heated due to of flowline in remote locations. The Panarctic
metallic resistance. This heat is then uniformly tests shoul d serve to answer many questi ons per-
conducted to the flowline via the weldments. Heat taining to the SECT system's practical and economic
output of this system is estimated at 34 .vatts/ viability in remote offshore and Arctic production
meter. The system is controlled by remote tem- fields.
perature sensors spaced along the pi pe 1 i ne whi ch
energi ze the system any time the temperature fall s Heat can be applied in other ways that may
below a preset minimum. The system is electrically seem unconventional at first glance. For example,
isolated due to the confinement of the current to heat capacity of the hydrocarbon stream can be
the ID of the heat tube. In a test performed at the increased by recycl ing a compatible 1 iqui d, pre-
site, hydrate formation was induced in the flowline ferably one with large heat capacity, and certainly
and successfully melted util izing the SECT system. in sufficient quantity to build the heat supply to
the desired level. Fresh water, sea water or
Glycol/alcohol is injected into the gas stream oilfield brine have greater density and almost
at two points: downstream of the wing valves on the twi ce the heat capaci ty that gas, condensate
tree and immediately above the production packer. or crude oil exhibit. One of these waters might be
The latter location is serviced by a 1/4" diameter used, taking care not to heat it to a temperature
injection line run through the tubing hangar and where scale would form; or a portion of the liquid
strapped to the 5-1/2" tubing. condensate or crude oil could be warmed and recir-
cul ated. Some speci ally compounded heat transfer
NEW IDEAS fluid might be developed with large heat capacity,
unique fluid properties and salt contamination
There are many who contend that gas hydrates resistance which would make it well-suited to such
pose no significant production problem and that applications.
hydrate control technology was fully developed 25
years ago. While it is true that the basic tech- The recycle principle might be applied by
niques for gas hydrate control - application of using concentric flow 1 ines to pump the warm heat
heat, injection of ethylene glycol, and injection transfer fluid - water, oil, or special fluid -
of methanol - remain essentially unchanged, some through the annulus to a point downstream from the
substantial improvements have been made during the submerged wellhead where the concentric pipe would
last two decades. end. There the heat transfer fluid would commingle
with the gas, condensate, and any free water, then
Glycol injection is not as well suited as return to the producti on platform vi a the concen-
methanol for controlling gas hydrates in a high- tric, or inside line. In any of these recycle
pressure flow string or flow line because it is arrangements, the key to mi nimum heat transfer is
very eas ily CQntami na ted with sa lt, and the wa ter to lower the temperature di fference between the
it picks up must be evaporated in order to regen- fl u i d contents of the 1 i ne and its envi ronment.
~r~te ~nd recover the glycol. Nevertheless, glycol Extra heat is suppl ied only to be wasted through
1nJect10n has numerous applications and its tech- the pipe walls but in quantity sufficient to
nology is very well-defi ned. Glycol i njecti on maintain the temperature of the fluid mixture (well
would be enhanced by any process which will remove production and recycle fluid) safely above its
salt from the glycol and maintain its concentration hydrate poi nt.
at an acceptable level, say 0.5 percent. Contempo-
rary glycol recl a i mers vacuum di s ti 11 the glycol Perhaps these are some of the more important -
from the salt residue, a thermally-inefficient and and more urgent - of the new developments needed
labor intensive process that needs to be replaced. to refine and improve the techniques of gas hydrate
Some promise is shown for new methods involving control. As the industry moves into deeper waters
electro-dialysis. farther from shore and into the remote areas of the
offshore Arctic with the attendant use of subsea
Where large quantities of methanol may be completions and floating production systems de-
required to produce large wells flowing at high manded by these 1 ocat ions, costs associ ated with

452
c~rrently accepted hydrate control techniques are 10. Hammersch~i dt, E.G., "Preventi ng and Removi ng
llkely to become prohibitive. Economics, then, Hydrates 1 n Natural Gas Pipe Lines", Gas Age,
will eventually dictate the development of new vol. 83, no. 9, pp. 45-49, 63 (Apr. 27, 1939);
methods or improvements on older methods which can Gas, vol. 15, no. 5, pp. 30-34, 94 (1939); Oil
be adapted to meet the requirements of these new and Gas Journal, vol. 37, no. 52 pp. 66 69
envi ronments. 71,72 (1939). " ,
11. Pol derman, L.D., "The Glycol s as Hydrate Point
ACKNOWLEDGEMENTS: Depressants in Natural Gas Systems", Proc. Gas
Condo Conf., Univ. of Okla. Norman Okla.
The author wi shes to acknowl edge the i n- (1958). "
valuable assistance of r~essrs. Laurance Reid of 12. Bleakley, W.B., "Shell Reviews Underwater Well-
Laurance Reid Associates, Inc., and Norman Giese head Experience - and Likes What It Sees", Oil
of Marathon Oil Company in the preparation of and Gas Journal, vol. 69, no. 34, pp. 106, 108,
thlS paper. (Aug. 23, 1971).
13. Personal Communication, 1978.
REFERENCES AND BIBLIOGRAPHY: 14. Personal Communication, 1978.
15. Anon, "Offshore Arctic Gas: Can It Be Produced
1. ~amilerschmid~, E.G., "Formation of Gas Hydrates Economically?", World Oil, vol. 185, no. 5,
ln N3tural Gas Transmission Lines", Ind. Eng. pp. 106I-106M (October 1977).
~em., vol. 26, pp. 851-855 (Aug. 1934).
16. C~rso.n, ~,.B., "A New Method for Heat Tracing
2. Deaton, W.lvi. and Frost, E.M., "Gas Hydrates and Plpellnes , ASME Technical Paper No. 74-Pet.-35
Their Relation to the Operation of Natural Gas (1974).
Pi~e Lines·, U.S. Bureau of Mines Mono. 8, 1948.
17. Personal communication, Aug. 22, 1978.
3. Mc"arthy, E.L., Boyd, W.L. and Reid, L.S. "The 18. Burpee, W.E. and Carson, N.B., "Skin Effect
Water Vapor Content of Essentially Nitrogen- Current Tracing", Technical Paper presented at
Free Natural Gas Saturated at Various Condi- IEEE, 1975, Paper No. PCI 75-45.
tions of Temperature and Pressure," Trans. 19. Makogan, Yu 1. and Sarkis' yants G.A. "Pre-
A.I.M.E. (1950), 189,241. -- vention of Hydrate Formation in the Ext~action
4. McKetta, J.J. J-r:- and Wehe, A.H. "Use thi s and Transport of Gas", Moscow, 1966, National
Cha~t for Water Content of Natural Gases," Pet.
Resea rch Council of Canada Techni ca 1 Trans 1 a-
Reflner (1958),37, No.8, 153. -- tion No. NRCC-15476 (1976).
5. Hammerschmi dt, E.G. "Calcul ation and Determi n- 20. Bleakley, W.B., "Mobil's r-1ethanol Injection
ation of the Moisture Content of Compressed System Prevents Gul f Hydrate Formati on", Oi 1
Natural Gas," Western Gas (1933),2.,9-11,29. and Gas Journal, vol. 68, no. 49, pp. 65,"
6. Sharma, S.C. Equilibrium Water Content of (Dec. 1970).
Gaseous Mixtures, Ph.D. Dissertation Univer- 21. Hicks, R.H. et al, "A Prefabricated and Auto-
sity of Oklahoma (1969). ' mated Offshore Gas Production and Dehydration
7. Sharma, S.C. and Campbell, J.M., "Predict Faci 1ity", Paper presented at 3rd Ann. Offshore
Natural Gas Content ',vi th Total Gas Usage", Tech. Conf. Houston, TX, 1971, OTD Paper #1387.
paper presented at the 48th NGPA Annual Con- 22. Thomas, S.J., "Design of Offshore Gas Platform
vention, March 11-13, 1969, Dallas, Texas. Facilities", 9th Ann. Heart of Amer. Pipeline
8. McLeod, W.R. Applications of Molecular Refrac- Oper. &Maint. Inst. Mtg., Liberal, Kan., 1973,
tion to the Principle of Corresponding States. Select Paper.
Ph.D. Thesis, University of Oklahoma (1968). 23. Katz, D.L., et al. Handbook of Natural Gas
9. McLeod, W.R. and Campbell, J .M., "Predi cti on Engineering. McGraw-Hill Book Co. ,Inc. (1959).
of the Critical Temperature and Pressure, and 24. London, F. "The General Theory of Molecular
Density of Natural Gas", paper presented at Forces," Trans. Faraday Soc. (1937), 38, 8.
the 48th NGPA Annual Convention March 11-16
'-___19~_9"'_QtllJCls, l~)(as. ' _ _ _....J..._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
,

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

/" \ 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.