Measurement and Prediction

of HydrateĆPhase Equilibria for

Reservoir Fluids
Bahman Tohidi, SPE, Ali Danesh, SPE, A.C. Todd, SPE, and R.W. Burgass, HeriotĆWatt U.

Summary effect of these compounds on the hydrate boundary can play an im-
Problems associated with gas hydrates in the production and trans- portant role in determining the hydrate-free zone.
portation of unprocessed wellstreams can be avoided by either pre- 3. For systems where the hydrate prevention approach is econom-
venting hydrate formation or allowing the formation of hydrates, ically nonviable, the transfer of hydrates as slurry in pipelines is an
but preventing their aggregation, and transporting them as slurry. attractive option. In this case, information on the amount and com-
The first approach, which is the current practice in the industry, position of different phases, particularly the amount of hydrates, is
can be made more cost effective by determining the hydrate-phase very valuable in the design and operation of transfer lines.
boundary more reliably. For the second approach, it is necessary to In this paper, after addressing the effect of electrolyte solutions
determine the amount of hydrates to be transported as slurry. and heavy hydrate formers on the hydrate boundary, the measure-
This paper reviews the effect of electrolyte solutions and heavy ment and prediction of the amount and composition of different
hydrate formers (such as benzene, cyclohexane, and methylcyclo- phases in the presence of gas hydrates are discussed.
pentane) on the hydrate-free zone and discusses new methods and
equipment for measuring the amount and composition of different Effect of Electrolyte Solutions on HydrateĆFree Zone
phases in hydrate-forming conditions. An in-house numerical mod- For efficient and economical pipeline design and operation, phase
el has been successfully employed for prediction of the hydrate-free equilibria, as well as the boundary of hydrate formation with and
zone and the compositional data. without salts and other chemical inhibitors, must be precisely
known. A recent survey4 among 15 operators in the North Sea
Introduction showed that two-thirds of them use a simple empirical correlation
Gas hydrates are solid crystalline compounds stabilized by the in- reported by Hammerschmidt5 in 1939 or engineering experience to
clusion of suitably sized gas molecules inside cavities formed by predict or design inhibitor injection rates. Despite using modern
water molecules through hydrogen bonding. They resemble ice in thermodynamic models to predict hydrate formation conditions in
appearance, but unlike ice, they may form at temperatures well the absence of inhibitors, operators are much less confident about
above the ice point. Gas hydrates have been recently reviewed by using them to determine inhibitor injection rates. This might be be-
Sloan.1 cause the reliability of thermodynamic models for predicting the ef-
One serious concern in the North Sea is that the subsea gathering fect of inhibitors, particularly salts, has not been fully demonstrated
networks and pipelines are prone to hydrate formation, giving rise for real reservoir fluids.
to pipeline blockage, operational problems, and other safety con- A reliable electrolyte model estimating the salt-inhibition effect
cerns. These can be avoided by either of the following two ap- may eliminate or significantly reduce the use of expensive chemi-
proaches. cals. Englezos and Bishnoi6 applied the Pitzer’s activity model to
1. Preventing the hydrate formation by heating and/or insulating calculate the activity of water in the water-rich phase and hence the
the pipe or by adding chemical inhibitors to operate, with a safety inhibition effect of single electrolyte solutions. In their model, they
margin, outside the hydrate boundary zone. neglected gas solubility in the water-rich phase by assuming that the
2. Allowing the formation of hydrates but modifying their growth change in water activity is only caused by the presence of salts. Aas-
to prevent aggregation of hydrate crystals and hence avoiding the berg-Petersen et al.7 used a combination of equation of state (EOS)
blockage by transporting hydrates as slurry. and electrostatic contribution to predict gas solubility in single elec-
The available information on hydrate formation and prevention trolyte solutions. They successfully modeled the gas solubility of
have been mostly generated by studies on gaseous systems in pure different gases in two single electrolyte solutions at reservoir tem-
water. Although the formation of hydrates in oil and condensate sys- peratures. Englezos8 and Tohidi et al.9 used different EOS in con-
tems or in the presence of electrolyte solutions is basically the same junction with the Aasberg-Petersen et al.7 approach to model the hy-
as that in gas mixtures and can be described similarly by numerical drate-inhibition effect of single electrolyte solutions.
models, there are significant differences between the systems that In a recent communication, Tohidi et al.10 used an approach simi-
warrant special considerations for oil-transfer lines. Three areas lar to Aasberg-Petersen et al.7 and developed a rigorous thermody-
pertinent to oil- and/or gas-condensate transportation are investi- namic model for predicting phase equilibria in electrolyte solutions
gated in this paper. and successfully applied it to hydrate calculations. They modeled
1. Oil wellstreams may contain a much higher water cut than gas the saline water phase with an EOS combined with the modified De-
systems that can prohibit the economical use of chemical inhibitors bye-Hückel11 electrostatic term, using only one adjustable parame-
to prevent hydrate formation. On the other hand, the water cut in oil ter known as the interaction coefficient. The water/salt interaction
wellstreams is formation water and the salts dissolved in it may in- coefficients have been determined with vapor pressure depression
hibit hydrate formation. Efficient modeling of the inhibition effect data at 373.15 K and freezing point depression of single salt solu-
of salts on hydrate formation will give the information required for tions and expressed as functions of temperature and salt concentra-
a more economical use of expensive inhibitors. tions. The gas/salt interaction coefficients have been optimized by
2. Oil- and gas-condensate systems contain a significant amount using gas solubility measurements in single electrolyte solutions.12
of intermediate hydrocarbon compounds that are currently being In extending the model to mixed electrolyte solutions, Patwardhan
considered as nonhydrate formers. Recent results2,3 indicate that and Kumars’13 approach was employed to relate the activity of wa-
some of these compounds are indeed strong hydrate formers. The ter in a mixed electrolyte solution to those of single electrolyte solu-
tions. Common salts, such as NaCl, KCl, CaCl2, Na2SO4, NaF,
Copyright 1996 Society of Petroleum Engineers
NaBr, MgCl2, SrCl2, BaCl2, and their mixtures, have been
modeled.10 Although the model was primarily developed to predict
Original SPE manuscript received for review Nov. 16, 1994. Revised manuscript received
Nov. 29, 1995. Paper peer approved Jan. 8, 1996. Paper (SPE 28884) first presented at the
the hydrate-inhibition effect of salt solutions, it could be employed
1994 SPE European Petroleum Conference, London, Oct. 25–27. to predict other thermodynamic properties such as water vapor pres-

SPE Production & Facilities, May 1996 69

sure and freezing point depressions caused by the presence of electro- TABLE 1—COMPOSITION (MOLE%) OF GAS MIXTURE, GAS
lyte solutions and gas solubility in saline water.10,12 CONDENSATE, AND BLACK OIL
Gas mixture{ Gas condensate¥ Black oil§
Heavy Hydrate Formers and HydrateĆFree Zone
C1 85.932 73.95 23.08
Until recently, in the oil and gas industry n-butane has been regarded
as the heaviest hydrate-forming compound, and anything heavier C2 6.754 7.51 4.09
than it was thought to be a nonhydrate former. Although this ap- C3 3.126 4.08 6.09
proach could be adequate for gaseous mixtures, it is not so for all oil- i-C4 0.708 0.61 2.18
and gas-condensate systems that contain significant amounts of hy- n-C4 0.882 1.58 4.51
drocarbon compounds heavier than n-butane. Some of these com- i-C5 – 0.50 2.33
pounds have an effective van der Waals’ diameter that theoretically
should allow them to enter the large cavities of structure-II gas hy- n-C5 0.571 0.74 3.31
drates. Furthermore, Ripmeester et al.2,3 have suggested the pres- C6 s – 0.89 4.30
ence of a third structure, called H, with cavities larger than those of C7 + – 7.19 50.11
structures I and II. This would allow the formation of hydrates by CO2 1.306 2.38 –
even larger molecules in the presence of a help gas. N2 0.721 0.58 –
While available models can accurately predict the hydrate equi-
{ Gravimetrically prepared in this laboratory.
libria for synthetic and simple mixtures, they are generally optimis- ¥ Bottomhole sample with a dew point of 42.62 MPa at 377.15 K.
tic—i.e., under predicting the hydrate zone—for oil and rich-gas § Black oil with a bubble point of 9.411 MPa at 373.15 K.
condensate. 14 This could be attributed to the presence of heavy hy-
drate-forming compounds in the above fluids. TABLE 2—COMPOSITION OF SYNTHETIC AND
The first equilibrium data on structure-H gas hydrates was re- FORTIES FORMATION WATER
ported for methane/adamantane by Lederhos et al.15 Mehta and
Sloan16,17 have reported structure-H hydrate data for some other Synthetic Forties
Formation Water Formation Water
heavy compounds with methane. In a recent communication,18 they
presented a thermodynamic model for structure-H hydrates and de- Salt wt% wt%
termined the Kihara parameters for four structure-H hydrate for- NaCl 8.460 6.993
mers. CaCl2 3.043 0.735
Danesh et al.19,20 and Tohidi et al.21 showed that benzene, me-
MgCl2 0.865 0.186
thylcyclopentane, and cyclohexane can form gas hydrates in the
presence of a help gas, such as methane. They also determined the KCl – 0.066
Kihara parameters for benzene and cyclohexane that can be used to SrCl2 – 0.099
predict their effect on hydrate-phase equilibria. In addition to meth- BaCl2 – 0.036
ane, they used nitrogen as a help gas in their experiments.
By taking into account the effect of heavy hydrate formers, which
are commonly regarded as nonhydrate formers (inhibiting hydrate Experiment
formation), improvement in hydrate calculations is expected, which
is particularly important for oil- and gas-condensate fluids. Set-Up. Two separate hydrate rigs (identified as Rig 1 and Rig 2)
with different designs were used in the experiments. A detailed de-
scription of the experimental set-up and test procedure is given else-
Amount of Hydrates
where.23 Central to both rigs is a high-pressure equilibrium cell.
As mentioned earlier, the transfer of hydrates as slurry in pipelines Test fluids are confined in the cell where its temperature is con-
using chemicals, or operating at conditions, that modify the growth trolled within "0.05 K. The pressure of the cell is monitored by
of crystals and prevent their aggregation is an attractive option for strain-gauge pressure transducers calibrated against a dead-weight
high water-cut systems (where water salinity is not enough for hy- tester with an estimated accuracy of "7 KPa.
drate inhibition). As a result, most investigators are involved in the
development/testing of growth-modifying chemicals22 or the study Test Fluids.
of the texture and transportability of the hydrates at flowing condi- 1. Methane from Air Products U.K. Ltd., instrument grade.
tions. However, developing/testing of a thermodynamic model for 2. Ethane, 99.9% pure.
predicting the amount of hydrates to be transferred as slurry is 3. Propane from Air Products, instrument grade.
equally important. 4. Iso butane, BOC Ltd. instrument grade 100%.
Although very little information on the growth modifiers has 5. Normal butane, BOC Ltd. instrument grade 100%.
been released to the public, the general view is that these chemicals 6. Normal pentane, Sigma-Aldrich 99)% high-pressure liquid
do not significantly affect the phase behavior of hydrate-fluid sys- chromatography (HPLC) grade.
tems. As the hydrates are finely dispersed in fluid phases, the as- 7. Carbon dioxide, research grade 99.9% pure.
sumption of equilibrium at pipeline conditions is, therefore, justi- 8. Nitrogen, BOC Ltd., 99.998 %.
fied. Lithium chloride is supplied by Fisons, specified laboratory reagent
There is, however, very little data available on the amount and (SLR) grade 98% minimum assay. Other salts are all AnalaR grade
composition of the phases in systems with hydrates, reflecting the and the solutions were made by weighing the salt and distilled water
difficulty of isolating and sampling different phases. The objective on a balance to the nearest 0.01 g. An oscillating “U” tube densitom-
of this study was to develop and evaluate a numerical model as an eter was used to check the solutions.
engineering tool to determine the amount of hydrates formed at
equilibrium conditions for transportation of unprocessed well- Methods.
streams in subsea pipelines. Determination of Hydrate Dissociation Points. The equilibrium
The experimental work initially investigated the formation of hy- cell was thoroughly cleaned and evacuated before being filled with
drates in a number of binary mixtures. Xenon was chosen as one of the sample. The hydrocarbon fluid to be tested was introduced to the
the components of the binary mixtures used in the compositional cell and at the same time the cell volume was increased until the de-
work for both practical and theoretical reasons.23 Later, the method sired pressure and volume was attained. An HPLC pump was then
was successfully adapted to a North Sea gas condensate in the pres- used to inject water into the base of the cell. With the cell contents be-
ence of pure water and methanol, as well as a multicomponent gas ing mixed, the temperature was then lowered to form hydrates. The
mixture in the presence of pure water and formation water. Tables formation of hydrates caused a rapid decline in the pressure and their
1 and 2 show the compositions of the fluids and the formation water. presence was confirmed visually where possible. The temperature

70 SPE Production & Facilities, May 1996

was then raised stepwise, allowing at least 3 hours for equilibrium to be large quantities of gas were released from the free-water phase (col-
reached at each temperature. The temperature, T, and pressure, P, were lected for AA analysis).
logged continuously and the equilibrium data was plotted on a scatter- Water Content of the Hydrate Phase. The water introduced into
gram. The point at which the slope of P vs. T plot sharply changed was the cell contained a very low concentration (approximately 2 ppm)
considered as the hydrate dissociation point. This was also confirmed of lithium chloride so it would not affect hydrate dissociation condi-
by visual observation. tions. As hydrates exclude salts, lithium chloride was used as a trac-
Compositional Tests. For these tests, the cell was loaded in the er for determining the quantity of water converted into hydrates by
same manner as described earlier. An accurately weighed amount monitoring the change in lithium concentration in free water. The
of sample was introduced to the cell in each test. The water injected water was analyzed with a Varian Spectra AA-10 atomic absorption
was also accurately weighed. Oil- and gas-condensate fluids were spectrometer. Potassium chloride with a concentration of 2,000 ppm
loaded above their saturation values. was used as an ionization suppressant for satisfactory results. For
The following method was adapted to form a significant quantity each analysis, a set of standards was used to calibrate the AA and
of “slushy” hydrates and to avoid water being trapped among hy- the original water introduced into the cell was also analyzed as a
drate crystals. The method employed was that after forming hy- control.
drates in the cell, the temperature was then raised to a point close to For electrolyte solutions, it was not possible to employ AA to find
dissociation where only a few hydrate crystals were present. The the amount of hydrates formed. Using the same principle regarding
temperature was then lowered slowly and cycled alternately until the exclusion of salts from hydrate structure, the change in density
the desired point was reached. was measured to determine the amount of water bonded.
With Rig 1, the cell contents were removed through the top valve
with the cell stationary and in the vertical position at a constant pres- Thermodynamic Description of the Phases
sure by simultaneously introducing mercury. The vapor phase was
The Valderrama24 modification of Patel and Teja (VPT) EOS with
collected, after passing through a separator, in a gas meter that had
the nondensity dependent (NDD)25 mixing rules as well as Peng-
previously been flushed with helium. When the first drop of water
Robinson26 EOS can be used for the calculation of fugacity of each
reached the separator, a second gas meter was attached before col-
component in the vapor, V, liquid hydrocarbon, L2, and water rich,
lecting the water phase. The released gas from the water phase, as
L1, phases. The hydrate, H, phases were modeled with the ideal solid
its pressure was reduced to atmospheric pressure, was collected in
solution theory,27 with the Kihara potential parameters. A detailed
the second gas meter. A sufficient quantity of water containing no
thermodynamic description of different phases is described else-
hydrates was removed for atomic absorption (AA) analysis. At this
where.10 Three- (L1-H-V) and four- (L1-L2-H-V) phase hydrate
point, the cell pressure was released and its temperature raised to
point and flash calculations were used to predict experimental data.
dissociate all hydrates present. The remaining water was then re-
moved for checking the final material balance.
When using Rig 2, the main difference from the previous proce- Results and Discussion
dure was that the phases were passed through a gas chromatograph Fig. 1 shows experimental and predicted dissociation conditions for
(GC) sampling loop at pressure. The cell pressure was maintained the gas mixture in the presence of pure water and Forties formation
by the use of a backpressure regulator. water. The maximum error in predicting potential hydrate formation
The gas composition of the vapor phase and the gas released from temperature is less than 0.5 K.
the hydrates and water were determined by a GC calibrated using Experimental and predicted hydrate-dissociation conditions for
gas standards gravimetrically prepared with compositions close to the North Sea black oil sample with pure water, Forties formation
the tested mixtures. water, synthetic formation water, and Forties formation water plus
Hydrates formed in real reservoir fluids were floating at the sur- 8.67 wt% methanol are depicted in Fig. 2. The heavy end of the
face of the water phase. Thus, we relied on the hydrates not passing black oil has been characterized as normal tetradecane by matching
through the small opening of the top valve when sampling the water the predicted and measured bubble points. In all cases, four phases
phase. This was noticed to be the case for the condensate tests, as no of hydrates, water, oil, and vapor are present, and despite the com-

Fig. 1—Hydrate dissociation conditions for a gas mixture.

SPE Production & Facilities, May 1996 71

 Fig. 2—Hydrate dissociation conditions for a black oil.

Fig. 3—Hydrate dissociation conditions for produced dry gas.

plexity of the system, the model predictions are in good agreement All the predicted results (except one high-pressure point at 20 wt%
with the experimental data. NaCl) are in good agreement with the experimental data.
Notz et al.28 have reported experimental hydrate data on a pro- Experimental and predicted hydrate dissociation conditions for
duced gas, a gas condensate, and a black oil sample in different pro- the gas-condensate sample in the presence of 8 wt% methanol solu-
duction scenarios. They have also examined the reliability of four tion is presented in Fig. 4. For the phase behavior model, the heavy
commercially available models. The models used empirical formu- end of gas condensate was characterized as normal tridecane to
match the measured molecular weight of C7+. A good agreement
las for predicting the inhibition effect of methanol or NaCl and none
is demonstrated.
had the option of predicting the inhibition effect of reservoir brine In relation to the effect of heavy hydrate formers, Fig. 5 shows the
or reservoir brine plus methanol.28 The thermodynamic model de- experimental and predicted dissociation conditions for methane,
scribed in this paper was evaluated against the previous data and methane/benzene, and methane/cyclohexane gas hydrates. The pre-
compared with the results predicted by other models.29 dictions are in good agreement with the experimental data. Note the
Fig. 3 presents the experimental and predicted hydrate conditions significant shift of the dissociation pressures to lower values caused
for the produced gas with distilled water and 20 wt% NaCl solution. by the presence of benzene or cyclohexane.

72 SPE Production & Facilities, May 1996

 Fig. 4—Hydrate dissociation conditions for the gas condensate in the presence of methanol.

Fig. 5—Effect of benzene and cyclohexane (both previously ignored) on the hydrate-phase boundary of methane.

Fig. 6 presents the hydrate-phase boundary of nitrogen, nitrogen/ Table 3 presents the results of the compositional tests on the gas
methylcyclopentane, and nitrogen/cyclohexane. As shown in the mixture in the presence of pure water in the L1-H-V three-phase re-
figure, the hydrate-free zone of nitrogen is reduced significantly be- gion. The predicted amount and composition of the vapor phase are
cause of the presence of methylcyclopentane or cyclohexane. in good agreement with the experimental values. The experimental
These observations agree with our previous results where the and predicted compositions of the gas in hydrates are in acceptable
contribution of heavy hydrate formers were neglected, resulting in agreement, with the exception of C2 and CO2. The reason for this
an over prediction of dissociation pressure of a live oil.14 Indeed, discrepancy is not yet clear, though it could be caused by exper-
if benzene, cyclohexane, and methylcyclopentane were not hydrate imental error or an error in calculating the C2 solubility in the free
formers, they would have been expected to expand the hydrate-free- water or the Kihara potential parameters used for C2. Comparison
zones. between the composition of the vapor phase and the gas in hydrates

SPE Production & Facilities, May 1996 73

 Fig. 6—Effect of methylcyclopentane and cyclohexane (both previously ignored) on the hydrate-phase boundary of nitrogen.

TABLE 3—RESULTS OF COMPOSITIONAL TESTS ON MULTICOMPONENT GAS MIXTURE IN THE PRESENCE

OF PURE WATER AND FORTIES FORMATION WATER
Test with Pure Water Test with Forties formation water
T=284.8 K, P=3.591 MPa T=284.5 K, P=5.366 MPa
Water=5.029 moles/mole gas mixture Water=4.987 moles/mole gas mixture
Composition of vapor phase and gas released from hydrates on a nitrogen and water-free basis
Vapor, Hydrate, Hydrate, Vapor Vapor, Hydrate, Hydrate,
Component Vapor Exp. Pred. Exp. Pred. Exp. Pred. Exp. Pred.
CO2 1.68 1.24 0.37 0.65 1.28 1.23 – 0.63
C1 88.57 89.22 67.89 63.52 87.43 88.47 69.90 65.00
C2 6.47 6.20 8.63 12.34 6.47 6.42 8.54 11.31
C3 1.67 1.60 17.29 17.35 3.04 1.99 16.69 17.35
i-C4 0.29 0.32 4.54 4.29 0.40 0.42 3.73 4.24
n-C4 0.80 0.79 1.28 1.85 0.85 0.84 1.14 1.47
n-C5 0.52 0.64 0.14 Nil 0.53 0.63 0 0
Experimental and predicted mole % of equilibrium phases
Phase Experimental Predicted Experimental Predicted
Vapor 14.85 14.88 15.06 15.35
Hydrate 11.63* 12.28 9.96 9.29
Water 73.52 72.84 74.98 75.36
Moles of gas 0.022 0.022 0.019 0.016
in hydrates
*Calculated by assuming 100% cage occupancy and using measured volume of gas in hydrates. Measurement for water bonded into hydrates failed due to the contamination in the
free water sample.

shows that, although the concentrations of light compounds are low- and the contribution of intermediate/heavy components of reservoir
er in the hydrate gas, the concentrations of the intermediates are sig- fluids on hydrate formation should be considered for accurate pre-
nificantly higher than those in the vapor phase. diction of hydrate-free zone. However, for the latter, the extent of
The predicted and measured results of the compositional tests on the effect on real reservoir fluids needs further investigation.
the gas condensate in the presence of water and methanol are pres- 2. New equipment and test procedures have been developed that
ented in Table 4. Calculated vapor compositions, mole% vapor, and not only allow reliable measurement of hydrate-free zone bound-
the amount of water converted to hydrates are in good agreement aries, but also the amount of hydrates formed to be transferred as
with the experimental data. slurry in pipelines.
3. Novel experimental data on the amount and composition of hy-
drates on synthetic and real reservoir fluids have been reported.
Conclusions 4. A numerical model has been developed and successfully eva-
1. The significance of electrolyte solutions and heavy hydrate- luated against hydrate data for different fluids, including North Sea
forming compounds on hydrate formation has been demonstrated. gas condensate and black oil samples at subsea transfer conditions.
The results suggest that the inhibition effect of electrolyte solutions In the comparison with four commercial packages, the model was

74 SPE Production & Facilities, May 1996

 TABLE 4—COMPARISON OF EXPERIMENTAL AND CALCULATED EQUILIBRIUM VAPOR PHASE COMPOSITIONS (MOLE%)
AND MOLES WATER CONVERTED TO HYDRATE FOR GAS-CONDENSATE
Pure Water Water/Methanol (30 Wt%)
T=283.25 K, P=2.848 MPa T=270.22 K, P=4.027 MPa
Moles water/moles gas-condensate=13.354 Moles water/moles gas-condensate=3.632
Component Experimental Predicted Experimental Predicted
N2 0.65 0.74 0.96 0.72
CO2 1.76 2.08 1.99 2.30
C1 86.46 86.76 86.88 86.76
C2 7.29 7.17 6.92 7.12
C3 2.03 1.92 1.94 2.17
i-C4 0.21 0.21 0.20 0.21
n-C4 0.69 0.72 0.41 0.48
i-C5 0.13 0.13 0.05 0.07
n-C5 0.15 0.15 0.08 0.08
C6 + 0.63 0.07 0.44 0.03
MeOH – – 0.13 0.04
H2 O – 0.05 – 0.01
Mole% vapor 5.30 5.26 13.68 14.57
Moles of water converted 0.042 0.046 0.048 0.046
to hydrates ("0.007) (" 0.005)

found as reliable with the extra benefit of thermodynamic consisten- 7. Aasberg-Petersen, K., Stenby, E., and Fredenslund, A.: “Prediction of
cy. The model showed its capability in calculating the hydrate-free High-Pressure Gas Solubilities in Aqueous Mixtures of Electrolytes,”
zone for complex systems where methanol plus formation water Ind. Eng. Chem. Res. (1991) 30, No. 9, 2180–2185.
were present. None of the commercial models are reported to be able 8. Englezos, P.: “Computation of the Incipient Equilibrium Carbon Diox-
ide Hydrate Formation Conditions in Aqueous Electrolyte Solutions,”
to predict the hydrate-free zone in the presence of mixed-electrolyte
Ind. Eng. Chem. Res. (1992) 31, No. 9, 2232–2237.
solutions, or the combined effect of methanol and formation wa- 9. Tohidi, B. et al.: “Gas Hydrates Modeling, Effect of Gas Solubility in
ter.29 Saline Water,” presented at 1993 Intl. Nonrenewable Energy Sources
5. The composition and amount of hydrates formed at equilibri- Congress, Tehran, Iran, Dec. 26–30.
um conditions can be predicted with an acceptable accuracy by the 10. Tohidi, B., Danesh, A., and Todd, A.C.: “Modeling Single and Mixed
developed model. Electrolyte Solutions and Its Applications to Gas Hydrates,” Chem.
Eng. Res. and Des. (May 1995) 73(A), 464–472.
Nomenclature 11. Debye, P. and Hückel, E.: “Theory of Electrolytes: Freezing Point Low-
ering and Related Phenomena,” Physik Z. (1923) 24, No. 9, 185–206.
H+ hydrate phase 12. Tohidi, B. et al.: “Gas Solubility in Saline Water and Its Effect on Hy-
L1+ water-rich phase drate Equilibria,” presented at the 1995 Intl. Offshore and Polar Engi-
L2+ liquid hydrocarbon phase neering Conference (ISOPE-95), the Hague, the Netherlands, June
P+ pressure 11–16.
T+ temperature 13. Patwardhan, V.S. and Kumar, A.: “A Unified Approach for Prediction
of Thermodynamic Properties of Aqueous Mixed-Electrolyte Solu-
V+ vapor phase
tions. I. Vapor Pressure and Heat of Vaporization,” AIChE J. (1986) 32,
No. 9, 1419.
Acknowledgments 14. Avlonitis, D.A. et al.: “The Formation of Hydrate in Oil-Water Sys-
Different parts of this work were supported by the Engineering and tems,” Proc., 4th Intl. Conference on Multiphase Flow, Nice (1989) 15.
Physical Sciences Research Council (ESPRC) through its agency 15. Lederhos, J.P. et al.: “Structure H Clathrate Hydrate Equilibria of Meth-
ane and Adamantane,” AIChE J. (1992) 38, No. 7, 1045–1048.
the Marine Technology Directorate (MTD) Ltd., BP Research and
16. Mehta, A.P. and Sloan, E.D.: “ Structure H Hydrate Phase Equilibria of
Exploration, Chevron Petroleum U.K. Ltd., Health and Safety Methane + Liquid Hydrocarbon Mixtures,” J. Chem. Eng. Data (1993)
Executive, Esso E&P U.K. Ltd., Amerada Hess Ltd., Deminex U.K. 38, No. 4, 580–582.
Oil and Gas Ltd., Marathon Oil U.K. Ltd., and Shell U.K. E&P, 17. Mehta, A.J. and Sloan, E.D.: “Structure H Hydrate Phase Equilibria of
which is gratefully acknowledged. Paraffins, Naphthenes, and Olefins with Methane,” J. Chem. Eng. Data
(1994) 39, 887–890.
References 18. Mehta, A.J. and Sloan, E.D.: “A Thermodynamic Model for Structure-H
Hydrates,” AIChE J. (1994) 40, No. 2, 312–320.
1. Sloan, E.D.: Clathrate Hydrates of Natural Gases, Marcel Dekker Inc., 19. Danesh, A. et al.: “Benzene Can Form Gas Hydrates,” Chem. Eng. Res.
New York City (1990). and Des. (July 1993), 71(A), 457–459.
2. Ripmeester, J.A. et al.: “A New Clathrate Hydrate Structure,” Nature 20. Danesh, A. et al.: “Hydrate Equilibrium Data of Methyl Cyclo-Pentane
(1987) 325, 135. with Methane or Nitrogen,” Chem. Eng. Res. and Des. (March 1994)
3. Ripmeester, J.A., Ratcliffe, C.I., and McLaurin, G.E.: “The Role of 72(A), 197–200.
Heavier Hydrocarbons in Hydrate Formation,” AIChE Spring Meeting, 21. Tohidi, B. et al.: “Equilibrium Data and Thermodynamic Modeling of
Session 44, Hydrates in the Gas Industry, April 1991. Cyclohexane Gas Hydrates,” Chem. Eng. Sci. (1996) 51, No. 1,
4. Report prepared by Atomic Energy Authority (AEA) Technology for 159–163.
the Health and Safety Executive (HSE), “A Critical Review of Hydrate 22. Behar, E. et al.: “Plugging Control of North Sea Production Facilities by
Formation Phenomena,” OTH 93 413, HSE Books, Crown copyright, Hydrates,” Annals of the New York Acad. of Sci. (1994) 715, 94–105.
(1994). 23. Tohidi, B. et al.: “Hydrates Formed in Unprocessed Wellstreams,” paper
5. Hammerschmidt, E.G.: “Gas Hydrate Formations,” Gas (1939) 15, No. SPE 28478 presented at the 1994 SPE Annual Technical Conference and
5, 30. Exhibition, New Orleans, Sept. 25–28.
6. Englezos, P. and Bishnoi, P.R.: “Prediction of Gas Hydrate Formation 24. Valderrama, J. O.: “A Generalized Patel-Teja Equation Of State for Po-
Conditions in Aqueous Electrolyte Solutions,” AIChE J. (1988) 34, lar and Nonpolar Fluids and Their Mixtures,” J. Chem. Eng. Japan
1718–1721. (1990) 23, No. 1, 87–91.

SPE Production & Facilities, May 1996 75

25. Avlonitis, D., Danesh, A., and Todd, A.C.: “Prediction of VL and VLL with National Iranian Oil Co. He holds a BS degree in chemical
Equilibria of Mixtures Containing Petroleum Reservoir Fluids and engineering from Abadan Inst. of Technology, and a PhD deĆ
Methanol with a Cubic EoS,” Fluid Phase Equilibria (1994) 94, gree in petroleum engineering from Heriot-Watt U. Ali Danesh
181–216. is a professor in the Dept. of Petroleum Engineering at HeriotĆ
26. Robinson, D.B. and Peng, D-Y.: “The Characterization of the Heptane Watt U. in Edinburgh. He holds a BS degree in petroleum engiĆ
and Heavier Fractions for the GPA Peng-Robinson Programme,” GPA neering from Abadan Inst. of Technology and a PhD degree in
Research Report 28 (1978). chemical engineering from Manchester U. His research interests
27. van der Waals, J. H. and Platteeuw, J. C.: “Clathrate Solutions,” Adv. include reservoir fluids and flow in porous media, and he
Chem. Phys. (1959) 2, No. 1, 1–57. teaches courses in PVT phase behavior and multiphase flow in
28. Notz, P.K., Burke, N.E., and Hawker, P.C.: “Measurement and Predic- pipes. Adrian C. Todd is a professor and head of the Dept. of PeĆ
troleum Engineering at HeriotĆWatt U. He is involved in research
tion of Hydrate Formation Conditions for Dry Gas, Gas Condensate, and
of oilfield scale, phase behavior of reservoir fluids, water injecĆ
Black Oil Reservoirs,” paper OTC 6745 presented at the 1991 Annual
tion, and stressĆrelated rock characterization. He holds BS and
Offshore Technology Conference, Houston, May 6–9. PhD degrees in chemical engineering from Loughborough U. of
29. Tohidi, B. et al.: “Phase Equilibria in the Presence of Saline Water Sys- Technology. Rhoderick W. Burgass is a research associate in the
tems and Its Application to the Hydrate Inhibition Effect of Produced Dept. of Petroleum Engineering at Heriot-Watt U. working in the
Water,” paper SPE 28884 presented at the 1994 European Petroleum PVT group. His main research work has been in gas hydrates. He
Conference, London, Oct. 25–27. holds an MPhil degree in petroleum engineering from Heriot-
Watt U.
SI Metric Conversion Factors
°F (°F)459.67)/1.8 +K
psi 6.894 757 E)00 +kPa

Bahman Tohidi is a senior research associate in the Dept. of PeĆ

troleum Engineering at Heriot-Watt U., supervising the research
related to reservoir fluids and gas hydrates. Previously, he was Tohidi Danesh Todd Burgass

76 SPE Production & Facilities, May 1996