Gas Hydrates and Offshore Drilling

Predicting the Hydrate Free Zone

K.K. ØSTERGAARD, B. TOHIDI,a A. DANESH, AND A.C. TODD
Department of Petroleum Engineering, Heriot-Watt University,
Riccarton, Edinburgh EH14 4AS, United Kingdom

ABSTRACT: A well-recognized hazard in offshore drilling is the formation of

gas hydrates in the event of a hydrocarbon flow into the well bore from the res-
ervoir (e.g., a kick). This could potentially block the BOP stack, kill lines and
chokes, obstruct the movement of the drill string, and cause serious operation-
al and safety concerns. Currently, salts are added to the drilling fluids to inhib-
it hydrate formation in offshore and arctic drilling. For deep water drilling,
even saturated saline solutions may not provide the required protection, unless
combined with chemical inhibitors. The reported experimental data on gas
hydrate formation in drilling fluids are very limited and in some cases incon-
sistent. The available predictive methods are generally empirical correlations
based on limited data and with limited application. In this presentation, a ther-
modynamic model capable of predicting the hydrate free zone in the presence
of salts (NaCl, KCl, CaCl 2, NaBr, Na-formate, etc.) and chemical inhibitors
(methanol, ethanol, ethylene glycol, glycerol, etc.) is presented. The model
developed has been employed to predict the hydrate free zone in drilling fluids
designed for offshore and deep water applications. The predictions are com-
pared with experimental data and an empirical correlation, demonstrating the
reliability of the thermodynamic model.

INTRODUCTION

In offshore drilling, the pressure of the drilling fluid and the relatively low seabed
temperature could provide suitable thermodynamic conditions for the formation of
hydrates in the event of a kick. This can cause serious well safety and control prob-
lems during the containment of the kick. Hydrate formation incidents during off-
shore drilling are rarely reported in the open literature, partly because they are not
recognized. However, two cases have been reported,1 where the losses in rig time
were 70 and 50 days, respectively.
A recent study2 showed that oil based drilling fluids inhibit hydrate formation by
2.7 to 5.5°C in a pressure range of 500 to 4,600 psig (lower inhibition at higher pres-
sures), but they adversely affect the required degree of subcooling for hydrate for-
mation, the rate of hydrate formation, and possibly the extent of hydrate formation.
These adverse effects, together with the cost and the environmental concerns in
using oil based drilling fluids, significantly affect the applicability of oil based drill-
ing fluids in offshore operations.

aTelecommunication.Voice: +44 131 451 3672; fax: +44 131 451 3127.
bahman.tohidi@pet.hw.ac.uk

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The formation of gas hydrates in drilling fluids can cause problems in at least two
ways:3
1. Gas hydrates can form in the drill string, blow-out preventer (BOP) stack, choke,
and kill lines. This could result in potentially hazardous conditions—flow blockage,
hindrance to drill string movement, loss of circulation, and even abandonment of
the well.
2. Since gas hydrates consist of more than 85% water, their formation can remove
significant amounts of water from the drilling fluid, hence, changing the properties
of the fluid. This could result in salt precipitation, an increase in fluid weight, or the
formation of a solid plug, particularly for water based drilling fluids.
The hydrate formation conditions of a kick depend on the composition of the kick
fluid, as well as on the pressure and temperature of the system. For a typical natural
gas composition, it can be equivalent to 120 m of water at a seabed temperature of
4°C. Salts are generally added to avoid hydrate formation in drilling fluids. As a rule
of thumb, the inhibition effect of a saturated saline solution is not adequate for avoid-
ing hydrate formation in water depths of greater than 1,000 m.1 Therefore, a combi-
nation of salts and chemical inhibitors that can provide the required inhibition should
be used.
The experimental data on gas hydrate formation in drilling fluids are very limited
and in some cases inconsistent. The available predictive methods are generally em-
pirical correlations based on limited data and with limited application. In production,
transmission and processing of reservoir fluids, the available thermodynamic meth-
ods can predict hydrate formation temperature with an accuracy better than 1 K,4
whereas in predicting hydrate formation conditions in drilling fluids, the available
empirical methods have much lower accuracy (by almost one order of magnitude).
The error in predicting the hydrate free zone in drilling fluids can result in either
formation of hydrates or over-inhibited drilling fluids. The former could have serious
operational and safety consequences and the latter could increase the cost of opera-
tion, reduce the flexibility in preparing the drilling fluid, and increase the possibility
of salt precipitation and correlation. Recent studies showed that the economics and
safety of offshore drilling operations can be significantly enhanced by improving the
accuracy of predictive methods in estimating hydrate formation conditions in water
and oil based drilling fluids.
In this presentation, available experimental data on water freezing point depres-
sion of salts and chemical inhibitors, together with available vapor–liquid equilibri-
um (VLE) data, have been used to extend an in-house thermodynamic model to salts
and chemical inhibitors commonly used in drilling fluids. The predictions of the
resulting thermodynamic model are compared with experimental data and an empir-
ical correlation to demonstrate the reliability and superiority of the thermodynamic
model.

THERMODYNAMIC MODELING

The Heriot-Watt university hydrate model, HWHYD, uses the Valderrama modi-
fication of the Patel and Teja (VPT) equation of state (EoS) with a non-density de-
pendent (NDD) mixing rule to model all fluid phases. Ice is modelled as a subcooled
ØSTERGAARD et al.: OFFSHORE DRILLING 413

liquid. The hydrate phases are modelled by the solid solution theory of van der
Waals-Platteeuw, as implemented by Parrish and Prausnitz. The Kihara model
for spherical molecules is applied in order to calculate the potential function for
compounds forming the hydrate phases. The general multiphase flash routine, as
described by Cole and Goodwin, is adapted in the model.
Salts are modelled by combining the EoS with a modified Debye-Hückel electro-
static term with only one binary interaction parameter. Water vapor pressure depres-
sion data at 373.15 K and freezing point depression data of single electrolyte
solutions have been used to optimize water–salt interaction parameters, which have
been correlated with salt concentration and temperature. No binary interaction
parameters between salts and chemical inhibitors have been employed. A detailed
description of the numerical modelling approach is provided elsewhere.5
Binary interaction parameters (BIP) between each chemical inhibitor and water
have been optimized, using freezing point depression and VLE data. Where avail-
able, VLE data have been used to optimize BIP between chemical inhibitor and com-
ponents, which can be present in reservoir fluids at high concentrations (i.e.,
methane, ethane, propane, carbon dioxide, and nitrogen).

RESULTS AND DISCUSSION

TABLE 1 lists the salts and chemical inhibitors available in the HWHYD model.
The list covers components common to sea and formation water, as well as inhibitors
frequently used in drilling and production. The hydrate inhibition effects of the
above compounds are compared in F IGURE 1. The figure presents the predicted
hydrate inhibition effect of 10 wt% aqueous solutions of the compounds listed in

TABLE 1. Salts and chemical inhibitors in HWHYD

Salts Chemical inhibitors
NaCl methanol
KCl ethanol
CaCl2 monoethylene glycol (MEG)
Na2SO4 diethylene glycol (DEG)
NaF triethylene glycol (TEG)
KBr glycerol
MgCl2
SrCl2
BaCl2
NaBr
Na-Formate
K-Formate
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FIGURE 1. Effect of 10 wt% of salt or chemical inhibitor on the hydrate free zone of
methane hydrates.

TABLE 1. As shown in the figure, the inhibition effect ranges from about 1 K for
10 wt% TEG to almost 6.5 K for 10 wt% MgCl2.
Below, the predictions of the developed thermodynamic model (HWHYD) are
compared with experimental data and available correlations. The objective is to eval-
uate the accuracy and reliability of the thermodynamic model in predicting the
hydrate-free zone in the presence of salts and chemical inhibitors commonly used in
offshore drilling.

Hydrate Prevention in Drilling Using Formate Salts

Formate brines have been extensively investigated for their use as drilling and
completion fluids.6 They were developed and proved to meet the design criteria
required for deep slim-hole drilling; for example, cover large density range, very low
crystallization temperatures, low corrosion potential, and are easily recyclable. Fur-
thermore, formate brines also have the advantage of inhibiting hydrate formation.
FIGURE 2 presents the experimental methane hydrate free zone in the presence of
pure water and 10, 20, and 30 wt% aqueous solution of potassium formate. Some
scattering in the experimental data is observed, especially for 10 wt% potassium for-
mate at high pressure. Two sets of predictions are also shown in F IGURE 2, that of
the HWHYD model and values predicted by Fadnes et al.8 A good agreement can be
seen between the predictions from the HWHYD model and the experimental data,
even at high salt concentrations.
ØSTERGAARD et al.: OFFSHORE DRILLING 415

FIGURE 2. Experimental and predicted hydrate free zone of methane in the presence
of potassium formate.

Hydrate Prevention in Drilling Using Glycerol

Glycerol is commonly used in water based drilling fluids to suppress the forma-
tion of gas hydrates. Drilling fluids based on salt–glycerol mixtures have proven to
meet property requirements for deep water drilling as well as being cost-effective.9
FIGURE 3 presents the experimental and predicted hydrate free zones for methane
hydrates in the presence of pure water, and glycerol/water solutions with 25 wt% and
50 wt% glycerol. A good agreement between the experimental data and the
HWHYD predictions can be observed, demonstrating the success of the thermody-
namic model.

Comparison of HWHYD and Empirical Correlation

Yousif and Young11 proposed a correlation to predict the inhibition of gas
hydrates in drilling fluids due to the presence of salts and glycerol. They correlated
the hydrate temperature suppression with mole fraction and degree of ionization for
chemical inhibitors and salts, respectively. The correlation is based on experimental
hydrate equilibrium data of drilling fluids containing various amounts of NaCl,
NaBr, KCl, CaCl2, and glycerol measured in five different laboratories. The correla-
tion proposed by Yousif and Young includes higher concentrations of inhibitors than
the original Hammerschmidt equation.12
FIGURE 4 shows the experimental and predicted hydrate free zone for a natural
gas in the presence of saline water. Both the thermodynamic model developed in this
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FIGURE 3. Experimental and predicted hydrate free zone of methane in the presence
of glycerol.

FIGURE 4. Experimental and predicted hydrate free zone of a natural gas in the pres-
ence of saline water.
ØSTERGAARD et al.: OFFSHORE DRILLING 417

work (HWHYD) and the correlation proposed by Yousif and Young have been used
to predict the hydrate free zone. The predictions from the correlation are in good
agreement with the experimental data for the 15 wt% CaCl2 solution, whereas sig-
nificant deviations are observed for the 23 wt% CaCl2 solution (about 5 K). The
HWHYD predictions are in good agreement with the experimental data for all con-
centrations, demonstrating the reliability of the thermodynamic model.
FIGURE 5 presents the experimental and predicted hydrate-free zone for a gas
mixture in the presence of 2.5 wt% NaCl and 10, 35 and 60 wt% glycerol. The
HWHYD thermodynamic model predicts the hydrate free zone consistently and with
a maximum deviation of about 1 K. The predictions from the correlation are incon-
sistent and show a deviation of about 5.5 K at 2.5 wt% NaCl and 35 wt% glycerol,
whereas they are in good agreement with the experimental data at 2.5 wt% NaCl and
10 and 60 wt% glycerol. The latter concentration of inhibitor, however, is well above
the concentrations used to develop the correlation.
The error in prediction of the hydrate free zone in drilling fluids could result in
either over-inhibited drilling fluids (FIG . 4) or formation of gas hydrates (F IG . 5). The
latter could have serious operational and safety consequences, and the former could
increase the cost of operation, reduce the flexibility in preparing the drilling fluid
(e.g., low density mud), and increase the possibility of salt precipitation and corro-
sion. FIGURE 6 shows examples of estimated quantities of salt or chemical inhibitor
required to compensate for the inaccurate predictions in the hydrate free zone, per
100 barrels of water in drilling fluid. For example, in the case of 5.5 K deviation in

FIGURE 5. Experimental and predicted hydrate free zone of a gas mixture in the pres-
ence of NaCl/glycerol solutions.
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FIGURE 6. Amount of inhibitor required to compensate for deviation in predictive

method.

FIGURE 5, an extra 4,000 kg of glycerol per 100 barrel of water is required to com-
pensate for the error.
The correlation due to Yousif and Young11 is based on thermodynamic principles.
It is believed that some of the discrepancies observed between the correlation pre-
dictions and the experimental data at some salt/chemical inhibitor concentrations are
partly due to inaccurate experimental data. Recently, a number of publications13–15
have recommended experimental techniques that could improve the reliability of
experimental data, particularly hydrate phase free zone measurements in the pres-
ence of salts and chemical inhibitors.

CONCLUSIONS

A comprehensive thermodynamic model, capable of predicting the hydrate-free

zone in the presence of salts and chemical inhibitors commonly used in drilling flu-
ids, has been described. Easily available water freezing point and/or vapor pressure
depression data have been used to evaluate the parameters required for modelling
salts and chemical inhibitors.
The predictions of the thermodynamic model have been compared with experi-
mental hydrate dissociation data for gas mixtures in the presence of high concentra-
tion of salts and/or chemical inhibitors, simulating drilling fluids for deep water
operations, demonstrating its reliability.
ØSTERGAARD et al.: OFFSHORE DRILLING 419

The predictions of the thermodynamic model have also been compared with a
correlation designed to predict hydrate point suppression in drilling fluids. The com-
parison demonstrated the superiority of the comprehensive thermodynamic
approach over the empirical correlation. However, it is likely that the correlation has
been partly based on inconsistent experimental hydrate data.
Improved accuracy in predictive techniques could reduce the cost and improve
the safety of drilling operation for deep water applications.

REFERENCES

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