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HYDRATE CONTROL IN
DEEPWATER DRILLING
Gas hydrate formation during deepwater
offshore drilling and production is a wellrecognized operational hazard. In water
depths greater than 1,000 ft, seabed conditions of pressure and temperature become
conducive to gas-hydrate formation. In a
well-control situation, although the kick
fluid leaves the formation at a high temperature, it can cool to seabed temperature with
an extended shut-in period. With high
enough hydrostatic pressure at the mudline,
hydrates could form in the blowout-preventer (BOP) stack and choke and kill lines, as
has been observed in field operations.
The current practice in deepwater drilling
is to suppress the hydrate-formation temperature by use of highly saline drilling fluids formulated from NaCl or other salts.
This solution is applicable for the Gulf of
Mexico but insufficient for the conditions
encountered in Norwegian deep waters. At
extreme water depths or extremely low
mudline temperatures, this thermodynamic
inhibition alone may not be sufficient to
prevent hydrate formation. Instead, the use
of kinetic inhibitors or crystal modifiers, in
conjunction with thermodynamic inhibitors, may allow successful operations in
such an environment. The definition of
kinetic inhibitors (to distinguish them from
the classic thermodynamic inhibitors, such
as polar compounds and electrolytes)
comes from the effect of the chemicals on
the nucleation and growth of natural gas
hydrates, both of which are time-dependent, stochastic processes.
DEEPWATER DRILLING FLUIDS

A literature review indicated that 20 to 23

wt% NaCl/polymer drilling-fluid systems are
the most commonly used fluid formulations
for deepwater drilling. Drilling with these
systems has been successful in water depths
up to 7,500 ft. A major operator in the Gulf
of Mexico drilled wells in water depths ranging from 2,000 to 7,500 using mainly 20
wt% NaCl- and PHPA-based drilling fluids.
They experienced an average of one or more
gas kicks per well. In one incident, at a water
depth of 2,900 ft, difficulties disconnecting
the BOP were suspected to have been caused
by hydrate formation. It is clear that the
higher the density, the shallower the water
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depth where hydrates could exist, which

prompts the question of why it has been possible to drill in water depths up to 7,500 ft
without encountering hydrates. The following can be cited as a possible explanation:
(1) good well-control procedures, (2) little
or no gas kicks encountered, (3) the gas kick
is of very low-gravity gas (mostly methane),
(4) the effect of metastability, (5) high circulation rates and short shut-down periods,
and/or (6) the presence of other inhibitors
that are unaccounted for.
POL AR AND SURFACE-ACTIVE
ADDITIVES

Surfactants or alcohols are known to

decrease the surface tension of water, which
will enhance the rate of gas diffusion in the
bulk water during hydrate formation.
Hydrate-crystal growth is controlled by the
rate of gas diffusion from the bulk of the
water to the crystal surface. Consequently,
the presence of these compounds in the
water results in a rapid hydrate growth.
Anionic and nonionic surfactants were
found to cause a dramatic increase in the rate
of gas consumption on hydrate formation.
Alcohols and glycols are well-known
hydrate thermodynamic inhibitors. Alcohols
and glycols, when dissolved in aqueous solutions, normally hydrogen bond with the
water molecules and make it difficult for the
water molecules to participate in the hydrate
structure. However, their effect on the kinetics of hydrate formation is somehow different. Results show that the addition of alcohol or glycol actually enhances the rate of
hydrate formation, meaning that the pressure of small amounts of polar compounds is
worse than having none. One explanation
for this behavior was that polar molecules
act as templates for nucleation when they
exist at low concentration. Also, the presence of drilling-fluid additives like bentonite, barite, and lignite, with their tremendous surface area, could provide a surface on
which gas molecules could be adsorbed.
This behavior could cause the physical
entrapment of gas in quantities larger than
the amount of gas dissolved in the water.
The adsorbed gas that is dispersed within the
bulk water with the solid particles is readily
available for encapsulation in the hydrate

structure. This probably explains earlier

observations about the increase in the rate
and amount of hydrate formation in drilling
fluids formulated with these additives.
KINETIC INHIBITION AND
CRYSTAL MODIFIERS

The kinetic inhibition of gas hydrates generally refers to the process by which the
nucleation and growth of hydrate crystals
are altered (modified) by use of a low concentration of mostly polymeric- and surfactant-based chemicals. The inhibitors may
cause one or more effects: (1) delay the
appearance of the critical nuclei (kinetic
inhibitor), (2) slow the rate of hydrate formation (crystal modifier), and/or (3) prevent the agglomeration process (crystal
modifier). These chemicals do not disrupt
the thermodynamic equilibrium of the
hydrates. Currently, there is no clear understanding of how some of these chemicals
affect the growth or the morphology of the
hydrate. However, it is possible for these
chemicals to control the growth and the
agglomeration of the hydrate crystals by
adsorbing at the crystal/liquid interface. An
analogous approach is used by the ice cream
industry to control the growth of the ice
crystals. In both of these processes, mixing
(shear) plays an important role in mechanically smoothing the texture of the slurry.
Working with high-salinity drilling fluids, as in deepwater drilling, reduces the
options in selecting a good kinetic inhibitor
and crystal modifier. Another challenge
working with these inhibitors is their surface activity. Because of all the surface areas
present in drilling fluids, unless the
inhibitors have a specific affinity toward the
hydrate surface, one most likely will have
to cover all the solid surfaces before the
inhibitor starts to work. More work is
required before suitable kinetic inhibitors
or crystal modifiers for drilling fluids can
be recommended.
L ABORATORY MEA SUREMENTS

A thermodynamic testing program was conducted in two stages. In the first stage, aqueous solutions of selected thermodynamic
inhibitors formulated in seawater as the base
fluid were tested. This stage was necessary to
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establish a baseline for the best inhibitors to

be used in the subsequent drilling- and spotting-fluids formulations. In the second stage,
drilling-fluid formulations and two solids
free spotting fluids with the best combinations of the thermodynamic inhibitors
screened in the first stage were tested.
RESULTS

The tests produced a number of conclusions

covering the suitability and performance of
various fluid formulations. The following
are the generalized conclusions.
The most common drilling fluids used in
deepwater drilling are the 20 to 23 wt%
NaCl/polymer systems. Drilling with
these systems has been successfully
achieved in water depths up to 7500 ft.
On a weight basis, NaCl is the most effective hydrate inhibitor followed by KCl,
CaCl2, NaBr, sodium formate, and calcium nitrate.
Ethylene glycol had the best performance
among the glycols tested in this work.
Sodium formate increases the degree of
suppression over that of NaCl but has the
tendency to precipitate at low temperatures and high concentration.
A drilling fluid formulation was formulated from 5 wt% KCl+15 wt% NaCl+10
wt% ethylene glycol that has a maximum
hydrate suppression of 32.1F.
Two new solids-free spotting fluids were
developed. The first fluid did not form
hydrates under an extreme degree of subcooling, while the second suppressed the
hydrate temperature by 45.4F.
The synthetic drilling fluid with 30 wt%
CaCl2 in the internal phase did not form
hydrates under extreme subcooling.
However, hydrates did form when the concentration of CaCl2 was reduced to 15 wt%.
The organic phase of the synthetic
drilling fluid slightly suppresses the
hydrate equilibrium temperature but, at
the same time, increases the rate and
amount of hydrate formation resulting
from the higher gas solubility.
This article is a synopsis of paper SPE
38567, Hydrate Control During Deepwater Drilling: Overview and New Drilling
Fluids Formulations, by H. Ebeltoft,
Statoil; M. Yousif, IITRI Westport Technology Center; and E. Soergaard, Norsk
Hydro, scheduled for presentation at the
1997 SPE Annual Technical Conference
and Exhibition, San Antonio, Texas, 58
October. Please read the full-length paper
for additional details, illustrations, and references. The paper from which this synopsis was taken has not been peer reviewed.
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