Preventing formation of hydrate plugs

The prevention of hydrate-plug formation and safe removal of hydrate plugs represent 70% of
deepwater flow-assurance challenges; the remaining 30% deal with waxes, scale, corrosion, and
asphaltenes. Before considering prevention of hydrate plugs, it is important to consider safety
problems involving hydrate plug removal.
Contents
1 Hydrate formation
2 Prevention methods
o 2.1 Example 1: hydrate formation in a pipeline
3 Drilling fluids and drillstrings
4 Technologies for hydrate-plug prevention
o 4.1 Dispersants or antiagglomerants
o 4.2 Kinetic inhibitors
o 4.3 Emulsifiers
o 4.4 Slurry flow
o 4.5 Insulation and heating
5 References
6 Noteworthy papers in OnePetro
7 External links
8 See also
Hydrate formation
What is a typical pressure at which hydrates will form? Hydrate-formation data, at a typical deep
seafloor temperature of 39F, were averaged for 20 natural gases (listed in Chap. 6 of Ref. 1
[1]
)
with an average formation pressure of 181 psia. Of the 20 gases, the lowest hydrate-formation
pressure was 100 psig for a gas with 7 mol% propane, while the highest value was 300 psig for a
gas with 1.8 mol% propane. Because systems usually operate at much higher pressures than 181
psia to obtain an economic energy density, hydrates are a possibility whenever small (n-butane
or smaller) hydrocarbons come into contact with water.
In Predicting hydrate formation, a hand calculation method, accurate to 75%, is given for hydrate
formation.
Prevention methods
There are four techniques to prevent hydrate formation:
Remove the free and dissolved water from the system with separators, glycol dehydrators,
molecular sieves, or other methods
Maintain high temperatures so that hydrates do not form
Maintain low pressures to keep all phases fluid
Inject some inhibitor to prevent hydrate formation
The first of these methods of prevention is the most reliable. It may not be viable, however, to
remove water because of remote locations, submersion, or other factors. For these reasons, flow
channels are frequently operated with inhibitor injection at the well, followed by dehydration at a
downstream point. The prediction accuracy of hydrate formation (for the second and third
prevention techniques) is acceptable for the energy industry, within 10% pressure for well-
defined fluids at temperatures greater than 32F and pressures below 5,000 psig. In the fourth
method, predictions can also indicate the free-water concentration of thermodynamic inhibitors,
such as methanol (MeOH), monoethylene glycol (MEG), or salts (in drilling fluids), which are
injected to compete with the hydrate structure for water molecules.
A hand calculation method for inhibitor concentration in the free-water phase is discussed later
in the chapter. Remember that inhibitors are also in small, but significant, concentrations in
vapor and liquid hydrocarbon phases. Because the total-flow fractions of these latter two phases
are so large, much of the injected inhibitor is consumed in the vapor and liquid hydrocarbon
phases. Inhibitor partitioning is also summarized with hydrate inhibition in Example 1.
Example 1: hydrate formation in a pipeline
Notz provided a case study of hydrate formation, shown in Fig. 1, for a Gulf of Mexico pipeline
fluid.
[2]
To the right of the diagram, hydrates will not form, and the system will exist in the fluid
(hydrocarbon and water) region. However, hydrates will form in the region at the left of the line
marked Hydrate-Formation Curve, and hydrate-prevention measures should be taken.
F
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[2]

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Hydrate inhibition occurs in the aqueous liquid, rather than in the bulk vapor or oil/condensate.
While most of the methanol dissolves in the water, a significant amount of methanol either
remains with the vapor or dissolves into the liquid hydrocarbon phase. Even though the
concentration of methanol in the vapor or liquid hydrocarbon is small, with low water amounts,
the majority of methanol may be consumed by the vapor or liquid hydrocarbons because the
hydrocarbon-phase fractions are much larger than the water-phase fraction.
In Fig. 1, Notz showed that the gas temperature increases from 30 to 45 miles with warmer
(shallower) water conditions. From 45 to 50 miles, however, a second cooling trend is observed
because of the Joule-Thomson gas-expansion effect. Methanol exiting the pipeline in the vapor,
aqueous, and condensate phases is usually counted as a loss because of the expense of
regeneration. However, a few companies are considering methanol recovery from the aqueous
phase.
Drilling fluids and drillstrings
Hydrates can plug drillstrings, blowout preventers, chokes, and other equipment, sometimes
requiring the abandonment of drilling operations because of safety constraints.
[3]
Water-based
drilling fluids are particularly susceptible to hydrate formation. The most important variable
affecting hydrate formation is the activity of the water, which is decreased by chemicals that
dissolve by bonding to water molecules. Water hydrogen bonds with alcohols or glycols or forms
very strong coulombic bonds with salt ions. These bonds effectively compete with water hydrate
bonds and prevent hydrate formation until much lower temperatures are reached, in the same
way that, in winter, ice is prevented by the addition of antifreeze (glycol) to a car radiator.
It is important to recognize that other nonsoluble drilling-fluid components (e.g., mud solid
particles or fluidizers) may affect the kinetics or rate of hydrate formation to determine how
rapidly hydrates will form or decompose. However, the hydrate-formation temperature and
pressure conditions are determined by water-molecule availability, as impacted by the water-
soluble components. An interesting example of a kinetically inhibited drilling fluid was recently
proposed by the use of lecithin, which prevented hydrate dissociation in an Arctic hydrate well
application.9 See the discussion on kinetic inhibition.
Technologies for hydrate-plug prevention
With the state-of-the-art methods of hydrate prevention, we turn to hydrate-plug prevention
technology. In addition to the conventional inhibitors MeOH and (acronym?)MEG, there are
three new types of hydrate inhibitors, sometimes called low-dosage hydrate inhibitors, which
were tested in the field during the 1990s. However, even with the low inhibitor concentrations,
for long tiebacks between wellheads and platforms, chemicals typically represent the most
expensive flow-assurance solution. Slurry flow and heating/insulation represent, respectively, the
fourth and fifth methods of hydrate prevention. A discussion of each method follows.
Deep ocean temperatures are fairly uniform at about 39F, except for some anomalous deepwater
current environments. Gulf of Mexico deepwater wellhead pressures represent some of the
highest in the world, at 15,000 psia. Such a combination of low temperatures and high pressures
provides high driving forces for hydrate formation. Hydrate-plug prevention requires a system
that can withstand a substantial subcooling (T = hydrate equilibrium temperature minus typical
deepwater temperature of 40F) of up to 35F; high-pressure pipelines have high hydrate-
equilibrium temperatures.
Dispersants or antiagglomerants
The object of these chemicals is to convert water into finely dispersed hydrate particles that can
be transported in a hydrocarbon liquid. These chemicals are typified as long-chain quaternary
ammonium salts, which easily form hydrates, replacing part of both the water and guest
frameworks. While three of the four branches of a quaternary nitrogen salt form as a part of the
hydrate structure, the fourth acts as a long tail that protrudes from the hydrate structure and
prevents agglomeration of the hydrates into a larger mass. There must be substantial hydrocarbon
liquid to disperse the hydrates; the maximum water volume is 40% of the total liquid phase.
The commercial use of dispersants began in the Gulf of Mexico in 2001, after laboratory studies
showing T = 45F subcooling.
[4]
These dispersants are particularly effective in hydrate-plug
protection upon line shut-ins and restarts. However, more-extensive field testing should be done.
As these inhibitors come into commercial use, environmental concerns for water purity will have
to be resolved.
Kinetic inhibitors
These chemicals are polymers with carbon backbones and pendant groups, which adsorb into
partially formed hydrate cages to keep the polymer anchored along the hydrate-crystal surface.
Growing hydrate crystals are forced to grow around the polymer, stabilizing the hydrates as
small particles in the aqueous phase. No liquid hydrocarbon need be present. Field tests have
shown these chemicals to be effective at subcoolings up to T = 20F, at dosages from 550 to
3,000 ppm in the water phase.
[5]
There is concern about these chemicals with respect to
performance on shut-in and restart; also, a substantial amount of hydrate normally forms upon
inhibitor failure.
Emulsifiers
These chemicals work by stabilizing small hydrate particles in an oil phase. Some oils contain
natural emulsifiers such that, even with favorable hydrate formation conditions, the water, which
might convert to hydrates, is stabilized within the oil phase.
[6]
To date, efforts to identify the
stabilizing components, remove them, and re-insert them in a noninhibited oil have been
unsuccessful. Artificial emulsifiers have been shown to be effective, preventing hydrate plugs in
flow loops.
[7]
There are concerns about these chemicals regarding the expense of tailoring them
for each oil application and the cost associated with emulsion breaking.
Slurry flow
This method uses the concept from Austvik
[8]
: hydrates that form in the fluid phases will not
adhere to the pipe wall. The ideal slurry system has the use of a subsea separator to remove the
majority of produced water and subsequent rapid heat exchange to seafloor temperatures in the
hydrate region, causing rapid hydrate formation as a liquid-phase slurry. It should be noted that
subsea/downhole separation will help every hydrate-prevention scheme, by removal of most of
the free-water fraction that forms hydrates.
A substantial industrial research effort is being spent on development of rapid techniques for
hydrate-slurry formation in the fluid. Slurry tests of several proprietary systems have been
sponsored by a consortium of energy companies. While this method is the most economical of
the hydrate-inhibition techniques, it is also the most ambiguous, in terms of likelihood of success.
In particular, there is a concern about agglomeration of hydrate particles during shut-ins.
Insulation and heating
Because fluids come from the reservoir at high temperatures, a lowcost solution is to preserve the
reservoir temperature (or add heat to the line) to keep the system out of the hydrate region. There
are three types of insulation listed in ascending order of cost: coatings applied to pipes; pipe-in-
pipe (PIP) or bundling; and vacuum-insulated pipes or pipes with insulating gases. Of the three
types, the last is so expensive that it is not in commercial use, and with the PIP method, the
repair of leaks is a concern. If a bare pipe is considered as the baseline cost, insulation can easily
double to quadruple the installed-pipe cost. At the 2000 SPE Flow Assurance Forum, it was
estimated that insulation was less efficient than expected approximately 50% of the time. For
example, a recent Gulf of Mexico flowline experienced an overall-heat-transfer coefficient of 2
Btu/(hr-ft
2
-F), while the design coefficient was 0.176 Btu/(hr-ft
2
-F), the latter being a typical
value for such applications.
In combination with insulation, line heating may be done through resistance or induction heating,
with practice favoring the former. Heating costs are very high, second only to chemical treatment,
and the power for heating is generated on platforms, where typically only 5 to 10 MW may be
available. There is evidence that short lines (< 20 miles) can be handled with heat management;
however, heating solutions may not be practical at line lengths greater than 50 miles.
References
1. API RP 10B, Recommended Practice for Testing Well Cements, 22nd edition. 1997.
Washington, DC: API.
2.
2.0

2.1
Notz, P. 1994. The Study of Separation of Nitrogen from Methane by Hydrate
Formation Using a Novel Apparatus. Paper IIIb presented at the 1993 Intl. Conference on
Natural Gas Hydrates; E.D. Sloan, ed. J. Happel, and M.A. Hnatow, Annals of the New
York Academy of Sciences, 715, 425.
3. Barker, J.W. and Gomez, R.K. 1989. Formation of Hydrates During Deepwater Drilling
Operations. J Pet Technol 41 (3): 297301. SPE-16130-PA.
http://dx.doi.org/10.2118/16130-PA
4. Frostman, L.M. and Przybylinski, J.L. 2001. Successful Applications of Anti-
agglomerant Hydrate Inhibitors. Presented at the SPE International Symposium on
Oilfield Chemistry, Houston, Texas, 1316 February. SPE-65007-MS.
http://dx.doi.org/10.2118/65007-MS
5. Fu, S.B., Cenegy, L.M., and Neff, C.S. 2001. A Summary of Successful Field
Applications of A Kinetic Hydrate Inhibitor. Presented at the SPE International
Symposium on Oilfield Chemistry, Houston, Texas, 13-16 February 2001. SPE-65022-
MS. http://dx.doi.org/10.2118/65022-MS
6. Fadnes, F.H. 1996. Natural Hydrate Inhibiting Components in Crude Oils. Fluid Phase
Equilibria 117: 186.
7. Palermo, T. et al. 1997. Pilot Loop Tests of New Additives Preventing Hydrate Plug
Formation. Proc., Multiphase Conference, Cannes, France, 133.
8. Austvik, T. 1992. Hydrate Formation and Behaviour in Pipes. PhD dissertation,
Norwegian University of Science and Technology, Trondheim, Norway.
9.