ABC Guide To Gas Hydrates Awareness: Revision: 1.0 Oct 2002

ABC Guide to Gas Hydrates Awareness
Contents
Contents
What is Water?
Density of Water
3
5
From solid to liquid
Universal Solvent
Methane
What are hydrates?
8
9
Physical and chemical properties of gas hydrates
Composition of gas hydrates
Appearance and texture of gas hydrates
10
Hydrate formation in wells

How hydrates form during shutin conditions?
12
12
How do hydrates form during cold production?
13
How do Hydrates form during Interventions?
13
Impact of Hydrates
How do hydrates impact Well Productivity?
Hydrate Models
14
14
15
Modeling the potential for hydrate formation
15
Are hydrates just associated with gas wells?

What is the difference between prevention
and remedial action?
General Prevention Guidelines
16
16
Good Practices for Prevention

Operational Prevention Procedures
17
17
18
Removal of Free Water
18
Maintaining High Temperatures
18
Maintaining or Reducing Pressures
19
Field Experience
19
Chemical
20
Heat Method
23
Hydraulic
23
Revision: 1.0 Oct 2002

Contents
Components of the Well Design for Hydrate Control
Subsea Wellhead & Tree
25
25
Riser / BOP Stack
25
Completion String
26
DST String
26
Surface Controlled Subsurface Safety Valves
26
Chemical Injection Lines
28
Safety Issues
29
Hydrate Formation in Flowlines and Pipelines
29
Case Examples
30
Example 1
30
Example 2
31
Example 3
31
Example 4
32
Example 5
32

Section 1
What is Water?
Water is truly a remarkable substance. It is the most common
compound on the surface of the earth, occurring as anything from tiny
dewdrops to vast oceans. It is the basis of all life on earth - life originally emerged from water, and water plays a role in all living processes.
And its special nature means that it plays a part in a vast number of
chemical reactions, from rusting to
Hydrogen is the smallest atom
nuclear power production. Its
of all. It consists of one proton
unusual properties also permit the
(positive) at its core, and one
formation of "Gas Hydrates", so an
electron (negative) revolving
understanding of the basics of water
around it in a 3-D shell: it is
will help us understand the formation
very light and always changing.
of gas hydrates.
One of the "many" unusual things
about water is that it commonly
occurs in three phases of matter that is solid, liquid and a gas. Few
other substances are ever found
naturally in more than two states.
H 20
Hydrogen
Water is a simple compound of two simple and

abundant elements - a dipole molecule consisting of
two positively charged atoms of hydrogen (H) and one
negatively charged atom of oxygen (O).
The formula H2O may be simple but the structure of water is complex.
The atoms in water are said to be bonded together "covalently". This
means that the hydrogen and oxygen atoms share electrons. Hydrogen
atoms only have one electron, so each hydrogen atom donates its
electron to the oxygen
Oxygen atoms are heavier than hydrogen
atom and receives one
atoms, with 8 protons in its nucleus and 8
electron in return. The
electrons revolving around in two outer
arrangement of these
shells.
shared electrons has an
Because its
important effect on
outer shell
water's chemical propis incomerties. The shared elecplete as it
trons are not located
would
evenly within the
Oxygen
prefer to
molecule, but clustered
contain the 8 electrons, and oxygen atom
towards one end, away
is keen to link up with other atoms with
form the centre of the
one or two electrons to spare.
hydrogen atoms.
Electrons are more nega-

Section 1
tively charged so this makes one end of
the molecule more negatively charged
that the other. This difference in
charge is called polarity, so that is why
water is said to be a polar compound.
One effect of this is that the negative
end of one water molecule is often
drawn to the positively charged
nucleus of a neighbouring hydrogen
H 2O
atom - because unlike charges attract
each other. This is called a "hydrogen
bond". These bonds mean that water molecules will cluster together. It
is this clustering that gives water some of its unusual properties.
Hydrogen bonds are strong enough to
bind, but weak enough to break easily.
Molecules of other substances tend to
take on a regular shape, building up
with neat and even spacing between
atoms. In a water molecule the two
atoms of hydrogen always aim to bond
with the oxygen atom in a very precise
and idiosyncratic alignment - they seek
a resting alignment at an angle of
precisely 104.5 deg from each other.
Hydrogen is so small and

quick it can get in close to
other atoms. Its positively
charged nucleus comes so
close to oxygen electrons that
the attraction between them
is unusually strong. The
larger oxygen atom steals
hydrogen electrons, so this
part of the molecule is
slightly electropositive
Every water molecule wants to form a

three dimensional structure with its
neighbours. Liquid water is made up of
billions of tiny crystal like structures.
Liquid
Water stays liquid because its molecules

Water
hang together so strongly that only a
few molecules can escape to become
gaseous. When it is frozen into ice, the
molecules are organised into a regular,
but widely spaced, lattice of crystals.
But when ice melts the hydrogen bonding immediately draws the water
molecules together again.
Scientists have
"discovered" 36
different types of
water, with different
combinations of
hydrogen and
oxygen, and varia-
There is a special kind of water called "heavy

water", in which oxygen combines with
deuterium instead of hydrogen. Deuterium is a
special kind of hydrogen with an extra neutron
in the nucleus of each atom. Heavy water is used
in nuclear reactors where it helps keep energy
levels under control

Section 1
tions of "heavy" and "light" water. But these remain a purely academic
realm for us. It is convenient but overly simple to call water H2O; in
fact very little water is H2O. This is simply the base water that picks up
minerals on its journey; only distilled water - the pure water of scientists - is actually H2O.
Liquid water is dynamic and chaotic, always on the move in curves and
spirals. Its molecules press together in constantly shifting confusion,
readily disassembling and rearranging themselves around other molecules. Despite water's ever changing fluidity, its structure is immensely
strong.
Density of Water
Liquid water is unique because it expands when it freezes. The laws of
physics dictate that the solid phase of a substance will be denser than
its liquid state, and something solid will sink in liquid. But water is
different. Like all other liquids, it
shrinks as it cools. But as it reaches The mystery of the Bermuda
4 deg C (39F) something unexpected
Triangle
happens. At 4 deg C water reaches its has been
maximum density - and contains its
linked to
Bermuda
maximum energy. Below 4 deg C it
the
Triangle
begins to distend, its density diminamazing
ishing instead of increasing.
properties
of water.
As temperatures drop, expansion
At its
continues, and as water freezes into
densest water forms strong
solid ice it increases its original
cage like structures that, at
volume by 9 % but it becomes lighter
specific temperatures and presthan liquid water. A liquid normally
sures, can trap other molecules
becomes denser as it cools, its moleinside. Dense and structured
cules slowing up and crowding
water sinks to the ocean
together as the liquid shrinks. But ice
bottom where it traps methane
is an open porous structure with
- to form a sea bed gas hydrate.
fewer molecules in the same space.
An underwater landslide can
Instead of closing ranks as they cool,
release this methane causing it
water molecules open outward, they
to rise to surface uncontrollink in delicate structures and lattice
lably. Any ships would lose
work, light and buoyant on the water
their buoyancy and sink, and
below.
nearby aircraft would lose their
At its densest, the structure of water engines due to oxygen starvation or explosion on contact
is tightest; the temperature of 4 deg
with methane. Debris would
C allows hydrogen bonds to keep
sink into the low density water
oxygen atoms spaced in the densest
beneath, leaving no trace.
possible structure, with water mole-

Section 1
cules clustered into 3-D structures that resemble prisms or hexagonal
cages (hexamers) - like two tetrahedrons together; these structures are
central to waters behaviour. As the water temperature drops, some of
the hydrogen bonds, having already reached the temperature for
optimum density, are forced to regroup for water to expand. While
trying to maintain their angle of 104.5 to the oxygen atoms the
pressure causes the bonds to break and reform water molecules with a
more open and lighter structure.
From solid to liquid

It takes a great amount of energy to turn solid water (ice) into liquid,
since this involves changing a liquid from a lighter to a denser form,
disrupting the hydrogen bonds in ice. Whereas the bonds in liquid
water are constantly breaking and reforming, researchers have
discovered that a high proportion of the bonds in ice are stronger.
If every single hydrogen bond had to be broken, the required energy
would be even greater; in fact, liquid water in the form of melted ice
retains some of the crystalline characteristics of ice, and one third of its
hydrogen bonds remain intact.
Universal Solvent
Sometimes called the universal solvent, water dissolves almost everything it meets to some
If a drop of water touches a crystal of salt the
degree (depending
water will dissolve the salt almost immediately.
upon conditions). Its
But if we try and melt table salt without water
molecules interfere
we would need to produce heat of 800 deg C!
with every other
Salt melts effortlessly in water because
molecule they meet,
pushing atoms apart, sodium and chloride ions are constantly
looking to attach themselves to molecules of
surrounding them,
and thereby changing other substances. When in a solid state the
two are stable and strong. But as soon as they
them.
are surrounded by
The structure of water water they are off,
provides one clue to
negative chloride to
its amazing ability to positive hydrogen
dissolve compounds.
and positive
In order for
sodium to negative
substances to be
oxygen. So salt
dissolved they have to dissolves in a flurry
be encapsulated, and of charged atoms this is only possible if which is why salty
the molecules of the
water conducts
liquid form a 3-D
electricity

Section 1
structure. If water molecules arranged themselves in flat or linear
structures, they would not have the adaptability to dissolve anything.
The other factor allowing water to dissolve most substances is its electrical polarity - the electropositive hydrogen atom seeks to attach itself
to any negative ions that it encounters and the negative oxygen atom
then looks to claim any positive ions it can claim.

Section 1
Methane
Methane is a colorless, odorless gas
with a wide distribution in nature and
is the principal component of natural
gas. It is formed during anaerobic
(without oxygen) decomposition of plant
and animal matter. This type of decomposition commonly occurs in marsh
type areas where organic material sinks
below the water level and decomposes
without exposure to free oxygen.
Methane bubbles can commonly be
seen rising to the water surface in
marsh or bog areas and it is for this
reason that methane is also know as
"marsh gas". The "firedamp" of coal
mines is also chiefly composed of
methane which was trapped in the coal
seams during there formation.
Natural gas is a mixture
containing about 75%
methane, 15% ethane, and
5% other hydrocarbons, such
as propane and butane.
Methane
Ethane
Other Hydrocarbons
Other
Methane molecule is tetrahedral in structure in which

one central Carbon atom is
surrounded by four
Hydrogen atoms located at
each apex of the structure.
At room temperature, methane is a gas

less dense than air. It melts at -183C
and boils at -164C. It is not very
soluble in water. It is combustible, and
mixtures of about 5 to 15 percent in air
are explosive. Methane is not toxic
when inhaled, but it can produce suffocation by reducing the concentration of
oxygen inhaled. A trace amount of
smelly organic sulphur compounds are
added to give commercial natural gas a
detectable odour. This is done to make
gas leaks more readily detectible and
thereby reduce the risk of a gas leak
resulting in an explosion or asphyxiation.
The principal use of methane is as a fuel. The combustion of methane

is highly exothermic or "heat-giving". The by-products of methane
combustion carbon dioxide and water.
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(l)
H = -891 kJ
The energy released by the combustion of methane, in the form of

natural gas, is used directly to heat homes and commercial buildings.
It is also used in the generation of electric power.
8

Section 1
What are hydrates?

Natural gas hydrates (or clathrates) are crystalline compounds formed
by water with natural gases and associated liquids. The hydrates are
solid ice-like crystals composed of cages of
water molecules surrounding 'guest' hydrocarbon gas molecules such as methane,
ethane, propane, etc. Like pure ice,
hydrates can block any type of flowline,
production tubing, and pipeline. However,
unlike ice, hydrates can form at much
higher temperatures than 32F. Gas
hydrates of interest to the petroleum industry are composed of water
and the following eight molecules: methane, ethane, propane,
isobutane, normal butane, nitrogen, carbon dioxide and hydrogen
sulfide.
Here are some useful facts regarding hydrates:
i
i
i
Hydrates can form in gas, gas-condensate and black oil systems.
Hydrate formation temperatures are very dependent upon the gas composition.
Richer gases (those with higher propane and butane concentrations) will tend to
form hydrates at higher temperatures and lower pressures.
Hydrate formation temperatures are inhibited by brine concentrations
One cubic foot of hydrates can contain 180 standard cubic feet of gas.
Hydrate blockages can occur very rapidly. Transient operations such as start-up,
shutdown and blowdown are very susceptible to hydrate blockages because this
is when the production system is likely to drop into the hydrate formation region.
Physical and chemical properties of gas hydrates

Composition of gas hydrates
Gas hydrates are solid compounds which can form in places where
water contacts, at higher pressures and at a lower temperatures, light
components such as the smaller hydrocarbons (mostly only methane,
ethane and propane/butane play arole in hydrate formation in
production facilities), Sulphur Dioxide (H2S) and Carbon Dioxide (CO2).
The pressure-temperature region in which hydrates are stable depends
on the composition of the production stream and can, for a given
composition, be quite accurately calculated by computer programs. The
larger part of gas hydrates ( 90 % by weight) consists of water whereas
the remaining 10 per cent of the weight of gas hydrates obviously corre-

Section 1
sponds to the weight of the gas which is trapped in the hydrate lattice.
When stated in terms of volume, typically 150-180 m of natural gas
can combine with 0.8 m3 of water to yield 1 m of gas hydrates. Gas
hydrate formation and dissociation is chemically fully reversible which
means that the gas and water from which gas hydrates are composed
evolve chemically unaltered if these hydrates are melted.
3
Appearance and texture of gas hydrates

The appearance of gas hydrate crystals is similar to those of ice.
Individual crystals are transparent (as ice crystals) but agglomerates of
hydrate crystals are white (similar to snow, which is a porous agglomerate of small ice crystals). Note that hydrate deposits which are formed
in production installations always are agglomerates of many small
crystals and thus have a snow-like appearance. Much like wet snow,
water-wet hydrate crystals tend to stick to each other thereby forming
hydrate accumulations which may eventually block a flowline.
Depending on the flow regime these hydrate accumulations sometimes
build up as a gradually thickening layer which adheres to the surface
of a flowline under other flow conditions wet hydrates may rather
suddenly jam a pipeline.
Depending on the flow regime these hydrate accumulations sometimes
build up as a gradually thickening layer which adheres to the surface
of a flowline under other flow conditions wet hydrates may rather
suddenly jam a pipeline.
Thickening layers
Sudden jamming
The texture of hydrates changes during time. Because hydrates consist

of water and gas, hydrates grow predominantly at locations where both
the water and gas are in abundant supply. This is why hydrate growth
is most pronounced at the interface between liquid water and gas or
between liquid water and liquid hydrocarbons which are in saturated
with gas. When liquid water is in contact with gas or with gas-saturated oil, a thin hydrate film rapidly forms at this interface. Hydrate
growth in the bulk hydrocarbon phases is much slower because of the
low water content whereas only a small amount of gas dissolves in the
bulk water phase.
10

Section 1
The density of gas hydrates typically
Heat of Dissociation
ranges between 900 and 950 kg/m3.
This is defined as the
One cubic meter of liquid water will,
energy required to break a
when combining with gas to form
mole of a substance into
hydrates, result in the formation of 1,22
is simpler constitiuents
m3 of hydrates. Characteristic properties
of hydrates are their low thermal conductivity's and large heats of
dissociation. The thermal conductivity of gas hydrates is approximately
0.5 W/Km which is one quarter of the thermal conductivity of ice.
Approximately 450-500 kJ of heat is
Joule (J)
needed to dissociate 1 kg of hydrates
The joule is a standard
into liquid water and gas at atmospheric
unit of energy and is
pressure and zero degrees centigrade.
equal to 1 watt per second
This is approximately 1.5 times the heat
required to convert ice into liquid water. One of factors responsible for
this large heat of dissociation is the gas expansion during the dissociation process.
11

Section 1
Hydrate formation in wells

Hydrates will usually not form in wells during steady state production
but only during shutin, during a cold restart of production and during
well interventions.
How hydrates form during shutin conditions?

Hydrate Formation Curve
Hydrate
Forming
Region
Hydrate
Formation
Curve
Pressure (psia)
During shutin hydrates can

only form in the hydrate
stability zone. If no or inadequate preventive action is
undertaken, the rate of
hydrate formation in stagnant
wells is usually limited by:
a) The amount of water which
can be contained in the
vapour phase.
Hydrate
Free
Region
Temperature (oF)
b) The diffusion rate of gas
Hydrates can only exist for indefinite

periods inside the so-called hydrate
stability zone of a well. This zone is
defined as the section of a well which
resides in the hydrate region during
c) By the rate at which water will shutin. Usually the hydrate stability
zone comprises only the upper
be transferred from deeper
parts of the well to the hydrate sections of a well and typically
extends from the wellhead down to a
stability zone under the
depth of several hundreds of metres
influence of a thermal
below which depth the temperatures
gradient.
are becoming too high for hydrates to
remain stable.
through the water phase and
of water through the oil phase
near water/oil and water/gas
interfaces.
Therefore, only relatively small amounts of hydrates will form in

a) Parts of the wellhead which were not drained after shutin.
b) Near water gas and water/oil interfaces (if these reside within the
hydrate stability zone during shutin).
c) In the free gas zone underneath the wellhead.
Therefore, unless the well has been out of production for weeks, rather
than days, it is unlikely that massive amounts of hydrates which
completely block the well over significant distances can have formed
under stagnant conditions. Instead, it is much more likely that some
12

Section 1
wellhead valves can not be opened during an attempted production
restart. Most wells become blocked by hydrates shortly after an
(initially successful) production restart from cold.
How do hydrates form during cold production?

Hydrate growth proceeds very rapidly if the (gaseous and liquid) hydrocarbon phases intermingle with cold water during production. For
example, a situation in which gas percolates through a column of cold
and uninhibited water is one of the most favourable conditions for
hydrate formation. Hydrates also form very rapidly when (after a cold
restart of the production) an oil/water interface which resided in the
hydrate stability zone is broken up. When hydrates are formed in situations as sketched above, it is likely that hydrates will be present over a
long distances within the hydrate stability zone. Note that these
hydrates will not form a single solid plug. Instead, the well will be effectively blocked by one or more relatively short patches of compacted
hydrates (which initially still may contain large volume fractions of
liquid water, gas and oil). The length of these compacted patches will be
of the order of metres rather than tens of meters. Hydrates in between
these compacted patches will be more loosely distributed and
embedded in water, gas and oil.
How do Hydrates form during Interventions?

Probably most hydrate problems in wells occur during drilling and
completion operations and other well interventions. Often, these
problems are caused because the possibility for hydrate formation is
overlooked.
In some instances hydrate plugs formed during completion operations
because the well was filled with uninhibited (sea-) water prior to perforation of the well. Due to the subsequent percolation of gas through
cold water in the hydrate stability zone the well became rapidly plugged
by hydrates. Often the production of gas is started after perforation of
the well under the assumption that the cold water residing in the
hydrate stability zone will be produced out of the well before gas is
produced. Even in case such an assumption is validated by means of
transient multiphase flow calculations there remains a risk that the
production must be interrupted before the cold water is produced out
of the well but gas is already moving upwards towards the hydrate
stability zone. In such a situation there is a considerable probability
that the well will be hydrated up.
13

Section 1
Impact of Hydrates
Hydrates icidents have major business implications for Shell and the
rest of the industry. Recorded incidents are responsible for costs of
tens (and probably hundreds) of millions of dollars in areas such as
safety & environmental incidents, repairs, non-productive time,
deferred production, contractual penalties etc.
How do hydrates impact Well Productivity?

Hydrates directly impact Well Productivity:
i
i
They can plug the well (especially during start-up) a plugged well doesn't flow.
They can block meters and pressure tranducers leading to inaccurate optimisation or allocation of artificial lift - especially gas lift. Measurements of flow rate
by differential pressure across an orifice plate are particularly prone to blockage.
They can plug the DHSV or tree valves, leading to a loss of barriers when rigging
up. Intervention times may therefore be extended.
Because hydrates form at surface or at shallow depths, interventions

are more hazardous when hydrates are present.
14

Section 1
Hydrate Models
Modeling the potential for hydrate formation
There are two aspects to modeling the potential of hydrate formation in
a production system. The first is to predict the hydrate formation region
and the second is to predict the temperature/pressure profile of the
production system over the life of the field for a range of operating
conditions (both steady state and transient). The model generally is a
thermodynamic model and is used to calculate the hydrate equilibrium
curve, also know as the hydrate disassociation curve. This is a
prediction of temperature, at a given pressure, above which hydrates
will not form.
Hydrate Formation Envelope

2500
30% MeOH
10% MeOH
20% MeOH
Pressure (psia)
Hydrate
2000 Forming
Region
Hydrate
Formation
Curve
1500
1000
500
Hydrate
Free
Region
0
30
40
50
60
70
80
Temperature (oF)
Given a fluid composition, the hydrate formation

envelope can predicted using a hydrate model.
The hydrate model can also predict curves for
different levels of methonal inhibition such as
those shown for 10%, 20% and 30% MeOH above.
Modeling can
also be done
to represent
al the effects
of inhibitors
including
depression of
the hydrate
disassociation
temperature,
depression of
the freezing
point of water,
reduction in
the vapour
pressure of
water (i.e.
dehydrating
effect) and
inhibitor
partitioning.
15

Section 1
Are hydrates just associated with gas wells?

It is typically understood that free gas and free water is required for
hydrates to form. Recent developments in deepwater has determined
otherwise. Oil wells flowing above the bubble point with C1 to C4
hydrocarcon light ends in the flow stream
have been mixing with condense water,
C1 H4 - Methane
reminisces of completion fluid or small
C2 H6 - Ethane
amounts of produced water and forming
hydrate without gas breaking out of solution
C3 H8 - Propane
typically during shut-in periods. Therefore,
C4H10 - Butane
fluid properties are critical for determining
hydrate equilibrium curve. If a oil or gas
well during shut-in, startup or normal operations are within the
hydrate forming window, then measures should be taken to prevent
hydrate formation. Please note some system operate free of plugs even
though they are in the hydrate stable region. Factors such as GOR,
bubble point pressure, water cuts have not effectively been tested todate to better define hydrate formation in oil wells.
What is the difference between prevention and

remedial action?
Creating conditions that inhibit the formation of the hydrate crystals
and/or consolidation of the crystals into a solid state can prevent
hydrates. If the hydrate has formed, remedial action can be taken to
remove partial or complete blockage of formation of hydrate crystals.
16

Section 2
General Prevention Guidelines

This section contains general prevention guidelines for hydrate
prevention in completions, testing and interventions operations and is
based on common cross operator practices.
Good Practices for Prevention

There are specific elements in completions, well testing and intervention that should be considered when the potential for hydrate development exist. Within these operations, a hydrate control method
selection process should be carried out systematically to cover all the
operational phases, i.e. normal operations, planned and unplanned
shutdowns and startup situations.
i
i
Define a complete hydrate control strategy for all operating conditions.
Start each operation with a risk assessment and each job with a job safety
analysis.
i
i
Pressure testing - the test fluid should incorporate a hydrate inhibitor.
Flush all lines that may be exposed to wellbore fluids - remove any non-inhibited
water from system.
Pre-heating surface wellhead equipment BOP's choke and kill lines, risers
through the use of booster line) prior to shutting in the well to maintain existing
wellbore temperature above the hydrate stable forming temperature.
Be aware of all pressure drops in the

system that may cause Joule
Thompson cooling of the produced
fluids.
Brainstorming sessions and peer assist should be should be employed in the

define process.
The displacing fluids (after/ prior to flowing well) should incorporate a hydrate
inhibitor.
Joules-Thompson Cooling
This effect is the cooling that
occurs during a pressure
drop as a gas passes
through an orifice.
Add a safety factor to the inhibitor

volume for unexpected increases in the
potential water produced.
Ensure injection lines are properly sized and located to meet current and future
inhibition goals.
17

Section 2
i
Diameter selection and insulation requirements should be co-ordinated with

corresponding requirements to flow related issues such as scale, wax and
hydrate control.
In oil wells, evaluate the potential for wax and incorporate control method in
hydrate/wax inhibition plan.
Operational Prevention Procedures

Most operators incorporate two
or three hydrate control
methods into their strategy.
This is generally done to
handle hydrate prevention
through the full life cycle of
the well.
As previously stated, the
components required for
hydrate formation are free
water and natural gas, low
temperatures and high
pressure. Hydrate prevention
procedures in intervention,
completion and well testing
operations must therfore focus on:
i
i
i
The Four Elements
High
Pressure
Water
Hydrate
Conditions
Natural
Gas
Low
Temp
removal of free water

maintaining high temperatures in the hydrate free region
maintaining or reducing pressures
Planning, reporting, proper data collection and vigilance are important

components in preventing hydrate formation.
Removal of Free Water

In the downhole environment of wells, removal of free water is not yet a
viable option, and therefore, current emphasis is chemical inhibition,
which targets free water so that it is not allowed to mix with gas and
freely crystallize.
Maintaining High Temperatures

A workable hydrate control strategy is to keep flowing (steady state)
temperatures throughout the subsea system above the hydrate forming
range. High reservoir temperatures are maintained through the use of
18

Section 2
insulation, additional heating via hot fluids, electrical heating and
exothermic chemical reactions. Insulation is industry's leading choice
to minimize heat losses to the ambient environment. Proper insulation
allows the produced fluid to retain enough heat to flow at elevated
temperatures all the way to the rig or platform. Insulation increases
upfront cost, but has proven to be less expensive over the life of a well.
Maintaining or Reducing Pressures

Pressure is generally controlled by depressurizing and effectively
moving the system pressure out of the hydrate-forming region.
Downhole pressure control valves allow for depressurization during well
testing and completions.
Field Experience
Both gas and oil wells are susceptible to hydrate forming. Certain
gases and water can form hydrates under the combination of high
pressure and low temperature. In many oil wells, dissolved gas in oil
comes out of solution as the pressure drops and combines with free
water to form hydrates. Free water may be produced or condensed
from the vapor phase of the gas. The risk of forming hydrates is the
greatest when the well is cold. This condition usually exist during
production start-up or while the well is shut-in after a flow period. The
cooldown process begins immediately after the well is shut-in.
The following table sets forth water depths in which hydrates are likely
to form in well testing and completion operations. The deeper the water
depth, the greater the chance hydrates will form near surface due to
subcooling in the riser.
WATER DEPTH
(FT)
<1000 ft
<2000 ft
<3000 ft
RISK OF HYDRATE
FORMATION PROBLEMS GAS WELL
Probable at low water

cuts during shutdowns
(SD).
Probable at low water
cuts during SD.
Probable during flowing
at low WC with pressure
drop & during SD.
RISK OF HYDRATE
FORMATION PROBLEMS OIL WELL
Not likely at zero to low

WC.
Not likely at zero to very
low WC. Probable during
SD.
Probable during SD especially if gas breaks out of
solution while flowing.
The table is valid for new completions and well testing where little or no
water is anticipated. It is important to be reminded that hydrates will
typically form regardless of water depth, if free gas (solution gas) and
19

Section 2
water (condensation inside tubing), low temperature and high pressure
are present. In oil wells with gas in solution producing above the
bubble point, hydrates have also formed.
Hydrate Control Methods

The different hydrate control methods can be defined as:
i
i
Chemical e.g. inhibitors applied using injection lines and bullheading practices,
Hydraulics e.g. depressurization used to evacuate the riser using gaslift, reducing
the pressure above the downhole tester valve (during DST) and circulating
inhibited fluid inside tubing
Heat control e.g. bullheading of heated fluids such as mud; insulation applied to
riser, wellhead, tubing and flowlines.
Chemical
Chemicals are injected into the flow stream or pumped as a
displacement fluid to inhibit the formation of gas hydrates in well operations. Chemicals selected for hydrate control or prevention are
generally in the category of thermodynamic or kinetic. The most widely
used chemicals are alcohols such as methanol and glycol in well
testing, production and intervention operations along with salts such
as KCl, CaCl2, NaCl, CaBr2 and others in drilling and completion operations.
Methanol
Methanol is the most commonly recommended
Methanol
inhibitor. It is a thermodynamic inhibitor that both
inhibits and melts hydrates. Glycols, specifically MEG
is sometimes pumped to melt hydrates but is
generally not very effective at dissolution of hydrates.
Methanol is the most widely used, with greatest inhibition of the alcohols, and the most cost effective.
Methanol dissolves in any free water accumulations
to prevent hydrate formation. Methanol is generally
mixed in an aqueous solution. It is typically mixed at
10 - 40 wt% but can also be used neat. The aqueous solution helps to
stabilize methanol and prevent vaporization at warmer temperatures
(i.e. flashpoint 100 weight percent methanol is approximately 51oF).
Insufficient chemical inhibition by concentration or rate, especially
methanol, can serve to accelerate hydrate formation. Studies have
shown that under-inhibited methanol systems form hydrates faster
than systems without methanol inhibitors.
20

Section 2
Glycols
Monoethylene glycol (MEG) is the most widely used glycol for the inhibition of gas hydrates. It is not very effective in the dissolution of
hydrates. It has a higher molecular weight and lower volatility than
methanol. It is generally mixed in an aqueous solution between 20 and
80% by volume. Precautions must be observed when testing lubricators or using glycol solutions as a displacement fluid in subsea wellheads, since glycol solutions may separate out, causing glycol to sit on
top of the water phase.
Industrial Methylated Spirits (IMS)
Another alcohol based solution used due to it relatively low corrosive
impact to titanium heat exchangers has also been effective at hydrate
inhibition in the proper concentration. It generally is a clear, colorless,
volatile liquid generally composed of 95% ethyl alcohol, 1,5% benzene,
and 3.5% butyl alcohol. It has a higher molecular weight than
methanol and significantly less effective at dissolution than methanol.
Methanol
Ethanol
Isopropanol
Glycol
MOLECULAR WEIGHTS
EFFECTIVENESS
The effectiveness of alcohols is inversely proportionate to its

molecular weight.
RELATIVE
DENSITIES
Methanol
Hydrates
Glycol
Salts
In completion and well testing operations, the salt content in the
completion fluid or drilling mud is sufficient to inhibit hydrates
formation. Most intervention work without a rig onsite is performed in
the produced fluid environment and requires alternative inhibition
techniques to salt. The amount of salt that has to be mobilized and the
surface mixing capacity required makes it unattractive in a non-rig
setting.
21

Section 2
Kinetic Inhibitors
Kinetic inhibitors are low dosage inhibitors that can significantly
reduce inhibitor volume; long term cost and provide a safer and easier
product handling. BP has supported the development of kinetic
inhibitors called Threshold Hydrate Inhibitors (T.H.Is). T.H.I.s delay
hydrate nucleation and/or crystal growth by extending the operating
range within the hydrate-forming window. They are a water soluble, low
dosage product that usually separates out with the aqueous production
phase. Kenetic Inhibitors can also be mixed with a methanol or glycol
aqueous solution to reduce the volume of methanol and glycol required
with increasing water cut.
Formulas of some Kenetic Inhibitors
[ ]
[ ]
PVP
PVCap
[ ]
[ ]
[ ]
[ ]
[ ]
Poly(VP/VC)
VC-713
Carbon
Nitrogen
Oxygen
Hydrogen
Hydrate Dispersant
Hydrate dispersants are again low dosage inhibitors that can significantly reduce inhibitor volume; long term cost and provide a safer and
easier product handling. Shell has supported the development of
hydrate dispersants called Hydrate Growth Inhibitors (HGI's). HGI's do
not prevent hydrates from forming but prevents them from agglomerating or bonding together.
Emulsion Additives
Emulsion additives attempt to prevent agglomeration of hydrate
crystals and thereby enable transport of hydrates.
Both THI's and HGI's are successful in limited window and may have to
be supplemented with methanol.
22

Section 2
Heat Method
There is no real industry consensus on the application of heat
methods. The majority of the testing efforts for flowlines have been
made in improved insulation with vacuum insulated tubing (VIT)
proving to be the most effective to date. Insulated tubing main applications are for permafrost stabilization, heavy oil recovery (steam flood),
paraffin/asphaltene control and, of course, gas hydrate control.
Vacuum Insulated Tubing (VIT)
VIT is a tube within a tube with a vacuum annulus. The thermal
conductivity for VIT is in the range of .002 versus 0.2 for most other
insulated tubulars2. This rating has attracted many companies to use
VIT in gas hydrate control. Recently, design engineers are focusing on
the connection. In some cases, the connection is an unacceptable
weak links in the design since the connection cannot offer the insulation efficiency in the range of the tube body.
Direct Heating
The most reliable heating device is heat tracing which is currently
utilized for surface equipment. Electric heating devices run on
wireline have applications in wellbores where the top of a hydrate plug
can be accessed. The tool has been used to melt hydrates in 4 "
tubing offshore Norway.
In deepwater operations, heat has been applied by circulating heated
mud or water in the riser to prevent hydrate formation during planned
shut-ins. Devices used are steam generators, tube heat exchangers and
electric immersion heaters.
Hydraulic
Depressurization is the most commonly employed hydraulic inhibition
method. It is a planned prevention alternative that can be used in
conjunction with inhibitor injection and with thermal insulation
depending on operating conditions. During well test operations, several
deepwater operators have installed downhole pressure control valves in
the test string that when closed allows for depressurization of the
tubing from the valve to the surface.
Fluid displacement prior to start-up and shutdown during well testing
and completions is an effective prevention method. Well test strings
have been displaced with inhibited fluid prior to cleaning up and flow
testing wells. This has prevented produced fluids mixing with insufficiently inhibited brines and forming hydrates.
23

Section 2
Modeling of Hydrate Behaviour in Problem

Wells
Data collection and simulations are important for both the plan to
prevent hydrate formation and the necessity of remedial action to
remove them. Setting up and maintaining a thermal model based on
initial conditions to monitor performance could be used operationally
for the following:
i
i
i
Increasing the available time to implement hydrate control measure

Reducing inhibitor consumption
Helping determine when to start inhibition prior to shutdowns or start-ups.
Collecting the following data, calculating the required values and

running models assists in developing a hydrate prevention and control
plan.
i
i
i
i
i
i
i
Tubing dimensions and operating limits.

Temperature profile based on produced fluids anticipated.
Anticipated water production rate
Formation water salinity
Reservoir hydrocarbon composition
Well pressure
Calculated hydrate equilibrium condition for produced fluids.
If all the required data is not available, assumptions have to be made

based on nearest well or fields with similar conditions to be able to
estimate inhibition rate, type inhibitor, the potential degrees of subcooling. This data can then build a model to predict impact on the base
equilibrium curve due to changes in treatment volume and rates and
produced fluid composition ( % water cut or anticipated water condensation in the tubulars on startup).
24

Section 3
Components of the Well Design

for Hydrate Control
Subsea Wellhead & Tree
The trees are generally
massive steel structures of
great thermal capacity. The
trees are expected to hold
substantial amount of heat
at flowing conditions. It was
common belief that the
cooldown time of trees to
ambient temperature was 8
to 10 hours because of the
amount of heat held by steel.
Numerical simulations and
other models have proved
the cooldown time is less
than two hours with a subsea ambient temperature of 40 degrees F
and a wellhead temperature of 110 degrees F. A typical design now
requires 4 hours "no touch time" during cooldown before hydrates form
to allow for startup or other preventative measures to be implemented.
Therefore, the design of the subsea tree needs to include protection
against cooldown based on thermal modeling and operating philosophy.
Riser / BOP Stack

The Riser/BOP stack is an important consideration in Completion and
DST operations. The hydrostatic head of the riser fluid in conjunction
with subcooling temperatures can push wellbore conditions into the
gas hydrate envelope. Hydrate inhibition in these components are
generally handled by chemical inhibition of the mud or brine used
during the operation. There is generally no insulation applied.
Typically, in subsea operations, an umbilical string with chemical
injection lines is connected to the BOP stack that allows potential
chemical inhibition below, across and above the BOP stack. Umbilical
containing a small " line could also allow for the circulation of heated
fluid across the BOP stack and inside the riser. Booster strings, 2 3/8"
and 3 " OD have also been run inside of risers to allow for the circulation of heated or inhibited fluids. Fluids can be heated on location
using a heat exchanger or electrical heating units in a pit.
25

Section 3
Production risers are filled with a gelled diesel packer fluid to reduce
the hydrostatic head and extend the cooldown time. Gas lift of fluids in
the riser with inert gases or gas lift gas through gas lift valves preinstalled or could also be achieved through coil tubing to prevent
hydrate formation in the riser. Methanol injection in the riser can also
prevent hydrate formation. Bullheading into each riser is an option but
requires a significant volume of MeOH. Stabilized crude could be used
to bullhead down the riser below the hydrate forming depth.
Completion String
The completion string design varies based on the
production system installed from tubing run in a
subsea completion, to a fix or floating platform with
surface tree. In strings connected to a fix or floating
platform, insulated tubing will normally be installed if
cooldown is predicted to occur rapidly i.e. less than 6-8
hours. Normally chemical inhibitor injection or insulation alone will meet operators criteria for extending
the cooldown time before hydrate formation is likely to
occur. Sometime both are required. Some operators
may elect to use chemical injection in combination
with depressurizing the tubing above the tree or
SCSSV. In wellbores that are completed subsea, the
same considerations apply. Insulation is required from
the subsea tree to a minimum depth of 300ft below
mudline where the effect of deepwater subcooling still
has the greatest impact on a typically unconsolidated
formation.
DST String
The DST string is generally not insulated for hydrate control purposes.
Typical deepwater system designs have chemical injection capability
below the mudline and at the wellhead. The DST string can be depressurized above the tester valve and inhibited fluids can be circulated
down the annulus through a circulating valve to prevent hydrates.
Surface Controlled Subsurface Safety Valves

Subsurface safety valves are an MMS requirement for potential well
control in the event of loss or damage to wellhead, tree or any
component above the mudline. The setting depth requirements are
based on MMS specifications and a number of other factors.
26

Section 3
The following should be considered when determining the SCSSV
setting depth:
i
i
i
i
A fail safe setting depth according to the operating manual
Operating friction as related to type of SCSSV and sealing

elements.
i
i
Safety factor.
Gradient of annulus and control/balance line(s) fluids.

SSSV first closed pressure from functional test data.
Calculated tubing pressure at SCSSV during open flow conditions.
Minimum depth allowable by regulatory requirements.
The extent of scale or paraffin deposition should be

considered in determining the SSCSV setting depth.
Where subsurface controlled SSSV's are selected, well
effluents and producing characteristics become the
governing factors in selection and design.
The position of the valves in the hydrate-forming region of
the wellbore should be a major factor in the setting depth
and design of SSSV.
The potential problems that can occur with the valve
placement in the hydrate-forming region are as follows :
During shut-in:
Below a close valve where oil and water has been produced,
hydrates can form during rapid cooling of the fluids after shut-in.
(oil or gas well)
Below a close valve, condense water forms due to rapid cooling after shut-in,
mixes with solution gas in the oil and form a hydrate plug. (oil well)
During shut-in, gas can leak through a close valve and mix with cold fluids above
the valve and form a hydrate plug. (oil or gas well)
During cold startup:
When the valve is opened, uninhibited water that settled above the valve mixes
with gas that was trapped below the valve and forms a hydrate plug. (gas or oil
well)
When the wellbore above the valve has been depressurized, opening the valve
allows uninhibited produced fluids to move up the wellbore and cooldown forming
a hydrate plug. (gas or oil well)
27

Section 3
It is also important to note the following:
i
i
Water condensation can occur below the SSSV as the wellbore cools down.
Hydrate formation takes place at the gas/water and oil/water interfaces where the
gas and water molecule concentrations are high. However, without agitation, the
hydrate layer maybe thin.
i. When cold gas meets cold water, rapid hydrate formation and hydrate blockage
can occur.
Chemical Injection Lines

Chemical injection lines are generally ", 3/8" or " in diameter.
Thickness varies with the required pressure rating i.e. ' line with
10000 psi rating 0.065". The typical deepwater design is usually two
" or " lines, each capable of delivering 3 -12 GPM under 10000 psi.
Inhibitor type, depth of injection and injector pump limitations also
influences inhibitor line sizing and rate. The maximum inhibitor rate is
limited by maximum injection pressure at the surface. The surface
injection pressure must exceed the wellbore pressure plus the friction
pressure minus the hydrostatic head of the column of inhibitor in the
line form the surface to the injection point.
Inhibitor injection is independent of oil and/or gas production rates .
The volume of inhibitor to prevent hydrate plugging is proportional to
the water production rate and well pressure. (This is not to say that oil
wells producing no measurable water at surface will not form a hydrate
plug during shut-in when condensation occurs downhole.) The
inhibitor weight fraction in the aqueous phase determines the amount
of hydrate inhibition gained i.e. 10% wt., 20% wt, 40%wt and so on.
The inhibitor injection rate also varies inversely with the well temperature and the salt concentration in the produced formation water. As
the well temperature rises and wellbore conditions move out of the
hydrate-forming region, hydrates will not form.
The chemical injection point is typical below the depth hydrate will
form except in DST operations where there may be high risk of
damaging the control line below the subsea wellhead.
28

Section 3
Safety Issues
Hydrate Formation in Flowlines and Pipelines
Hydrate formation in a production system can result in serious, and
sometimes fatal, accidents. Hydrate safety problems are caused by
three characteristics:
Hydrates have densities like
ice. A dislodged hydrate plug
can be a projectile with
speeds up to sonic velocity.
With these velocities and
densities there is sufficient
momentum to cause two
types of failure at a pipeline
constriction (valve or orifice)
or at a sharp change in
direction (bend, elbow, or tee).
Hydrates can form either
single or multiple plugs.
There is no method to predict
which will occur. High differential pressures can be
trapped between plugs, even
when the discharge end of the
plugs are depressurized.
Hydrates contain as much
as 180 volumes (STP) of gas
per volume of hydrate.
When the plugs are dissociated by heating, any
confinement causes rapid gas
pressure increases which can
lead to pipeline ruptures.
A Hydrate Projectile
A hydrate plug moves down a

flowline at very high velocities.
Where the pipe bends, the hydrate plug can

rupture the flowline through projectile impact.
Trapped High Pressure

Low Pressure
Low Pressure
High Pressure
Hydrate
Plug
Hydrate
Plug
Wellhead
Satellite
Trapped High Pressure

Heat Addition
Gas
Hydrate Plug
Pipeline Rupture
Gas
Hydrate Plug
29

Section 3
Case Examples
Example 1
This example shows the problems that unexpected hydrate formation
can cause. The riser was circulated to Glycol before opening the tree
valves. However, a section at the top of the riser was not circulated
effectively (due to the location of the return line) and seawater was
trapped just below the stuffing box. When the tree valves were opened
the gas and cold seawater mixed and formed a hydrate plug.
As soon as the wireline toolstring moved down the "ice" plug, gripped
the wire and also fell down the riser - trapping the toolstring across the
tree valves! The slickline toolstring was then stuck hard across the tree
- unable to move up or down. The only way out was to pump methanol
slickline
into the riser until
the "ice" plug
CAMCO Hydraulic Sub-Sea
Retrievable Stuffing Box
Location of hydrate formation
dissolved. This
(trapped seawater)
Lifting Yoke
caused NPT on the
5 1/8 LD Single Hydraulic BlowOut Preventer and Upper
Flushing port
vessel of 12 hours
glycol out
umbilical
(approximately
10ft Long Riser Section
25,000).
10ft Long Riser Section
5 1/8 10,000 psi
API - 6BX Flanges
umbilical line
20ft Long Riser Section with

5 1/8 Upper Flange
7 1/16 Lower Flange
5 1/8 ID Single Hydraulic

Blow-Out Preventor
5 1/8 ID Single Hydraulic BlowOut Preventor
Crossover Spool with Lower
Flushing Port
glycol
in
5 1/8 ID Hydraulic Wireline

Cutting Gate Valve
7 1/16 15,000 psi

API - 6BS Flange
2 No Accumulator Bottles
API Guide Frame with Blank

Spool Centre
Tree Connector
Location of stuck
toolstring
The lesson learned

was to not engage
the seals on the
stuffing box during
glycol circulation
until glycol was seen
coming out the top
of the riser. The
stuffing box was
then locked and
tested and then the
tree valves were
opened. No
problems were
encountered
following this procedural change.
Subsea Production Tree
WELLHEAD
30

Section 3
Example 2
Hydrates may also occur in an apparently dead
well: The platform had a well that was killed
with brine and dead. However over time some
gas migration occurred and hydrates formed at
the surface.
Gas
Oil
Water
Example 3
Hydrates can cause serious problems with downhole safety valves.
Gas
Oil
Water above
downhole
safety valve
If the downhole safety valve is

shut and the fluids segregate
out, then little if any hydrates
should form. However if the
valve is of a self-equalising
type, then during equalisation,
there will be a flow of fluid
through the downhole safety
valve. The fluid will initially be
gas and this flow of gas
through the valve will cause
further cooling (the gas is
already cool as the well is
shut-in. The gas will flow into
the water sitting above the
valve and the pressure will
increase. These combinations
offer the perfect conditions for
hydrate formation and have in
the past caused many
problems (blockages) with
these types of valves.
31

Section 3
Example 4
A slickline drift became stuck in hydrate across the Xmas Tree whilst
preparing to add perforations to a platform gas well.
Recent Hydrates Incidents

4000
A20
A23
Pure Water
3500
Pressure (psig)
Sea Water
HYDRATES
3000
2500
Stuck in hydrates
across tree
Pump IMS
2000
RIG up slickline
1500
Flow well at 3% choke to

increase temperature and
decrease pressure
3rd perf run - stuck in

hydrate at seabed
1000
2nd perf run
500
Bleed-off pressure
above DHSV
NO HYDRATES
1st perf run
0
30
35
40
45
50
55
60
65
70
75
80
85
90
Temperature (degF)
This figure shows that the pressure / temperature conditions at the

tree were clearly within the hydrate envelope (to the left of the hydrate
curve shown), and it is thought that water must still have been present
in the surface lines, despite flushing with base-oil. IMS (Industrial
Methylated Spirits) was pumped until communication could be established past the blockage, then the hydrate was dispersed by flowing the
well gently to quickly warm the tree and move outside the hydrate
envelope. About a day of rig-time was lost as a result of this incident.
Example 5
Another hydrate problem occurred during a platform completion,
hydrates in the tubing at seabed prevented recovery of a wireline
conveyed perforating gun. Again the conditions were within the hydrate
envelope. Pumping IMS failed to remove the plug, so the DHSV was
closed, and the pressure above slowly bled-off. The differential pressure
across the plug finally caused it to move up hole (cushioned by the
liquid in the tubing above). This moved the perforating guns and when
these subsequently fell back down the well, the cable parted. The wire
was fished, leaving the guns held by the partially dissolved hydrate
plug. The DHSV was opened (to avoid damaging the valve when the
guns fell down). When the hydrate fully dissolved the guns dropped to
the sump. During this operation there were considerable concerns
about possible sudden movement of the plug and damage to the Tree.
32

ABC Guide To Gas Hydrates Awareness: Revision: 1.0 Oct 2002

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ABC Guide To Gas Hydrates Awareness: Revision: 1.0 Oct 2002

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ABC Guide to Gas Hydrates Awareness

From solid to liquid

Physical and chemical properties of gas hydrates

Composition of gas hydrates

Appearance and texture of gas hydrates

Hydrate formation in wells

How do hydrates form during cold production?

How do Hydrates form during Interventions?

Modeling the potential for hydrate formation

Are hydrates just associated with gas wells?

Good Practices for Prevention

Removal of Free Water

Maintaining High Temperatures

Maintaining or Reducing Pressures

Revision: 1.0 Oct 2002