hydrates

section 13

hydrates (deepwater drilling)

 section 13

hydrates (deepwater drilling)

section 13 Scomi Oiltools

physical characteristics 2
hazards 3
seafloor instability 3
borehole instability 4
gas release 4
hydrate formation 4
free gas 5
other concernss 5
detection 5
before drilling 5
during drilling 6
mitigation 7
geological interpretation 7
casing design 7
cement design 7
pressure regulation 7
mud temperature regulation 7
drilling fluid additives 7
non aqueous fluids 8
bits and bha 9
drilling parameter 9
special equipment / requirements 9
Section

13 gas hydrates (deepwater drilling)

gas hydrates (deepwater drilling)

physical characteristics
A gas hydrate is a crystalline solid, similar to ice, except that the crystalline structure is stabilised by the
guest gas molecule within the cage of water molecules.

Hydrates are part of a group of substances known as clathrates which is Latin for “to enclose with bars”.

Hydrate Structures:

Although most marine hydrates that have been analysed are methane hydrates, C2, C3, C4, H2S and CO2
are also known to produce hydrates with water. Hydrocarbons larger than nC5 cannot form hydrates
with water because of limited host molecule cage size. Heavy hydrates (e.g. nC4) form hydrates first
(at lower pressures and higher temperatures), in preference to lighter components (e.g. C1).

Gas hydrate formation is an exothermic process.

Hydrates form as either:

ƒ Finely disseminated particles interspersed within the sediment acting to cement the pore spaces
of sediment; or
ƒ Concentrated bands (layers or nodules) interspersed with hydrate-poor, anomalously dry layers.
May resemble ice-like rods or blobs.

Accumulations may be several hundred metres thick. They also appear to have the capacity to fill
sediment pore space and reduce permeability so that hydrate-cemented sediments act as seals for
gas traps.

Hydrates are a gas concentrator. The BCC (body-centred cubic) crystal structure of methane hydrates
allows a volume ratio of 160:1 methane to water.


Concentration occurs at depocenters (thickest part of sediment), probably because most gas in hydrate
is from biogenic methane. Therefore it is concentrated where there is a rapid accumulation of organic
detritus (from which bacteria generate methane) and also where there is a rapid accumulation of
sediments (which protect detritus from oxidation).

Hydrates are found in marine sediments on the continental slope and rise, and in the arctic permafrost
under specific pressure and temperature regimes known as the gas HSZ (Hydrate Stability Zone).

Whether or not gas hydrate actually forms depends on the amount of gas available.

HSZ can be identified on seismic reflections by the BSR (Bottom Simulating Reflector).

HSZ can be effected by:

ƒ Pressure and temperature conditions - an increase in water temperature changes the location of
the HSZ so that the gas hydrate may become unstable and dissociate in certain areas. Underlying
free hydrocarbons would then vent to the sea floor.
ƒ Gas composition – specific gravity can effect the pressure/temperature range over which hydrates
are stable.
ƒ Liquid-phase composition – solutes may act to depress the hydrate formation temperature at a given
pressure.

Several factors can lead to changing pressure/temperature conditions, potentially causing gas
dissociation:
ƒ Drilling operations
ƒ Sediment and mud re-deposition (earthquakes, volcanic eruptions, gravity slides)
ƒ Interglacial/glacial conditions (removal of ice will decrease pressure and increase temperature)
ƒ Sea-level rise and fall
ƒ Enrichment by longer chain hydrocarbons
ƒ Aeolian winter cooling and summer heating conditions

Dissociation can be explosive if pressure and/or temperature change too quickly (e.g. Barents Sea).

Hydrates can occur in water depths beyond 300m, depending on temperature and pressure conditions.
Hydrates may occur up to 1000m below the seabed. Theoretically, the presence of other gasses (C2 and
higher) may extend the Hydrates Stability Zone (HSZ) to higher temperature and/or lower pressure
conditions.

Large hydrate deposits that formed from gas in deeper reservoirs will occur from the lower limit of the
HSZ upwards. Shallower deposits may also occur due to gas vents or fractures or from the generation of
biogenic gas within the seabed.

Apart from the pressure/temperature conditions required for the formation of gas hydrates, the
distribution of gas hydrates may be largely controlled by structural and stratigraphic factors. A source
of biogenic gas and a migration pathway are both fundamental for formation of the hydrates.

hazards
seafloor instability
Mud volcanoes may result from hydrate dissociation and subsequent flow of fluid towards the seafloor.
They are a potential problem since soil in the crater is very unconsolidated and could be filled with
hydrates. They may also be (periodically) reactivate.

Dissociation of massive hydrates leaves a formation that offers less support to any sediments or
structures above including the rig, anchors, wellhead and well foundations. For example, landslides
may occur on the steep continental slopes where hydrates occur.


Section

13 gas hydrates (deepwater drilling)

High weight of the subsea wellhead and BOP on formations weakened by hydrate dissociation may
cause buckling of the conductor.

borehole instability
Hydrate saturated layers are characterised by an extremely low permeability that prevents infiltration
of drilling mud and the formation of a mud cake. The absence of a protective layer opens the gas
hydrate deposits to temperatures above hydrate equilibrium and to chemically active solutions.
This results in hydrate decomposition.

Decomposition of hydrates may be accompanied with a sharp weakening of intergranular bonds

and fluidising of a part of the rock allowing ejection in to the well. This process, accompanied by an
intensive formation of caverns and shearing rock, may cause seizing of tools, hole fill, stuck pipe and
hole washouts.

gas release
Intensity of hydrate decomposition and gassing of a drilling mud are determined mainly by the excess
temperature of drilling mud above the equilibrium temperature of hydrate in a layer.

An unknown and changing kick volume due to hydrate dissociation must be considered.

Gas evolving from hydrates at high pressure results in an intensive saturation and ejection of drilling
mud from the well.

Potential exists for liberation of gas from the hydrates at or below the seabed prior to setting conductor
or surface casing. Risk to rig is limited in deepwater.

Volume changes associated with thawing and formation of hydrates may cause very high collapse
pressure on tubulars (casing and conductor).

Hydrates behind casing may dissociate, migrate up and generate extra annular pressure on tubulars
(casing and conductor) well above the hydrate zone. This is possible because there is not necessarily a
seal above a hydrates layer. It can be a problem if surface casing/conductor is not designed to withstand
these annular pressures.

Little is known about blow-outs from solid hydrates. The production potential of hydrates is probably
quite low, and any blow-out would probably stop without intervention within a relatively short period.

During cementing, the cement hydration heat may dissociate hydrates in the borehole wall and cause
gas channelling and bad cement bond.

Hydrate cuttings may accumulate in mud tanks, slowly releasing gas as they dissociate.

hydrate formation
Gas, originating from hydrate dissociation or from a bad cementation of a deeper zone, could percolate up
possibly reforming.

Formation of gas hydrates during deepwater drilling operations can lead to a number of problems:

ƒ Choke and kill-line plugging which prevents their use in well circulation
ƒ Plug formation at or below the BOP which prevents well pressure monitoring below the BOP
ƒ Plug formation around the drillstring in the riser, BOP or casing which prevents drillstring movement


ƒ Plug formation between the drillstring and the BOP which prevents full BOP closure
ƒ Plug formation in the ram cavity of a closed BOP which prevents the BOP from fully opening
ƒ During periods of no circulation (or low circulation) hydrates may form which restrict/prevent mud
circulation

Hydrates require several hours to form and to plug subsea equipment, however, once they form a plug
they will not move under an applied pressure differential.

As hydrates form they draw water out of the drilling fluid leaving solids that may form a plug or block.

free gas
It is possible that the presence of has hydrates may be acting as a seal to underlying hydrocarbons. These
hydrocarbons may vent at the seafloor at the location of pock-marks.

If free gas from below hydrates is encountered and blows out, the consequences can be more
serious. The course of the incident will be similar to a “normal” shallow gas blow-out, with very high flow
rates and potential loss of well.

other concerns
Concentrated methanol is acidic (pH ≈ 5). Destruction of concrete or cement stones becomes noticeable
at pH ≤ 6.5. The destructive action of methanol increases under pressure.

Dissociation of hydrates into gas and water can be a slow process depending on heat transfer and
crystal structure. For drilling activities this means that hydrates may occur in an environment outside
the pressure/temperature stability zone. In this case the danger exists that no precautions are taken.

detection
before drilling
1) High resolution seismic surveys in conjunction with 3D interpretation.
2) Anomalous pore-water sulphate gradients may be a potential indicator of gas hydrates in
deepwater sediments. Reaction of sulphate with gas from hydrates results in pore waters that are
partially depleted with sulphate relative to their environment.
3) Anomalous low salinity in seabed sediments provides a good indication of hydrate presence.
Upon freezing, the NaCl in pore waters is excluded from the hydrates structure. The excess salt diffuses
away over time. If a well enters the hydrate, chances are that some hydrate will dissociate due to a
higher temperature in which process fresh water is liberated and dilutes the pore water.
4) Search for a BSR (bottom simulating reflector) by interpretation of the seismic survey.

ƒ BSR (bottom simulating reflector) signifies the occurrence of in-situ gas hydrates, but gas
hydrates may still be present even if no BSR is observed.
ƒ Volume of gas is not indicated by the presence or strength of the BSR.
ƒ BSR might be lower than the HSZ due to the “capillary undercooling effect”. That is, the gas
hydrate growth is dependent on the size of the pores. Gas hydrate will only form in smaller pores
at lower temperatures than the theoretical HSZ indicates. Consequently, when the larger pore
spaces are filled, the hydrate will tend to grow as a displaced inclusion or segregated layer rather
than penetrating into smaller pores.


Section

13 gas hydrates (deepwater drilling)

5) Predict the presence of Hydrates based on a theoretical HSZ.

Sea Level 18ºC

13ºC
500 7ºC
0
4ºC
1000
10º

1500 Sediment -
3ºC 0 20º
water Interface
Depth in meters

10º 30º
2000
3ºC 0 20º 40ºC

2500 2ºC 10º 30º

1.5ºC 0 20º
3000 40ºC
10º 30º
3500 Hydrate zone
20º C 2H 6, C 3H 8, 40ºC under the oceon
4000 30º H 2 S,CO 2 , Assumed geothermal
gradient = 27.3º C / 1000m
4500 40ºC

Figure 1. An example of the hydrate stability zone in an outer continental margin setting.
[ Modified from Kvenvolden (1988) ]

during drilling
1) A watch should be kept at surface for gas bubbles and for hydrates in mud return.
2) Maintain observation of the wellbore discharge with a ROV if visibility is sufficient.
3) Monitor background gas in drill mud – drilling operations through hydrates will be characterised
by gas cut mud caused by dissociated hydrate gas.
4) Monitor ROP - hydrates are harder than liquid or gas in formation pores, so drilling rate would be
expected to decrease.
5) Pressurised coring - to measure and quantify, sidewall samples.
6) Consider static temperature gradients to identify HSZ.
7) Logging.

Mud log Pronounced gas kick associated with a hydrate due to thawing during
drilling
Dual Induction log Relatively high resistivity kick in the gas hydrate zone. Long normal
separates from the short normal due to thawing next to the bore hole
Calliper Usually indicates an oversized well bore due to spalling from the
decomposition of a hydrate
Sonic log Increase in acoustic velocities
Spontaneous potential Relatively small spontaneous potential deflection in a hydrate zone when
(SP) compared to a free gas
Neutron porosity Increase in neutron porosity, in contrast to a normal apparent reduction
in neutron porosity in a free gas, due to the gas volume reduction which
allows a large increase in water volume in the thawing hydrate zone
Temperature log Thermal conditions within the HSZ

Note: if the well is not logged soon after the penetration of a hydrate it can thaw beyond the maximum
sensing depth for normal well logging tools and not appear on the log surveys.

8) RFT samples.


mitigation
geological interpretation
High resolution seismic survey.

casing design
ƒ
Set casing before encountering hydrates to provide well control.
ƒ
Case off hydrate zone at the first opportunity to improve probability that hydrates are retained in
place, and to stop further gas from entering the well bore.
ƒ
Design casing to withstand full displacement to gas. This also applies to casing strings terminating
above the HSZ as gas liberated from hydrates in lower zones may migrate up through the annulus/
formation.
ƒ
Thermal isolation of casing from produced fluids and drilling mud may be required to reduce hydrate
thawing.

cement design
ƒ
Cement as high as possible, preferably into the previous casing string.
ƒ
Ensure thermal isolation of casing.
ƒ
Foamed cements are effective in minimising gas influx due to the mechanism in which they
maintain pressure on the formation with the inclusion of nitrogen.
ƒ
Use cements that have a low heat generation to minimise hydrate disassociation.

pressure regulation
Increase mud weight to offset the gas cut. Maintain sufficient overbalance

To stabilise hydrates:
Increase mud weight to facilitate hydrate stability.

To destabilise hydrates:
Decrease the system pressure below hydrate stability.

mud temperature regulation

To stabilise hydrates:
Reduce system temperature to within the HSZ by:
ƒ Cool mud.
ƒ Decrease circulation time to minimise mud heating by formation.
ƒ Decrease circulation rate to minimise friction related heat generation.
ƒ Reduce ROP.
ƒ Use smaller mud motors.

To destabilise hydrates:
Maintain system temperature to keep fluids outside of HSZ by:
ƒ Heat mud.
ƒ Control circulation rates to minimise cooling. Where possible keep some circulation going at all times.

drilling fluid additives

The effects of components added to a drilling fluid to change hydrate stability are approximately
additive.

Mud samples should be tested to determine the temperature of gas hydrate formation before field use.


Section

13 gas hydrates (deepwater drilling)

thermodynamic inhibitors
ƒ Adjust the hydrate stability conditions so that higher pressures and lower temperatures will be
required for hydrate stability.
ƒ Can completely prevent hydrate formation in a certain temperature-pressure envelope where it
would otherwise occur. Beyond this envelope hydrates form as per normal.
ƒ Not sufficient for many of the more extreme environments.
ƒ Examples: Electrolytes, alcohols, glycols etc.
ƒ Large amounts of these additives are usually required to be effective, usually of the order of 10 to
40% by volume. This is expensive and may effect the other functions of the mud.
ƒ On a per mass basis NaCl is the most effective.
ƒ Glycol/methanol may be spotted down the choke/kill lines and BOP stack to prevent plugging
in a kick situation or whenever pumping is stopped for an extended period of time.
ƒ From experience, the most effective inhibitor used in deepwater so far is a high aqueous
concentration of salt/glycol/glycerol (balanced to provide correct mud weight and viscosity) in the
mud system to obtain a low freezing point in combination with a polymer as a chemical inhibitor.
ƒ Mixtures of glycerol + salt, glycerol + PHPA + salt or polymer + oil-in-water can serve as a safe,
environmentally friendly, and cost-effective gas hydrate inhibitor for drilling fluids.
ƒ 20% (w/w) NaCl with 20% (v) glycerol can give a thermodynamic suppression of close to 50 ˚F.
ƒ Pills may be placed in BOP stack and choke and kill lines.
ƒ Some typical components of mud (e.g. bentonite, barite and polymers) promote the rate of hydrate
formation because they actually stabilise hydrates at higher temperatures than pure water.

kinetic inhibitors
ƒ May work in three ways: Delay nucleation, Slow growth, Prevent Agglomeration.
ƒ It is suspected that kinetic inhibitors of hydrate formation do not act in the first of the above three
mechanisms.
ƒ Retard but NOT PREVENT hydrate formation.
ƒ Will slow the process and/or prevent the formation of large blocks.
ƒ May be able to function at very low concentrations. e.g. 0.01 to 1%
ƒ Such additives as bentonite, surfactants and alcohols or any surface-active species may potentially
effect the rate at which hydrates form. Many have been discovered to actually act as kinetic
promoters.
ƒ WBM contain many sites for crystal nucleation which allow hydrates to form faster than they do in pure
water.

kinetic stabilisers
Slow rate of disassociation. (See section on Lecithin).

non aqueous fluids

A thermodynamic inhibitor but also a kinetic promoter. NAF is a good inhibitor, however, once
initiated, the rate of formation is much greater in an NAF than WBM. This is probably a result of the
high solubility of gas in the oil phase and the large surface area of the dispersed water phase.

Hydrates do not form easily in NAF. Temperature extent of gas hydrate formation can be inhibited
significantly but not necessarily prevented in NAF.

Addition of dissolved solids, e.g. CaCl into the aqueous phase of NAF reduces the gas hydrates formation
temperature even further


lecithin
Lecithins are a group of compounds that are glyceryl esters of two fatty acid molecules. They are
esterified at the third carbon atom with phosphoric acid, which in turn is bound by ester linkage to a
nitrogen base.

They are a mixture of surface-active species. Lecithin will ‘coat’ the surfaces of shale and other solids.

Lecithin is a kinetic promoter which speeds the rate of hydrate nucleation.

It prevents agglomeration. Widely used in the ice-cream industry for this purpose.

Slows growth of larger masses by adsorption onto the surface of crystals.

Does not significantly effect the hydrate thermodynamic equilibrium conditions.

It is believed that surface adsorption is a key mechanism by which lecithin slows the rate of hydrate
melting. This property allows for minimal disassociation of hydrates in the formation and may contribute
to stabilising hydrate cuttings long enough for them to be brought to surface.

bits and bha

Minimise well bore diameter to minimise hydrate dissociation.

drilling parameter
ƒ Control drilling and circulation rates to manage the quantity of gas in the well.
ƒ Ensure that some circulation occurs periodically to prevent cooling at critical times.
ƒ Test mud gas samples to confirm the presence of hydrates.

special equipment / requirements
ƒ
Select equipment with appropriate seals to minimise hydrate migration into the wellhead and
surrounds, causing mechanical blockages and release problems during abandonment of wells.
ƒ
Consider insulation of well control equipment to decrease rate of heat transfer during extended
shut-in periods.
ƒ
Contingency planning for the occurrence of gas hydrates during well control operations should
consider long shut-in periods. Maintenance of temperature in subsea BOP above static mud line
temperature by previous mud circulation cannot be relied on as an adequate hydrate preventive
measure.
ƒ
Mud mat and seal to direct dissociating gas away from BOP equipment.
ƒ
Surface BOP.
ƒ
Drill without a riser – treat as per shallow gas.
ƒ
Simulation indicates that during deepwater riserless drilling using a seawater mud, a hydrate zone,
if encountered, will remain mostly intact.
ƒ
Shale shaker and mud tank areas should be well ventilated.