TAMU - Pemex

Offshore Drilling

Lesson 12B
Hydrates

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Lesson 21 - Hydrates
 What are they?
 Why are they important?
 Where are they found?
 Conditions for existence
 Drilling-related problems
 Remedies -
 Procedures
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Hydrates - What are they?
 Gas Hydrates are solids formed
from hydrocarbon gas and liquid
water
 They resemble wet snow and can
exist at temperatures above the
freezing point of water
 They belong to a form of
complexes known as clathrates
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 “The Burning
Snowball”

Methane hydrate
supporting its
own combustion

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Clathrates - What are they?
 Clathrates are substances having a lattice-
like structure or appearance in which
molecules of one substance are completely
enclosed within the crystal structure of
another
 Hydrates consist of host molecules (water)
forming a lattice structure acting like a
cage, to entrap guest molecules (gas)
LATIN: “clathratus” means to encage
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 Types of Hydrates
The following gases when combined with
water under the right conditions are known
to produce hydrates:

 Natural gas molecules ranging from

methane to isobutane
 Hydrogen sulfide
 Carbon dioxide
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 Hydrates - Why are they
important?
 A very large potential source
of natural gas
 A hindrance to the natural gas industry
 Often cause plugging of lines and
equipment (like an “ice” plug)
 In drilling, under well control situations,
hydrates may plug lines and chokes
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 A Natural Gas Resource?
 Conditions for hydrate formation are
satisfied in more than 90% of the ocean
floors, but hydrates will only be present if
there is a source of natural gas and a
structure suitable for gas accumulation
 It has been estimated that total worldwide
hydrate resources are as much as 1016 m3,
or twice as large the combined fossil fuel
resource.
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 A Natural Gas Resource?
 Possibly as much as 98% of the hydrate
resource is below the world’s oceans
 The remaining 2% that is found on land,
below permafrost, is estimated to be twice
the size of the conventional natural gas
resourse
 Natural gas has been produced from
hydrates for decades in Russia

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 A Natural Gas Resource?

 It is estimated that gas contained in

naturally occurring gas hydrates may
exceed 16 trillion tons of oil equivalent

 One cubic foot of hydrate can hold 170

standard cubic feet of gas

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 A Problem in the Natural
Gas Industry?
 In the 1930’s it was discovered that
natural gas hydrates were blocking gas
transmission lines, frequently at
temperatures well above the freezing
point of water
 This discovery led to the regulation of the
water content in natural gas pipelines

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 A Problem in the Natural
Gas Industry?
 It has since been determined that gas
hydrates may exist at temperatures as
high as 20-30 oC.

 As the pressure increases, hydrates can

exist at higher temperatures

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 A Problem in Drilling?
 Where hydrates are present in-situ in
petroleum reservoirs, they can cause
blowouts if drilled into inadvertently
 Extreme conditions of temperature and
pressure mean that hydrates may form
during the drilling process if fluids
containing water come into contact with
the reservoir fluids

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 A Problem in Drilling?
 Formation of solid hydrates can plug up
subsea risers, choke and kill lines, and
BOPs
 Conditions during well shut-in are
particularly favorable for hydrate formation
if high pressures are combined with falling
temperatures and there is sufficient time
for equilibrium to be reached

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 A Problem in Drilling?
 Water depths near the West Shetlands
and Hebrides rapidly reach 1,000 meters
or more, with seabed temperatures down
to -2oC
 In the deepwater regions of the Gulf of
Mexico the seabed temperature is
typically around 4oC or even lower
 Such extreme conditions present risks of
hydrate formation
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Where are Hydrates found?
 Hydrates are found in situ in the deep
oceans of the world, on the ocean
floor or in the sediments below the
seafloor
 Hydrates are found in situ in
permafrost regions
 Hydrates are also found in
extraterrestrial environments
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17
18
 Hydrate-
forming
conditions
for natural
gases

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Temperatures Profile in the Gulf of Mexico
0

2,000

4,000

6,000
Depth, ft

Sea Floor
8,000

10,000

12,000

14,000

16,000
30 35 40 45 50 55 60 65 70 75 80
Temperature, oF
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Temperatures Profile in the North Sea

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 Pressures @ 8.6 lb/gal

2,000

4,000

6,000
Depth, ft

8,000

10,000

12,000

14,000

16,000
0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000
Pressure, psi
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(not the GOM)

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 Results of a
typical hydrate
thermodynamic
test

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 Schematic of
constant-volume
temperature
ramping
experiment

The probability of hydrate formation increases as

you move towards the supercooled temperature

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Hydrate-Related Drilling Problems

 Choke and Kill line plugging

 Plugging of wellbore below the BOPs
 Plug formed around the drillpipe inside
casing, in the the BOPs or in the riser,
preventing drillstring movement
 Plug formed in the BOPs preventing full
BOP closure
 Plug keeping BOPs from opening

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Hydrate-Related Drilling Problems

There are two basic types of hydrate-

related drilling problems:

 Drilling through formations already

containing natural hydrates, and

 Experiencing drilling conditions that may

be conducive to formation of hydrates

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Techniques for drilling through
Zones containing Hydrates
 Reduce the temperature of the drilling
mud
 Drill at “controlled” drilling rates (not too
fast - to reduce heat generation rates)
 Increase mud weight - if possible
 Increase mud circulation rate to ensure
turbulent flow to achieve better cooling
and to remove any gas
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 Techniques to avoid Hydrate
Formation while Drilling

 Keeping the temperature above, or the

pressure below hydrate formation
conditions
 Using chemicals to depress the hydrate
formation point, i.e., use “thermodynamic
inhibitors” such as methanol, glycols and
salts (methanol is very toxic)

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Techniques for avoiding Hydrate
Formation while Drilling - cont’d
 Adding chemicals that reduce the rate of
nucleation of hydrate crystals
 Adding chemicals to reduce the rate of
growth of hydrate crystals which have
nucleated
 Adding chemicals that tend to prevent
agglomeration of crystals, so that solid
plugs do not form (kinetic inhibitors)
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 Thermodynamic Inhibitors
 Basically, thermodynamic inhibitors
reduce the temperature at which
hydrates will form
 The inhibitor dissolves in the water
phase, increasing the stability of the
liquid water with respect to the hydrate
 An inhibitor like methanol will also enter
the gas and liquid hydrocarbons
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Thermodynamic Inhibitors - cont’d
 Salts are the most commonly used
inhibitors: NaCl, KCl and CaCl2
 Saturated NaCl (26%) provides a ~21 oK
margin relative to pure water
 Glycols and glycerols can also be used
 Mixed inhibitors can be used and their
effect is approximately additive
 20-23% NaCl polymer muds are the most
commonly used for deepwater drilling
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 Kinetic Inhibitors
 Kinetic inhibitors work by reducing the
rate of nucleation of hydrates, the growth
rate of the crystals, or the agglomeration
of the crystals
 They cannot prevent hydrate formation,
but they may increase the delay between
the time when a fluid enters the hydrate
zone and the formation of a blockage
 These have not been tested in drilling
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Remedies

Depression
of hydrate-
formation
temperatures
with
methanol and
diethylene
glycol

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Remedies
40% 20%
Inhibition of
hydrate
formation
temperatures
0%
caused by glycol

Glycols may
experience
severe viscosity
increases at
cooler
temperatures
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Remedies

Oil-based and synthetic-based muds also require

inhibition, since they contain a water phase
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Remedies

Note that
below ~3,000 ft
water depth,
inhibition with
salt alone can
not guarantee
a hydrate-free
environment

Seawater
temperature
profile

Effect of gas gravity, mud weight and

salt content on hydrate stability 37
Well Control Remediation Methods
 Prevent hydrocarbons from entering the
wellbore
(adequate mud weight, rapid shut-in)
 If hydrocarbons enter the wellbore,
prevent them from reaching the wellhead
(monitoring, bullheading)
 If hydrocarbons reach the wellhead and
BOP, prevent formation of hydrates
(high salinity mud; glycol mud standby)
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Well Control Remediation Methods - cont’d
 If hydrates do form, eliminate them
(methanol on standby for pumping
down kill line, heated seawater ready to
be pumped up riser)
 Methods for removing hydrate blockages:
 Depressurization to dissociate the hydrate
 Addition of chemical inhibitors to melt the
hydrate
 External heating to dissociate the hydrate
 Mechanical (drilling)
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 References
 Clathrate Hydrates of Natural Gases, by E.
Dendy Sloan, Jr., Marcel Dekker, Inc., New
York,1998.
 The Properties of Petroleum Fluids, by William
D. McCain, Jr. PennWell Books, Pennwell
Publishing Company, Tulsa, Oklahoma, 1990.
 “Controlling, Remediation of fluid hydrates in
deepwater drilling operations,” by B.Edmonds,
R.A.S. Moorwood and R. Szczepanski,
Ultradeep Engineering, March 2001.

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 References - cont’d
 IADC Deepwater Well Control Guidelines.
International Association of Drilling
Contractors. Houston, Texas, 1998.
 “Lab work clarifies gas hydrate formation,
dissociation,” by Yuri F. Makogon and Stephen
A. Holditch. Oil & Gas Journal, Feb.5, 2001.
 “Experiments illustrate hydrate morphology,
kinetics,” by Yuri F. Makogon and Stephen A.
Holditch. Oil & Gas Journal, Feb.12, 2001.
 SPE, OTC...
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THE END

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