The gas hydrates are the causes of great headaches in the
operations surrounding gas and low temperatures, but in their
Jesús Minakata
Reynosa, MEXICO - 2003
Special thanks to William Durham from the Hydrates
investigation department of the Lawrence Livermore
National Laboratory from the University of California,
Keith Palmer from Elmar and to Thomas Tucker from
Halliburton Energy Services, L&P for the help and
information provided for the elaboration of this article.
All the illustrations and most of the information
contained in this article were obtained from public
network in Internet.
natural form they constitute a vast power source for the future.
“Gas Hydrates” are gas
molecules surrounded by a
crystalline water connection in ice
form (fig.1), they have a very similar
appearance to ice crystals, the
most common in nature are the
methane hydrates and constitute a
very dense form of this gas (1 cubic
meter of methane hydrate is
equivalent to 164 cubic meters of
methane gas at atmospheric
pressure and 25°C).
Fig. 1 Structure of a Methane Hydrate molecule
constituted by a methane molecule surrounded
by six water molecules (CH4-6H2Ò). The water
molecules in ice form, united by a crystalline
connection, surround the methane molecule.
This crystalline formation constitutes the
densest form of methane gas (a cubic meter of
methane hydrates contains the equivalent of
164 m3 of methane gas, both at atmospheric
pressure and 25°C).
The methane is not the only gas
able to form hydrates, the hydrates
form easily from more complex
molecules of natural gas (ethane,
propane, butane, etc...) and even
from carbon dioxide molecules.
The methane hydrates are stable
at temperatures below -79°C, but
under certain high pressure
conditions, its formation is possible
at temperatures above 25°C.
To predict the behavior of
hydrates under different conditions
of pressure and temperature a
phase diagram must be used (fig.2)
where there is possible to locate the
physical state of the gas in different
scenarios. By checking the working
conditions in a phase diagram it is
easy to avoid hydrate formation in
situations in which its presence
could be risky or even dangerous.
The concept of gas hydrates has
been studied thoroughly during the
last decade and although its
knowledge goes back in science to
more than 200 years, its effects and
benefits have been studied and
known for only a couple of decades.
Fig. 2 Graph that shows the border conditions during hydrate formation at different pressures and temperatures for a mix of methane, gas
and fresh water. The presence of sodium chloride or ethylene-glycol move the curve to the left, while the presence of Carbon Dioxide,
Hydrogen Sulfide or other hydrocarbons move it to the right. (Courtesy of the Lawrence Livermore National Laboratory of the University
of California)

Therefore, in comparison to the recoverable methane

Lately, the interest in this peculiar state of natural
gas has spread widely, not only because of the
amount of problems that it causes in the oil industry
(plugs in ducts and pipelines that, when breaking off,
acquire ballistic speeds that damage pipes and injure
workers, or blockages in BOP’s or control lines, which
increase the risk operations) but by the enormous
power potential that it represents.
According to recent studies it’s been found that the
methane reserves contained in nature in hydrate form
could be equivalent to more than double of the total
coal, petroleum and natural gas reserves combined.
And approximately 20,000 billion cubic meters of
methane gas are trapped in hydrate form in nature1
and approximately 99% of these are located in marine
sediments offshore2.
1. Kvenvolden K: “Gas Hydrates – Geological Perspective and Global Change,” Reviews
2.
og Geophycs 31, no.2 (May 1993) 173-187.
Makogan YF: Hydrates of Hydrocarbons, Tulsa, Oklahoma, USA: PennWell Books,
1997.
gas reserves, that are considered in 250 billion cubic
meters, we could talk about 80 times more methane
than the current methane available in natural reserves
in free form. This is the reason why it is considered one
of the power sources of the future.
Another important consideration is that thanks to its
capacity of compaction, the methane turned into
hydrates is an easy way of transporting gas, since it is
a solid compound, stable, and occupies a smaller
volume (almost 200 times at atmospheric pressure).
Although to obtain the hydrate formation in a totally
pure form is difficult (generally they are contaminated
with molecules of common ice, free gas and water)
once formed they can remain in solid state, without
melting, by periods of 25 hrs and at temperatures of
up to 30 °C. Its hardness at - 2°C is 20 times greater
than ice but its dissociation is easy when the hydrate
is physically deformed.
Fig. 3 At low temperatures (blue lines), the methane hydrates dissociate quickly after a fast depressurization. At higher temperatures (black
lines), the dissociation is completed after periods of up to 25 hours. (Courtesy of the Lawrence Livermore National Laboratory – University
of California)

This is a good indication that abrupt pressure drops

In several experiments made in the Lawrence during winter temperatures could generate hydrates,
Livermore National Laboratory of the University of stable enough to preserve themselves to up to 25 hrs
California by Durham, Stern and Kirby; the behavior of at atmospheric pressure. Nevertheless, on slow
hydrates was studied when pressure drops at different depressurizations, the life of hydrates is not greater
temperatures. When depressurized slowly, the than 5 hrs3.
dissociation of hydrates is quickly when arriving at
temperatures near to 0°C; however, during fast
depressurizations, the hydrates dissociate at low
temperatures (< -20°C) but stay associated at higher
temperatures (> -20°C) during up to 25 hrs (fig 3).
3. Durham, W: “Methane Hydrate,” Science & Technology Review 1999 LLNL
Homepage http://www.llnl.gov/str/Durham.html
 Problematic in Gas Wells with High Pressure and Adverse Conditions of Temperature

Leaks in Equipment.

In opposition to which a lot of people in the oil patch

think, the leaks in the equipment do not form hydrates.
The displacement of already formed hydrates by the
fluid that is flowing through the leak is what we find in
pipes and equipment, and they are accumulated in
points of reduction of the internal diameters.

In any gas pipe, cooling will be evident in and after

expansion points of the gas, in other words, if we are
venting a well with 8,000 psi WHP by an 8/64" choke,
the part of the line that will freeze will be the one
located after the choke (fig 4). Also, if a closed space
is being vented (tank), where there is no continuous Fig. 4 Line after venting a gas well with 7000 psi in head by an
restitution of the gas mass, the expansion produced by 8/64” strangler. The freezing of the line after the strangler due to
the gas expansion is observed.
the reduction of mass in a constant volume will also
generate a cooling effect.

Of the same way, when we lose grease seal in a Hydrate Plugs.

pressure control equipment, the parts freezing are
those where the gas begins to expand, (stuffing box
and line wiper), freezing in the flow tubes section of the
PCE will never be observed because gas expansion
does not exist in this space.
Cooling happens because of a very simple
thermodynamic effect specific to gases, since to get
expanded they require absorbing energy and
increasing their temperature, they absorb this energy
from the environment surrounding them. This effect is
used in all refrigeration apparatus, the gas gives
energy when it is compressed and absorbs energy
when it expands, is for this reason that the interior of
the refrigerators is cold and the compressors of the
refrigerators are hot.
Leaks in the equipment, when conditions are
appropriate for the formation of hydrates, become a
riskier scenario as when flow exists through a leakage
point, the hydrates already formed floating in the fluid
within a confined space, move towards the leakage
point and form a plug by accumulation.
In operations with wireline in wells with high
pressure and low temperatures it is very probable
hydrate formation. The simple diffusion of the gas
through the water used to test or to equalize the
pressure is enough to form them, it is easy to find them
in gas wells with water production of low salinity, or
after perforating wells filled with fresh water.
The most critical points of the equipment in the
process of hydrate formation are those that are
exposed to surface/environment temperature, below
ground level, the geothermal gradient helps to
maintain the conditions outside the border of hydrate
synthesis, nevertheless in the x-mas trees and
pressure control equipment the conditions are optimal
when the surface temperature is less than 10°C and
the wellhead pressure is greater than 1,500 psi (see
fig 2). The atmospheric conditions and the wind are
factors that decrease the temperature of the surface
equipment and favor the formation of gas hydrates.
 Gas hydrates have the appearance of snow, when
they accumulate and get compacted, they take a white
solid form, harder and lighter than ice (fig 5). Hydrates
tend to adhere to surfaces with high coefficients of
heat transfer, e.g. steel.
When performing operations with wireline, the
hydrates tend to adhere to the strands of the cable,
and to the walls of the pressure control equipment,
when the cable returns to surface and passes through
the flow tubes, the hydrates formed in its surface are
scraped off and accumulates in the Tool Catcher. This
situation that can dangerous when inhibitors are not
used to avoid the formation of gas hydrates, as they
can form a plug, trap the cable and prevent the tool to
get fully in the lubricators.
Fig. 5 Contaminated gas hydrates with injection grease,
recovered from a pipe elbow of the venting line of the well
Patriota 1. Surface temperature 15°C, WHP 6000 psi and water
in the line (Dic -29 -2002).
How to identify them? What to do?
Since the hydrates form within the equipment and is
impossible to corroborate their existence visually, it is
important to observe the external indicators to be able
to assure that there is hydrate formation when an
operation is performed.
The first step is to define the border conditions
where gas hydrates will form and identify the parts of
the equipment that can be affected by its formation. If
the pressure and temperature conditions are within the
zone of stability of hydrates (see fig 2), and there is
water in the well, it is necessary to use some type of
inhibitor.
If this precaution was not taken or it was not possible
to get some type of inhibitor and it was decided to
continue, it is very important to monitor any strange
behavior in the tension, the sheave wheel motion or
the operation of the equipment. Generally, it is
common to observe that the tool trap (if this has an
external indicator) does not close or to notice unusual
resistance when pulling out of the hole. It is critical to
take measures as soon as any indication of hydrate
formation is noted to avoid getting stuck with a hydrate
plug, with the body of the tool or even more serious
situations where hydrate plugs can give away due to
differential pressure and cause serious incidents like
cable rupture, loss of tools and, in the most drastic
cases, harm personnel.
It is also common to observe venting lines plugged
with hydrate plugs. In these cases, a fast pressure
drop is observed and if appropriate care it is not taken,
pressure can still be present in the line before the plug
creating a very dangerous situation.
When the formation of a hydrate plug is suspected
in the venting line the following rules must be followed:
1. Never try to open/disconnect any part of
equipment exposed to pressure if this opposes
some kind of resistance when trying to
open/disconnect.
2. Pump inhibitor (methanol is the most effective)
to try dissolving the hydrate plug.
3. If an additional pumping point is not available,
warm up the venting points to melt the
obstruction.
4. Totally vent the well and if necessary, repeat
the three previous steps as required.
When the problem is generated by hydrates adhered
to the line (this happens generally in wells of high
pressure, gas producers with water, or fresh water
before a perforating operation) some kind of inhibitor
must be pumped through any additional pumping port
in the BOP, the amount of inhibitor will depend on the
speed at which the cable in pulled out of the hole, the
amount of water produced by the well, and/or the type
of inhibitor used and its characteristics.
 Usually, the recommended ratio is 50% antifreeze
and 50% water to avoid freezing.
Another common case is hydrate formation due to
the use of fresh water to test lubricators or to equalize
pressures to open valves. In these circumstances, and
mainly in temperatures below 10°C, represents the
perfect scene for hydrate gas formation. If possible,
antifreeze must be used to test or to equalize
pressures, but if it is too late for this preventive
measure, it is very important to act fast and with
extreme caution.
When fresh water and gas get in contact, in addition
to high pressure and low temperature, hydrates start
forming. The formation of hydrates is not
instantaneous, diffusion of gas happens gradually and
generally the crystallization process makes the
diffusion difficult (this situation happens when both
components are at the same pressure, if the water is
at atmospheric pressure and it is exposed to gas at
high pressure, with low temperatures, the formation of
a compact hydrate block is almost instantaneous).
When you start moving the logging cable, the same
movement of the cable facilitates the migration of gas
and favors the hydrate formation all along the water
column. In these cases, it is recommended to maintain
the cable in movement. If the cable stays still, the
hydrates will tend to adhere to the cable and form a
solid plug within the lubricators. Also we have to
remember that pulling the cable out of the hole
accumulates ice in the tool catcher which also favors
the formation of plugs, thus it is preferable to run in
hole instead of pulling out of the hole when
experiencing an event with hydrates formation.
When a plug is formed, It is important to maintain
grease injection at the same pressure as the wellhead
pressure (otherwise the existing differential pressure
can break the hydrate plug, and if the cross-sectional
area of the plug is large enough, the generated forces
could even break the cable) and to try to inject
methanol right away or, if methanol is not available,
find a way to warm up the lubricators to eliminate the
gas hydrates.
Another way to facilitate the hydrate dissociation is
lowering the pressure, but it is important to remember
that if a hydrate plug is already formed, pressure
differential through the plug should be avoided, i.e.,
grease injection must be cut immediately.
To have an idea of the amount of force that a
suddenly detached hydrate plug could generate, let’s
take an example from a common operation with
wireline. If we have a well with 7000 psi in the wellhead
and we use lubricators with 3" ID, the grease injection
must be 20% greater to the pressure in head, which is
8,400 psi. If a hydrate plug forms over the cable, inside
the lubricators, there would be a differential pressure
of 1,400 psi acting on the upper face of the plug,
calculating the cross-sectional area of 7 square
inches, the resulting force would be 9,896 lbs
(approximately 4.5 tons), enough to cause
considerable damage.
Examples.
It is easy to ignore this type of situations, mainly when it is common to think that they are sporadic or they happen
in leases where the temperatures are extremely low as it could be in Alaska, Canada, Russia or Argentina,
nevertheless in any lease in where the adequate conditions appear for the formation of hydrate, can be subject to
this type of problematic.
Well: Ciclón 1
Date: Dic -24 -1998
Operation: Dummy Run
Company: Schlumberger
Description.
During a perforating operation, the equipment was
ready to start a dummy run with a 2 1/8" dummy bar.
The well had 4,500 psi WHP and the surface
temperature was 6°C.
Equipment was tested with 6000 psi, the lubricators
were left full of water and with 0 psi. Grease was
injected at 5,500 psi and when trying to release the
tool from "Tool Catcher" it was impossible. After
several attempts without success, the swab valve was
closed again. There was a pull out while manipulating
the cable trying to release the tool. When the
lubricators were lifted from the wellhead, an ice
cylinder was observed surrounding the tool.
Analysis.
When opening the well with the lubricators full of water
at atmospheric pressure, a block of hydrates was
immediately formed in the body of the lubricators.
Under these conditions and with a WHP of 4500 psi
the gas diffusion was so fast that it formed a single
solid cylinder.
Since grease injection was never suspended a
differential pressure of almost 1,000 psi was
generated among the cylinder generating 7,000 lbs of
force pushing downwards.
The time used while trying to release the tool was
enough for the exerted force to break the hydrate plug
as well as the weak point.
This problem could be avoided by testing the
lubricators with brine or with water mixed with
antifreeze, and the rupture of the weak point could be
avoided by cutting the grease injection immediately
when the presence of an hydrate plug was identified.
Well: Patriota 1
Date: Dic-26-2002
Operation: Fas Drill Plug Setting
Company: Halliburton
Description.
During the third run, and after having several
problems to pass through the "Tubing Head" of the
well, it was decided to lower the plug directly in the well
without making the dummy run, this due to the form of
the plug, which would facilitate its entrance through the
4½ " pipe.
The well had 6,000 psi WHP and the surface
temperature was 10°C. The operation took place near
midnight.
It was necessary to equalize pressures before
opening the master valve (Frac-Stack). This operation
was already made before in two previous runs with a
higher surface temperature and with day light. Fresh
water was used to equalize pressures, the valve was
opened and it began to lower.
An obstruction was found again at the tubing head
and after several attempts it was decided to pull out of
the hole. When beginning to POOH an unusual
resistance in the line was observed, almost all the
cable RIH was recovered, but the original mark in the
drum showed 15 cm below the starting depth. The tool
got stuck before the tool catcher.
It was requested to the personnel in charge of the
Frac-Stack to close the lower master valve, since the
space between the end of the plug and the lower
master valve was smaller to 30 cm (it was possible to
damage the plug and the valve gate). As the personnel
in charge of the valve refused to close it, it was decided
to wait for day light to proceed with the authorization
and close of the lower master valve.
The cable was left with a tension of 100 psi and the
unit was turned off. Before dawn the weak point failed
and the tool got trapped between the tubing head and
the body of the lubricators, It was necessary to kill the
well to recover the tool.
Analysis.
Although pressures were equalized before opening
the well, the high pressure and the low temperature,
as well as the use of fresh water during the pressure
test, contributed to the formation of gas hydrates.
When equalizing pressures, the hydrate formation is
as fast as the diffusion of the gas through water. When
recovering the tool, sections in the lubricator already
had hydrates formed and when forcing the tool to enter
the lubricators, the gas hydrates were compacted
forming a plug which solidified when the tool got stuck
and the cable stayed static for several hours.
The grease injection was never suspended, it was
regulated to a pressure of 7,500 psi which generated
a differential pressure of 1,500 psi through the plug,
equivalent to 10,600 lbs force applied on the hydrate
plug.
When the plug failed, the hydrate cylinder formed
pushed the tool with almost 5 tons of force towards the
tubing head, broke the weak point, folded the setting
tool adapter kit and destroyed the plug.
 In the cable, plastic deformation is not observed
which means the steel failed by impact (fig 6). In the
setting tool adapter kit, plastic deformation in the
tension mandrel is observed. The tension mandrel is
built with a solid steel bar of ½ "(fig 7 and 8), this is
another indicative of the force which impelled the tool
against the tubing head.

Fig. 8 Detail of the Fas Drill plug after recovering the tool.

The problem in this well would be avoided by using

a mixture of ethylene-glycol with water. If grease
injection would being suspended when the tool got
stuck the rupture of the weak point and the destruction
of the plug and setting tool as well as the fishing
procedure would be avoided.

Fig. 6 Detail of the end of the cable. Note the lack of plastic
deformation in the cable which indicates a failure by impact.

Fig. 7 Detail of the damage suffered by the setting tool adapter

kit, the tension mandrel that is behind the setting sleeve is a ½"
solid steel bar.
Well: Kriptón 2
Date: Jan -26 -2003
Operation: Fas Drill Plug Setting
Company: Halliburton

Description. Analysis.

After setting a plug in 4 ½ " pipe, tool was pulled out
of the hole. It was noted an abnormal tension when
arriving to the lubricators.
The well had 7,000 psi WHP and surface
temperature was around 8°C.
Ethylene-glycol mixed with water to 25% was used
because of an error while handling the antifreeze,
which was already premixed to 50%.
Although an error in the mixture of ethylene-glycol
was made, the operation was performed correctly to
recover the tool in a safe way without risking neither
the equipment nor the well.
It is probable that an injection of pure ethylene-glycol
when rcovering the cable would help to achieve full
dissociation of the gas hydrates and would help to
recover the setting tool since the first attempt.

Running in hole operation performed without

problems. When the cable was pulled out of the hole,
around 150 m from surface, it was noticed that the tool
trap didn’t close and abnormal tension was noticed
when arriving to the BOP.

The cable was ran in hole again and it was kept in

motion between 200 and 300 m while the well was
vented, the injection pressure was kept slightly above
the pressure in the wellhead.

After reducing the wellhead pressure to zero the

hydrate dissociation was noticed, as it was possible to
close the trap, and the tool was recovered to surface.
Well: Visir 1
Date: Jan -28 -2003
Operation: Perforating
Company: Halliburton

Description.
After retreiving the perforating guns and closing the
well swab valve, when venting through the venting port
of the BOP, the port got plugged with hydrates.
The well was full of fresh water. Pressure raised to
6,500 psi after perforating and surface temperature
was 10°C.
When trying to vent the lubricators, after retrieving
the guns, it was noticed a fast pressure drop in the
pressure gauge of the BOP and a decrease in gas flow
in the venting port. The pressure dropped to 0 psi and
no more gas came out. Resistance was observed
when trying to disconnect the lubricators and water
with ice began to flow through the venting port (fig 9)
reason why it was chosen to inject antifreeze through
the auxiliary ports in order to try to eliminate the
hydrate plug formed in the venting ports. After
pumping 10 liters of pure ethylene-glycol, it was
possible to finish venting the lubricators which still
contained 500 psi.
Analysis.
In this well it wasn’t necessary to equalize pressures
to open the valves as it was a new well and WHP was
0 psi. The problem occurred after perforating as the
well was full of fresh water. The gas that migrated
through the cable to surface found suitable conditions
to mix itself with the water that was at surface to form
hydrates.
In this case, although the glycol injection solved the
problem, it’s easier to avoid this type of situations filling
the well with brine instead of fresh water, this helps to
inhibit the hydrate formation.
Also, glycol injection while pulling out of the hole is
a practice that avoids the hydrate formation in the
lubricators and its possible accumulation in the venting
points.

Fig. 9 The flow of water and ice is observed through the

venting port of the BOP after disconnecting the venting hose to
verify zero flow in this point

Conclusions.
After the analysis made in the previous pages we
can conclude that most of the problems that involve
hydrates are avoidable with an adequate planning of
the work and a good coordination and communication
when they happened.
• Kvenvolden K: “Gas Hydrates – Geological Perspective and Global
Change,” Reviews og Geophycs 31, no.2 (May 1993) 173-187.
• Makogan YF: Hydrates of Hydrocarbons, Tulsa, Oklahoma, USA:
PennWell Books, 1997.
• Durham, W: “Methane Hydrate,” Science & Technology Review 1999
LLNL Homepage http://www.llnl.gov/str/Durham.html
• Zuo, J., Zhang D.: “Gas Hydrate Formation in Aqueous Solutions
Containing Methanol and Electrolytes,” Laurance Reid Gas Conditioning
Conference, Norman,Oklahoma;February 21- 24, 1999
• Collet T., Lewis R., Uchida T.: “Hydrates”, Oilfield Review, Schlumberger
Summer 2000. pp 42-57

Most of the problems with hydrates in wireline

operations are caused by lack of information and
knowledge of the people, often this lack of information
causes that operators in the field attribute the
problems related to hydrates to another type of
situations or causes that have nothing to do with these.

Unfortunately, and mostly because of lack of

knowledge, there isn’t enough documentation about
this kind of problems which contributes negatively to
the lack of planning and lack of precaution required in
this type of situations.

As a curious fact, all the cases used as examples

were exploratory wells in which similar conditions were
present, high pressure, low temperature and fresh
water. This is an unquestionable indicative of the extra
caution required during winter season in this type of
wells.

Bibliografy.