OTC 19730

Removal of a Hydrate Plug From a Subsea Christmas-Tree Located in

Ultra-Deep Waters With the Aid of a Heat-Releasing Treating Fluid
E.A. Evangelista, C.M. Chagas, J.A.F. Melo, J.D.H. Rocha, Ney B. Filho, and L.C.C. Marques, Petrobras

Copyright 2009, Offshore Technology Conference

This paper was prepared for presentation at the 2009 Offshore Technology Conference held in Houston, Texas, USA, 4–7 May 2009.

This paper was selected for presentation by an OTC program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract

The paper describes the actions taken to re-entry a well located in ultra-deep waters (1541 m water depth) whose
sub sea Christmas-tree was blocked by a solid hydrate plug and therefore could not be liberated by means of its
standard releasing tools.

A heat-releasing treating fluid – the so-called self-generated nitrogen (SGN) fluid – was successfully applied to
heat and dissociate the hydrate plug, which was totally blocking the locking mechanism of the Production Vertical
Connection Mandrel (PVCM) of the tree. The heat applied around the Xmas-tree body was conveyed by the
pumped SGN fluid batches. By doing so, the hydrate plug was completely dissociated (melted down) and then the
unlatching mechanism became operational again.

This paper comprehensively describes the steps of this different hydrate treatment job. In broad terms, a
technically challenging job which encompassed the following issues: - development of a “tailor-made”
environmental-friendly SGN formulation, - heat exchange simulations to design the optimum volume for the SGN
treatment batch, - a review of the theoretical aspects of hydrate formation/dissociation, - use of an
instrumented/insulated drill pipe riser (DPR), - and job safety procedure reviews. A PLT logging tool (PLT) was
also used to keep a record of the temperature profile inside the DPR.

In view of the pioneer aspects of the operation, the combined use of an ROV and PLT was of paramount
importance to monitor every step of the operation since its very beginning. Along the job, the Christmas-tree, the
reactivity of the treating fluid batches, the temperature changes, and the hydrate blockage, were monitored on a
permanent basis. The combination of these two tools has provided precious pieces of information that have
enabled us to gain insight into what was going on along the job and take the necessary measures to its real-time
optimization.

Introduction
Hydrate and paraffin blockages are currently the major causes of oil production losses in Campos Basin´s
deepwater scenarios. In many instances, these blockage problems have been solved by means of a treatment
with the heating-releasing SGN fluids.

One typical Campos Basin ultra-deepwaters well (1541 m water depth, 4ºC at seabed) completed with a subsea
Christmas-tree (within the hydrate formation envelope) was initially producing to a floating production plant
through a subsea flowline (FL). This well was scheduled for a routine work-over job whose objective was to
replace the damaged FL by a brand new one. Briefly, in order to retrieve the line, first it is necessary to unlatch it
from the Production Vertical Connection Mandrel (PVCM) located aside the Xmas-tree. See Figure 1. From this
point on, the line has to be pulled out and winded on a reel for later work-over or disposal. The main thing is that
2 OTC 19730

the work-over job we had done to retrieve the line was not successful at all. Both mechanical and the back-up
hydraulic unlock system were not operational. So, the launching vessel had to be sent to another location while
we started trying to gain a better understanding of the type of problem we were facing there. Subsequently, the
Xmas-tree was carefully re-inspected by an ROV and a hydraulic leaking in the unlocking system was detected.
New attempts to actuate the mechanical unlatching system were made but unfortunately they caused a physical
damage to it. No possibility of overhauling it was on hand.

Vertical Connection Mandrill

Fig.1 - Sub Sea Christmas-Tree Schematics

Based upon our previous experience in Campos Basin we came up with an educated guess that the problem we
were in front of was a hydrate plug which had been built inside the MCVP. The presence of a hydrate plug would
explain these operational failures. Such a conclusion was based on hydrate formation simulations for the existing
conditions at the seabed, viz, 1541 m water depth and seabed temperature of 4ºC, as per depicted in Fig. 2. It is
very likely that gas had accumulated inside the MCVP area, where it had contacted moisture - or free water - and
ended up forming a solid hydrate plug.
OTC 19730 3

Hydrate Formation Phase Diagram

400

350

300

Pressure (bar)
250

200 Hydrate
Envelope
150

100

50

0
-5 0 5 10 15 20 25 30
Temperature (C)

Figure 2- Hydrate Formation Envelope

So, a multi-disciplinary task group was formed to address the problem. The envisioned alternatives proposed by
this group were the following: the use of a tailor-made electrical heating submarine system (EAHS) developed by
Petrobras R&D Center (CENPES) and, as a second option, to promote a heat-releasing reaction to dissociate the
hydrate, using the so-called self–generated nitrogen (SGN) fluid system. In reality, the first alternative was not
successful. A total of three attempts to heat the Christmas-tree were made, but they brought no palpable results
at all. The EAHS is a sort of piece of equipment which still requires some improvements to achieve a good level of
reliability.

In stark contrast to this, we were successful to dissociate the hydrate plug. We have managed to accomplish that
by combining the use of: an insulated drill pipe and - last but not least - a tailor-made SGN placement tool.

At this point, it is important to emphasize the friendly-environment nature of the SGN fluid system used in the job.
The only products generated by the SGN reaction are: the inert Nitrogen gas and Sodium Chloride brine.
Environmental concerns are ever growing all over the world and that is not different for Petrobras which has an
institutional policy to carrying out all activities in full respect of the environment.

Job Planning Development

It is of paramount importance to be able to count on a multidisciplinary team working in concert whenever the use
of non- trivial solutions is mandatory. As is always the case, a balance must be stroke between economics,
environmental concerns and what is technologically possible. Field experience, good judgment, expertise and
“thinking out of box” also play an important role on such a situation. Even though this statement may sound a
cliché, that is the unique approach that produces good results on such a scenario. It was not different at this time.

The starting point of this whole mental process was to get a better understanding of what was actually avoiding
the FL unlatching from the MCVP. After considering all possibilities, the only conclusion we came up to was that
a hydrate plug had built up inside the MCVP. In order to destabilize a hydrate plug one of two different actions
must be taken: In very simple terms, thermodynamics states that by properly changing pressure or temperature
(or both) it is possible to move the hydrate out of its crystallization envelope. Nonetheless, as there was no way to
change the pressure under the actual field conditions, heating the hydrate was the only solution left.

At this point some fundamental questions arose: Is it feasible to apply enough heat to the body of the Christmas-
tree to destabilize the hydrate? Is it possible to control the SGN reaction not to exceed a limit temperature to
prevent permanent damage to the existing elastomers (gasket, o-rings, external linings, etc) either in the
Christmas-tree or in the drillpipe riser used to convey the SGN fluids? Furthermore, is it possible to control the
SGN reaction to spot the heat spike where it is really needed? Certainly, these challenging questions had to be
addressed before getting started.
4 OTC 19730

A Brief Description of the SGN Fluid System Chemistry and Application

The SGN fluid system is not novelty in the oilfield industry.i Essentially, it comprises the exothermic red-ox
reaction generated from the (proper) mixing of two nitrogen-containing salt solutions, namely, Ammonium
Chloride (NH4Cl) and Sodium Nitrite (NaNO2) solutions. Under specific conditions, in presence of a catalyst, the
two salt solutions react as follows:
catalyst
NaNO2 (l ) + NH4Cl(l) > N2 (gas) + NaCl(l) + 2H2O(l) H= - 312,5 kJ. mol-1

As we can see this reaction gives off a large amount of heat per mole and its reaction products – Nitrogen gas
and (table-salt) Sodium Chloride - are not harmful to the environment. Theoretically, under adiabatic conditions a
liter of a 3 Molar SGN solution is able to give off an amount of thermal energy to heat 1 liter of water from
ambient temperature up to 250 0C. Figure 3 depicts a previous SGN job done to dissociate a hydrate plug that
was clogging the tree cap latching mechanism. The “clouds” above and around the Christmas-tree are composed
of Nitrogen gas and it is a visual indicator that the SGN reaction is in progress.

Figure 3 – A Subsea Christmas-tree Surrounded

by Nitrogen Gas Bubbles from the SGN Reaction.

In some specific applications, the SGN fluids can be emulsified in non-polar liquid phases like liquid paraffin (C14 -
C16) or bio-diesel. The combination of the thermal energy released by the reaction and the solvency power
provided by organic solvents enhances the efficiency of melting (and solubilizing) the solid mixture of alkane
molecules (paraffins) that make up the vast majority of organic deposits. Also, the emulsified SGN formulation
enables a better control of its reaction kinetics, thus broadening its range of applications.

On the Use of SGN Fluid System by Petrobras

Petrobras has achieved a large experience on using the SGN fluid system. For instance, in the upstream segment
SGN has been applied to different offshore basins located along the Brazilian coast.ii In reality, hundreds of SGN
operations have been successfully carried out for melting and suspending paraffinic (paraffin-rich) deposits under
different of operational conditions.iii In contrast to that, on a few occasions we have applied the SGN method to
dissociate hydrates that were blocking valves and flowlines. SGN fluids have also been used on a pioneer
operation to free a pig stuck by a massive paraffin deposit in a submarine flowline of a well producing to an
FPSOiv,v This system has also been used to remove formation damage caused by paraffin deposition in the
reservoir in some onshore shallow wells.vi

As the SGN operations are recurrent in Campos Basin, the three Stimulation Boats that operate in the area
(under Petrobras´ contract) are equipped with an independent and exclusively-dedicated plant to the proper
handling & pumping of the SGN fluids.
OTC 19730 5

SGN has also been used by Petrobras in both its mid- and down-streams segments. A list of SGN utilizations on
these segments include: paraffin melting, hard-emulsion destabilization, dispersion and fluidization of different
kinds of sludges and other organic deposits, collected in storage tanks and slope pits existing in different sites
like: refineries, booster stations and crude oil-tankersvii

How to Carry-out the Destabilization of the Hydrate that was Blocking the Christmas-tree?

In order to destabilize the hydrate that was blocking the Christmas tree, two options were initially considered: the
first one was to apply a technique recently developed by CENPES, the so-called “Electrical Submarine Heating
Device (ESHD)”, or the recurrent solution for this sort of problem: the SGN Fluid System. Both alternatives were
subject of discussion, because of the innovation, in the first case, and the fact that a SGN job was had never been
successfully used at this water depth. The decision we have arrived to was that SAES would be “first plan” and in
case of failure, then, SGN would be tried.

It is worth noting that a factor that could unquestionably influence the operational success was the submarine sea
currents at the bottom parts of the sea. Statistics shows that the sea currents hovering around 2 knots on the mud
line are frequent. Under these circumstances, the heat transferred to sea water can be large enough to cool down
the SGN fluids to the point that the reaction can not be started. According to simulations carried out by CENPES,
the SGN reaction rate is very close to zero at temperatures below 10 0C. So, to assure the SGN fluids make it to
the mud line at above this temperature two things need to be done: Either shortening the residence time of the
SGN fluid in the pipe string (by increasing the pumping rate) or a thermal insulated pipe string should be available
for the job.

With the aid of a thermohydraulics simulator (PipesimTM), a suite of simulations was carried out to find the thermal
profiles, and quantify the amount of heat lost by the SGN fluids to seawater at different pump rates. These
simulations were run for two strings (different ID´s) of thermal-insulated drillpipe riser (DPR) available in our
pipeyard. One of these simulations printouts is depicted in Figure 4.

Fig 4 – Temperature Profile Simulations

for the Two Different Insulated DPR´s
6 OTC 19730

As per Figure 4, one can realize that the use of an insulated DPR would mitigate the heat exchange (between the
SGN fluids and the surrounding seawater) on such a way that the SGN fluids would arrive to the mud line at
temperatures higher than 83 0C. According to these results, the threatening of “freezing” the SGN reaction could
be discarded once an insulated pipe could be used. Based upon these simulations we have also decided to use
a low-concentration SGN formulation as well. The bottom line here was to avoid any eventual damage to the
DPR´s external insulating layer (polyethylene-made) brought about by overheating.

It is interesting to mention that in some of our pioneer hydrate dissociation operations we faced some problems to
monitor both the pressure and temperature along the pumping job. In fact, the malfunctioning of downhole gauges
was somewhat recurrent. Should you not have a good control of these parameters you can not optimize the SGN
operation as a whole. Also is clear that carrying such a kind of highly-exothermic reaction without adequate
control can lead to dire mechanical failures and HS&E-related troubles. Due to that, this time we have decided
to run in hole a Production Logging Tool (PLT),TM supplied by a Logging Company, to monitor both pressure and
temperature along the DPR while the SGN fluids pumping job was in progress. As we had anticipated, the results
provided by this logging tool were outstanding. It showed a good performance all along the job, was very useful to
monitor the SGN exothermal reaction, prevented the DPR from being overheated and; helped us to spot the
reaction heat spike around the body of the Christmas-tree almost 100% of the pumping time. A printout of thermal
profile along the DPR during the pumping job is depicted in Figure 5. According to this figure the SGN fluids
temperature peaked circa 110 0C below 800 m-depth in the DPR. This temperature is high enough to dissociate
the hydrate but is not sufficiently high to cause any damage to the DPR.

Fig 5 – Thermal Profile in the DPR During the SGN Pumping Job
OTC 19730 7

Figure 6 shows the schematics of the Subsea Christmas-tree - and its PVCM – that was plugged by a hydrate
and was submitted to the SGN job

Fig 6 – The Christmas- tree Schematics

The Home-made Campanula

Another in-house tool had to be designed, manufactured and revamped to link up the bottom end of the DPR to
the Christmas tree´s PVCM then making the SGN pumping job feasible. Figure 7 depicts this campanula-shaped
(inverted funnel) tool right above its final position.

During the SGN fluids pumping time the DPR string plus the 3,2 metric ton - weight campanula tool are slacked-
off and /or pulled-out so that the string free-point is set around the campanula. This is to rule out the possibility of
causing a mechanical damage to the Christmas-tree and helping the rig compensator to actuate suitably.

The
Campanula

Fig 7 – The Campanula Tool Right Above the PVCM

Acknowledgments

The authors are indebted to Petrobras for permission to publish this paper. The authors are also indebted to the
following Petrobras R&D Center specialists: C. N Khalil and Nelson O. Rocha for running the SGN experiments,
and Eduardo Gaspari for running the thermohydraulics simulations.
8 OTC 19730

Conclusions

-The use of a DPR was absolutely necessary to the success of the SGN operation .
-The combined use of a DPR and the PLT tool has improved the reliability and the efficiency of the SGN operation
carried out to dissociate the hydrate plug.
-The final conclusion is that we have managed to heat and dissociate the hydrate plug, which was clogging the
locking mechanism of the Production Vertical Connection Mandrel (PVCM) of the tree, thus unlatching the subsea
flowline.

References

iii
Davies, D. R. and Richardson, E. A. “Field Application of in situ Nitrogen Gas Generation System”, SPE 9653.
SPE Middle East Oil Technical Conference, Manama, Bahrain, March 9-12, 1981.
iii
Neumann, L. F., Khalil, C. N., Santos, I. e Linnard, C. A. “Thermochemical Process To Remove Paraffin
Deposits in Subsea Production Lines”, OTC paper 7575, Offshore Technology Conference in Houston, Texas,
May 1994.
iii
Assayag, M., Coelho, M. V., Minami, K., “Procap-3000: Following the Pathway to 3,000 m Water Depth”,
Deepwater Technology, October, 2001, 63 -73
iii
Marques, L. C. C., Pedroso, C. A., Paixão. L. C. A.: New Flow Assurance Solutions to Hydrate and Paraffin
Blockage Problems in Deepwaters, OTC paper 15190 presented at 2003 SPE offshore Conference Technology,
Houston, May, 5-8
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Marques, L.C.C., Pedroso, C.A., Neumann, L.F., “A New Technique to Troubleshoot Gas Hydrates Buildup
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Romeu, R. K, Khalil, C. N. and Rabinovitz, A .”Paraffin Precipitation in the Formation in Dom Joao Field,
Brazil”, SPE 21108, SPE Latin American Petroleum Engineering Conference, Rio de Janeiro, October, 14-19,
2002
iii
Rocha, N. O , Khalil, C. N., Leite, L. C., F.; Goja, A. M.: “Thermochemical Process to Remove Sludge from
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