Professional Documents
Culture Documents
Are K. Thomsen
Norwegian Petroleum Directorate, Stavanger, Norway
Are Lund
SINTEF, Trondheim, Norway
ABSTRACT Another important factor for undertaking the study was the fact that
NPD has no regulatory requirements regarding reporting of hydrate
This study was undertaken by the Norwegian Petroleum Directorate formation which does not lead to a hazardous situation. NPD has little
and SINTEF to identify hydrate problems occurring in pipelines on information inhouse regarding extent and frequencies of hydrate
the Norwegian continental shelf. A brief review of hydrate formation. NPD also saw a need for gaining more knowledge about
dissociation theory is given. Three major techniques for hydrate hydrate formation in pipeline systems, frequencies and different
removal are discussed, as well as hazards related to hydrate plug methods for removing hydrates. The study should also consider
removal. Questionnaire answers from 15 companies operating in potential risk involved during removal of hydrate plugs. One experience
Norwegian waters 'show three specific occurren~es of hydrate plugs in from the study undertaken in 1990 was that the questionnaire had to be
the North Sea. Problems from other geographical areas are also more detailed regarding technical information about the pipeline
discussed. Hydrate problems are reported for a wide variety of pipe system.
lengths, diameters, profiles, insulation characteristics and fluids. Most
problems occur during normal operation.
257
Hydrates may be dissociated by means of pressure reduction, heat
addition and inhibitor injection. The processes involved in these
phenomena are iinportant, as they are also coupled to potential hazards.
The most comprehensive review of gas hydrates can be found in Sloan
(1990).
DISSOCIATION PROCESSES
258
~--------------~-------I~
b-----------~ __--____ ---I~
Ta Temperature Ta Temperature
Figure 2 Hydrate dissociation by temperature increase. Figure 3 Hydrate dissociation by methanol
Ta is the ambient temperature. injection. Ta is the ambient temperature.
phase will be at thermodynamic eqUilibrium, but because the hydrate at sea bottom conditions. During two-sided depressurization it might be
phase is not at thermal equilibrium with its surroundings, more hydrate advantageous to retain a small pressure difference, to be able to detect
will dissociate until all phases are at thermal and thermodynamic the melting of the final blockages.
equilibrium at point C. The dissociation process will stop, and the main
difference between the two states before (point A) and after methanol It is also possible to combine pressure reduction with inhibitor injection.
injection (point C) is that some hydrate has been dissociated and the Several advantages are obtained with this powerful hydrate plug removal
pressure has been increased. !Det~od. First of all, if. an inhibitor is injected upstream the hydrate plug,
It WIll be transported mto the porous plug when the pressure is reduced
downstream. Water produced into the pores of the plug will then be
HAZARDOUS SITUATIONS DURING HYDRATE PLUG REMOVAL inhibited and may not be able to form ice, and the porosity of the
hydrate plug will increase continuously. If an inhibitor like methanol is
One aspect of hydrate plug melting by pressure reduction which needs applied, the dissociation rate will increase even more; with much lower
special attention, is that the heat which is most readily available is the probability of hazardous situations.
one coming in through the pipe walls from the surrounding medium
(sand, water etc.). This means that the part of the plug which melts first, Temperature increase is not generally an applicable method for removal
is the outermost layer along the wall. This is the part that is keeping the of hydrate plugs in subsea pipelines, but a short look at hazardous
plug in place. If there is a large pressure difference across the plug, situations caused by the temperature increase method in process
there is a possibility that it will be shot through the pipe like a projectile equipment might be useful.
when it comes loose from the wall. This is a possible explanation for a
number of accidents in connection with hydrate plug removal. Often,
the pressure has been reduced on one side only (down to atmospheric A common way of removing hydrate plugs in process equipment (pipes,
pressure), and the plugs have come loose and caused large amounts of valves, scrubbers, separators etc.) is heating the plugged unit with hot
material damage and even fatalities (Kent and Coolen, 1991). water or steam. This is a very effective way, but caution is required.
When the ambient temperature is increased beyond the hydrate
A hydrate plug in a pipeline will have a porosity depending on the fluid equilibrium temperature for the given pressure, the hydrate starts to
system. In general, a gas system will produce low porosity plugs, while dissociate, and produced gas and water will raise the pressure. A
an oil system will result in higher porosity because of inclusion of w'ater pressure-temperature development described by curve B-D in Figure 2
and oil droplets. During the melting of porous plugs, the melting rate in will occur. This means that as long as there is hydrate left to dissociate,
the plug interior might be of the same order as the rate along the wall. and the fluids are not able to escape, the pressure will increase to the
This results in a slushy, grainy snow-like mass, which has less potential eqUilibrium pressure corresponding to the temperature of the hot water,
for damage if the plug comes loose. If the pressure on one side is which normally is at a dangerous level. In laboratories at the university
reduced to a level where the corresponding hydrate equilibrium of Moscow, pressures of several thousand bar have supposedly been
temperature is below O'C, the water produced in the pores will freeze. produced in this way (Makogon, 1994). Catastrophic rupture of process
This process will release heat, and the temperature of the plug is not equipment may occur.
likely to drop below O·C. The ice may close the pores in the plug, and
eventually stop the propagation of the pressure reduction. The melting The heat added will first dissociate the hydrate closest to the pipe wall. If
will then take place mainly along the wall. A wedge-shaped melting this process takes place along the whole plug - which can easily happen
zone will move along the plug-wall interface, reduCing the contact area for short plugs in process equipment - the plug may come loose from
between plug and pipe wall. At some point this contact area will become the pipe wall and may again be shot through the pipe as a projectile, if
too small to hold the plug, which may be shot through the pipe with care is not taken to equalize pressures upstream and downstream.
high kinetic energy, damaging pipe and equipment.
Injection of methanol is a common way of dissociating hydrate plugs in
One way of avoiding this is to depressurize both sides of the plug if at the North Sea, usually in combination with pressure reduction.
all possible. The plug will then be stationary, and the melting process Inhibitors used in combination with pressure reduction will reduce the
will be both safer and quicker. Lowering the pressure such that the risk of developing hazardous situations. No hazardous situations
equilibrium hydrate temperature is below O'C should be avoided. Ice connected to hydrate plug dissociation have yet been attributed to
formation will prolong the melting process substantially. This sets a inhibitor injection alone.
bound for the attainable melting rate, as generally only a relatively small
temperature difference in relation to the surroundings can be obtained
259
INQUIRY RESULTS A group of four companies describe hydrate problems and incidents
from other geographical locations than the North Sea. On-shore gas
All petroleum companies active in Norwegian continental waters were pipelines with diameters from 3" to 12" and lengths of 8 km to 80 km
sent a questionnaire regarding hydrate problems in pipelines. are described as having hydrate problems when ambient temperatures
Experience from the previous inquiry (Johnsen, 1990) indicated that have been low. One company reports problems with a 3", 4.5 km
very detailed questions on pipe diameter, length, fluid composition, subsea gas pipeline in a more southern climate. A common feature of
pressure and temperature conditions etc. were needed to analyze the the reported incidents from another company is that their onshore lines
reports. In addition, questions on production history leading up to the had been shut down at low temperatures and high pressures, and
problems, estimates of hydrate amounts, removal procedures and problems occurred at start-up. Wet gas lines, of different lengths,
general company procedures, awareness and experience transfer were diameters of 2" to 19", and with rather "bumpy" profiles are reported
included. A full report on the inquiry is found in Lysne et al. (1994). as having hydrate problems whenever sea temperatures are low enough.
It is of special interest to note that one company sometimes uses pigging
The relatively low number of reported incidents (three companies) must to clear "hydrate slush" from the pipes. This procedure is generally
be seen in relation to the short period of only three years. A total of six not advisable at all, because of the danger of packing the hydrates
incidents of hydrate problems in pipeline transport were reported in the together and creating plugs.
earlier study (Johnsen, 1990).
Only three of the companies discuss hydrate problems in the North Sea
The received data were mostly adequate to fulfil the main goals of this in their reports. One describes a large-diameter gas pipeline of 350 km
study; to chart incidents and company procedures and awareness. The length which was completely plugged. This was due to an ice plug used
answers vary from short denials of any problems, to hundreds of pages to isolate another pipe branch accidentally entering the pipe and acting
of documentation of pressure and temperature conditions, detailed as a nucleation site for hydrates. Inhibitor injection for several weeks
pipeline profiles, etc. A summary appears in Table 1. was needed to clear the plug. Another company offers documentation
of two separate plug incidents in the North Sea. One took place in a 9"
More than half the companies (8) report no problems with hydrate oil and gas pipeline of 12 km length, with a very bumpy profile. The
formation in pipelines. Some of them indicate extensive research efforts plugging was due to a faulty valve, letting water enter the stagnant
resulting in procedures and knowledge used to avoid possible problems, pipeline. Pressure reduction and a large batch of methanol was used to
while others describe the need for hydrate awareness as small, and rely remove the hydrates over a period of 24 hours. The other incident took
on e.g. "warmer climates" to avoid problems. place in a 6", 12 km un insulated test- and service pipeline. After an
inhibited shut-down, the line was restarted without the proper
procedures for inhibitor injection being followed. Hydrates were
localized close to the processing facility, and were quickly removed by
methanol injection downstream, and by spraying of hot water on the
outside of the exposed pipe. The third company discusses aspects of
Table 1 Summary of received questionnaire answers hydrate formation in as", 7 km flat-profile oil pipeline. Temperature
drop and unplanned shut-downs are identified as critical factors.
Company Problems Type Solution Experience Procedures for organizing and transferring hydrate knowledge differ
(NS: North transfer between the companies, from no procedures in one company, to an
Sea) extensive package with hydrate courses specialized and adapted for all
relevant technical levels within one of the others.
1 No - - NlA
2 Yes onshore MeOH+ No formal COMPANY PROCEDURES FOR HYDRATE CONTROL OR
plugs depres- PREVENTION
surization
3 No - - N/A All companies which have hydrate activities seem to evaluate the
possibility for hydrate formation by the use of so-called handbook
4 No - - Special
work
methods or different advanced computer programs. The handbook
methods are usually reliable if a liquid hydrocarbon' phase
descriptions (condensate/oil) is not present. The computer programs which are used,
are mainly based on hydrate theory from van der Waals and Platteeuw
5 Yes subsea Inhibitor + None (1959), which is known to give satisfactory results for most engineering
plugs depres- purposes.
surization
6 No - - N/A Glycols (usually monoethylene glycol) are most often used for
7 Yes (NS) subsea MeOH+ None continuous hydrate inhibition. These chemicals also often behave as
plugs Alcohol corrosion inhibitors. Methanol is used or going to be used by about half
of the companies which need inhibitors. The same chemicals are used at
8 Yes (NS) subsea MeOH, heat Extensive shut-down or start-up.
plugs and course
depres- package The methods used for calculation of the total amount of inhibitors
surization needed, have only, been given by one company, which has developed a
multiphase computer program handling the inhibitor distribution in all
9 Yes onshore Heat + Publication phases. Many computer programs in use only give the amount of
plugs depres- of inhibitors needed for the water phase, ignoring inhibitor distribution to
surization experience gas and liquid hydrocarbon phases. The additional amount of inhibitors
10 Yes subsea and Inhibitor + Courses needed has to be evaluated from tables or experimental data. The
onshore depres- received answers do not indicate whether or not this is done.
plugs surization
Four of the 15 companies have described formal procedures for
11 No - - NlA treatment of hydrate problems. Other companies seem to make field
specific proc,edure's as needed. .. .
12 Yes (NS) subsea MeOH+ N/A The usual ways to treat hydrate problems an a pipeline seem to be;
plugs depres- for a partly clogged pipeline, methanol is injected upstream the
surization hydrates.
13 No - - NlA for a completely clogged pipeline, depressurization is used prior to
methanol or glycol injection.
14 No - - None
15 No - - Yes
260
Table 2 Range of system characteristics for reported
(c)
hydrate problems in pipeline transport.
60
Pipeline Characteristic Extreme values reported
Pipeline length 5 - 350 km 50
Pipe inner diameter 2" - 30"
Insulation From none, to both coating and
trenching 40
Fluids Gas system - oil system
Pipeline profile From flat, to extremely buckled
30
20
DISCUSSION
One interesting trend to note, is that companies having experienced
't. Hydrate temperature
severe hydrate problems, seem generally much more aware of the risks 10
in later operations, and have better procedures ready in case of re-
occurrences. From the information. received, it is clear that problems of
hydrate formation in pipelines are not restricted to special cases, special o~---r---,--------~---p---,-
fluids or special pipe characteristics. Table 2 shows the range of 15 4015 8015 12015
different characteristics which were reported for problematic pipelines.
(m)
The clearest indication of beginning hydrate problems for a pipeline in
operation seems to be an increasing pressure drop. It is important that
operators learn to recognize this sign, in addition to knowing the Figure 4 Fluid temperature profiles along the Tordis-Gullfaks C
hydrate-favouring pressure and temperature conditions. If the hydrates flowline as a function of shut-down time
are identified at an early stage, inhibitor injection or production rate (Lysne et aI., 1992).
increase may be enough to remove them before a hydrate plug is
developed.
Start-up of pipelines after long shut-downs where fluids have reached
ambient sea temperature, is one of the major trouble areas. To start the
flow, the line, has to be, pressurized, and temperature and pressure in subsea pipelines in the Mexican Gulf, the Mediterranean and the
conditions will often be well inside the hydrate stability region. It is Persian, Gulf.
important to try and inhibit the fluids before such a shut-in, and also
before the start-up is performed - although this often presents practical
problems. CONCLUSIONS
Pressure reduction and methanol injection are clearly the most favoured The reported occurrences of hydrate formation show that the problem
methods of removing hydrates once they have formed. A method which appears more frequently than in the previous study, even if the last
is not often possible to use on transport pipelines (especially subsea study was undertaken for a relatively short period of time. The two
ones) but all the more usual in process facilities, is the spraying of hot studies together make it clear that it is also important that awareness of
water or steam on the pipe outside to melt hydrates. All these potential risk during removal of hydrate plugs is recognized. A
procedures and their accompanying possibilities for hazardous minority of the companies state that they have formal procedures in
situations were discussed earlier. place for hydrate removal. The general knowledge about hydrate and
hydrate related problems vary widely in the different companies, and
It is worth noting that most of the reported incidents of hydrates have hopefully this is an area for improvement in the future.
occurred during normal operation (including shut -down and start-up),
and are seldom due to abnormal events or pure accidents. It seems It has been found that hydrate problems occur for a wide variety of pipe
about 75% of hydrate problems occur during normal operation. lengths, diameters, profiles, insulation characteristics and fluids. Most
However, this number is not entirely accurate, due to several companies problems occur during normal operation.
lumping incidents together in their reports.
In relatively short pipelines, hydrate formation conditions are usually
only reached in the case of low flowrate or during a shut-down. As an
example, Figure 4 shows the' temperature profile of the pipeline from
Tordis to Gullfaks C in the North Sea, at different times after shut-down, REFERENCES
from steady state simulations with the OLGA multiphase flow simulator
(Lysne et al., 1992). Johnsen H.K. (1990). "Kartlegging av hydratproblemer i
petroleumsvirksomheten", Report for the Norwegian Petroleum
Figure 4 shows that the temperature at the Tordis manifold and at the Directorate (in Norwegian).
Gullfaks C riser reaches possible hydrate formation conditions about 9
hours after shut-down. Kent, R.P., Coolen, M.E. (1991). "Hydrates in Natural Gas Lines",
paper presented at Mobil safety conference.
For long pipelines, insulation characteristics are generally of low
importance. The flowing fluids will fairly rapidly (especially at shut- Lysne D., Sa:ther G., Lund A. (1992). "Evaluation of potential hydrate
down) reach ambient temperatures. For subsea pipelines, this is well problems for Tordis field development", Multiphase Transportation
inside the hydrate envelope at most operation pressures. Other measures ill - Present Application & Future Trends, conference at Rf/lros, Norway.
have to be taken to avoid hydrates - mostly chemical inhibition. One
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hydrate problems altogether. This is a false sense of safety, as sea- An inquiry among petroleum companies with operational responsibility
bottom temperatures can be low on most continental shelves. This sense on the Norwegian continental shelf, 1991-93", report. no.STFII
of security should also vanish in light of reports of hydrates occurring F94008, SINTEF, Trondheim, Norway
261
Lysne D. (1995). "Hydrate plug dissociation by pressure reduction",
Dr.ing. thesis, Norwegian Institute of Technology (NTH), preprint.
Makogon Y. F. (1994). "Russia's Contribution to the Study of Gas
Hydrates", Ann. N.Y. Acad. Sciences Vol 715, pp 119-145, New York.
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262