SPE 63122
Anti-Agglomerant Hydrate Inhibitors for Prevention of Hydrate Plugs in Deepwater
Systems
L.M. Frostman, SPE, Baker Petrolite
Copyright 2000, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2000 SPE Annual Technical Conference and
Exhibition held in Dallas, Texas, 14 October 2000.
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Abstract
Anti-agglomerant low dosage hydrate inhibitors (LDHIs)
give operators an additional tool for controlling hydrates in
their systems. In contrast to kinetic and thermodynamic
hydrate inhibitors, anti-agglomerant LDHIs inhibit hydrate
plugging, rather than hydrate formation. Thus anti-
agglomerant LDHIs allow hydrates to form but keep the
particles small and well dispersed. Fluid viscosity remains
low, allowing the hydrates to be transported along with the
produced fluids. Emulsification of the produced fluids is not
necessary; in fact, anti-agglomerant LDHIs have aided in
demulsifying several black oil emulsions. In the laboratory,
anti-agglomerant LDHIs have been shown to be effective up
to 40 F below the hydrate formation temperature, at pressures
up to 7000 psi, and for shut-ins up to two weeks in duration.
In addition, extensive laboratory testing and formulation work
have been performed to ensure that the anti-agglomerant
LDHIs are compatible with system metals, elastomers, and
treatment chemicals, and that the products will not plug
umbilicals nor cause upsets in surface facilities. After a
comprehensive laboratory evaluation, an anti-agglomerant
LDHI was selected for field testing in a deepwater, Gulf of
Mexico oil well. The product protected the system throughout
the 1.5 month trial, including two brief shut-ins. This paper
presents the results of the laboratory and field tests.
Introduction
The co-production of water with petroleum fluids leads to
numerous problems that diminish the profitability of oil and
gas production. Historically, the problems were primarily
associated with corrosion, scale formation, and
demulsification, but recently much emphasis has been placed
on control of natural gas hydrates. Natural gas hydrates are
ice-like materials consisting of individual gas molecules
surrounded by cages of water in a crystalline structure. The
thermodynamic stability of these structures increases as
pressure increases and temperature decreases.1 While natural
gas hydrates have been a nuisance to gas and oil producers for
decades, it has only been in recent years with the ever-
expanding emphasis on offshore production that the true
extent of hydrate problems have come to light. Control of
hydrates is now considered by many to be the number one
priority for flow assurance projects for one simple reason:
natural gas hydrates can completely block production in nearly
every system which produces some water and experiences
cold temperatures / high pressures.
Traditionally, natural gas hydrates that can form in oil and
gas production systems have been controlled using either
thermodynamic hydrate inhibitors, such as methanol and
ethylene glycol, or by insulating the system to remain outside
of the hydrate region. Thermodynamic hydrate inhibitors,
which also include salt, shift the conditions at which hydrates
are stable to higher pressures and lower temperatures.
Sufficient quantities of thermodynamic hydrate inhibitors are
injected such that hydrates remain unstable throughout the
system. Unfortunately, injection rates can be high (0.25-1 bbl
methanol per bbl water produced for deepwater systems),
leading to high capex and opex costs. Insulation leads to even
higher capex costs, and while opex costs are significantly
lower, thermodynamic hydrate inhibitors are still needed for
extended shut-ins and cold well startups.
Producers and service companies have thus devoted
significant resources to looking for alternatives to traditional
hydrate control techniques. Recently, kinetic hydrate
inhibitors have been applied in place of or in conjunction with
thermodynamic hydrate inhibitors.2,3 Kinetic hydrate
inhibitors are typically water-soluble polymers that delay
hydrate nucleation and / or growth. While kinetic hydrate
inhibitors are cost effective in some fields, there is a concern
that hydrates can form during extended shut-ins. In many
cases, a secondary hydrate control mechanism (e.g., blowing
down the flowline) is needed for extended shut-ins.
Anti-agglomerant LDHIs give operators an additional tool
for controlling hydrates in their systems. In contrast to kinetic
2 L.M. FROSTMAN
and thermodynamic hydrate inhibitors, anti-agglomerant
LDHIs prevent hydrate plugging, rather than hydrate
formation. Thus anti-agglomerant LDHIs allow hydrates to
form but keep the particles small and well dispersed. Fluid
viscosity remains low, allowing the hydrates to be transported
along with the produced fluids. Emulsification of the
produced fluids is not necessary; in fact, anti-agglomerant
inhibitor LDHIs have aided in demulsifying several black oil
emulsions. In the laboratory, anti-agglomerant LDHIs have
been shown to be effective up to 40 F below the hydrate
formation temperature, at pressures up to 7000 psi, and for
shut-ins two weeks in duration. Figure 1 summarizes the
different hydrate inhibitor mechanisms.
Demonstrating the performance of an anti-agglomerant
LDHI is just the first step in qualifying it for use, particularly
in deepwater systems. Given the costs associated with
remediating problems in deepwater systems and the
corresponding deferral of production, each new deepwater
production chemical is put through a series of rigorous
qualification tests. Note that similar, though perhaps less
stringent, procedures would apply to onshore or shallow water
systems. The process starts with a complete system analysis
of the field where the product is to be applied. Extensive
laboratory testing and formulation work are then performed to
ensure that the anti-agglomerant LDHI is compatible with
system metals, elastomers, and treatment chemicals, and that
the products will not plug umbilicals nor cause upsets in
surface facilities. Subsequently, closely monitored field tests
are performed to gain insight to the performance of the
product in real systems. Throughout this process, computer
modeling is used to predict the conditions at which hydrates
are thermodynamically stable, thus facilitating experimental
design and interpretation of results.
The name Low Dosage Hydrate Inhibitor (LDHI) is most
often used to refer to anti-agglomerant hydrate inhibitors,
though it can also be used to refer to kinetic hydrate inhibitors.
For the purposes of this paper, the anti-agglomerant hydrate
inhibitor used in this study will be referred to as an LDHI.
Reported herein are the results of the first field test of an anti-
agglomerant LDHI in a Gulf of Mexico deepwater subsea
system. Laboratory results and thermodynamic modeling of
the system will also be discussed.
System Description
A Deepwater Gulf of Mexico system was chosen for the first
field test of a new anti-agglomerant LDHI. The platform,
located in 1980 ft of water, supported 10 dry tree wells and 2
subsea wells. At the time of the field test, only one subsea
well was flowing. Subsequently, a second well was brought
onto production. The subsea wells were located in 1772 ft of
water approximately 4 miles from the platform. The subsea
equipment consisted of a subsea header and dual 4 inch
flowlines which were round-trip piggable and uninsulated.
The subsea well of interest typically produced 3600
BOPD, 0-10 BWPD, and 2.3 MMSCF/D. Normal operating
conditions are shown in Table 1. Paraffin inhibitor is injected
downhole, and the line is pigged every 5 8 days. Topsides,
SPE 63122
fluids from the subsea well were commingled with production
from several dry tree wells in a header. Fluids then proceed
through an IP separator, an LP separator (where they are
commingled with fluids from the remaining dry tree wells),
and a chemelectric treater. Water removed from the LP
separator and chemelectric treater is sent to a skimmer then
overboard. Both defoamer and emulsion breaker are injected
in the topsides equipment. Prior to bringing on the second
subsea well, the total platform produced 27,000 BOPD, 1150
BWPD, and 28 MMSCF/D.
As the flowline was uninsulated, the temperature of the
produced fluids was expected to drop from the wellhead
temperature to 42 F rapidly. Most of the pressure drop
occurred in the riser. Worst case operating conditions were
taken as 1200 psi and 42 F. Pigging the flowline increased
the hydrate formation tendency due to the increase in pressure.
While this was a short-term effect, conditions of 1475 psi and
42 F were considered. Finally, the worst case conditions
were expected to occur during shut-in and the subsequent
start-up. To protect the wellhead, the hydrate inhibitor must
be able to control hydrates at 2500 psi and 45 F. Prior to this
field trial, methanol was injected continuously at roughly 350
gal/day.
Based on the PVT report for these reservoir fluids, the
GOR was approximately 600 scf/stb. Because of the low
water cut, it was very difficult to get a sample of the water
from this well. During the field test, a small sample of water
was obtained. Subsequent analysis showed this sample to
contain 29,000 ppm Cl-. This translated to a salt content of
approximately 4.8 wt%.
Laboratory Testing
Hydrate Inhibition
In laboratory testing, the LDHI was applied at 1.5 wt% of the
aqueous phase, which is equivalent to 0.72 gal / bbl water.
For optimum performance at this low dosage rate, a minimum
of 15,000 ppm TDS was necessary in the aqueous phase.
Performance test results are listed in Table 2 for a variety of
fluids. Two types of tests were performed. Standard
screening tests were performed in small sight glass cells
referred to as rocking cells. Evaluation of hydrate inhibitor
performance is primarily by visual observation (see Table 2
for performance criteria). The high pressure test was
performed in an autoclave equipped wherein the torque
required to turn the mixer gives a measure of in situ viscosity.
In both types of tests, the cells were filled with oil and brine
phases, pressurized with gas, cooled to 40 F, shut-in for 1 -
14 days, then agitated (rocking cells) or stirred (high pressure
test).
These tests suggest the LDHI performs well under a wide
variety of conditions, including high pressures, high
subcoolings, and extended shut-ins. In particular, the LDHI
controlled hydrate plugging under conditions expected in the
field trial.
SPE 63122 ANTI-AGGLOMERANT HYDRATE INHIBITORS FOR PREVENTION OF HYDRATE PLUGS IN DEEPWATER SYSTEMS
Capillary Compatibility and Stability
After confirming product efficacy in field fluids, the
operators next greatest concern was to ensure the product
would have no detrimental effects on the production system.
Static stability tests were first performed at both high (190 F)
and low (40 F) temperatures. These temperatures were
chosen to mimic the downhole and seabed temperatures,
respectively. For each test, samples of the LDHI were placed
in bottles and held at the appropriate temperature for 7 days.
The resulting products were clear, fluid, and free of
precipitates, indicating that the LDHI was stable over at least
the temperature range of 40 F 190 F. Performance tests
and chemical analyses of a batch of LDHI stored in the field
for over one year suggested no degradation in this time frame.
Capillary stability tests were also performed at 190 F and
40 F to ensure the LDHI would not cause plugging of the
chemical injection system. These tests consisted of pumping
neat LDHI through an 800 ft x 0.155 inch ID coil with a 40
micron outlet filter at the appropriate temperature, shutting the
system in for several days, then restarting the system. Any
increase in viscosity, solids deposition, or tendency to plug
would manifest itself by a rising differential pressure across
the capillary column. The LDHI showed no such rise in
differential pressure at either temperature and no deposits
were found on the filter. This verified the products suitability
for injection through a long umbilical and downhole capillary.
Materials Compatibility
Extensive corrosion and materials compatibility tests verified
that the LDHI was compatible with all materials that would be
exposed to neat inhibitor in the subsea system. A detailed
description of the materials compatibility testing program is
beyond the scope of this paper and will be discussed in a
future paper.4 Tests did indicate that neat LDHI was slightly
corrosive to C1010 and AISI 4130 steels, and potentially more
detrimental to Viton than methanol. However, at this facility,
the C1010 steel was located only in the flowline and AISI
4130 steel was located only in the tree. In both instances, the
hydrate inhibitor would be significantly diluted by the
produced fluids and should pose a negligible corrosion
problem. Also, since Viton was only found in the platform
methanol pump and the LDHI would only be in contact with
the Viton while the methanol was being displaced from the
umbilical, the operator decided that mild incompatibility over
a short time frame was not a concern.
Chemical Compatibility
Chemical compatibility tests demonstrated that the LDHI was
compatible with both methanol and the paraffin inhibitor in
use in the subsea well. The LDHI was soluble in methanol.
Solutions of 10%, 50%, and 90% LDHI in methanol were
stored at both 40 F and 190 F for one week. The solutions
all proved to be stable under these conditions. Additionally,
prior to beginning the aforementioned capillary tests,
methanol was flushed from the capillary column with the
LDHI. At the end of the tests, the LDHI was flushed from the
3
capillary column with methanol. In both instances, no signs of
incompatibility between the LDHI and methanol were noted.
The LDHI and paraffin inhibitor were immiscible. When
shaken together 50/50, they separated into two clear liquids.
No solids or high viscosity phases were seen at either room
temperature or 190 F. Performance tests also indicated that
the paraffin inhibitor did not adversely affect the LDHI
performance, and vice versa.
Fluids Compatibility
Tests both on site and in the laboratory suggested that the
LDHI would not cause any emulsion or water quality
problems in the system. In the field, fresh oil/water samples
were taken and treated with 4.2 ppm, 8.4 ppm, 12.6 ppm, and
10,000 ppm hydrate inhibitor based on the total fluids. The
first three doses correspond to treating the water in the subsea
well with 1%, 2%, and 3% the LDHI based on the water,
respectively. The final concentration was used to determine if
excessively high concentrations would cause any upset. In
these tests, fresh oil/water samples were taken. Half of each
sample was dosed with LDHI and the other half left untreated.
Samples were then shaken and heated to 120 F. Oil was
thiefed from each sample and centrifuged to determine
BS&W.
As shown in Table 3, the hydrate inhibitor actually
improved oil/water separation. In all cases, the water quality
looked good and the interfaces were sharp in the presence of
the hydrate inhibitor. Additional experiments in the lab
demonstrated that in field oil / synthetic field brine mixtures
containing 1.5 wt% the LDHI (based on the brine), water
separated faster and cleaner at room temperature in the
presence of the hydrate inhibitor. Similarly, the interface is
sharper and cleaner at 176 F in the presence of hydrate
inhibitor.
Viscosity at Low Temperatures
Deliverability of any chemical inhibitor is another key issue
for Deepwater systems, particularly those with long tiebacks.
High capex costs associated with chemical injection systems
leads operators to install small umbilical tubes and capillaries.
The viscosity of the LDHI is 23 cP at 40 F and 11 cP at
77 F. Under normal operating conditions, sufficient LDHI
was easily applied through the 4 mile umbilicals with a small
chemical injection pump. The low viscosity also facilitated
filling the umbilical.
Hydrate Modeling
Computer Modeling Procedures
As part of the preparation for and analysis of the field test, the
Multiflash gas hydrate modeling software from Infochem was
used to estimate the thermodynamic gas hydrate stability
curve for the reservoir fluids. These results predict the
conditions (pressure and temperature) at which gas hydrates
will be stable. Thus for a particular field situation, the degree
of subcooling experienced can be determined. The program
can also determine the effect of adding thermodynamic
4 L.M. FROSTMAN
inhibitors such as methanol and account for its partitioning to
the hydrocarbon phases.
Hydrocarbon and brine compositions based on the subsea
well were used in the Multiflash program to predict the
hydrate stability curve. The complete reservoir fluid
composition was used in combination with the salt analysis
obtained during the field test.
Results and Discussion of Computer Modeling
Results of the computer modeling predictions for the reservoir
fluids (4.8 wt% salt, 600 scf/stb GOR) are shown in Figure 2.
Table 4 shows an analysis of the hydrate predictions for this
system. Subcooling is the difference between the temperature
at which hydrates are stable and the operating temperature.
The higher the subcooling, the more likely hydrates are to
form.
Theoretical thermodynamic predictions suggested hydrates
could form during normal operations of the subsea well. The
likelihood of formation increased during pigging operations
and shut-ins / start-ups. These hydrates could cause a plug.
Unfortunately, it is not currently possible to theoretically
predict hydrate plugging. This system produced a very low
water cut (<1%). It is not unusual for low water cut black oils
to flow without plugging, even though hydrates may be
forming. However, as the water cut increases, the plugging
tendency also increases. All oils studied to date do plug if the
water cut is high enough. The water cut at which an oil is
expected to begin forming hydrate plugs is difficult to predict
and requires extensive flow loop studies. The critical water
cut for plugging in Deepwater Gulf of Mexico oils varies from
<1% to 45%. The situation is further complicated by the fact
that if hydrates are forming and depositing in the flowline, the
measured water cut will be artificially low. Similarly, in situ
water cuts in subsea flowlines can be an order of magnitude
higher than the water cut measured at the platform due to
water hold-up. Continuous hydrate inhibition was thus
recommended to mitigate the possibility of hydrate blockages.
Field Test
Hydrate Inhibitor Injection
LDHI was injected via the existing methanol injection system.
First the LDHI was pumped at an estimated 1000 1300
gal/day using the Haskel methanol pump to displace methanol
from the umbilical. This high injection rate was continued
until 330 gal of LDHI had been pumped, which was sufficient
to displace the methanol from the umbilical and slug the
system with approximately 100 gal of the inhibitor. Then the
LDHI was switched to a smaller Checkpoint pump and the
rate decreased to 15 gal/day. After the LDHI concentration in
the system leveled out, the injection rate was further reduced
to 10 gal/day. Grindout of the oil suggested that the well was
producing about 2 bbl water per day. At that point, the LDHI
injection was slowed to 2.5 gal/day. This was the lowest
injection rate attainable with the chemical injection pump.
The LDHI was injected for 1.5 months. During this time,
the water cut rose slightly. LDHI injection was adjusted to
give approximately 1 gal LDHI per bbl of water produced.
SPE 63122
This dosage rate is higher than needed, but given the
uncertainties in measuring very small water production rates,
it was prudent to slightly overtreat the system.
Water samples from the subsea well were difficult to
obtain due to the low water cut. LDHI residuals were thus
measured in the wellhead oil samples and in commingled
fluids, particularly the outlet from the skimmer. During the
course of the test, injection rates of the paraffin inhibitor,
defoamer, and demulsifier remained unchanged from their
pre-test values. Two brief shut-ins (<24 hours) were
experienced during the test, neither attributable to the LDHI.
Overall, no upsets were seen as a result of injecting the LDHI.
Results and Discussion
LDHI Residuals. Within 24 hours of after initial injection
of chemical, the LDHI was detected in oil and water samples
collected throughout the system. The highest recorded LDHI
residual in the skimmer water outlet was 270 ppm due to the
100 gal slug of the LDHI. It took 32 hours from the time the
injection rate was reduced to 15 gal/day until the LDHI
residual in the skimmer water leveled out at 150 ppm. If all
the hydrate inhibitor partitioned to the water phase, the
concentration in the skimmer outlet water would have been
about 310 ppm. Thus a significant fraction of the LDHI
partitioned to the oil phase in this system. This observation
was consistent with laboratory results.
After the LDHI injection rate was reduced to 10 gal/day,
the residual in the skimmer dropped to 100 ppm within 18
hours. With the injection rate at 2.5 gal/day, the LDHI
residual in the skimmer water was below the detection limit
(20 ppm) of the analytical technique.
Flowline Pressure Drop. The pressure drop across the
flowline is shown in Figure 3. As noted previously, the line
was pigged every 5-8 days. In between pigging runs, the
flowline pressure drop gradually, indicative of solids
deposition. Pigging returns suggested this was primarily wax.
During pigging operations, the pressure drop across the
flowline increased sharply due to the increased resistance of
the pig. Data shown in Figure 3 represents pressure readings
taken every 3-6 hours. Because of the short time frame of the
pigging operations, the pressure drop spikes recorded during
pigging are not necessarily indicative of the maximum
pressure drop experienced, i.e., no significance should be
attached to the height of the pressure drop spikes.
After LDHI injection was started, an interesting
phenomenon was noted: the rate of pressure drop increase
between pig runs became slower. If hydrates were depositing
in any significant quantities, the pressure drop slope should
have increased and/or additional spikes in the pressure drop
should have occurred. Instead, indications were seen of lower
deposition rates than before the field test. The paraffin
inhibitor injection rate averaged 25-30 ppm and was not
increased during LDHI injection. This phenomenon was later
duplicated in the second subsea flowline several months after
this test.
SPE 63122 ANTI-AGGLOMERANT HYDRATE INHIBITORS FOR PREVENTION OF HYDRATE PLUGS IN DEEPWATER SYSTEMS 5

Two suggestions have been put forth. It is possible that
the LDHI may enhance the performance of the paraffin
inhibitor and/or have some paraffin inhibition properties itself.
Alternatively, it is possible that hydrates are co-depositing
with the paraffin and injection of the LDHI inhibits this
process.
Some additional evidence for the latter came several
months later while both subsea lines were operating. At the
time, the operator was not injecting any hydrate inhibitor.
During a pigging operation, the line plugged. The line was
remediated using hot oil via coil tubing. Hot oiling returns
showed evidence of hydrate particles. The plug and pig
eventually broke free. When the plug emerged, it was a rigid
deposit a hammer was needed to break the plug apart.
Deposits from a subsequent pigging run contained 32 wt%
water (with the remainder being primarily wax and oil). In
addition, the deposits had an internal temperature of 27 F,
which could occur due to hydrate dissociation. Taken
collectively, this evidence suggests codeposition of wax and
hydrates in the subsea flowlines.
BS&W. BS&W was monitored by grindouts of the oil
exiting the chemelectric treater and by recording the BS&W
shown on the LACT monitor. The addition of the LDHI did
not adversely affect the BS&W levels in the production
system.
Toxicity. The skimmer outlet water was sampled prior to
the LDHI injection and again when the LDHI residual was
100 ppm. Acute toxicity studies were performed using mysid
shrimp. The 48 hour No Observed Effect Concentration
(NOEC) for both samples was 6.25%. Thus the 100 ppm of
LDHI had no adverse effect on overboard water toxicity.
Subsequent to this field trial, the EPA approved the
manufacture, sale, and use of this LDHI in accordance with
TSCA.
Oil and Grease. Oil and grease counts were measured
using Freon extraction and IR analysis. There were several
upsets during the test, none of which was attributable to the
LDHI. For instance, there was an upset in progress just prior
to the beginning of the LDHI injection. The skimmer was also
upset during the morning of the second day due to a closed
outlet valve. The results show that the LDHI did not
adversely affect overboard water quality. In fact, the lowest
oil and grease measurement recorded corresponded to the
highest LDHI residual concentration, consistent with the
observed improvement of oil-water separation during LDHI
injection.
No hydrate problems were detected during the LDHI
injection, even during two brief shut-ins. In fact, there was
some evidence that the LDHI reduced solids deposition in the
flowline. The LDHI did not adversely affect overboard water
quality: both oil and grease counts and aquatic toxicity tests
remained within the normal operating range of this platform.
The LDHI did not cause any emulsion problems and the
BS&W counts remained low.
Acknowledgements
The author wishes to thank the management of Baker Hughes,
Inc. and Baker Petrolite for permission to present this paper,
the Account Representative for obtaining well data and
collection of samples, and members of the Baker Petrolite
Technology group for their help in generating supportive data.
The author also wishes to acknowledge Dr. Veet Kruka for
useful discussions and suggestions instrumental in developing
this anti-agglomerant LDHI.
References
1. Sloan, E.D., Jr.: Clathrate Hydrates of Natural Gas, second
edition, Marcel Dekker Inc., New York (1998).
2. Corrigan, A. et al.: Trials of Threshold Hydrate Inhibitors in the
Ravenspurn to Cleeton Line, paper SPE 30696 presented at the
1995 SPE Annual Technical Conference and Exhibition, Dallas,
Oct. 22-25.
3. Mitchell, G.F. and Talley, L.D.: Application of Kinetic Hydrate
Inhibitor in Black-Oil Flowlines, paper SPE 56770 presented at
the 1999 SPE Annual Technical Conference and Exhibition,
Houston, Oct. 3-6.
4. Campbell, S.E. et al.: Ensuring Systems Compatibility for
Deepwater Chemicals, paper SPE 65006 accepted for
presentation at the 2001 International Symposium on Oilfield
Chemistry, Houston, Feb. 13-16.
SI Metric Conversion Factors
cP x 1.0* E - 03 = Pa s
mile x 1.609 E + 00 = km
feet x 3.048 006 E 01 = m
in x 2.54* E + 00 = cm
MSCF x 2.831 685 E + 04 = m3
gal x 3.785 434 E + 00 = L
bbl x 1.589 882 E + 02 = L
(F 32) x 5.55* E 01 = C
psi x 6.894 757 E + 00 = kPa
*
Conversion factor is exact.

Conclusions
The 1.5 month field test successfully demonstrated the
applicability of the LDHI in a subsea tieback. After the
methanol injection line was flushed with the LDHI, TABLE 1SUBSEA SYSTEM CONDITIONS
approximately 100 gal of the LDHI were injected into the Wellhead Wellhead Flowline Flowline
flowline. Even at this high concentration (about two orders of Conditions Press. (psi) Temp. (F) Press. (psi) Temp. (F)
magnitude higher than the normal treatment rate), the LDHI Normal 1075-1225 144 550-625 42
did not upset the production system. The injection rate was Pigging 1350-1500 144 700-950 42
optimized to 1 gal LDHI/bbl water. Shut-In 1900-2500 45-48 up to 1360 42
6 L.M. FROSTMAN SPE 63122

TABLE 2LDHI PERFORMANCE TEST RESULTS

Final Est.
Aqueous Filling Press. Temp. Shut-in Subcooling
Gas Oil Phase Inhibitor (psig) (F) Time (hr) (F) at 40 F Results*

85% C1 Black Oil 1.5% none 1400 40 72 25 fail

15% C3 (Field Sample) NaCl
85% C1 Black Oil 1.5% 1.5% 1400 40 72 25 pass
15% C3 (Field Sample) NaCl LDHI
85% C1 Condensate A 1.5% 1.5% 1400 40 24 29 pass
15% C3 NaCl LDHI
95% C1 Condensate A 1.5% 1.5% 1400 40 336 21 pass
5% C3 NaCl LDHI
Synth. Condensate B 1.5% 1.5% 9500 40 24 40 pass
Field Gas NaCl LDHI

* Interpretation of Results:
PASS = no hydrates form OR if hydrates form: crystals remain small (usually barely visible), crystals do not agglomerate, crystals
do not stick to any surfaces, and fluid viscosities remain low
FAIL = hydrates form plugs or deposits, AND/OR fluid viscosities increase significantly

No Inhibitor
TABLE 3EFFECT OF LDHI ON OIL-WATER SEPARATION hydrates, possible plug

LDHI Dosage % BS&W with % BS&W of

(ppm) LDHI Corresponding Blank MeOH, Ethylene Glycol
no hydrates
4.2 1.7 2.0
short times long times
8.4 1.0 1.1
Kinetic Inhibitor
12.6 1.8 3.0 no hydrates hydrates, possible plug
10000 1.4 10
Anti-Agglomerant
dispersed hydrates
Fig. 1Types of hydrate inhibitor mechanisms. Assume that in
the absence of hydrate inhibitors, hydrates are stable and can
TABLE 4ESTIMATED HYDRATE FORMATION potentially form a plug. If sufficient thermodynamic inhibitor,
CONDITIONS such as methanol or ethylene glycol, is added, no hydrates will
Hydrate form. Kinetic hydrate inhibitors delay hydrate formation and
Temp. Pressure Stability Subcooling growth, so at short times no hydrates will form. At long times
(anywhere from minutes to weeks, depending on conditions),
(F) (psia) Temp. (F) (F)
hydrates will eventually form and can potentially form a plug.
Worst-case 42 1200 55 13 Anti-agglomerant LDHIs allow hydrates to form, but keep the
Operating particles small and well dispersed in the liquid hydrocarbon
Pigging 42 1475 58 16 phase.

Shut-in / 45 2500 63 18
Start-up
SPE 63122 ANTI-AGGLOMERANT HYDRATE INHIBITORS FOR PREVENTION OF HYDRATE PLUGS IN DEEPWATER SYSTEMS 7

5000
GOR = 600 scf/stb
4.8 wt% Salt
4000
Pressure (psia)

3000

2000

1000

0
30 40 50 60 70
Temperature (F)
Fig. 2Hydrate stability curve.

1100

1000

900
Flowline Delta P (psi)

800

700

600

500

Start of LDHI injection

400
6-Mar 16-Mar 26-Mar 5-Apr 15-Apr 25-Apr 5-May 15-May 25-May
Date

Fig. 3Flowline pressure drop before and during LDHI field test.