Copyright 2006, Society of Petroleum Engineers

This paper was prepared for presentation at the 2006 SPE Gas Technology Symposium held
in Calgary, Alberta, Canada, 1517 May 2006.
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Abstract
Gas production and transportation pose challenges for
operators. Unprocessed gas streams in production and flow
lines containing brine and hydrogen sulfide are particularly
corrosive and susceptible to forming hydrates and scale
deposits. Methanol is often added to such streams for hydrate
prevention; however, methanol increases the corrosion
tendencies of pipes and equipment because it can deactivate
some Corrosion Inhibitors (CI) and adds oxygen to the system.
As a result, if hydrates are controlled with methanol, the
system requires extra amounts of properly selected corrosion
inhibitors to counteract the oxygen induced accelerated
corrosion.
Corrosion rates of tubular steel exposed to sweet and sour
brines were investigated. The sweet conditions contained
carbon dioxide saturated brine, methanol, corrosion and gas
hydrate inhibitors. Hydrogen sulfide was added to the system
to create a sour environment. Methanol and hydrogen sulfide
present in wet gas streams create an environment difficult for
corrosion control; they accelerate corrosion rates to the point
of rendering some commercial corrosion inhibitors unsuitable
for corrosion protection. It was discovered that some gas
hydrate inhibitors offer both, hydrates and corrosion
protection. In addition it was found that the corrosion
inhibiting properties of these gas hydrate inhibitors were
enhanced in the presence of hydrogen sulfide.
The dual action of the Low Dosage Hydrate Inhibitor
(LDHI) described here can limit or even eliminate Corrosion
Inhibitors in highly corrosive methanol containing sour
gas/water streams; thus, LDHI application improves
production and transportation economy by replacing high
volumes of methanol with less costly volumes of LDHI and
providing additional operational savings on CI.
Introduction
Gas hydrates form when water molecules crystallize around
guest molecules. The water/guest crystallization process has
been recognized since its discovery by Sir Humphrey Davy in
1810 it is well characterized and occurs with sufficient
combination of pressure and temperature.
1
Light
hydrocarbons, methane-to-heptanes, nitrogen, carbon dioxide
and hydrogen sulfide are the guest molecules of interest to the
natural gas industry. Depending on the pressure and gas
composition, gas hydrates may build up at any place where
water coexists with natural gas at temperatures as high as
30C (~85F).
Formation of undesired gas hydrates can be eliminated or
hindered by several methods. The thermodynamic prevention
methods control or eliminate elements necessary for hydrate
formation: the presence of hydrate forming gas, the presence
of water, high pressure and low temperature. The elimination
of any one of these four elements from the system would
preclude the formation of hydrates. Heating and insulating
transmission lines is a common mechanical solution to the
hydrate problem often encountered in long subsea pipelines.
Gas dehydration is another method of removing a hydrate
component. However, in a practical oil and gas operation,
water can be economically removed to a certain minimum
vapor pressure only and residual water vapors are always
present in a dry gas. Hydrate plugs in "dry" gas lines have
been reported in the past.
2
Tubular failures due to corrosion and pipelines plugging
with solid hydrates are major concerns for gas production and
transport operators. Hydrate plugs can form in a short time,
often within a few hours at hydrate formation pressure and
temperature (p/T) conditions. Corrosion is a significantly
slower process taking months or years to manifest itself with
hardware failing. Nevertheless, both processes can result in
catastrophic consequences if left unchecked.
The addition of chemicals to the gas/water streams is the
most common method of preventing corrosion and hydrate
formation. Small amounts of commercial corrosion inhibiting
compounds are applied to mitigate corrosion. Large amounts
of alcohols, glycols and salts are being utilized to control
hydrates. These additives (THI) thermodynamically
destabilize hydrates and effectively lower the temperature of
hydrate formation. They function by bonding to water
molecules through hydrogen bonds or solvation.
Unfortunately, oxygen carried with hydrate preventing solvent
addition has strong negative impact on corrosion rates.
Replacing thermodynamic inhibitors with hydrate growth
SPE 100474
Corrosion Mitigation With Gas-Hydrate Inhibitors
R. Hoppe, R.L. Martin, SPE, M.K. Pakulski, SPE, and T.D. Schaffer, SPE, BJ Chemical Services
2 SPE 100474
inhibitors that are ten to several hundred times more efficient,
offers a significant cost reduction to gas producers and
pipeline operators.
The non-thermodynamic hydrate inhibitors called Low
Dosage Hydrate Inhibitors (LDHI) are further categorized into
Anti-agglomerants (AA) and hydrate growth inhibitors. The
latest are subdivided into Kinetic Hydrate Inhibitors (KHI)
and Threshold Hydrate Inhibitors (ThKI).
Incidentally, the most corrosive environment in the
oilfield, oxygen contaminated sour brine and gas is the most
susceptible to hydrates formation due to hydrate promoting
properties of hydrogen sulfide (H
2
S). Figure 1 illustrates a
dramatic hydrate equilibrium shift toward lower pressure and
higher temperature with increased concentration of hydrogen
sulfide in methane. The difference in hydrate formation
temperature T is 14C (25F) between 100% methane gas
and 20% H
2
S in methane at intermediate pressure 10,000 kPa
(1,450 psi).
100
1000
10000
100000
-10 -5 0 5 10 15 20 25 30
Temp. deg C
P
r
e
s
s
u
r
e
,

k
P
a

Methane 100%
5% H2S in Methane
10% H2S in Methane
20% H2S in Methane
Fig. 1: Comparison of hydrate formation in CH
4
/H
2
S
mixtures. Hydrate equilibrium curves simulated with software
package Hydrate 5.2, DBR, Edmonton, Canada.
Hydrate prevention with methanol and glycols can be quite
expensive due to the high effective dosages required, 20% to
50% of the water phase. Ethylene glycol is usually recovered
downstream and recycled. Methanol is not usually recovered
and poses an environmental problem. Methanol partitions to
the oil or condensate phase and is carried to refining facilities
where it has to be washed out. It greatly increases oxygen
demand of any water effluent resulting in the possibility of
discharge permit violations and/or additional expenses for
wastewater treatment. Methanol accelerates equipment and
tubular corrosion due to acidic impurities and dissolved
oxygen, and aggravates potential scale problems by lowering
scaling salts solubility in water and precipitating most known
scale inhibitors.
3
Some work has been done in the past to quantify the effect
of methanol on steel corrosion in sour systems. Siegmund et
all
4
concluded that dissolved oxygen in technical grade
methanol is the major factor accelerating corrosion rates.
Martin
5
suggested corrosion inhibitors that function in
brine/methanol sour-environments while Thieu and Frostman
6
reported field experience with hydrate suppression in sour-
systems. They did not report any laboratory data concerning
CI and LDHI effectiveness. Dahlmann and Fenstel
7
attempted
to design molecules displaying both LDHI and CI properties.
This approach requires the inhibitor to bind to a metal surface
and hydrate crystals. The task is achievable by designing
molecules having two different ends, hydratephillic and
metallophillic. It is not clear how much each property is
compromised by having them both. This new technology is
not being applied in the oilfield at this time.
A certain class of KHI displays amine functionality
8
.
Being amine derivatives these compounds are potential
corrosion inhibitors. Standard corrosion testing procedures
were applied to these LDHI in various conditions to measure
their impact on corrosion rates and how they interfere with
commercial CI.
Results and Discussion
Ambient Pressure Corrosion Testing
Wheel Corrosion Test. The test, NACE ID182 measures
weight loss of 1018 steel coupons submerged in NACE brine
(7.33% NaCl, 0.7539% CaCl
2
and 0.1% MgCl
2
) saturated with
CO
2
and sealed. Bottles containing tested samples are
mounted on a wheel turning continuously for 24 hours at 65C
(150 F). Weight loss of coupons exposed to inhibited and
uninhibited (blank) brines is compared and inhibitor efficiency
is calculated.
Two known gas hydrate inhibitors were tested,
polyvinylpyrrolidone (PVP) and oligomeric (LDHI).
Table 1
Laboratory Corrosion Results
Wheel Corrosion Test
Hydrate Inhibitor
Concentration
% Corrosion Inhibition
PVP ---
0.01% None
0.1% 8%
0.3% 12%
LDHI ---
0.01% None
0.1% 12%
0.3% 83%
Minimal anti-corrosion properties of the PVP compound
were observed in this test while LDHI oligomer displayed
reasonable anti-corrosion activity at typical kinetic hydrate
inhibitor concentrations.
SPE 100474 3
Copper Strip Corrosion. Condensate, a liquid mixture of
light hydrocarbons, is usually associated with natural gas
production. This valuable light-end petroleum fraction can be
blended directly into gasoline without any processing if it
displays no copper corrosion. Traces of sulfur compounds in
condensate are responsible for the copper corrosion.
Two solutions of LDHI one 10% in water and another one
10% in kerosene were prepared for testing. For a reference, a
clear condensate (200 mL) from central Texas, USA was
added to equal volume of tap water in a separatory funnel and
vigorously shaken for two minutes. Water was allowed to
separate and drained. The top condensate layer was collected
and submitted for the copper strip corrosion test (ASTM
D1838). The same procedures were repeated with addition of
20 mL LDHI kerosene solution to test #2 and 20 mL LDHI
water solution to test #3. In the test, freshly polished copper
strips are exposed to the fuel for three hours at 50C (122F).
Next, the strip color is compared to standards and the results
are graded accordingly to visible coloration. Freshly polished
copper coupon receives grade 1a; the next best ones are 1b, 2a,
2b, 2c... Results in Table 2 indicate relatively minor copper
corrosion.
Table 2
Laboratory Test Results
Copper Strip Corrosion
No Description Results
1 Blank 2c
2 LDHI / Kerosene 1b
3 LDHI / Water 1b
Rating 1b obtained for condensate treated with LDHI
chemical is practically the best result one can expect to get.
This rating is significantly better than the 2c for the untreated
condensate. The results indicate that the LDHI that is soluble
in the hydrocarbon phase, but would preferentially partition
into the water phase is capable of mitigating the effect of
corrosive sulfur compounds dissolved in the condensate.
Ambient Pressure Linear Polarization Resistance Testing.
Series of Linear Polarization Resistance tests were performed
at ambient temperature in 2000 mL glass resin kettles.
Corrosion rates were monitored using a linear polarization
resistance instrument with 3 electrode probes. Tests were 24-
hour exposures of AISI 1018 (UNS G10180) steel electrodes
to stirred solutions at laboratory temperature. In all CO
2
tests
(called sweet conditions), the brines (3% NaCl, 0.3% CaCl
2
x
2H
2
O) were CO
2
sparged for the duration of the test. For sour
condition tests, the brines were also saturated with CO
2
, 1 g/L
of Na
2
Sx9H
2
O) was added, then the kettle was sealed for the
balance of the test.
Corrosion rates were sometimes determined by weight loss
of the reference electrode. Electrodes were cylindrical with a
surface area of 9 cm
2
. Tests were performed using mixtures of
75% brine and 25% technical grade MeOH except test #1,
which was performed with 100% brine. Methanol was aerated
prior to adding it to the brine in test #2. It was determined
before that various grades of methanol i.e. reagent quality or
solvent obtained from the field display identical performance.
Measured corrosion rates are collected in Table 3.
Observations It is not surprising that regardless of
conditions, sweet or sour systems displayed extremely high
corrosion rates without any corrosion inhibitor, particularly
when methanol was saturated with air prior to the testing (exp.
#1-3, 13). LDHI did not offer much corrosion protection in
the sweet environment and can even cancel the protective
effect of a wrongly selected CI (exp. #4-7). Several corrosion
inhibitors are effective in sweet mixtures of brine, methanol,
and LDHI (exp. #8-12). The same LDHI becomes an
effective CI in sour systems (exp. #13-15). Quaternization of
LDHI leads to a surfactant type molecule with enhanced
affinity to the metal surface. The derivative has improved
corrosion inhibition properties in both, sweet and sour systems
(exp. #16, 17).
Table 3
Corrosion Rates in H
2
O/MeOH System
With Various Corrosion Inhibitors
Exp.
#
LDHI CI Gas Av. mpy
1 - - CO2 73
2 - - CO2 112
3 - - CO2 44
4 0.3% - CO2 35
5 1% - CO2 52
6 - A1 CO2 2.1
7 0.3% A1 CO2 33
8 0.3% B1 CO2 0.9
9 0.3% C1 CO2 2.2
10 0.3% D1 CO2 1.4
11 0.3% E1 CO2 0.8
12 0.3% H1 CO2 1.5
13 - - H2S/CO2 40
14 0.3% - H2S/CO2 1.7
15 1% - H2S/CO2 0.9
16 0.15%* - CO2 14
17 0.15%* - H2S/CO2 2.2
*Quaternized LDHI (converted to AA, see reference 8a) was
used in the last two experiments.
High Pressure Corrosion Testing
LPR Results in Sour Gas Systems. Originally the testing of
LDHI was for a sour gas gathering system to assure there is no
incompatibility between the hydrate inhibitor and incumbent
commercial corrosion inhibitor, CI-A. The corrosion inhibitor
was evaluated at a concentration 200 ppm alone, as well as in
the presence of 10% methanol/LDHI and against 10%
inhibited methanol normally used in the system.
Test conditions: 50C (122F), ~ 125 rpm
Pressure: 550 psi (3800 kPa)
Gas composition, Mol%: CO
2
10%, H
2
S 22%, CH
4
68%
Brine: Central Alberta ~ 3% TDS
Test duration: 94 hours
4 SPE 100474
Detailed Test Protocol . Brine was charcoal filtered and then
purged with CO
2
for two hours. The pH was then adjusted to
5.0 with hydrochloric acid. The autoclave cell is constructed
of Hastelloy C-276 and has a capacity 300 mL. The tests were
carried out with 200 mL of brine or approximately two-third
full. A three-electrode assembly was suspended from the lid
of the autoclave, keeping the bottom clear for a teflon-coated
magnetic stir-bar. The configuration of the electrodes was a
closely spaced equilateral triangle, with each cylindrical
electrode having a 9.5 mm x 12.5 mm geometry. The
reference electrodes were made from Hastelloy C-276 while
the working and counter electrodes were 1018 carbon steel.
The electrodes were cleaned and weighted. The quoted
surface area of 4.55 cm
2
has been used for the corrosion rate
calculations. A thermistor probe held at the center of the cell
by a Hastelloy sleeve sensed the temperature of the fluid in the
autoclave. Purging and changing the headspace of the
autoclave was done by means of an offset Hastelloy tube fitted
with a pressure gage and sour-service needle valve. LPR
measurements were obtained at 30 minutes intervals by
connecting the cell to a PC4-300 potentiostat and controller,
via Gamry ECM8 multiplexer. Data acquisition was done by
means of Gamry PC105 software package.
Autoclave Filling and Pressuring Procedure. For all three
tests, purged brine (200 mL test #1, 180 mL for tests #2 and
#3) was placed into an autoclave cell, followed by an injection
of 200 ppm (40 L) of the corrosion inhibitor, CI-A. For
experiment #2, 20 mL of methanol (purged with CO
2
for 10
minutes to remove oxygen) was added making a 10%
methanol solution in brine. For experiment #3, 20 mL of
methanol and hydrate inhibitor were added to 180 mL brine in
the autoclave.
After sealing and purging, each cell was pressurized with
acid gas composed of 28% CO
2
, 72% H
2
S to 175 psi (1200
kPa) and the pressure was increased to 550 psi (3800 kPa)
with methane. The final initial headspace gas composition
was 10% CO
2
, 22% H
2
S and 68% CH
4
(all gas concentrations
are expressed in Mol%). Carbon dioxide and hydrogen sulfide
have greater solubility in water than methane; hence, the end
headspace gas composition was methane enhanced. Each test
cell was placed inside a heating mantle and brought to 50C
(122F) via proportional temperature controllers (5-10 min).
At this point, the Gamry instrument started collecting LPR
data for a period of 94 hours.
Observations. Figure 2 depicts the LPR data collected from
all three autoclave experiments. The data indicate a quite
large corrosion rate in the CI-A/MeOH system. Apparently,
the inhibitor CI-A was deactivated with 10% methanol present
in the solution. This CI-A deactivation cannot be attributed to
a presence of oxygen in the cell because the solvent was
purged with CO
2
to remove any dissolved oxygen from the
solution.
Figure 3 shows the same data on an expanded Y-scale, so
that some differentiation can be made between experiments #2
and #3. One notes two short periods of activity on the CI-
A/MeOH/LDHI cell. These may reflect a protective film
breakdown and reformation. One cannot be sure whether this
would stabilize over a longer period test. However, the
perturbation is quite minor when the scale of the Y-axis is
taken into the account.
0
2
4
6
8
10
12
14
16
18
0 10 20 30 40 50 60 70 80 90
Time, hours
C
o
r
r
o
s
i
o
n

R
a
t
e
,

m
p
y
CI-A,MeOH LDHI,MeOH,CI-A CI-A
Fig. 2: LPR data collected from cells 1-3 (full Y-scale).
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
0 10 20 30 40 50 60 70 80 90
Time, hours
C
o
r
r
o
s
i
o
n

R
a
t
e
,

m
p
y
LDHI,MeOH,CI-A CI-A
Fig. 3: LPR data collected from cells 2-3 (expanded Y-axis
scale).
Figure 4 shows the corrosion potential of each cell as a
function of time. Using a Hastelloy C reference electrode, one
can determine the rest or corrosion potential of each cell. In
some systems, the less negative the value of Ecorr, the more
passive the cell. However, in the sour environment, this set of

SPE 100474 5
data has only a limited value because the system is not
passivated.
-25
-20
-15
-10
-5
0
0 1
0
2
0
3
0
4
0
5
0
6
0
7
0
8
0
9
0
Time, hours
C
o
r
r
o
s
i
o
n

p
o
t
e
n
t
i
a
l
,

m
V
CI-A,MeOH LDHI,MeOH,CI-A CI-A
Fig. 4: Corrosion Potential Data from cells 1-3.
The gravimetric and visual inspection results obtained
from each cell are provided in Table 4.
Table 4
Gravimetric and Visual Inspection Results
of Corroded Electrodes
Cell Fluid Corrosion mpy Visual
CI-A blank 0.4 Minor pitting
CI-A/ MeOH 5.0 Severe pitting
CI-A/ MeOH / LDHI 0.3 Minor pitting
The results indicate a standard commercial corrosion
inhibitor doesnt perform in the presence of methanol, leading
to a significant damage of tubular iron and equipment.
Addition of LDHI can compensate for an inferior CI in the
presence of methanol.
Autoclave Corrosion Testing at Sour Conditions. Machine
milled, single sided C1018 steel disks were submerged in an
autoclave containing the test solution and pressurized with
CO
2
and H
2
S mixtures. The disks were pre-corroded for 12
hours in the test solution without the sour gases.
Test conditions: 35C (95F), stirring at 120 rpm
Pressure: 241 psi (1660 kPa)
Gas composition: 16 mol% CO
2
, 84 mol% H
2
S
Brine: DI water, purged with N
2
for 1h
Test duration: 12 hours pre-corrosion + 6 days
After completion of each test, the weight loss and pitting
of the disks was calculated in mm/yr. Results are presented in
the table below.
Table 5
Corrosion Rates of Steel Disks in
Sour Solution and Various Additives
Experiment
Number
Composition
Corrosion
mm/year
Pitting
mm/year
1 DI Water only 0.442 0
2 66% MeOH 0.324 11.7
3
66% MeOH, 0.25%
CI-B*
0.091 2
4
40% MeOH,
+ LDHI
0.193 0
5
40% MeOH, 0.25%
CI-B + LDHI *
0.208 0
6 10% MeOH, + LDHI 0.21 0
7
10% MeOH, 0.25%
CI-B* + LDHI,
0.191 0
*CI-B commercial corrosion inhibitor different than CI-A
The testing purpose was to investigate the effect of a
partial replacement of methanol with LDHI. Large
concentrations of MeOH result in severe pitting of steel
unacceptable in the field environment. Even a large dosage of
commercial corrosion inhibitor lowered the overall corrosion
rate but did not prevent pitting (exp. #2, #3). Replacing some
methanol with a significantly less volume of LDHI
dramatically lowered corrosion rates and eliminated pitting.
Notice that the corrosion rates with or without the inhibitor
CI-B are almost the same. CI-B can be eliminated without
affecting iron corrosion (compare exp. #4 and #5 with #6 and
#7).
Conclusion
Preventing hydrates formation with methanol is more
complicated than simply adding sufficient amounts of the
solvent to gas/water streams. Methanol increases corrosion
rates and deactivates some corrosion inhibitors. The tested
LDHI displays CI properties in some environments. The CI
properties are enhanced at sour conditions. Converting LDHI
to a quaternary ammonium compound further improves its CI
activity. However, the required LDHI effective concentration
is usually significantly higher than the typical loadings of a
commercial corrosion inhibitor.
When planning a corrosion and hydrates protection
program for any field operation one has to consider several
factors:
sweet or sour stream
methanol, LDHI or both chemicals for hydrates
prevention
select CI compatible with hydrate inhibitors
assure LDHI is not deactivated by CI
6 SPE 100474
It is highly recommended to test new CI and LDHI prior to
field application to avoid unpleasant surprises. Methanol is
often replaced with LDHI as a less expensive solution to gas
hydrate problems. If selected CI and LDHI are compatible, it
is possible to achieve further savings by using less CI in the
presence of LDHI.
Acknowledgements
Authors thank the management of BJ Chemical Services for
approving the publication of this work and Dr. William
Clements for helpful review comments.
Nomenclature
LDHI Low Dosage Hydrate Inhibitor including Kinetic and
anti-agglomerant inhibitor
CI Corrosion Inhibitor
KHI Kinetic Hydrate Inhibitor
THI Thermodynamic Hydrate Inhibitor
AA Anti-agglomerant Hydrate Inhibitor
PVP Polyvinylpyrrolidone
TDS Total Dissolved Solids
Mpy mils per year corrosion rate, 1 mpy=0.0254 mm/yr.
ThKI Threshold Kinetic Inhibitor
LPR Linear Polarization Resistance
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