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Corrosion Inhibitor and Oxygen Scavenger for use as MEG Additives in the
Inhibition of Wet Gas Pipelines

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Proceedings of the Annual Offshore Technology Conference · March 2014

DOI: 10.4043/25070-MS

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OTC-25070-MS

Corrosion Inhibitor and Oxygen Scavenger for use as MEG Additives in the
Inhibition of Wet Gas Pipelines

MN Lehmann, A Lamm, HM Nguyen, CW Bowman, and WY Mok, Baker Hughes; M Salasi and R
Gubner, Curtin
University of Technology

Copyright 2014, Offshore Technology Conference

This paper was prepared for presentation at the Offshore Technology Conference Asia
held in Kuala Lumpur, Malaysia, 25–28 March 2014.

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
reviewed by the Offshore Technology Conference and are subject to correction by the
author(s). The material does not necessarily reflect any position of the Offshore
Technology Conference, its
officers, or members. Electronic reproduction, distribution, or storage of any part
of this paper without the written consent of the Offshore Technology Conference is
prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words;
illustrations may not be copied. The abstract must contain conspicuous
acknowledgment of OTC copyright.

Abstract

The transportation of wet gas fluid in carbon steel pipelines for onshore
processing offers an economically attractive strategy.
Although a substantial saving in capital cost can be realized, the risks of hydrate
formation and corrosion damage are two of
the main issues with such an approach. The standard industrial practice is to apply
chemical solutions to reduce the risks. A
thermodynamic hydrate inhibitor, such as monoethylene glycol (MEG) and corrosion
inhibitors are commonly utilized to
provide hydrate and corrosion control, respectively. Other production chemicals,
such as an oxygen scavenger, may also be
deployed as part of the risk management process. Consequently, the main challenge
to the corrosion inhibitor is to provide
corrosion protection throughout the production and processing facility while
subjected to high temperatures in the MEG
regeneration process and exposure to other production chemicals. Thermal stability
and performance assessments should be
an important aspect of the qualification process in the selection of corrosion
inhibitors. This paper presents data from a
laboratory corrosion inhibitor evaluation program, using thermally stressed
MEG/chemicals fluids under simulated wet gas
pipeline operating conditions, which resulted in the successful qualification of a
corrosion inhibitor for the production
facility.

Introduction

For large offshore gas projects where thermodynamic hydrate inhibition is required
for continuous long-term protection,
monoethylene glycol (MEG) is selected over methanol because MEG has significantly
less solubility in the gas and liquid
hydrocarbon streams than methanol. Consequently, MEG losses are lower when compared
to methanol, despite the necessity
for a greater quantity of MEG per degree of hydrate temperature suppression.

Due to the quantities needed for operation, the MEG must be recovered from process
streams and recycled. The current
implementation of MEG regeneration and reclamation processes into notable offshore
projects has shown to be operationally
reliable, and has overcome many operator concerns about the detrimental effects
that formation water could have on their
MEG regeneration units. Some examples of successful developments that incorporate
MEG processing include Statoil’s
Ormen Lange and Åsgard B (Norway), ConocoPhillip’s Britannia Satellites (UK),
Reliance KG-D6 (India), BP’s Shah Deniz
(Azerbaijan), and Woodside Pluto (Australia).

The most cost-effective recovery of offshore gas involves the transport of

unprocessed gas/condensate in carbon steel
pipelines over long distances. During transport, corrosive fluids are generated
when the hot produced gases, containing
carbon dioxide, cool and condense low pH water that contains carbonic acid
(reaction1).

CO2 (g) + H2O (l) ↔

H2CO3 (aq) (1)

The CO2 corrosion of carbon steel has been extensively studied. Iron carbonate is
formed when iron in the pipeline wall
reacts with carbonic acid (reaction 2). The iron carbonate that forms at acidic pH
values does not necessarily develop a stable
protective film. In unsaturated solutions the iron carbonate can dissolve into the
production fluid and cause problems
OTC-25070-MS

downstream as a consequence of re-precipitation.

Fe (s) + H2CO3 (aq)" "

FeCO3 (s) + H2 (g) (2)

Corrosion can be controlled with the application of a film-forming corrosion

inhibitor (FFCI) at the natural pH of the fluids,
or by artificially elevating the pH of the fluid to precipitate a stable protective
corrosion film.

The principal of pH stabilization is to raise the pH of the fluid and increase the
carbonate ion (CO32-) concentration and so
precipitate any dissolved iron ions (Fe2+) as stable iron carbonate (FeCO3)
films.1,2 The practice of pH stabilization has been
used since 1972, but it has only been used in conjunction with monoethylene glycol
(MEG) or diethylene glycol (DEG) for
hydrate prevention.3 In such systems the glycol is regenerated and circulated in a
closed loop and the pH stabilizer is mixed
with lean glycol. In theory, any base can be used to neutralize the dissolved
carbon dioxide to generate carbonate ions.
However, tertiary amines such as N-methyl-diethanolamine (MDEA) are chosen due to
the thermal stability of the amine and
its ability to recycle in the MEG loop, thus reducing the on-going amount of base
needed for neutralization.

In full pH stabilization, the pH stabilizer is used to control corrosion rates

below a specified level. Partial pH stabilization
employs a smaller amount of pH stabilizer (MDEA) in conjunction with an added FFCI
that further lowers the corrosion rate.
The iron carbonate films that form protect the pipe from carbonic acid and water,
hindering further corrosion unless this film
is eroded away.2

Lean MEG (80 to 90% MEG) containing pH stabilizer and FFCI is usually injected at
the wellhead past the choke, where it
initially co-mingles with produced fluids. The use of pH stabilization is
sustainable as long as the produced water that is
formed develops primarily from water condensation. If any formation water is
produced from the wells, then there is a
significant potential for scale formation due to expansion cooling and the elevated
pH from stabilization. Formation waters
usually contain calcium and barium ions, so calcite and barite formation is highly
probable, with the former being the
dominant scale, other than iron carbonate.

To circumvent calcite formation, a scale inhibitor can be applied in the MEG or at

a separate injection point at the wellhead,
either prior to the choke or downhole. However, there is great debate as to whether
scale inhibition can be effective under
conditions of pH stabilization. When formation water does break through, the
general philosophy is to switch to a mode
where corrosion inhibition is maintained by the FFCI, and the scale inhibitor is
used to control scales formed from
depressurization and cooling (such as carbonate scales and barium sulfate,
respectively).4,5,6
Rich MEG (~60% MEG) formed in the flow lines is sent to a host facility or to shore
for pretreatment that initially removes
the condensate and gas in a 3-phase separator. It is then sent to storage tanks,
awaiting subsequent recovery of the MEG and
addition of the pH stabilizer for final recirculation back to the wells. Storing
the rich MEG prior to treatment provides a final
opportunity to degas the rich MEG and skim any hydrocarbons carried over. The
recovery of the MEG is achieved by two
main processes: reconcentration and regeneration.

Reconcentration utilizes a reboiler and a distillation column to convert the rich

MEG, by boiling off the water, into lean
MEG. Sustainable reconcentration is only viable when condensed water is the basis
of the hydrate risk. However, when the
rich MEG contains dissolved salts, the system becomes susceptible to corrosion,
glycol degradation, and fouling from
precipitating salts and other solid contaminants that build up in the MEG circuit.7

MEG regeneration for produced fluids that contain formation water is carried out by
initially flash heating the rich MEG to
leave precipitated and non-volatile salts in a flash separator in a process called
reclamation. This separator usually operates
under vacuum (0.10 to 0.15 bar) and vaporizes the MEG at a temperature low enough
to avoid decomposition of the MEG
(170 to 195° C). The vaporized MEG and water are then passed through a distillation
tower to remove water off the top of
the column and to produce the lean MEG at the bottom of the tower. This lean MEG is
sent to storage and later reinjection
into the flowline. The term "reclamation" refers to the process of removing solids,
which are usually separated using a
centrifuge or filter.

There are two approaches to reclamation depending on the production profile of the
gas field, and the likelihood and amount
of formation water to be produced. The first approach is termed full reclamation
(Fig. 1) where the total rich MEG stream
undergoes reclamation. The other approach is the slip-stream reclamation process
(Fig. 2). This entails only taking a portion
of the total returned MEG stream that undergoes reconcentration and passing it
through a salt removal system.

The overall design of the MEG reconcentration system depends on the salt production
rate. When salt production rates are
high it is necessary to run the whole MEG stream through a reclamation unit to
remove salt and water. However, when salt
OTC-25070-MS

production rates are low it is possible to regenerate most of the MEG via a pre-
concentrator, and control the salt content in
the lean MEG by running a slip stream through a reclamation unit. This approach
becomes operationally difficult if the MEG
is alkaline and contains reasonably high levels of calcium and iron salts, which
usually result in scaling of the reboiler. This
is addressed in full and slip-stream reclamation by employing a pretreatment stage
to remove calcium and iron carbonates
and other sparingly soluble salts to prevent their precipitation in the reboiler
and the buildup of MEG-metal ion complexes in
the reclamation unit. Slip-stream processes were incorporated into the respective
Norsk-Hydro Ormen Lange (Norway).
Statoil Snøhvit/Hammerfest (Norway), BP Shah Deniz and the Chevron Gorgon MEG
recovery processes. In each of these
fields the production rate for formation water is expected, or will be controlled,
to be relatively low.

The main advantage of slip-stream reclamation is that the reconcentration operation

is not wholly dependent on the operation
of the reclamation unit. There is greater flexibility in running the reclamation
unit, as long as the specification for the highsolubility
salts (chlorides) concentration in the bulk lean MEG is met. Normally, the maximum
salt content in the lean MEG
is specified to be around 20 g/l. Another consequence of reclaiming a slip stream
is that the size and the CAPEX investment
for the reconcentration and reclamation trains are expected to be significantly
reduced. For example, the diameter of the
MEG column is expected to be reduced to about half, and the capacity of the
reclamation unit can be minimized, as lean
MEG rather than rich MEG is transferred to the reclamation unit. Furthermore, in
contrast to a full-stream reclamation where
all salts and non-volatile chemicals are removed from the MEG loop, a slip stream
enables chemical additives and pHstabilizers
to be retained and re-used. Slip streaming also vaporizes a smaller portion of the
total MEG, reducing the system
heating and cooling requirements.

The main disadvantage of the slip stream like that of the MEG regeneration system,
is that impurities of salts and particulates
will accumulate in the closed MEG loop and impact the density and viscosity of the
MEG, and create the potential for salts to
precipitate in different parts of the system. As the MEG/water phase accumulates
particulates from corrosion, completion
fluids or salts from acetic acid, this increases the chance of plugging and
corrosion.
Organic acids may also be contained in the gas, condensate or the produced water.
Although organic acids are normally
volatile they will not flash out upon heating and depressurization of the rich-MEG
and hydrocarbons. Instead, the organic
acids will react with the alkalinity (bicarbonate and carbonate content), contained
in the formation water to produce carbon
dioxide gas. This gas will flash off upon heating and depressurization, reducing
the effective alkalinity and lowering the
effective pH of the MEG.8 As this elevates the corrosion potential of the rich MEG,
additional pH stabilizer must be added to
counter this effect. As the MEG cycles, the organic acids will accumulate in the
flash separator and partition to the MEG in
the reclamation unit. It is generally accepted that acetate concentrations of less
than 2g/L should be maintained in the lean
MEG. Above this level the corrosion strategy may need to be changed from pH
stabilization to FFCI to avoid top-of-line
corrosion.

Fig. 1: Full reclamation scheme that removes all the salts to prevent scaling in
the pipelines
OTC-25070-MS

Fig. 2.Typical slip-stream MEG reclamation scheme employing a reconcentration

stage9

One significant concern in using recovered MEG for hydrate control is the
introduction of oxygen into the MEG loop via a
variety of mechanisms. This is thought to be one of the key parameters that
controls fouling in the system.10-15 Oxygen
present in the lean MEG injection lines can cause significant pitting to the carbon
steel, and certain CRA lines, especially in
the presence of MEG and chlorides.12 Secondly, the released iron ions from
corrosion may precipitate as iron oxide particles
and block the injection nozzle. Thirdly, small iron carbonate particles that may be
present in the MEG may be converted to
iron oxide in the presence of oxygen. Interestingly, it has been observed that iron
carbonate particles do not have a tendency
to form tenacious scale, as compared to iron oxide particles that were found to
stick to surfaces, and deposit as a scale.6 The
formation of iron oxide ultimately degrades the MEG quality. Control of the oxygen
level in the lean MEG is important.
The secondary effects of having such particles in the MEG system is the potential
for these particles to stabilize emulsions in
the primary HP and LP separators, leading to condensate under-carry in the
pretreatment stages and then over-carry, or even
foaming, in the fractionation column.

Dissolved oxygen may enter via the MEG makeup or from being dissolved in the
production chemicals, acids and bases used
in the system, unless provision is made to have these chemicals nitrogen blanked.
Even so, commercial nitrogen gas may
contain up to 3% of oxygen gas that can produce an appreciable amount of dissolved
oxygen residual. Natural gas may be
used as an alternative blanket. Another critical aspect that must be reviewed is
the scavenging of oxygen that is introduced
into the MEG unit via the MEG makeup and via small leaks into the parts of the
plant that operate under vacuum. To
circumvent this contamination an oxygen scavenger can be dosed into the lean MEG.
Ideally, the selected chemical is
nonvolatile, and can be removed with salts during reclamation so that it has low
potential to concentrate or foul in the MEG
circuit.

Bacteria in a gas systems can originate from poorly treated hydrotest water,
completion fluids and acidizing fluids and the reinjection
of sump piles or tanks back into the process system. Several strains of bacteria
can use ethylene glycol and
propylene glycol as sole sources of carbon.16-19 Consequently, there exists the
potential for microbiologically induced
corrosion (MIC), resulting from any bacterial activity that may be sustained by the
MEG or produced water. Although
concentrations above 10% MEG have shown toxic effects on yeasts and fungi from
soil, this may not be the case for glycol
utilizing bacteria. Additional nutrients provided by the brine and condensate may
allow for a greater risk of bacteria in the
flowlines than in the MEG service lines. Thus, it is a good approach to address MIC
by considering the use of a biocide that
is compatible with the MEG system and can be used in batch treatments of the
flowlines and downstream equipment.
OTC-25070-MS

The selection of a FFCI and other production chemicals as additives to the MEG
becomes significantly more complicated
that merely testing individual chemistries alone for desired performance. The
ensemble of chemicals envisioned to be added
to the MEG must be screened for overall desired performance to account for any side
reactions and incompatibilities. The
concentration of these chemicals or their reaction products can build up,
potentially fouling the MEG circuit. Temperature
extremes in the production and MEG recovery systems increase the potential for
these side reactions. Ultimately, the
corrosion inhibitor will be a critical component of an ensemble of compatible
chemicals that must meet the operational
specifications yet minimize the risk for fouling the system.

This work highlights a portion of an extensive range of compatibility, oxygen

scavenging and corrosion tests that were
undertaken to ascertain the suitability of production chemicals to be used as MEG
additives for a large Australian offshore
gas development, employing slip-stream reclamation for MEG recovery.

Experimental

The development of compatible production chemistries for use as MEG additives

requires meeting a range of operational
criteria and performance specifications, without showing deleterious effects in the
MEG processing train.

Three main areas are reported: (1) The development of an oxygen scavenger that
functions in the presence of 80%v/v MEG
(Lean MEG); (2) Evaluation of the thermal stability of the corrosion inhibitor in a
MEG additives package; (3) Confirmation
of the corrosion inhibitor performance at conditions expected in the gas production
system.

Table 1: Critical performance criteria for MEG Additives

Corrosion Inhibitor Oxygen Scavenger Scale Inhibitor

Inhibit at acceptable shear rates Ability to remove dissolved oxygen
in presence of lean MEG
Scale inhibitor performance for
operationally observed scale formation
Thermally stable Thermally stable Thermally stable
Low foaming Partitions to MEG/Water phase
in reboiler for removal Compatible with corrosion inhibitor
Low emulsion tendency Ability to scavenge at low
and elevated pH Compatible with brines

In addition to the critical areas listed in Table 1, further testing may include
comprehensive corrosion testing in the presence
of sand and a range of brine and condensate types, oil cuts, and shear rates. If
the products such as the scale inhibitor are to
be delivered to the wellheads prior to reconstitution with the flowback of brine,
condensate and MEG, then these chemicals
may need additional qualification for subsea delivery with respect to
compatibility, deliverability and stability.
Solutions
Tables 2 and 3 show the brine chemistries used in this study. The effectiveness of
the oxygen scavenger was assessed in
lean MEG brine mixtures (Table 3), with the solutions adjusted to pH of 7.5±0.5 and
9.5±0.5. This was to reflect the
respective scenarios where the MEG system is utilizing a film-forming corrosion
inhibitor (FFCI) and a scale inhibitor (SI),
or is in pH stabilization mode. The observed pH measurements of the MEG and brine
mixtures were corrected due to the
impact of the MEG content.20

Table 2: Chemical composition of brine solution

Cations ppm Anions ppm

Sodium 8,615 Chloride 12,000
Magnesium 22 Bicarbonate 1,900
Calcium 280 Sulfate 80
Potassium 170 Acetate 1,500
Strontium 25
Barium 27
OTC-25070-MS

Table 3: Rich and lean MEG chemical compositions

Name Composition
Lean MEG MEG (industrial grade), 80 % by weight; Test Brine (see Table 1), 20 % by
weight
Rich MEG
MEG (industrial grade), 40 % by weight; Test Brine (see Table 1), 10 % by weight;
Deionized water, 50 % by weight

Results and Discussion

Oxygen Scavenger Testing

Dissolved oxygen levels were measured in a closed vessel assembly using a Jenway
Model 970 dissolved oxygen (DO) meter
having a resolution of 0.01 mg/l (10 ppb). This meter utilized a membrane-covered
electrochemical sensor. To verify
dissolved oxygen levels were below or approaching less than 20 ppb, measurements
were made using a Chemetrics
Dissolved Oxygen Test Kit (ULR CHEMets Kit Cat # K-7540, range 0-40 ppb). These
reagents can come in a variety of
different ampoules for the analysis of dissolved oxygen in various ranges (ppb and
ppm). Later in the project a moresophisticated
Hach Orbisphere meter, with a detection range of 0.6 to 2000 ppb and a resolution
of 0.8 ppb, was utilized for
measuring dissolved oxygen content. The analysis technique of the Orbisphere was
based on the optical sensing of dissolved
oxygen and enabled more accurate determination, especially at low levels (less than
10 ppb).

Oxygen Scavenger Performance

The mechanical integrity of the MEG system in terms of gas leaks is usually checked
by conducting a vacuum pressure hold
test, and ensuring dissolved oxygen levels in the MEG/brines are ideally below 20
ppb. Any lean MEG being deployed to
wellheads and subsea manifolds via carbon steel service lines usually requires
oxygen levels below this specification.
Although the scavenging of dissolved oxygen from water injection and water floods
is well documented, the removal from
particularly lean MEG is less understood. Determining oxygen scavenging performance
in the laboratory is challenging,
especially when attempting to measure levels in the range of parts per billion.
Good laboratory practices, air-tight equipment,
and the latest technology for dissolved oxygen monitoring aid in obtaining reliable
data at these low levels.

Oxygen removal is considered in four scenarios; (1) in Rich MEG and (2) Lean MEG
where pH values > 7 so as to anticipate
pH stabilization conditions, and at pH values < 7 in (3) Rich MEG and (4) Lean MEG,
when corrosion inhibition is
controlled only by the use of the FFCI.

Testing revealed that only treatment with very large doses of specific oxygen
scavenger chemistries, reduced the dissolved
oxygen level of lean MEG from an initial 1 ppm to a 20 ppb dissolved oxygen
residual. It was somewhat surprising that
traditional chemicals like ammonium bisulfite (ABS) showed such poor performance.

The diminished reactivity was attributed to fact that it is known that polyols
(such as MEG and Mannitol) terminate radical
scavenging reactions involved in oxygen reduction and consequently reduce the rate
of reaction.21,22 Furthermore, ABS was
found to be even less effective at the lower pH specification. This is because the
HSO3-ion is a weakly acidic species with a

2-;

pKa of 6.97. The rate of oxygen scavenging is directly dependent on the

concentration of the free sulfite ion SO3

HSO3
−
⇌SO32−
+ H+ (3)
Ka = [SO32-][H+] / [HSO3-] (4)
Thus [SO32-] = ([HSO3-])( Ka ) / ( [H+] ) (5)

The rate of the oxidation of sulfite ion at pH <4 is extremely small, but it
increases with increasing pH. Consequently,
performance of sulfite-based oxygen scavengers was expected to be more demanding at
pH of 7.5±0.5 than compared to a pH
of 9.5±0.5.

To compensate for the poor performance of existing products, new products were
sought that could reduce the dissolved
oxygen levels in a reasonably short period of time (less than 1-2 hours) from
saturated conditions (6-7 ppm). Testing
initially focused on a pH of 9.5±0.5. Alternate inorganic oxygen scavengers based
on sodium bisulfite (SBS), and even
OTC-25070-MS

sodium thiosulfate were screened with no relative success. A number of different

organic chemistries were also assessed for
performance, and are shown in Table 4.

An oxygen scavenger formulation based on a mixture of hydroxyl amine and quinone

showed good promise at a pH of 9.5,
and reduced saturated lean MEG solutions down to less than 20 ppb in 2 hours at a
dosage rate of approximately 700 ppm.
However, at the lower pH of 7.5 the product struggled to reach 100 ppb in a 12-hour
period.

Table 4: Summary of best-performing treatments in oxygen-saturated (7 ppm) lean MEG

General Chemistry of Product Treatment Rate

(ppm) Residual Oxygen (ppb) Time
(min) pH
Sulfite 1 1280 2300 60 9.5
Sulfite 2 with Catalyst 1 1280 1200 60 9.5
Hydroxyl Amine 2560 < 20 960 9.5
Sulfite 2 with Catalyst 1 280 >100 60 9.5
hydroxyl amine and quinone 320 50 276 9.5
hydroxyl amine and quinone 640 < 20 86 9.5
hydroxyl amine and quinone 1280 < 20 80 9.5
hydroxyl amine and quinone 2560 < 20 71 9.5
Triazolidine
chemistry
12500 590 240 9.5
Quinone 8000 25 240 9.5
Sugar 2000 5000 60 9.5
Reactive Organic acid
(as 10% active solution)
5000 200 120 9.5

A product based on hydroxylamine reduced the level of oxygen present in the fluid
to < 20 ppb. However, the application
rate was 2,560 ppm and the test duration was approximately 16 hours. Likewise, the
quinone-based product was found
effective at a pH of 9.5 but at extremely high dosage rates. Such high treatment
rates become impractical with respect to
field logistics, as well as the more important risk of causing fouling in the MEG
regeneration system. An organic-based
mixture showed good performance and reduced the dissolved oxygen of lean MEG at a
pH of 9.5, from approximately 7 ppm
to 20 ppb in less than 1.5 hours at a rate of 640 ppm.

As the number of chemistries able to treat saturated lean MEG appeared limited,
testing efforts were redirected to treating
lean MEG containing lower levels of dissolved oxygen (~1 ppm). Although this was
thought much more representative of
the MEG contained in the MEG circuit, saturated conditions reflect fresh MEG that
may become oxygen contaminated in the
field. Table 5 shows a range of results for formulations screened for performance
at the reduced dissolved oxygen levels (~1
ppm).
OTC-25070-MS

Table 5: Summary of best-performing treatments in lean MEG containing approx. 1 ppm

of dissolved
oxygen

Chemistry Treatment Rate

(ppm)
Residual oxygen
(ppb) Time (min) pH
Multiple Component Organic Mixture 2560 140-500 150 7.5
Multiple Component Organic Mixture 1500 <20 120 9.5
Multiple Component Organic Mixture 1280
70
<20
29
120
9.5
Sulfite 2 with Catalyst 1 2560 600 120 9.5
Sulfite 2 with 25 ppm Catalyst 2 320 70 135 9.5
Sulfite 2 with 50 ppm Catalyst 2 2560 50 30 9.5
Sulfite 2 with 100 ppm Catalyst 2 1280 35 25 9.5
Sulfite 2 with Catalyst 3 640 <20 ppb 20 9.5

During this period novel additives were discovered that could catalyze the reaction
of sulfite ions in MEG. This led to the
development of a propriety product that was found to successfully reduce the
dissolved oxygen levels in saturated lean MEG
to below 20 ppb at a pH of both 7 and 9. Tables 6 to 8 display a summary of test
results showing the performance of the
proprietary product. Optimization of this new oxygen scavenger showed that it
reduced dissolved oxygen levels to below 20
ppb in oxygen saturated lean MEG solutions, at a pH of 7.5 and in the presence of
organic acid, FFCI and scale inhibitor, in a
7-hour period, when dosed at a treatment rate of 500 ppm. In the absence of organic
acids and MEG treatment chemicals,
this time can be significantly reduced to less than 1 hour, and is consistent with
previous finding that oilfield chemicals have
the potential to inhibit the oxygen scavenging.21,22 Under saturated conditions and
at pH 10, only 100 ppm of the proprietary
product is needed to reduce dissolved oxygen levels to below 20 ppb in a 14-hour
period. This is consistent with the fact that
the reaction is more facile at higher pHs. Studies conducted at lower dissolved
oxygen levels showed that a treatment rate of
250 ppm of the proprietary product reduced the dissolved oxygen concentration from
~1000 to less than 20 ppb in 1.3 hrs for
pH 10 and 0.76 hrs for pH 7.5. This may initially appear unexpected with respect to
the notion that the reaction is more
favorable at higher pH values. However, it should be balanced with the observation
that under the more demanding
conditions of a pH of pH 7.5, a treatment rate of 100 ppm reduced the dissolved
oxygen concentration from ~1000 to less
than 20 ppb in 1 hr. These results exemplify that the oxygen scavenging reaction is
a chain-propagated reaction and relies on
initiation kinetics to initiate the reaction (i.e., radical reaction), hence the
variability. Indeed, with the limited data collected it
appears that the general rates of reactions appear similar for a variety of
concentrations. However, the initial concentration of
oxygen scavenger is inversely proportional to the induction time of the reaction.
This translates to the observation that it
takes longer for the reaction to initiate as the concentration of oxygen scavenger
is reduced. However, once the reaction
commences it occurs very quickly.
OTC-25070-MS

Table 6: Test results of the proprietary oxygen scavenger (OS) in oxygen-saturated

(6 ppm) mixtures, at
an initial pH of 7.5 and a temperature of 25° C

80/20 (wt.%)
MEG/ x
FFCI
(ppm)
Scale
Inhibitor
(ppm)
Organic
Acid (g/l)
Oxygen
Scavenger
(ppm)
Final
Dissolved
Oxygen
(ppb)
Time (hr) Comments
Brine 3000 20 1.5 100 >20 ppb -
After adding the OS, pH dropped
to 7.45. The pH was adjusted to
7.49.
Brine 3000 20 -100 >2 ppm -
At low pH (7.5), 100 ppm of OS
couldn’t reduce the oxygen level of
the air-saturated solution to less
than 20 ppb in a 24 hour period.
Brine 3000 20 1.5 100 >2 ppm -
At low pH (7.5), 100 ppm of OS
couldn’t reduce the oxygen level of
the air-saturated solution to less
than 20 ppb in a 24 hour period.
Brine 3000 20 1.5 250 >20 ppb -
The pH of the solution was
increased to 8.48 after 24 hours.
DW2 ---250 <20 ppb 0.46
No organic acid added. MEG and
DI was base solution.
Brine ---250 <20 ppb 0.84 No organic acid was present.
Brine 3000 20 1.5 500 <20 ppb 7

Notes; 1: pH values corrected for MEG; 2: pH adjusted with MDEA

Table 7: Test results of the proprietary product in 80:20 MEG/brine mixtures at

reduced oxygen levels at
pH 7.5 and a temperature of 25° C

FFCI
(ppm)
Scale
Inhibitor
(ppm)
Organic Acid
(g/l) pH1
Initial
Dissolved
Oxygen1
(ppb)
Oxygen
Scavenger
(ppm)
Final
Dissolved
Oxygen
(ppb)
Time (hr)
--1.5 7.9 ≈
960 500 <20 0.27
3000 20 1.5 7.5 ≈
1000 100 <20 1
3000 20 1.5 7.5 ≈
1000 250 <20 0.76
3000 20 1.5 7.5 ≈
920 500 <20 0.27
3000 20 1.5 7.5 67 20 <20 0.34
3000 20 1.5 7.5 135 20 <20 0.65

Notes; 1: pH values corrected for MEG

OTC-25070-MS

Table 8: Test results of the proprietary oxygen scavenger in 80:20 MEG/brine

mixtures at reduced oxygen
levels at pH 10 and a temperature of 25° C

FFCI
(ppm)
Scale
Inhibitor
(ppm)
Organic
Acid (g/l) pH1
Initial
Dissolved
Oxygen1
(ppb)
Oxygen
Scavenger
(ppm)
Final
Dissolved
Oxygen
(ppb)
Time (h) Comments
3000 -1.5 10.1 > 6000 500 <20 -
The DO level was
only monitored
after 16 hours was
below 20 ppb.
3000 -1.5 10.1 > 6000 100 <20 14
3000 -1.5 10.0 ≈
1000 250 <20 1.33
3000 -1.5 10.3 132 20 <20 0.92
3000 -1.5 10.2 60 20 <20 0.51

Notes; 1: pH values corrected for MEG

Qualification of Film-Forming Corrosion Inhibitor (FFCI) in MEG Additives Package

After qualifying the proprietary oxygen scavenger, verifying the stability and
performance of the MEG additives chemical
package was required. This would ensure that the ensemble of additives did not
negatively impact the performance of the
corrosion inhibitor after passing through the MEG recovery systems. Three of the
best-performing oxygen scavengers from
the qualification testing were included into a MEG additives package, and then each
package was thermally treated and
assessed for the tendency to form deposits (gunk), emulsions and cause foaming. The
other components of the MEG package
included the FFCI, scale inhibitor, and a biocide (as a contingency for MIC). Table
9 shows the overall test matrix
examined.

Evaluation of Gunking Tendency

Gunking tests reflect evaluation of the MEG additives package in a worst-case

scenario, at relatively high oxygen scavenger
concentrations, due to the fact that the treatment rate for the oxygen scavengers
had not been optimized, when this testing
was undertaken.

Each 50 ml sample of a mixture of brine, MEG and condensate was transferred into
test tubes and then sealed into an
autoclave for thermal ageing. The samples were exposed to a temperature of 170° C
for a period of 72 hours under an
atmosphere of 100% carbon dioxide. After cooling, each test solution was examined
for any signs of precipitation or
deposition, or the presence of sticky, greasy or inorganic solid compounds.
OTC-25070-MS

Table 9: Sticky Deposit Sample Test Matrix

No. Brine/MEG/Condensa
te Ratio
FFCI
2X MRC, ppm
Oxygen scavenger
Chemistry
Oxygen
Scavenger
2X MRC, ppm
Biocide
2X MRC, ppm
Scale Inhibitor
2X MRC, ppm
SDA1 10/40/50 3000
Multiple Component Organic
Mixture
3600 1000 20
SDA2 10/40/50 3000 Variant of Proprietary Product 3600 1000 20
SDA3 10/40/50 3000 Proprietary Product 3600 1000 20
SDB1 20/80/0 3000
Multiple Component Organic
Mixture 3600 1000 20
SDB2 20/80/0 3000 Variant of Proprietary Product 3600 1000 20
SDB3 20/80/0 3000 Proprietary Product 3600 1000 20
SDC1
20/80/0 +580 mM
MDEA 3000
Multiple Component Organic
Mixture
2000 1000 N/A
SDC2
20/80/0 +580 mM
MDEA 3000 Variant of Proprietary Product 2000 1000 N/A
SDC3
20/80/0 +580 mM
MDEA 3000 Proprietary Product 2000 1000 N/A

MRC: Minimum recommended concentration

OTC-25070-MS

Results from the Sticky Deposit Tests

Examination of the test samples shown in Fig. 3 indicated that the organic
scavenger mixture (SDA1) produced minor solids
at the solution interface after thermal aging. The samples containing newly
developed oxygen scavengers (SDA2 & SDB2)
and (SDA3) became highly colored but contained no solids. All three oxygen
scavengers in the presence of MDEA (SDC1,
SDC2, and SDC3) showed no solids at temperature, but caused slight precipitation
when allowed to cool to room
temperature. In addition, the presence of MDEA displayed red color solutions with
SDC2 and SDC3.

Before Aging After Aging

SDA1, SDA2, SDA3 SDA1: Particles in the interface

SDA2: Heavy color degradation in the Cond
SDA3 Heavy color degradation in the Cond

SDB1, SDB2, SDB3 SDB1: Slight color degradation

SDB2: Heavy color degradation
SDB3: Heavy color degradation

SDC1, SDC2, SDC3 SDC1: Slight color degradation

SDC2: Red color degradation
SDC3: Darker red color degradation

Fig. 3: Images of the sticky deposit test results

After the initial sticky deposit tests were complete, there was some concern that
temperatures in some MEG
regeneration/reclamation circuits may be as high as 170°
C, and extending to 185°C. At close to these temperatures MEG
itself commences to decompose. A test was undertaken to determine if the MEG
additives package was liable to produce
OTC-25070-MS

solids at higher temperatures, but below the MEG degradation temperature.

Untreated MEG and MEG dosed with the FFCI at 3,000 ppm, as well as the scale
inhibitor at 20 ppm were exposed to 185°
C
for a period of 72 hours, in an autoclave purged with nitrogen, and then stored
with 400 psi nitrogen overpressure. Fig. 3
shows a comparison of the samples.

Fig. 4: Images, from left to right, of untreated MEG, untreated MEG but heated, and
thermally treated MEG (with FFCI and SI), held at
185°C for 72 hours

Fig. 4 indicates that the untreated MEG samples, both heated and unheated, are
colorless. Although there is distinct
discoloration in the MEG sample containing the CI and SI, there were no apparent
signs of gunking nor was there any
precipitation of solids evident.

Evaluation of Emulsion Tendency MEG Additive Package

Table 10 highlights the test matrix used to evaluate the emulsion tendency of the
MEG additives after thermal aging. Each
mixture shown in the emulsion test matrix was vigorously sheared for a period of 2
minutes (Blender speed approx. 5,000
rpm). The time taken for the two phases to completely resolve was recorded and
photographed. Chemicals were deemed
acceptable for use if the phases resolve within 5 minutes, without signs of
emulsion or solid formation. The condensate used
for emulsion testing was comprised of the mixture shown in Table 15. When designing
a chemical package for application it
is often difficult to obtain uncontaminated condensate samples, or large enough
volumes for extensive testing. Under such
circumstances an acceptable compromise is to use a synthetic blend that matches
field compositions. However, final
performance testing should always be undertaken on actual field samples.

Table 10: Emulsion Sample Test Matrix

No. Brine/MEG/Condensate
Ratio
Temp
(°C)
FFCI
2X
MRC,
ppm
Oxygen scavenger
Chemistry
Oxygen
Scavenger ppm
Worst Case
Scenario, ppm
Dose rate of
Biocide 2X MRC
SE A1
30% / 20% / 50%
+ 295 mM MDEA
20 3000 Multiple Component Organic Mixture 2000 1000
SE A2 30% / 20% / 50%
+ 295 mM MDEA
20 3000 Variant of Proprietary Product 2000 1000
SE A3 30% / 20% / 50%
+ 295 mM MDEA
20 3000 Proprietary Product 2000 1000
SE A4 30% / 20% / 50%
+ 295 mM MDEA 50%
90 3000 Multiple Component Organic Mixture 2000 1000
SE A5 30% / 20% / 50%
+ 295 mM MDEA
90 3000 Variant of Proprietary Product 2000 1000
SE A6 30% / 20% / 50%
+ 295 mM MDEA
90 3000 Proprietary Product 2000 1000

MRC: Minimum recommended concentration

OTC-25070-MS

Results from Emulsion Tendency Tests

Table 11: Time taken for emulsion to completely resolve into two phases

Mixture Oxygen Scavenger (2,000 ppm) Temperature (°C) Emulsion break Time (s)
SE A1 Multiple Component Organic Mixture 20 90
SE A2 Variant of Proprietary Product 20 57
SE A3 Proprietary Product 20 36
SE A4 Multiple Component Organic Mixture 90 96
SE A5 Variant of Proprietary Product 90 104
SE A5 Proprietary Product 90 110

SE A1 SE A2 SE A3

SE A4 SE A5 SE A6

Fig. 5: Images of the emulsion test results

OTC-25070-MS

Emulsion tests conducted with worst-case dose rates of the chemical additives, all
showed acceptable break times that were
below the 5-minute specification. All tests had two distinct phases, with the
condensate phase clear of any water content.
However, it was noted that the MEG/brine phase did contain entrained condensate.
Emulsion tests with untreated MEG/brine
and condensate mixtures revealed a similar level of entrained condensate. The
conclusion that the additives package afforded
no greater impact on the entrained condensate, than observed in the untreated
mixtures was verified by the independent
laboratory.

Evaluation of Foaming Tendency of MEG Additives Package

Table 12 displays the test matrix used to evaluate the foaming tendency of the MEG
additives after thermal aging. Foaming
tendencies were determined by sparging 200 ml of each mixture with 100% CO2 at a
flow rate of 2.8 L/min for two minutes
in a 1000 ml graduated cylinder. The gas tube was fitted with a frit which was 12
inches long with a diameter of 7/16 inch.
The initial foam height and the time for collapse were recorded. Chemicals are
deemed to have passed the foaming test if the
foam height is less than 500 ml, and the collapse time is less than 1 minute. This
scaled criterion was devised to reflect
foaming tolerances that may be expected in a MEG reclamation unit.

Table 12: Foaming Tendency Test Matrix

No. Brine/MEG/Condensate
Ratio Temp (°C) FFCI
2X MRC, ppm
Oxygen scavenger
Chemistry
Oxygen Scavenger ppm
Worst Case Scenario,
ppm
Dose rate of
Biocide
2X MEC, ppm
F A1
30% / 20% / 50%
+ 295 mM MDEA
20 3000
Multiple Component Organic
Mixture
2000 1000
F A2 30% / 20% / 50%
+ 295 mM MDEA
20 3000 Variant of Proprietary Product 2000 1000
F A3 30% / 20% / 50%
+ 295 mM MDEA
20 3000 Proprietary Product 2000 1000
F A4 30% / 20% / 50%
+ 295 mM MDEA 50%
90 3000
Multiple Component Organic
Mixture 2000 1000
F A5 30% / 20% / 50%
+ 295 mM MDEA
90 3000 Variant of Proprietary Product 2000 1000
F A6 30% / 20% / 50%
+ 295 mM MDEA
90 3000 Proprietary Product 2000 1000

MRC: Minimum recommended concentration

Results for Foaming Tendency of MEG Additives Package

Table 13 highlights that thermally aging Rich MEG that respectively contained one
of three different oxygen scavengers
incorporated into the MEG additives package, appeared to have almost no impact on
the foaming tendency of the aged rich
MEG. Indeed all passed the criteria of having a maximum foam height of less than
500 ml, and a collapse time of less than 1
minute.

Table 13: Time Taken for Foam Collapse

Mixture Oxygen Scavenger

(Worst case scenario of 2000 ppm) Temperature (°C) Foam Height (ml)
Criteria <500
Collapse Time (s)
Criteria <60
F A1 Multiple Component Organic Mixture 20 60 2
F A2 Variant of Proprietary Product 20 60 5
F A3 Proprietary Product 20 60 4
F A4 Multiple Component Organic Mixture 90 90 5
F A5 Variant of Proprietary Product 90 60 2
F A6 Proprietary Product 90 40 2
OTC-25070-MS

Corrosion Testing of the FFCI in the Presence of the Oxygen Scavenger

Tests were carried out to determine the effect of the additives MEG package on the
effectiveness of the film-forming
corrosion inhibitor (FFCI). To mimic the potential shear rates that are likely
observed in gas production systems, corrosion
tests utilized high-speed autoclave test (HSAT) equipment, with corrosion coupons
mounted in a rotating cage. The
corrosion rate specification was to achieve a maximum corrosion rate of 0.05
mm/year. As the corrosion inhibitor is a critical
application in MEG systems, corrosion testing was carried out by two independent
laboratories and the results compared. In
all instances the data reported has been verified by an independent laboratory.

Corrosion testing was conducted on condensate free rich MEG solutions (Table 14),
containing the chemical additives that
had been thermally aged at a temperature of 170° C. Prior to thermal treatment the
MEG/brine solutions were mixed with
synthetic condensate (Table 15) and allowed to separate. This allows partitioning
of the additives, as may be expected in the
production system.

Test Procedures

Table 14: Chemical composition of test brines and rich MEG

Chemical Species Brine Solution (mg/L) Concentration in Rich MEG Mixture (mg/L)
Na+ 41,950 4195
K+ 865 86.5
Mg2+ 110 11
Cl60,000
6000
-HCO3 9,500 950
2SO4
400 40
Organic Acids
Organic Acid mixture shall be added to the rich
MEG solution
750
TDS 112,810 11281

Table 15: Makeup of synthetic condensate

Component Comment Condensate

Mol. %
Isopar M Used as a replacement for paraffinic hydrocarbons with MW of hexane and
above) 98
Toluene Used as a replacement for benzene + toluene 1
Xylene Used as a replacement for ethyl benzene + (Ortho + Meta + Para) xylene +
1,2,4 trimethyl-benzene 1

For each HSAT test run 120ml of the brine solution in Table 18 was mixed with MEG
(480 ml) to afford a lean MEG
mixture that was comprised of 80:20 MEG /brine solution. The lean MEG mixture was
diluted with de-ionised water in a
1:1 ratio, to produce the rich MEG mixture (40% MEG, 10% brine, 50% de-ionised
water). Organic acids (750 mg/l) were
then added to the rich MEG mixture. This was dosed by adding 694.9 mg/l of acetic
acid (or 0.833 ml in 1200 ml) and 55.1
mg/l of propanoic acid (or 0.066 ml in 1200 ml) to the rich MEG. The metal coupons
used in the corrosion tests were X65
coupons machined to a fine grit.
The rich MEG samples were thermally aged by placing 1200 ml of the rich MEG dosed
with the FFCI and the proprietary
oxygen scavenger. The autoclave was fitted with a head and cage enclosing two
hastelloy electrodes that were clamped to
the cage, to allow for stirring of the coupons in the vessel. The fluids were then
sparged with 100% carbon dioxide for up to
1 hour to deoxygenate the solutions. The vessel was then pressurized up to
approximately 10 bars, with 100% carbon dioxide
gas. The rich MEG mixture and additives were then heated while stirring to a final
temperature of 170° C, for a minimum of
6 hours. After the time expired the solution was cooled to room temperature before
depressurizing and opening the
autoclaves. Synthetic condensate samples were prepared by mixing the constituents
shown in Table 19, and 300 ml added to
each test mixture, resulting in a final volume of 1500 ml. The autoclave heads were
reassembled, and a nitrogen gas sparge
OTC-25070-MS

was maintained to remove dissolved oxygen. Degassing was effected by stirring (to a
vortex) at 800 rpm for 2 hours, before
heating the mixture, to the desired test temperature.

Final test mixtures were prepared by transferring the condensate/rich MEG solutions
into a separating funnel. The mixtures
were allowed to separate for a period of 1 hour, until no significant condensate
was entrained in the MEG/brine. Taking care
that no hydrocarbon phase was added, the MEG/brine phase was then separated back
into the test vessel. The solution was
then sparged with high purity nitrogen for approximately 12 hours, and then with
CO2 or CO2/H2S for an additional one-hour
period. The coupons were then placed back into the solutions and the autoclave
sealed. The vessel was then pressurized and
depressurized over five cycles to a maximum pressure of 20 bar with the test gas,
before holding the vessel to a final test
pressure of 20 bar. The autoclave was then heated to a test temperature of 28° C.
The gas supply was left open during the
initial stirring of the solution for a minimum time of 20 minutes to guarantee
saturation of the test solution with the test gas
mixture. When the autoclave reached the text temperature the rotation of the cage
was commenced to cause a 50-Pa shear
stress (rotation rate was based on diameter of the HSAT cage). Once rotating, the
pressure and temperature of the test vessels
were monitored continuously during the 7 days of the test period.

Coupons were analyzed at the end of the 7-day test period by immediately removing
the test specimens from the vessel, and
cleaning the coupons in de-ionized water and ethanol (or IPA) before drying with
high-purity nitrogen gas. The coupons
were cleaned in Clarke’s Solution for a period of 90 seconds (ASTM G1-03 2011). The
corrosion rate of non-oxidized
material in the Clarke’s Solution was determined by exposing a freshly ground and
cleaned specimen in the same batch of
solution. The weight loss of the control sample was then considered when
calculating the corrosion rates of the actual test
samples. The weight loss of each coupon was determined before and after being
cleaned in Clarke’s Solution. The corrosion
rate was calculated from the weight loss (in mm/year) taking into consideration the
control sample. Each specimen was
inspected for signs of pitting by optical microscopy. Special consideration was
given to the leading edge of the test
specimens. If pits were present, pit depth and density was determined.

Results for Corrosion Inhibitor Performance of MEG Additives Package

Three test scenarios were considered to demonstrate corrosion inhibition

performance; (1) Performance in lean MEG to
determine the expected corrosion rates in the service lines that may be expected to
deliver the inhibited MEG to wellheads
when running under FFCI; (2) Performance in rich MEG under FFCI corrosion control
with neutralized pH stabilization and
scale control to reflect the condition when pH stabilization is swapped to full
FFCI mode; and (3) Rich MEG under full FFCI
corrosion inhibition, which reflects the scenario of greatest corrosion risk and
dependence on the performance of the FFCI
and its respective thermal stability. Table 15 summarizes the test data obtained
for the scenarios examined.

The initial tests in lean MEG utilizing standard type coupons (unwelded) under
conditions of pH stabilization of rich MEG
solution with FFCI (1,500 ppm) Oxygen scavenger (1,800 ppm) at 35°C, including H2S
in the gas, afforded a corrosion rate
of 0.011 mm/y. Corrosion rates in coupons containing welds were found to be 0.012
mm/y. This was much lower than the
required criterion of 0.05 mm/yr but was expected due to the high pH of the rich
MEG mixture.

The FFCI was then tested in rich MEG but in the absence of pH stabilisation
(neutralized MDEA), at the design temperature
of 28° C and a shear stress level of 50 Pa, resulted in corrosion rates of 0.044
mm/y for the standard coupon and 0.049 mm/y
for coupons containing weld segments. Again, this was lower than the required
criterion of 0.05 mm/y and was in agreement
with a second corrosion laboratory running the same procedure.

In the third scenario the corrosion inhibitor was evaluated under full FFCI
control, at the design temperature of 28° C. In
these tests the FFCI was tested at both 1X and 1.5X MRC, in the presence of worst
case scenario of 1800 ppm of oxygen
scavenger. In addition, hydrogen sulfide was also added to the system by
introducing Na2S solution (5 ppm in the
MEG/aqueous phase). Testing at a shear of 50 Pa afforded corrosion rates of 0.04
mm/yr, at both treat rates but were less
than the desired rate of 0.05 mm/yr.

Testing was repeated by a third independent corrosion laboratory, (capable of sour

service) to validate the corrosion rate in
the presence of 25 ppm hydrogen sulfide, rather than have sodium sulfide added to
the brine. Replicate tests at 28° C in the
OTC-25070-MS

presence of the FFCI and 1,800 ppm of oxygen scavenger afforded corrosion rates of
0.04 mm/yr and were in line with test
results of validating laboratory, using the same testing technique.

Corrosion tests were undertaken to evaluate the demand on the FFCI when the
temperature and shear rate was raised above
the design specification of 28°
C and 50 Pa to a much higher temperature of 35°
C, with a shear rate of 61 Pa. To
accommodate these conditions the dose of the FFCI was increased to 1.5X MEC.
Furthermore, these tests were in the
absence of any H2S in the gas. Tests were also in the presence of 1500 ppm of the
newly developed oxygen scavenger, and
were conducted at 7 days with 20 bar of 100% CO2. The resulting corrosion rates of
0.108 and 0.159 mm/yr were determined
by two independent laboratories. A second series of HSAT tests with the FFCI at 2X
MRC and a shear stress of 50 Pa, were
conducted which initially commenced at 35° C, but were then reduced to 28° C after
two days. The corrosion rates were
assessed to be 0.08 mm/yr for two replicates, and were only slightly higher than
the required criterion of 0.05 mm/yr. These
tests indicated that temperature was an important parameter for corrosion
performance of the FFCI.

Table 15: Summary of Corrosion Inhibition Performance

Test Scenarios MDEA Additives FFCI

ppm
OS
ppm
SI
ppm
Test Conditions Corrosion
Rate
(mm/yr) Shear
Stress (Pa) Temp. (°C ) 100%
CO2
H2S
Lean MEG N/A FFCI, SI,OS 1500 1800 20 50 35 20 bar 25
0.011
0.012
(welds)
Rich MEG with
FFCI
And neutralized
pH stabilization
and scale
control
295 mM
neutralize
d with
HCl
FFCI, SI,OS 1500 1500 20 50 28 20 bar 25
0.044
0.049
(welds)
Rich MEG
under FFCI N/A FFCI, OS 1500 1800 0 50 28 20 bar
5 ppm
Na2S
solution
0.041
Rich MEG
under FFCI N/A FFCI, OS 2250 1800 0 50 28 20 bar
5 ppm
Na2S
solution
0.042
Rich MEG
under FFCI N/A FFCI, OS 1500 1800 0 50 28 20 bar
25ppm
in gas
0.041
Rich MEG
under FFCI N/A FFCI, OS 2250 1800 0 50 28 20 bar
25ppm
in gas
0.042
Rich MEG
under FFCI
N/A FFCI,OS 2250 1500 0 61 35 20 bar 0
0.108
Lab1
0.159
Lab2
Rich MEG
under FFCI N/A FFCI, OS 3000 1500 0 50
35 (2 days)
28 (5 days) 20 bar 0 0.080
Rich MEG
under FFCI N/A FFCI, OS 3000 1500 0 50
35 (2 days)
28 (5 days) 20 bar 0 0.080

FFCI :MRC=1500 ppm; OS: Oxygen Scavenger; SI Scale Inhibitor

OTC-25070-MS

Conclusion

An ensemble of MEG chemical additives, developed to support hydrate inhibition in

offshore gas production, was tested to
demonstrate suitable performance in corrosion inhibition and compatibility for use
in MEG recovery systems.

Conventional oxygen scavengers were found to be ineffective in scavenging dissolved

oxygen from lean MEG (80/20)
solutions. At a pH of 7.5 (FFCI conditions) many inhibitors were unable to reduce
the dissolved oxygen in a time period of
less than two hours. While at a pH of 9 (pH stabilization conditions) none
considered could achieve, with reasonable dose
rates, meeting the 20 ppb specification at all. Consequently, a more-efficient
proprietary inorganic oxygen scavenger was
developed. With an applied treatment rate of 250 ppm, the oxygen scavenger was able
to reduce 1 ppm of dissolved oxygen
in Lean MEG to 20 ppb, in 0.76 hours at a pH of 7.5, and 1.33 hours at a pH of 10.

The ensemble of chemicals was found to have thermal stability in rich MEG brines to
a minimum temperature of 170°
C.
Laboratory tests suggest that at these temperatures the additives are unlikely to
form solids or sticky deposits. However,
certain oxygen scavengers contributed to color changes, while an organic-based
oxygen scavenger produced some minor
solids at the solution interface. Consequently, it is expected that the ensemble
should not cause fouling in the reclamation
unit of the MEG recovery system. The thermally treated MEG additives package showed
no significant emulsion or foaming
tendencies.

Corrosion tests were performed by primarily two independent testing laboratories

following the same high shear autoclave
testing methodology, and validated the performance of the thermally aged film
forming corrosion inhibitor in the presence of
a MEG chemical additives package. The corrosion inhibitor was able to meet
specification of less than 0.05 mm/yr at a shear
stress of 50Pa, either when pH stabilization or FFCI was employed at temperatures
of 28°
C.

References

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between internal corrosion control method, scale control and MEG handling of a
multiphase carbon steel pipeline carrying wet gas
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OTC-25070-MS

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