IBP1014_19

COMBINED H2S SCAVENGER / CORROSION

INHIBITOR TO ADDRESS INTEGRITY
CHALLENGES OF A MATURE OILFIELD
Marko Stipanicev1, Øystein Birketveit2, Vibeke
Hatloe3, Jody Hoshowski4, Alyn Jenkins5, Maria
Lioliou6, Tore Rindalsholt7
Copyright 2019, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Pipeline Conference and Exhibition 2019, held
between 03 and 05 of September, in Rio de Janeiro. This Technical Paper was selected for presentation by the
Technical Committee of the event according to the information contained in the final paper submitted by the
author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is
presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion, or that of its
Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Pipeline
Conference and Exhibition 2019.

Abstract

Production of mature oil and gas fields requires managing the related risks and limitations
imposed by reservoir souring upon assets and production integrity. The corrosive effect of H2S
in combination with export gas H2S specifications, escalates operational expenditure. The
treatment of produced fluids can, in a worst-case scenario, reduce production output if the
appropriate tools for managing elevated H2S levels are not in place. Herein presented is a case
where production from a subsea field was restricted by the amount of H2S produced due to
constrains in the topside gas processing system. The objective of the work was to remove
significant amounts of H2S from produced fluids during transit via subsea production pipelines;
scavenging H2S during multiphase flow, whilst maintaining corrosion and scale inhibition.
A novel multiphase H2S scavenger was incorporated into the incumbent subsea
corrosion inhibitor. The work included identification of suitable multiphase H2S scavenging
chemistry, tailoring of the multifunctional chemical to retain corrosion inhibition properties,
and confirmation that this new chemistry did not deleteriously impact performance of other
production chemicals used nor the production process itself. The experimental development
work demonstrated that the combined product containing a nitrogen free scavenger can deliver
suitable H2S scavenging capacity while maintaining corrosion inhibition performance. The
qualification work supported a full-scale field test that demonstrated suitability of the new
multifunctional chemical. The new environmentally acceptable combined corrosion inhibitor
and H2S scavenger enables higher production rates from the subsea field without modification
of the chemical injection system or topside process system.

Keywords: H2S, subsea, corrosion inhibitor, multifunctional product

1. Introduction

Downhole tubing, subsea pipelines, and vessels used in oil and gas production are often
manufactured from carbon steel. However, produced fluids invariably contain a variety of
______________________________
1
Ph.D., Technical Support Lead - Schlumberger, 2M.Sc., Technical Manager - Schlumberger, 3M.Sc. Project
Leader - Schlumberger, 4B.Sc., Corosion Team Leader – Schlumberger, 5M.Sc., Asset Integrity Advisor -
Schlumberger, 6Ph.D., Principal Engineer – Equinor ASA, 7B.Sc., Principal Engineer - Equinor ASA

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corrosion species including acidic gases (CO2 and H2S) and organic acids (acetic, propionic,
and formic acid) that will corrode carbon steel (Byars, 1994). Corrosion caused by CO2 or H2S
will frequently manifest as localized corrosion or under deposited corrosion if the produced
fluids are not effectively treated with production chemicals. In sour oil fields (defined as those
with >0.5 mol% H2S present in the gas phase), several different polymorphous iron sulfide
scales form because of corrosion of the carbon steel infrastructure. These include mackinawite
(FeS), troilite (FeS), pyrrhotite (Fe1-x), greigite (Fe3S4) and pyrite (FeS2); the specific type of
iron sulfide that will form is largely dependent upon the system temperature and pH (Ning et
al, 2013). Under deposit corrosion can take place beneath these scales or if they breakdown in
localized areas, pitting corrosion will occur.
Corrosion due to H2S can be mitigated through injection of inhibitors, H2S scavengers,
or commonly both products are injected separately. However, this paper summarizes the work
carried out to develop and apply in an oilfield a new multifunctional corrosion inhibitor / H2S
scavenger for use subsea in a sour offshore field located in the Norwegian North Sea. The use
of combined products has several advantages compared to the use of mono-functional
chemicals. Using combination products reduces the chemical storage facilities required
offshore and reduces the amount of chemical injection equipment needed. Additionally, for
subsea chemical applications, the use of combined products decreases the number of chemical
injection umbilicals required. Overall, the use of multi-functional products reduces the costs
associated with installing chemical injection equipment on an offshore installation

2. Field Description

The field of concern (Field X) is in the Norwegian Continental Shelf and consists of
several oil deposits which have been extracted with seven subsea templates and two satellite
wells. The field is produced by means of secondary oil recovery utilizing seawater injection to
maintain reservoir pressure. The production from Field X is routed to a nearby installation
(Field Y) through high-pressure and low-pressure pipelines (A2 and B1 respectively). Figure 1
provides a schematic overview of the Field X process system, chemical injection (subsea scale
and corrosion inhibitor) locations and the average oil, gas and water production rates for each
pipeline. The subsea system is much more complex with distribution of the subsea chemicals
over several templates. Additionally, recirculating flows and topsides equipment including
hydrocyclones, floatation units are omitted from the diagram for simplicity.

Figure 1. Schematic of Field X production to installation Y

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Initially, Field X gas process system was not directly treated with H2S scavenger. To
compensate for this, Field Y was over treated with a triazine H2S scavenger before the two gas
streams commingle (Figure 2). This had been an acceptable solution for several years. However,
as the H2S production from the X wells increased during field life, the wells at Field X had to
be choked down for the following reasons:

1. It was not possible to treat the gas phase efficiently via the existing triazine-based H2S
scavenger injection system. This resulted in H2S concentration in the export gas above
specification.
2. The gas phases in the low-pressure parts of the process system, e.g. degasser, had H2S
concentrations in range of 2000-3000 ppm. This represents increased health and safety
risks when sampling or performing maintenance tasks.
3. Triazine-based H2S scavenger contributed to 20% of the harmful species present in the
produced water discharged from fields X and Y.

Figure 2. Schematic of gas treatment at field Y Process

Consequently, removal of H2S produced by Field X wells had to be implemented

upstream in the X process system. Based on similar experience with two wells form Field Y, a
subsea applied multiphase H2S scavenger was recommended as potential solution (Lioliou et
al). Due to limited availability of subsea chemical injection lines, the product had to be
multifunctional. In addition to H2S scavenging capabilities it had to maintain corrosion
protection of the low and high-pressure production flowlines (A2 and B1) at a level comparable
to the incumbent subsea corrosion inhibitor. In addition, the product had to be suitable for
subsea deployment and have no negative impact on the chemical injection system, production
process or affect the efficacy of the scale inhibitor.
Moreover, because production chemicals used in the Norwegian North Sea are subject
to strict environmental regulations, the new combined H2S scavenger and corrosion inhibitor
had to be environmentally acceptable.

3. Product Design and Testing

3.1 Performance Evaluation

Several multiphase H2S scavengers were screened for application in subsea Field X.
The main challenge for some scavengers (e.g. glyoxal) was the compatibility with amine-based
corrosion inhibitors. Those scavengers either nullified the performance of corrosion inhibitors
or were incompatible with corrosion inhibitors upon blending together. The non-nitrogen H2S
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scavenger EDDM ((ethylenedioxy)dimethanol) showed that it can deliver effective H2S

removal while not having a deleterious effect on corrosion inhibitor performance. While many
other chemistries were found to significantly affect or even nullify the performance of the
amine-based corrosion inhibitor, EDDM allowed further optimization of the formulation
increasing robustness of the final product. Corrosion inhibition performance of the incumbent
corrosion inhibitor (Product A) versus combinations of three multifunctional H2S scavenger
and corrosion inhibitor blends (Products B, C and D) was assessed in the laboratory. Testing
was performed using a rotating cylinder electrode (RCE) test at 72 °C, 0.99 bar CO2, 28.5 g/l
NaCl, 23.65 mmol/l total alkalinity with 7.86 mmol/l acetate.
The results summarized in Table 1 show that a blend of the incumbent corrosion
inhibitor with EDDM (Product D) gave equivalent corrosion performance to Product A.
Moreover, Product D gave significantly improved performance compared to a blend of MBO
(3,3′-methylenebis[5-methyloxazolidine]) H2S scavenger with the incumbent inhibitor (Product
B) and a blend of glyoxal H2S scavenger with the incumbent inhibitor (Product C).

Table 1. Summary of Corrosion Inhibition Performance Results

Dose Average Corrosion

Chemical Description
(ppm) Rate (mm/yr)
Product A Incumbent Corrosion Inhibitor 20 0.03
Product B 50:50 Blend of MBO H2S Scavenger & Incumbent CI 50 0.35
Product C 50:50 Blend of Glyoxal H2S Scavenger & Incumbent CI 50 0.08
Product D 50:50 Blend of EDDM H2S Scavenger & Incumbent CI 50 0.03

Moreover, corrosion inhibition performance testing using the RCE in H2S-containing

environments demonstrated that some inhibitor aids and synergists in the incumbent inhibitor
had negligible impact on corrosion inhibition (Table 2). Therefore, the final multifunctional
product developed and selected for field trial (Product G) consisted of a 70:30 blend of EDDM:
incumbent corrosion inhibitor but with the synergist and inhibitor aids removed.
Sour RCE testing was conducted at 80 °C with 20 Pa wall shear stress, 0.55 bar CO2,
0.14 bar H2S, 28.5 g/l NaCl, 12.3 mmol/l total alkalinity with 6.1 mmol/l acetate.

Table 2. Summary of RCE Results Performed with H2S

Average
Average
Dose Corrosion
Chemical Description Inhibition
(ppm) Rate
(%)
(mm/yr)
Blank 1 N/A - 0.35 -
Product A Incumbent CI 30 0.02 94.5
Product E Incumbent CI with synergist removed 30 0.03 91.1
Product F Incumbent CI with synergist and inhibitor aid removed 30 0.05 83.8
Product G 70:30 blend of EDDM H2S Scavenger & Incumbent CI
100 (*) 0.03 91.2
with synergist and inhibitor aid removed
*100 ppm of multifunctional product contains comparable amount of amine filmer as
30 ppm of incumbent corrosion inhibitor.

In addition to the laboratory generated information, knowledge about the amount of H2S
required to be scavenged in Field X process was crucial when tailoring the final product. A H2S
mass balance analysis for Field X determined the amount of H2S produced and the volume of
Product G required to scavenge the H2S in the low and high-pressure flowlines to acceptable
levels. Moreover, the amount of amine filmer in the novel product should not have negative
impact on the separation process topside. Therefore, the concentration in the system for the
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amine was maintained at the same level based on the incumbent corrosion inhibitor injection.
The following assessments had to be completed before moving forward with the trial of
Product G in the field:
 Elastomer, plastics and metals compatibility testing
 Long term thermal stability testing
 Interaction of Product G with incumbent topside scale inhibitor. This testing is critical
for minimizing deleterious impact of iron scales and related separation challenges.

3.2 Materials Compatibility Testing

The corrosivity of Product G towards 316 stainless steel and carbon steel grade C1018
specimens was investigated by exposing specimens to neat chemical at 20oC and 90oC for 30
days. In these tests, the general corrosion and tendency to pitting was assessed based on
ASTMG31 - 12a. Obtained results are shown in Table 3 and Product G was found to be non-
corrosive to 316 but corrosive towards C1018. However, the carbon steel test was for
information purposes only as there is no carbon steel in the chemical injection system.

Table 3. Alloy Compatibility for Product G

Alloy Temperature (°C) Corrosion rate (mm/y) Corrosion attack morphology

316 20 0.001 Uniform
316 90 0.001 Uniform
C1018 20 0.58 Uniform
C1018 90 1.12 Localized

The compatibility of Product G towards different elastomers present in the injection line
was also tested, with the results given in Table 4. In these tests Product G was compatible with
all materials tested.

Table 4. Compatibility Results of Elastomers and Plastic to neat Product G for 14 days at 20 °C

Material Swelling Hardness (shore A)

Viton (75 Shore hardness) -5 % 2 units
Nitrile (75 Shore hardness) 3% -2 units
PTFE 0% 0 units

3.3 Long Term Stability Testing

Long term stability testing of the multifunctional product was performed at -10, 4, 20
and 90 °C for 30 days and at the end of the test, kinematic viscosity curves were obtained. The
product remained stable after exposure to these tests and the viscosity was lower than 200 cP
at 4 °C in all scenarios.
Product G was submitted to filtration testing pre-and post-exposures at 4°C for 4 and 8
weeks (Stipanicev et al). After exposure at 4°C for 4 and 8 weeks, Product G was passed through
a 0.75mm ID alloy coil at 25°C and 5.5 bar for 5 filtration cycles and the differential pressure
(dP) across a 2 μm filter recorded. The obtained dP profiles and kinematic viscosity curves are
shown in Figure 3. No significant changes in differential pressure during filtration or in the
viscosity curves were recorded.

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Figure 3. Left: dP Profiles for Non-Aged and Aged Product G. Right: Viscosity Profiles for Product G

3.4 Compatibility with Incumbent Scale Inhibitor

The interaction of the combined H2S scavenger and corrosion inhibitor (Product G) with
the incumbent topside scale inhibitor was investigated using Dynamic Scale Loop (DSL)
testing. Test conditions and pass/fail acceptance criteria applied to the DSL testing is shown in
Table 5 and the test water chemistry provided in Table 6.

Table 5. Test Conditions and Pass/Fail Acceptance Criteria Applied to The DSL Testing

Parameter Value
System pressure 17.3 bar
System temperature 85°C
Coil dimensions 1mm ID, 3 m length
Flow rate: 6 ml/min combined, split at pumps
pH 7.2
Pass criteria scaling time ±15% compared to time of Incumbent Scale Inhibitor

Table 6. Water Composition Used for DSL Testing (Representative of Field X)

Na K Mg Ca Ba Sr Cl SO4 HCO3
(mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l) (mg/l)
28
10700 240 705 570 74 19800 1500 965
(60*)
*60 mg/l was used in the DSL test to reduce time required for blank.

DSL results are summarized in Table 7. There is some variation in the test results,
however, these are within experimental error. The findings suggested a lack of competing
interaction between chemistries when introduced in the process stream.

Table 7. Dynamic Tube Blocking Tests

Product Dose Time dP Increase

(ppm) (min) (mbar)
Blank (with 60 mg/l Ba) - 39 69
Incumbent Scale Inhibitor 5 93 69
Incumbent Scale Inhibitor/ Multifunctional Product G 5/40 88 69
Incumbent Scale Inhibitor/ Multifunctional Product G 5/5 83 69

4. Field Application

Production from the H-template wells was routed to the A2 line during the field test.
The retention time in the subsea production system was 4 to 6 hours, depending on the location
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of each template. The H2S concentrations were measured at the gas outlet of each process unit.
In addition, a range of other analyses (full ion analysis, total alkalinity, organic acids, suspended
solids, corrosion inhibitor, scale inhibitor and EDDM residual concentration) were performed
onshore on water and oil samples. To get the H2S mass balance calculated as accurately as
possible, the water chemistry and CO2 concentration in the gas must be known. Water
compositions as analyzed and used in simulations are shown in Table 8.

Table 8. Water composition used in calculations

Ion (mg/L Total Acetic

Location alkalinity acid
Na K Mg Ca Ba Sr Fe Cl SO4 (mM) (mg/l)
1st stage sep. 10620 253 524 590 10 60 2.0 18550 953 10.8 158
2nd stage sep. 11483 289 873 593 3 31 1.9 19817 1892 8.3 47
Degasser 11383 283 732 625 9 49 1.7 19167 1400 9.4 122

The pH of the water in the separator is one of the key parameters for mass balance
calculations. Table 9 shows the conditions and the calculated pH values at equilibrium, based
on measurements of the CO2 concentration in the gas phase, performed during the field test. It
also depicts the pH values used in the mass balance (best estimated real pH).
Table 9. pH Calculations Based on Multiphase Equilibrium

End of 1st stage End of 2nd stage Degasser

Parameter
line A2 separator X line B1 separator X X
P (barg) 38 29 20 11 0.4
T (°C) 70 70 67 67 67
CO2 (ppm) 0.95 0.95 0.95 0.95 7
H2S (ppm) 250 250 495 495 2800
pH at equilibrium 6.29 6.39 6.48 6.71 6.75
Estimated pH - 6.34 - 6.60 -

A H2S distribution model has been used previously to calculate the amount of H2S being
produced in the A2 and B1 flowlines (Lioliou et al). The model is based on a multiphase
equilibrium program that considers the phase distribution of the gases and includes water
evaporation. Previous H2S scavenger tests have proved that the model is accurate for this
purpose, and much easier to use than a full multiphase equilibrium study (Lioliou et al and
Birketveit et al). Figure 4 shows the process schematic with the amount of H2S produced in total
from each line and the distribution among the three phases through the process.

Figure 4 Baseline H2S-Distribution Through the X Separation System

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The data in Figure 4 was used as baseline data and similar mass balance calculations
were calculated for selected dosages of the multifunctional product injected to the X subsea
templates. Table 10 shows the dose rates for Product G in liters per day; ppm with regards to
total fluids and ppm based on the water phase.
Table 10. Field Dose Rates of Product G

Dosage test product On total fluids On water phase

Date/Time A2 H Total B1 A2/H B1 A2 B1
(l/d) (l/d) A2/H (l/d) (l/d) ppm ppm ppm ppm
Baseline 0 0 0 0 0 0 0 0
Day 1, Morning 629 127 756 638 71 63 90 76
Day 2, Morning 857 482 1339 826 126 82 159 99
Day 2, Evening 670 379 1049 701 99 70 124 84

Table 11 shows the amount of the H2S scavenger component (EDDM) in Product G
injected compared to the amount of H2S removed, based on the mass balance calculations.

Table 11. Efficiency Data for the H2S Scavenger Component (EDDM) in Product G

A2/H B1 Total Scavenged A2/H B1 A2/H B1 Total

Date/Time Efficiency liters
kg/d H2S kg/d EDDM
EDDM / kg H2S
Baseline 314 409 723 Baseline 0 0 - - -
Day 1, Morning 196 199 395 327 734 619 5.2 2.5 3.5
Day 2, Morning 108 144 252 470 1299 801 5.3 2.5 3.8
Day 2, Evening 113 177 290 432 1018 680 4.3 2.5 3.3

The efficiency for the B1 line was significantly better than for the A2 line. This can be
explained by the higher pH, which results in more H2S available in the water phase where the
reaction takes place. This was confirmed by the sulfide ion concentration measured in the two
separators. In addition, there were several recirculation flows back to the 2nd stage separator,
allowing more time for the reaction to proceed. The injection dose rates and measured EDDM
residuals are shown in Figures 5 to 7.
120
Product Injected to A2

100 Product Injected to H

Product / EDDM (ppm)

EDDM (1.stage separator)

80

60

40

20

Time (date:hour)

Figure 5. A2 and H Concentration of Product G Injected with Measured Residuals of EDDM

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120
Product injected to B1

Product / EDDM (ppm)

100 EDDM (2.stage separator)

80

60

40

20

Time (date:hour)
Figure 6. B1 Concentration of Product G Injected with Measured Residuals of EDDM

120
Total Product

100
EDDM (degasser)
Product/ EDDM (ppm)

80

60

40

20

Time (date:hour)
Figure 7. Total Concentration of Product G Injected with Residuals of EDDM From the Degasser.

The ratio between the amount of EDDM injected and the residual EDDM (unreacted)
analyzed for each flowline were approximately the same, with spent EDDM showing 36-47%.
Figure 8 shows measured EDDM residuals plotted versus iron concentration and suspended
solids. The ion analysis data show relatively stable values with variations within the accuracy
of the measurement methods. Interestingly, the iron concentration increases slightly with
increasing dose of Product G. At the same time, suspended solids measured in the system were
significantly reduced. This indicates that EDDM improves control of iron sulfide scales by
reducing the concentration of sulfide available in the water phase.
During the trial, the injection of the scale inhibitor was unchanged during the test period
and the concentration of scale in the system reduced (Figure 8). Residual measurements
remained consistently around, 15-20 ppm for the first stage separator and 50 ppm for the second
stage separator.

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35 5.0
Suspended solids
4.5
30 Dissolved iron

4.0

Suspended Solids (mg/l)

25 3.5

Dissolved iron (mg/l)

3.0
20

2.5

15
2.0

10 1.5

1.0
5
0.5

0 0.0
0 10 20 30 40 50 60 70 80 90
Residual EDDM (mg/l)
Figure 8. All Measured EDDM Residuals Plotted with Iron Concentration and Suspended Solids

5. Conclusions

A novel multiphase H2S scavenger was successfully incorporated into the incumbent
subsea corrosion inhibitor utilized in a North Sea field in the Norwegian Continental Shelf. The
new product was tailored to retain excellent H2S scavenging and corrosion inhibition properties,
while at the same time ensuring that it would not impact performance of the other production
chemicals used nor the production process itself.
The new combined formulation of corrosion inhibitor and H2S scavenger (Product G)
enables higher production rates by allowing increased production rates of high H2S contributing
wells. This was achieved without any requirements for modification of the chemical injection
system or topside process system. In addition, the reduction of available sulfide in the water
reduced the precipitation of iron sulfides previously shown to be a challenge for the water
treatment process topside.

6. References

A. G31-72: Standard Practice for Laboratory Immersion Corrosion Testing of Metals, ASTM
International, West Conshohocken, USA, 2004.
Birketveit, Ø., Experiences with H2S-scavenging in Subsea Multiphase Flow, NACE
CORROSION 2017: TEG 202X Flow Assurance in Oil and Gas Production, New Orleans,
USA, NACE 2017.
BYARS, H.G., Corrosion Control in Petroleum Production, TPC Publication 5, NACE
International, (Houston, TX: NACE, 1999) p. 26-32
NING, J., ZHENG, Y., YOUNG, D, BROWN, B. and NESIC, S., “A Thermodynamic Study
of Hydrogen Sulfide Corrosion of Mild Steel”, NACE CORROSION 2013, Orlando, USA,
2013
LIOLIOU, M.G., SANDRØD, J., STIPANICEV, M. and BIRKETVEIT, Ø., Qualification and
Field Performance of Subsea H2S Scavenger Injection. Oilfield Chemistry Symposium Geilo,
Norway, Tekna, 2017.
STIPANICEV, M., BIRKETVEIT, Ø., AVALDSNES, O.G., Tailoring Chemicals for
Continuous Injection Downhole via Capillary Line and “Sensitive” Jewelry, NACE
CORROSION 2017, New Orleans, USA, NACE 2017.
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