Copyright 2007, Society of Petroleum Engineers

This paper was prepared for presentation at the 2007 SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 28 February2 March 2007.

This paper was selected for presentation by an SPE Program Committee following review of
information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes without the written consent of the Society of Petroleum Engineers 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 where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, Texas 75083-3836 U.S.A., fax 01-972-952-9435.

Abstract
Tanks used to store produced water on Floating, Production,
Storage and Offloading units (FPSOs) are extremely
susceptible for generation of high hydrogen sulfide (H
2
S)
levels due to the activity of sulfate-reducing bacteria (SRB).
The FPSOs operated by Petrobras in the Campos Basin,
offshore Brazil, all contain slop water tanks, while some also
have upstream oil-water separation tankage. Slop water,
comprised of produced water, ballast water from oil cargo
ships and deck water, contains SRB and their nutrients
required for generating H
2
S. Additionally, solids
accumulations at the tank bottoms provide an excellent
environment for microbial growth.
A 2002 field trial on an FPSO confirmed the viability of
combined batch treatments of anthraquinone and of a THPS
blend to control H
2
S biogeneration better than previous
treatment programs. Anthraquinone, a non-toxic SRB
inhibitor, and THPS, an oilfield biocide, act synergistically to
effectively control the H
2
S biogeneration in this environment.
The combined chemical treatment strategy has now been
implemented successfully on six Petrobras FPSOs. Flexibility
has been important in developing the treatment programs since
operating parameters are different for each FPSO and change
due to increased water production rates. Options include the
ability to inject the chemicals continuously or batchwise at
different locations and to alter the volumes and ratios of
chemicals for optimizing control over H
2
S and corrosion.
This paper describes the individual FPSO water flow and
storage systems and discusses the customized chemical
treatment programs. Included are field H
2
S data showing the
progression of the programs as they are being continually
adjusted to optimize H
2
S generation and cost effectiveness.
Also included are results of laboratory microbial studies
showing the synergy of anthraquinone and THPS and of
corrosion studies which have impacted the direction of usage
of these chemicals.
With over 100 FPSOs operating worldwide, the described
treatment program can significantly affect the safety and
environmental aspects of processing water containing SRB.

Introduction
The use of Floating, Production, Storage, and Offloading
(FPSO) and Floating, Storage and Offloading (FSO) units to
produce oil and/or process oil and water associated with
offshore production has increased to about 106 units currently
in operation worldwide.
1
These FPSOs/FSOs are ships
containing multiple tanks for separating oil and water, storing
oil prior to offloading into tankers, and processing waters.
Produced water typically flows into slop tanks where it may
also combine with drainage water from decks or ballast water
from cargo ships. Slop tanks are in many cases the final
separation stage in which residual entrained oil is removed
from the water prior to its discharge to the sea, offloading or
reinjection. Environmental concerns dictate that the total oil
and grease (TOG) is a crucial water quality criterion before
discharge, but the level of hydrogen sulfide (H
2
S) is also
critical due to its high toxicity and corrosivity to carbon steel.
Oil-water separators and slop water storage tanks are
prime locations for activity of sulfate-reducing bacteria (SRB)
and the subsequent generation of high levels of H
2
S. SRB are
particularly abundant in most oilfield waters, including
seawater. The slop waters also typically contain all of the
nutrients required by the SRB for their growth and
dissimilatory respiration, reducing sulfate to sulfide.
Environmental conditions in the slop water tanks, especially
the presence of sludge and solids deposits at the bottom of the
tanks, are quite favorable for these anaerobic bacteria to form
biofilms. These solids are also protective to the SRB and
make chemical biocide treatments difficult for controlling the
bioactivity. Health, safety, and environmental aspects
associated with the presence of the toxic gas on offshore
structures make it necessary to implement effective SRB
and/or H
2
S control procedures while still maintaining
compliant water for discharge.
Petrobras currently operates ten FPSOs/FSOs in the
Campos Basin, approximately 180 km northeast of Rio de
Janeiro, Brazil. The FPSOs are located in water depths from
160 to 1240 meters. Some units have production facilities
(FPSOs), while others (FSOs) only receive produced oil and
water from other platforms. All have slop water tanks with
varying degrees of SRB activity depending on the producing
fluids composition and reservoir characteristics. The fields
submitted to seawater injection are prone to biogenic H
2
S
generation and those with low salinity formation water and

SPE 106106
Flexible Treatment Program for Controlling H
2
S in FPSO Produced-Water Tanks
E.D. Burger, SPE, EB Technologies; C.A. Andrade, Petrobras; and M. Rebelo and R. Ribeiro, Baker Petrolite
2 SPE 106106
low reservoir temperature tend to be the most susceptible. As
described previously, the dual treatment program of a biocide,
tetrakishydroxymethyl phosphonium sulfate proprietary blend
(THPS), and a biostat, anthraquinone (AQ), was extremely
successful at controlling the H
2
S biogeneration on one of the
Petrobras FPSOs.
2
This dual treatment program has
subsequently been implemented on five additional FPSOs as
its effectiveness has continued to be validated under the
varying water and SRB conditions on each unit. Discussed in
this paper is the progression of the program as it has been
customized and continually adjusted by individual FPSO to
optimize the control of H
2
S generation and cost effectiveness.
Also presented are laboratory data showing the synergy of
THPS and AQ in dual treatments and results from corrosion
studies with the two chemicals.

FPSO Descriptions. Fig. 1 shows the tank layout in a typical
FPSO. Flowlines to and from subsurface wells and other
platforms/structures are connected to the surface facilities on
the FPSO deck through the turret located on the bow. The
FPSO is anchored at the bow, but is able to rotate around the
stationary turret. For one specific FPSO, tanks 3BB, 3BE,
6BB, and 6BE are for oil-water separation, while the
remaining tanks are mainly for oil storage. The slop water
tanks are in the stern of the vessel and are typically either
2000 m
3
or 4000 m
3
capacity. The FPSO is 337 m long, 54 m
wide, and 28 m deep with a maximum oil storage capacity of
about 320,000 m
3
(2,000,000 bbls).
The water processing schemes on each FPSO/FSO are not
identical due to the varying amounts of oil, water, and gas
processed and the production source. Each ship receives
production from other platforms, while some also have their
own production wellheads. FPSOs/FSOs are equipped with
tri-phase separators, electrostatic heaters and hydrocyclones
for oil-water separation, and oil and slop tanks for storage.
Figs. 2-4 show simplified schematics for the water systems on
four of the FPSOs. As will be discussed below, there are two
basic chemical treatment programs utilized to control the H
2
S
biogeneration on the FPSOs. The first type is represented by
the initial FPSO implementing the AQ-THPS treatment
program as presented previously.
2
Chemical treatments are
made directly into the slop water tanks as shown schematically
in Fig. 2. Water from separators and from deck drains is
processed by hydrocyclones to remove entrained solids and oil
and is then transferred sequentially to the port (BB) slop tank
and the starboard (BE) slop tank before being discharged
overboard. The second basic treatment program includes
chemical injection into the water phase of the separation tanks
in addition to the slop water tanks as shown schematically in
Fig. 3. Oil from the separators is de-watered in electrostatic
heaters, with the THPS and AQ injections into the residual
water flowing back to the separators. Water from the
separators is then processed by hydrocyclones before flowing
into dirty and clean slop water tanks. The water processing on
FPSO-4 (Fig. 4) is different from the other two processing
schemes. If high levels of settled water in the oil cargo tanks
interfere with crude offloading operations, the water is
transferred to the slop water tanks. These slop tanks are
treated only when necessary with THPS and AQ to control
H
2
S biogeneration.
Chemical Descriptions. Anthraquinone is an insoluble
polycyclic hydrocarbon that is generally non-toxic to plants
and animals. Studies have shown that anthraquinone
uncouples the electron transfer process in SRB that is required
for the bacterias respiration using sulfate. Specifically, ATP
synthesis is interrupted as AQ partitions into the SRB cell
membrane. When this metabolic pathway is blocked, the SRB
are incapable of reducing sulfate to H
2
S. However, the
bacteria are able to respire using other available electron
acceptors and will biodegrade the AQ present, resulting in the
restoration of H
2
S biogeneration. AQ is effective at micro-
molar concentrations, but the duration of sulfide inhibition is
limited in oilfield environments due to the presence of other
bacteria, sludge, and solids associated with production. AQ
appears to be effective for most SRB populations found in the
oilfield, but studies have shown that some crude enrichment
cultures are resistant to the AQ. Likewise, non-SRB other
than some methanogenic bacteria are apparently unaffected by
the presence of AQ.
3-5

The particle size of the solid anthraquinone is critical in
the sulfide inhibition process since molecular AQ is required
to partition into the SRB cell membrane. The slight water
solubility of AQ (~70 g/L) provides these molecules, but the
availability is dependent upon the surface area of small
particles. Mechanical grinding of AQ can reduce the particle
size to less than about 10 m, imparting a moderate, but
limited effect. In order to increase the efficacy of AQ in
oilfield waters, a dialkali salt of anthracenediol, moderately
soluble at high pH, is used in the treatments. Injection of this
solution into an anaerobic water forms sub-micron sized
colloidal particles of anthrahydroquinone as the treatment
solutions pH is instantaneously reduced to essentially the
water pH. These small particles coat the interior surfaces of
pipelines and vessels and subsequently become incorporated
into the biofilm where they provide a time-release treatment
and a continual source of the sulfide inhibitor.
Anthrahydroquinone is easily oxidized by the bacteria to AQ.
Both substances are inhibitory and, in fact, the change in
oxidation states most likely is the cause for the inhibitory
effect in SRB. This paper will refer to AQ solutions or
treatments, but technically the product employed on the
FPSOs is a proprietary formulation of an anthracenediol,
dialkali salt, solution.
THPS is a non-foaming, broad-spectrum biocide that is
less toxic to aquatic and marine species than other biocides
currently registered for oilfield use. Bacteria are killed by
disruption of proteins in the bacterial cell membrane and
inhibition of lactate dehydrogenase activity.
6
THPS was
selected as the biocide of choice for these FPSO applications
based on its efficacy of kill in system-specific waters in
laboratory tests as well as its performance in a variety of
oilfield waters. THPS also offered high effectiveness against
SRB and general aerobic and facultative anaerobic bacteria,
sustained control of bacterial growth, performance
independent of H
2
S, and relatively low toxicity.
2
The THPS
utilized on the FPSOs discussed in this paper is a concentrated
proprietary-blended product, but will be referred to as THPS.

SPE 106106 3
Laboratory Efficacy Studies
A series of laboratory studies was performed to evaluate the
synergistic effects of AQ and THPS at inhibiting H
2
S
biogeneration from a planktonic SRB consortium at low
dosages. Previous studies had shown that the biostat and
biocide were synergistic at high concentrations in biofilm
columns with sessile SRB.
7
The current study used the same
SRB consortium (from the Prudhoe Bay, Alaska, seawater
system) and SRB medium. Culture tubes (15-ml) with
medium were inoculated and the SRB were allowed to grow
for either two or four days before treatment with either one or
both substances at low doses (1 to 5 mg/L active with the AQ
provided from anthracenediol, disodium salt solutions). H
2
S
concentrations were monitored for about three weeks to
determine the treatment effects compared to the untreated
controls. Each condition was studied in quadruplicate.
The results of the study are summarized in Figs. 5 and 6 as
averages of the measured sulfide concentrations in the four
replicate culture tubes at each condition. Treatments during
the end of the lag phase (after two days of growth) were more
effective than those made during log phase growth (after four
days), presumably due to the number of bacterial cells within
the tubes. However, other than treatments with 1 mg/L each
of AQ and THPS during log growth, low concentrations were
quite effective for extended durations. Preliminary studies
with treatments during log growth had indicated that neither 1
mg/L THPS nor 0.5 mg/L AQ would be effective individually;
that 10 mg/L THPS would be partially inhibitory; that 5 mg/L
AQ would be 100% inhibitory for at least seven days; and that
the level of NaOH associated with the AQ treatment solutions
would not affect the SRB activity. While the current study
was not performed using an SRB consortium from the
Petrobras oilfield, the results confirm that combinations of the
two substances at extremely low concentrations are quite
effective and indicate that a cost effective specified level of
H
2
S control should be achievable by optimizing the AQ to
THPS ratio. Such was the plan on the FPSOs.

Case Studies and Current Status
FPSO-1. The slop water tanks on this FPSO (designated in
this paper as FPSO-1 and shown schematically in Fig. 2) had
been operating with about 30 mg/L dissolved H
2
S in the water
prior to field testing a dual AQ-THPS treatment program in
2002-2003.
2
The previous program using glutaraldehyde was
unsuccessful in controlling the H
2
S biogeneration due to the
configuration and dynamics of the vessels and the inability for
the biocide to effectively contact and control the sessile SRB
in sludge and solids at the bottom of the tanks. The AQ-THPS
program was selected to replace the glutaraldehyde for its
overall lower toxicity and its method of attacking the problem
by both killing planktonic bacteria with the biocide and
controlling the sessile and surviving planktonic SRB with the
biostatic AQ. The colloidal particles of AQ released upon
injection of the solution directly into the water phase would
stay suspended, contacting the SRB free-floating in the water
and effectively coating all surfaces of the tank. The remaining
AQ particles would eventually loosely agglomerate, settle and
become incorporated into the heavier biofilm at the bottom of
the tank.
The positive field trial results led to implementation of a
full scale treatment program initiating in 2003. The results
had indicated that the programs cost effectiveness could be
optimized by increasing the AQ to THPS ratio and switching
to a continuous THPS injection. However, while the latter has
not been implemented due to operational concerns, treatments
of both chemicals have been adjusted to maintain the
dissolved H
2
S level in each tank at about 5 mg/L (Fig. 7), well
below the operator specified limit of 10 mg/L. The occasional
H
2
S upward spikes have been mainly due to high levels in the
upstream processed water since neither THPS nor AQ will
scavenge prior generated H
2
S and no treatments for H
2
S
control are made in the upstream separation vessels. Currently
each slop tank is treated with about 500 liters of THPS and
300 liters of AQ solution each week. The THPS is applied as
a slug dose once weekly to each tank inlet; the AQ is applied
twice weekly (alternating 100 and 200 liters). While AQ
treatments in pipelines are mainly dependent upon surface
area in the system, treatment volumes in these slop tanks have
been required to increase in order to maintain control of the
H
2
S because the processed water rate has approximately
tripled during the past four years. The optimal cost
effectiveness has been maintained with the current AQ to
THPS ratio, although total chemical volume required could
potentially be reduced by increasing AQ and decreasing
THPS. Overall, the average equivalent AQ solution
concentration (i.e., the concentration if the total volume of AQ
solution used in the batch treatments was injected
continuously) employed to treat both slop tanks on FPSO-1 is
about 40 ppmv based on discharged water rate.

FPSO-2. Fig. 3 describes the water processing scheme on
FPSO-2. A dual AQ-THPS treatment program was
implemented in July 2003 to control high levels of H
2
S
biogeneration in the water processing system, optimizing the
previous program using a non-blended THPS. Not only was
AQ added to the treatments, but the water phase in the oil-
water separators was targeted as a primary source of SRB
activity. Microbiological surveys had indicated that SRB
levels in the separator and slop water tanks were all on the
order of 10
6
cells/ml, resulting in dissolved H
2
S levels of 10-
30 mg/L in the separators and 60-70 mg/L in the slop water
tanks. Both THPS and AQ were initially injected as batches
into the water effluent from the electrostatic heater-treater and
into each slop water tank at relatively high concentrations to
gain control over the system. Monitoring focused on the total
oil and grease (TOG) in discharge water in addition to the H
2
S
level to confirm that the THPS and AQ had no adverse impact
on water quality and that the treatments were having their
intended effect. Chemical residuals in the slop water were
also monitored routinely during the initial phases of the
treatment program to assure a safe discharge of the water.
Within several cycles of chemical treatments, the dissolved
H
2
S in the slop water system was under control and below the
specified operational limit. Optimization of the program to
reduce chemical volumes and cost began immediately. First,
THPS injection was converted from periodic batches to
continuous injection into the water effluent from the
electrostatic treater. Over the next six months, the THPS was
reduced stepwise from 150 ppm (based on total water
4 SPE 106106
discharge rate) to about 65 ppm in combination with periodic
batch treatments of AQ. Initial AQ treatments were 800 liters
per tank (Separators 3BB and 3BE; Slop tanks BB and BE)
every 10 days. These volumes were reduced during the
optimization process, but finalized at 600 liters in order to
maintain acceptable H
2
S levels. Fig. 8 summarizes the
average measured H
2
S concentrations in the separators and
slop tanks in addition to the average equivalent AQ treatment
concentration for the years 2003-2005. During this timeframe,
the processed water rate increased about 50% to about 6000
m
3
/day. After stabilizing the treatment program in January
2004, the injected THPS concentration was 60-65 ppmv, the
average equivalent AQ solution concentration was maintained
at about 40 ppmv total for the four injection locations, and
dissolved H
2
S levels had stabilized at 3-4 mg/L. However,
from August 2004 through May 2005 the average equivalent
AQ concentration was decreased to about 20 ppmv through
further treatment optimization, thereby allowing the dissolved
H
2
S levels to increase to a still acceptable 4-6mg/L.
The AQ-THPS treatment program was halted in mid-2005
on FPSO-2 for a field test program of a different chemical
technology. That test was deemed unsuccessful and
terminated after about one year. The previous AQ-THPS
treatment program has now been re-implemented.

FPSO-3. The dual AQ-THPS H
2
S control program was
implemented on FPSO-3 beginning in January 2004. The
water processing scheme for this unit is comparable to that on
FPSO-1 (Fig. 2). Due to the high water rates, chemical
treatments are made only into Slop Tank BB, with carryover
of residuals sufficient to control the H
2
S biogeneration in Slop
Tank BE also. Initial treatments of 600 liters THPS and 400
liters AQ solution per day into Slop Tank BB were required to
gain control of the bioactivity, but over a period of four
months the treatment program was optimized by decreasing
volumes monthly until dissolved H
2
S levels stabilized at the
current 5 mg/L level as summarized in Fig. 9. While the
processed water rate had increased from about 5000 m
3
/day to
over 8000 m
3
/day, chemical volumes remained essentially
steady from mid-2004 until early 2006. Fig. 10 shows that
average equivalent THPS and AQ concentrations of 20-30
ppmv have been maintained following the optimization
process.
The results obtained on FPSO-3 indicate that frequent low
concentration treatments are able to control H
2
S to a steady
level by maintaining control over the SRB activity. They also
suggest that the use of equal volumes of the two products
might also contribute to the consistent control.

Other FPSOs and FSOs. Treatments on FPSO-4, FSO-5,
and FPSO-6 with AQ and THPS have been initiated during the
past year and are currently undergoing optimization.
Relatively low water rates on these FPSOs (on the order of
2000 m
3
/day each) lead to high residence times and high H
2
S
biogeneration in the slop water tanks. The water processing
scheme on FPSO-4 is represented by that shown in Fig. 4. If a
significant amount of water still remains in the crude oil
following separation, then that water settles out of the crude
while stored in the cargo tanks. It is then transferred to the
slop water tank system to assure that the TOG and H
2
S are
acceptable prior to discharge. THPS and AQ treatments are
made only when necessary directly into the water layer in
these slop tanks. This occurs several times per month with
typically 400 liters of THPS and 200 liters AQ solution per
tank. The majority of the produced water processed on FPSO-
4 is of acceptable quality to be discharged without flowing to
the slop water system and subsequently requires no treatment
for H
2
S control.
FSO-5 is a unit with no production capabilities and no
separation facilities. Crude oil from other platforms is
transported to FSO-5 for storage in cargo tanks prior to
offloading to tankers. Separated water from the bottom of
these cargo tanks is transferred to the two slop water tanks, if
necessary, prior to being discharged. About 400 liters of both
THPS and AQ solutions are used per week per tank for H
2
S
control on FSO-5, although the treatment frequency depends
on the volume of water processed and retention time in the
tanks.
The processing scheme on FPSO-6 is comparable to that
depicted in Fig. 3. H
2
S control treatments are currently about
600 liters each THPS and AQ solution per slop water tank per
week. The chemical volumes are higher on FPSO-6 compared
to FSO-5 due to higher water rates and the growth of SRB in
the upstream water-oil separation system. As with FPSO-4
and FSO-5, operators monitor the situation and implement
treatments when needed. Chemical volumes have not yet been
optimized, although expected increases in water rates,
especially on FPSO-4 and -6, will require possible changes in
the treatment programs.
Petrobras operates four additional FPSOs in the Campos
Basin. One of these operates comparable to FPSO-3 and is a
candidate for implementing the AQ-THPS treatments for the
slop water system. The other three units are relatively new
with startups during the past two years. They are not yet
processing high water volumes and have no H
2
S problems.

The Effect of Chemical Treatments on Corrosion
The AQ-THPS treatment program on FPSO-2 was
implemented in July 2003. About one year later, relatively
severe corrosion was observed in pumps, hydrocyclones, and
piping downstream of the separator tanks (Figs. 11 and 12). In
order to ascertain the possible cause for this corrosion,
laboratory studies were carried out.

Coupon Weight-Loss Test. Corrosion rates for the original
produced water were determined by weight loss of coupons.
8

Two coupons made of AISI 1020 carbon steel were mounted
in each of two internally Teflon-coated steel cells. One cell
was filled with deaerated produced water; the other with the
same produced water plus 70 ppm THPS and 150 ppm AQ
solution. The cells were closed, pressurized to 20 psig
nitrogen, and heated to 40C under agitation for 96 hours. The
coupons were then removed, evaluated visually and
microscopically for corrosion products, cleaned, and weighed.
The results showed a significant increase in corrosion rate
(CR) in the THPS + AQ environment (Fig. 13). However it
was not possible to identify which product was responsible for
this increase. The condition of the coupons in each cell after
the corrosion study is shown in Fig. 14. Visually the
specimens exhibit localized corrosion in both conditions (with
SPE 106106 5
and without chemical additions), confirming that the FPSO
produced water is corrosive itself due to dissolved CO
2
, the
presence of SRB, and dissolved sulfide.

Linear Polarization Resistance (LPR) Test. In the next step
of the corrosion tests, LPR was used to separately determine
the effects of each chemical product on carbon steel corrosion.
The test was run at 40C in a 1-liter glass cell. Initially the
corrosion rate for the carbon steel test specimens was
determined in a synthetic produced water (synthetic brine
containing 45 g/L NaCl). After stabilization of the measured
polarization resistance (in 32 hours), THPS (at 70 ppmv) was
added to the cell. AQ solution (at 150 ppmv) was added eight
hours later. Measurements were taken at one-hour increments
during the test. The results presented in Figs. 15 and 16
indicated an instantaneous increase in the corrosion rate (Fig.
15), or decrease in polarization resistance (Fig. 16), when
THPS was added to the brine. An opposite behavior was
observed with the addition of AQ.
Table 1 summarizes the pH and REDOX potential in
FPSO-2 produced water upon sequential treatments. THPS
reduces the pH more than one unit while having no effect on
the potential. The alkaline AQ solution increases the pH back
to the original level in the deaerated produced water while
decreasing the potential by over 400 mV.
The evaluation of product addition effects on the produced
water (Table 1) and of corrosion rates results (Figs. 13 and 15)
imply that the THPS was responsible for the increase in
produced water corrosiveness, probably due to its extremely
acidic pH of about 3. The biocide was being injected
continuously into FPSO-2s tanks, reducing the produced
water pH (originally low at about 6.15) by at least one unit.
The AQ addition has the ability to neutralize the negative
effects of the THPS on corrosion, since it is an alkaline
solution (pH > 13) and also decreases the REDOX potential to
a high negative level. Unfortunately, AQ was batch treated
into each tank only every ten days, which was not sufficient to
counteract the effects of the continuous THPS addition.

Further Treatment Optimization Plans
The results of the treatment program on FPSO-3 have
indicated that H
2
S biogeneration can be controlled very
effectively with frequent, low concentration doses of AQ and
THPS. These results suggest that continuous injection of AQ
solutions on those FPSOs with water flow directly from
separators into the slop water tanks will further optimize the
treatment and improve cost effectiveness. The overall volume
required for AQ solution should decrease with continuous
injection if supplemented by batch THPS treatments.
Batching THPS is preferred over continuous injection to
minimize the potential for corrosion and also to penetrate
better into the biofilm on the tank surfaces. The biocidal
effect of periodic THPS treatments at high concentrations on
all of the bacteria in the system will allow the AQ to more
efficiently contact the remaining viable SRB.
Results from the laboratory efficacy studies indicate that
AQ has a more pronounced effect on H
2
S biogeneration than
THPS has on an active concentration basis. This implies that
increasing the AQ to THPS ratio will improve efficacy of the
combined treatment program. Further optimization will focus
on reducing THPS volumes while slightly increasing AQ
solution volumes. This will decrease the overall chemical
volume required to maintain H
2
S control. The cost
effectiveness of offshore treatment programs is dependent not
only on the chemical costs, but also on the logistics and costs
involved with transportation and storage of the product
containers.
Corrosion in the FPSO water handling system is a critical
aspect of the treatment program. As discussed, corrosion is
not only due to the CO
2
, SRB, and H
2
S in the produced water,
but can be caused by the chemicals employed in the
treatments. Optimization of the program will also include
monitoring corrosion rates using on-line corrosion probes
(electrical resistance and coupons) installed in the
hydrocyclone inlet lines.

Conclusions and Recommendations
A dual treatment program of anthraquinone (a biostat) and
THPS (a biocide) has been successful at controlling H
2
S
biogeneration in FPSO slop water tank systems.
The anthraquinone-THPS treatments have been
customized and optimized for the specific conditions on
six FPSOs/FSOs in the Campos Basin (Brazil).
Corrosion in the produced water handling system on one
FPSO has been attributed, based on results from
laboratory corrosion studies, to the continuous injection of
the acidic THPS (pH 3), which reduced the already low
pH of the water even further.
The anthraquinone solution was found in laboratory
studies to counteract the high corrosiveness of the THPS
due to the AQs high pH and low REDOX potential. The
periodic anthraquinone treatments in the field (on FPSO-
2) were not sufficient to negate the THPS corrosivity.
Future treatment optimization efforts will focus on
increasing the anthraquinone to THPS ratio and
employing continuous anthraquinone injection, thereby
decreasing overall volumes of chemicals to achieve the
same or better level of H
2
S control while reducing the
potential for corrosion.
Corrosion monitoring should be included in any chemical
treatment program.

Acknowledgements
The authors wish to acknowledge the managements of
Petrobras and Baker Petrolite Corporation for support and for
permission to publish this paper.

References
1. 2006 Worldwide Survey of Floating Production Storage and
Offloading (FPSO) Units, poster insert in Offshore, (Aug.
2006) 66.
2. Penkala, J.E., Shioya, N., Bastos, E.C., Andrade, C., Penna, M.,
Baldotto, H.A., Salma, T., and Burger, E.D.: A Cost Effective
Treatment to Mitigate Biogenic H
2
S on a FPSO, paper NACE
04751, presented at NACE Corrosion 2004, New Orleans,
March 28 April 1, 2004.
3. Burger, E.D. and Odom, J.M.: Mechanisms of Anthraquinone
Inhibition of Sulfate-Reducing Bacteria, paper SPE 50764
presented at the 1999 SPE International Symposium on Oilfield
Chemistry, Houston, Feb. 16-19, 1999.
6 SPE 106106
4. Cooling, F.B., III, Maloney, C.L., Nagel, E., Tabinowski, J., and
Odom, J.M.: Inhibition of Sulfate Reducing Respiration by 1,8-
Dihydroxy-anthraquinone and Other Anthraquinone Deriva-
tives, Appl. Environ. Microbiol. (Aug. 1996) 62, 2999.
5. Odom, J.M.: Anthraquinone Inhibition of Methane Production
in a Ruminant Animal, US Patent 5,648,258, (July 1997).
6. NACE International Task Group 075: Selection, Application,
and Evaluation of Biocides in the Oil and Gas Industry,
Technical Committee Report Publication 31205, (Feb. 2006) 16.
7. Burger, E.D., Crews, A.B., and Ikerd, H.W.: Inhibition of
Sulfate-Reducing Bacteria by Anthraquinone in a Laboratory
Biofilm Column Under Dynamic Conditions, paper NACE
01274 presented at NACE Corrosion 2001, Houston, March 11-
16, 2001.
8. ASTM G31-72(2004), Standard Practice for Laboratory
Immersion Corrosion Testing of Metals, ASTM International
(2004).


Table 1. Effect of Additions on pH and REDOX Potential
Sequential Stages pH E
redox
, mV (Ag/AgCl)
1) Original produced water 6.15 -48.0
2) Original produced water after
N
2
purge (CO
2
removal)
7.90 -150.9
3) 2) + THPS addition (70 ppmv) 6.82 -142.9
4) 3) + AQ Solution addition (150
ppmv)
7.82 -562.2



4C
SLOP
BB
SLOP
BE
8BB
8BE
5C
7BB
7BE
6BB
6BE
5BB
5BE
3BC
4BB
4BE
3AC
3BB
3BE
2C
2BB
2BE
1BB
1BE
1C
BB
Tank
C
Tank
BE
Tank
Turret (in bow)
Cross-section

Fig. 1 Typical tank layout on an FPSO.


Separator
Electrostatic
Treater
Slop
BE
Slop
BB
Hydrocyclones
A B
Discharge
Oil & Water
from Wells and/or
Platforms
Oil Oil to
Cargo Tanks
Test
Separator
Water
Water
Degasser

Fig. 2 Water processing scheme for FPSO-1 and FPSO-3.
Chemical treatment locations into slop water tanks indicated.

Tank
Separator
Electrostatic
Treater
Slop
BB
Slop
BE
Hydrocyclone
A B
C
Discharge
Discharge
Oil & Water
from Platforms Oil
Water
Oil to
Cargo Tanks

Fig. 3 Water processing scheme for FPSO-2. Chemical
treatment locations into separator and slop water tanks indicated.


Water from
Drains
Separator
Electrostatic
Treater
Hydrocyclones
A
Discharge
Oil & Water
from Wells Oil
Separator
Water
Water
Degasser
Atmospheric
Separator
Oil
Cargo
Tanks
Treater
Oil & Water from
Platform
Slop
Tank
BE
Slop
Tank
BB
B

Fig. 4 Water processing scheme for FPSO-4. Chemical
treatment locations into slop water tanks indicated.


0
10
20
30
40
50
60
70
0 5 10 15 20 25
Time since Inoculation, Days
S
u
l
f
i
d
e
,

m
g
/
L
Control
Code 1,1
= AQ1, THPS1
(mg/L)
0,5
2,0
1,5
2,5
Treat on Day 2

Fig. 5 Efficacy of AQ and THPS Treatments made on Day 2
during lag phase growth. Concentrations indicated are in mg/L
active substance.

SPE 106106 7
0
10
20
30
40
50
60
70
0 5 10 15 20 25
Time since Inoculation, Days
S
u
l
f
i
d
e
,

m
g
/
L
Control
Code 1,1
= AQ1, THPS1
(mg/L)
0,5
2,0
1,5
2,5
Treat on Day 4

Fig. 6 Effiacy of AQ and THPS treatments made on Day 4 during
log phase growth. Concentrations indiated are in mg/L active
substance.


0
1
2
3
4
5
6
7
8
Nov-04 Feb-05 May-05 Sep-05 Dec-05 Mar-06 Jul-06 Oct-06
D
i
s
s
o
l
v
e
d

S
u
l
f
i
d
e
,

m
g
/
L
Slop BE
Slop BB

Fig. 7 Dissolved H
2
S levels in FPSO-1 slop water tanks.


0
5
10
15
20
25
30
Mar-03 Jun-03 Oct-03 Jan-04 Apr-04 Aug-04 Nov-04 Feb-05 May-05 Sep-05
A
v
e
r
a
g
e

H
2
S

L
e
v
e
l
s
,

m
g
/
L
0
25
50
75
100
125
150
A
v
e
r
a
g
e

E
q
u
i
v
a
l
e
n
t

P
r
o
d
u
c
t

C
o
n
c
e
n
t
r
a
t
i
o
n
,

p
p
m
v
Separators
Slop Tanks
AQ Solution, ppmv
THPS, ppmv
Total Average Equivalent
AQ Concentration
Continuous Average
THPS Concentration

Fig. 8 H
2
S levels and treatment concentrations for FPSO-2.

0
5
10
15
20
25
30
35
40
Oct-03 Jan-04 Apr-04 Aug-04 Nov-04 Feb-05 May-05 Sep-05 Dec-05 Mar-06 Jul-06 Oct-06
H
2
S
,

p
p
m
SLOP BE
SLOP BB
THPS-AQ
treatments initiated

Fig. 9 Average monthly H
2
S Levels in FPSO-3 Slop Water Tanks.




0
10
20
30
40
50
60
70
80
90
Oct-03 Jan-04 Apr-04 Aug-04 Nov-04 Feb-05 May-05 Sep-05 Dec-05 Mar-06 Jul-06 Oct-06
A
v
e
r
a
g
e

P
r
o
d
u
c
t

C
o
n
c
e
n
t
r
a
t
i
o
n

(
e
q
u
i
v
a
l
e
n
t

p
p
m
v
)
AQ Solution, ppmv
THPS, ppmv

Fig. 10 Product treatment concentrations for FPSO-3.




Fig. 11 Deposits and corrosion observed inside hydrocyclone
after THPS + AQ treatments.

8 SPE 106106


Fig. 12 Corrosion damage on hydrocyclone pump shaft.


0.1581
0.3346
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
FPSO Produced Water (PW) FPSO Produced Water (PW) + 70 ppmv THPS + 150
ppmv AQ
C
o
r
r
o
s
i
o
n

R
a
t
e
,

m
m
/
y
r
FPSO Produced Water (PW)
+ 70 ppmv THPS + 150 ppmv AQ

Fig. 13 Corrosion rates after immersion testing of coupons with
and without chemicals addition.


CONTROL THPS + AQ

Fig. 14 Visual appearance of corrosion coupons after immersion
testing. Upper photographs show corrosion products; lower are
after corrosion product removal.
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0 10 20 30 40 50 60 70
Time, Hours
C
o
r
r
o
s
i
o
n

R
a
t
e
,

m
m
/
y
r
Add 70 ppmv THPS
Add 150 ppmv AQ

Fig 15 Results from LPR test showing effect of separate
chemical additions on the corrosion rate (CR).

0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
0 10 20 30 40 50 60 70
Time, Hours
P
o
l
a
r
i
z
a
t
i
o
n

R
e
s
i
s
t
a
n
c
e
,

o
h
m
-
c
m
2
Add 70 ppmv THPS
Add 150 ppmv AQ

Fig. 16 Results from LPR test showing effect of separate
chemical additions on the polarization resistance (1/CR).