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SPE 155123

TOTAL’s industrial experience in sea water desulfation


Pierre Pedenaud, Christian Hurtevent, Salima Baraka-Lokmane, TOTAL

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Conference and Exhibition on Oilfield Scale held in Aberdeen, UK, 30–31 May 2012.

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 th e paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
Large quantities of sea water are injected in oil and gas fields all over the world for pressure maintenance support and
sweeping efficiency of the reservoir in order to maximize the hydrocarbon production. Many difficulties are linked with sea
water injection such as risks of reservoir souring, loss of injectivity, incompatibility between sea and reservoir waters. One
specific problem is the risk of sulfate based scale formation like barium sulfate. Indeed sea water contains around 2800 mg/l
of sulfate and some reservoir contains high concentration of barium and strontium. If nothing is done to prevent the mixing of
these two waters, scale deposits will occur at the producer wells once the breakthrough happened, with the loss of production.
One solution is to remove the sulfate from sea water prior to injection, and this is possible by using the nanofiltration
process.This desulfation process based on membrane technology is in operation in TOTAL sites for more than 10 years and it
works very succesfully.
This paper presents the feedback of ten years of operations both on the desulfation process and also on the scale
prevention strategy. Based on the experience of three big desulfation units operated offshore on FPSOs, this paper presents
the various parameters of this process such as the operational constraints, membrane cleaning requirements, need for efficient
pre treatment, membrane life time, and efficiency in sulphate removal. Moreover at the beginning anti scale injection was
installed on the producer wells to inhibit the residual sulphate coming from desulfation (40 ppm), however better efficiency
of process and sulphate elimination in reservoir showed that this residual risk is nil. Results showed that the choice of
desulfation is the best solution to prevent barium sulphate scale, even if this process can appear firstly as constraining and
costly.

Barium sulfate, a nightmare


TOTAL is the operator of the Girassol, Dalia and Pazflor FPSO in Block 17 off the coast of Angola by between 800 to 1500
metre water depth, the operator of Alima FPU off the coast of Congo by around 600 metre depth. Each of these fields has
numerous subsea production wells and numerous subsea water injection wells, for example Pazflor and Dalia have
respectively 25 and 37 producers and 22 and 31 injectors. Oil production from these fields is around 700,000 Barrel Oil per
Day (BOPD) and 600,000 Barrel of Water per Day (BWPD) with some wells having production as high as 40,000 BOPD.
Pressure maintenance and reservoir sweeping by the injection of water is mandatory for these fields development.
Various sources of water for pressure maintenance can be envisaged. The use of water from an aquifer was rejected due to
the cost of drilling and completing the subsea wells without any assurance that the aquifer would provide wells with
sufficient rates and that the water found would be suitable for injection. The use of produced water is also considered.
However, it was determined that there would be insufficient quantity, especially from the beginning of production.
Consequently, seawater injection is a necessary source of water for injection, it is injected alone or in commingles with
produced water, and for example Dalia has a water injection capacity of 405,000 BWPD for a sea water treatment capacity of
only 230,000 BWPD. Pazflor and Girassol treated sea water delivery is even higher with respectively 300,000 and 400,000
BWPD.
The problem is that each of these fields has one or more producer reservoirs containing barium and strontium at high
concentration typically around 200 ppm each. Mixed with the 2800 ppm sulfate of sea water this is the nightmare of
producers.
We will first investigate the consequence of the incompatibility of the sulfated sea water and reservoir water containing
barium. Then we will look at the possible solutions to solve the problem and mainly on the attractive nanofiltration
membrane process. We will then analyse the result of more than ten years of operations of this solutions and how it evolves.
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Sulfate scale formation, what is at stake?

The capacity to deliver the production is the first objective of any treatment designed to avoid the sulfate scale deposit to
impair, plug, and stop the oil mouvment from the reservoir to the export through the flowlines and topside facilities.
TOTAL has produced and is still producing several fields where the injection water, which is seawater, presents a
noteworthy incompatibility with the formation water. The effect of this incompatibility is precipitation of sulfate scale
deposits in the producing wellbores which must be protected from scaling shut. Precipitation in the producing wells
sometimes leads to significant losses of productivity and must, therefore, be avoided. Throughout this history of treating
sulfate scales, TOTAL has also examined the potential of sulfate scale deposits within the producing reservoir rock itself.
Insofar as can be ascertained, precipitation within the reservoir has not caused problems with respect to oil recovery or to oil
production rates. This is probably because the pore volume of the reservoir(s) is immense when compared to the precipitated
volume of sulfate scale.
Generally speaking, at the time of discovery of a new field, we are knowledgeable about the composition of waters
intended for injection, but much less is known about the composition of the formation connate water in the petroleum
reservoir that is to be produced. In the most frequent case, where an aquifer water sample is taken beforehand, the
concentrations of barium, strontium and calcium are well known for the aquifer. In some cases, where whole cores are taken
and preserved at reservoir conditions, some improvement may be made in connate water analyses.
Thermodynamic modeling does not provide a good estimate of residual scale problems, so we are left to estimate how
much scale may precipitate in situ and distant from the wellbore and how much is left to deposit at the producing wellbores.
These uncertainties can be highly problematic and lead to production losses.

The treatment cost is of course an important aspect of the problem, you need to minimise it. In this respect the context of
the field is a key aspect to consider. The classical solution of injecting scale inhibitor chemicals can become difficult and
costly in a deep offshore environment. In that case we have generally concepts with network of wells producing in the same
gathering line and subsequent difficulties in monitoring residual inhibitor levels. Moreover difficulties appeared also in the
placement of inhibitors in the reservoir which has high permeability and long perforation intervals, and the deep and remote
subsea wells. The high technical and economical risks using scale inhibition for such large scale waterflood projects in a
deepwater environment have to be compared with over solution like sulfate removal.

The reputation of a major oil company as an operator is also at stake when we deal with the development and operation of
high technological content solutions either the management of inhibitor injections in deep offshore context or the treatment
chain of desulfatation. We can add also here that radioactivity is an additional problem linked to sulfate scale deposit, due to
the co precipitation of radioactive isotope (radium 226, 228...). These NORM, Naturally occurring radioactive materials, can
accumulate in pipes, flowlines, tubing and vessels making problems of safety and problems of decommissioning when the
exploitation of the field is stopped.

Membrane nanofiltration an atractive solution

Squeeze treatment were envisaged for the first TOTAL FPSO. Conventional scale inhibitor squeeze treatments for Girassol
were rejected due to problems in the placement of the inhibitor and the monitoring of residual scale inhibitor levels. Further
complicating the potential use of conventional scale inhibitors was the distance of the subsea wells to the FPSO and the cost
of special equipment or procedures to inject the inhibitor. At the time of the Girassol development there was no intervention
boat available for such intervention and squeeze placement problems appeared for a squeeze operated from the FPSO. Based
on the successful use of sulfate removal process in the North Sea and the situation at Girassol, it was decided that removal of
the sulfate from the injected seawater was the only reliable technique that could prevent barium sulphate scaling. However,
unlike the early North Sea operations in which sulfate removal was used to supplement scale inhibition squeeze treatments,
the Girassol development needed sufficient sulfate removal so that scale inhibitor squeeze treatments could be eliminated
altogether.

Sulfate Removal Nanofiltration System Fundamentals.


The key requirement of the sulfate removal process is that the sulfate ions need to be selectively removed from seawater
while allowing sodium and chloride to remain in the injection water to maintain stable reservoir clays. This requirement was
achieved by the development of a specifically designed nanofiltration membrane process using some of the chemistry and
product design of the thin film composite membranes that were originally developed for reverse osmosis membranes used in
seawater desalination. However, the resultant nanofiltration membrane remains distinctly different from traditional reverse
osmosis membranes in that only divalent and especially sulfate ions are removed. This allows the membrane to operate at
nearly twice the recoveries or yields and at much lower operating pressures. The higher recoveries are due to the decreased
concentration of salt on the feed side of the membrane and the corresponding decreased potential for its precipitation or
concentration on the membrane surface. The lower operating pressure is due to the decreased osmotic pressure across the
membrane, which needs to be overcome in the operation of a membrane separation process.
SPE 155123

The seawater, following pretreatment to remove particles and bacteria, is initially pressurized to between 20 and 30 bar,
depending on the seawater temperature, against the membrane surface by the use of a feed pump and associated regulating
valve. The membrane rejects or repels the sulphate off its surface while allowing sodium and chloride to pass through. The
flow of the feed water across the membrane surface provides a self-cleaning mechanism as the sulfate, bicarbonate, and other
larger ions or particles are removed via the sweeping action of the concentrate or reject stream across the membrane surface.
The four major factors influences which ions are repelled or removed and which ions pass through the membrane are: a)
the pore size of the membrane, b) the chemical characteristics on the membrane surface, c) the thickness of the membrane
layer, and d) the layers supporting the membrane. The nanofiltration membrane effectively has a pore size in the 10 Å
(Angstrom) range and a strong negatively charged surface area. Chloride ions with an ionic diameter of 1.8 Å and a negative
one charge freely pass through the membrane. On the other hand, sulfate ions with an ionic diameter of 2.4 Å but with a
negative two charge are repelled or rejected off the surface. The positively charged cations such as sodium (0.98 Å) or
magnesium (0.65 Å) freely pass through the membrane to maintain electronic neutrality on both sides of the membrane. Due
to some variations of pore size and charge on the surface of the membrane, not all sulfate ions are rejected or repelled and not
all chloride ions are passed. Nevertheless, more than 99% of the sulfate ions remain on the feed side of the membrane (>99 %
rejection) while only about 5% of the chloride ions remain on the feed side of the membrane (~95% passage).

Figure 1: Spiral wound nanofiltration configuration.

To maximize the membrane area in the least amount of space, membranes are constructed into a spiral wound
configuration. See Figure 1. This configuration results in a membrane element or module that is the key process component
in a sulphate removal process. The spiral wound design contains two membrane layers that are connected over a permeate or
product water collector fabric to form an envelope. The membrane envelope is then wrapped around a perforated hollow tube
into which the permeate empties from the permeate collector fabric. A plastic netting is wound into the device on the
feedwater side of the membrane that allows the feed water to be transported across the membrane surface. As a result, the
feed water enters through the end of the membrane module and passes over the membrane surface using the plastic netting as
a spacer for the feed water. At the membrane surface, two separate streams are generated as the membrane separates the feed
water into one stream high in sulphate ions (reject) and one stream low in sulphate ions (permeate).

Six membrane modules are inserted into a vessel which convert the individual modules into a working separation unit.
The feed water to the six modules in series is separated into a product stream with low sulphates and high chlorides and the
reject stream with high sulphates and low chlorides. Generally these vessels are arranged in a 2:1 array in which the reject
streams of the first array are sent to the second array where additional product water and reject water is generated. See Figure
2. The advantage of such an arrangement is that one is able to obtain a maximum amount of product water from the
pressurized feed. By funneling the reject water from both vessels in the first array, sufficient crossflow velocity is maintained
in the second array to provide self-cleaning of the feed water channels within the membrane module.
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Figure 2. Array nanofiltration operation

The level of residual sulfate after the nanofiltration process is a key question as it is not feasible to obtain zero. The figure
3 gives for the Girassol case the precipitable quantities of scale for mixtures of formation water and seawater with varying
sulfate levels

Figure 3 : Precipitable quantity of sacle versus sulfate level

It appears from the simulation that 10 ppm sulfate was the theoretical level to avoid deposits, and according to Dow the
membrane supplier a two arrays sulfate removal plant could give 40 ppm. The decision was taken for the first unit on
Girassol to stay with this design considering that sulfate will precipitate in the reservoir and to keep an injection line in the
producer wells to limit the risks, at the time being, full precipitation of the residual sulfates in the reservoir is observed.
Moreover injection began with one array only then with less than 20 ppm sulfate (20 ppm expected), and after 4 years
the second array has been put on line, injection was with 30 ppm sulfate with new generation of membranes (40 ppm
expected).
On Girassol after 10 years of production, it appears that the level of sulfate in the produced water is still quite nil
indicating a full stripping of the residual sulfate in the reservoir.
On the other developments (Dalia, Rosa, Pazflor), it was decided to reinject produced water mixed with desulfated sea
water. Barium sulfate is maintained in solution in the injection stream by adding a scale inhibitor. When arriving in the
reservoir, due to adsorption of the scale inhibitor on the rock it is highly probable that all the sulphates in the injected water
precipitate in the reservoir. On Dalia after 7 years, no sulfate was measured in the produced water.
Today based on these experiences, on new developments where PWRI is applied, it was decided to remove all the
prevention systems for barium sulfate inhibition. (ie; continuous injection lines at the bottom hole of the wells on Girassol,
Dalia)
SPE 155123

Membrane desulfatation, the right choice

After ten years of operation the feedback in term of operation is largely positive (first membrane replacement on Girassol
after 8 years of operation, level of sulfate stays below 40 ppm), however it is not possible to consider the membrane unit
alone, it is the complete sea water treatment chain which must be considered. The figure 4 gives the scheme for the first three
units within TOTAL.

Figure 4: Sea water treatment scheme with media filtration

Indeed, nanofiltration membrane is chemically fragile: Chlorine and any oxidant is a poison, hydrocarbon will make
irreversible fouling. Any chemical injected upstream must be compatible with the membrane, the biocide is DBNPA, no
antifoam, other chemicals (Coagulant...) must be carefully selected, we observed irreversible fouling after some tests with
coagulant flocculant injection upstream media filters. Nanofiltration membranes are physically fragile: specific procedure for
start up and shutdown (Avoid water hammer, vacuum). In case of shutdown, preservation procedure must be applied.
Membranes need to be cleaned from time to time by acid and alkali solutions. Frequency is highly dependent of
upstream pre-treatment. The feedback is a cleaning frequency once every 3 months.
With aging membrane the sulfate residual content will progressively increased as it is shown on the figure 5 example,
replacement has to be done when it will reach 40 ppm (Membrane life time is highly dependent of the pretreatment,
guarantee is 3 years, feedback shows that more than 6 years is achievable).

Figure 5: Sufate residual content at SRU outlet (pink points) and SRU downstream pressure.
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However it has to be noted that the membrane behaviour can deteriorate very rapidly if the pre treatment chain have
some problems, we experienced problems in one or other site during some period of time. For example a loss of media from
the media filters happened due to corrosion of the collector which plugs some membranes; also a bad deoxygenation had
increased the biofouling on the membranes.
Membrane fouling can have various origins. Biological development (biofouling) linked to bacteria development, must
be eliminated by a good chlorination at the sea water lifting point, regular batch of biocide (DBNPA), good deoxygentaion.
Adsorption of organic material on the membrane surface are difficult to clean, oil and grease must be avoided in the upstream
process, only validated chemicals can be used. Particles deposition can affect the membrane surface and also the feeding
spacer, a good and efficient pre filtration is required. Mineral plugging by scale can affect mainly the second stage but even
the first one if there is some obstruction. To avoid this risk an anti scale in injected upstream the membrane and a strict
respect of the recovery factor is required. Chemical cleaning acid and alkali is the curative solution but can be difficult.
Moreover, after a change in the cleaning chemicals, it clearly appeared that the exact nature of the chemical and the
protocol used for cleaning can have a large impact on the membrane recovery. This is linked to a recent change in the
chemical supplier and we are currently looking for optimised chemicals. The figure 6 illustrates the inefficiency of the new
chemicals compared to previous cleaning. After the product change, the permeability is no more recovered during cleaning
and this on the two stages, and the normalized pressure (pressure drop between the inlet and the permeate corrected in
temperature to take into account the change in viscosity) is no more restored.

Figure 6: example of permeability (Lp) evolution and normalized pressure evolution (P norm)

Therefore a constant attention is required and skilled operators are necessary. Moreover particular attention is required
on the pre treatment design, as such TOTAL decided to put the deoxygenation upstream the SRU in order to limit the risk of
biological development and to ensure enough time for the de chlorination. The multimedia filtration also was design at a
filtration speed of 20 m/h only to have an optimum water quality and is followed by cartridge filtration at 5 micron. The
water intake is at -90 m to have far better raw water quality compared to the surface and also a lower temperature, around
17°C, to increase the desulfation membrane efficiency.

Improvments of the pretreatment


Despite the good behaviour of the membrane it appears that many problems were encountered in the pretreatment such as
corrosion on the various filter vessels, frequent change of the filtration cartridges (every 8 weeks) which required important
work load (considering the high flowrate it is nine filter of 156 cartridge each that have to b ereplaced manually).
If the water quality is good the cleaning frequency of the SRU is still every 3 months, and the more the cleaning the more you
affect the membrane lifetime and availability. Moreover media filter are bulky and heavy equipment.
SPE 155123

We therefore decided to focus on the SRU pre filtration and to develop the application of hollow fiber membrane micro
or ultrafiltration. This technology is increasingly used in fresh water industrial and municipal installations, UF filters to
below 0.02 microns (virus removal) and MF filters to below 0.1 microns (bacteria removal), it offers much higher protection
to the sulfate removal membranes (typical SDI below 1) and no cartridge filters required as guard filters. After pilot tests it
was selected for application on Pazflor as it appeared on the figure below;
To sum up the advantages it, improved availability, reduced chemical consumption, allows higher fluxes in downstream
SRU membranes, doesn’t need cartridge filters to purchase/ transport, change and dispose of, is less sensitive to upsets in
feed quality, less sensitive to corrosion issues, reduced weight and potentially space. The only drawback is a higher Capex.

Figure 7: Sea water treatment schematic Pazflor FPSO

The Pazflor start up of water injection was done in September with this technology, and is up to now in accordance to
what we expect.

Nanofiltration is profitable
To make post mortem analysis to compare inhibition squeeze solution and nanofiltration solution in a particular field is
difficult as it depend highly on assumptions. However some of our experiences showed that the nanofiltration is reliable and
able to deliver a good water quality. When squeeze solution is selected, in some cases it suffered some inefficiency such as
new injector drilling, well re-entry, cleaning operations, high cost of squeeze, loss of production...This lead to some major
additional cost which is particularly true for subsea wells deep offshore developments.

Conclusion
After more than ten years of SRU operations, four big units, TOTAL is very confident in the technology described in this
paper and consider that as a standard and base case for sulfate scaling problem when sea water injection is considered,
particularly for deep offshore. It appears that the level of sulfate in the produced water is still quite nil indicating a full
stripping of the residual sulfate in the reservoir.

Today, on new developments where PWRI is applied mixed with desulfated sea water, it was decided to remove all the
prevention systems for barium sulfate inhibition. Barium sulfate is maintained in solution in the injection stream by adding a
scale inhibitor. When arriving in the reservoir, due to adsorption of the scale inhibitor on the rock it is highly probable that all
the sulphates in the injected water precipitate in the reservoir.

Despite this, the SRU plant, including its pre treatment, is constraining in term of follow up and operation and required the
attention of trained operators. The risk of damaging the membrane is very high if operated poorly or incorrectly designed and
8 SPE 155123

installed, therefore company know-how is crucial.

The introduction of hollow fiber membrane technology offshore as a pretreatment will certainly largely improve and secure
the SRU operation, TOTAL is proud to be one of the pioneers of this domain.

References
1. Van Khoi Vu, Elf Exploration Angola, Christian Hurtevent, Elf Exploration Production, and Roy A. Davis, The
Dow Chemical Company “Eliminating the Need for Scale Inhibition Treatments for Elf Exploration Angola's
Girassol Field”, paper SPE60220
2. Wayne Evans, Veolia Water Solutions and Technologies, Foudil Cheglibi, Pazflor FPSO Manager, Total E&P
Angola; Pierre Pedenaud, Total E&P; “Seawater Treatment on Pazflor FPSO, Operated by Total E&P Angola:
Incorporation of Membrane Pre-Filtration Upstream of Sulfate Removal” 7th annual deepwater Angola summit
February 11 and 12 2009.
3. O’Donnell, Keith, "Membrane Technology Works on North Sea Platform", Oil and Gas Journal, December 6, 1996.
4. Hardy, J. A., and I. Simm, "Low Sulfate Seawater Mitigates Barite Scale", Oil and Gas Journal, December 2, 1996.
5. Hardy, J. A., Barthorpe, R. T., and J. S. Rhudy, "Scale Control in the South Brae Field", SPE Production and
Facilities, May 1994.
6. Vu, V. K., Latapie, D., and R. A. Davis, "Barite Scale Prevention for Elf Angola’s Girassol Field Using Sulphate
Removal Technology", Deep Offshore Technology Conference, Stavanger, Norway, October, 1999.

Nomenclature
SRU : Sulfate Removal Unit
SDI : Silt Density Index
UF: Ultrafiltration
MF: Microfiltration
PWRI: Produced Water Re Injection
NORM : Naturally occurring radioactive material
FPSO: Floating Production Storage Offloading
FPU Floating Producing Unit
BWPD Barrel water per day
BOPD Barrel oil per day

Acknowledgements
The authors wish to thank TOTAL in allowing the publication of this paper.