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WATER TREATING INSIGHTS

Challenges of Water Treating for Chemical


Enhanced Oil Recovery
John M. Walsh, Shell Exploration and Production, and Lisa Henthorne, Water Standard

Chemical enhanced oil recovery Other factors are now coming recently, implementation of CEOR has
(CEOR) using polymers, surfactants, together to provide what appears to be been mostly driven by the national oil
and alkalis is not an entirely new a push to CEOR. A significant fraction companies (NOCs). This is particularly
technology. Its application peaked in of world oil production is from mature true in Oman and China. Most of the
1986 (Manrique et al. 2010). Following fields. While there will continue to be recent large-scale activity in CEOR has
the oil price collapse that occurred price fluctuations, supply and demand occurred in Petroleum Development
in the mid-1980s, the number of volumes will inevitably drive up the Omans Marmul field (Al-Mutairi and
significant new CEOR projects and the price of oil in the long run. Kokal 2011) and Chinese National
oil volumes involved have been small. For the past 25 years, most CEOR Petroleums Daqing and Shengli fields
However, with the recent sustained projects have been small. Nevertheless, (Chang et al. 2006; Nguyen et al. 2011;
oil prices of the last several years and many small projects, plus the larger Ji-Cheng and Kao-Ping 2008; Yang et
a few success stories, CEOR is staging projects in China and Oman, have al. 2006). An NOC views the higher
acomeback. contributed to an understanding of UR of CEOR as an added incentive
In this article, the challenges and water/chemical/reservoir interactions. because it demonstrates sustainable
opportunities of these projects are This has lead to an ability to formulate development and a commitment
discussed. The scope of this discussion the chemistry for optimal recovery and to long-term management of oil
is limited to topsides facilities in reduced the uncertainty and risk in resources. Economic viability, of
general and water treatment in reservoir response. In the fields where it course, is taken into account, but on a
particular. Design issues, whether has been practiced, relatively encouraging relatively long time horizon.
onshore or offshore, are discussed results have been obtained, and a Historically, interest in CEOR
from both the water injection side small but dedicated group of industry on the part of the international oil
and the handling of back-produced practitioners and academic experts are companies (IOCs) has followed strictly
polymer for disposal injection or developing an understanding of reservoir economic terms. But that situation
forrecycle. response that can be applied globally. is changing. Most of the major
The chemicals available have IOCs are under intense pressure to
Drivers for CEOR improved in effectiveness, and their secure replacement volumes. Given
CEOR involves flooding a reservoir costs have come down. IFP Energies that NOCs in general have 10 times
with an alkaline/surfactant/polymer nouvelles estimates the current cost the proven reserves of IOCs, one
(ASP) combination, a surfactant/ for CEOR at USD 1030/incremental of the ways that an IOC can secure
polymer mix, or a polymer-only barrel of oil, with polymer flooding replacement volumes is to establish
injection. While CEOR can provide at the lower end of the scale and itself as the partner of choice among
an increase in ultimate recovery (UR), surfactant flooding at the higher end. the NOCs.
there remains uncertainty in just how Besides the purely economic CEOR is being readily adopted by
much of an increase will be obtained. factors, there are other factors. Until a number of regional oil companies,
The literature describes increases in
UR from 0 to approximately 30% of
oil originally in place for CEOR floods John Walsh is SPE Technical Director for Projects, Facilities,
(Delshad 2010). The historical cost and Construction and a chemical process engineer at Shell.
of chemicals for CEOR is relatively Hecan be reached at John.M.Walsh@shell.com.
expensive. As a result of recovery
uncertainty and relatively high cost,
for nearly 20 to 25 years, the cost-
to-benefit ratio has been relatively
marginal and speculative.

August 2012 Oil and Gas Facilities 9


WATER TREATING INSIGHTS

with particular interest being

Normalized polymer concentration (dimensionless)


10
demonstrated by operators in the
moderately heavy oils of western 10 centipoise @10 sec1 and 25C
6 centipoise @2 sec1 and 46C
Canada. In many of these applications,
primary or secondary recovery has
been under way for years. Without
1
some form of enhanced oil recovery
(EOR), recovery would be abruptly
curtailed. In other cases, CEOR allows
very aging fields to continue to be
economically productive. Compared
0.1
to steamflood or steam-assist gravity
drainage (SAGD), a polymer flood
requires less capital expenditure and,
therefore, is an attractive alternative
for moderate-viscosity (<2000-cp)
oil. Also, polymer flood is attractive 0.01
100 1,000 10,000 100,000
in cases where a steamflood would
increase the H2S concentration to Injection water salinity (ppm)
unacceptable levels.
Fig. 1Effect of salinity on polymer concentration for specific viscosities (Ayirala
These developments, together etal. 2010).
with the incentive of higher UR, are
driving companies at least to consider
the option of CEOR. A number of rock material, formation water, and the At the other extreme, in a
companies have CEOR projects chemical cocktail (polymer, alkali, or polymer flood, the concentration of
that are progressing through the surfactants). In many cases onshore, hydrolyzed polyacrylimide (HPAM)
project maturation funnel. Currently, choices are limited for the source of required to achieve a target viscosity
worldwide oil production supported the water, and water treating must increases as salinity increases, as
by CEOR is about 400,000 BOPD. beemployed. shown in Fig 1. This is the well-known
If even half of the development The ionic composition of the Flory theta solvent effect (i.e., the
projects are implemented, there will injection water plays a crucial role polymer unwinds in a compatible
likely be a fivefold increase in the in CEOR success. Clay swelling solvent providing high viscosity, and
number of facilities and in the barrels is well understood, and the water it balls up in an incompatible solvent,
of oil involved in CEOR in the next chemistry required to prevent it is providing less viscosity). Thus, the
5to10years. now reasonably well established. cost of polymer increases as a function
Generally speaking, there must be of the injection water salinity. Also,
Technical Challenges sufficient divalent cations to prevent ferrous iron, sulfide ions, and oxygen
in Water Treating ion exchange and collapse of the clay cause the polymer to degrade and
Water treating challenges occur on structure. Therefore, the concentration loseviscosity.
both the injection side and the back- of divalent cations cannot be below a In a surfactant flood, injection
produced side. The injection water certain threshold, which depends on water chemistry is even more of an
must be compatible with the formation the clay concentration and type. economic issue because it directly
affects reservoir response. The
optimal salinity of a surfactant flood
can vary greatly as a function of the
Lisa Henthorne is senior vice president and chief technology surfactant chemistry and the reservoir
officer with Water Standard. She holds three US patents and dynamics. The objective is to achieve
has multiple patents pending in water treatment technology. the lowest interfacial tension between
Much of her present work is focused on developing customized the water and oil. Fig. 2 demonstrates
water chemistries to enhance oil recovery in low salinity and a representative example of the
chemical enhanced oil recovery. relationship between salinity and
surfactant concentration.

10 Oil and Gas Facilities August 2012


WATER TREATING INSIGHTS

membrane fouling. Fouling is both a


5.0 design challenge and a challenge for
Injected salinity (% sodium chloride)

4.0 surveillance and operation. A rigorous


3.0 monitoring and response program is
required (Davis and Southwell 2007).
When membranes become fouled,
2.0
the permeate rate decreases. Other
factors can decrease the permeate
Optimum rate, so monitoring must be based on
1.0 curve
normalized performance indicators.
Biological fouling, or biofouling,
0.5 poses the most significant challenge
(Henthorne 2010). Controlling
biofouling is a function of biocide
dosingintermittent is far superior
0 0.2 0.4 X Sor
Soap
0.5 0.8 1 to continuous dosing for membrane
Soap/(soap+surfactant) applicationscombined with
conservative designs that reduce or
Fig. 2Optimal salinity for representative surfactant flood. The x-axis is the soap eliminate conditions for biogrowth.
fraction at the waterflood residual oil saturation (X Sor
Soap
). The lines represent percentage However, monitoring by itself is
oil recovery. The points are laboratory measurements that verify the curves that are insufficient. At an early stage of
shown (Hirasaki 2010; Hirasaki 2011).
fouling, adjustments need to be made
to the prefiltration system, biociding
Reservoir souring is just as much ofthis technology has been significant, program, or chemical cleaning system
of an issue with CEOR as it is with with a current capacity of close to (e.g., chemicals, dose, and duration).
conventional waterflooding, and 10million BWPD (Reyntijens 2012). Operators must carry out a specified
manipulation of ionic composition As with other technologies, uptake response when a key performance
offers hope to minimize souring appears to follow an S curve, which indicator exceeds a target. In most
through injection of nitrate or requires a critical mass of applications membrane systems, fouling is already
reduction in sulfate concentration. and experience before industrywide well progressed before it is detected,
Also, oxygen and biological control are acceptance will occur. and irreversible fouling can occur
persistent issues in any flood where the Water treating techniques for soonafter.
source water contains oxygen. Oxygen achieving various water chemistries, Membranes (both hollow fiber
in a polymer solution can severely such as sulfate removal, nanofiltration and spiral wound) can also function
degrade the viscosity. for divalent ion removal, reverse as pretreatment in the form of
Water compatibility is determined osmosis, and remineralization, are microfiltration or ultrafiltration
by the potential for sulfate scaling being practiced both onshore and technology. These represent one of
of producer wells. If, for example, offshore for the industrial, municipal, the fastest growing technologies in
the injection water is seawater (high and agricultural sectors. Onshore the water treating industry. Given
concentration of sulfate) and the applications include desalination of the significant uptake curve for
formation water contains barium or seawater for drinking and irrigation, this technology both onshore and
strontium, then sulfate scaling will steamflood, and, in a few cases, offshore, there is wide recognition of
occur in the producer wells. This is produced-water treating for surface its importance, and adoption for use
the driver for installation of sulfate discharge. The applications are wide as pretreatment upstream of SRM
rejection membranes (SRMs). SRMs ranging, and significant expertise is packages is becoming widespread for
were first installed offshore for the required to apply lessons learned from new systems. Hollow fiber membranes
Marathon South Brae field in 1988 to one application to another. Many of are also being considered for oxygen
mitigate sulfate scaling. Since then, these applications use membrane removal. In this case, fouling
offshore installations were relatively technologies to achieve the desired susceptibility is the major unknown
few until about 2004 or so when water chemistry. that might be obviated by placement
the total barrels treated surpassed Membrane technologies require downstream of an ultrafiltration or
2million BWPD. Since then, uptake reliable pretreatment to prevent SRM system.

August 2012 Oil and Gas Facilities 11


WATER TREATING INSIGHTS

Recently, Total started polymer viscosity can likely be performed polymer from the back-produced
flooding the Dalia field in deepwater withconfidence. CEOR fluids.
offshore Angola. On average, However, the presence of polymer One of the interesting
8,000BWPD are being injected using changes two other key aspects of the developments in water treating back-
desulfated seawater from an SRM produced water. First, it is known that produced fluids is in chemical treating
system. Polymer concentration is at low concentration (<500 mg/L), of ASP fluids. In a recent application of
about 900 mg/L. A 750-kg bag of HPAM polymer promotes coagulation hydrophilic/lipophilic deviation (HLD)
polymer is consumed every 1.5 days. and flocculation of oil drops. It is theory, George Hirasaki and his group
An increase in daily oil production was a common component of deoiling at Rice University (Pena et al. 2005)
seen soon after polymer injection. It products used to treat produced have identified cationic surfactants
is too early for back-produced fluids. water. At higher concentrations, that act as strong demulsifiers to
Once the back-produced fluids contain though, the produced water viscosity break ASP emulsions. Typical ASP
detectable concentrations of polymer, and viscoelastic properties become back-produced fluids are composed
the produced fluids will be routed to a dominant. The only information at this of tight emulsions of small oil drops
disposal well (Morel et al. 2012). Other time is from theoretical considerations, in water that are stabilized by the ASP
operators have larger offshore polymer which suggest that back-produced chemicals. Thechemistry of these
flood projects under development. fluids containing polymer are more demulsifiers is specific in the sense
For many polymer projects, sensitive to shearnot shear thinning that only oneparticular compound
treating back-produced CEOR fluids of the polymer, but oil/water emulsion seems to work with any particular
will be a challenge. One of the early tendency. In other words, for a given ASP formulation. Nevertheless, when
deterrents to CEOR in the 1980s shear rate, a back-produced fluid the proper chemistry is selected,
was the difficulty of separating and containing polymer will have higher settling time is reduced from 12 hours
metering the oil. Reservoir response oil-in-water concentration and smaller to 12 minutes (Nguyen et al. 2011).
was essentially unknown for many oil drops. If this is indeed the case, Apparently, the cationic surfactant
applications because accurate oil- back-produced fluids will be more demulsifier pushes the ASP surfactant
production rates could not be difficult to deoil. As important as away from the oil/water interface.
determined because of inadequately this question is, it remains largely From a high-level perspective, it is not
designed separation facilities. unexplored. The literature describing a surprise that a chemical strategy is
Designing the separation facility field experience is ambiguous successful in treating such a chemically
remains a challenge. andunclear. stabilized emulsion.
A polymer flood will result Second, polymer increases One of the avenues being pursued
in back-produced water with at jetting of bubbles in a flotation unit. is to degrade the polymer in the
least twice and up to an order The bubbles tend to form jets, rising back-produced fluids. Because the
of magnitude greater viscosity rapidly and causing secondary flow, polymer is shear sensitive, mechanical
compared to conventional produced making it more difficult to evenly degradation is an obvious idea. The
water, depending on the polymer disperse bubbles in the presence of key will be to degrade the polymer
concentration and extent of polymer polymer and significantly reducing molecules without shearing the oil
degradation. While this is significant, the performance of a flotation unit. drops. There is some hope that this
it can be taken into account in Perhaps this problem can be solved by could be done. The size scale of the
equipment design. Water viscosity better design of bubble distribution polymer molecules is on the order of
differences are already well known in systems. After all, bubble distribution nanometers, while the size scale of the
the industry, and equipment design is an area of flotation design that has oil drops is on the order of microns.
models accurately account for the been steadily improving over the years. Thus, two different size scales are
effect. The produced fluids in the This is another question that remains involved. Further, the viscous stress
Norwegian sector of the North Sea relatively unexplored. required to degrade the polymer is less
are hot and, therefore, have about Perhaps all of these problems than that required to shear oil drops.
half the viscosity of produced water can be overcome by new equipment Thus, a device that generates nano-
in the deepwater Gulf of Mexico. This designs. The literature on the Daqing scale viscous shear, while avoiding
viscosity difference, from temperature field suggests this may be the case, micron-scale turbulence, might do
alone (and not polymer), is adequately including an example of an innovative the job. High Reynolds number
taken into account in water treating technology that has recently been turbulent eddies must also be avoided
system design. Extrapolation to higher installed to separate and recycle the because, according to Richardson

12 Oil and Gas Facilities August 2012


WATER TREATING INSIGHTS

and Kolmogorov (Davidson 2004), be addressed in the early stages of specialized in water treating and
turbulence generates an energy theproject. have developed deep expertise in
cascade that inevitably leads to all three areas critical to water
micro-scale eddies of the kind that Opportunities in treating: chemistry, equipment, and
will shear oil drops. Altogether, these WaterTreating process lineup.
requirements lead to ultrasound In addition to the technical challenges Chemical companies are pursuing
treatment as the best candidate. mentioned, there are significant the opportunities vigorously. This
Such devices might be expensive for opportunities as the industry is not a surprise. Obviously, CEOR
large volume flows; this remains to implements CEOR projects. While involves intense chemistry and,
bedetermined. the technology is complex and therefore, offers a market opportunity.
Chemical degradation is also knowledge in this area is specialized, There is another reason that is perhaps
being evaluated. Typical polymers the commercial barrier to entry is not less obvious. Chemical suppliers
used in CEOR can be degraded using high. Relatively few patents remain in have a first-row seat at the game.
hypochlorite. Perhaps there are other effect. Few if any intellectual property Upstream chemical suppliers typically
treatments that would be possible. In barriers exist. The main barrier to employ 10 times the number of field
proppant fracturing, the viscosifier entry is expertise. staff compared with almost every
polymers are designed for injection Deep expertise in water treating other oilfield services provider on
at high viscosity and backflow at low is required. If history is a guide, NOCs an equivalent revenue basis. Field
viscosity. This is required for optimal and IOCs will look for this expertise services are the main value driver for
proppant placement. It is achieved from the consultants, chemical chemical providers, and they see the
in various ways, such as thermal or suppliers, equipment suppliers, field problems firsthand. The top-tier
enzymatic degradation. Perhaps there academia, and the engineering upstream chemical suppliers are very
is a similar strategy that could be consultant companies. Pockets of effective at capturing the challenges
used to lower the viscosity of CEOR expertise are developing. of water treating and developing
polymers in back-produced fluids. Selecting appropriate technology newproducts.
Obviously, in this case, the polymer and designing an integrated process On the equipment side, the
would need to maintain high viscosity requires expertise. There is a wide situation is a bit different. The
through the reservoir and only become variation in the level of expertise major equipment suppliers see an
degraded during or shortly after available from the engineering firms. opportunity to sell more sophisticated
backproduction. Most do not have the expertise water treating equipment (i.e., those
In all of these water treating required to select and design systems with greater process intensity) to
challenges, the devil is in the details. that not only perform well but also onshore CEOR projects. Given the
Seemingly small decisions can make are simple to operate. On the other difficulty of treating back-produced
the difference between a system hand, some engineering companies fluids, settling tank residence time
that performs well with minimum have established an industry niche becomes impractical. Therefore, it
operating expenses and high uptime by providing expertise together makes sense to use hydrocyclones,
vs. a system that is chronically difficult with engineering. Such companies flotation, and nutshell filters. It appears
and costly to operate. Operators that are notable in that they send staff to though, based on pilot and field tests,
suffer water treating problems often workshops and encourage staff to that the equipment performs only
do not tally the real cost of those publish papers. They offer consulting about half as well as hoped. Shear
problems. The staff time required to in addition to engineering. Such thinning, higher oil concentrations,
solve water treating problems can be companies add significant value smaller drops, and bubble jetting make
high and can put significant strain on toaproject. these fluids more difficult to treat than
the staff resources of an organization. Knowledge of how to design expected. For onshore applications,
In many cases, if communication CEOR water treating systems is this merely means that twice the
between the reservoir chemist and certainly specialized, but credible capacity must be installed. However,
the water treatment specialists expertise is available. Many of the for offshore applications, this poses
could be in place from the time the experienced international service a significant problem because of the
CEOR cocktail formulation and providers have recognized the limited space and weight available for
water chemistry requirements are opportunities in this area for several water treating.
developed, it is expected that many of years. The most successful of these Overcoming these problems
these consequential decisions could companies are those that have may require development of new

August 2012 Oil and Gas Facilities 13


WATER TREATING INSIGHTS

technology and possibly a fundamental methods or industry nonprofit ment and Applied in the Peoples Republic of
understanding of the back-produced institutions to manage information, China. Paper SPE 89175. J Pet Technol 58 (2):
8489. http://dx.doi.org/10.2118/89175-MS.
fluid properties. Not only would this dictate standard testing procedures, Davidson, P.A. 2004. Turbulence: An Introduction
be expensive, but there are relatively or recommend industry guidelines for Scientists and Engineers. Oxford University
few laboratories, test sites, and people relative to water treatment in the oil Press, USA.
who can do the work. The equipment industry. Compounding this situation, Davis, R.A., and Southwell, G. 2007. Practical
suppliers feel that there is not a large the number of people who can bridge Considerations in Ensuring Cost Minimization
in the Design and Operation of Sulfate-Remov-
enough market to justify a large the gap between the science and al Systems. Paper SPE 109129 presented at the
effort, and they may be correct. Such the application is relatively few and International Oil Conference and Exhibition in
companies tend to have a keen sense actually decreasing with time as the Mexico, Veracruz, Mexico, 2730 June. http://
of the cost and potential market for industry demographics mature. dx.doi.org/10.2118/109129-MS.
developing new technology. While It is too early to say how all of Delshad, M. 2010. SPE Training Course on
Chemical Enhanced Recovery, Houston, 23
CEOR will clearly increase in volume, this will work out. The industry may November.
it may not capture more than a few find clever ways to handle the back- Henthorne, L. 2010. Trends in Pretreatment for
percent of the total global water produced fluids. If not, an expensive Seawater Reverse Osmosis. Water Conditioning
treating market. The offshore market development effort may be required. and Purification 52 (11): 2224.
will be even smaller. In which case, No one can really say for sure at this Hirasaki, G. 2010. Introduction to Consortium
on Processes in Porous Media Consortium,
push from resource holders may be time. One fact is clear: CEOR is yet Rice University, 3May.
required rather than technology pull another development to add to the Hirasaki, G.J., Miller, C.A., Puerto, M. 2011. Re-
from the equipment companies to list of oil industry challenges where cent Advances in Surfactant EOR. SPE Journal
provide new technology. water treating expertise is required, 16 (4): 889907.
It is encouraging that expertise is including heavy oil steamfloods, Ji-Cheng, Z. and Kao-Ping, S. 2008. Consider-
able Potential Remains After Daqing Polymer
developing in the consulting, services, hydraulic fracturing for tight gas and Flood. Oil & Gas J. 106(35): 6166.
and supplier sectors. However, this tight liquids, coal seam methane, sour Manrique, E., Thomas, C., Ravikiran, R., Izadi,
will likely not be enough. As the NOCs hydrocarbons, and hydrate control. M., Lantz, M., and Romero, J. 2010. EOR:
and IOCs begin to take ownership for The list is already long and is having an Current Status and Opportunities. Paper SPE
water, they are beginning to realize that effect on the cost and speed with which 130113 presented at the SPE Improved Oil
Recovery Symposium, Tulsa, 24-28 April 2010.
in-house expertise is required as well. hydrocarbons can be brought http://dx.doi.org/10.2118/130113-MS.
A key to a successful project is a high to market. Morel, D., Vert, M., Jouenne, S., Gauchet, R.,
level of expertise among all partners. As always, we hope that this article and Bouger, Y. 2010. First Polymer Injection in
has provided some food for thought. Deep Offshore Field Angola: Recent Advances
Summary and Conclusions Debate on this or other water treating on Dalia/Camelia Field Case. Paper SPE
135735. Oil and Gas Fac. 1 (2): 4352.
While there is significant interest and issues is welcome. Nguyen, D., Sadeghi, N., and Houston, C.
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Despite recent improvement in the Al-Mutairi, S.M, and Kokal, S.L. 2011. EOR Po- Emulsions. Paper SPE 143987 prepared for
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14 Oil and Gas Facilities August 2012

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