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Summary In the oil industry, water-in-oil emulsions are by far the most
This case history tracks the continual improvement cycle for the commonly encountered. As a rule of thumb, the type of emulsion
fluid-separation process of a heavy-oil/oil-sands production facility that forms is determined by the relative abundance of the two
in northern Alberta over a period of 3 years. The major challenge phases. When a phase is in excess, the phase that has the smaller
posed by the operator of this 13 to 16°API crude oil was to move fraction is dispersed in the other. However, there are a number of
away from injection of two separate demulsifier formulations to factors that will also influence this rule of thumb (Schramm 1992;
injection of a single product. This was not an easy task because of Schubert and Armbroster 1992).
the very different conditions that existed at the two injection loca- Emulsions are stabilized by a surface-active agent or surfactants,
tions. The first location was at a series of injection points upstream which are termed emulsifiers. These species concentrate at the oil/
of the gathering stations before separation where temperatures water interface and form interfacial films that reduce the interfacial
could reach subzero conditions, and the second was at the battery tension and promote emulsification and dispersion of droplets. Many
receiving facility where heating increased temperatures to 100°C. naturally occurring emulsifiers are present in crude oil and include
Water cut and shear were also very different, and the operator asphaltenes, resins, organic acids, and bases (Eley et al. 1988). All
required a very strict 0.2% basic sediments and water (BS&W) on these emulsifiers tend to concentrate in the higher-boiling-point
the crude exiting any of the four treater tanks. To complicate issues fractions and therefore in heavier crude oils. It is understood that
further, crude-oil viscosity ranged from 500 to 5,000 cp. these emulsifying components are major constituents of interfacial
A unique bottle testing method was developed and used to films, and numerous laboratory studies have been performed looking
simulate the field conditions as accurately as possible. Details at various emulsifying components and their ratios to one another
are given on the chemistry of the individual components of the (Verutto and Kilpatrick 2008; Spiecker and Kilpatrick 2004; Kumar
demulsifier determined to be so crucial to adequate performance et al. 2002; Baydak et al. 2008; Zaki et al. 2000). Other production
and how this was optimized in the field after being identified from chemicals can also act as emulsifiers, such as corrosion inhibitors,
the bottle tests. scale inhibitors, and drilling fluids. Fine solids can act as mechanical
Results show how careful consideration was given to the stabilizers. These solid particles have to be much smaller than emul-
concentration of the demulsifier bases in the blends, and show sion droplets and concentrate at the oil/water interface wetted by
the curious observation that dilution of the final product made a both the oil and water. The efficacy of solids in stabilizing emulsions
big difference to the final performance in the field. Elaboration is depends on particle size, interactions, and the relative wettability of
given on potential mechanisms explaining the dilution effect, and the particles. Some studies have proposed that solids are by far one
this paper will conclude with observations on how careful design of the most influential parameters on emulsion stability (Poindexter
of field testing followed by field implementation can indeed solve et al. 2006). Solids can include sand, asphaltenes, waxes, clays,
complex separation issues and address individual well, battery, and silts, corrosion products, mineral scales, drilling mud, and drilling
field requirements. loss control media.
Emulsions are unstable systems because there is a thermody-
Introduction namic drive for a liquid/liquid system to separate and reduce the
Emulsion Background and Theory. Oil and gas are rarely pro- interfacial area and energy. Many emulsions can be stable over
duced from a reservoir alone, often being associated with produced a long period of time because they possess a kinetic stability.
water. This mixed production creates many issues, one of which This leads to another classification system of emulsions based on
is the formation of emulsions. Separation of the crude oil from stability:
the water is one of the most critical and fundamental process 1. Loose emulsions separate in a few minutes.
challenges in production operations. Emulsions can be difficult to 2. Medium emulsions separate in 10 minutes or more.
treat and can cause operational issues such as production of off- 3. Tight emulsions can be stable for hours or days and in some
specification (wet) crude and (oily) water, high pressure drops in instances may never resolve.
pipelines, and tripping of separators (Schramm 1992). Generally a tight emulsion has a much smaller dispersed-phase
Emulsions can be encountered through the entire production and droplet size (< 1 m) and a high degree of stabilizing surfactants
processing cycle of crude oil: in the reservoir, wellbore, production or solids present. A loose emulsion has a larger dispersed-phase
tubing and wellheads, process vessels, export pipelines, and during droplet size (> 1 to 10 m) and a low degree of stabilizing sur-
petroleum processing. The process of separating water from crude factants or solids.
is called demulsification or dewatering. In refineries, the process of Many factors affect the stability of emulsions, and these have
removing washwater from crude oil is called desalting. been reviewed exhaustively in the literature (Kokal 2005; Strassner
Crude-oil emulsions are a dispersion of water in oil and can be 1968; Kokal and Al-Ghamdi 2006; Yarranton et al. 2000):
classified into three categories: 1. Temperature. As well as affecting the physical properties
1. Water-in-oil emulsions of the crude oil, namely viscosity, temperature also affects the
2. Oil-in-water emulsions properties of the produced water, interfacial films, and emulsi-
3. Multiple or complex emulsions fier solubilities in the crude oil and water. The viscosity of the
emulsion decreases with increasing temperature because increas-
ing the temperature decreases the viscosity of the crude oil. This
can especially be prevalent when a crude oil contains paraffinic
Copyright © 2010 Society of Petroleum Engineers
components, and application of heat can eliminate an emulsion
This paper (SPE 117177) was accepted for presentation at the International Thermal problem by redissolving paraffins into the crude oil. Temperature
Operations and Heavy Oil Symposium, Calgary, 20–23 October 2008, and revised for
publication. Original manuscript received for review 31 July 2008. Revised manuscript
also serves to increase the energy of a fluid, thereby increasing the
received for review 01 December 2008. Paper peer approved 20 December 2008. number of droplet collisions and promoting coalescence.
Recycle
tanks
Field Background and Fluid-Separation mimicking application in the field, and then after an appropriate
Challenge residence time, increase the temperature and dose in additional
This case history tracks the continual improvement cycle for the chemical to mimic application at the battery. On the basis of the
fluid-separation process of a heavy-oil/oil-sands production facil- results, a new single demulsifier product was identified that was
ity in northern Alberta over a period of 3 years. One of the major a blend of EO/PO block polymers and an alkoxylated amine. The
challenges posed by the operator of this 13 to 16°API crude oil changeover was completed by the end of June 2007. The new prod-
was to move away from injection of two separate demulsifier for- uct was very good for fast water drop, and the BS&W of the ITPS
mulations to injection of a single product. This was not an easy and FWKO were much improved compared to previous trends.
task because of the very different conditions that existed at the two However, BS&W was not as low as 0.2%. During this time, there
injection locations. The first location was at a series of injection were significant operational issues with the functionality of the
points upstream of the gathering stations out in the field, before heater treaters, and in nearly all cases, at least one of the treaters
separation, where ambient temperatures could reach subzero con- ran cooler than 100°C. As an example, the Treater 1 trends have
ditions (> −40°C). The ambient conditions affected the in-line been plotted in Fig. 2, and it can be seen that when the temperature
temperature of the flowlines, decreasing arrival temperatures at the decreases, the BS&W increases, especially in the last quarter of
battery from approximately 15 to 20°C to as low as 7 to 12°C. The 2007 where the treater temperature decreased from 115 to 100°C
second injection location was at the battery receiving facility where and the BS&W coming out the treater increased from an average of
heating increased temperatures to approximately 100°C. Water cut between 0.2% and 0.35%. In order for a single demulsifier product
and shear were also very different, and the operator required a very to be as effective as possible, the temperature and operation of the
strict 0.2% BS&W on the crude exiting any of the four treater treaters needed to be as smooth and constant as possible.
tanks. To complicate issues further, crude-oil viscosity ranged from The change in chemistry had not given the necessary impact
500 to 5,000 cp, and the crude oil came from a relatively shallow to the overall export BS&W that the operator had anticipated.
play resulting in wellhead temperatures barely reaching 20°C. Therefore, further attempts at optimization were made, and it was
A schematic of the plant battery is given in Fig. 1. Fluids arrive found that using a dilution of the same chemistries, especially in
from the field to an inclined two-phase separator (ITPS). From the field, but also at the battery, made significant improvements to
there they pass through a heat exchanger to a free-water knockout the BS&W and treatments. This change to a diluted product came
vessel (FWKO). Fluids then passed through four parallel heater only 1 week after the change to a single chemistry and after appli-
treaters to sales. Various recycling and skimming operations can cation of a diluted product (30% active instead of 50% active). The
be in operation (Fig. 1). improvements were proposed when better penetration occurred
Injection of two different demulsifier products in the field and at in the oil with the increased solvent content of the demulsifier.
the battery occurred for several years (both were mixtures of EO/ However, even with this improved penetration and dehydration of
PO block polymers and alkoxylated resins) with relatively trouble- the oil, it was acknowledged that this was just too challenging a
free operation. The lease automatic custody transfer (LACT) base task to perform alongside decreasing the BS&W of the LACT to
sediment and water (BS&W) was below the 0.5% specification. below 0.2% after several months of trying to optimize on a single
However, in mid-2007 it was a requirement to not only move to product in the field (at a variety of concentrations) and at the
a single demulsifier product for application in the field and the battery. Therefore, further optimization of demulsifier products
battery, but also to decrease the BS&W to 0.2%. The reasons for occurred, which brought a new product to be applied at the battery
these changes were to ease logistical and operational issues by while keeping the same product out in the field.
moving to one product, and the BS&W specification was to have Some general plant trends have been plotted in Figs. 3 and 4
more of a buffer between the actual BS&W of the LACT and the that show the evolution of the LACT BS&W with total oil- and
sales specification of 0.5%. water-flow rates (Fig. 3) and then the LACT BS&W with the
In order to enable use of a single product in both the field injec- overall (total) demulsifier-injection rate (Fig. 4). In Fig. 3, there
tion locations and at the battery, a redesign of the bottle tests was is a direct relationship between the LACT BS&W and the vol-
required in order to simulate the real field conditions and passage ume of water the field produced and handled at the battery. As
of a single demulsifier product through the system. Some subtle the produced-water rates increased, the LACT BS&W increased,
changes were to initially perform the bottle tests on cold fluids too. This would suggest that the water-handling limitations of
0.45
120
0.40
0.35 110
Temperature (C)
0.30
BS&W %
100
0.25
90
0.20
0.15 80
0.10
70
0.05 Treater 1 BS%W
Treater 1 temperature
0.00 60
12/04 03/05 06/05 09/05 12/05 03/06 06/06 09/06 12/06 03/07 06/07 09/07 12/07 03/08 06/08 08/08
the battery were being exceeded and that the plant had become trends remained constant at approximately 0.2 to 0.3%. During
more challenging to operate with the increased volume of water. this optimization, the demulsifier usage was altered for both the
Residence times also significantly decreased as the produced-water upstream and downstream applications. During the last 6 months
rates increased from 8000 to 16000 m3/day (50,500 to 101,000 of this demulsifier optimization (the first half of 2007), the LACT
B/D). Another potential issue is that the emulsion could actually BS&W noticeably increased to 0.4%, and further demulsifier
pass the inversion point in some locations because this increase in optimization ceased in order to try to control the rising BS&W.
produced water is a water-cut change of approximately 64 to 80%, The big increase in demulsifier-injection rate in the second half
although experimentation to confirm this has not been performed. of 2007 was because of a change to a more dilute product in an
It can be seen from Fig. 4 that optimization of the original demul- attempt to gain better demulsifier penetration into the crude oil to
sifier combination injection rate had occurred from 2005 to 2007, enable cold treating. Returning to Fig. 3, a slow increasing trend
and it was possible to reduce the overall demulsifier consumption in the LACT BS&W occurred from early 2005 to the end of 2006
from 150 to 90 ppm (based on oil). During this time, the BS&W (A), explained by increasing water-production rates and generally
18000 0.7
Oil rate
Water rate
16000 LACT BS&W 0.6
Crude oil and water rate (m /day)
14000
0.5
3
12000
LACT BS&W %
C
10000 0.4
B
8000 0.3
A
6000
0.2
4000
0.1
2000
0 0
12/04 03/05 06/05 09/05 12/05 03/06 06/06 09/06 12/06 03/07 06/07 09/07 12/07 03/08 06/08 08/08
Fig. 3—Crude-oil and water rates vs. the LACT BS&W (arrow indicates change in demulsifier chemistry).
0.6
250
BS&W %
0.4
150
0.3
100
0.2
50
0.1
Demulsifier usage
LACT BS&W
0 0
12/04 03/05 06/05 09/05 12/05 03/06 06/06 09/06 12/06 03/07 06/07 09/07 12/07 03/08 06/08 08/08
Fig. 4—Demulsifier usage vs. the LACT BS&W (arrow indicates change in demulsifier chemistry).
decreasing demulsifier-injection rates. At the beginning of 2007, an the battery and received by the ITPS vessel. When this happened,
increasing trend was experienced in the LACT BS&W (B), and this the ITPS received a large slug of wet-oil emulsion followed by
was commensurate with a marked increase in the produced-water an even larger slug of free water. This added to the difficulty of
rate. By the end of June of 2007, the new single demulsifier product operating the ITPS in terms of interface control and correct water
was introduced. Even though further increases in produced-water levels, as well as loading the FWKO with oil emulsion and starv-
rates occurred, the increasing trend in BS&W was halted where it ing it of water. The solids would also cause a pad buildup in both
has maintained an average of 0.4% (C). While on face value the the ITPS and FWKO.
change in demulsifier did not decrease the BS&W to the target
of 0.2%, the change was positive because it ensured faster water Conclusions
drop and more efficient separation at the plant even with massive
The following conclusions can be made from the field testing,
increases in gross fluid throughput. It resulted in maintaining a
sampling, and demulsifier optimization exercise:
less severely increased BS&W. It can be seen that optimization
• Injection of two separate demulsifier products before mid-2007
continues with the new product combination to reduce the injection
gave relatively trouble-free operation. A change to the BS&W
rate to the most economical concentration.
requirement and a desire to move to a single demulsifier prod-
A corrosion inhibitor was injected in the field at a rate of
uct applied in the field and at the battery gave some significant
approximately 1000 L/d, equivalent to approximately 60 ppm
treatment challenges.
based on total fluids. It was a water-soluble/oil-dispersible product
• A redesign of the bottle-test procedure was required in order to
applied to all the main areas coming in from the field. Bottle testing
more accurately mimic the field application of a single demulsi-
showed that this corrosion inhibitor significantly interfered with
fier product.
the speed of water separation and resulted in a baggy interface in
• The general increase in BS&W seen at the LACT was most
the bottle. The field separation equipment also shows higher effi-
likely attributable to the large increase in gross fluid through-
cacy of fluid separation during periods where the corrosion inhibi-
put—mostly water. Residence times would be much reduced,
tor is offline, especially the water quality outlet to the skimmings
plant operability would have been constantly changing, and the
tanks. Furthermore, the crude oil itself being produced on this lease
emulsion may have passed through its inversion point.
had relatively low asphaltene content for the weight of the crude.
• The change in demulsifier chemistry was positive because it
This resulted in the crude being relatively nonviscous. Therefore,
halted the increasing trend in BS&W commensurate with large-
cold treatment of the crude was a viable option. The crude also
scale water-rate increases.
contained a significant amount of entrained gas because it was
• The corrosion inhibitor injected in the field was shown to inter-
difficult for the gas to separate from the crude at low temperatures
fere significantly with the speed of water separation and resulted
in the field. Only after heating at the battery did large-scale gas
in a baggy interface in the bottle test.
breakout occur. Therefore, the produced fluids and gases displayed
• Large quantities of entrained gas in the crude resulted in large-
very different physical forms in the field and at the plant, which
scale foaming in the battery, and application of an antifoaming
indicated that two demulsifier products were likely to be required
agent was recommended to help maintain a clear and discrete
to treat the overall lease. The large-scale gas breakout in the battery
interface.
created a lot of foam in the process vessels, particularly the ITPS
• Pigging operations of the infield pipelines brought slugs of solids,
and FWKO, which led to poor interface control and excursions
emulsions, and free water into the battery adding further to the
of water into the sales crude. This continual disturbance created
difficultly of operating the plant.
wide swings in the composition of fluids flowing to the FWKO,
thus leading to large deviations from the set point in the operating
temperature of the FWKO. Application of an antifoaming agent References
is anticipated quite soon in order to try to improve LACT BS&W Al-Bastaki, N., Abbas, A., and Zubari, H. 2003. Improving the Production
even further. of Heavy Emulsion Crudes in the Bahrain Field: Experimental and
To complicate treatment further, the main infield pipelines were Field Investigations. Paper SPE 81450 presented at the Middle East
pigged twice weekly and production fluids and solids pushed to Oil Show, Bahrain, 9–12 June. doi: 10.2118/81450-MS.