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for Water, Energy and Air SM

ESSENTIAL INNOVATION FOR THE PETROLEUM INDUSTRY

VOLUME

03

Energy & Water: finding a


balance
between essential resources

A Sharper Focus 2 for 1 Maximized


on Desalting Production & Asset Integrity
LETTER FROM EDITOR
Has there ever been a time in deposits and simultaneously provide corrosion inhibition to the metal
history that the upstream industry surface, has paid dividends to water injection systems by significantly
has faced as much scrutiny as it improving their integrity and dramatically enhancing production by
does today? On what seems like a maximizing water injectivity.
daily basis, our industry is dealing Shifting our attention downstream, many of the new crudes coming
with tighter operating regulations, to market present significant refining challenges in the form of high
whether it is in offshore drilling, solids loadings, high acid number, elevated metals content and high
fracturing operations in shale gas plays, infrastructure integrity density. These so-called opportunity crudes can provide greater
profit opportunities to refiners, so long as they can successfully treat
management or the critical area of water management. Central to
them without running into emulsion problems in the desalter or upset
the discussion in all of these areas is the industrys commitment to
conditions in the waste water treatment plant. To probe the science
the responsible and sustainable development of natural resources. associated with the desalting process, Nalco scientists have developed
a new high-pressure dynamic desalting unit. This issue of Cutting
The worlds population continues to grow and the rapid industrialization
Edge highlights how this pioneering tool has led to better simulations
of countries like China and India is projected to place a huge burden
of opportunity crude processing and the development of more cost-
on the global energy market. To meet this demand, new hydrocarbon-
effective desalting solutions.
based production is required, production from existing assets needs
to be maximized and the asset life cycle needs to be safely extended. As regulations tighten in the petrochemicals industry, producers are
Technology plays a pivotal role in meeting each of these requirements. continuously challenged to minimize the environmental footprint of
their operations. This is especially evident in the manufacture of
Recent advances in directional drilling and slick-water fracturing have
styrene, where current chemical additives used to minimize the self-
enabled the production of vast gas resources from tight, shale plays
polymerization of the product stream are being phased out. Following
that were previously uneconomical to produce. However, the fracturing
extensive research, Nalco has introduced its PRISM technology that
process requires significant quantities of water, placing a huge demand
retards styrene polymerization and features superior environmental
on local fresh water sources. Furthermore, flow-back water following
properties to current industry standard chemistry, offering styrene
a frac job must be extensively treated before its disposal or reuse.
manufacturers a step-change in environmental compliance.
Responsibly managing the use, and reuse, of water is critical to the viability
of producing these gas reserves and to the reputation of the oil and gas Solving real-world problems and adding value to a customers
industry as a whole. operation starts with developing a thorough understanding of the
system. In many cases, this requires a comprehensive analytical
This issue of Cutting Edge features a novel friction-reduction technology
investigation of process fluids or deposits. Youll read here how
that enables flow-back water to be reused in subsequent frac jobs
our dedicated Analytical Technologies Group brings state-of-the-art
with minimal processing. This significantly reduces fresh water usage
analytical tools to the petroleum industry, with an example of how the
and enables the flow-back water to be viewed as a valuable resource
use of X-ray Microscopy has successfully solved catalyst poisoning
rather than a waste stream. In fact, this new technology won the
and oilfield scaling problems.
U.S. Presidential Green Chemistry Challenge Award for its favorable
environmental properties. Because the technology reduces the frictional Nalco is dedicated to enabling our customers to meet their regulatory
losses associated with the high-pressure pumping of frac fluids into the and corporate commitments while developing our planets natural
formation, significant energy savings are realized. resources in responsible and sustainable ways. I am confident that
as you read this issue of Cutting Edge, youll see our commitment
It is quite common for production infrastructure to be in service well
to developing and providing the latest technologies that help our
beyond its original design life, and because production systems typically
customers deal with their growing and dynamic challenges.
handle extremely corrosive fluids, preserving their long-term integrity is a
critical priority. In many cases, deposits that form in pipelines or vessels David Horsup, Ph.D.
create an extremely corrosive environment that may lead to a failure in a
matter of weeks or months. Deposits in water injection systems can rapidly
plug the sand-face around the injectors, resulting in significantly reduced
injectivity and decreased production. As youll read in this issue, Clean n
Vice President, Research
Cor technology from Nalco, which was specifically designed to remove Energy Services

CUTTING EDGE 2
COVER STORY
ENERGY & WATER:
FINDING A BALANCE BETWEEN
ESSENTIAL RESOURCES
The incredible expansion of shale gas developments in
North America has brought with it an expanded demand
for water. Nalco stimulation technologies ensure that
water management is sustainable, both environmentally
and economically.

15
FEATURE STORIES

A SHARPER FOCUS ON DESALTING PUTTING THE OILFIELD UNDER ON A SUSTAINABLE PATH TO MAXIMIZING PRODUCTION AND
Faced with widely fluctuating THE MICROSCOPE POLYMER CONTROL ASSET INTEGRITY
crude oil prices, reduced Complex technical challenges Many of the products that people Many of todays oilfields have
utilization rates, stricter are nothing new to the oilfield, utilize daily, from automobiles to been producing oil and gas for
environmental regulations... but sometimes problems arise food containers, share a common years, and as they mature, they
that cannot ... petrochemical face an unavoidable fate...

4 7 10 13
building block...

For more information about the Nalco technologies featured in this issue, please call 1-281-263-7000 or email CuttingEdge@nalco.com

NEWS AND UPDATES


nalco opens new technology center in INDIA
New 38,000 square foot facility will be a primary support center for the Energy Services business.
18
CUTTING EDGE 3
a
on desalting
Faced with widely fluctuating crude oil prices, reduced utilization rates, stricter environmental regulations
and an uncertain economic environment, refineries that are configured to process opportunity crude
oils have a profit advantage. While opportunity crude oils are defined as any refinery feedstock obtained
at discounted prices, they generally constitute either newly produced crudes with little processing
information or existing crudes with known processing challenges.

For example, Canadian crude oils derived from oilsands production are often characterized by higher
solids contents, higher total acid numbers (TAN) and higher densities than benchmark crude oils. With
typical discounts of $8 $10/bbl, one North American refinery stands to add $3.5M per year in profits for
every 1,000 bbl of Canadian crude processed without upset. But without the right strategies in place to
manage known processing challenges, this profit potential can erode quickly.

CUTTING EDGE 4
Typical problems associated with opportunity crude processing include: A Dynamic Development
Oil undercarry and/or oil-coated solids in the The Nalco Downstream Research Group has constructed unique
desalter brine effluent laboratory-scale equipment to more accurately simulate the desalting
process. The Dynamic Visual Desalter (DVD), for example, generates
Impacts on wastewater treatment operations water-in-oil emulsions under flow conditions and operates at normal
A wider emulsion band stabilized by asphaltenes desalting temperatures and pressures, making it capable of simulating
or inorganic solids challenging process conditions observed at refineries. The emulsions
are subsequently separated in the presence of elevated temperatures
Reduced dehydration or desalting efficiencies (up to 250F), elevated pressures (up to 150 psig), electric fields (0
Solids carryover leading to higher fouling rates in 6000 VAC) and chemical demulsifiers. The desalting cell is equipped
the hot preheat exchanger train with a glass window to observe the interfacial rag layer (Fig.1). The
new simulation equipment allows Nalco to investigate potential
Increased energy consumption, corrosion, and other desalting problems and develop site-specific control programs prior to
downstream impacts to the FCC, coker and other units deployment at a customer site.

Danger to Desalters
As the first unit operation in most refineries, the desalter may be
severely impacted by opportunity crude processing. The role of the Oil
desalter is to effectively wash crude oil and remove contaminants
that could lead to fouling, corrosion and quality problems with the end
product further downstream. In the desalting process, the crude oil
stream comes into intimate contact with a small amount of wash water
(ca. 5 vol. %) to extract salts and other contaminants into the water Emulsion
phase. The resulting water-in-oil emulsion is subsequently separated
inside the desalter vessel by employing electric fields, high temperature
and demulsifier chemicals. Using laboratory testing and a detailed
audit of the crude unit to provide chemical, mechanical and operational
Water
recommendations, the Nalco RESOLV Desalter Management Program
is designed to mitigate the negative impacts described above in the
downstream processing unit and wastewater treatment plant.

Selection of an effective emulsion breaker product for refinery


desalting applications is generally determined by a batch electrostatic
Fig. 1 Emulsion layer in the desalter cell
coalescence method, also known as a portable electric desalting (PED)
test. The PED test is a static test in which a water-in-oil emulsion
is prepared by blending a fixed volume of water and crude oil under As seen in Fig. 2, the DVD accepts chemically treated or untreated
controlled conditions. The emulsions are resolved with the assistance raw crude oil, which is fed by gear pump to a preheat unit. This is then
of constant heating and intermittent application of an electric field. The combined with a water feed at the header of the mixing device, which
resolution of the emulsion is observed, as the volume of water resolved uses the impeller action of a centrifugal pump to generate an emulsion.
in a centrifuge tube at fixed intervals during the testing. The pump is rheostat-controlled to allow adjustment of the droplet
size distribution (Fig. 3). The combined water-in-oil stream is sent to a
The PED test method is useful for comparing the relative efficacy of desalting cell where it passes through an electrode grid system. The
emulsion breaker formulations to dehydrate crude oil, but has limited electric field generated by the grid facilitates emulsion separation and
ability to predict other key performance indicators (KPIs) for desalting effluent brine is removed at the bottom of the desalter. The desalted
including salt removal efficiency, solids removal efficiency, brine crude is removed through a pressure relief valve at the top of the
effluent quality and interfacial rag quality. desalter. Typical crude oil residence times of 15 20 min. are possible
with proper control of the oil-water interface level.

CUTTING EDGE 5
50% Rheostat 80% Rheostat 100% Rheostat
2 ppm max 1 ppm max 1 ppm max
100x 100x 100x

Fig. 2. Dynamic Visual Desalter (DVD) Fig. 3. Optical micrographs of emulsions generated at various
settings of the mixing pump

A desalter simulation trial was performed to gauge the effectiveness of Nalco technologists are using the DVD to develop new
the grids for coalescing an emulsion (Fig. 4). Raw crude oil (33 API) was desalting chemistries. Possible applications and/or
treated with 13 ppm emulsion breaker. The desalter inlet temperature simulation scenarios include: iron, calcium, inorganic
(250F), wash water feed and mixing rate were maintained constant solids and other contaminant removal; rag collapse and
throughout the experiment. Samples of the raw and desalted crude oil and control with various emulsion breaker chemistries; oil
effluent brine were collected after processing at each voltage condition for undercarry control; and dehydration aids. Projects are also
one hour. The raw crude chlorides and BS&W (basic sediment & water) in development with various customer research groups to
were 130 160 ppm and 1.0 2.0 vol. %, respectively. As expected study upset scenarios and challenging situations at refinery
for normal desalter operation, salt removal directly correlated with the locations processing opportunity crudes.
desalters ability to dehydrate the crude oil, and dehydration efficiency
increased with increasing applied grid voltage. Optimize the Opportunity
Projections suggest that the percentage of opportunity
40 7% crude oils will increase from 5% of all crude processed
Extractable Chlorides (ppm)

35
today to 11% over the next two years. The increased
Extractable Chlorides (ppm) 6%
usage of opportunity crude oils as refinery feedstock will
30 BS&W (vol %) invariably lead to more frequent desalter upsets. The ability
5%
to anticipate and offer cost-effective programs to manage
BS&W (vol %)

25
4%
these upsets depends upon the ability to recreate field
20 observations in the laboratory. The Nalco Dynamic Visual
3% Desalter is a unique simulation tool that allows KPIs for
15 desalting to be measuredindicators that are unobtainable
2% from conventional static test equipment. The ability to
10
provide the customer with simulated trial data is another
5
1% reason why Nalco is the essential expert in opportunity
crude desalting.
0 0%
0 500 1000 3000
Grid Voltage (V)
Fig. 4. Extractable chlorides and BS&W of desalted crude oil

CUTTING EDGE 6
Putting
Oilfield
the

Microscope
U N D E R T H E

Complex technical challenges are nothing new


to the oilfield, but sometimes problems arise
that cannot be solved with traditional diagnostic
tools or analytical methods. The Nalco Analytical
Technologies Group was developed specifically to
address these types of challenges.

CUTTING EDGE 7
Comprised of highly skilled researchers with extensive analytical Fluorescence Microscope (XRFM) to the Nalco suite of analytical
and application experience, the team provides a diverse range tools. This novel characterization tool combines capillary X-ray
of analytical services to both support current customer needs optics with a video microscope capable of 100X magnification
and develop the next generation of diagnostic technologies for (see Figure 1). The end result is a transformation of optical
increasingly challenging oil and gas production environments. observations into elemental maps.

The Nalco Analytical Technologies Group has an extensive array


of powerful analytical tools, each designed to help identify X-ray Guide Tube
the chemical nature of a wide variety of both liquid and solid
samples from all areas of the petroleum industry. Only by Camera
developing a comprehensive understanding of the chemical
Detector
nature of an oilfield deposit, for example, and coupling this with
extensive operational knowledge, can we begin to understand
the root cause for the deposit formation and provide a Mirror
recommendation for cost-effective mitigation.
Sample
Because the challenges that operators face keep changing, the
arsenal of analytical tools Nalco provides must also continuously Transmission Detector
evolve. An example of this is the recent addition of an X-Ray
Fig. 1. X-Ray Fluorescence Microscope in action

Analysis in Action
In materials analysis, the location of an element can often
be more important than the concentration of the element,
a fact that was made clear in a recent collaboration
with a customer in the Gulf of Mexico. The operator
experienced poisoning of their Minox catalyst and was
1 mm 1 mm
looking for the cause.
Photo of sliced Minox bead a) Elemental map of aluminum in bead
Minox catalysts, palladium on an aluminum oxide bead, are
used for effective removal of oxygen from fluids, primarily
the deoxygenation of seawater prior to injection into the
formation for pressure maintenance. The active palladium
catalyst resides on the surface and its concentration is
small relative to the total weight of the bead.

Zinc is a common contaminant that can poison


the palladium catalyst; analysis of the beads using
conventional X-ray fluorescence (XRF) showed a 1 mm 1 mm

concentration of 0.1% (w/w) zinc. However, it did not b) Elemental map of palladium c) Elemental map of zinc in bead
answer the question, Where was this zinc? Was it in bead
evenly distributed throughout the bead, or did it reside at
the surface where it was deactivating the catalyst? Elemental maps of the sliced Minox bead (upper left)
acquired by the XRFM show that the beads interior was composed of
The answer came by slicing the Minox bead in half to a) aluminum (upper right),
acquire an elemental map of the bead using the XRFM. b) palladium resided on the surface of the bead (lower left), and
c) zinc also resided on the surface of the bead (lower right).
The analysis showed that the zinc was in the proximity
of the active palladium catalyst, thereby deactivating the This indicated that zinc was in the proximity of the active palladium catalyst,
catalyst (see adjacent images). thereby deactivating the catalyst.

CUTTING EDGE 8
In another example, Nalco recently collaborated with a West Texas customer to analyze the
composition and structure of a sample of calcium carbonate scale, a common and problematic form
of scale that provides flow assurance challenges in the oilfield. In Figure 3a, one can clearly see
stratification in the sample, but what does this signify? The XRFM was able to discern details that
could not be observed using conventional techniques (Figure 3b). X-ray mapping showed a distinct
chemical difference between the two halves; while both halves contained the same amount of calcium
(39%), they differed in their relative concentration of sulfur and strontium.

700m

Fig. 3a: Calcium Carbonate Scale Fig. 3b: Elemental map of edge via XRFM

This guided the Nalco team to conduct additional analysis of the sample using X-ray diffraction
which indicated that the two halves were actually different crystalline forms of calcium carbonate:
the top half was calcite while the bottom half was aragonite. Continued elemental mapping of the
sample using the XRFM showed a distinct blue line at the leading edge of the aragonite surface
which was attributed to the presence of strontium (strontium has been shown to play a role in
precipitation of aragonite1). The XRFM did not detect any other elements along the leading edge of
the aragonite, thus the presence of strontium sulfate was unlikely. Carbon and oxygen cannot be
detected using the XRFM, so the data was consistent with the presence of strontianite (SrCO3), a
compound with an aragonite-like structure. With this knowledge in hand, the Nalco team was able
to develop a tailored mitigation strategy to address both crystal forms of calcium carbonate scale
present and identify the presence of strontianite as a likely template for aragonite formation.

Analytical Support Drives Sustainable Solutions


Regardless of an operators production challenges, the need for detailed analytical support
is critical to make informed decisions. The range of services provided by the Nalco Analytical
Technologies Group - including its new XRFM - can provide this support allowing production
decisions to be made that are both economically and environmentally sustainable throughout the
life of an asset.

1
Sunagawa, I., Takahashi, Y., Hiroyuki, I., J. Mineralogical and Petrological Sciences. 102,174-181 (2007)
Minox is a Trademark of Minox Technology AS.

CUTTING EDGE 9
On a Sustainable

PATH
control
t o p o l y m e r

CUTTING EDGE 10
STYRENE PRODUCTION
shutdowns. An inhibitor provides superior control during normal
operations; in fact, the faster the reaction rate of an inhibitor, the more
effective it is in reducing polymer formation.
Technology Offers Cost-Effective,
Sustainable Polymer Control During emergency shutdowns, a retarder is essential to protect
the unit from excessive polymer buildup. For example, should the
From automobiles to food containers, many of the products
plant lose power, it may also lose the ability to pump hot process
that people utilize daily share a common petrochemical
stream out of the distillation towers and to inject additional inhibitor
building blockstyrene. This ubiquitous molecule, which
or retarder. The extended residence time at elevated temperatures
is most commonly produced in a catalytic process starting
can cause excessive polymer buildup if not properly controlled, and
from ethylene and benzene, must be purified in a series
in severe cases, a solid block of polymer filling the distillation tower
of distillation towers to yield high-quality, polymer-grade
can result. An inhibitor may be quickly consumed, without any means
styrene monomer. However, at the elevated temperatures
available to replenish it. Due to its slower reaction rate, a retarder will
encountered in these towers, styrene may undergo a self-
remain effective longer for prolonged protection. The ratio between
initiating polymerization reaction, which negatively impacts the
inhibitor and retarder should be carefully considered to provide
efficiency of the process and the yield of monomer produced.
optimal cost performance during normal operation, while ensuring
safety during a shutdown.
An Integrated Approach to Polymer Control
Two types of chemistries are commonly used to prevent Rewards Carry Risks
styrene polymerization. The first, a class of slow-reacting
While DNBP is a reliable and cost-effective retarder, it is also highly
nitrophenolic compounds known as retarders, slow the
toxic and requires stringent handling procedures to minimize exposure
inherent polymerization rate of untreated styrene. The most
risks. In addition, residual DNBP typically exits the styrene unit with
common retarder is 2,4-dinitro-6-sec-butylphenol, or DNBP.
heavy tars, and while the tar stream can be used as a fuel source, the
The other type consists of a group of compounds called true
presence of DNBP presents NOx emissions concerns.
inhibitors, which are proprietary, fast-acting formulations that
more effectively lower the styrene polymerization rate but are These risks have led many countries to regulate DNBP usage in
consumed much faster than a typical retarder. As Fig.1 shows, recent years. In 2009, Thailand became the first country to place an
once the inhibitor is consumed, polymerization resumes at the outright ban on the use of DNBP. This increased regulation, coupled
rate of an untreated system. with internal company mandates to improve safety practices, have
motivated solutions providers to develop so-called green retarders
(GRs)more environmentally sustainable alternatives to the highly
effective, though highly toxic, retarders used today.
UNTREATED
Rate of Polymer Formation

INHIBITED
Two main criteria must be followed when developing a GR: it must
be less toxic than DNBP, and it should have similar polymerization
control properties (i.e. reaction rate). Cost is also a key factor in the
adaptation of GR technology. While the GR concept has existed for
RETARDED some time, the costs of such products have been prohibitively high
until recently. Nalco Prism GR technology was developed specifically
to meet these criteria. As Table 1 shows, Prism GR not only exhibits
lower toxicity than DNBP, but it also has lower water solubility, a
desirable property that reduces the risk of contaminating the water
Time
system in the event of accidental release. It also has a negligible
potential to generate NOx.
Fig. 1 Comparison of Relative Reaction Rates for Retarders,
True Inhibitors, and an Untreated System The GR demonstrates comparable polymer control to DNBP, and
provides protection during an emergency shutdown, as laboratory
test results indicate (Fig. 2). In addition, manufacturing process
Styrene polymerization is optimally controlled through a
improvements have made Prism GR technology cost competitive
combined use of an inhibitor and retarder, which ensures
with DNBP.
polymer control during both normal operations and emergency

CUTTING EDGE 11
Table 1. Comparison of DNBP and Prism GR

Acute Toxicity Oral Water Solubility NO x Potential


LD 50 (mg/kg) (mg/L) (kg/T )

DNBP 27 52 250

PRISM GR > 5000 0.02 Negligible

Assessing Risks
To prevent catastrophic events and polymer solidification during an emergency shutdown, many plants have emergency
shutdown response procedures in place. These procedures commonly include gravity feeding cold ethylbenzene to dilute and
cool the tower contents, and using generator-powered pumps to remove the tower contents or to add supplemental chemical
additives. One can often estimate the time required to carry out these procedures to the point where the tower is considered
safe from polymer buildup. This time varies widely from plant to plant due to differences in emergency response mechanisms,
specific column design, and operating conditions.

Ideally, the protection time offered by a


0.8
treatment program (retarder + inhibitor) should be
PRISM Green Retarder
greater than the time required to implement the
DNBP
% Polymer at Steady State

emergency procedures. Nalco has developed several 0.6


proprietary methodologies to determine the protection
time afforded by a given polymer control program. These
methods examine a styrene plants design, its specific 0.4
operating conditions, and the inhibitor and retarder
dosages. An experimentally determined rate of polymer
accumulation can then be determined so that the right 0.2

response plan can be formulated.


For example, the desired protection time for one plant
was defined as the time elapsed after emergency 0.0 85/1 hr 85/4 hr 110/1 hr 110/2 hr 120/1 hr
150 ppm 150 ppm 120 ppm 240 ppm 500 ppm
shutdown until the polymer concentration became
so high that the process stream was too viscous to Fig. 2
pump. To determine the polymer level at which the
viscosity becomes excessively high, Nalco scientists A Comprehensive Styrene Strategy
conducted a series of viscosity measurements using
Styrene producers are facing increasingly stringent environmental
styrene monomer containing various levels of polymer.
regulations and operating cost pressures. As such, they need to
These tests demonstrated that above a 20% polymer
implement processes that will keep their plants running at the highest
content in the tower, the fluid viscosity significantly
levels of safety and efficiency. Our field-proven Prism GR technology,
increases to the point that the pump gets dangerously
coupled with comprehensive methodologies to assess polymerization
close to its operational limit. This polymer content was
risks during emergency shutdowns, provides a solution that offers lower
therefore used as the upper limit for the risk assessment
toxicity and comparable performance to DNBP during operations both
experiments.
routine and non-routine.

CUTTING EDGE 12
Cleaning to the Core
Many of todays oilfields have been producing oil and gas for Another side effect of fouling is the increased potential
years, and as they mature, they face an unavoidable fate: water for corrosion in injection tubing, pipelines and production
breakthrough. The onset of water production brings increasingly equipment, leading to high replacement and maintenance costs.
complex and costly disposal challenges to an operator. The most Compounding the challenges further is the tendency for these
popular method for disposing of produced water onshore has been oily deposits to act as a breeding ground for common oilfield
reinjection into the formation or into disposal wells. The injection bacteria, leading to microbiologically influenced corrosion (MIC).
of produced water has always posed issues for producers, chief Whether this buildup takes weeks or many months to occur, the
among them being increased restriction of the wells due to the inevitable outcome is the same: increased incidence of leaks,
buildup of both organic and inorganic deposits. These deposits higher operating costs and decreased production revenue.
may form on filters, in trunk lines (Fig. 1), in downhole tubing, Typical composition of these deposits can be seen below (Fig. 2),
or at the sand-face around an injector, limiting the amount of although the composition may vary significantly from field to field.
water that can be re-injected into the formation. This bottleneck
Other
in the process can lead to reduced production, a problem that Sulfur 3%
is only compounded if the water is also being used for pressure 9%
maintenance in the reservoir.
Biomass
10%

Hydrocarbon
Sand 40%
10%

Iron
14%
Fig. 1 Heavy
Asphalt
foulant build up in
14%
a produced water
injection pipeline Fig. 2 Typical oilfield deposit composition from produced water systems

CUTTING EDGE 13
.18.

In response to these challenges, Nalco corrosion .16. WI Well 1


WI Well 2
scientists developed Clean n Cor EC1509A, a .14.

INJECTIVIT Y BPD/PSI
new patented technology for cleaning heavily .12

fouled systems that imparts superior corrosion .10

control at the same time. Clean n Cor technology .08

is formulated with inhibitor chemistries with .06

superior interfacial properties which work to .04

remove the oily deposits from the metal surface, .02


Faulty water flow meter Flow meter problems resolved
and then lay down a corrosion inhibitor film .00
(treat rate 1/3 of target) Clean n Cor EC1509A injected at 100 ppm

resulting in a clean and protected pipe that 8/30 9/6 9/13 9/20 9/27
DATE
10/4 10/11 10/18 10/25

provides maximum throughput. Conventional


corrosion inhibitor technologies simply adsorb to Fig. 4 Impact of the Clean n Cor technology on water injectivity
the deposits thereby allowing the underlying pipe
surface to continue to corrode unabated.
Impact on water injectivity
Clean n Cor technology has been successfully
During this field evaluation, the injection rate for water injection well 1 began to
applied in the field many times. In one such
increase immediately upon the application of Clean n Cor EC1509A with a 75%
application, corrosion probes were placed both
increase in injectivity over the two-month evaluation. For water injection well 2,
upstream and downstream of the chemical
however, the injectivity continued to decrease even with the application of the
injection point, and injection pressures and water
chemical. Upon investigation, this was traced to a faulty flow meter resulting in a
injection rates were also monitored. Two weeks
70% undertreat in target chemical injection. Once this was identified, the chemical
into the test, both probes were removed from the
was injected at 100 ppm and the injectivity increased in a similar fashion to the
system for visual inspection (Fig. 3).
first injector.
Untreated Clean n Cor Technology This significant increase in injectivity also resulted in a corresponding increase in
oil production for the asset. Once the system was clean and corrosion was under
control, the chemical injection rates were reduced to maintenance levels.
Clean n Cor technology was developed originally to treat those systems where
hydrocarbon deposits were the primary cause of fouling. And while oily deposits
are often the culprit, sometimes they are only part of the problem, as the
hydrocarbon can serve as a glue that entrains solids on the internal surfaces of
the infrastructure. In instances where the deposit contains significant quantities
of iron sulfide bound together with hydrocarbon, a new technology was specifically
developedClean n Cor XFe, EC1538A. This product contains the same fouling
and corrosion prevention components as the original chemistry, but it is also
formulated with a chemistry specifically designed to dissolve iron sulfide and
prevent further deposition.
Furthermore, in instances where significant quantities of paraffin and asphaltenes
Fig. 3 Photographs of untreated (left) and treated are present in a deposit, Clean n Cor XP EC1539A may be a preferred treatment
(right) probes option. This new product contains a specific paraffin and asphaltene dispersant
formulated with the original Clean n Cor chemistry.
While the probe upstream of the chemical
injection already showed signs of foulant build-up, Clearly, it is critical to have a good understanding of the composition of
the probe exposed to Clean n Cor technology the problematic deposit before a cost-effective mitigation program can be
was still clean and free of any deposit and, upon recommended. The Nalco Analytical Technologies Group provides this as part of a
adequately cleaning the system, EC1509A offered comprehensive analytical service offered to our customers. (See associated article
95% corrosion protection. in this publication).
It is evident that in order to meet the worlds growing demand for energy, operators
are expected to maximize production from aging assets, some of which are
operating well beyond their original design life. Our suite of Clean n Cor products is
the latest in a line of asset integrity tools that help ensure injection systems remain
clean and corrosion-free thereby maximizing production and minimizing the risk of
failure throughout the lifecycle of the asset.

CUTTING EDGE 14
COVER STORY

finding a However, the extremely tight porosity of shale

balance
formations means that some form of stimulation is
required to extract the gas entrapped in the rock. The
most commonly used stimulation methodslickwater
fracturingis a hydraulic fracturing technique in which a
water-based fluid is injected down a well and out into the
shale formation at intense rates and pressures, causing
the formation rock to fracture and opening up channels
between essential resources for gas to flow to the wellbore. Slickwater fracture (frac)
jobs use an aqueous-based fluid containing a polymeric
friction reducer that allows for faster pumping of the fluid
into the formation, and a granular propping agentor
The incredible expansion of shale gas developments in North proppantsuch as sand that is carried into the
America has brought with it an expanded demand for water. formation and serves to hold the fractures open once the
Nalco stimulation technologies ensure that water management is treatment is complete.

sustainable, both environmentally and economically. Technological advances in friction reducers and
proppants have made hydraulic fracturing an increasingly
Natural gas plays a key role in meeting the worlds burgeoning energy reliable and trusted stimulation technique for shale
demands, and its a role that is only expected to increase. In North America gas, but a major challenge remains: water. Each stage
alone, discoveries in the last six years have uncovered vast reserves of of a slickwater fracturing treatment requires tens of
natural gas in tight shale formations. These reserves are estimated at more thousands of barrels of fracturing fluid, 90 to 99% of
than two quadrillion cubic feet of natural gasa 200-year supply providing which is water. Furthermore, each slickwater treatment
more energy than Saudi Arabias 200 billion barrels of oil reserves. generates a great deal of wastewater, much of which
is the fracturing fluid that flows back out of the well
These discoveries have coincided with a rising demand for clean and efficient post-stimulation. This flowback water, combined with the
energy sources, making natural gas production from tight shale formations production brine or produced water coming out of the
an increasingly attractive enterprise. reservoir on a long-term basis, creates a serious water
management challengeone which Nalco is devoting a
great deal of time and resources to solve.

CUTTING EDGE 15
Shale Gas Plays, United States Lower 48 & Canada
BASINS SHALE GAS
PLAYS
STACKED PLAYS
Shallowest/Youngest

Deepest/Oldest

Nalco Adomite has worked with our Well Service Company partners in all shale plays shown above
to implement successful fracturing treatments through the use of our diverse product line.

The Produced Water Challenge Produced Water: Problem or Opportunity?


Compared to fresh water, produced and flowback water contain elevated The reuse of produced water may be desirable from a cost-savings
levels of dissolved solids which present processing and disposal perspective, but it introduces another potential problemwill the
problems. U.S. state agencies responsible for minerals management will fracturing chemical additives be compatible with the high-TDS produced
not allow water containing greater than 10,000 ppm TDS (Total Dissolved water? Of particular concern is the potential for elevated mineral ion
Solids) to be discharged into waterways, meaning that water from shale levels to inhibit the performance of the friction reducer, the key chemical
gas plays has three possible fates. 1) It can be purified using various component of the fracturing fluid. The quality and composition of produced
treatment methods, many of which may not be easy or cost-effective to water can vary widely, both across North America as well as individual
administer. 2) It can be re-injected into underground disposal wells, a shale plays. As a result, a friction reducer that is effective in brines with
relatively direct approach in western states but more challenging in the high concentrations of sodium and potassium may not function well in
eastern U.S., where access to suitable disposal wells is extremely limited. hard water (which contains high levels of divalent cations).
3) It can be recycled and reused in subsequent fracturing treatments. The Nalco Adomite Research Group has brought its expertise in water and
polymers to bear on this compatibility concern. The result is an evolution
Of the three, reuse is often the most cost-effective and convenient.
in friction reducer technology over the past decade to include products
Reusing produced water saves money, by reducing both disposal costs
that are effective in high TDS waters. The Adomite Group has developed
and the need to obtain water for the fracturing treatment. Fracturing one
an evaluation protocol using a friction loop to identify the most effective
shale gas well can consume over 3 million gallons of water, and in the
friction reducer for each water situation. For instance, Figure 1 illustrates
northeastern United States alone, 25 to 30 wells are fractured every day.
the friction reduction performance in the friction loop, over time, for seven
With this immense and growing need for water, produced water is quickly
different products in produced water from the Woodford shale.
becoming an essential resource.

CUTTING EDGE 16
80 80
ASPFFR900 ASPFFR900
70 70
% Friction Reduction

% Friction Reduction
60 60

FR-B FR-C
50 50
FR-C
40 40
FR-D FR-E
30 30

20 20
FR-F
FR-E
10
FR-F
10
FR-G FR-G
FR-B
0 0 FR-D
0 1 2 3 4 5 0 1 2 3 4 5
Time (min) Time (min)
Fig 1. Friction reducer performance in produced water from the Woodford shale Fig 2. Friction reducer performance in synthetic Marcellus produced water
(9.9% NaCl, 1.8% CaCl 2 , 0.4% MgCl 2 , 0.1% KCl, 0.08% SrCl 2 ) (10.6% NaCl, 3.4% CCl, 2.9% CaCl 2 , 0.03% FeSO , ); Friction reducer
Friction reducer concentration = 0.033% concentration = 0.033%

Figure 2 shows the performance of the same seven products in produced Nalco has established a set of comprehensive standards in which a
water from the Marcellus shale. These results demonstrate the need for chemical cannot contain:
careful screening to find an optimal solution. For example, while product
Any BTEX, carcinogens, teratogens, reproductive toxins
FR-B provides reasonably high friction reduction in less than 1 minute
in Woodford produced water, it provides very little friction reduction in Any priority pollutants (U.S. EPA List 40, CFR) or U.S. EPA Safe
Marcellus produced water. Drinking Water Act contaminants
Chemicals that would be considered persistent, bioaccumulating,
Evaluating various friction reducers under a range of water conditions
or toxic by North Sea standards
to find the ideal solution for each field is just one way to improve
the cost-effectiveness of an operators shale assets. Another way is From this set of standards has come an award-winning dispersion
developing improved chemistries that comply with new and more rigorous chemistry known as ULTIMER, a technology that eliminates the
environmental regulations while also maintaining high performance, even hydrocarbons and surfactants required in standard latex polymer
in the harshest of fracturing waters. chemistry, thus providing environmental sustainability gains. Winner
of the U.S. Presidential Green Chemistry Challenge Award, Ultimer is
Meeting the Challenge, Reaping Rewards a strictly water-based chemistry that yields more soluble dispersion
As shale gas fracturing activities keep expanding, water demands products. These products exhibit greatly improved performance relative
will keep rising. Meeting this demand while adhering to tighter water to standard latexes, particularly in heavier brines and marginal waters
usage and disposal regulations can be done, but only with a smart and with high hardness levels. In addition, they are highly effective in cold-
sustainable water management strategy that includes produced water. water conditions, where other polymers struggle.
The Nalco Adomite Research Group will keep developing more robust
and versatile fracturing chemistries that will work in any water system, One of the most recent additions to the Ultimer product line is also one
ensuring that operators maintain sufficient water supplies to complete of the most environmentally benign. ASPFFR900 hydrocarbon-free
their frac jobs and feed North Americas growing appetite for gas. dispersion polymer meets Nalco standards criteria and exhibits very low
ecotoxicity under North Sea test protocols, as the table below shows. In
Ultimer ASP FFR900: Environmentally addition, the polymer has exceptional friction reduction performance in
Friendly Slickwater Fracturing waters of even the poorest quality.
Hydraulic fracturing has historically taken place in remote areas of North
America, but no longer. As activity picks up in the Marcellus shale ASP FFR900 North Sea Ecotox Data
(spanning five states in the northeastern U.S., including Pennsylvania
Test Desired Value (s) Result Conclusion
and New York), fracturing treatments are now being carried out in more
28 Day >20% >20% Inherently
populated areas and are being met with increasing public scrutiny. As Biodegradable Biodegradable
the industry becomes more regulated, it will need more environmentally
Log P < 3.0 -0.9 Non-bioaccumulating
compliant chemicals.
EC50 (72 hr) > 10 mg/ml 166 mg/ml Generally non-toxic
Skeletonema
costatum

CUTTING EDGE 17
NEWS AND UPDATES
Nalco launches new India Technology Center
In August, Nalco opened its new, state of the art Technology Center in Pune,
India. This 38,000 square foot facility will be a primary support center for
the Energy Services business. The facility will eventually employ more than
100 chemists and engineers of which approximately three quarters will have
advanced degrees. The facility will focus on providing technical support to our
customers throughout the Eastern hemisphere. It will subsequently transform into
another Center of Innovation for Energy to complement our other global facilities.
The facility also includes an advanced analytical technologies laboratory that will
provide diagnostic services to a wide range of customers.

R&D social networking


Knowledge is truly a corporations differentiator, however, communication often
limits the ultimate success that can be achieved. Nalco brings the strength
of over 600 R&D experts worldwide to bear on solving customers technical
challenges in a diverse range of industries and geographies. In order to leverage
this intellectual capital, Nalco recently launched a web-based R&D portal that
leverages the power of social networks. Through this portal, researchers can
readily identify individuals with specific skill sets and capabilities, share technical
information and solicit the community for answers to technical challenges. The
R&D portal truly enhances speed to market for new technologies and facilitates
the development of superior solutions to technical challenges through the
provision of a central connectivity hub. It provides the forum for our distributed
global research team to Connect, Collaborate & Innovate.

Nalco partners with NASA on Tecfusion event


Traditional scientific training can often lead to a linear, siloed approach to
innovation that does not lend itself well to the fast-paced development needs
of the energy industry. Some of the best ideas for new technologies come from
being exposed to areas outside of a persons direct field of operation. In order to
fuel creativity and drive innovation, Nalco recently partnered with NASA (National
Aeronautics and Space Administration) and Penn State University through the
Tecfusion program. This program was set up to leverage technologies that were
originally developed for the space program and are now being brought to market
by small start-up corporations. Specific technology areas that are of interest
to Nalco were identified, and the extensive database of NASA technologies
was then searched for potential matches. Based upon the results, various
technologies were reviewed by the Nalco innovations team and invitations were
subsequently extended to companies of most interest. A day-long Tecfusion
Summit hosted by Nalco, brought together representatives from these companies
and Nalco researchers to investigate the potential for these new technologies.
The first Tecfusion event was held in Naperville, IL in 2010 and, a second
energy-specific Tecfusion summit was held in Sugar Land, TX in January.

CUTTING EDGE 18
Publications & Industry Presentations

UPSTREAM DOWNSTREAM
Achieving Sustainable, Optimal SAGD Operations by Observations from Heavy Residue Pyrolysis: A Novel
Erick Acosta was published in the Journal of Petroleum Method To Characterize Fouling Potential and Assess
Technology, 2010, 62(11), 24-28. Antifoulant Additive Performance was published by Chris
Russell, Ron Sharpe and Simon Crozier in the September
Optimization of a Microbial Control Program to Minimize 2010 issue of Energy & Fuels 24, 5483-5492.
the Risk of Microbiologically Influenced Corrosion by Vic
Keasler and Brian Bennett was published in the September Analytical Characterization of Sediment Formed in Soy
2010 issue of Oil and Gas EURASIA. Oil-Based B20 Biodiesel by Timothy P. McGinnis and Kim
B. Peyton was published in the September 2010 issue of the
Analysis of Bacterial Kill Versus Corrosion from use of Journal of ASTM International, Vol. 7, No. 8.
Common Oilfield Biocides by Vic Keasler, Brian Bennett
and H. McGinley was published in the proceedings of the Mitigate Corrosion in Your Crude Unit by Nigel P. Hilton
8th International Pipeline Conference paper # IPC2010- was published in the September 2010 issue of Hydrocarbon
31593, 2010. Processing, Vol. 89, No. 9.

Analysis and Identification of Biomarkers and Origin Opportunities, Problems, and Solutions a paper focusing
of Color in a Bright Blue Crude Oil by Priyanka Juyal, on the desalting of heavy and high solids crudes, by Brad
Andrew Yen, Stephan J. Allenson , Amy M. McKenna, Ryan Mason and Sam Lordo was published in the March 2010
P. Rodgers, Christopher M. Reddy, Robert K. Nelson, A. issue of Hydrocarbon Engineering Vol. 15, No. 3., 48-57.
Ballard Andrews, Esha Atolia, Oliver C. Mullins, and Alan G.
Marshall (a joint publication with Florida State University, Quench Oil Fouling and Viscosity Control in Primary
Woods Hole Oceanographic Institution and Schlumberger), Fractionators by Maria Beata Manek, Meha Shah, and
was presented at Petrophase 2010 and was published in Daniel Frye was presented at the March 2010, 13th Annual
Energy & Fuels 2011, 25, 172-182. ARTC (Singapore).

Study of Live Oil Wax Precipitation with High Pressure Fortis Metal and Popcorn Passivation of Butadiene
Micro-DSC by Priyanka Juyal, Tran Cao, David Fouchard, Units: An Environmentally Friendly Alternative by Jessica
Andrew Yen and Rama Venkatesan (a joint publication with Hancock, Maria B. Manek, Robert Presenti, Lisheng Xu
Chevron), was presented at Petrophase 2010 and was also was presented at the September 2010, BASF Licensee
accepted for publication in Energy & Fuels. Experience Exchange Meeting (Vienna, Austria).

Flow Assurance in the Ultradeep/Deep Water Regime Process Gas Compressor Fouling & Washing Mitigation:
was given by Stephen Allenson as the keynote address in A Better Understanding of Fouling Phenomenon &
the Flow Assurance section of Petrophase 2010. Compressor Design Techniques was presented by Satoshi
Hata, Junichi Horiba, and Sheri R. Snider (joint presentation
A poster entitled Development and Application of a Scale with Mitsubishi Japan) at the March 2010, AIChE Spring
Inhibitor for Electrical Submersible Pumps Suitable for Meeting and 6th Global Congress on Process Safety.
Very Cold Weather by Kevin Spicka and Sandra Linares-
Samaniego was exhibited at the 2010 SPE Moscow Oil &
Gas conference.

CUTTING EDGE 19
Nalco Companys Energy Services
Want to work. . .
Division has outstanding opportunities
for excellent scientists in all areas of
the oil and gas industry. From the
perforations to the gasoline pumps,
Nalcos team of scientists provide In a dynamicenvironment,
cutting edge, cost-effective solutions to grapplingwith some of the
critical real-world problems. Whether most critical research and
its helping to maximize oil and gas
technologicalchallenges
production in a declining asset,
ensuring the safe and reliable
facing our worldtoday?
production from extreme environments
like ultra-deepwater, or minimizing Alongsideworld-class
energy consumption during refining scientists, renownedglobally
operations, Nalco has a team of highly
for their technicalexpertise?
trained scientists driving innovation in
this technically demanding field.
For a companycommittedto
Our global R&D Center is located in makinga differencein the lives
the beautiful city of Sugar Land, just of the worlds population?
outside of Houston, Texas. Our new R&D
Center serving the eastern hemisphere
is located in Pune, India. We have
excellent opportunities at both locations
for outstanding, innovative scientists,
preferably with a PhD in a technical
discipline. Prior exposure to the oil
industry is preferable but not a
prerequisite. Strong communication
skills, a willingness to travel, and a
creative, positive attitude are essential.
Nalco Company offers a competitive
salary and an exceptional
benefits package.

Please visitwww.nalco.com to review current opportunities


NALCO COMPANY
Energy Services Division:7705 Highway90-A SugarLand,Texas 77478 USA
Europe: Ir.G.Tjalmaweg1 2342 BV Oegstgeest The Netherlands
Latin America: Av. das NaesUnidas17.891 6 Andar04795-100 So Paulo SP Brazil
Essential Expertise Asia Pacific: 2 International
BusinessPark #02-20 The StrategyTower2 Singapore609930
for Water, Energy and Air SM
India: KumarPlanetIT MagarpattaCity Road Hadapsar Pune India411028

We rely on the diversity of our workforce to drive our growth and success. Our competitive salaries and benefits,
as well as unlimited opportunities for professional growth and development, make Nalco a great place to work. EOE

RESOLVE, PRISM, Clean n Cor, ULTIMER, ASP, Fortis, Nalco, the logo and the tagline are trademarks
of Nalco Company. 2011 Nalco Company All Rights Reserved. 02/11
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