for Water, Energy and Air

SM

An Ecolab Company

ESSENTIAL INNOVATION FOR THE PETROLEUM INDUSTRY

VOLUME

04

View
n
o
i
s
o
r
r
o
C Window
Real-Time

into the

Super heroes and

Polymer have in Common?

What do

Lightening the Load:

Emulsification Enhancements Boost
Heavy Oil Production

LETTER FROM EDITOR

One of my favorite quotes that
epitomizes the struggle that so many
companies have in coming up with
the next Big Thing is from James
Bertrand once we rid ourselves
of traditional thinking we can get
on with creating the future. This
is exactly why so many companies struggle to meet their full
potential. They are driven by safe incrementalism that is the
product of thinking within the perceived confines of the problem.
They are not able to free themselves from the constraints of
conventional thinking and challenge the status quo to get to the
right answer, not simply the easy answer. Being able to rise above
the trees, and navigate a path out of the forest is what distinguishes
the leader from the follower.
The most innovative people have an incredible ability to draw upon their
diverse backgrounds and experiences and connect the dots between
challenge and potential solution. They see the connection between
apparently disparate fields and mine the intersections for sources
of innovation stimulus. The most successful companies provide the
infrastructure to enable this process to go on as an inherent part of their
innovation culture. This is the fundamental approach that Nalco has
taken to drive innovation. This has enabled the launch of a suite of truly
game-changing technologies in addition to delivering on some of the more
conventional, incremental improvements.
In this issue of Cutting Edge, we take a closer look at how Nalco is
significantly expanding its global R&D footprint in order to drive innovation.
At its core, this expansion is focused on leveraging the deep-set culture of
innovation that exists within Nalco across the new R&D centers globally to
enable the development of the next Big Thing. The recent merger with
Ecolab has also created a fertile portfolio of technologies and capabilities in
which to mine for the solutions to the major challenges facing our industry
today and tomorrow.
The new 3D TRASAR Technology for Crude Overhead systems is an
example of a real game-changing technology. This patented innovation
enables the real-time measurement and control of corrosion in an
overhead system. It is well-known that typically 90% of all corrosion
damage occurs in only 10% of the time. This breakthrough technology
allows a real-time view into the corrosion window allowing for a proactive
and reliable approach to corrosion mitigation.
Similarly, during the manufacture of butadiene, catastrophic failures
can occur due to the rapid and uncontrolled formation of so-called
popcorn polymer. This effect can lead to a dramatic breach of

CUTTING EDGE 2

the integrity of a system with environmental, safety and loss of

production consequences. Traditional methods of control have limited
effectiveness and typically have unfavorable environmental profiles.
The new Nalco FORTIS passivation program offers significant
performance enhancements over current programs and minimal
environmental impact.
Heavy oil production continues to make up an increasing portion of the
global crude production slate. Due to the heavy and viscous nature
of this crude, traditional production methods cannot be used, and in
many cases, heat or diluents are needed to enable production. This
significantly increases lifting costs and in the case of solvent use, can
bring associated health, safety and environmental considerations.
Nalcos patented Biphasic Viscosity Reducer Technology was
developed specifically to address these challenges. Using only water
as the diluent, the technology enables the production of a meta-stable
oil-in-water emulsion that exhibits a fraction of the viscosity of the
crude and is readily broken when the emulsion reaches the separation
train. This new technology is fast attracting the attention of many
global heavy oil producers.
One of the major flow assurance challenges encountered during
production operations is that of mineral scale formation. This can
often build up rapidly either down-hole, in production tubing or on
the topside resulting in production decreases and in some cases,
corrosion and emulsion challenges. In many cases, monitoring
scale inhibitor residuals does not paint a complete picture of what is
actually occurring in the system. Nalco has recently pioneered the
use of Electron Microscopy coupled with Electron Dispersive X-Ray
Spectroscopy to truly probe what is actually happening in the system
and assess the level of protection afforded by a scale control program.
This is changing the way the industry thinks about scaling and
subsequent mitigation strategies.
Delivering on our innovation promise is critical to the success of our
customers operations and to Nalco. We are committed to focusing
our resources on the right high-impact targets that provide the
industry with differentiated, step-change technologies that enable the
responsible and sustainable development of natural resources. Being
able to rise about the trees and navigate a path to the next Big Thing
is our passion and it is this that drives us to remain the leader in this
competitive market place.
David Horsup, Ph.D.

Vice President, Research

Energy Services

COVER STORY
A REAL-TIME VIEW
INTO THE CORROSION WINDOW
In refinery processing, the corrosion window refers to the
relatively brief period of time in which an upset to normal operation
causes rapid corrosion in the overhead condensing system of a
crude atmospheric distillation unit. The corrosion window typically
follows the empirical observation that 90% of crude-unit overhead
corrosion occurs during only 10% of operating time.

15
FEATURE STORIES

LIGHTENING THE LOAD:

EMULSIFICATION ENHANCEMENTS
BOOST HEAVY OIL PRODUCTION

SCALING NEW HEIGHTS: HIGH TECH

MONITORING SOLUTIONS FOR
BETTER SCALE MANAGEMENT

A commonly held opinion in the

oil and gas industry is that the
era of easy oil is over....

The presence of water in an oil

field brings with it the potential
for mineral scale formation.
Scale deposition from
many mineral sources...

WHAT DO SUPERHEROES AND

POLYMER HAVE IN COMMON?

GROWING THE INNOVATION

FOOTPRINT

Its not only Superman that

can bend steel, polymer can
too! What real harm can
polymerization...

As our thirst for hydrocarbon

based products grows, new
technology plays a critical
role in enabling the continued
production of...

10

13

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

DIAGNOSTIC SOLUTIONS
The Nalco global team of trained analytical scientists in the Diagnostic Solutions Group provides advanced problem
solving and consulting to the petroleum industry.

18
CUTTING EDGE 3

THE

Lightening LOAD
Emulsification Enhancements Boost Heavy Oil Production
A commonly held opinion in the oil and gas industry is that

During conventional production of heavy oil, the high

the era of easy oil is over. Light to mid-grade oil reserves,

viscosity of the crude creates a large pressure drop across

which tend to be easier to produce and process, are being

the system, from the base of the production tubing through

replaced by a growing share of unconventional sources

the upstream flowlines and into the separation facility. The

including heavy oil and bitumen. Heavy oil currently

end result? Loss of production over the lifetime of the

accounts for nearly 70% of global crude oil reserves , a

reservoir, greater equipment wear, increased intervention

proportion that is expected to increase to satisfy global

rates and higher production costs. Because heavy oils

energy demand. In response to heavy oils growing influence

higher viscosity is at the root of these production challenges,

in the energy marketplace, operators continue to look for

recovery enhancements have historically focused on viscosity

more efficient production methods.

reduction through costly and often labor-intensive processes.

CUTTING EDGE 4

Diluent injection represents a slightly more conventional approach

to improving heavy oil production. Utilizing between five to twentyfive percent diluent based on the volume of produced oil, this
method requires a relatively small capital investment for field-wide
implementation. Although the diluent is partially recovered and
recycled at downstream processing facilities, costs for continuous
operation can be significant, as are the HS&E concerns around
transportation, storage and handling of a highly flammable solvent.
Current production limitations have created opportunities for new
innovation, particularly for technologies that require limited up-front
capital expenditure and minimal modification to existing production
facilities. The Biphasic Viscosity Reducer technology, or B-VR, is
one such innovation that fills the technology gap by inducing the
formation of a readily transported heavy oil-in-water emulsion using
conventional production. The chemically induced emulsion does
not require additional heat or diluent, is highly flow-able and stable
under production conditions. Unlike conventional emulsion treatment
programs, it will rapidly break to yield dry oil.

A Two Phase Solution

The patented B-VR technology utilizes proprietary chemistry in
conjunction with produced water as a carrier solvent to invert the
production stream from an oil-external to water-external system.
The viscosity of produced fluids is significantly decreased, facilitating
fluid transport throughout the system and eliminating many of the
production challenges associated with heavy oil. (Figure 1).
Enhancing production through chemical emulsification is a concept
that has been utilized historically. However, the excessive stability
of the emulsion produced has created adverse secondary effects.
Previously, chemical emulsification technologies were selected only
with emulsion stability in mind. To that end, chemical additives were
selected that would significantly lower the interfacial tension between
oil and water, producing very small oil droplets that were not easily
separated from the water at the end of the transport process. This
can lead to significant separation problems where the goal is to provide
dehydrated oil with typically less than one percent water for sale.

B-VR +
Mixing
Energy

High viscosity, oil

external emulsion

Low viscosity, water

external emulsion

Fig. 1 A microscopic view

In a critical break from older chemical methodologies, the B-VR technology
controls emulsion droplet size in such a way as to prevent the formation
of extremely stable emulsions. Mixtures of oil and water stabilized by the
B-VR chemical used in the field yielded an average oil droplet diameter
of 213 m; by comparison, historical surfactant methodologies produce
droplets with an average diameter of 8-15 m (Figure 2). While both
emulsions are highly flowable, the B-VR emulsion is roughly 200 times
more breakable, which is attributed to the droplet size difference alone.
The improved performance is demonstrated in the production system by
an emulsion that remains stable under flowing conditions, but is breakable
using standard separation equipment and traditional chemical demulsifiers.
Effective viscosity reduction with the B-VR technology requires a minimum
threshold volume of free water (which excludes any water encapsulated
inside the heavy oil) to allow heavy oil droplets to form. A thorough
evaluation of various oil/water systems has shown that while significant
viscosity reduction could be obtained with less than 15% free water,
optimal reduction typically occurs between 20-40% water cut. Because
factors such as oil density, viscosity, temperature, water cut and salinity
vary greatly from location to location, the volume of water needed for a
flowable emulsion must be evaluated on a case-by-case basis.
In the field, B-VR-induced oil-in-water emulsions are formed by simply
injecting chemical and water into flowing systems, either downhole or at a
topside manifold. The combined action of the chemical and mixing energy

16

EXP 3
(Mean = 213 microns)

14
Counts/sec (Sqr Wt)

For example, in situations where the oil is too viscous to flow in

the reservoir, thermal recovery techniques such as steam-assisted
gravity drainage (SAGD) and cyclic steam stimulation (CSS) have
been used to heat and decrease the viscosity of the heavy oil to
promote flow into the producing well. While both SAGD and CSS
are incredibly efficient in terms of percent oil recovery, both require
significant up-front capital investment and have come under intense
scrutiny for the impact that their significant energy consumption and
waste stream generation have on the environment.

12
10
8
6
4
EXP 4
(Mean = 221 microns)

2
0

Chord Length (Microns)

1

10

100

1000

Fig. 2 Droplet size distribution for emulsions made with two B-VR products

CUTTING EDGE 5

(typically provided by the downhole pump) shears the oil into droplets that are suspended in the injected water, which acts as a carrier
solvent for the droplets and isolates the oil from the pipe wall to reduce the drag effects of viscous fluids.

An Efficiency Boost
The B-VR technology platforms operational value was evident in recent field trials in South America, where an 8 API gravity crude required
naphtha to be injected as a diluent at a dosage of 35% by volume to facilitate production. A treatment consisting of 600 ppm of B-VR
chemical and 25% by total volume of produced water was injected down the backside of the well and mixed with the heavy crude by an
electric submersible pump (ESP) to form the water external emulsion.
As a result of this treatment, naphtha injection at the wellhead was cut from an average of 503 to 12 bpda reduction of nearly 98
percentwhile production rates and system pressures remained relatively unchanged. Field operators determined that naphtha injection
at the wellhead could be eliminated completely, but separation efficiency in the plant suffered slightly (Figure 3). Previous attempts to
eliminate diluent during production resulted in a substantial increase in system pressure, ultimately shutting in the well (Figure 4).

160

600

140

Napthta Injection (bbl/day)

500

120
400

100
80 PSI

300

60

200

40

Wellhead Injection Rate

100

20

Wellhead Pressure

10

12

14

16

Day

Fig. 3. Tracking naphtha injection and wellhead pressure during

B-VR injection

Pressure (PSI)
Diluent Injection Volume (bbl/day)

700
600
500
400
300
200
100
0

Normal Production
With Diluent

B-VR Treatment Program Unassisted Production

Fig. 4. Average pressures at the SW-4 wellhead based on production method

CUTTING EDGE 6

Field Study of Heavy Oil Viscosity Reduction

for Production Transport. John Pinto, Giovanni
Annichiaricco, Marcus Faust Jr., Magda Montanez,
Ramon Parra, Thomas Weathers Jr., 2011 World
Heavy Oil Congress.
Biphasic Viscosity Reducers as Production Aids for
Viscous Oils. Marcus Faust Jr., Thomas Weathers Jr.,
2011 SPE International Symposium on Oilfield Chemicals.

1000
800

Ultimately, the B-VR technology was successfully

deployed with minimal capital investment and minor
modification to system operations, and allowed
the operator to optimize their heavy oil production
potential in an environmentally sustainable way.

900

Total cost savings for the field trial, factoring in the

total costs of chemical and water injection, resulted
in a net savings of $6,446 (US) per day, per well
based on reduced naphtha injection and handling
costs. At this location, treatment with B-VR was
estimated to generate a total savings of $2.3MM per
year, in addition to minimizing operational risks to
personnel and the environment .

SCALING

NEW HEIGHTS:

High-Tech Monitoring Solutions

for Better Scale Management
The presence of water in an oil field brings with it the potential
for mineral scale formation. Scale deposition from many mineral
sources, including calcium carbonate and sulfates of barium, calcium
and strontium, creates flow assurance challenges for operators
from the near wellbore to production tubing and topside processing
equipment. An ideal scale management program maximizes
hydrocarbon production and minimizes the cost of scale control,
thereby maintaining the economic viability of the operation.

CUTTING EDGE 7

Mitigation and prevention programs are critical for sustained

production in oil and gas fields. Chemical methods of scale control
include scale squeeze treatments, in which a scale inhibitor
is pumped into the water-producing zone of a formation and
returns with the produced fluid at sufficiently high concentrations
to prevent scale precipitation. Continuous chemical injection is
also an option. Monitoring for the presence of scale inhibitor
chemical and the scaling ions in the produced fluid is a key
part of a successful scale management program. Monitoring for
suspended solids in terms of their concentration, mineral type,
composition, and morphology is also recommended to improve the
understanding and gauge the risk of scale formation.

Suspended-solids monitoring
Monitoring for suspended solids is also often recommended, especially
in relatively long-reach horizontal wells. It is useful to understand not
only the amount of suspended solids recoverable from a given volume of
produced water, but their composition and morphology as well. Figure 2
outlines a process to recover and characterize suspended solids contained
in produced water.
A Scanning Electron Microscope equipped with Energy Dispersive
X-Ray Spectroscopy (SEM/EDS) can be used to identify the chemical
composition of the solids, in addition to their crystal morphology. This
enables the operator to distinguish between scale particulates and drilling
or completion additives containing barite or calcite. SEM/EDS systems
equipped with a low-vacuum mode are recommended to reduce specimen
changing and eliminate the need to apply a conductive coating to the
specimen. In low-vacuum mode, the instrument introduces a small
amount of air into the specimen chamber. These air molecules, oxygen
and nitrogen, are ionized by the incident electrons. These ions neutralize
electrons on the surface of the specimen and eliminate charging so that a
non-conductive specimen can be observed.
Essential Expertise
for Water, Energy and Air

Suspended Solids and Environmental

Scanning Electron Microscopy (ESEM)
Analysis Program
Fig. 1 The cross section of a pipe that experienced scale

build-up and flow assurance challenges

Brine chemistry monitoring

Frequent monitoring for changes in water chemistry is
recommended for all water-producing wells, and becomes
even more critical in the case of a seawater flood, a secondary
recovery technique in which seawater is injected into the
formation via an injection well to displace residual oil and sweep
it to adjacent production wells. Because the compositions of the
formation and injected waters can differ significantly, the use
of preliminary modeling to predict scaling tendency and risks
associated with well production fluids is common.
A laboratory-derived Minimum Inhibitor Concentration (MIC) is
used to define whether a particular system is protected against
predicted scale formation risks. If the scale inhibitor chemical is
present at a concentration above the MIC, then it is assumed that
the well is protected. It is often observed that the actual field
MIC differs significantly from the laboratory-derived MIC; however,
this approach works reasonably well if combined with monitoring
of the scaling-ion concentrations (those present as well as those
apparently missing in action).

As part of the scale

management program,
suspended solids from the
produced water can be
analyzed for composition,
amount and size to
determine the effectiveness
of the downhole and topside
scale control program.

OIL

Produced fluid sample

H2O

SEM of suspended solids

on filter surface

SEM of suspended solids

on filter surface

H2O
50ml
Barium Sulphate Drilling Mud

Barium Sulphate Scale Crystals

formed with no Scale Inhibitor

Whatman 0.45m
SFCA Filter
Calcium Carbonate Scale Crystals
No Scale Inhibitor present

Fragment of Corrosion
Resistant Alloy (CRA)

Barium Sulphate Scale formed in the

presence of Scale Inhibitor (SI<MIC)

Wax Crystals recovered from

Produced Water

Fig. 2 Suspended solids analysis by SEM/EDS

CUTTING EDGE 8

SM

Fig. 3 SEM micrographs coupled with elemental analysis using EDS confirmed
calcium carbonate in a well, despite steady scaling ion concentrations

Before Squeeze

After Squeeze

Fig. 4 SEM micrographs comparing suspended solids on a filter at 50X before

the squeeze (left) and at 25X after the squeeze treatment (right)

Suspended-solids monitoring is an effective tool to assess

the frequency at which a scale squeeze must be repeated in
production wells. It can also help the operator determine the
root cause of overboard oil-in-water excursions. Of critical
importance for long-reach wells, this monitoring identifies
those areas in the formation where an inhibitor squeeze
has not achieved optimal placement, (i.e., where high
inhibitor residuals, well above MIC, are accompanied by high
concentrations of suspended solids).
Suspended-solids monitoring also offers opportunities to
simplify scale surveillance in complex subsea architectures,
where the need for frequent sampling of individual wells can
cause significant hydrocarbon deferment. It achieves this by
the fact that, so long as suspended-particulates counts in a
commingled flow stream are sufficiently low, all wells in this
stream shouldin principlebe under effective control. Only
when counts begin to rise is frequent individual sampling of
wells recommended. Of course, the risks associated with this
reduced level of surveillance for much of the scaling lifecycle
must be balanced against the benefits of reduced sampling.
SEM/EDS analysis can identify scale issues when traditional
methods of monitoring (scaling ion concentration and scale
inhibitor residuals) show no immediate concerns. For
example, Figure 3 shows calcium carbonate grains observed
in a well that also exhibited steady scaling ion concentrations.
Based on these findings, a scale squeeze treatment was
recommended and executed. SEM/EDS analysis after the
squeeze confirmed that the treatment was necessary and
successful (Figure 4).
Nalco widely employs a suspended-solids surveillance method
in offshore and onshore operations around the world to
support scale programs and optimize both continuous and
batch inhibitor applications. The recent purchase of a new
SEM/ EDS unit by the Diagnostic Solutions Group in Sugar
Land, TX further strengthens Nalcos capabilities to provide
a more real-time assessment of a scale control programs
efficacy. Ultimately, this will give the operator greater
confidence in their flow assurance management strategies
and their ability to optimize production.

Fig. 5 SEM/EDS systems are used to support scale management

programs at Nalco Sugar Land, TX; Naperville, IL; Macae, Brazil;

Leiden, The Netherlands; and Aberdeen, UK facilities.
Publications
1. Jordan, M.M, Mackin, K., Johnston, C.J and Feasey, N.D. Control of Hydrogen Sulphide Scavenger Induced Scale and the Associated Challenge of
Sulphide Scale Formation within North Sea High Temperature/High Salinity Fields Production Wells. Laboratory Evaluation to Field Application SPE 87433.
Presented at SPE International Symposium on Oilfield Scale, Aberdeen, 26-27 May 2004.
2. Jordan, M.M, Johnston, C.J. and Robb, M. Evaluation Methods for Suspended solids and Produced Water as an aid in Determining Effectiveness of Scale
Control both down-hole and Topside SPE 92663. Presented at SPE International Symposium on Oilfield Chemistry 2-4th February 2005, Houston, Texas.

CUTTING EDGE 9

What do

Superheroes
& Polymer
have in common?

Its not only Superman that can bend steel, polymer

can too! What real harm can polymerization do? It
can cause some unwanted by-products, increase
viscosity, restrict flow, but the real burden is
usually the clean-up and removal during a
turn-around. This is not the case within the
butadiene industry, where polymerization, if
not properly controlled, can cause extensive
system damage (Figure 1).

CUTTING EDGE 10

To prevent these occurrences the industry has adopted

guidelines for mechanical cleaning and chemical
passivation of process equipment. The commodity
chemical commonly used for metal passivation is
sodium nitrite; however, this material presents safety
and environmental hazard concerns, expensive disposal
costs and is difficult to apply. To address this Nalco has
developed the FORTIS passivation program, a more
effective and environmentally friendly alternative to
commodity chemicals.

polymerization systems. Popcorn polymerization propagates

at a constantly accelerating rate, with the rapid expansion of
the hard polymeric mass leading to numerous problems, such
as premature shut downs, unit damage, and environmental
concerns. Once a popcorn seed is present in the system,
the popcorn polymerization proceeds faster and is much
more difficult to control. Some of the seeds cannot be easily
removed by mechanical means, and are unlikely to be washed
out of the system due to their lack of solvency in most
common solvents. Even after the equipment and the storage
facility have been thoroughly cleaned, residual particles of
popcorn polymer seeds may remain in hard to reach areas.
With time these become sites that promote unwanted polymer
growth. Since it is virtually impossible to remove all the seeds
completely, several chemical approaches have been used to
passivate residual seeds. Nitrogen dioxide, iodine, and sulfur
compounds are effective, but they are very difficult to use
because they are corrosive, hazardous and must be used in a
completely dry system.
Ideally a butadiene passivation program would be: (i)
effective at lower temperatures; (ii) easy to apply; (iii) easy
to monitor; (iv) environmentally friendly; and (v) non-toxic.

Fig. 1 Butadiene process equipment damaged by uncontrolled

popcorn polymer formation

Although almost a century has passed since Kondakow

observed an abnormal polymerization process in
2,3-dimethylbutadiene, the mechanism of spontaneous
popcorn polymerization still remains a bit of a mystery.
The most elusive aspect is the initiation step - how does
the first popcorn nucleus form, especially in a system
of conjugated dienes? Although there is no concise
answer, it is commonly believed that the propagation of
popcorn polymer occurs via proliferous polymerization
an abnormal reaction encountered in free-radical

Metal surface passivation using sodium nitrite, a technology

commonly reported in the 1940s is still used due to its
demonstrated dual capability to passivate metal surfaces
and popcorn seeds. Nevertheless, sodium nitrite has low
metal surface and popcorn seed passivation efficiency
compared to that of other materials, and there are no
means of monitoring its performance. Sodium nitrite
requires a high initial dosage (1 to 4% by weight), high
temperatures (close to 100C), and since it is sold as
a solid, is difficult to handle and introduce into the unit.
Furthermore, sodium nitrite creates waste disposal issues
and presents safety and environmental concerns. (LD50
= 180 mg/kg). Thus the current chemical treatment
method for metal passivation leaves significant room for
improvement.
The FORTIS passivation program offers many advantages
over traditional treatment options, namely its multichemical approach to passivation of butadiene process
equipment. Due to the unique nature of butadiene
fouling, Nalco has developed a program that addresses
the two main areas of concern, metal passivation and
popcorn inhibition, individually. The metal passivator,

CUTTING EDGE 11

EC3243A, is effective at lower temperatures (ca.

80C) and lower concentrations than the commodity
chemical. In a similar fashion the popcorn passivator,
EC3362B, effectively terminates radical sites, and
has successfully passivated popcorn seeds in both
laboratory studies and field tests.
EC3243A passivates a metal surface by changing the
oxidation state of iron from hematite to magnetite.
The effective conversion of a metal surface from
hematite (brown-red) to magnetite (gray-black) results
in a protective layer that will mitigate corrosion and
reduce the rate of initiation of free-radical polymeric
fouling. In the laboratory, the passivation efficiency
of EC3243A relative to sodium nitrite was evaluated
by treating previously corroded carbon steel coupons
with aqueous solutions of the passivation chemicals.

4 wt% NaNO2 1 wt% EC3243A

Fig. 2 Coupons before (left) and after (right) treatment with

EC3234A and sodium nitrite solutions

Figure 2 shows the corroded coupons before and after

treatment with a 4% solution of sodium nitrite or a
1% solution of EC3243A for 48 hours at 80C. The
coupon treated with EC3243A developed a magnetite
protective layer, as indicated by the grey/black
coloration. The coupon treated with sodium nitrite
showed little change.

CUTTING EDGE 12

Fig. 3 Passivated popcorn seeds grown in

2,3-dimethylbutadiene vapors for 3 weeks

The other component of the FORTIS program

is the popcorn passivator, EC3362B. In the
laboratory, experiments to evaluate the relative
inhibitor performance were conducted to test the
passivation effects over an extended period of time.
Popcorn seeds previously immersed in aqueous
solutions of the chemicals were allowed to grow in
2,3-dimethylbutadiene vapors for three weeks, and
their growth was compared to that of an untreated
seed. The impressive effect of EC3362B passivation
is shown in Figure 3. While sodium nitrite was able
to reduce the seed growth by a factor of 3 relative
to the untreated seed, EC3362B was able to reduce
the growth of the seed by a factor of 15, when
compared to the untreated seed growth.
So although popcorn polymer may be able to bend
steel, unlike Superman, there is a way to stop it. The
Nalco FORTIS passivation program is effective at
popcorn passivation, uses lower metal passivation
temperatures, lower dosages, is easily applied and
monitored, and is environmentally friendly.

Growing
the innovation

Footprint

As our thirst for hydrocarbon-based

products grows, new technology
plays a critical role in enabling the
continued production of hydrocarbons
and the manufacture of fuels and
petrochemical feedstocks. Having
a critical mass of R&D intellectual
capital coupled with a deep rooted
culture of innovation is vital in order
to succeed in this environment.
Over the past two years Nalco has
significantly expanded its innovation
footprint around the globe to
include new innovation centers in
Pune, India; Shanghai, China and
Campinas, Brazil. Furthermore, with
the acquisition of the enhanced oil
recovery company TIORCO, a new
state of the art research center was
commissioned in Denver, Colorado.
Recently in Sugar Land, Texas, the
Energy R&D center was further
expanded with the opening of a new
15,000 sq. foot laboratory to house
the Downstream R&D group.

CUTTING EDGE 13

The new Innovation Center in Pune, India, is Energy

Services Eastern hemisphere R&D hub. The facility has
over 50 scientists and engineers, 70% of whom have PhDs
from premier institutes in India and around the world. Great
attention has been paid to standardizing the equipment,
processes and level of training in order to ensure the output
from this facility is of the same high standard as
our established laboratories.

the Nalco R&D team also works closely with customers, Nalco field
engineers, and technologists at regional technical support centers to
provide solutions to todays high-value technical challenges. This may
involve field support or being able to simulate process conditions in a
laboratory environment. By having the research team exposed to realworld technical support projects in addition to research ensures that
they gain a first-hand appreciation of operational challenges and that
their research work remains focused on viable solutions that can be
implemented rather than scientific curiosities.

Do not go where the path may

lead, go instead where there is
no path and leave a trail. R. Emerson

The facility in Shanghai, China has over 60 scientists and

engineers and is strategically located to service water and
process needs across industries including downstream
refining and petrochemical businesses. Similarly, the facility
in Campinas, Brazil has approximately 15 scientists and
engineers and supports our upstream business in addition
to the paper and biofuels industries.

Innovation Centers
Regional Technical Support Centers
These innovation centers are chartered with developing
new, differentiated technologies that will enable the
future state of the petroleum industry. Research projects,
which typically last from six months to three years, are
directly aligned with industry needs. Projects are locally
coordinated but typically involve an extended global team
of scientists that collaborate to drive the work forward.
Open, regular communication is critical to success. In
addition to leading the development of new technologies,

CUTTING EDGE 14

In order to drive the creative process of developing the next

breakthrough technology, the R&D team is continually challenged
to think beyond the obvious and look outside their immediate fields
for sources of innovation stimulus. Examples of this include recent
collaborations with NASA and the Methodist Hospital in Houston to
mine technologies in these fields that may have functionality that can
be leveraged into the petroleum industry. Connecting with new sources
of innovation stimulus, and collaborating both internally or externally
to quickly bring to the marketplace differentiated, innovative solutions
is the backbone to the Connect Collaborate Innovate strategy that
was recently implemented throughout Energy Services R&D.
Looking beyond the trees for sources of innovation stimulus and
then connecting the dots between technologies is the fundamental
process of innovation. With the recently announced merger of Nalco
and Ecolab, the worlds leading provider of cleaning and sanitization
solutions, many opportunities now exist for doing exactly this within
the new expanded company. Furthermore, the newly merged company
has more than double the original number of scientists and engineers
(total of 1400), in 10 innovation centers around the globe. With an
active patent portfolio of over 5,800 patents there exists a wealth of
knowledge that is a fertile resource for continued innovation.
The future of the petroleum industry is bright. However, it will take
sustained, focused innovation to meet the continued challenges our
industry poses us. Nalco has clearly made a commitment to innovation
leadership and continues to invest heavily to ensure tomorrows
challenges are being addressed today.

Discovery consists of seeing

what everybody has seen and
thinking what nobody has
thought. Albert von Szent-Gyorgy

COVER STORY

View
n
o
i
s
o
r
r
C oWindow
Real-Time

into the

In refinery processing, the corrosion window refers to the relatively brief period of time in which an upset
to normal operation causes rapid corrosion in the overhead condensing system of a crude atmospheric
distillation unit. The corrosion window typically follows the empirical observation that 90% of crudeunit overhead corrosion occurs during only 10% of operating time. This window normally opens during
interruptions to normal operation, such as crude tank switches and processing of slop oils or opportunity
crudes. Because periods of unstable operation are infrequent and/or short-lived, traditional approaches to
corrosion monitoring tend to detect corrosion problems only after significant damage has already occurred.

CUTTING EDGE 15

A Break from Traditional Treatments

Traditional methods for controlling corrosion in the overhead condensing
system include the installation of corrosion monitoring devices, the
use of caustic, and other chemical solutions. Some refiners also elect
to upgrade the metallurgy of the overhead condensing system and all
associated piping, a relatively high-cost option.
When properly applied, traditional approaches provide acceptable
corrosion control during periods of normal operation; however, these
methods are neither sensitive enough nor employed with sufficient
frequency, reliability and accuracy to facilitate a timely response within
the corrosion window.
The refining industry is actively seeking new solutions that can
instantaneously and accurately detect significant changes in the
corrosive environment. Furthermore, the applied solution must proactively
correct any corrosion issues in an effective and timely manner. The Nalco
response to this challenge is the 3D TRASAR Crude Overhead Analyzer
(Fig. 1), an automated, on-line analyzer that continuously measures pH,
chlorides, and iron contents in refinery process water.

Monitoring Outside the Corrosion Window

Both refiners and chemical suppliers use a combination of wet chemistry
tests and mechanical devices to monitor the corrosive environment in
crude overhead condensing equipment. Wet chemistry tests, which
often include measurements of pH, chloride, ammonia, sulfide, and
iron contents in the overhead accumulator water, are limited in their
effectiveness at monitoring and controlling corrosion by the frequency at
which these test are performed. Sampling and testing of the overhead
accumulator water is generally performed by refinery personnel or the
chemical supplier as part of a routine service plan. The frequency of this
sampling may vary from once per shift to once per week, and the test
protocols may be limited to simple pH and chloride measurements.
The result is minimal data collection, with most of the sampling occurring
during periods of stable operations. Although 90% of corrosion occurs
during upsets in the crude unit, sampling and data collection during
these periods are often neglected while refinery staff works to return the
crude unit to stable operations.
The most frequently measured parameter in the crude unit overhead
accumulator water stream is pH, which may be checked 4 to 10 times a
day. While some refiners have installed online pH probes to monitor the
process water, manual pH measurements remain the norm, primarily
due to the low reliability of online probes and their need for frequent
calibration. Chloride, iron, and ammonia contents in the process water
are measured much less frequentlynormally 1 to 5 times per week
due to the complexity and time required to complete these tests.
Manual wet chemistry results must be reported accurately and rapidly
if corrosion issues are to be addressed proactively. Test accuracy is
significantly affected by human error, variation in test methods, and
the temptation to take shortcuts during analysis. Just as important, the
length of time between sampling, testing, and reporting results impacts
the value of the data. For example, a typical 4 to 6 hour turnaround

CUTTING EDGE 16

Fig. 1 Photo of 3D TRASAR Crude Overhead Analyzer

time may be adequate during normal operation or for comparison to
performance metrics, but does not allow a timely response within the
corrosion window.

Peering Inside the Corrosion Window

The ability to respond proactively to corrosion issues requires accurate,
frequent, and timely testing. This suggests the need for effective, realtime monitoring solutions, which is precisely what the Nalco 3D TRASAR
Crude Unit Overhead Analyzer provides.
Process water from the crude unit overhead is continuously sampled
and fed through the 3D TRASAR Analyzer for automated, on-line
analyses. Specially designed pH electrodes provide a real-time measure
of the accumulator water pH. Chloride and total iron analyses are
typically measured once per hour, depending on system conditions. The
analyzer processes samples continuously, both during normal operation

and inside the corrosion window. The real-time monitoring approach

increases the accuracy and repeatability of measurements by eliminating
human error, sample contamination, and sample aging effects.
Access to the 3D TRASAR Analyzers output is much more convenient
compared to manual sample processing. All data collected by the
analyzer is streamed wirelessly to the Nalco proprietary 3D TRASAR
server where it can be viewed in table or graphical format by both
Nalco and operations personnel, providing a real-time snapshot of unit
performance and a better view into the corrosion window.

NALCO Analyzer Beta Test Data

80

70

60

Cl (ppm)

50

pH #1
pH #2
pH #3

40

Fe

30

20

10

0
9/8 0.00

pH & Fe (ppm)

Cl

0
9/8 3.00

9/8 6.00

9/8 9.00

9/8 12.00

9/8 15.00

9/8 18.00

9/8 21.00

9/9 0.00

9/9 3.00

9/9 6.00

Fig. 2 The analyzer captures a chloride excursion with corresponding

changes in pH and iron levels.
The Nalco 3D TRASAR Analyzer was field tested at several refineries
in North America, Asia and Europe. In one application, the 3D TRASAR
Analyzer captured a significant increase in chloride levels over a 6-hour
period (Fig. 2). A corresponding increase in iron content and a decrease
in pH level were also observed. The highly correlated trends in the
parameter values indicated that immediate corrective action was required
to prevent a significant spike in corrosion.
Results from additional field trials have demonstrated the 3D TRASAR
Analyzers value in providing timely data that allowed proactive
adjustments to corrosion control programs. Prior to the installation of
the analyzer, one North American refinery faced recurring corrosion
issues that forced unscheduled shutdowns to replace damaged overhead
bundles. The combination of real-time data and active participation
by the operations team and Nalco field engineers helped the refinery
decrease the average corrosion rate in the overhead system by more than
60%. The next stage in development of the 3D TRASAR Analyzer is the
addition of closed-loop, automated control of the chemical portion of the
corrosion control program (Fig. 3).

Fig. 3 Schematic of crude unit overhead system with on-line

analyzer control of corrosion program

Closing the Corrosion Window

To be truly effective, a corrosion control program must go
beyond the current industry practice of periodic sampling and
manual sample processing. Real-time data capture is critical to
detecting and closing the corrosion window before significant
damage occurs. To this end, the Nalco 3D TRASAR Analyzer
was developed to provide continuous, accurate, and repeatable
measurements of the pH, chloride, and iron levels in the crude
unit overhead system. Around-the-clock monitoring of these key
parameters captures the critical 10% time period of operations
when 90% of corrosion occurs.
Early detection of these corrosion windows permits timely and
effective chemical solutions to be applied. Ongoing development
continues to extend the analyzers capability to automate its
control responses, thus providing additional capability for
controlling overhead corrosion, extending equipment life,
avoiding unplanned shutdowns, decreasing costs of off-spec
material production and reprocessing, and reducing crude unit
maintenance costs.

CUTTING EDGE 17

NEWS AND UPDATES

Diagnostic Solutions
The Nalco global team of trained analytical scientists in the Diagnostic Solutions
Group provides advanced problem solving and consulting to the petroleum
industry. Using state of the art analytical techniques and many years of
experience, this team of scientists probes the chemical nature of various
samples that are encountered throughout the petroleum industry. In conjunction
with our research scientists and field engineers, this information is then used to
make recommendations to optimize plant operations.
Recently the Diagnostic Solutions Group introduced a new first level scaling
tendency evaluation tool. From a detailed water analysis, saturation indices are
calculated for six different types of scale using a version of the ScaleSoftPitzerTM
model developed at Rice University. To request this evaluation as part of your
next water analysis, request Test List SI_OFC.

Publications & Industry Presentations

UPSTREAM
Gulf of Mexico Asset to Minimize the Risk of Corrosion.
Renato De Paula, Vic Keasler, Brian Bennett, Carrie Keller,
and Robert C. Adams. NACE 2012.

Emulsion Characteristics and Novel Demulsifiers for

Treating Chemical Induced Emulsions. D. Nguyen,
N. Sadeghi, C. Houston, SPE Enhanced Oil Recovery
Conference 2011.

Multi-Faceted Approach for Optimizing a Microbial

Control Program. Vic Keasler, Brian Bennett, Carrie Keller.
SPE International Conference on Oilfield Corrosion 2012.
Paper # SPE-154645.

Field Study of Heavy Oil Viscosity Reduction for

Production Transport. John Pinto, Giovanni Annichiaricco,
Marcus Faust Jr., Magda Montanez, Ramon Parra, Thomas
Weathers Jr., 2011 World Heavy Oil Congress.

Development and Application of MEG Reclamation

Process Compatible Corrosion Inhibitors for Upstream Oil
and Gas Developments. Ryan Harrington, Mark Gough,
Steve Davoren, 18th International Corrosion Congress 2011.

Biphasic Viscosity Reducers as Production Aids for

Viscous Oils. Marcus Faust Jr., Thomas Weathers Jr., 2011
SPE International Symposium on Oilfield Chemicals.

Optimization of a Microbial Control Program in an Aging

Separation of Produced Emulsions from Surfactant

Enhanced Oil Recovery Processes. George J. Hirasaki,
Clarence A. Millera, Olina G. Raneya, Michael K. Poindexter,
Duy T. Nguyen, John Hera, Energy and Fuels, 2011.
Use of Foamer to Deliquify Natural Gas Wells with DryGas-Lift System. Fenfen Huang, Duy Nguyen, Adam Rowe,
Gas Well Deliquification Workshop, 2011.
Deliquification Strategy for North Everest. Sabina
Rattan , Karl Stevens, Duy Nguyen, Gas Well Deliquification
Workshop, 2011.
Selection of the Right Demulsifier for Chemical
Enhanced Oil Recovery. Duy Nguyen, Nicholas Sadeghi,
SPE-International Oil Chemicals, 2011.
CUTTING EDGE 18

Study of Live Oil Wax Precipitation with High Pressure

DSC. Juyal, P; Cao, Tran; Yen, A.T; and Venkatesan, R.,
Energy Fuels, 2011, 25, 568-572.
Analysis and Identification of Biomarkers and Origin
of Blue Color in an Unusually Blue Crude Oil. Juyal, P;
Mckenna, A.M; Yen, A.T; Rodgers, R.P; Reddy, C.M; Nelson,
R K; Ballard, A. Andrews; Allenson, S; Mullins, O.C; and
Marshall, A.G. Energy Fuels, 2011, 25, 172-182.

UPSTREAM

DOWNSTREAM

Effect of Aging on Asphaltene Inhibitor Product

Beyond the Desalter; Brad Mason; Hydrocarbon

Engineering, v 16, n 10, October 2011.

Recommendation. Juyal, P.; Le, V; Yen, Andrew,

T; Allenson, S.J. Journal of Dispersion Science and
Technology, (2011) 32:8, 1096-1104.
Application of Emulsion Viscosity Reducers to Lower
Produced Fluid Viscosity. Stephan J Allenson, Andrew T
Yen and Frank Lang. OTC 22443. Proceedings of Offshore
Technology Conference, 4th 6th October 2011, Rio de
Janeiro, Brazil.
Analysis and Comparison of Paraffinic Field Deposits
to Cold Finger Deposits on a Brazilian Campos Basin
Crude Oil. Susan Garner, Priyanka Juyal, Crystal Hart, ,
David Podgorski, Amy M McKenna, Claudio Ziglio, Ryan P
Rodgers, Stephan Allenson, Alan G Marshall. Paper OTC
22660. Proceedings of Offshore Technology Conference,
4th 6th October 2011, Rio de Janeiro, Brazil. (Joint
publication with Petrobras and Florida State University)
Evaluation of Kinetic Hydrate Inhibitor Performance by
High Pressure Differential Scanning Calorimetry. Kevin
McNamee. Paper OTC 21604. Proceedings of Offshore
Technology Conference, May 3, 2011, Houston, TX.
Characterization of Crude Oil and Asphaltenes from an
Elevated GOR Production Well in the Gulf of Mexico.
Nikhil Joshi, Priyanka Juyal, Frank Lim, Amy M McKenna,
David Podgorski, Vickie Ho, Andrew T Yen, Ryan P Rodgers,
Stephan J Allenson, Alan G Marshall. 12th Intl Conf. on
Petroleum Phase Behavior & Fouling, London, UK, July
10th-14th (2011).

Rise of European Ethanol; Tony OBrien, Phil Bureman and

Kim Peyton; Biofuels International, October 2011.
Peroxy Radical Activated Addition of tert-Butylcatechol
to 2,6-Di-tert-butyl-7-Substituted Quinone Methide
Polymerization Retarders; Andrew R. Neilson and
Christopher F. Morrison; Organic Process Research &
Development, November 11, 2011.
Green Retarder Technology for the Styrene Industry. Ana
Guzman, Carmen Monfort and Ana Olivares (Repsol Qumica
Tarragona); Lisheng Xu, Javier Florencio, Vincent E. Lewis,
and Christopher F. Morrison (Nalco), EB/SM Technology
Conference, San Francisco, CA, June 5- 7, 2011.
Flux Oil Stream Import to Quench Systems - Risks and
Impacts. Andre Bernard, Thomas Pickett, Dan Frye, and
Beata Manek, AIChE Spring Meeting, Chicago, IL, March
13-17, 2011.
Nalco - Your Partner in Delivering Improved Ethylene
Plant Reliability. Andrew Neilson, 15th Annual ROPTC, Bali,
Indonesia, January 2011.

Combined Rheometry and Differential Scanning

Calorimetry Study of Wax Precipitation in Live Fluids
under Pressure. Priyanka Juyal, Tran Cao and Andrew Yen.
12th Intl Conf. on Petroleum Phase Behavior & Fouling,
London, UK, July 10th-14th (2011).
Reversibility of Asphaltene Flocculation with Chemical
Inhibitors. Priyanka Juyal, Vickie Ho, Andrew Yen and
Stephan Allenson. 12th Intl Conf. on Petroleum Phase
Behavior & Fouling, London, UK, July 10th-14th (2011).

CUTTING EDGE 19

Essential Expertise
for Water, Energy and Air

An Ecolab Company

SM

If youd like to join a team focused on solving real-world

problems and building technologies that have a positive
impact on the planet, visit www.nalco.com today.
Energy Services Division: 7705 Highway 90-A Sugar Land, Texas 77478 USA
Europe: A-One Business Center Z.A. La Pice 1 Route de lEtraz 1180-Rolle Switzerland
Gulf Office: P.O. Box 17063 Jebel Ali Free Zone Dubai, United Arab Emirates
Latin America: Av. das Naes Unidas 17.891 6 Andar 04795-100 So Paulo SP Brazil
Asia Pacific: 2 International Business Park #02-20 The Strategy Tower 2 Singapore 609930
India: Kumar Planet IT Magarpatta City Road Hadapsar Pune India 411028
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

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FORTIS and 3D TRASAR, Nalco, the logo and the tagline are trademarks of Nalco Company.
All other trademarks are the property of their respective owners.
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