Oilfield Chemistry at Thermal Extremes

Keng Seng Chan

Suresh Choudhary
Abdul Hameed Ahmad Mohsen
Mathew Samuel
Kuala Lumpur, Malaysia

The thermometer is running both ways for the E&P industryoilfield activities are
performed in hotter and colder surface conditions and also at higher bottomhole
temperatures. As operators reach deeper and from more remote locations, fluid
chemistry is racing to keep up.

Laurent Delabroy
Houston, Texas, USA
Juan Carlos Flores
Villahermosa, Mexico
Greig Fraser
Aberdeen, Scotland
Dan Fu
Tyumen, Russia
M. Nihat Gurmen
Sugar Land, Texas
Joseph R. Kandle
Tri-Valley Oil & Gas Corporation
Bakersfield, California, USA
Siri M. Madsen
ConocoPhillips
Stavanger, Norway
Fred Mueller
Corpus Christi, Texas
Kevin T. Mullen
Nizhnevartovsk, Russia
Hisham A. Nasr-El-Din
Saudi Aramco Research and Development
Dhahran, Saudi Arabia
Jim OLeary
BP
Houston, Texas
Zhijun Xiao
Shell International Exploration and
Production Inc.
Houston, Texas
Rishat Radikovich Yamilov
Sibneft-Khantos
Khanty-Mansiysk, Russia

Some 56 million years ago, the Earth was much

warmerthe blanket of ice in the Arctic did not
exist.1 Over time, the climate cooled, the waters
froze, and life adapted to the changing thermal
environment. Today, the technologies used to
recover hydrocarbon resources from beneath
these frigid northern climates and other
challenging thermal environments are also
evolving and adapting, helping oil and gas
producers extract difficult-to-reach reserves.
After nearly a century and a half of hydrocarbon production, the oil and gas industry now
finds itself at a turning point. Oil and natural gas
prices recently reached record highs. Although
price spikes have occurred in the past, there is a
growing consensus among analysts that the
current situation is not an artifact of current
market conditions. Instead, there is a fundamental
and potentially widening gap between our
demand for oil and natural gas, and our ability to
produce them.

The oil and gas industry has picked much of

the low-hanging fruit, and remaining resources
will increasingly be found in deeper, more
remote, and more complex reservoirs. Dramatic
developments in E&P technology combined with
reductions in cost and risk are needed to make
these remote resources viable.
To access remaining reserves, engineers are
confronting colder subsea wellheads, hotter
bottomhole temperatures and surface temperature extremes that challenge personnel, equipment and fluid chemistry. Increasingly advanced
chemical technologies are required to facilitate
drilling, completion and production operations.
In this article, we discuss the challenges to
oilfield chemistry posed by extreme thermal
environments. Case histories from Siberia, the
Middle East, the Gulf of Mexico, the USA and the
North Sea provide an overview of how new
chemistry and engineering solutions are helping
operators efficiently drill and produce the
Earths remote hydrocarbon resources.

For help in preparation of this article, thanks to

Jean-Philippe Bedel, Liz Morris and the staff of the
Aberdeen CSL; Brett Cardwell, Marie Dessinges, Mike
Parris and Paulo Rubinstein, Sugar Land, Texas; Terry
Dammel, Emmanuel Therond and the staff of the Houston
CSL; Chris Fredd, Oklahoma City, Oklahoma, USA; Mitch
Gentry, Bakersfield, California; Paul Howard and the staff of
the NSA Stimulation CSL, Sugar Land, Texas; Andre Rainey,
Midland, Texas; Henk Romijn and the staff of the Well
Services Safety and Environment group, Moerdijk,
The Netherlands; the staff of the Kuala Lumpur CSL,
Malaysia; and the staff of the Tyumen CSL, Russia.

BIGORANGE, CemCRETE, DeepCEM, DeepCRETE,

GASBLOK, PowerCLEAN, SuperX, SXE and YFGO are
marks of Schlumberger.
1. Kerr RA: Signs of a Warm, Ice-Free Artic, Science 305,
no. 5691 (September 17, 2004): 1693.
2. For more on the Schlumberger CSLs: Abbas R,
Cunningham E, Munk T, Bjelland B, Chukwueke V, Ferri A,
Garrison G, Hollies D, Labat C and Moussa O: Solutions
for Long-Term Zonal Isolation, Oilfield Review 14, no. 3
(Autumn 2002): 1629.

Oilfield Review

On the Front Line of Changing Trends

Experience has shown that the most efficient
problem-solving occurs when technological
resources are located close to the problem. To
respond to this need, Schlumberger operates
Client Support Laboratories (CSLs) in Houston,
Sugar Land, Aberdeen, Kuala Lumpur and
Tyumen, Russia. The CSLs provide an essential
link between product development and field
operations by supporting the introduction of new
technology, assisting in training field personnel
and solving local drilling and production
problems.2 The CSL engineers, scientists and
technicians also participate in community
education, outreach programs and interactions
with local universities, and take part in many
other activities that contribute to the
development of people and technology directly
related to the E&P industry. Strategically
located, the CSLs support nearly all
hydrocarbon-producing regions of the world.
The newest of the CSLs is located in Tyumen,
2,100 km [1,305 mi] east of Moscow. The Tyumen
CSL provides technical training, new-technology
implementation and technology support for field
operations and clients throughout Russia. Like
the other four CSLs, the laboratory and its staff
focus on developing and delivering specific
solutions for regional E&P problems.
The Challenge of Surface Temperature
From extreme heat to bitter cold, the drilling
locations for many of our remaining oil and gas
reserves challenge both the equipment and fluid
chemistry required to construct and complete
wells. Beneath the frozen tundra of Western
Siberia lie more than 40% of the worlds proven
gas reserves and substantial amounts of oil.
Drilling in this environment, particularly during
the winter, is difficult; keeping these wells
flowing can be even more daunting.
For example, in typical sandstone reservoirs
in Western Siberia, permeability to oil ranges
from 2 to 4 mD. Hydraulic fracturing often
provides incremental production-rate increases
of threefold or more. Aggressive fracturing
designs have yielded production increases of four
to five times the initial rate. These fields were
among the first to be developed with the
extensive use of hydraulic fracturing along with
some of the largest proppant available in the
industry to hold fractures open.

Autumn 2006

Before Cenoman water could be used for

fracturing operations, engineers at the Tyumen
Client Support Laboratory (CSL) performed
studies to determine the waters suitability for

would not only meet environmental and legal

requirements for oilfield water supplies in
Russia, but also significantly reduce fracturingfluid preparation time on location.

30
20
10
Temperature, C

For much of the year, temperatures in

Western Siberia stay below freezing (right). In
these harsh conditions, conventional hydraulic
fracturing equipment and chemistry have proved
inefficient or worse yet, ineffective. Key to the
hydraulic fracturing process is the mixing of a
carrier fluid capable of transporting proppant
from the surface into a hydraulically induced
fracture that is often thousands of meters below
the surface. In warmer climates, fracturing gels
and other chemicals are most efficiently mixed
in a dynamic process called mix-on-the-fly in
which water, chemicals and proppant are
accurately measured, blended and pumped
downhole in a single process. However, in the
extreme cold of Siberia, mixing-on-the-fly has
been impractical since the mix water must be
heated to above 25C [77F] before fracturing
chemicals can be added. Therefore, engineers
have used a process called batch mixing to blend
fracturing fluids.
In batch mixing, water is typically heated in
tanks, and large quantities of fracturing polymer
and other chemicals are added and mixed for an
hour or more per tank. Not only is the process
inefficient, it requires large quantities of energy
to heat the water and leaves the fracturing fluid
susceptible to bacterial contamination. Often,
the batch-mixing process takes six to seven
hours to blend enough fluid for a typical
fracturing operation.
The harsh conditions of Western Siberia
combined with long mixing times, primitive
roads and generally poor working conditions
have limited the number of fracturing operations
performed to only two or three per week. To
improve overall fracturing efficiency, Schlumberger
Integrated Productivity & Conveyance Center
(IPC) engineers in Sugar Land, Texas, redesigned
equipment, processes and chemistry to effectively reduce treatment time by an average of
eight hours per fracturing operation (see
Improving Oilfield Service Efficiency, page 69).
Eliminating the batch-mixing process was
crucial in reducing treatment time. To do this,
the thermal limitations of the mixing process had
to be overcome. At 1,100 to 1,900 m [3,610 to
6,230 ft] below the surface of Western Siberia,
there is a warm-water aquifer known as the
Cenoman formation. Water from the Cenoman
formation is accessible from most production
locations and is produced to the surface at
temperatures approaching 50C [122F], well
above the 25C generally required for fracturingfluid preparation. Engineers believed that the
use of the naturally heated Cenoman water

0
10
20
30
40
Jan

Feb

Mar

Apr

May

Jun

Jul

Aug

Sep

Oct

Nov

Dec

Month

> The cold of Siberia. Temperatures in the oil fields of Siberia average below
freezing for at least seven months of the year.

Sample Origin
South
Priobskoe,
sampled
09/22/05

Monastery
Island,
Well 4327,
Pad 242

Megion Novo
Pokurskoe,
Well 252,
Pad 30

South
Priobskoe,
Right Bank,
Well KNS 2

South
Priobskoe,
Well KNS 1,
Pad 3

South
Priobskoe,
Well KNS 2
9.3

Boron, mg/L

10.9

17.1

7.7

4.4

15.4

Iron, mg/L

10.25

13.30

5.61

2.56

2.29

9.8

Bicarbonates, mg/L

401.39

315.47

91.29

362.46

273.52

392.0

Magnesium, mg/L

76.55

97.68

96.27

30.53

118.34

90.64

Total hardness, mg/L

359.0

401.0

517.0

158.0

459.0

358.0

9,983.0

9,946.0

11,657.0

3,261.0

9,865.0

9,490.0

Chloride, mg/L

> Natural boron crosslinker. Water from the Cenoman formation contains sufficient amounts of boron
to quickly crosslink guar fracturing fluids (image top). Water analyses for six samples are shown in
the table (bottom).

Oilfield Review

fracturing. Analysis showed that the water

contained significant levels of boron as well as
high levels of magnesium and other elements
that contribute to hardness (previous page,
bottom). Further studies showed that the
presence of boron accelerated the crosslinking of
typical fracturing fluids, such as high pH borate
gel, making them difficult to control. When
blended with Cenoman water, common
fracturing fluids also showed poor stability at
projected downhole temperatures, probably
because of the lowering of pH due to
precipitation of divalent metal hydroxides such
as calcium hydroxide [Ca(OH)2] and magnesium
hydroxide [Mg(OH)2].
To minimize the impact of boron and the
hardness of the Cenoman water, the CSL team
investigated the use of a complexing agent. They

found that adding a chemistry that complexes

boronwhen added before polymer hydration
effectively inhibited the early crosslinking
tendency (below). At the wellsite, pretreatment of
the Cenoman water in combination with new
equipment designs not only eliminated the need
for batch mixing, but also produced significant
improvements in fluid performance.
In Siberia, front-line CSL and client
personnel developed a unique stimulation
solution using local resources. More than 80
hydraulic fracturing operations have been
performed with the new fluid system. Time on
location has been reduced by an average of eight
hours, and in all wells treated, 100% of the
proppant was properly placed with no observed
reduction in fracture conductivity.

YF135RGD Cenoman water, Monastery Island

YF135RGD Cenoman water, South Priobskoe
YF135RGD Cenoman water, Right bank
YF135RGD Cenoman water, Megion Novo Pokurskoe

2,500

Viscosity, cP

2,000

1,500

1,000

500

0
0:00:00

0:14:24

0:28:48

0:43:12

0:57:36
1:12:00
Time

1:26:24

1:40:48

1:55:12

2:09:36

1,800

110

1,600

100

Apparent viscosity, cP

No complexing agent in Cenoman waterSample 1

No complexing agent in Cenoman waterSample 2
No complexing agent in Cenoman waterSample 3
Temperature
Temperature
Temperature

1,200
1,000
800
600

80
70
60
50
40

400
200

20

0
1

9 10 11
Time, min

12

13

14

15

16

17

18

19

20

> Stabilizing fracturing fluid. Consistometer tests conducted at 100C [212F] show that the addition
of a complexing agent to Cenoman water from four different locations stabilizes the viscosity at 500
to 800 cP [0.5 to 0.8 Pa.s] across time (top). The peaks are an artifact of consistometer tests.
Conversely, without the complexing agent, high initial viscosity was observed, followed by a sharp
drop-off within minutes of elevating the sample temperature (bottom), demonstrating the instability
of untreated samples.

Autumn 2006

Out of the Cold and into the Heat

Far from the cold of Siberia, in the hot deserts of
Saudi Arabia, Schlumberger CSL engineers faced
another well stimulation problemsurface
temperatures so high that products were
becoming difficult to handle and were failing
before being pumped downhole.
Oil and gas production in Saudi Arabia comes
primarily from carbonate reservoirs. Reserves
trapped in these limestone and dolomite formations often require matrix stimulation to produce
at optimal levels. Retarded acid, created by
emulsifying acid in diesel, has long been used to
stimulate these carbonate reservoirs.3 Generally,
acid and diesel oil are mixed at a 70:30 ratio. An
emulsifier is used to generate and stabilize the
solution (above).
At these ratios oil-external emulsions are
inherently unstable. To compensate for this, high
concentrations of emulsifier are used to maintain
stability during treatment. Prior to pumping, the
emulsion is maintained by constant mixing.
Emulsified hydrochloric acid [HCl] is about 15 to
20 times more retarded, or less active, than
regular HCl. The reaction rate of HCl with
carbonate depends on the surface area of the
rock exposed to the acid. In emulsified acid
systems, since diesel is the external phase, the

30

100 cP
0

Temperature, C

90

1,400

> Oil-external emulsion. Shown are droplets of

acid emulsified in diesel (yellow). A small volume
of the emulsion is poured into a beaker of water.
Since the emulsion is oil external, droplets of the
diesel, acid and surfactant blend will form round
droplets in the aqueous solution.

3. Nasr-El-Din HA, Solares JR, Al-Mutairi SH and

Mahoney MD: Field Application of Emulsified AcidBased System to Stimulate Deep, Sour Gas Reservoirs
in Saudi Arabia, paper SPE 71693, presented at the
SPE Annual Technical Conference and Exhibition,
New Orleans, September 30October 3, 2001.
Nasr-El-Din HA, Al-Anazi HA and Mohamed SK:
Stimulation of Water Disposal Wells Using Acid-inDiesel Emulsions: Case Histories, SPE Production &
Facilities 15, no. 3 (August 2000): 176182.

Old SXE emulsion

New SXE emulsion

25

Stability, h

20

15

10

0
84

92

110

132

136

Surface temperature, F

> Emulsions for higher temperatures. Both new and old formulations of SXE
emulsion were evaluated over a 24-hour period. Previous SXE formulations
were unstable across a range of surface temperatures as indicated by an
erratic drop in viscosity (orange). The new system is stable at all surface
temperatures studied (green).

200
Volume of old product required (calculated)
Emulsifier used, 1,000 galUS

160

Old product, gal consumed

New product, gal consumed

120

80

40

2000

2001

2002

2003
Year

2004

2005

2006

> Impact of new chemistry on emulsifier usage. Since the new product was
introduced in 2004, both new (green) and old (pink) products have been used.
These amounts are significantly lower than the calculated volume of old
product alone (gray).

4. Nasr-El-Din et al, 2001, reference 3.

For more on acidizing and acid fracturing in carbonate
reservoirs: Al-Anzi E, Al-Mutawa M, Al-Habib N,
Al-Mumen A, Nasr-El-Din H, Alvarado O, Brady M,
Davies S, Fredd C, Fu D, Lungwitz B, Chang F, Huidobro E,
Jemmali M, Samuel M and Sandhu D: Positive
Reactions in Carbonate Reservoir Stimulation,
Oilfield Review 15, no. 4 (Winter 2003/2004): 2845.
5. http://www.bbc.co.uk/weather/world/country_guides/
results.shtml?tt=TT002770 (accessed September 13, 2006).
6. U.S. Minerals Management Service document:
Deepwater Gulf of Mexico: Americas Emerging Frontier:
http://www.gomr.mms.gov/homepg/whatsnew/techann/
000022.html (accessed July 11, 2006).

7. OLeary J, Flores JC, Rubinstein P and Garrison G:

Cementing Deepwater, Low-Temperature Gulf of
Mexico Formations Prone to Shallow Flows, paper
IADC/SPE 87161, presented at the IADC/SPE Drilling
Conference, Dallas, March 24, 2004.
8. For more on deepwater cementing technology: Carr G,
Pradi E, Christie A, Delabroy L, Greeson B, Watson G,
Fett D, Piedras J, Jenkins R, Schmidt D, Kolstad E,
Stimatz G and Taylor G: High Expectations from
Deepwater Wells, Oilfield Review 14, no. 4
(Winter 2002/2003): 3651.

initial contact of acid to rock is minimized. This

allows deeper penetration of the acid into the
matrix before the acid is spent. Once pumped
deep into the fracture, the emulsion breaks and
the fluids separate, allowing the entrained acid to
attack and stimulate the carbonate reservoir rock.4
Keeping these emulsions stable after mixing
and before pumping them downhole has long
been a challenge in the hot desert environment.
During the summer months, daytime temperatures rise well above 120F [48C].5 To minimize
exposure of the systems to high daytime
temperatures, the treating fluids are typically
blended at night. Prior to use, remixing often
requires four hours or more and must be done
before surface conditions become too hot.
At the CSL in Kuala Lumpur, engineers and
scientists worked to resolve this problem. The
challenge was to develop an emulsifier that would
be stable at both the high surface temperatures
and the much hotter downhole conditions, often
approaching 300F [149C] (above left). Following
extensive local product evaluation at the CSL in
Kuala Lumpur, engineers in Saudi Arabia fieldtested a new SXE SuperX concentrated
hydrochloric acid emulsion formulation using
U108, a new emulsified-acid system additive, on
conventional acid-stimulation jobs in both producing and injector wells. This was followed by 10
successful deep-gaswell acid-fracturing stimulations for Saudi Aramco. In all cases, the new
emulsion proved to be stable more than 24 hours at
surface conditions.
In one case, a vertical gas-production well in
the South Ghawar field was hydraulically
fractured using the new SXE fluid system. At the
point of fracture, the limestone and dolomite
formation had an average permeability of 3.3 mD,
a temperature of 298F [148C] and a pressure of
5,000 psi [34.5 MPa]. Although surface
temperatures before pumping were above 100F
[38C], little mixing was required on location
prior to beginning fracturing or matrixstimulation operations. Initial surface injection
pressure was 8,900 psi [61.36 MPa], dropping to
6,972 psi [48 MPa] after fracturing. Production of
gas increased from 27 MMcf/d [764,640 m3/d] at
1,671 psi [11.5 MPa] to 34 MMcf/d [962,880 m3/d]
at 2,021 psi [13.93 MPa].
Not only were all wells successfully fractured,
but on average, the concentration of emulsifier
required to blend a stable fluid was reduced
by 80%, and time on location was decreased by
as much as six hours, significantly reducing the
cost of each treatment (left).

Oilfield Review

Its Cold at the Seafloor

Far from the extreme heat of Saudi Arabia, E&P
operators continue the search for energy
reserves deep below the ocean floor. In the Gulf
of Mexico (GOM), wells drilled in water depths
exceeding 1,000 feet [305 m] account for about
two-thirds of GOM oil production, a percentage
that is expected to continue to increase. These
fields contribute 17% of US oil production and 7%
of US gas output. Since the start of 2000, new
deepwater drilling added oil and gas reserves
totaling over 4.5 billion barrels [715 million m3]
of oil equivalent (BOE), a 58% increase over the
total deepwater reserves discovered from 1974 to
1999.6 In 2000, the US Minerals Management
Service (MMS) estimated that more than
50 billion barrels [7.9 billion m3] of equivalent
recoverable oil and gas remain to be discovered
in the deepwater GOM.
Drilling in this deep environment presents
unique challenges for equipment, processes and
fluid chemistry. Cementing operations through
low-temperature formations that are also prone
to shallow water flows are increasingly common
in the deepwater GOM and other locations
around the world including West Africa and
South America.
Near-freezing temperatures, flowing water
and formation material, gas-charged sands and
lost circulation challenge engineering teams as
they attempt to place and cement essential
surface casing strings. These cold temperatures
slow the cement hydration process, compromising gel- and compressive-strength development that are critical for structural support of
the wellhead and for minimizing fluid migration
behind the casing.
More than 60% of the deepwater wells in the
GOM have experienced shallow water flows
during drilling, a situation that poses a major
concern for drillers.7 Failure to achieve primary
cementing often leads to gas migration, costly
remedial cementing operations, or in the worst
case, well abandonment.
Conventional foamed cements have long been
used to combat these problems. However, these
cement systems are logistically complicated and
difficult to model and place, and present concerns
about long-term cement integrity. Schlumberger
engineers at the Houston CSL worked with
product center researchers to develop a new
cementing system specifically for the problems
associated with deepwater cementing.
The result was the DeepCEM deepwater
cementing solutions family of additives used in
combination with a fast-hydrating variant of the

Autumn 2006

DeepCRETE system
at 12 lbm/galUS
Conventional Class G
system at 15.8 lbm/galUS
Extended lightweight
system at 12 lbm/galUS
0

0.05

0.10
Permeability, mD

0.15

0.20

20

40
Solid fraction, %

60

80

DeepCRETE system
at 12 lbm/galUS
Conventional Class G
system at 15.8 lbm/galUS
Extended lightweight
system at 12 lbm/galUS

DeepCRETE system
at 13.5 lbm/galUS
Lightweight bentonite
extended system at
13.5 lbm/galUS
Sodium silicate extended
system at 13.5 lbm/galUS
0

200
400
600
800
Natural fluid loss with no fluid-loss additive, mL

1,000

> Stacking particles. By blending specific particle sizes (top), mixes of solids
and fluids can be made to have more fluidity, yet have more solids in
suspension (center graph). In the case of DeepCRETE cementing systems, a
specific mix of particle sizes produces a cement that is more easily pumped,
has lower permeability (top graph), lower fluid loss (bottom graph), and greater
durability, and also requires lower quantities of gas-migration additives.

CemCRETE concrete-based oilwell cementing

systemDeepCRETE deepwater cementing
solution.8 Through the adjustment of particle-size
distribution (PSD), DeepCRETE cement systems
can be prepared over a wide range of densities,
and provide intrinsic fluid-loss control, fast

setting times and compressive-strength development. Mixed in the same way as conventional
cements, DeepCRETE slurries are optimized to
accommodate the low bottomhole temperatures
and difficult cementing conditions encountered
in deepwater wells (above).

Temperature, C
Pressure, bar

30

0.6

25

0.5

20

0.4

15

0.3

10

0.2

0.1

Rate, standard cm3/min

To aid BP, the Houston CSL performed

multiple computer simulations to help optimize
centralizers, predict thermal effects of circulation and evaluate the effect of mud-removal
efficiency. Also performed were simulations of
heat-transfer effects, multiple temperature
gradients, well deviation, formation types and
the effect of varying fluid rheology on flow
dynamics. Key to the simulation process was the
output from temperature simulators that helped
CSL technicians optimize displacement and
cementing-fluid properties.
In deepwater applications, cement-sheath
mechanical properties are critical in maintaining zonal isolation and the longevity of the
wellbore. Even though initial cement placement
and set properties may appear optimal, changes
in wellbore temperature during production
cause expansion and contraction of the casing.

The low water content of these systems

enhances early gel- and compressive-strength
development, and the low densities minimize the
risk of losses in low fracture-gradient formations
(below). Using additional products such as
GASBLOK gas migration control additive or
DeepCEM additives can further provide inherent
resistance to shallow water and gas invasion.9 In
cold environments, DeepCEM additives provide
dispersion without retardation and a set
enhancer that produces a short transition time
between the slurry-liquid state and the setcement state.
In 2002, cementing surface casing strings on
two wells in the GOM presented a serious
challenge for BP. At water depths greater than
6,000 ft [1,829 m], wellhead temperatures are
near freezing and bottomhole static temperatures often remain below 50F [10C].

0
0

10

15

20

25

30

0.6

25

0.5

20

0.4

15

0.3

10

0.2

0.1

Rate, standard cm3/min

Temperature, C
Pressure, bar

Time, h
Temperature
Pore pressure
Gas rate
Piston rate

0
0

15

10

20

25

Time, h

> Gas invasion. Conventional extended cements are subject to gas invasion during the setting process.
At a specific point in time, the column of cement no longer transmits hydrostatic pressure. Thus, the
pressure exerted on the formation is below pore pressures. During this period, and depending on the
properties of the cement, gas may invade the annulus (top right). By its very nature, cements based
on engineered particle-size distributions avoid this problem by tightly packing particles in what
otherwise might be void spaces, preventing gas intrusion (bottom right). In comparative tests,
conventionally extended cement allows gas to migrate into the slurry (top left- yellow above magenta
curve), while DeepCRETE cements do not (bottom-yellow below magenta curve). The blue curve
represents test temperature.

10

Debonding or cracking may occur, creating a

microannulus, or path, for gas and other
wellbore fluids to migrate to the surface. The
DeepCRETE system was evaluated against
thermal cycling of as much as 200F [93C]
(next page). These tests suggested that the
cement sheath should maintain its integrity
throughout the life of the well.
The engineering team designed and pumped
more than 2,000 bbl [318 m3] of DeepCRETE
cement on two separate deepwater wells for BP.
Both slurries successfully cemented 20-in. casing
strings without incident. The combination of
advanced fluid chemistry, laboratory testing and
computer simulations performed by the CSL team
demonstrated the effectiveness of fit-for-purpose
cementing systems in a challenging thermal
environment. Since its introduction, DeepCRETE
slurries have been placed in more than 200
deepwater wells in the GOM and have helped
overcome many of the problems associated with
less advanced cementing systems.
Low LossesLow Damage
As shallow oil and gas reserves deplete, the E&P
industry has moved to hotter and deeper wells.
Whether a well is considered high temperature
depends on time and geographic areawhat was
considered a high-temperature well yesterday may
be considered normal tomorrow. More than half of
wells producing today have bottomhole temperatures (BHTs) ranging from 200 to 300F, a range
once considered hot. Estimates indicate that
around 5% of wells producing from sandstones
have BHTs greater than 300F, a percentage that
is expected to increase with time.
As with completions of ordinary wells,
excessive loss of completion fluids can lead to
formation damage and, worse yet, well-control
problems. Small volumes of thick fluids, or pills,
to control loss of fluid to the formation or for well
control, are often composed of high concentrations of crosslinked polymers such as hydroxyethyl cellulose (HEC), with or without bridging
agents such as calcium carbonate. These pills rely
on a combination of viscosity, solids bridging and
polymer filtercake buildup across permeable
zones to control fluid flow into the formation.
Unlike fracturing fluids, these pills need to be
stable for long periods of time. At elevated
temperatures, usually above 250F [121C], most
polymers begin to degradeviscosity is lost and
bridging agents alone cannot provide adequate
fluid-loss control. This situation is further
complicated when higher density divalent brines
are used, because they tend to inhibit polymer

Oilfield Review

Acceptable Compression

Traction Warning

Conventional Cement
Tangential stress at 150 min from start of simulation

No Microannulus
145

Tangential stress, psi

130

Casing
Cement

115

Formation

101

Tensile strength

87

Traction failure

72

Tangential stress
in cemented
annulus

58
43
29
14

0.0 1.7 3.4 5.0 6.7 8.4 10.1 11.8 13.4 15.1 16.8
Distance from well axis, in.

Acceptable Traction

DeepCRETE Cement
Tangential stress at 150 min from start of simulation

No Microannulus

Tangential stress, psi

Acceptable Compression

63.1
57.3
51.6
45.9
40.1
34.4
28.7
22.9
17.2
11.5
5.7
0.0
-5.7
-11.5
-17.2

Casing
Cement
Formation
Tensile strength
Traction failure
Tangential stress
in cemented
annulus

0.0 1.7 3.4 5.0 6.7 8.4 10.1 11.8 13.4 15.1 16.8
Distance from well axis, in.

> Thermal cycling. In deepwater environments, cements must withstand long-term thermal cycling that occurs as wells are taken on and off production.
Changes in wellbore temperatures may be dramatic as the casing cools down in the absence of warm production fluids. These temperature variations
cause expansion and contraction of the casing, transmitting compressional and tangential stress to the cement sheath. If the cement does not have
sufficient elasticity, and tensile and shear bond strength, it may debond from the casing, or fail in tension, creating the potential for hydrocarbon leakage
to the surface. Simulator output from conventional cement (top) and DeepCRETE systems tests (bottom) across a thermal cycling range of 40 to 200F
show that conventional cements risk tensile, or traction, failure (tangential stress approaches traction failure), while DeepCRETE cements exhibit much
higher tensile strength and tend to have greater shear-bond integrity than conventional cements.

hydration or minimize the polymers ability to

retain crosslinked structures.
Bridging agents themselves can cause
reductions in permeability or formation damage.
Studies with various particulate systems ranging

from calcium carbonate to oil-soluble resins and

fibers have shown varying levels of permeability
reduction.10 Typically pills comprising polymer
and bridging agent require some level of
remediation, such as an acid treatment, to

remove the deposited materials and polymer

damage after the completion process.11 Because
of the presence of acid-sensitive clays in some
sandstones, remedial-acid treatments may
actually do more harm than good.

9. GASBLOK systems control annular gas migration during

cementing. These systems include a nonretarding liquid
that provides fluid-loss control and gas-migration control
properties for cement slurries at temperatures from 80 to
160F [27 to 71C] across a wide range of densities
as low as 10.5 lbm/galUS [1,258 kg/m3]. The GASBLOK
additive is a suspension of polymeric microgels that act
as fluid-loss reducers by rapidly plugging the pore
throats of the cement filtercake. The microgels in the
interstitial water of the cement matrix reduce cement-

matrix permeability and decrease the continuity

between pores during the critical liquid-to-solid
transition phase, further limiting gas migration.
For more on the GASBLOK system: Bonett A and
Pafitis D: Getting to the Root of Gas Migration,
Oilfield Review 8, no. 1 (Spring 1996): 3649.
10. Samuel M, Marcinew R, Al-Harbi M, Samuel E, Xiao Z,
Ezzat AM, Khamees SA, Jarrett C, Ginest NH, Bartko K,
Hembling D and Nasr-El-Din HA: A New Solids-Free

Non-Damaging High Temperature Lost-Circulation Pill:

Development and First Field Applications, paper
SPE 81494, presented at the 13th SPE Middle East Oil
Show, Bahrain, June 912, 2003.
11. For more on completion fluids and processes: Ali S,
Bowman M, Luyster MR, Patel A, Svoboda C,
McCarty RA and Pearl B: Reversible Drilling-Fluid
Emulsions for Improved Well Performance, Oilfield
Review 16, no. 3 (Autumn 2004): 6268.

Autumn 2006

11

0.1 micron

> Micrograph of micelles. Viewed through a transmission electron microscope, VES molecules
dispersed in an aqueous solution tend to associate and form rod-like structures that then entangle and
create a viscosifying effect. This image shows small rod-like micelles.

> VES contact with a hydrocarbon. A 10% VES fluid has high viscosity (left). On contact with a
hydrocarbon solution, the viscosity is broken and the solution flows easily (right).

New, nondamaging, polymeric viscoelastic

surfactant (VES) fluids have demonstrated
distinct advantages over polymer-base fluids
when applied to hydraulic fracturing, diversion,
matrix stimulation, sand control and acid
fracturing.12 Recently, engineers at the Kuala
Lumpur CSL responded to increasing borehole
temperatures and formation-damage problems
by developing a VES, solids-free, surfactant base,
fluid-loss pill for high-temperature completions
in Saudi Arabia.

12

The VES pill system requires only two

products, a blended zwitterionic-base surfactant
and heavy brine.13 Similar to other VES systems,
the VES surfactant forms long structures
called micelles when blended with brines (top).
Micelles are relatively long structures that
entangle to increase viscosity. Typical
formulations will not pass through a size-6 mesh
screen, with 0.747-in. [1.91-mm] openings, even
without the presence of solids. However, in the
presence of hydrocarbons or formation water, the

viscosity tends to break, leaving virtually no

damaging residue behind (bottom).
In laboratory analysis under simulated
downhole conditions, fluids engineers at the
Kuala Lumpur CSL found that the VES pill was
stable at 350F [177C] for more than 24 hours,
and at 280F [138C] for more than a week (next
page, top). The pill was also subjected to heating,
cooling and shear cycles (next page, middle).
Testing confirmed that the viscosity decreased
slightly at elevated temperatures and was shear
thinning, but recovered almost completely as
temperature and shear were reduced. Further
tests indicated that increasing brine density and
blending with divalent brine tended to increase
viscosity and improve thermal stability.
Having defined and thoroughly tested the
new VES pill system, CSL engineers worked with
Saudi Aramco to field-test the fluid on a 14,270-ft
[4,350-m] well in Saudi Arabia, where bottomhole temperatures were expected to reach 270F
[132C]. Formation porosity ranged from 7 to
20% in the zones of interest. After the well was
perforated, the overbalance pressure was
controlled at 430 psi [2,964 kPa] while running
the gravel-pack assembly in the borehole.
Borehole fluids had previously been displaced
with 11.1-lbm/galUS [1,330-kg/m3] calcium
chloride [CaCl2] brine. An initial fluid-loss rate
was established at 60 bbl/h [9.5 m3/h].
Engineers blended approximately 50 bbl
[7.9 m3] of VES pill using 10% surfactant by
volume and CaCl2 brine. The fluid was spotted
across the loss zone at a rate of 1 bbl/min
[0.16 m3/min]. As the gel pill reached the
perforations, an incremental pressure increase
of 250 psi [1,724 kPa] was noted. Further pills of
16 and 20 bbl [2.5 and 3.2 m3] were spotted
across the perforated zone, resulting in pressure
increases of 550 and 650 psi [3,791 and
4,481 kPa], respectively. No brine was lost during
the first 10 hours after injection.
After removing the tubing-conveyed perforation guns, circulating the borehole and increasing the brine density to 11.5 lbm/galUS
[1,378 kg/m3], engineers noted that the fluid loss
had gradually increased to an average of 7 bbl/h
[1.1 m3/h] of over a three-day period. Another
30 bbl [4.8 m3] of VES pill was spotted, reducing
the brine loss to 1.6 to 2.2 bbl/h [0.25 to
0.35 m3/h] while running the screens, packer and
service-tool assemblies into the hole. A fluid-loss
rate of 2 to 6 bbl/h [0.32 to 0.95 m3/h] was
maintained during the subsequent four-day
period. After successfully hydraulically fracturing the formation, engineers tested the well at

Oilfield Review

Viscosity, cP

Temperature,
F

1 s-1

10 s-1

40 s-1

100 s-1

170 s-1

Time,
h:min

Viscosity, cP

Temperature,
F

1 s-1

10 s-1

40 s-1

100 s-1

170 s-1

87

3,433

919

366

246

182

0:00

75

12,612

2,021

671

324

212

104

3,571

920

356

237

173

0:05

100

19,353

2,688

819

373

237

146

12,825

2,302

693

413

278

1:00

200

359

281

242

219

207

204

28,947

4,655

1,298

749

491

1:30

300

225

71

35

22

17

249

15,048

2,373

652

374

244

2:00

325

546

104

38

20

14

277

18,065

2,611

676

377

242

2:30

350

263

71

32

19

14

302

1,713

781

451

356

297

3:30

350

508

98

36

19

13

311

781

480

341

295

264

4:30

350

498

94

34

18

12

323

266

238

220

213

207

5:30

350

522

101

37

19

13

325

251

225

207

201

195

6:30

350

383

96

41

24

17

333

147

149

152

152

153

7:30

350

661

127

47

24

17

353

42

58

73

81

87

362

18

31

46

54

61

375

11

24

33

42

> Thermally stable viscosity. VES solutions impart viscosity across a wide range of temperatures, and at low shear rates. The apparent viscosity of a
10% VES fluid blended with 12.7-lbm/galUS [1,522-kg/m3] calcium bromide [CaBr2] completion fluid shows that even at 375F [191C], the fluid retains some
viscosity (left). To improve the viscosity retained at elevated temperatures, tests were conducted using 15% VES fluids blended with 12.5-lbm/galUS
[1,498-kg/m3] calcium chloride [CaCl2] brine plus 5% methanol. After seven hours, significant viscosity was retained (right) even at 1 s-1 shear rate,
indicating the fluids applicability as a lost circulation pill.

Autumn 2006

300

250

200
150
150
100

Temperature, F

250

200

Viscosity, cP

60 MMcf/d [1.7 million m3/d] at a flowing

wellhead pressure of 3,900 psi [26.9 MPa]. Saudi
Aramco considered this first field test of the VES
pill system a success.
Saudi Aramco and the CSL engineering team
pushed the fluid system to more than 310F
[154C] on their next test well. Pressure-transient
analysis indicated a transmissibility of more than
500,000 mD-ft/cP, nearly 14 times greater than the
first test.14 Engineers realized that keeping fluids
in the hole would be a serious challenge. The well
was completed with 231 ft [70.4 m] of perforations, then hydraulically fractured and gravel
packed. The initial overbalance was 450 psi
[3.1 MPa] with 11.5-lbm/galUS CaCl2 brine in
the wellbore.
The initial stabilized fluid-loss rate was
6 bbl/h. Engineers believed that this low rate was
the result of formation damage. With the release
of the frac-pack service tool, losses increased to
60 bbl/h. Several VES pills were pumped successfully, reducing losses to between 20 and 30 bbl/h.
However, increased fluid viscosity alone could
not control fluid losses in this well.
Calcium carbonate bridging agents blended
with the VES pill successfully reduced losses to
between 1 and 4 bbl/h [0.16 and 0.64 m3/h].
Although bridging agents were required, the near
elimination of losses allowed the operator to
maintain pressure control and successfully
complete the well. Generally, subsequent treatment to remove residual VES pill material is

100
50
Viscosity

50

Temperature

0
0

50

100

150

200
250
Time, min

300

350

400

450

> Stability with thermal cycling. Laboratory tests demonstrate that VES fluids retain much of their
viscosity through thermal cycling events. Over a 612-hour period, only a slight decrease in viscosity
(red) was noted as the VES fluids were cycled from 75 to 280F [24 to 138C] (blue).

not required. However, when necessary, a

solution of 5 to 10% mutual solvent completely
breaks the pill, often returning nearly 100% of
the original permeability.
The engineers and scientists at the Kuala
Lumpur CSL responded to a local client problem
with a customized solution that achieved both
simplicity and effectiveness under the extreme
conditions of temperature, permeability and
complex well operations. The VES pill system has
subsequently been used successfully on many
wells within and outside of the Middle East.

12. For more on VES fluids: Kefi S, Lee J, Pope TL, Sullivan P,
Nelson E, Nuez Hernandez A, Olsen T, Parlar M,
Powers B, Roy A, Wilson A and Twynam A:
Expanding Applications for Viscoelastic Surfactants,
Oilfield Review 16, no. 4 (Winter 2004): 1023.
Al-Anzi et al, reference 4.
13. A zwitterionic compound contains positive and
negative charged groups, with a change in net charge
depending on the pH of the solution. Amino acids such
as alanine, glycine and histidine are examples of
zwitterionic compounds.
14. Transmissibility is a parameter relating to the properties
of a reservoir, specifically the fluid flowing through it, the
direction of flow, and the fluids position relative to other
elements of the reservoir system.

13

14

16
14

Crosslink-delay time, min

Extending Crosslink-Delay Times

at High Temperatures
The fluids used in hydraulic fracturing
operations must have sufficient viscosity to keep
the fracture open during the pumping process
and to help transport proppant down the length
of the fracture. The flow regime while pumping
down the wellbore is turbulent, helping to
transport the proppant. During this phase of the
fracturing treatment, drag reduction can become
more important than the carrying capacity,
particularly in deep wells.
To minimize drag and pumping pressures,
most fracturing fluids are designed to crosslink
after traveling the depth of the well and before
entering the fracture, referred to as delayed
crosslinking. The delay is usually a function of
both time and temperature.
Fluids with delayed crosslinking times are
blended at the surface with delayed-crosslinking
agents that allow the fluid to be pumped
downhole at lower viscosities, thus reducing
pumping pressures. In time, usually on the order
of a few minutes, the crosslinker activates and
viscosifies the guar fluid, helping to carry
proppant deep into the open fracture.
Deep-well fracturing operations challenge
the chemistry and physical properties of
fracturing fluids. This is primarily because of the
long traveltime between the surface and the
fracture, and the subsequent early rise in
fracturing-fluid temperature that interferes with
the crosslink-delay mechanism. Early in 2005,
Tri-Valley Oil & Gas Corporation required a
unique fracturing fluid for a deep, hightemperature well in California. The objective was
to stimulate potential untapped resources of
Vedder Sand between depths of 18,000 and
18,500 ft [5,486 and 5,639 m].
With a bottomhole static temperature of
350F, the long fracturing-fluid traveltime down
the wellbore and high treatment pressures were
of primary concern to the operator.
Schlumberger field engineers working with the
Stimulation CSL in Sugar Land reviewed the
hydraulic fracturing program and determined
that a fluid with an adjustable crosslink-delay
time in the range of 4 to 12 minutes would be
required to transport proppant downhole and
into the hydraulic fracture while minimizing
surface treating pressures. With proper crosslink
delay, the fracturing fluid can withstand the long
shear time in the tubulars without compromising
proppant-transport characteristics.

12
10
8
6
4
2
0
Old

Short delay
Medium delay
Crosslinker

Long delay

> Adjusting delay times. The new crosslinker helps engineers accurately
control crosslinking-delay times. The three available versions of the product
offer short, medium and long delay times.

Guar polymers reach their thermal limit as

the exposure temperature approaches 325F
[163C]. Therefore, water-base fracturing fluids
generally use guar derivatives like carboxymethyl
hydroxypropyl guar (CMHPG) at higher temperatures for improved thermal stability. However,
the necessity for a long crosslink-delay time
ruled out this option. The long crosslink-delay
time would have negatively affected the stability
of the CMHPG fluid. On the other hand, not
delaying the crosslinking sufficiently would
expose the fluid to shear degradation.
The Sugar Land Stimulation CSL evaluated
YF100EC crosslinked water-base fracturing fluid,
a delayed, borate-crosslinked fracturing-fluid
system designed for high temperatures.15 This
fluid incorporates an encapsulated borate crosslinker. As the encapsulation around the borate
material slowly dissolves at high pH, the guar
begins to crosslink, thickening the fracturing
fluid. Optimally, this crosslinking should occur
just as the proppant enters the fracture.
Laboratory testing of the YF100EC encapsulated crosslinker showed that it could not
withstand the high wellbore temperatures long
enough for the fluid to reach the bottom of the
well and enter the fracture. The crosslinker used
in the YF100EC fluid system had a fixedthickness layer of encapsulating material,
limiting its usefulness in high-temperature
applications. Collaboration with the manufacturer produced a series of multilayered encapsulating crosslinker products. With three
thicknesses available, the new fluid system can
address short, medium and long delay times,
providing flexibility for a wider range of
treatment designs (above).

In February 2005, Tri-Valley and Schlumberger

engineers applied the new system to set a
fracturing record for Californias deepest
fracturing treatment. About 195,000 galUS
[738 m3] of fracturing fluid was pumped at
20 bbl/min at more than 12,000-psi [82.7-MPa]
surface pressure to successfully place 118,000 lbm
[53,524 kg] of sintered bauxite proppant.
The hydraulic fracturing treatment exceeded
Tri-Valleys expectations. With lower than
expected treating pressures the treatment
created a fracture that extended as far as 1,500 ft
[457 m] from the wellbore.
Green Chemistry
Today, chemicals used in the E&P industry are
required not only to perform at the edge of their
thermal limits, but also to comply with increasingly
demanding environmental requirements.
In the North Sea, operators face cold surface
temperatures, deep water, hostile seas and
complex, hot boreholes. While drilling and
production conditions become more difficult,
many of the common chemical formulations used
are quickly becoming environmentally unacceptable. Regulatory agencies in many countries are
15. Barton K, Fisher D, Gadiyar BR, Morales RH, Nelson E
and Sorrells D: Successful Application of a Unique and
Low Friction Frac-Pack Fluid in Gulf of Mexico Deep
Wells, paper SPE 94799, presented at the 6th SPE
European Formation Damage Symposium,
Scheveningen, The Netherlands, May 2527, 2005.
16. Guidelines to Regulations Relating to Conduct of
Activities in the Petroleum Activities, section 56b:
http://www.ptil.no/regelverk/r2002/Aktivitetsforskriften_
Veiledning_e.htm (accessed October 4, 2006).

Oilfield Review

120
Not allowed for discharge

Number of additives

100

Prioritized for substitution

Environmentally acceptable

80

Posing little or no risk

60
40
20
0
2000

2001

2002

2003

2004

2005

2006

2000

2001

Well production

2002

2003

2004

2005

2006

Well cementing
Type of service and year

> Green chemistry. The chart shows the progression of Schlumberger chemistries toward
environmental acceptability in Norway during the last seven years. By the end of 2005, black
products had been eliminated from well production and cementing.

Most of COPNos stimulation operations are

in soft chalk formations with a bottomhole static
temperature of nearly 250F. Many of the
treatments performed are with regular HCl, a
system that generally requires many additives.
During 2004 and 2005, all of the additives used by
the BIGORANGE XVIII vessel in conventional
acid treatments were replaced by greener
alternatives, except for the acid-corrosion inhibitor.
Acid-corrosion inhibitors have historically had
poor environmental profiles. Since no known
chemical formulations met both the environmental and performance criteria, these products
were difficult to replace.
To meet the changing demands of field
conditions in the North Sea, the Aberdeen
CSL would need not only to replace the product,
but also to increase its thermal stability from
200 to 280F while meeting the new environmental requirements.

demanding that greener products be used in

E&P operations, regardless of whether they will
be discharged into the sea (above).
Products used in acidizing have not
avoided the greening process. Operating
from the BIGORANGE XVIII offshore vessel,
Schlumberger works under contract with
ConocoPhillips Norway (COPNo) to deliver
matrix-acidizing operations for wells in the
Norwegian sector of the North Sea. As of
January 1, 2006, all treatment additives and
fluids used in Norwegian waters were subject to
updated environmental requirements, called
Zero Harmful Discharge. This legislation
requires operators in Norwegian waters to have
zero discharge of environmentally harmful
chemicals, the so-called red and black
chemicals.16 Operators must now select
chemicals with properties that are least harmful
to the environment, thus encouraging suppliers
to develop greener chemicals.

Engineers with the Green Chemistry section

at the Aberdeen CSL established several
collaborative projects with outside suppliers
known for their expertise in oilfield-corrosion
inhibition. With support from Schlumberger
safety and environment professionals in
Moerdijk, The Netherlands, and the
Schlumberger Corrosion Engineering Laboratory
in Sugar Land, Texas, the older cinnamaldehyde
quaternary amine corrosion inhibitor was
replaced with an environmentally acceptable
formulation in early 2006, making Schlumberger
the first company to offer a full range of HCl
treatment fluids with all additives classified as
environmentally acceptable in Norway.
All components of the new system were
tested to determine biodegradation, potential for
bioaccumulation and toxicity. Ecotoxicological
tests determined that all of the chemical
components of the new inhibitor, B208, exhibit
greater than 60% biodegradation while providing
the same thermal stability and corrosion
protection as its predecessor when used at the
same concentration and under the same
conditions (below).
Cleaning out Sand from Hot Wells
Most fluids used for oilfield operations are waterbase. They tend to be readily available, less
harmful to the environment and often less costly
than oil-base fluids. However, studies have shown
that in some situations, water-base systems can
promote clay swelling and emulsion blocking,
and can potentially alter the wettability of pore
throats, thus damaging reservoirs. Hydrocarbonbase fluids are typically chosen to minimize
these effects.
It is usually more difficult to viscosify an oilbase fluid than a water-base fluid, particularly
when maintaining a solids-free system. In the
1960s, aluminum salts of carboxylic acids such as
aluminum octonate were used to raise the

Corrosion

Formulation
Acid

Product
code

Pitting
Concentration,
gal/1,000 galUS Specification
Actual

Product
code

Concentration,
%

Product
code

Concentration,
gal/1,000 galUS

28% HCl

A259

0.60

A201

20.0

28% HCl

B208

0.60

A201

20.0

A153

4.2

15% HCl

A259

0.50

15% HCl

B208

0.50

7.5% HCl

A259

0.50

10% HCl

B208

0.50

0 preferred
3 maximum

0 preferred
3 maximum

0 preferred
3 maximum

0
0
0

Rate, lbm/ft2
Specification

Actual

0.020
maximum

0.006

0.020
maximum

0.007

0.020
maximum

0.007

0.010
0.012
0.009

> Matching corrosion performance. In laboratory corrosion tests on #13 chrome steel, the new B208 inhibitor gives nearly the same corrosion protection
as the older less environmentally friendly product, A259.

Autumn 2006

15

350

Viscosity, cP at 10 s-1

300
250
YFGO IV
PowerCLEAN-OB

200
150
100
50
0
80

90

100

110
120
130
Temperature, F

140

150

160

4,000

Viscosity, cP

3,500

170

400
at 40 s-1
at 100 s-1

at 170 s-1
Temperature, F

350

3,000

300

2,500

250

2,000

200

1,500

150

1,000

100

500

Temperature, F

70

50

0
0
0:00:00 0:28:48 0:57:36 1:26:24 1:55:12 2:24:00 2:52:48 3:21:36 3:50:24 4:19:12 4:48:00
h:min:s

> Gelled-oil performance. Gelling oil with VES chemistry (photograph) generates
substantially higher and more sustainable viscosity than conventional chemistries (top).
The oil-base PowerCLEAN-VES fluid retained sufficient viscosity at elevated temperature
to help remove borehole debris and suspend material across a range of temperatures
and flow conditions (bottom).

16

viscosity of oil-base treating fluids.17 The

moderate level of thermal stability and solidscarrying capacity demonstrated by these systems
have led to their use as fracturing fluids.
In the 1970s, aluminum phosphate ester salts
replaced aluminum carboxylate salts, slightly
increasing both thermal stability and solidstransport efficiency. Today, these salts remain
the preferred method for viscosifying oil-base
fracturing fluids.
Scientists believe that aluminum complexes
and phosphate ester molecules produce long
polymer chains that thicken the oil by an
associative mechanism. Varying the quantities of
aluminum compound and phosphate ester
controls the viscosity of these systems. Typically,
increasing the concentration of various esters of
phosphoric acid improves high-temperature
performance. However, this often results in high
viscosities in the surface system, making the
fluid sticky and difficult to pump.
Common gelled-oil systems exhibit performance shortfalls in many of todays wells. The
viscosity in conventional oil-base systems is
sensitive to product concentration and base-oil
quality, and often generates high friction
pressures during pumping. This is particularly
problematic for coiled tubing (CT) sand-cleanout
operations, which required careful control of
circulating pressures and carrying capacity.18
Although VES materials have been successfully used to generate viscosity in water-base CT
cleanout fluids, the thermal and chemomechanical performance of these fluids did not
outweigh their formation-damage potential in
wells operated by Saudi Aramco in the northern
area of Saudi Arabia. In these water-sensitive,
high-temperature formations, conventional gelledoil systems are typically used for CT sand-cleanout
operations. However, to maintain carrying
17. Samuel M, Nasr-El-Din HA and Jemmali M: Gelled Oil:
New Chemistry Using Surfactants, paper SPE 97545,
presented at the SPE International Improved Oil
Recovery Conference in Asia Pacific, Kuala Lumpur,
December 56, 2005.
18. For more on sand cleanout: Ali A, Blount CG, Hill S,
Pokhriyal J, Weng X, Loveland MJ, Mokhtar S, Pedota J,
Rdsj M, Rolovic R and Zhou W: Integrated Wellbore
Cleanout Systems: Improving Efficiency and Reducing
Risk, Oilfield Review 17, no. 2 (Summer 2005): 413.
19. Samuel M, Card RJ, Nelson EB, Brown JE, Vinod PS,
Temple HL, Qu Q and Fu DK: Polymer-Free Fluid for
Hydraulic Fracturing, paper SPE 38622, presented at
the SPE Annual Technical Conference and Exhibition,
San Antonio, Texas, October 58, 1997.
Nasr-El-Din HA, Samuel E and Samuel M: Application of
a New Class of Surfactants in Stimulation Treatments,
paper SPE 84898, presented at the SPE International
Improved Oil Recovery Conference in Asia Pacific,
Kuala Lumpur, October 2021, 2003.
20. For more on sand cleanout with coiled tubing: Ali et al,
reference 18.

Oilfield Review

capacity and minimize friction pressures,

operators often resorted to foaming the gelled-oil
systems with fluorosurfactants, adding complexity
and further reducing environmental acceptability.
The Kuala Lumpur CSL responded to this problem
by exploring novel methods for viscosifying
hydrocarbon-base fluids.
In water-base fluids, surfactants can form
various types of micelles such as spherical,
worm-like, rod-like, lamellar and vesicular.19 The
specific micelle produced depends on the nature
of the surfactant, its charge, tail length, head
structure and the base-fluid composition. The
formation of a given type of micelle in the fluid
system is maximized by adjusting the type of salts
present, the pH and other conditions.
In aqueous fluids, the surfactants are selfassembled to form micelles with their head
group oriented towards the aqueous phase. In
hydrocarbon solutions, scientists theorize that
the VES materials assemble with their head
groups at the core of the micelles, leading to the
formation of inverted micelles. In this special
micelle, the hydrocarbon tail of the surfactant
can entangle with the hydrocarbon-base fluid.
Data from simulations and laboratory
analysis conducted at the Kuala Lumpur CSL
demonstrated that VES materials can be used in
hydrocarbon-base fluids to generate stable
viscosities. Relative to conventional gelled-oil
systems, smaller concentrations of additives
produce a several-fold increase in viscosity
(previous page). For CT cleanout operations, the
oil-VES fluid demonstrates high viscosity at low
shear, yielding improved solids-suspension
characteristics. Technicians at the CSL also
found the oil-VES system to be significantly less
sensitive to variations in oil characteristics.
During the last three years in Saudi Arabia,
the new PowerCLEAN-OB engineered fill
removal service successfully removed sand from
more than 30 wells in which water-sensitive
formations were exposed. The bottomhole
temperature of those wells ranged from 220 to
280F [104 to 138C]. Foaming was not required
for most of these treatments. On average, dieseloil volume requirements were reduced, while the
carrying capacity and static-suspension characteristics of the cleanout fluids increased.20 In two
direct comparisons on wells in Saudi Arabia,
several hundred feet of sand were removed with
12% lower circulating pressures and in just over
half the time using the new oil-VES cleanout fluid
(above right).

Autumn 2006

Conventional Gelled Oil

PowerCLEAN-OB

A166

A168

Directionally drilled

Directionally drilled

Expected fill

375 ft

275 ft

Perforations

7,333 to 7,346 ft
7,371 to 7,394 ft

7,436 to 7,458 ft
7,476 to 7,500 ft

TD

7,885 ft

7,798 ft

Actual fill

404 ft

320 ft

Pump rate

1 bbl/min

1 bbl/min

Well

Pump rate reduced when using

nitrogen; maximum pressure 3,000 psi
Circulation pressure

2,500 psi

2,200 psi

Time taken

36 h

20 h

> Cleaning out sand in Saudi Arabia. On two similar wells, the PowerCLEANOB VES oil-base system reduced cleanout time using coiled tubing by more
than 40% and reduced circulating pressure by 300 psi [2,068 kPa].

Extending the Limits

Since the beginnings of the modern oil and gas
industry, engineers and scientists have
continued to push the limits of technology. From
the first well stimulations using nitroglycerin, to
drilling and producing wells deep beneath the
oceans, our industry has continued to evolve.
As we reach further for Earths remaining
hydrocarbon reserves, surface and downhole
temperatures continue to challenge the chemistries used in drilling and completions, and
those that keep current wells producing. The
thermal challenges facing the E&P industry are

too broad to be completely covered in this

article. The cases we present highlight only a
few recent developments. The road ahead not
only promises continued advances in the
thermal performance of oilfield chemistry, but
also improvements in instrumentation and
completion technologies designed to meet the
ever-increasing thermal challenges of todays
drilling and production environments. DW

17