AGH DRILLING, OIL, GAS • Vol. 30 • No.

1 • 2013
http://dx.doi.org/10.7494/drill.2013.30.1.191

Candice Palmer*, Zbigniew Sito*

NITROGEN AND CARBON DIOXIDE FRACTURING FLUIDS

FOR THE STIMULATION
OF UNCONVENTIONAL SHALE PLAYS

1. INTRODUCTION

The International Energy Agency estimates that natural gas has a 21% share in the
global energy mix with oil (34%) and coal (27%) holding the first and second largest shares
respectively. Natural gas is a vital energy source for electricity generation, industrial purpo-
ses, heating applications in commercial and residential buildings, and other applications.
Due to the abundance of natural gas reserves across the world and the pressure to meet
increasing global energy demand, partly driven by global population growth and global
economic development in particular in Asia and Latin America, there will be increasing
growth in the development of unconventional gas reserves. By way of illustration, Figure 1
shows the historical and projected sources of natural gas in the US from 1990 to 2035.
Interestingly, by 2035, the US Energy Information Administration (EIA) predicts that unco-
nventional gas sources will dominate natural gas supply with shale gas and tight gas consti-
tuting 70% of the supply.
The increasing pressure to develop unconventional gas reserves will require advance-
ments in hydraulic fracturing, particularly hydraulic fracturing fluids. An archetypal fractu-
ring fluid consists of a fluid system (e.g. water, oil, gas, and alcohols), chemical additives,
and proppant (e.g. sand). This fluid mixture has two main functions, which is to enable
fracture initiation and to facilitate proppant transport. For efficient fracture initiation, the
fracturing fluid must be able to create and extend a fracture at subsurface levels by transmit-
ting hydraulic energy from the surface into the given reservoir. For effective proppant trans-
port, the fracturing fluid must have sufficient viscosity to transport the proppant from the
surface into the fracture. When proppant transport has been achieved, chemical additives
are used to reduce the viscosity of the fracturing fluid to maximize the fracture conductivity.

* Air Products and Chemicals

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 Fig. 1. US Natural Gas Production 1990–2035 (trillion cubic feet)
(Source: US EIA)

When analysing the design of an ideal fracturing fluid system (i.e. base fluid, additives,
and proppant), several physical and chemical parameters need to be achieved for successful
well stimulation (Economides and Martin, 2007). These parameters include:
– Ease of operational preparation and inexpensive cost.
– Good compatibility between the rock formation and the fracturing fluid; for example,
water-based fracturing fluids are unsuitable for highly water sensitive formations
because they can hinder significantly the mass transport of gas and/or oil from the
fracture to the surface.
– Sufficient maintenance of the desired viscosity at a given reservoir temperature to faci-
litate suspension and proppant transport into the fracture.
– Low fluid loss properties to prevent water saturation and clay swelling of the for-
mation.
– Strong flowback characteristics to enable easy and rapid removal from the formation
without causing formation damage.
– Good proppant suspension that allows effective transport into the fracture.
– The ability to pump easily the fracturing fluid into the well bore, which minimizes
losses in friction pressure in the pipe and in the fracture.

In reality, satisfying these ideal parameters is rarely achieved; hence, considerable

effort has been invested by researchers and practitioners in industry and academia to impro-
ve the performance of fracturing fluids.

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2. NITROGEN AND CARBON DIOXIDE FRACTURING FLUIDS

Nitrogen and carbon dioxide fracturing fluids can be used as alternative fracturing
fluids to water based treatments when there are concerns about water sensitivity and clay
swelling. Specifically, they can offer several advantages, which include:
– Rapid cleanup of flowback fluid.
– Non-damaging impact in water sensitive formations.
– Enhanced production of natural gas and oil in low permeability and low porosity for-
mations.
– Suitability for shallow formations and depleted gas reservoirs.
– Reduced water requirements.
The main types of nitrogen and carbon dioxide fracturing fluids are energized, foam,
straight gas (mists), and cryogenic liquids. Foam fracturing fluids typically consist of
a water-based system and a gas phase of nitrogen and/or carbon dioxide in the range of 53%
to 95% by volume. Below 53%, the fracturing fluid is considered energized, and above
95%, the fracturing fluid is considered a mist. Cryogenic liquids have also been used as
fracturing fluids; however, they are rarely employed in commercial operations due to spe-
cial piping and equipment requirements.
In North America, well operators have been using nitrogen and carbon dioxide fractu-
ring fluids since the 1970s for the stimulation of unconventional shale and coal bed methane
plays. To demonstrate the use of nitrogen and carbon dioxide based fracture treatments, the
summary, presented below, discuss some experiences from various operators in the Devo-
nian, the Montney and the Marcellus shale plays. For reference, a map of the North America
shale plays is presented in Figure 2.

Fig. 2. North American Shale Plays (Source: US EIA)

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2.1. Nitrogen based treatments in the Devonian shale play

Located in the Appalachian Basin, the Devonian shale play includes several for-
mations such as the Huron, Cleveland, and Rhinestreet, which are located in Kentucky,
Virginia, and West Virginia. This shale play is highly developed, where the total active re-
gion is estimated to be 8,675 square miles and the undeveloped region is estimated to be
1,994 square miles (EIA, 2011). Evaluating the characteristics of the Devonian shale rock
reveals that it has a low permeability, low porosity, high water sensitivity, and a high pro-
portion of natural fractures. Due to these characteristics, nitrogen fracture treatments has
been used since 1978 as the most common used well stimulation method (Gottschling,
1985, Grundmann, 1998).
In 1981, one of the early uses of nitrogen gas treatments was reported by Baker Hughes
in the Devonian Shale play, where they carried out five stimulation treatments with well
depths ranging from 730 m to 1070 m (Abel, 1981). The author cites that the main advanta-
ges of nitrogen gas treatments include: prevention of formation damage due to the inertness
and compressibility of nitrogen; prevention of clay swelling and water saturation that would
adversely affect hydrocarbon permeabilities; elimination of clean up issues related to liquid
based treatments; and, reduction of lost time in the production process used to recover liqu-
id based fracturing fluids.
Elsewhere, in 1985, work carried out by BJ Titan Services reports the use of nitrogen
gas and proppant (20/40 mesh sand) treatments in 17 field tests across the Devonian shale
play including regions located in West Virginia and Ohio (Gottschling, 1985). In compa-
rison to fracturing with nitrogen gas treatments alone, the author reports that the use of
proppant and nitrogen gas treatments increased the production rates of the wells.
In 1998, work carried out by Halliburton and Basin Energy explains that liquid nitro-
gen fracturing can be used successfully as a treatment fluid because the cold temperature
of the fluid causes fragmentation of the fracture face, which opens up efficiently the indu-
ced fracturing (Grundmann, 1998). In term of equipment requirements, the liquid nitrogen
was pumped using five high rate nitrogen-pumping units, which differs from nitrogen gas
treatments that require eight to ten units. In summary, the author reports the successful use
of liquid nitrogen as a fracturing fluid.
Recent technological advancements in hydraulic fracturing fluids have led to operators
experimenting with newer chemical formulations such as nitrogen foams containing visco-
elastic surfactants. For example, in 2009, BJ Services reports that operators in the Lower
Huron have used chemical additives, such as guar or viscoelastic surfactants, to increase the
viscosity of the fracturing fluids, which will aid the transport of proppant into the fracture
(Rowan II, 2009). However, the author explains that the use of guar and guar derivatives is
inexpensive and common practice, but they often leave a residue in the well formation that
hinders that gas production rates. Consequently, operators are forced to use breakers, such
as ammonia persulfate or sodium chloride, to break up the residue. In contrast, recent deve-
lopments in viscoelastic surfactants have allowed operators to reduce the number of chemi-
cal additives used in fracturing fluids because foaming agents and breakers are not required.

194
However, the author acknowledges that the use of viscoelastic surfactants can be expensive
because a high surfactant loading is required.
In another publication, to optimize the well completion process in the Lower Huron
Shale region in 2010, EQT Corporation carried out a comparative study into different nitro-
gen based fracturing fluids namely nitrogen gas fracture stimulations, nitrogen foam fractu-
re stimulations, and hybrid nitrogen fracture stimulations (Wozniak, 2010). For clarification
purposes, the composition of the different fracture treatments is presented in Table 1.

Table 1
Composition of Fracture Treatments in Volumes per Stage used for a Comparative Study
into Nitrogen based fracturing fluids (Wozniak, 2010)

Fluid Type N2 Volume (scf) Water Volume (bbl) Sand (Ibs)

Nitrogen 1,000,000 <10 0

Foam 800,000 300 40,000
Hybrid 900,000 50 15,000

The authors report that they expected that the total estimated quantity of gas recovera-
ble from a well, defined as the estimated ultimate recovery (EUR), for nitrogen foam treat-
ments would be higher than nitrogen gas treatments. However, unexpectedly, the produc-
tion data from the comparative study contradicted their prior assumption because the nitro-
gen gas treatments offered the highest EURs and analysis of their results revealed that
the well performance from nitrogen gas fracture treatments were 28% higher than foamed
fracture treatments and 8% higher than ultra higher quality nitrogen foam treatments. Con-
sequently, as a direct result of this study, EQT Corporation have changed considerably their
operational practices, where they have discontinued using foamed fracturing fluids in the
Lower Huron formation and the Cleveland shale region in Kentucky at the beginning of
2010. Moreover, EQT Corporation state that the use of nitrogen gas fracture treatments
offers an additional economic benefit because they are approximately US $50,000 cheaper
than nitrogen foam and hybrid fracture treatments (Wozniak, 2010).

2.2. Nitrogen and Carbon Dioxide treatments in the Montney Play

The Montney shale gas play is located in the Western Canada Sedimentary Basin span-
ning a total area of 2961 km2, where it is considered very important to the Canadian natural
gas supply. Many operators within the Montney play use carbon dioxide and nitrogen based
fractures treatments to achieve improved rates of hydrocarbon production.
Due to the unconventional nature of the Montney play, operators have attempted
to carry out field trials to evaluate the performance of different fracturing fluids; however,
due to the heterogeneous nature of the shale play, some authors have not reached a general

195
consensus about the optimal fracturing fluid. For example, RPS Energy Canada Ltd, Enfrac
Inc, and Ferus Inc carried out a collaborative study to compare slick-water fracturing fluids
and energized fracturing fluids using nitrogen and carbon dioxide, where they selected
66 horizontal wells in 2011. When examining the results from the production data, they
showed that energized fracturing fluids, in particular carbon dioxide based fluids, offer con-
siderable superior performance compared to slick-water fracture treatments. In addition,
other advantages of using energized fracturing fluids are identified such as reduced water
consumption and improved cleanup (Burke et al., 2011). In contrast, in 2009, Halliburton
and Trident carried out a field trial into various well stimulation fluids namely carbon dioxi-
de foam fracturing fluid, ultrahigh quality (88% CO2 by volume) biopolymer foam, and
slick-water fracturing fluid. When analysing this publication, on one hand, the authors
concluded that the slick-water fracturing offered the best initial production rates, and on the
other hand, the authors stated that the stratographic reservoir differences might invalidate
the relative comparison between the well stimulation treatments. Furthermore, the authors
acknowledged the difficulty in selecting comparable candidate wells for fracture treatments
(Romanson et al., 2010, Vincent, 2009).

2.3. Nitrogen, Carbon Dioxide and Slickwater treatments in the Marcellus Play

The Marcellus shale play is situated in the Appalachian Basin, which spans across se-
veral eastern states in the United States such as Pennsylvania, West Virginia, Ohio, New
York, Maryland, and Virginia. According to the EIA, the active area (10,622 square miles)
is mainly located within Pennsylvania and West Virginia and the undeveloped area consists
of the remainder of the region representing 84,271 square miles (EIA, 2011).
Due to the unconventionality of the Marcellus shale play, many authors have debated
the characterization of the shale rock in relation to issues such as water sensitivity and
pressurization of the formation (Perkins, 2008, Myers, 2008). For several years, nitrogen
fracture treatments have been widely used in the Marcellus shale play. However, since
2006, Perkins (2008) reports that slickwater treatments are gaining increasing dominance in
the Marcellus shale play due to success stories about slickwater treatments in the Barnett
shale play and advancements in chemical additives that has allowed operators to achieve
higher production rates of natural gas and oil.

2.4. Carbon Dioxide treatments in North American shale plays

The Milk River and Medicine Hat Formations are located in Southern Alberta, Cana-
da, where the reservoirs often have low permeabilities and high clay content. In 2002,
a field trial was carried out into different carbon dioxide energized fracturing fluids to im-
prove understanding of the overall economics of increasing gas production as opposed to
focussing narrowly on the reduction of costs. The study found that the use of energized
carbon dioxide foams offered significantly increased production in long-term production
rates (Tulissi and May, 2002).

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 Elsewhere, Gupta (2008) explains that liquid carbon dioxide has gained prevalence as
a hydraulic fracturing fluid since the 1980s due to the chemistry and thermodynamic pro-
perties of the fluid. Unlike slick-water fracturing fluids, the use of liquid carbon dioxide as
a fracturing fluid negates the need for chemical additives. The main advantages of using
liquid carbon dioxide are that capillary fluid retention and clay swelling do not occur. When
analysing the attributes of liquid carbon dioxide as a fracturing fluid, the physical properties
of this fluid must be considered. One disadvantage of using cryogenic fracturing fluids is
that they have a higher rate of leak-off compared to conventional fluids. However, due
to the compressibility of cryogenic fluids, when they are pumped at a high pressures and
low temperatures into a well, the fluid can expand volumetrically upon exposure to lower
pressure and high temperature of the formation. This volumetric expansion creates a ther-
mal expansion effect that hinders the leak off rate from the fracture into the reservoir, which
propagates the fracture width (Gupta, 1998).

2.5. Nitrogen treatments in Western Siberia

In Western Siberia, the production of gas reserves in the Cenomanian formation plays
a significant role in the Russian natural gas supply. Since these reserves have been in pro-
duction from the 1980s, much of the reservoirs have become depleted, where they suffer
from low pressures. Many gas operators have attempted to use conventional stimulation
techniques, such as water-based crosslinked fluids, which were unsuccessful because they
caused problems such as polymer damage and prolonged cleanup times. To improve the
well stimulation process, gas operators have now turned to using foam fracturing fluids
because they are suitable for under pressurized gas wells and they offer faster cleanup times
(Oussoltsev et al., 2008). Work carried out by Schlumberger and Gazpromneft investigated
the use of nitrogen foam stimulations using 70% quality with a viscoelastic surfactant. The
study found that there was a substantial reduction in clean up time, a reduction in formation
damage, and promising production data in depleted zones. From an operational standpoint,
the authors concluded that the expansion of foamed fracturing would require developments
in infrastructure and operation logistics(Oussoltsev et al., 2008).

3. CONCLUSION

Nitrogen and carbon dioxide fracture treatments have been successfully used for the
stimulation of unconventional shale plays that are characterized as shallow, depleted, low
permeability, low porosity, water sensitive and under pressurized. The use of nitrogen and
carbon dioxide treatments as an alternative to water based treatments is prevalent in the
Devonian and the Montney shale plays. The main advantages of nitrogen and carbon dioxi-
de treatments include improved well cleanup, prevention of formation damage and reduced
water requirements. However, further technological advancements are required to address
the shortcomings of nitrogen and carbon dioxide treatments, which include high leak off
rate especially when used as a cryogenic liquid, and high pumping pressure relative to water
based treatments.

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